Documnt Project

CONTENTS
Page No.
CHAPTER 1 1-15
COMPANY PROFILE 01
1.0 INTRODUCTION 10
1.1 Principle of liquefaction 10

1.2 Requirement of nitrogen liquefier 12
1.3 Objectives of the work 12

1.4 Physical and Chemical Properties of Nitrogen 13
1.5 Main applications 14
CHAPTER 2 16-24
2.1 Literature survey 16
2.2 Different Process 23
CHAPTER 3 25-32
3.1 Selection of the Process 25
3.2 Process Design and detailed Manufacturing process 26
CHAPTER 4 33-40
4.1 Material and Energy balances 33
4.2 Plant location and layout 37
4.3 Safety 38
Conclusion 41
Bibliography 42
CHAPTER 1
COMPANY PROFILE
Motto: Service Society through Industry
Nagarjuna Fertilizers and Chemicals Limited (NFCL) is engaged in the manufacture of Urea
Fertilizer in the complex located at Kakinada, East Coast of Andhra Pradesh. NFCL is the
Flagship Company of the Nagarjuna Group, a well-diversified and fast-growing group in
India. It is the first Natural Gas based Fertilizer Complex in South India. The plant is located
around 5 Km off North East of Kakinada Town on barren land, which around 1 Km from
Kakinada Port.
The Kakinada Fertilizer Project was originally conceived in the year 1974 by Shaw Wallace
group and it was handed over to Nagarjuna Group in the year 1985. The resurrection of the
project and its implementation against tremendous odds was the result of the vision and
indomitable courage of the groups founder late Shri K V K Raju.
The initial years of Project faced tremendous turbulence and it took until September 1988 to
finally obtain all the clearances, the major hurdles being environmental clearances and tying
up financial assistance. The project, which was at one time considered dead, has risen like a
phoenix from the ashes. The Fertilizer Plant with Ammonia, Urea & related Offsites facilities
went into commercial production from Aug 1, 1992.
Subsequently, NFCL undertook an expansion program in 1995 and the expansion plant of
identical capacity as the original plant was installed but based on naphtha as feedstock
(considering the shortage in Natural Gas availability) went into commercial production on
March 19, 1998 with a stream of Ammonia, Urea & related additional Offsites facilities.
Ammonia Plant-II was designed to have the flexibility of mixed feed / fuel operation
(Naphtha + Natural Gas) in any proportions.
INFRASTRUCTURE FACILITIES:
Location: Agricultural town close to market
Water: Godavari River
Gas: Gas Authority of India Ltd. (GAIL) & Reliance Industries Limited (KGD6)
Area : 1127 Acres Total Area, (121 Acres Built-up Area, 789 Acres Green Belt, 160 Acres
Water Bodies and 57 Acres Landscapes, Roads & Non Built-up Area)
SPCE Chemical Engineering

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Railway Siding: Connected to South Central Railway
PROCESS DESCRIPTION
AMMONIA PROCESS:
The feed stock natural gas, is desulphurised by conversion of stable organic sulphur
compounds into Hydrogen Sulphide in presence of Nickel Molybdenum catalyst followed by
absorption of Hydrogen Sulphide on Zinc Oxide bed. The desulphurised natural gas is mixed
with superheated steam to give steam to Carbon ratio of 3.3:1, preheated and fed to the
catalyst tubes in Primary Reformer. The Primary Reformer is a side-fired furnace with radiant
burners. The natural gas which is predominantly methane undergoes following reactions
producing Hydrogen and Carbon Oxides:
CH4 + H2O ------------- 3 H2+ CO - heat
CO + H2O ------------- CO2 + H2 + heat
The process gas from the tubes is gathered by a collector system and sent to the Secondary
Reformer.
The Secondary Reformer is a refractory lined vessel containing Nickel catalyst. Air from
atmosphere comes in contact with the process gas from Primary Reformer. Combustion of
some part of Hydrogen and Methane occurs consuming the total oxygen in the air and the
temperature rises to about 1300 deg. C. This supplies the heat needed for completion of the
endothermic reaction in the catalyst bed. Nitrogen needed for ammonia synthesis gets
introduced in to the system in the Secondary Reformer through the process air. The gas
leaving Secondary Reformer contains residual Methane of 0.6%. The exit gas from Secondary
Reformer is cooled to about 380 deg. C in the Waste Heat Boiler where high-pressure steam
is generated.
The carbon-monoxide formed in the reforming step is converted to CO2 by water gas shift
reaction in two stages, namely, high temperature shift conversion and low temperature shift
conversion. The HT shift reaction takes place in presence of iron oxide chromium oxide
catalyst and LT shift reaction takes place in presence of copper oxide zinc oxide catalyst. The
shift conversion reaction being exothermic, steam is produced by heat recovery.
The reaction-taking place in the shift conversion can be represented as:
CO + H2O --------- CO2 + H2 + heat
The process gas leaving the CO conversion step contains in addition to Hydrogen and
Nitrogen, large quantity of CO2 and small quantities of CO, Argon and Methane. The CO2
present in the process gas is removed in the CO2 removal section using Giammarco
Vetrocoke process. Here, CO2 absorbed in potassium Carbonate solution is regenerated by
reducing the pressure and addition of heat in two stage regenerators. The regenerated solution
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is pumped back to the absorber. Thus, the system operates in closed circulation. The CO2 gas
stripped from the solution in the regenerators is cooled and sent to Urea plant.
The process gas exit absorber now contains only traces of CO and CO2. Since carbon oxides
act as poison to the ammonia synthesis catalyst, the residual carbon oxides present in the
process gas are converted into methane in a methanator reactor containing nickel catalyst.
This step is the reverse of reforming reaction and consumes a small amount of hydrogen.
The methanator exit gas after cooling and removal of condensate is the synthesis gas with
some inerts. This gas is compressed from 24 Kg/Cm2g to 134 Kg/Cm2g in a centrifugal syn
gas compressor. Also, there is a recirculation stage in the compressor where the recycle of
unconverted gas along with the compressed make up gas are further compressed to about 142
Kg/Cm2g. This gas after pre-heating is admitted to ammonia synthesis converter containing
promoted iron catalyst, where Hydrogen and Nitrogen combine to form ammonia with
evolution of heat. The ammonia synthesis reaction is:
N2 + 3 H2 ------------- 2 NH3 + heat
The gas from the converter is cooled in a series of heat exchangers including a Waste Heat
Boiler. The condensed ammonia is separated and the uncondensed gases are recirculated back
to the converter via the recirculator compressor. The product ammonia is cooled to a
temperature of -33 deg. C by means of ammonia refrigeration system. The inerts level in the
synthesis loop is kept low by taking an inerts purge and sending the same to the purge gas
recovery unit where ammonia and Hydrogen are recovered and the remaining off gas is used
as fuel. The product ammonia is pumped to the ammonia storage tanks or directly to Urea
Plant.
PROCESS DESCRIPTION EXPANSION PLANT:
The process description for expansion Ammonia and Urea plants are identical to the existing
plant as they are based on the same process technologies. However, the feed stock being
Naphtha, whose sulphur content is higher than Natural Gas an additional desulphurisation
section (pre-desulphurisation section) is added wherein the sulphur content is reduced to less
than 10 PPM by catalytic conversion of organic sulphur compounds to H2S. An Adiabatic
pre-reformer is also added wherein the higher hydrocarbons in Naphtha are converted to
Methane. The reaction-taking place in the Adiabatic Pre-reformer is as follows:
Cn Hm + H2 O ------ Cn 1 Hm 2 + CO + 2 H2 Heat
The process gas from the Adiabatic Pre-reformer is fed to the primary reformer.
Return Naphtha System:
In the expansion Ammonia plant, two separate Naphtha condensation and recovery systems
are provided. In case of any plant shutdown the vaporised feed and fuel Naphtha are
condensed and sent back to the Sweet Naphtha Tank and raw Naphtha Tank respectively.
Thus no Naphtha is wasted or discharged into atmosphere.

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UREA PLANT:
The production of Urea requires ammonia and CO2 as the inputs, both of which are available
from Ammonia plant. The CO2 from ammonia plant is compressed to about 160 Kg/Cm2 and
sent to the Urea Reactor. Liquid Ammonia is pumped using high-pressure reactor feed pump
and along with recycle carbamate enters into Urea Reactor. Urea Reactor operates at about
156 Kg/Cm2 and 188 deg. C.
Following reactions take place in the Urea Reactor:
2 NH3 + CO2 -------- NH2COONH4 (Ammonium Carbamate) + heat
NH2COONH4 ----- CO (NH2)2 + H2O heat (Urea)
The product stream from the Urea Reactor contains in addition to Urea, large quantity of
unconverted ammonia, CO2 and water. The ammonium carbamate in the product stream is
recovered in three stages viz., high pressure stage, medium pressure stage and low pressure
stage by decomposing the carbamate into ammonia and CO2, separating the gases from the
liquid product stream and recondensing the gases back to carbamate solution which is
recycled back to the Urea Synthesis Reactor. In this process, the product stream becomes
richer and richer in the urea content. In the high-pressure section, separation of Ammonia and
CO2 in the falling film of liquid in the tubes is stripped by ammonia vapor. Medium pressure
steam supplies the required heat.
As the Urea Reactor operates with excess ammonia, the excess ammonia is recovered in
ammonia condenser. The product stream leaving the low-pressure section contains 70% Urea.
This is further concentrated in the vacuum concentrators to get 99.8% Urea melt. This molten
Urea is pumped to the top of urea prilling tower and fed into a prilling bucket. The prilling
tower of 22-M diameter and 75 M free fall height operates under natural draft. The Urea prills
from the bottom of the prilling tower are transported through mechanized belt conveyor
system into urea storage silo or directly to urea bagging plant. The bagged urea is dispatched
by rail wagons/road trucks.
MAJOR OFFSITE UNITS AT NFCL, KAKINADA
Raw water is received from Samalkot reservoir, 13 KMs away from plant site. It flows by
gravity through underground water pipe lines (2 Nos.) of 1-M diameter. Water contains
impurities. The suspended solids in the water are removed by flocculation which is aided by
addition of alum and polyelectrolyte. Chlorine is also added as biocide. The suspended solids
undergo flocculation in the clarifloculator and form sludge at the bottom. The overflow water
from the clarifloculator is filtered in sand filters and used for various purposes like in cooling
towers, service water, drinking water etc.

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The turbidity of the final filtered water is less than 2 NTU.
The sludge is removed from the bottom of the clarifloculator and sent to effluent treatment
plant for further treatment.
DM PLANT :
The pre-treatment of raw water only removes suspended matter. However, the filtered water
contains dissolved impurities, which can cause problems like scaling, corrosion etc. in the
boilers on the heat transfer surfaces while raising steam. The steam generated will also be
impure and can result in problems like scale formation on turbine blades etc. Hence to
eliminate such problems the water is treated to remove dissolved solids. This is known as
demineralisation and is accomplished by "Ion Exchange Resins".
The water to be purified first flows through Active Carbon Filters (ACF) where oil and
chlorine are removed, then into the Strong Acid Cation Exchanger (SAC) containing resins.
Here the hydrogen ions will be exchanged for the cations in the water (for example if water-
containing NaCl is passed through SAC, the resin exchanges Hydrogen with Na in the water
to form HCl in water). Thus the cationic resin retains the cation (Na) and release hydrogen
ions into water. The water virtually free of cations is sent to degasser tower where CO2 is
removed from water by blowing air and then water is fed to weak base anion exchanger. Here
the hydroxide ions will be exchanged for the anions (Chlorine is retained by the resin and
Hydroxide ion released to form HOH in water). Silica is removed in strong base anion
exchanger having resin. Thus NaCl in water is replaced with HOH after passing through
cation and anion exchangers, to form pure water. Minute traces of dissolved solids, which
escape, are removed in mixed bed exchanger. The effluent of mixed bed is very pure water
with pH = 7 and conductivity = 0.1 2.2 mhos/cm. This water is used for steam production.
The cation and anion exchanger resins after certain throughput will get exhausted and lose
their capacity for ion exchange and require regeneration. This is done by HCl for SAC and
NaOH for WBA and SBA and both for mixed bed. During the process of regeneration the
resins get recharged.
The process and turbine condensate returning from the process plants may contain some
impurities, which needs to be removed. This is done in polishing units, which contains an
active carbon filter and a mixed bed and also a guard bed for process condensate. Thus the
condensates are purified and reused as D M water. Here also the resins are regenerated after
certain throughput.
COOLING TOWERS :
Both Ammonia and Urea have individual cooling towers. Ammonia cooling tower caters to
Offsite plants also. The towers are induced draft cross-flow type supplied by M/s. Paharpur
cooling towers.

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In the process plants after various exchanges of heat among the process streams some
quantity of heat is invariably rejected to cooling water in equipments like coolers, surface
condensers etc. The hot water returning from the plant is made to trickle down the cooling
tower through fills. A motor with fan fixed on top of the decks sucks air through the tower
fills. Part of water evaporates, taking heat from its own sensible heat. As a result the
remaining water gets cooled. The water vapour with air is pushed by the fans into the
atmosphere. Thus hot water enters the cooling tower and gets cooled.
The cold water is pumped backed to the various heat exchangers for heat pick up in the
process plants and the cycle continues.
INERT GAS PLANT (IG PLANT) :
During the start-up, shut down and certain special operation of the process plants we may
require an inert gas like Nitrogen (N2). Hence we are generating N2 in our Inert gas plant
supplied by M/s. Air products . The atmospheric air is compressed in Main air compressor.
The compressed air is passed through molecular sieves to remove carbon di oxide & water.
This moisture free air is cryogenically distilled to separate N2 . It can be obtained either in
liquid form, gaseous or combination of both. Liquid N2 is stored in bullets. The product N2
contains < 10 ppm Oxygen.
INSTRUMENT AIR :
The operation (actuation) of control valves requires compressed air with extremely low
moisture (dew point of about 40 Deg. C at atm pres). This instrument air is obtained by
compressing air and drying it in absorbers containing silica gel. Instrument air is available at
7 Kg/Cm2 g.
PLANT AIR :
Plant air is used for various services and utilities. It is also compressed air, but no moisture is
removed like in case of instrument air.
CAPTIVE POWER PLANT:
The plant electric power demand is met by the gas turbines. There are two gas turbine
alternator sets(GT-A & GT-B)capable of generating 6.77 MW each (at ambient conditions)
supplied by M/s. Turbo Technical, Italy and one gas turbine alternator set (GT-C) capable of
generating 17.5 MW (at ambient conditions) supplied by M/s. Thomassen
International,Germany .
GT-A & GT-B:
GT-A & GT-B have two stages, HP stage and LP stages. HP stage drives the air compressor
while LP stage drives the load. The source of energy is natural gas at 21 Kg/Cm2 g, which

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undergoes combustion with compressed air. The products of combustion are expanded in the
gas turbine to generate power.
The gas turbine exhaust gases leave at a temperature of about 540 Deg. C and still contain a
lot of recoverable heat. This heat is utilized to generate steam at 38 Kg/Cm2 g and 380 Deg.
C in Heat Recovery Steam generating boilers and the gases are let out at about 190 Deg. C.
These are also bi drum unit capable of generating 23 Te/hr steam using the exhaust flue gas
from gas turbines. There is a provision for supplementary firing of natural gas as a result of
which 60 Te/hr of steam can be generated. The incorporation of heat recovery boilers
increases the overall efficiency to 75% to 80% which would have been otherwise 20% to 21%
if the gas turbine were to generate electric power alone and the flue gases let out to
atmosphere at 540 Deg. C. This is known as "Cogeneration" principle.
GT- C:
GT-C has single shaft only. The source of energy is natural gas at 21 Kg/Cm2 g, which
undergoes combustion with compressed air. The products of combustion are expanded in the
gas turbine to generate power.
Heat is recovered from the gas turbine exhaust gases leaving at a temperature of about 540
Deg. C to generate steam at 107 Kg/Cm2 g and 515 Deg. C in Heat Recovery Steam
generating boiler(HRSG).The exhaust gases are let out at about 150 Deg.C.HRSG is capable
of producing 100 Tph of superheated steam with the supplementary firing in the duct
burners .There is also a provision of generating steam in this HRSG in the fresh air mode
without the exhaust gas .For this purpose FD fan is provided .
AUXILIARY BOILERS :
The MD type boilers (2 Nos.) of capacity 100 tones/hr each, supplied by M/s. Mitsui are
provided with a steam drum and a water drum which are interconnected by down comers and
risers. The steam drum is equipped with a set of steam purifiers inside to obtain the required
steam purity.
Feed water heated by the economizer enters the steam drum. The boiler water flows down to
the water drum through down comer tubes. The mixture of water and steam flows upwards
through riser tubes into the steam drum where steam is separated from water. The entrained
water droplets in steam if any are removed by the demister and scrubbers. Saturated steam
flows to the primary and secondary super heaters where it gets superheated. The final steam
obtained is at 107 Kg/Cm2 g and 515 Deg. C.
The boiler furnace is designed for combustion of natural gas/low sulphur heavy stock (LSHS)
or combination of other gases with NG/LSHS. Combustion air is drawn by the forced draft
fan and flows to the steam air heater (used if LSHS is fuel) and then to a Gas air-heater where
air is heated by recovering heat from flue gas.

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The flue gas leaving the furnace goes to the stack via superheater, economiser and gas-air
heater etc.
AMMONIA STORAGE:
During normal operation Ammonia produced in the Ammonia plant goes directly for Urea
manufacture. In case of Urea plant stoppage or running at low load, in order to avoid
stoppage or reduction of Ammonia plant load, two ammonia storage tanks each of 5000 MT
capacity are provided where liquid ammonia can be stored.
The storage tank is double wall double integrity type to ensure utmost safety. By double
integrity it is meant that the outer tank is also made of the same material (low temperature
carbon steel) as the inner tank and is equally strong. In case the inner tank leaks the outer tank
will be able to contain the Ammonia.
Due to heat ingress from ambient air & flashing of product liquid ammonia entering the tank
from the ammonia plant , vapour will be generated in the storage tank which are compressed,
cooled, condensed and sent back to the Ammonia storage tank. Whenever Ammonia is
required from the storage tanks for Urea plant it is pumped by ammonia transfer pumps.
Emergency power is provided for the refrigeration system. Sufficient precautions and
provisions have been incorporated to protect the storage tank from under and over pressure.
EFFLUENT TREATMENT PLANT (ETP) :
The major effluents generated in the process plants are normally treated in the process plants
itself except during upsets which is very rare. The ETP receives oily innocuous effluents from
cooling towers, boilers, oily water from process plants, floor washings, rain water and sludge
from clarifloculator and mostly serves as secondary treatment and back-up unit.
The sludge generated in the pre-treatment plant is thickened in the thickener and sent to
centrifuge where it is caked. The overflow is sent to the equalization pond. The effluents from
the process plants after correcting for pH and the acidic-alkaline water produced during
regeneration of ion exchange resins in the DM plant are sent to equalisation pond. Also the
oily effluents from various plants are treated in disc oil separators and sent to equalisation
pond. The water from the equalisation pond sent to holding pond from where it is pumped to
green belt.
BAGGING:
The prilled Urea from the Urea plant is transferred to the Bagging plant in belt conveyers.
The bagging plant has 8 bagging streams. Stream No.8 is also be used exclusively for
recovery of spillage Urea.

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The prilled urea enters the bunkers (one for each stream) designed for 50 MT of urea
capacity. Bunkers are provided with load cells. Each bunker has two independent electronic
bagging machines below. Filled bags are moved by slat conveyer for stitching and then
conveyed to wagon loading platforms or lorry loaders according to the requirement.
Any maintenance job or any problem in the bagging plant does not require Urea plant to be
shut down as the prilled Urea can be stored in silo capable of storing 30,000 MT Urea, which
can be bagged later.
CARBON-DI-OXIDE RECOVERY (CDR) PLANT:
Technology Supplier: Mitsubishi Heavy Industries (MHI), Japan.
CO2 Absorbent: KS-1 Solution, Proprietary Supply from MHI, Japan.
The Flue Gas from Primary Reformer enters the Flue Gas Quencher, where it is cooled to
40C. The Flue Gas is compressed to a pressure of 1.113 Ksc and enters the CO2 Absorber.
The CO2 in Flue Gas is absorbed by KS-1 Solvent, which is distributed from top through
packed bed system. Subsequent to contact with KS-1 Solution the Flue Gas is further washed
with DM Water in the top section of CO2 Absorber. The Flue Gas after removal of CO2 is
sent out to atmosphere through a stack provided at CO2 Absorber top. The CO2 rich solution
at 55C is pumped to the Lean / Rich Heat Exchanger. The Lean Solution is recycled back to
CO2 Absorber. The rich solution stream is heated up to 114 C and sent to CO2 Regenerator,
wherein CO2 is stripped off from rich solution by providing necessary heat to Reboiler using
Low Pressure Steam. The CO2 thus liberated is washed with DM water at the top of CO2
Regenerator, cooled to ambient temperature in a overhead condenser and sent to Urea Plants.
In view of adequate Natural Gas supply to NFCL by RIL, it was decided to switchover Unit-
II operations to full NG mode from the present operation of mixed Feed / Fuel (NG +
Naphtha). Subsequent to switchover from Naphtha / NG Mix to full Natural Gas mode in
Unit-II, there will be shortfall of CO2 which will be met through the CO2 Production from
CDR Plant
The Power & Steam demand required for CDR Plant is met through the existing offsite
facilities.

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1.0 INTRODUCTION
Generally in chemical process plants, nitrogen is extensively used as an inert medium by
virtue of its qualities. Nitrogen (N2) is a colorless, odorless and tasteless gas that makes up
78.09% (by volume) of the air we breathe. It is nonflammable and it will not support
combustion.
Nitrogen gas is slightly lighter than air and slightly soluble in water. It is commonly thought
of and used as an inert gas; but it is not truly inert. It forms nitric oxide and nitrogen dioxide
with oxygen, ammonia with hydrogen, and nitrogen sulfide with sulfur. Nitrogen compounds
are formed naturally through biological activity. Compounds are also formed at high
temperature or at moderate temperature with the aid of catalysts. At high temperatures,
nitrogen will combine with active metals, such as lithium, magnesium and titanium to form
nitrides. Nitrogen is necessary for various biological processes, and is used as a fertilizer,
usually in the form of ammonia or ammonia-based compounds. Compounds formed with
halogens and certain organic compounds can be explosive.
Nitrogen condenses at its boiling point, -195.8o C (-320.4o F), to a colorless liquid that is
lighter than water.
More nitrogen is used by customers than any other industrial gas. It is used in a broad
range of industries, including chemicals, pharmaceuticals, petroleum processing, glass and
ceramic manufacture, steelmaking and other metals refining and fabrication processes, pulp
and paper manufacture, and healthcare. Aside from N2, nitrogen may be referred to as GAN
or GN in its gaseous form, and LIN or LN in its liquid form.
1.1 Principle of Liquefaction

Liquefaction of gases is always accomplished by refrigerating the gas to some temperature
below its critical temperature so that liquid can be formed at some suitable pressure below the
critical pressure. Thus gas liquefaction is a special case of gas refrigeration and cannot be
separated from it. In both cases, the gas is first compressed to an elevated pressure in an
ambient temperature compressor. This high-pressure gas is passed through a countercurrent
recuperative heat exchanger to a throttling valve or expansion engine. Upon expanding to the
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lower pressure, cooling may take place, and some liquid may be formed. The cool, low-
pressure gas returns to the compressor inlet to repeat the cycle. The purpose of the
countercurrent heat exchanger is to warm the low-pressure gas prior to recompression and
simultaneously to cool the high-pressure gas to the lowest temperature possible prior to
expansion. Both refrigerators and liquefiers operate on this basic principle.
In a continuous refrigeration process, there is no accumulation of refrigerant in any part of the

system. This contrasts with a gas liquefying system, where liquid accumulates and is
withdrawn. Thus, in a liquefying system, the total mass of gas that is warmed in the
countercurrent heat exchanger is less than that of the gas to be cooled by the amount
liquefied, creating an imbalance mass flow in the heat exchanger. In a refrigerator the warm
and cool gas flows are equal in the heat exchanger. This results in what is usually referred to
as a "balanced flow condition" in a refrigerator heat exchanger. The thermodynamic
principles of refrigeration and liquefaction are identical. However the analysis and design of
the two systems are quite different because of the condition of balanced flow in the
refrigerator and unbalanced flow in liquefier systems.
The Joule-Thomson coefficient is a property of each specific gas. It is a function of

temperature and pressure, and may he positive, negative, or zero. For instance, hydrogen,
helium, and neon have negative J-T coefficients at ambient temperature. Consequently, to be
used as refrigerants in a throttling process they must first be cooled either by a separate pre
coolant liquid. Only then will throttling cause a further cooling rather than a heating of these
gases.
Another method of producing low temperatures is the adiabatic expansion of the gas through
a work-producing device such as an expansion engine. In the ideal case, the expansion would
be reversible and adiabatic and therefore isentropic. In this case, we can define the isentropic
expansion coefficient which expresses the temperature change due to a pressure change at
constant entropy. An isentropic expansion through an expander always results in a
temperature decrease. Whereas an expansion through an expansion valve may or may not
result in a temperature decrease. The isentropic expansion process removes energy from the
gas in the form of external work, so this method of low-temperature production is sometimes
called the external work method.

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1.2 Requirement of nitrogen liquefier
Nitrogen liquefier used to produce liquid nitrogen. Because of its low production cost and
relatively higher levels of safety is the most common cooling medium in the cryogenic
temperature range above 77 K. The application covers such diverse areas as:
Pre coolant in production of liquid helium and low temperature refrigerators
Cryotreatment of critical metallic components such as hubs, milling cutters, knives,

rollers, needles, dies and punches, bearings and precision measuring equipment,
Preservation of live biological material as blood, animal and human sperms, embryos,
bacterial cultures etc
Cold trap in vacuum systems and in adsorption pumps, and
Miscellaneous laboratory and industrial applications.
1.3 Objectives of the work

Prior to the making of the turbo expander based nitrogen liquefier, the thermodynamic processes
is to be designed and each equipment specifications are to be determined. A system runs
continuously when it follows definite processes in a cyclic path. Process design means,
determination of the type of thermodynamic processes included in the thermodynamic cycle and
fixing the points i.e. pressure and temperature. While designing the process, equipment
availability, constraints and cost should be kept in mind. Process design also includes the setting
the parameters up to the optimum condition that maximum amount of liquid will be obtained.

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1.4 Physical and Chemical Properties of Nitrogen
Nitrogen is present in atmosphere as a chemical element. Nitrogen can participate in all living
organisms and it constitutes 78% of the earths atmosphere. It is also present in both the
organic and also inorganic compounds. The nitrogen is also present in proteins and also
present in nucleic acids. In industries the nitrogen is obtained from the fractional distillation
of liquid air. Nitrogen is also present biological components like DNA and RNA.
Physical Properties
Nitrogen physical properties
Physical properties of nitrogen is given as,
Nitrogen is a gas without any color, taste and also without any smell which is one of
the physical property of nitrogen.
Nitrogen is relatively considered as inert gas which is one of the physical property of
nitrogen.
Nitrogen is also considered as the liquid which is similar to water in appearance.
The melting point of the nitrogen is -2100C
The boiling point of the nitrogen is -195.80C.
Nitrogen contains the two allotropic forms of solid a and b where the transition takes
place in between the two forms at the temperature of -2370C.
The vapor density of nitrogen is given as 14which is one of the physical property of
nitrogen.
Nitrogen has the soluble property; it is less soluble in water which is one of the
physical property of nitrogen.
Chemical Properties
Chemical properties of nitrogen:
The color of indicators is not affected by the nitrogen since it is a neutral gas which is
one of the chemical property of nitrogen.

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Nitrogen can combine with other elements and form some compounds under certain
temperature which is one of the chemical property of nitrogen..
At high temperature or low temperature nitrogen can form compounds through the
biological activity which can act as catalyst.
In accordance with the oxygen nitrogen forms nitrogen dioxide as well as nitric acid.
When nitrogen is combined with the hydrogen it forms ammonia and with sulfur it
form nitrogen sulfide.
Nitrogen is combined with certain metals at higher temperatures which forms the
active metals such as lithium and magnesium.
Nitrogen is a non flammable compound which does not support the combustion which
is one of the chemical property of nitrogen..
After ionization the energy of nitrogen is given as 1402kJ.mol-1.
The electronegativity of nitrogen due to the Pauling method is given as 3.0.
1.5 Main applications
Industries Applications:
Mostly purging explosive and toxic vessels and pipelines and sometimes for process reactions
Chemicals:
Nitrogen can be used for blanketing, as well as for:
- Storage for protecting raw materials or finished products in liquid form from the formation
of peroxides and/or gum, and from contamination by oxygenated components
- Regeneration of purification beds (alumina and molecular sieve)
- Preparation of catalysts and transportation of polymer powders
- Medium for the exhaust of emitted heat in fluid bed reactors
- Temperature Control in reactors.
Pharmaceuticals:
Nitrogen is used for inerting, cryo-grinding, lyophilisation, drying, liquid phase transfer of
products or synthesis intermediates; cryo-condensation of waste gases and low temperature
storage.
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Food and Beverage:
Liquid nitrogen: N2 is the most used cryogenic fluid, to chill, freeze or store food products.
Gaseous nitrogen: N2 is very commonly used in contact with foodstuffs to avoid oxidation or
micro-organism growth by inerting of liquids. Modified Atmosphere Packaging (MAP)
preserves and protects foods ( pure nitrogen or mixed with CO2)
Glass, Cement and Lime:
Nitrogen is used as an inert gas especialy to create, in combination with hydrogen, a

reductive atmosphere over the tin bath in the float glass process.
Healthcare
Low-temperature preservation of living tissues and cells
Laboratories & analysis:
Nitrogen is used as a carrier gas in gas chromatography for various industrial and hospital
analyses and quality control. Nitrogen is the balance gas of the calibration gas mixtures for
environmental monitoring systems and industrial hygiene gas mixtures. Nitrogen is largely
used as purge, drier or blanket gas for analyzers or chemical reactors (under gaseous state or
at low temperature liquid state).
Welding, Cutting & Coating
Heat treatment of various metals. Nitrogen is a component of the special mixtures used in
CO2 lasers
Oil and Gas:
Quality protection of products and facilities (blanketing)
Electronics:
Nitrogen is used as carrier gas for overall protection against impurities and oxidation in
semiconductor and soldering processes. In its cold and liquid form, N2 is used as a cooling
medium in the environmental testing of electronic devices.
Automotive & transportation:
Gas Assisted Injection Moulding requires pressures between 10 bar (145 psi) and 200 bar
(2900 psi) and a nitrogen content of between 98.0 % and 99.9 %.
Tires filling with nitrogen increases their lifetime and therefore decreases the recycling or
treatment of this waste.

Page 15
Other industries :
Pneumatic transportation of powdered flammable materials(charcoal).
DISADVANTAGES:
Complete removal of H2O, CO2 and hydrocarbons to prevent plugging in the low
temperature sections of the plant.
Developing effective low temperature insulations and lubricants
Complex heat balancing designs.
Preventions of explosive mixtures in oxygen rich regions.
CHAPTER 2
2.1 LITERATURE REVIEW
History of Liquefaction
Before 1877, a number of workers had discovered by visual observation in thick-walled glass
tubes that the permanent gases, including hydrogen, nitrogen, oxygen and carbon monoxide,
could not be liquefied at pressures as high as 400 atm. At first in 1877 oxygen gas is liquefied
by Cailletet and Pictet. It is the first permanent gases to be liquefied. The term 'permanent'
arose from the experimentally determined fact that such 'permanent' gases could not be
liquefied by pressure alone at ambient temperature, in contrast to the non-permanent or
condensable gases like chlorine, nitrous oxide and carbon dioxide, which could be liquefied
at quite modest pressures of 30-50 atm.

Page 16
Fig. 1 Cailletets gas compressor and liquefaction apparatus
Figures 2.1 show the apparatus which Cailletet used to produce a momentary fog of oxygen
droplets in a thick walled glass tube. The oxygen gas was compressed using the crude
Natterer compressor in which pressures up to 200 atm. were generated by a hand-operated
screw jack. The pressure was transmitted to the oxygen gas in the glass tube by hydraulic
transmission using water and mercury. The gas was cooled to -110C by enclosing the glass
tube with liquid ethylene, and was then expanded suddenly by releasing the pressure via the
hand wheel. A momentary fog was seen, and the procedure could then be repeated for other
observers to see the phenomenon.

Page 17
Simultaneously at the first liquefaction of oxygen by Cailletet, Pictet also liquefied oxygen in
the same year 1877.
Fig 2 Pictet's cascade refrigeration and liquefaction system
Figure 2.2 shows the cascade refrigeration system of Pictet, in which oxygen was first cooled
by sulphur dioxide and then by liquid carbon dioxide in heat exchangers, before being
expanded into the atmosphere by opening a valve. The expansion yielded a transitory jet of
liquid oxygen, but no liquid could be collected from the high velocity jet. The figure shows
how Pictet used pairs of compressors to drive the SO2 (-20C) and CO2 (-60C) refrigerant
cycles on a continuous basis, and this is probably the first example of a cascade refrigeration
system operating at more than one temperature level. His use of the cascade system inspired
others like KamerlinghOnnes and Dewar.
In 1883, the Polish scientists Olzewski and Wroblewski, at Cracow, had improved Cailletet's
apparatus by:
Adding an inverted U to the glass tube; and
Reducing the ethylene temperature to -136C by pumping it below atmospheric

pressure.
These improvements enabled them to produce small quantities of liquid oxygen in the U tube
and to liquefy carbon monoxide and nitrogen for a few seconds.

Page 18
Page 19
From first liquefaction of oxygen to 1895, there was little progress in the developments of
liquefiers. Then in 1895, Hampson in London and Linde in Munich simultaneously patented
compact and efficient air liquefiers which used self-intensive or regenerative cooling of the
high pressure air by the colder low pressure expanded air in long lengths of coiled heat
exchanger. In this simple way, the complications of cascade precoolers employing liquid
ethylene and other liquid cryogens were removed. A further advantage of this simple liquefier
was the absence of moving parts at low temperature, the cooling being produced by Joule-
Thomson expansion through a nozzle or valve. Carl von Linde made rapid progress in
developing this technological breakthrough. He was a professor and research worker at the
University of Munich, and he had his own company constructing refrigeration plant.
The Linde-Hampson is the simplest of all the liquefaction systems. A schematic of the Linde-
Hampson system is shown in Fig. 2.3 and the cycle is shown on the T-s plane in Fig. 2.4.
Fig. 3 Linde air liquefaction system Fig. 4 T-S Diagram of Linde cycle
Process 1 to.2 would actually be two processes: an irreversible, adiabatic or polytropic

compression followed by an after cooling to lower the gas temperature back to within a few
degrees of ambient temperature. The gas next passes through a constant-pressure heat
exchanger (ideally) in which it exchanges energy with the outgoing low pressure stream to
point 3. From point 3 to point 4, the gas expands through an expansion valve to P4. At point
4, some of the gas stream is in the liquid state and is withdrawn at condition f (saturated-
liquid condition), and the rest of the gas leaves the liquid receiver at condition g (saturated-
vapor condition). This cold gas is finally warmed to the initial temperature by absorbing

Page 20
energy at constant pressure (ideally) from the incoming high-pressure stream. The liquid air
produced is very less.
By 1898, Charles Tripler, an engineer in New York, had constructed a similar but much larger
air liquefier, driven by a 75 kW steam engine, which produced literally gallons of liquid air
per hour. Tripler discovered a market for liquid air as a medium for driving air expansion
engines (the internal combustion engine was still unreliable at that time) and succeeded to
launch his Liquid Air Company.
Fig. 5 Tripler's laboratory showing 175 kW steam driven multistage air
compressor and 25 dm h- air liquefier
In the year, 1902, a young French innovative engineer Georges Claude, with wide
connections in the scientific world of Paris, had succeeded in producing a piston expansion
engine working at the low temperatures required for the liquefaction of air. The increase in
cooling effect over the Joule-Thomson nozzle expansion of the Linde, Tripler, and Hampson
designs was so large as to constitute a second technological breakthrough. Claude developed
air liquefiers with piston expanders.

Page 21
Fig. 6 Claude air liquefaction system Fig. 7 T-S Diagram of Claude Cycle
The expansion through an expansion valve is an irreversible process. Thus if we wish to

approach closer to the ideal performance, we must seek a better process to produce low
temperatures. In the Claude system, shown in Fig. 2.6, energy is removed from the gas stream
by allowing it to do some work in an expansion engine or expander.
The Claude cycle is shown on the T-s plane in Fig. 2.7. If the expansion engine is reversible
and adiabatic, the expansion process is isentropic, and a much lower temperature is attained
than for an isenthalpic expansion, In the Claude system, the gas is first compressed to
pressures on the order of 4 MPa (40 atm or 590 psia) and then passed through the first heat
exchanger. Between 60 and 80 percent of the gas is then diverted from the mainstream,
expanded through an expander, and reunited with the return stream below the second heat
exchanger. The stream to be liquefied continues through the second and third heat exchangers
and is finally expanded through an expansion valve to the liquid receiver. The cold vapor
from the liquid receiver is returned through the heat exchangers to cool the incoming gas.
In 1882, KamerlinghOnnes set up a cryogenic laboratory at the University of Leiden in the

Netherlands. In 1866, Van der Waals had published his first paper on 'the continuity of liquid
and gaseous states' from which the physical understanding of the critical state and of
liquefaction and evaporation was to grow. This information inspired KamerlinghOnnes and
for the first time in 1908, he was able to liquefy helium. He had only 360 liters of gaseous
2
helium obtained by heating monazite sand from India. More than 60 cm of liquid helium
was produced by ones in his first attempt.

Page 22
Fig. 8 Kapitza system
Kapitza (1939) modified the basic Claude system by eliminating the third or low temperature
heat exchanger, as shown in Fig. 2.8. Several notable practical modifications were also
introduced in this system. A rotary expansion engine was used instead of a reciprocating
expander. The first or high-temperature heat exchanger in the Kapitza system was actually a
set of valved regenerators, which combined the cooling process with the purification process.
The incoming warm gas was cooled in one unit and impurities were deposited there, while the
outgoing stream warmed up in the other unit and flushed out the frozen impurities deposited
in it. After a few minutes, a valve was operated to cause the high-and low-pressure streams to
switch from one unit to the other. The Kapitza system usually operated at relatively low
pressures-on the order of 700 kPa (7 atm or 100 psia).
Around 1942 Samuel C. Collins of the department of mechanical Engineering at

Massachusetts Institute of technology developed an efficient liquid helium laboratory facility.
He developed Collins helium cryostat results economical and safe production of liquid
helium.

Page 23
Fig. 9 Helandt system
Helandt (Davies 1949) noted that for a high pressure of approximately 20 MPa (200 atm) and
an expansion-engine flow-rate ratio of approximately 0.60, the optimum value of temperature
before expansion through the expander was near ambient temperature. Thus, one could
eliminate the first heat exchanger in the Claude system by compressing the gas to 20 MPa.
Such a modified Claude system is called the Heylandt system, after its originator, and is used
extensively in high-pressure liquefaction plants for air. The system is shown schematically in
Fig. 2.9. The advantage of the Heylandt system is that the lubrication problems in the
expander are not difficult to overcome. In the air-liquefaction system, the gas enters the
expander at ambient temperature and leaves the expander at approximately 150 K (-190F),
So that light lubricants can be used.
From time to time a lot of modifications had been made in all these cycles to optimize the
results. The efficiency and performance of the components are increased, and so little
modification in those cycles can reach up to lowest temperature and produce liquid for longer
period.

Page 24
2.2 DIFFERENT PROCESSES
Liquid Nitrogen is created through a multistage processes which pulls the air around us,
separates the different elements present in the air (largely nitrogen, oxygen, argon, water
vapor, and carbon dioxide), and then converts nitrogen gas to its liquid form by cooling it
below its boiling point. There are several methods in which to accomplish this but some are
more affective then others due to the amount of demand for the product (liquid nitrogen) and
also what the end product is going to be used for (how pure does the sample of nitrogen need
to be).
The methods of creating liquid nitrogen only differ in the method by which the elements of
air are separated. The process by which liquid nitrogen is formed from its gaseous state is
more or less the same.
Nitrogen is produced by Cryogenic and Non cryogenic processes.
There are two major types of non-cryogenic processes: selective adsorption or differential
permutation through membranes to produce relatively pure oxygen or nitrogen
Smaller volumes may be produced as a gas by pressure swing adsorption (PSA) or

diffusion separation processes (permeation through specially designed hollow fibers).
These air separation processes use differences in properties such as molecular structure, size
and mass to achieve the desired degree of product purity.
Non-cryogenic processes
Pressure swing adsorption provides separation of oxygen or nitrogen from air without
liquification. The process operates around ambient temperature; a zeolite (molecular sponge)
is exposed to high pressure air, then the air is released and an adsorbed film of the desired gas
is released. The size of compressor is much reduced over a liquification plant, and portable
oxygen concentrators are made in this manner to provide oxygen-enriched air for medical
purposes. Vacuum swing adsorption is a similar process, but the product gas is evolved from
the zeolite at sub-atmospheric pressure

Page 25
.
Membrane technologies can provide alternate, lower-energy approaches to air separation. For
example, a number of approaches are being explored for oxygen generation. Polymeric
membranes operating at ambient or warm temperatures, for example, may be able to produce
oxygen-enriched air (25-50% oxygen). Ceramic membranes can provide high-purity oxygen
(90% or more) but require higher temperatures (800-900 deg C) to operate. These ceramic
membranes include Ion Transport Membranes (ITM) and Oxygen Transport Membranes
(OTM). Air Products and Chemicals Inc and Praxair are developing flat ITM and tubular
OTM systems, respectively.
Membrane gas separation is used to provide oxygen poor and nitrogen rich gases instead of
air to fill the fuel tanks of jet liners, thus greatly reducing the chances of accidental fires.
Conversely, membrane gas separation is currently used to provide oxygen enriched air to
pilots flying at great altitudes in aircraft without pressurized cabins.
This method takes advantage of the fact that different materials diffuse through polymer lined
tubes at different rates. Specifically nitrogen and argon diffuse at a slower rate than oxygen
and CO2.

Page 26
CHAPTER 3
3.1 SELECTION OF THE PROCESS
Cryogenic processes can produce very pure nitrogen. Adsorption and diffusion processes are
typically used to make lower purity product in relatively small amounts. This is attractive to
users when purity is not critical and alternatives (purchase of bulk liquid nitrogen, cylinders
of high pressure nitrogen, or local cryogenic production) are more expensive or impractical.
Gaseous nitrogen is valued for inertness. It is used to shield potentially reactive materials
from contact with oxygen.
Liquid nitrogen is valued for coldness as well as inertness. When liquid nitrogen is vaporized
and warmed to ambient temperature, it absorbs a large quantity of heat. The combination of
inertness and its intensely cold initial state makes liquid nitrogen an ideal coolant for certain
applications such as food freezing. Liquid nitrogen is also used to cool materials which are
heat sensitive or normally soft to allow machining or fracturing. Examples are used tires,
plastics, certain metals and even pharmaceuticals.
Nitrogen is produced in large volumes in both gas and liquid form by cryogenic distillation;
Cryogenic plants - Produce nitrogen, oxygen and argon as gas (and liquid) products using
very low temperature distillation to separate and purify the desired products. Cryogenic
plants are most commonly used to produce high purity products at medium to high
production rates. They can produce products as gases or as liquids.
Non-cryogenic plants - Produce gaseous nitrogen or oxygen products using near-ambient-

temperature separation processes.

Page 27
Non-cryogenic separation processes are most commonly used when high purify nitrogen or
oxygen is not needed(e.g. to produce nitrogen which is 98 to 99.5% oxygen-free, or oxygen
at about 93% purity) and when product demand is relatively low;
There are two major types of non-cryogenic processes: selective adsorption or differential
permutation through membranes to produce relatively pure oxygen or nitrogen. These air
separation processes use differences in properties such as molecular structure, size and mass
to achieve the desired degree of product purity.
3.2 PROCESS DESIGN

Modified Claude Cycle for Nitrogen Liquefier:
A modified Claude cycle is taken into consideration to design nitrogen liquefier to take the
advantage of both the turbo expander and JT valve. Instead of three heat exchangers as in the
Claude cycle, two numbers of heat exchangers are used in this liquefier. Last two heat
exchangers of the Claude cycle are combined to a single heat exchanger to reduce the cost of
the liquefier.
A turbo expander based nitrogen liquefier consists of following parts:
Compressor
Heat exchangers
Turboexpander
JT Valve
Phase separator
Cold box
Piping
Instrumentation

Page 28
A screw compressor will be installed to provide the compressed nitrogen gas. Heat
exchangers are vital components of any cryogenic refrigerator. To exchange high heat in
small area plate fin compact heat exchanger are used. The turboexpander is the heart of the
liquefier and it can used lowering the temperature to expectable amount adiabatically. JT
valve is used for isenthalpic expansion. Phase separator is used to separate liquid and gas.
Piping and other instrumentations are required to connect and control the systems. Whole
thing is kept inside the cold box.
Manufacture of nitrogen.
(i) Liquefaction of pure air

The manufacture of nitrogen, oxygen and argon from atmospheric air involves liquefying the
air and then separating it into its component parts by fractional distillation. Since nitrogen
and oxygen have very low boiling points (Table 3), they liquify at cryogenic temperatures.
Constituent Boiling Point/K, at atmospheric

pressure
Helium 4
Neon 27
Nitrogen 77
Argon 87
oxygen 90
krypton 120
xenon 165
carbon dioxide195 (sublimes) 195 (SUBLIMES)
Table 3 The boiling points of the gases that make up dry air.
When a bicycle tyre is pumped up, from atmospheric to a higher pressure, heat is produced.
Conversely, if gas at high pressure is expanded to a lower pressure, there is a drop in
temperature. Almost all methods of producing low temperatures depend on this property but
it is not a very efficient technique. A more efficient way is expansion in a turbine, where
mechanical work is extracted. Air separation plants use one or both of these methods, in
conjunction with heat exchangers to achieve cooling.
The pure air, already compressed to 6 atm, is cooled with the very cold product and the waste
(nitrogen if oxygen is being made and oxygen, if nitrogen is being made) in a series of heat
exchangers.
Eventually, this compressed air is cooled to about 100 K and then allowed to expand rapidly
(the expansion turbine) which cools it further until it is liquefied.
The key to the whole process is this use of the very cold nitrogen, oxygen and argon to cool
the incoming air prior to the expansion.

Page 29
(ii) Distillation of liquid air
The liquid air is separated into its constituent components by fractional distillation. At each
distillation the vapour is richer in nitrogen (the component with the lower boiling point),
while the liquid remaining contains more oxygen (the component with the higher boiling
point).
To produce pure oxygen the distillation system has two distillation columns, a 'high' and a
'low' column. Nitrogen plants often use a single column but some use two.
Nitrogen leaves the top of the column as a gas. Purity levels required by nitrogen users are
becoming increasingly stringent and it may be liquefied again and redistilled. It is unusual
for the nitrogen to have an oxygen content of more than 10 ppm and impurities contained in
nitrogen for the electronics industry are measured in parts per billion.
The liquid containing oxygen and argon is further purified by distillation in a second column.
To obtain high purity oxygen, further distillation is needed and argon is removed.
Since air separation plants operate at low temperatures, construction materials have to be
chosen carefully. Aluminium alloys and stainless steel are frequently used. They do not
become brittle at low temperatures.
Efficient plant insulation is necessary to make the process economic and safe. Perlite (an
expanded rock), glass wool and vacuum jacket techniques are commonly used (Figure 5).
Process Diagram

Page 30
Detailed Manufacturing Process

Page 31
The equipment associated with warm end for purification of air are :
1. Main Air Compressors
2. Chiller
3. Molecular sieve absorbers (contains solid granular desiccant)
The equipment associated with cold end for air separation process, storage of LIN and
subsequent GAN supply are :
1. Cold Box
2. Expander
3. Storage tanks
4. Vaporizer
Nitrogen plant is supplied by M/s AIR PRODUCTS LTD., UK.
Step 1: Air Compressor (air supply)
The free saturated air is sucked from atmosphere through a highly efficient dry-type suction
filter into the first stage of the horizontally balanced opposed, reciprocating air compressor.
Step2: Purification of Air (process skid)
This consists of purification of the air by removing moisture, oil traces and carbon dioxide in
the process air. Compressed air is chilled to 12 C in a chilling unit and evaporation cooler,
compressed air passes through the oils of the hilling unit at a temperature of 12 C to a
moisture separator, where the condensed moisture gets removed before entering into
Molecular Sieve Battery. Before sending the air to MOLECULAR SIEVE BATTERY, air is
Page 32
passed through an OIL ABSORBER where air becomes oil free. Chilled air passes through
the Molecular Sieve Battery consisting of Twin Tower packed with molecular sieves to
remove moisture and carbon dioxide present in the air.
Molecular Sieve absorber CHILLER UNIT
Molecular Sieve Battery operates on Twin Tower System, when one tower is under
production the other tower is regenerated by passing waste nitrogen gas at 200 C through a
REACTIVATION HEATER .After interval of 8 to 10 hours, the tower under production gets
exhausted and regenerated by similar process before use and, thus the cycle continues.
Any dust particle gets filtered in the DUST Filter before air enters the AIR SEPARATION
COLUMN all the equipments are mounted on process skid.
Step3: Expander (Expansion Engine)
The process air before liquefication in the air separation unit needs to be cooled to
temperatures sub-zero (cryogenic). The main portion of the air after the process skid enters
the expansion engine through the heat exchanger no.1 after pre-cooling. The temperature of
the air drops to around -165degC by the Expander which is a very highly efficient advanced
design with Teflon piston rings and completely hydraulic mechanism with leak proof ball
valves.

Page 33
Rest of air at (-80) degC from Heat Exchanger No.1 enters into a highly efficient
EXPANSION ENGINE, where the air further gets cooled down to (-150)deg C before
entering into bottom column. The liquefied air from both these streams collected at the
BOTTOM COLUMN is known as RICH LIQUID.
Note: we also supply plants with TURBO EXPANDERS.
Step 4: Air Separation Unit
After the process skid, the air enters the air separation unit (cold box)where the air converts
into liquid air by deep cooling at cryogenic (low temperatures)and is separated into liquid
oxygen and nitrogen.
Chilled, Oil-free and moisture-free air enters into multi-pass HEAT EXCHANGER No.1
where it gets cooled to (-80)deg C by cold gained from outgoing waste nitrogen and oxygen.
A part of air, this enters a multi-pass HEAT EXCHANGER NO.II or liquifier made of special
alloy tubes. This air cools to (-170)degC before passing through an expansion valve. Due to
Joule Thompson Effect after the expansion valve, air gets further cooled down and gets
liquefied before entering into Bottom Column .
The RICH LIQUID in the BOTTOM COLUMN enters into feed tray of top column.
Similarly the liquid nitrogen called POOR LIQUID enters into top column as a reflux &it
takes away the latent heat of condensing oxygen and gets vaporized whereas the liquid
oxygen flows down the trays of the TOP COLUMN into the condenser. Liquid Oxygen from
CONDENSER passes through a SUB-COOLER to a LIQUID OXYGEN PUMP.

Page 34
COLD BOX VAPOURIER

Page 35
CHAPTER 4
4.1 Mass and Energy balances
Production of the unit is 1.518 T/day of gaseous nitrogen and 0.15 T/day of liquid nitrogen of
99.9% purity.
So total nitrogen production = 1.67 T/day
= (1.67*1000) / (24*28)
= 2.4858 kg moles/hr
At Standard temperature and pressure,
1kg.mole occupies 22.4 m3
Nitrogen produced in volumetric units =2.4858*22.4
=55.68192 Nm3/hr
Standard analysis of air:

Component volume%
Nitrogen 78.03
Oxygen 20.99
Argon 0.94
Hydrogen 0.01
Helium 0.0003
Krypton 0.00011
Xenon 0.00009
Carbon dioxide 0.03-0.06
Moisture 0.02-0.05
Only Nitrogen balance
Quantity and intake air:
Total Nitrogen production is 40 Nm3/hr (Design)
30 Nm3/hr (Actual)
Air contains:
21% of oxygen

Page 36
79% of Nitrogen
Volume % of oxygen in air = 0.21
Volume % of nitrogen in air= 0.79
Quantity of air needed = 40/0.79 = 50.62 Nm3/hr
As air contains some amount of moisture content and carbon-dioxide which is removed in
molecular sieve absorbers.
Assuming 10% less of air ,then actual quantity of air needed = 50.62 + (50.62*0.1)
=55.683 Nm3/hr
Atmospheric conditions:
Temperature =30oC
Relative humidity= 60%
Enthalpy of air at 1atm and 30oC= 3701.80 kcal/kgmol
Enthalpy of air at 6.8atm and 38oC= 3766.23 kcal/kgmol
Now inlet air first goes to the compressor
Moles of air entering the compressor =55.683 Nm3/hr
=55.683*(1.292/28.84)
=2.4945kgmole/hr
(Density of air =1.292kg/m3 and molecular weight of air =28.84)
Enthalpy of air entering the compressor at 1atm 300 C = 3701.8 kcal/kgmol
= 3701.8*2.4945
= 9234.26 kcal/hr.
Enthalpy of air leaving the compressor = 3766.23*2.4945
= 9394.86 kcal/hr.
So change in enthalpy = 9394.86-9234.26 = 160.6 kcal/hr
After compression air passes through the chiller unit:

Page 37
Inlet parameters: 6.8 kg /cm2 pressure and 380C temp.
Outlet parameters: 6.5 kg/cm2 pressure and 80C temp.
Relative humidity= 60%
Vapour pressure of water at 380C = 49.692 mmHg
Partial pressure of water at 380C = 0.6*49.692
=29.82mmHg
Total pressure =760*6.8 = 5168mmHg
Now
P = (H1 *Pt.) / (Mw/Ma+H1) from Perrys handbook eqn 15.6
Where
P = partial pressure in mm Hg
Pt. = total pressure in mm Hg
Mw = molecular weight of water = 18
Ma = molecular weight of air =29
H1 = molal absolute humidity in kg moles of water vapor / kgmol of dry air
Substituting the values in the formula,
P= (H1*P1)/(M+N/Ma +H1)
29.82= H1*5168 /(8/28.84+H1)
H1= 3.6*10-3 kgmol of water vapour / kg moles of dry air
Let us assume that air coming from the chiller is saturated final humidity =100%
Vapour pressure of water at 80C =8.045 mmHg
Final partial pressure of water = 8.045 mm of Hg
Total pressure =6.5*760 = 4940mmHg
Using the above eqn we get
H2= 9.68*10-4 kgmol of water vapour / kg moles of dry air
Let amount of dry air is M kg moles

Page 38
M + (3.6*10-3) = 2.4945
M = 2.4945 (3.6*10-3)
= 2.4909
Amount of water it contained =2.4909 (0.0036- 0.000968)
=0.0065 kgmol/hr
Moles of air coming out of the chiller = 2.409- 0.0065 = 2.4844 kgmol/hr
ENERGY BALANCE:
From enthalpy charts
Enthalpy of air entering air =3766.23 kcal/kgmol
Enthalpy of leaving air = 3573.09 kcal/kgmol
Enthalpy of entering air = 2.4945* 3766.23
=9395.23 kcal/hr
Enthalpy of leaving air = 2.4945* 3573.09
= 8913.073 kcal/hr
Change in enthalpy of air = 482.157 kcal/hr

Page 39
4.2 Plant location and layout
But before making such a choice, he has to go through the detailed locational analysis
considering various factors, which influence his decision. It is a long-term strategic decision,
which cannot be changed once taken. An optimum location can reduce the cost of production
and distribution to a great extent. Thus great care and appropriate planning is required to
select the most appropriate location.
The efficiency of production depends on how well the various machines; production facilities
and amenities are located in a plant. An ideal plant layout should provide the optimum
relationship among the output, floor area and manufacturing process.
An efficient plant layout is one that aims at achieving various objectives like efficient
utilization of available floor space, minimizes cost, allows flexibility of operation, provides
for employees convenience, improves productivity etc. The entrepreneurs must possess the
expertise to lay down a proper layout for new or existing plants.
It differs from one plant to another. But basic principles to be followed are more or less same.
Plant layout is applicable to all types of industries or plants. At the end, the layout
should be conducive to health and safety of employees. It should ensure free and
efficient flow of men and materials. Future expansion and diversification may
also be considered while planning factory layout.

Page 40
4.3 SAFETY
Safety is an important aspect of any process industry. This department deals with the
identification of possible hazard sources and mitigation of the same. It is also deals with the
firefighting in case of any fire.
This department also includes:
Rescue operations at times of energy
Ensuring safe work places
Issue of permit to work
This department in NFCL is a strong department of 22 employees, all well trained in the
field of fire and safety, occupational health and safety & occupational hazards.
The department has installed a number of NEAR MISS INCIDENT REOORT REGISTERS
at various departments in the factory in order to achieve maximum accident free man-hours.
This department deals with the following major aspects identified in NFCL:
Fire
Corrosion
Toxicity
Hazards
There are 18 wind socks are installed at various points and 3 safe assembly points in the
industry.
The department issue permits for works. The works are of 3 types these are, Hot, Toxic and
Cold jobs. The fire and safety department issues class 1A permits for Hot jobs, class 1B
permits for Toxic jobs and class 2 permits for Cold jobs.
The department is fully equipped with all the necessary firefighting and hazard identification
equipment to fight all the four classes of fire.
To mention a few, the department has three fire tenders with water as well as foam. A mobile
ambient air monitoring van is also in place.

Page 41
Every year people are killed by breathing air that contains too little oxygen. Because 78
percent of the air we breathe is nitrogen gas, many people assume that nitrogen is not
harmful. However, nitrogen is safe to breathe only when mixed with the appropriate amount
of oxygen.
These two gases cannot be detected by the sense of smell. A nitrogen enriched environment,
which depletes oxygen, can be detected only with special instruments. If the concentration of
nitrogen is too high (and oxygen too low), the body becomes oxygen deprived and
asphyxiation occurs.
Precautions:
- When opening nitrogen cylinders or pipelines lines, insure that you are in a well-
ventilated space. Bleed off pressure slowly. A confined space with nitrogen present is a
killer.
- Avoid directly breathing nitrogen, when using it. A respirator will not save you if the
percentage of nitrogen in the atmosphere increases to 90%, displacing oxygen down to
around 11%. Only a self-contained breathing apparatus can be used in this type of
atmosphere. The results of overexposure to nitrogen can be sudden and immediate. If
oxygen the level fall below 18%, seek a safe environment immediately.
- If a co-worker has been overcome with nitrogen in a confined space, DO NOT rush in
unprotected to try to rescue. Then put on an SCBA, to attempt rescue of the person.
- Always test confined space atmospheres and continuously monitor it if compressed

nitrogen gas is being used in that atmosphere for purging.
- NEVER open a vessel that is under a nitrogen purge to look into it, without first having
a SCBA on and operating. The effects of nitrogen poisoning to the body is immediate, and
workers have been known to lose consciousness and fall into vessels that were open under a
nitrogen purge.

Page 42
- Shut off all cylinders and nitrogen supply tanks when finished with use. Properly
secure cylinders and tanks to a non-moveable structure. All empty and full containers should
be labeled.
Precautions when handling liquid nitrogen
1. Treat liquid nitrogen and any object cooled with liquid nitrogen with respect.
2. Take care not to allow liquid nitrogen to be trapped in clothing near the skin.
3. Wear safety glasses or a face shield when transferring liquid nitrogen.
4. Wear gloves when touching any object cooled by liquid nitrogen. Gloves should be
loose fitting, so they could be thrown off if liquid were to pour inside them
5. Use only approved unsealed containers. Never pour it into a coffee thermos. Never
seal it in any container (it will explode).
6. Never dip a hollow tube into liquid nitrogen; it may spurt liquid.
7. Never use in a small poorly ventilated room, and never dispose of liquid nitrogen by
pouring it on the floor. It could displace enough oxygen to cause suffocation. Nitrogen
gas is colorless and odorless--the cloud that forms when you pour liquid nitrogen is
condensed water vapor from the air, not nitrogen gas.
8. Do not store liquid nitrogen for long periods in an uncovered container (on the other
hand, never totally seal a container). Because the boiling point of oxygen, 90.1K, is
above that of nitrogen, oxygen can condense from the air into the liquid nitrogen. If
the air over the nitrogen circulates, this liquid oxygen can build up to levels which
may cause violent reactions with organic materials; even materials which are
ordinarily nonflammable. For example, a severe clothing fire could result from
ignition in the presence of liquid oxygen.

Page 43
First Aid
Suffocation: If person seems to become dizzy or loses consciousness while working with
liquid nitrogen, move to a well-ventilated area immediately. If breathing has stopped, apply
artificial respiration. If breathing is difficult, give oxygen. Call a physician. Keep warm and
at rest.
Frost bite: If exposed to liquid or cold gas, restore tissue to normal body temperature, 98.6F
(37C), followed by protection of the injured tissue from further damage and infection.
Remove or loosen clothing that may constrict blood circulation to the frozen area. Call a
physician. Rapid warming of the affected part is best achieved by using water at 106F (42C).
Under no circumstances should the water be over 112F (44C), nor should the frozen part be
rubbed either before or after rewarming. The patient should neither smoke, nor drink alcohol.
CONCLUSIONS
Cryogenic air separation technology has been successfully employed for many years to
supply nitrogen. It is todays preferred route for the supply of industrial gases to large
facilities. Integration of heat, refrigeration, process and waste streams between the industrial
gas process and other units within the overall facility can improve efficiency and decrease
cost.
Nitrogen generation such as PSA or membrane can be more cost effective than traditional
cryogenic distillation particularly if an extremely high purity 99.99 % is not required
Adsorption and other technologies for air separation continue to advance as more efficient,
highly packaged and compact gas generations are to be developed. Increased power
efficiency in PSA nitrogen generations is being driven both by process improvements and
enhanced adsorption materials. Nitrogen users will benefit from these advances as they
evaluate supply options for new facilities and manage increased demand at existing plants.

Page 44
Bibliography
1. Cryogenic Engineering, Springer new York ,part 1,pages 3-27 and 146-160
2. US Patent 4072023 - Air-rectification process and apparatus
3. Chemical and Petroleum Engineering journal, Air separation in plants with an

external source of refrigeration ,,volume 4 ,pages 825-829
4. American Chemical society journal , some aspects of gas separation at low

temperatures by W. H. Granville
5. air liquefaction: distillation

encyclopedia of separation science, 2007, pages 1895-1910,science direct
R. agrawal, D.M. herron

Page 45
6. "Glossary". The Brownfields and Land Revitalization Technology Support Center.
Retrieved 2009-12-21.
7. "How to bury the problem". Royal Society of Chemistry. Retrieved 9 January 2012.
8. "Development of Pressure Swing Adsorption". Human Research Roadmap. NASA.

Retrieved 9 January 2012.
9. "How do Pressure Swing Adsorption Nitrogen Generators Work?". Peak Scientific.

Retrieved 9 January 2012.
10. Vieth, W.R. (1991). Diffusion in and through Polymers. Munich: HanserVerlag

Page 46

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CONTENTS

1.1 Principle of liquefaction 10

1.3 Objectives of the work 12

1.5 Main applications 14

2.1 Literature survey 16

2.2 Different Process 23

3.1 Selection of the Process 25

3.2 Process Design and detailed Manufacturing process 26

4.1 Material and Energy balances 33

4.2 Plant location and layout 37

Motto: Service Society through Industry

Location: Agricultural town close to market

Water: Godavari River

SPCE Chemical Engineering

CH4 + H2O ------------- 3 H2+ CO - heat

CO + H2O ------------- CO2 + H2 + heat

The reaction-taking place in the shift conversion can be represented as:

CO + H2O --------- CO2 + H2 + heat

N2 + 3 H2 ------------- 2 NH3 + heat

PROCESS DESCRIPTION EXPANSION PLANT:

Return Naphtha System:

SPCE Chemical Engineering

Following reactions take place in the Urea Reactor:

2 NH3 + CO2 -------- NH2COONH4 (Ammonium Carbamate) + heat

NH2COONH4 ----- CO (NH2)2 + H2O heat (Urea)

MAJOR OFFSITE UNITS AT NFCL, KAKINADA

SPCE Chemical Engineering

SPCE Chemical Engineering

INERT GAS PLANT (IG PLANT) :

CAPTIVE POWER PLANT:

GT-A & GT-B:

SPCE Chemical Engineering

SPCE Chemical Engineering

EFFLUENT TREATMENT PLANT (ETP) :

SPCE Chemical Engineering

CARBON-DI-OXIDE RECOVERY (CDR) PLANT:

Technology Supplier: Mitsubishi Heavy Industries (MHI), Japan.

CO2 Absorbent: KS-1 Solution, Proprietary Supply from MHI, Japan.

SPCE Chemical Engineering

1.1 Principle of Liquefaction

In a continuous refrigeration process, there is no accumulation of refrigerant in any part of the

The Joule-Thomson coefficient is a property of each specific gas. It is a function of

SPCE Chemical Engineering

Pre coolant in production of liquid helium and low temperature refrigerators

Cryotreatment of critical metallic components such as hubs, milling cutters, knives,

Cold trap in vacuum systems and in adsorption pumps, and

Miscellaneous laboratory and industrial applications.

1.3 Objectives of the work

SPCE Chemical Engineering

Nitrogen physical properties

Physical properties of nitrogen is given as,

Nitrogen is also considered as the liquid which is similar to water in appearance.

The melting point of the nitrogen is -2100C

The boiling point of the nitrogen is -195.80C.

Chemical properties of nitrogen:

SPCE Chemical Engineering

After ionization the energy of nitrogen is given as 1402kJ.mol-1.

The electronegativity of nitrogen due to the Pauling method is given as 3.0.

1.5 Main applications

Nitrogen can be used for blanketing, as well as for:

Glass, Cement and Lime:

Nitrogen is used as an inert gas especialy to create, in combination with hydrogen, a

Low-temperature preservation of living tissues and cells

Laboratories & analysis: