M.

CHANDRA SEKHAR
(21065-CHPP-037)
This is to certify that M.CHANDRA SEKHAR(21065-CHPP-037) bonafide student of
Government Institute of Chemical Engineering ,Visakhapatnam studying Diploma In
Chemical Engineering ( Plastics & Polymers) has undergone sandwich training in
Nagarjuna Fertilizers and Chemicals Limited, Kakinada during the period 6 months from
JUNE 12 to DECEMBER 11.

During the period of training his conduct is found to be .

Mr. RAJA CHAND Mr. P. V. RAMACHANDRA RAJU

H.R. DEPARTMENT AMMONIA-|| SECTION HEAD,
NFCL(KAKINADA) NFCL(KAKINADA)

Mr. V. RAVI KUMAR TRAINING

DEPARTMENT NFCL
(KAKINADA).
The satisfaction that accompanies the successful completion of any task would be
incomplete without mentioning the people who made it possible and whose constant
guidance and encouragement grown all the efforts with success. This
acknowledgement transcends the reality of formality when we like to express deep
gratitude and respect to all those people behind the screenwho guided, inspired and
helped us for the completion of the report.
We are thankful to the especially to Mrs. Y.RAMADEVI
and Mr. V. NAVEEN VARMA for their concern in giving the opportunity to pursue
industrial training and for providing guidance.

and
sparing valuable time despite his busy schedule and also to all staff members NFCL
who engaged with us during the period of our training.

We wish to express our deep sense of gratitude to,

and wholehearted thanks to
. and our deep veneration to

In conclusion, I will remember my experiences in this industrial training and use the training
experience to prove my ability and work for the pride of the organization in all respects,
wherever I get an opportunity.

M.V.N.S. SANDEEP
20065-CH-038
 limited was first proposed by in
1974.Then in 1985 this project was handed over to
laid the foundation of the
in 1974.NFCL IS one of the member of this group.

121 acres built up area

729 acres green belt
160 acres water bodies
57 acres landscape, roads, non-built up area.
1127 acres in total
Godarigunta,beach road Kakinada
Godavari river water, samalkota reservoir
Natural gas from GAIL terminal
By South Central Railway

Process plant 1 –
Process plant 2 –
Utilities
Bagging

Cost 1180 crores Cost 970 crores

Schedule 42 months Schedule 30 months
Start up 1 august 1992 Start up 19march 1998

production at both plants are respectively.Ammonia

licensor is
Urea licensor is

Raw water treatment 1200m3/hr

DM plant 120m3/hr
ndensate polishing 310m3/hr
Cooling towers Urea: 10000m3/hr * 2
Ammonia: 18000m3/hr * 2
Inert gas plant 2200 Nm3/hr
Instrument air 300m3/hr
Emergency power 1375 KVA * 2
Effluent treatment 5000 mt * 2
Ammonia storage 5000 MT * 2
Urea silo 30000MT
Bagging plant 240 MTPH
Natural gas requirement 1.8 MSM3/DAY
Naphtha requirement 900MT/DAY
Water requirement 9 MG/day

BOILERS WATER TUBE BOILERS BY

GAS TURBINES BY

ZERO POLLUTION THROUGH-

a) Treatment of chemical pollutants
b) Recycling
c) Effluent control
740 acres green belt containing rare species of plants, birds, animals and
aquatic lives.
 Fertilizers are those substances, which must be added to the soil in
order to remove the deficiency of essential elements required for plant
growth.

To supplement what has been eaten up by the plants.

To supply them an additional tonic and good food. So, that they may grow
healthier and produce a better yield.
To maintain the pH of the soil in the range of 7-8.
By facilitate optimum growth and health.

Every compound containing nitrogen or phosphorus or calcium etc. cannotbe

used as a Fertilizer. The chief requisites of Fertilizer are:
The element present in the compound must be easily available to the
plant.
The substance must be soluble in water.
It should be stable, so that it may be made available to the plant for a long
time.
It should maintain the pH of the soil in the vicinity of 7-8
It should not be a poison for the plant.
It is also interesting to note that soil fertilization is not merely a matter of
supplying certain compound in given proportion. The most important factor,
which is of prime importance in the functioning of fertilizers, is the movementof
water in the soil. Application of lime opens the pores of the soil and enablesa free
circulation of water.
Another factor of importance in the functioning of the fertilizers is the actionof
CO2 on the material in the soil. CO2 is soluble in water and forms carbonic acid
which has a high solvent power for the carbonates of Ca and Mg and oxides of
Fe and Mn. These compounds are nearly insoluble in pure water.
Hence carbonic acid helps to circulate many fertilizing substances in the soil,which
are otherwise hardly available.

FERTILIZERS ARE CLASSIFIED AS:

Straight fertilizer
Compound fertilizer
Complex fertilizer
 A Fertilizer intended to supply only one nutrient is known is known as
straight fertilizer. Thisis used to supply additional nitrogen there by reducing
leaching loss. Potash is often added to pasture as a straight material.
Phosphate is also applied straight, but not much lesser extent than in mixed
fertilizers.
E.g.: Urea - NH2CONH2

A Fertilizer intended to supply more than one nutrient is called compound

fertilizer. Compound fertilizer production involves a chemical reaction.

These are prepared by mixing appropriate amountsof compound fertilizers like

ammonium salts, super phosphates, and potassium salts etc. and in this manner,
they supply more than one essential element to the soil

Molecular formula: NH3

Molecular weight: 17
Boiling point at 1 atmp: -33.4oC
Melting print at 1 atmp: -77.4oC
Critical temperature: 133oC
Specific gravity at -33.4oC compared to water at 4oC:0.6819
Liquid density at -33.4oC and one atmosphere: 681.9 kg/cu.m or 0.6819
gm/ml.
Specific volume of vapour at 0oC and 1 atmosphere: 1.30 cu.m/kg.
Latent Heat at - 33.4oC:327.4K cal/Kg
Relative density of vapour compressed to dry air at 0oC and 1 atmp: 0.597
Vapour Density at –33.4oC and one atmosphere: 0.8899 Kg/Cu.m
Ignition temp: 651o.
Toxicity/Hazard: combustible, explosive mixture with air corrosive to eyes,
skin and lungs.
Threshold limiting value (TLV): 50 PPM
Critical pressure: - 11.4 MPa
Ammonia smell can be detected at: 25 PPM
Early in the 12th century, several chemists tried to make ammonia from the
atmospheric nitrogen. German scientist fritz Haber discovered the process thatis
still used today. Robert le rossignol was instrumental in the development of
Haber’s process. They demonstrated their process in summer 1909 by
producing Ammonia air drop by drop at the rate 125ml/hr.
Then the process was purchased by a German company in 1913they produced20
tons/hr.

Ammonia plant is based on steam reforming of natural gas. Ammonia plantconsist

of the following sections
Natural gas supply
Desulphurization section
Reforming section
CO conversion section
CO2 removal section
Methanation
Process condensate stripping section
Ammonia synthesissection
Refrigeration section
Ammonia absorption section
Purge gas recovery unit
 Natural gas, which is used as feed stock and fuel for Ammonia Plant and
Power and Steam Generation Plant is supplied at Offsite Gas Metering Station
by Gas Authority of India Ltd. from gas wells located in Krishna-Godavari Basin
through pipe line. Natural Gas is supplied at a pressure of 44 Kg/Cm2g. After
metering in Offsites, natural gas for process feed is directly received at
Ammonia Plant battery limit at 40 Kg/Cm2 g and 40oC. Fuel gas through
separate header after pressure reduction is received at the battery limit at 3
Kg/Cm2g. Fuel gas is used for burners of Feedstock Pre-heater, Primary
Reformer, Auxiliary Super heater & Startup Heater in Ammonia Plant. Feed gas
received at battery limit goesto the desulphurization unit for Sulphur removal, if
any and subsequently processed to produce synthesis gas for Ammonia
production.

The natural gas feed stock supplied to NFCL contains no H2S, but it is
anticipated that future suppliesmay contain Sulphur compounds which have tobe
removed in order not to poison the reforming catalysts and the LT shift catalyst.
Natural Gas from battery limit is heated to 385oC in the Feed stock pre-heater,
and is passed through the Hydrogenator. A bed of
Nickel-Molybdenum catalyst isprovided to catalyze the hydrogenation of organic
Sulphur compounds to hydrogen sulphide. There are two types of organic Sulphur
compounds that may be present in the feed stock. One is called 'Normal Sulphur'
containing H2S, COS, CS2 and Mercaptans and the other is called 'Less Reactive
Sulphur', containing Thiophenes, Thioethers etc.In case of normal Sulphur except
Mercaptans Hydrogen recycle gas is not consumed whereas for less reactive
Sulphur, recycle hydrogen is consumed asper the following hydrogenation reactions

If Sulphur is present, natural gas is mixed with recycle gas from synthesis gas
compressor first stage discharge with flow of recycle gas around 1306 NM3/hr,in
order to avoid Carbon deposition on the catalyst due to catalytic cracking ofhigher
hydrocarbons if any. After preheating to 385oC, the gas mixture passes to
Hydrogenator Reactor and reacts to produce H2S. The above reactions are
exothermic but insignificant (which depends on the type of Sulphur that determines
the number of moles of hydrogen taken up). H2S produced in hydrogenator and
that already present in Natural Gas is then removed in H2S Absorbers, thereby the
gas will be free of H2S
:

ZnO reaction with ‘S’ depends on:

Type of Sulphur compounds.
Temperature: Increase in temperature will generally increase the ability of
ZnO to remove Sulphur.
Capacity: As ZnO reacts with Sulphur it gets saturated with Sulphur and
loses its activity. Normal life of ZnO catalyst depends on the H2S andSulphur
concentration in the natural gas.

Steam reforming is a vital part of the front end in plants producing

Ammonia. Developments in metallurgy have allowed steam reformers to be
operated at higher and higher levels of temperatures, pressures and heat flux.
The reforming process and the design of the reformer are based on the reaction
between methane and higher hydrocarbons present in the natural gas with steam
thereby generating CO, CO2 and Hydrogen. The Hydrogen producedby the
Methane reforming reaction is used to produce Ammonia by combiningwith
Nitrogen in the ratio of 3:1 which is the stoichiometric ratio of hydrogen and
nitrogen to produce ammonia.
The most important reactions taking place in the reformer are
 These reactions are taking place in the presence of a nickel-based catalyst.
The operating parameters maintained close to the equilibrium, are 769oC and
30.5 Kg/cm2 g and the maximum tube skin temperature allowable is880oC. The
methane concentration at the exit of the reformer is 14.03 %. The efficient
operation of the reformer at the above conditions will give rise to a methane
leakage at the exit of secondary reformer of 0.6%. The higher slippageof methane
has been designed taking advantage of PGR unit incorporated. In addition to the
recovery of hydrogen from the purge gas, there is energy saving due to the lower
heat flux required in the reformer resulting in reduced firing, thereby increasing
the life of catalyst and reformer tubes.

Raw synthesis gas is produced by reforming natural gas to an

intermediate level in the primary reformer using super-heated HS steam in
presence of a Nickel based catalyst at 33 Kg/cm2 g pressure. The hot
desulphurization natural gas and recycle gas mixture from 2nd H2S Absorber
outlet is combined with HS steam (37 Kg/Cm2 g 370oC) to give a steam to
carbon mole ratio of 3.3:1.0. A small quantity of condensate from condensate
recovery containing small percentage of Methanol and Ammonia is also mixed
with steam for subsequent recovery of H2 and to avoid pollution. The combined
steam-natural gas-recycle gas mixture (Mixed feed) is preheated to 520 oC in the
process gas convection coil located in the waste heat recovery section of the
primary reformer utilizing the heat from the hot flue gases, leaving the reformer
radiant section.
Following preheat, the gasesare distributed through hair pin tubes into vertical
reformer tubes filled with Nickel catalyst. The tubes are placed inside a Furnace,
where sensible heat and endothermic heat of reaction are absorbed inthe tubes
by radiation from a number of wall burners to the tubes. The primaryreforming of
natural gas is done in a Topsoe design side fired furnace, in comparison to the
top fired furnace, where the maximum heat input is concentrated in the top part
of the furnace. In the top fired furnace during startup conditions with low flow,
little or no heat of reaction in the tubes, the maximum temperatures may well be
found at the level of flames. In such furnaces, higher than desirable
temperatures may be present in the top part ofthe tubes even when the outlet
temperature is not higher than the level
recommended.

In the upper part of the top fired reformer, where the methane
concentration is high and hydrogen concentration is low, the potential for carbon
formation is present. Due to the radial temperature and concentration gradient in
the tube, the risk zone extends somewhat down along the hot tube wall. If this
zone reaches a temperature level where the rate of the cracking reaction
becomes sufficiently high, carbon formation will take place resulting in a "hot
band". Top fired furnaces are more prone to this kind of problem. Using the
side-fired furnaces eliminates the above disadvantages of using top fired furnace.
In case of side fired furnace, the reformer outlet temperature increasesgradually
from the top towards bottom. The tube skin temperature along the length of the
tube can be better-controlled in side fired furnace. The potential for carbon
formation with the age of the catalyst, the possibility of higher tube skin
temperature at the bottom than from the top is better controlled using side fired
furnace.
The primary reformer furnace consists of 190 tubes, inserted in two parallel
chambers called the radiant zone. Each chamber has got 95 tubes in asingle row.
Each row has been divided into 5 sections. Each section has got 19tubes.
Reformer tube outlets from both chambers are connected to hot collectors
through pigtails, which are placed outside the Primary Reformer radiant zone.
Hot collectors are again connected with cold collector. The furnace operates
with side firing of fuel gas on both sides of each row of tubesto develop a
process gas temperature of about 769oC at the catalyst tube outlet.
There are 360 side-fired burners arranged in 6 rows per wall. Each row is
having 15 burners. The type of primary reformer burners is of LP Radol Burner,
which is of rugged construction. Natural gas pressure reduced to 3 Kg/Cm2g at
Offsite is used as fuel for the LP Radol Burners. The flame shape should be flat
against the heated Muffle Block surrounding the air nozzle. The excess air shallbe
10%. The Reformer is loaded with 20.05 M3 of Nickel based unreduced catalyst
at bottom and 6.68 M3 of Nickel based pre-reduced catalyst at top.
Both are cylindrical having seven holes with OD 16 mm and height 11 mm. Inside
the catalyst tubes the natural gas steam reforming reaction takes place.

The following reactionstake place simultaneously, producing a mixture of

H2, CO, CO2, CH4 and excess H20 when hydrocarbons undergo steam reformingover
Nickel catalyst:

Reactions start at 500 oC for the higher hydrocarbons and 600oC for methane.

Reaction (3) requires small amount heat only, whereas the heat requiredfor
1 and 2 dominate the picture.

The effect of increasing reforming temperature on the effluent gas

composition is to reduce the methane and carbon dioxide content. On
decreasing reforming temperature, the effects are reversed. On decreasing
temperature, there is a theoretical risk of carbon formation according to the
Bourdard reaction when the gas is cooled.

Under the chosen conditions, the above reaction can only take place below
750oC because of the equilibrium conditions and above 650oC because the soot
formation reaction rate is too slow to have any practical importance below650oC.

The unit operation is most economical at conditions closely approaching

the design steam to carbon mole ratio of 3.3:1.0. However, increasing steam to
carbon ratio will shift the above equilibrium reactions to the right with a net
effect of decreased methane and carbon dioxide and increased carbon
monoxide and hydrogen in the reformed gas.
 As the reforming reaction proceeds with an increase in the number of
moles, a higher pressure will drive the reaction in the undesired direction,
resulting in a higher methane content at the reformer exit, if other factors remain
unchanged. In spite of the above effect, economy of design has required
reforming pressure to be increased in order to save on synthesis gas
compression costs. Also higher-pressure results in the additional advantage of
making the heat of condensation of gases exit the LT CO Converter available at
higher temperature thereby facilitating the recovery of this heat by BFW
preheating.
Hence, reforming pressure is fixed by an optimal balance betweenthe
reaction equilibrium on one hand and compression power and heat
recovery on the other. Equally important is the pressure drop across the
reformer tubes. An increase in pressure drop indicates possible catalyst
fouling or partial blockage of tubes due to some other reason.

In the operation of the primary reformer carbon may be formed partly

outside the catalyst, partly inside the catalyst. Carbon deposits outside the
particle will increase the pressure drop over the catalyst bed and deposits
inside the particles will reduce their activity and their mechanical strength.
Thermodynamically carbon formation is not possible under the conditions
foreseen, if equilibrium is obtained for eachstep. If the catalyst, however, is
poisoned, e.g. by Sulphur, it will lose its activity and carbon formation is
likely to occur. At very low steam to carbon ratio, there will be a possibility
of carbon formation, which would result in carbon deposits, especially
inside the catalyst particles. If the catalyst is insufficiently reduced, or if it
is partly oxidized during production upsets, without subsequent reduction,
carbon formation maytake place. Carbon deposition will hinder reforming
and reduce heat transfer so that the tube wall temperature will rise in that
zone producing 'hot bands' and subsequently 'hot tubes'. Precautions
should be taken toprevent carbon formation on reforming catalyst for
successful reformer operations.

The reformer furnace is designed to obtain maximum thermal efficiency

by recovering heat from the flue gases leaving the reformer
radiant section. The hot flue gas from top at 980oCpasses through
downward and horizontal flue gas duct. The flue gas blower induces the
desired draft of 375 MM WC. The flue gases enter the waste heat recovery
section and give up heat successively to the various coils. At theoutlet, the
flue gas temperature is reduced to approx. 170oC as any further reduction
in temperature may result in condensation of Sulphur compounds if any
present in the flue gas.

Combustion air to the forced draught radiant burners of primary

reformer and auxiliary steam super heater is supplied by Combustion Air
Blower, after preheating to 293oC in combustion air pre-heater by
recovering sensible heat of the flue gases.

:
The partially reformed gas exit Primary Reformer contains 14.03
mole % of CH4 (dry basis). The methane content is further reduced to 0.6
mole percent (dry basis) at high temperature in the secondary reforming
step. In the Secondary Reformer, the heat is supplied by combustion of part
of the gas achieved by mixing air into the gas as compared to the indirect
heat by firing in the Primary Reformer. This combustion providesheat for
the rest of the reforming in Secondary Reformer. The methane slip exit
Primary reformer is so adjusted that the processair supplying thereaction
heat in the Secondary Reformer will give the Hydrogen/ nitrogen ratio of 3:1
in the syn. gas. It is desirable to reduce the methane content of the process
gas to a low level in order to keep the level of inert gases low. The methane
content exit Secondary Reformer is dependent upon the methane slip at the
Primary Reformer outlet at specified conditions.
The high CH4 slip at outlet Primary Reformer gives rise to CH4 slip of 0.6
mole %(dry) at secondary reformer outlet at 943oC. Since air quantity is
fixed when PGR Unit is running, the H2:N2 ratio in the make-up gas is 2.78
which gives rise to 3:1 at Ammonia Synthesis Converter inlet by recovering
H2 from PGR. The inert concentration is maintained at 8% in Synthesis loop
at Converter inlet.
The partially reformed gas from primary reformer is directed to the
refractory lined Secondary Reformer at 31 Kg/Cm2g and 769oC. Process
air supplied by Process Air Compressor K-421 at 33 Kg/Cm2 g and 177oC is
preheated to 550 C in waste heat coils located in convection section of
primary reformer, passes vertically downward through the centrally located
Air Mixer to the Secondary Reformer. Instantaneous mixing and rapid
combustion of part of the partially reformed gas takes place with airin the
upper empty space of secondary reformer, resulting in a sharp riseof
temperature to about 1200oC. This combustion provides heat for the rest
of the reforming. From the empty space, the gas passes down the Nickel
catalyst bed where the reforming reaction is completed with simultaneous
cooling of the gas. The outlet temperature will be about 943oC and the
methane concentration will be approx. 0.6 mole percent. Inthe combustion
zone of Secondary Reformer, the following reaction takesplace between
process gas and air and O2 gets completely consumed.
2H2 + 02 2H20 + Heat (1)

Reaction (1) is predominant.

In the catalyst bed methane reforming reaction takes place as follows:

CH4 + 2 H2O CO2 + 4H2 - Heat

CO2 + H2 CO + H20 - Heat

(Shift Conversion)
The catalyst in the secondary reformer comprises of a layer of alumina
balls and alumina guard tiles at the top and 30 M3 Nickel based catalyst in
the middle. A layer of electro fused alumina lumps are also provided atthe
bottom over the refractory dome as catalyst support.

Reformed gas with unreacted process steam at 943oC from the

bottom of Secondary Reformer passes through the tube side of specialtype
of Waste Heat Boiler. This Waste Heat Boiler consists of two
compartments, which is cast able refractory lined. The total gas is passed
through tube side of the first compartment whereas the second
compartment has been provided with internal bypass to control exit
temperature. A temperature controller regulates flow through the bypassto
maintain HT Shift Converter inlet temperature at about 360oC. Sensible heat
of the process gas exit secondary reformer is utilized to generate KSsteam
in waste heat boiler. Boiler feed water from steam drum is fed to the shell
side of E-208 through number of down comers and steam/waterproduced
are sent back to the steam drum through number of risers by thermo
syphoning. During start up, the drum pressure is controlled to maintain
HT-shift converter inlet temperature and by bypassing the second
compartment of waste heat boiler through temperature controller.

:
Carbon monoxide present in the reformed gas is converted to CO2 in
two shift converters HT and LT. The following reaction is taking place inthe
shift converters HT and LT:

The exit gas from LT Converter will contain only about 0.22 mole % CO,
thereby increasing the yield of H2. The above-mentioned shift reaction
taking place in the converters HT and LT will only proceed in contact witha
catalyst. The equilibrium is favored by lower temperatures and high steam
to gas ratio, while the reaction rate will be higher at higher temperatures.
More steam to gas ratio may give an apparently lower conversion due to
the larger total volume resulting in a shorter contact
time. This means that for each catalyst there will be an optimum
temperature, depending on the activity and the quantity, which will give
optimum conversion. As the reaction results in a temperature rise, the
outlet gas will be at an unfavorable equilibrium if removal of heat has not
taken place before the conversion is completed. Thus, the conversion is
performed in two steps. The first step takes place in the HT shift converter
where a copper promoted Iron Oxide Catalyst is installed. The major part of
the conversion takes place in HT shift converter, causing a temperature
rise of 64C. The outlet temperature is about 424oC and outlet
co-concentration is 2.68 % which is fully acceptable for a conventional
catalyst being more rugged than the low temperature catalyst used in the
second step of the shift conversion. The low temperature catalyst consists
of specially prepared copper, zinc and aluminum oxides having amuch
higher activity, which means that it can be used at the lower temperatures
of 200oC at inlet and 218 oC outlet. The inlet temperature isfixed taking into
consideration the dew point of the gas mixture. The catalyst is less rugged
and loses it activity if the temperatures are higherthan 250 - 270oC.Here
the CO content is further reduced to about 0.22 mole % (Dry Basis)

The HT shift converter contains 70 M3 copper promoted iron oxide catalyst.

The reformed gas enters the HT shift converter at 360oC and
29.8 Kg/cm2g and flows through the catalyst bed. The outlet temperature is
424oC. At the main startup of the plant, the catalyst must be activated,
which is mainly a reduction of Fe203 to Fe304. The reduction will take
place at a temperature above 250oC, but the temperature should not be
allowed to exceed 400oC during the reduction in order not to decrease the
activity of the catalyst. When new, the catalyst can operate at a gas inlet
temperature of 350oC.
Afterwards, the optimum inlet temperature will be higher, but as
long as the outlet temperature has not reached 470oC, the activity will
only decrease slowly.
The cold catalyst can be heated by steam alone, both when oxidized and
reduced. Drops of liquid water on the hot catalyst may result in
disintegration of the catalyst. The catalyst isvery sensitive to salts, which
may be introduced with the steam. The content of chlorine in the gas
should be well below 0.1 ppm. The catalyst is not influenced by Sulphur in
the quantities present in this plant. The fresh catalyst contains, however,
about 0.3% sulphate, which will be given off as H2S during the first week of
operation. Normally the catalyst is not oxidized by steam alone, but should
be oxidized by adding a small amount of air to the steam before itis
accessible as it is pyrophoric in reduced state.

The final shift reaction is completed in Low temperature shift converter.

The gas leaving HTS is cooled to 200 oC before entering LT shift converterby
recovering waste heat successively in Waste Heat Boiler after
Co-converter Exchanger and BFW Pre-heater Exchanger and Trim Heater.In
Exchanger, KS steam is generated while cooling the gas to 340oC. Partof
gas is sent to the Trim Heater to preheat the Methanator feed inlet gas
partly. The gas then passes through the shell side of 2nd Exchanger and
gets cooled to 200oC. There is a bypass of 1st exchanger for controlling LT
Shift Converter gas at desired inlet temperature.

The LT Shift Converter contains 80.3 M3 of the catalyst consistingof

oxides of copper, zinc and aluminum. As the catalyst is extremely sensitive
to Sulphur which may be liberated not only from the preceding HT shift
catalyst but also from secondary reformer refractory material,
practically Sulphur
free. The chlorine may be present in process steam and quench water, due
to mal-operation of the water treatment system and process air due to
atmospheric air pollution in very small amounts.Besides chloridesand
Sulphur, gaseous Si compounds are also catalystpoisons. When the
catalyst is in a reduced state, temperatures above 250oC must normally be
avoided. A short exposure to 300oC will have noadverse effect on the
catalyst. Normal operation should take place at aslow a temperature as
possible. However, at temperatures near the dew point, the activity will
decrease because of capillary condensation of water inside the catalyst,
thus reducing the free area. During operation, the temperature should,
therefore, be kept at least 20oC above the dew point of the gas. The
reduced catalyst is pyrophoric and has to be oxidized before opening of
the converter. The normal operating temperature is between 200oC and
218oC.
The actual temperature of the inlet gas to LT shift converter to be
selected is dependent on the activity of the catalyst.
This unit provides process gas free of CO2 (limit 1000 ppm) for the production of
ammonia and necessary CO2 for Urea production. In this unit, CO2 in the process
gas is absorbed by the GV solution in the Absorber, thus providing process gas
with less than 1000 ppm of CO2. Stripping of the absorbed CO2 isdone in the two
regenerators and CO2 stripped is supplied to Urea Plant. CO2 removal section
know how is by Giammarco-Vetrocoke of Italy. The Vetrocokesolution consists of
K2 CO3, Vanadium Pentoxide, glycine and DEA where V2O5(Vanadium Pentoxide)
is the corrosion inhibitor and glycine/DEA are the activators. The chemistry
involved in thisunit is chemisorption and isexplainedas follows:

The reaction rate of (3) depends on the reaction rates of (1) and (2).
Reaction rate of (1) is slow and the activator activates this reaction by
quickly introducing the gaseous CO2 in the liquid phase. The activator
glycine reacts with CO2 and forms glycine carbonate according to the
reaction.

The sum of (4) and (5) gives (1).

In solution regeneration, reaction (3) is reversed by application of
heat and pressure reduction and the lean and semi-lean K2CO3 solution
is recirculated for further absorption of CO2. The process gas from
condensate removal vessel enters the CO2 removal section at 27.5
Kg/cm2g and 165oC and passes through the reboilers, LP Boiler and (DM
Water Heater) getting cooled down to 113.5oC and condensate is
separated in flash Vessel before entering the absorber.
The process gas enters the tube side of Exchanger giving its heat energyto
the GV solution at the shell side of Exchanger. The solution from the
bottom tray of (Regenerator under pressure) circulates through the reboiler
by thermal siphoning. The CO2 and H2O vapour along with solution enters
bottom below the bottom tray and serves as stripping medium. The heat
energy released in Exchanger shell is used to produce LS steam, which is
boosted, into HP regenerator through the ejectors. Theoutlet gas
temperature of Exchanger is 126.5oC. The gas outlet from Exchanger is
further cooled in DM water preheaters Exchanger. The gas is cooled down
to 113.5oC. The resulting condensate in the process gas is separated in
Vessel before entering the CO2 absorber.
In the CO2 Absorber process gas flows upwards counter current to
the solution flow (the solution is the regenerated GV solution from LP
regenerator). Semi-lean solution pumpstakes suction from the take-off tray
below the packing of LP regenerator and pumps the solution to the middle
of Absorber as semi-lean solution at 106oC. Lean solution pumpstakes
suction from the bottom of LP regenerator through the cooler and pumps
the solution to the top of the absorber as lean solution. cooler cools the
solution from 109oC to 65oC and in turn heats DM water from 40oC to
104oC. The make-up condensate to CO2 removal system is addedat the
suction of pumps at 59oC to maintain the water balance in the system.
At the bottom of absorbers where the bulk of CO2 is absorbed, the
high temperature improves the reaction rate for reaction No. (3) and for
reaction No. (5) according to which the CO2 is absorbed by K2 CO3. In the
top part of the absorber, the lower temperature reduces the CO2 vapour
pressure in the solution thereby minimizing the CO2 content in theprocess
gas. This is made possible by keeping the reaction rate (5) sufficiently high
even at this lower temperature by the OH concentrations in the lean solution
fed at the top.
Solution regeneration is carried out at two pressure levels, one at 1.04
Kg/Cm2g and other at 0.1 Kg/Cm2g for better utilization of stripping steam
compared to the usual technique in which great part of the
stripping steam exits the regenerator top as unused excess. The pressurein
regenerator is regulated to obtain a temperature increase between the
solution inlet and outlet of the regenerator in order to condense the
above-mentioned excess steam. The heat stored in the rich GV solution
outlet of LP regenerator, is recovered as flash steam which has been
experimentally verified to be practically pure steam.
From LP regenerator top is taken off a rich solution stream at 106.5oC
that feeds Regenerator at low pressure LP regenerator. In LP
regenerator,the flashed steam regenerates the rich solution stream taken
off from HP regenerator top. The liquid levels at the bottom of LP
regenerator and at the takeoff tray are maintained by controlling the flowof
lean and semi-lean solution from HP regenerator. The lean solution from
the bottom of LP regenerator at 109oCgets cooled in cooler and is
pumped by lean solution pumps at 65oC to the top of absorber. From the
take-off tray of LP regenerator, the solution goesto the Semi-lean pumpsat
106oC to be pumped to middle of absorber.
The acid gas stream from the top of the HP Regenerator is cooled in the
DM water preheater from 102oC to 96oC at 1.04 Kg/Cm2 g pressure. The
vapour condensed is removed in OH condensate separator. The acid gas
stream outlet of LP Regenerator at 94oC and 0.1 Kg/cm2 g is cooled in the
O/H DM water heater to 91oC and the vapour condensed is removed in the
LP regenerator 1st O/H condensate separator Vessel.Again, the acid gas is
cooled in the condensers to 40oC by cooling water. The vapour condensed
is separated in the LP regenerator 2nd OH condensate separator. The CO2
is fed to the Booster compressor or it can be vented to atmosphere.
Booster compressor boosts the pressure of CO2 from 0.1Kg/Cm2 g to 0.96
Kg/Cm2 g at 96oC. The discharge of Booster compressor joins the stream
of CO2 from HP regenerator at the outlet of Vessel and the mixed stream
gets cooled in the final OH condensers from102oC to 40oC by cooling water.
The water vapour condensed is removedin final OH condensate separator
and the CO2 saturated with water flows to Urea Plant. The ammonia Plant
battery limit conditions for the CO2 sentto Urea Plant are 0.6 Kg/cm2g and
40oC.
The use of compressor on a very limited acid gas stream allows to utilizein
the most advantageous way, the two pressure levels regeneration
technique. Since it allows to keep HP regenerator pressure at a lower level,
thereby increasing the flashing steam of the solution coming fromHP
regenerator with evident energy saving. At the same time, it allows to
obtain all CO2 for Urea production at higher pressure.
The condensate separated out at flash vessels flows to other Vessels
respectively under pressure whereascondensate from before Vessels are
pumped out by condensate pumps respectively as make up to CO2
removal section and balance as process condensate to stripping unit.
There are two numbers lean solution pumps one steam turbine drivenand
the other motor driven. Out of three semi-lean solution pumps, twoare
steam turbine driven and the other motor driven.
Two hydraulic turbines (DPTP-Differential Pressure Turbine Pumps) are
connected to the turbine driven semi-lean solution pumps through auto
clutch. The letdown turbines sends the rich solution from Absorber
bottom, which is at a pressure of 27.5 Kg/Cm2 g to the HP Regenerator
which is at a pressure of 1.04 Kg/Cm2 g. The discharge pressure of
hydraulic turbine will be about 9 Kg/Cm2g. The differential pressure 18.5
Kg/Cm2 g isutilized to drive the semi-lean solution pumps. This pressure
energy approximately amounts to a power of 215 kW in each hydraulic
turbine thus energy on steam driven turbines pumps is conserved to an
extent of 215 kW on each turbine, by clutching Hydraulic turbine to the
Semi-lean solution pumps.

As CO and CO2 are poisons to the Ammonia converter catalyst, the

unconverted CO and unabsorbed CO2 in the process gas are reduced to alimit
of less than 10 ppm by methanation reaction. In the process, CO andCO2 get
converted to CH4 which is an inert in the synthesis of ammonia.
In the Methanator, the reverse of reforming reaction takes place inpresence
of Nickel catalyst.
The reaction formulas are as follows:

The main reason why the reaction is reversed is the lower temperature
favoring formation of methane. Other critical variables governing the reactions
are pressure and steam content. However, within the allowabletemperature
range, the equilibrium conditions are so favorable that
practically only the catalyst activity determines the efficiency of the
methanation. The higher the temperature, the better the efficiency, but atthe
same time it means a shorter lifetime for the catalyst.

Furthermore in case of a possible breakthrough of CO2 and CO to the

methanator which would result in a higher temperature rise, a low inlet
temperature is preferred as this limits the temperature rise. After the
methanator the gas normally contains 10 ppm of CO + CO2. The
temperature rise of gas in methanator will normally be about 21oC.
Methanator contains 26 M3 of catalyst and has approximately the same
characteristics as of reformer, being nickel catalyst on a ceramic base. As
the reactions take place at much lower temperature than those prevailing in
the reformers, the catalyst must be very active at low temperatures.
The catalyst is sensitive to Arsenic, Sulphur and Chloride Compounds. The
adiabatic temperature rise per mole % of CO is 74oC and per mole %of CO2
is 60oC. The methanation reaction starts at a temperature of about 240oC
but in order to ensure a sufficiently low concentration of COand CO2 in the
effluent gas, the operating temperature would be from 280oC to 350oC,
depending on the catalyst activity and gas composition.The methanator
catalyst should not be exposed to catalyst temperatureabove 440oC for
longer periods of time, as it will damage the methanatorvessel.
Washed gas from CO2 removal (outlet of flash separator) goes to Gas/Gas
exchanger at 26.8 Kg/Cm2 g and 65oC and gets heated up to theinlet
temperature of 310oC by exchange of heat with hot methanator effluent
gas. A part of the outlet gas from Gas/Gas exchanger passes through trim
heater and gets heated up with HT converter outlet gas andjoins at the inlet
of methanator (resultant temperature is 320oC. The outlet gas from
methanator at 341oC gets cooled in the Gas/Gas
exchanger to 87.3oC and is further cooled down in final gas cooler to 41oC
by cooling water and the condensate formed is separated in the final gas
separator. The pure synthesis gas enters syn. gas compressorsuction at a
pressure of 25.1 Kg/Cm2 g and 41oC. Surplus syn. gas is taken out and
sent to Auxiliary boiler to be used as fuel. From the outletof final gas
separator, the process gas is also taken as recycle H2 to header to feed
recycle gas compressor.

Nickel carbonyl gas is a poisonous and toxic gas, which may be

present in methanator. Under certain conditions, CO in the process gas
reacts with the catalyst Ni to form Nickel carbonyl gas.

The favorable temp. range of the formation of this gas is between

45oC and 205oC. Hence methanator catalyst should never be allowed to
cool in the presence of CO containing gas. Rather it should be purged out
with N2 at the time of shut down. While heating the catalyst with process
gas containing CO, heating should be done faster in the range of 45oC to
20oC.

Process condensate from flash Vessels contains small amounts of

dissolved CO2, NH3 and Methanol. CO2 removal section OH condensate
from Vessels contain mainly dissolved CO2. The dissolved gases in the
condensate from the above separators are to be reduced to a tolerable
limit before sending it to DM Plant for further treatment. The condensate
from Vessels at 40oC is pumped by condensate pump to a flash separator,
which is a packed column and operating at atmospheric pressure. The
condensate enters the vessel on the top of the packed bed.Condensate
from Vessel at 41oC, from another vessel at 113oC and from inlet carbon
dioxide removal separator vessel at 165oC enters the flash separator
below the packed bed. Due to flashing mainly the dissolved CO2 and some
condensate evaporates and the vapour travel upwards coming in contact
with the downward flowing condensate from condensate pump in the
packed bed. The dissolved CO2 in the
condensate from condensate pump is stripped off and is vented to
atmosphere. The condensate from the bottom of the flash separator at
101oC enters Process Condensate Stripper, which is a tray type column
having 28 trays.
In the stripper, stripping of dissolved gasses is achieved by using
direct LS steam at the bottom. LS steam at 3.5 Kg/Cm2 g and 150oC is
used as stripping steam. The purified condensate from stripper bottom at
109oC is cooled in the Stripped condensate cooler by cooling water to
45oC. The cooled condensate is pumped to DM plant by stripped
condensate pumps at 3 Kg/Cm2 g.
The Ammonia Synthesis takes place in the Ammonia converter as per the
following reaction.

The reaction is limited by the equilibrium concentration and only part of the
Hydrogen and Nitrogen can be converted into Ammonia per pass through the
Catalyst bed. The equilibrium concentration of Ammonia is favored by high
pressure and low temperature. However, reaction rate is very much enhanced by
high temperature operations. There is a compromise between thermodynamic
equilibrium & reaction kinetics. As a result, there is an optimumlevel for the
Catalyst temperatures at which the maximum production is obtained. At higher
temperatures, the equilibrium percentage (which is the theoretically highest
obtainable concentration of Ammonia) will be too low while at lower temperature
the reaction rate will be too low. The Synthesis loop is designed for a maximum
pressure of 155 Kg/Cm2g and the normal operating pressure is in the range of
131-141 Kg/Cm2 g. The reaction temperature in the catalyst bed is 360 - 520oC,
which is close to the optimum level. The catalyst is a promoted iron catalyst
containing small amounts of non-reducible Oxides. Aconsiderable amount of
heat is liberated by the reaction (about 750 Kcal/Kg ofAmmonia produced), and
this is utilized for production of KS steam and for preheating Boiler feed water.
Only about 20% of the Hydrogen and Nitrogen flow contained in the Synthesis
gas at converter inlet is converted into Ammonia per pass, and it is therefore
necessary to recycle the unconverted synthesis gas to the converter. The
Ammonia Converter, is a Radial Type converter with the gas flowing through the
two catalyst bedsin Radial direction.The advantage of the Radial flow converter is
that the pressure drop is less.
The catalytic activity of small particles is very high and the special advantageof
the radial converter is to allow the use of small catalyst particles without a
prohibitive pressure drop.

The converter contains two catalyst beds with inter bed cooling after 1stbed.
There is also a provision of cold shot injection for better control of bed
temperatures. A total of 96 M3 Catalyst of type Topsoe KMI/KMIR is used. The
first bed has a volume of 28 M3 of KMIR Catalyst and the 2nd bed contains 68M3
of KMI Catalyst. The KMIR Catalyst is the pre-reduced and stabilized
catalyst of KMI type. Stabilization involves skin Oxidation of the Catalyst where it
takes-up an amount of 2% (Wt) of Oxygen. This pre-reduced catalyst is stable in air
below 100oC. Above 100oC it will react with air and spontaneously heats up. The
catalyst is activated by reducing Iron oxide to free Iron. This reduction is carried
out with circulating Synthesis gas. The Catalyst activity will decrease slowly
during normal operation and the lifetime of Catalyst is 8 to 10 years. Thisis again
influenced by the actual process conditions. Notably the temperature in the
Catalyst bed and the concentrations of Catalyst poisons in the Synthesis gas at
converter inlet. Sulphur compounds and compounds containing Oxygensuch as
water (H2O), Carbon Monoxide (CO) and Carbon dioxide (CO2) are all poisons to
the Catalyst and small amounts of the catalyst poisons will cause aconsiderable
decrease in Catalyst activity. Part of the poisoning effect is only temporary and
catalyst activity will recover somewhat when the gas is clean again. A certain
permanent decrease in the Catalyst activity will however remain and high
concentrations of Oxygen compounds at converter inlet even for short duration
should therefore be avoided.

Ammonia Synthesis reaction is affected by the following parameters:

Ammonia content in the feed gas
 Inert gas content in the feed gas
H2 to N2 ratio in the feed gas
Reaction temperature
Circulation Rate
Operating pressure
Catalyst activity

A low Ammonia concentration at converter inlet gives a high reaction rate

and thus a high production capacity. The Ammonia concentration at converter
inlet is dependent on the cooling level in the refrigeration chillers and the
operating pressure. At converter inlet 4.1 % NH3 corresponds to -5oC at a
pressure of 132 Kg/Cm2 g in the Ammonia Separator.

The Makeup gas contains 1.33% (Vol.) of argon and methane. These gases
are inerts in the sense that they pass through the Synthesis converter without
undergoing any Chemical changes. But a high concentration of inerts reduces
the partial pressures of Hydrogen and Nitrogen thereby reducing the conversion.
Therefore, a constant purge of gas from the loop is maintained to keep the inerts
level in the converter inlet at about 8%. The catalyst activity decreases with the
catalyst age. This can be compensated by either increasingthe loop pressure and
the circulation rate or by decreasing the inert level.

By the Synthesis reaction, 3 volumes of Hydrogen react with 1 volume of

Nitrogen to form 2 volumes of Ammonia. Therefore, the H2/N2 ratio in the loop
and makeup gas must be close to 3:1. A small change in H2/N2 ratio of the
make-up gas will result in a much bigger change in the H2/N2 ratio of the
circulating Synthesis gas. The H2/N2 ratio of the makeup gas should normally be
about 2.78 so that after addition of recovered hydrogen from PGR Unit the ratio
will be about 3.0. The Synthesis loop is designed for operating at the H2/N2 ratio
of 3.0, but special conditions may make it favorable to operate the loop at a
slightly different ratio in the range of 2.5 to 3.5. When the ratio is decreased to
2.5, the reaction rate will increase slightly (but fall again for ratiosbelow 2.5, while
on the other hand, the circulating Synthesisgas will be heavier.Therefore, the
pressure drop through the loop will increase and the Ammonia
separator efficiency may decrease, leading to increased Ammonia concentration
at the converter inlet. The H2/N2 ratio in the loop should be kept as constant as
possible. The ratio is controlled by the H2/N2 ratio in the makeupgas which will
have to be adjusted to get desired ratio in the circulating gas.
After making any change in the H2/N2 ratio of the makeup gas sufficient time
should be allowed for the system to find its new equilibrium before making
further changes.

The temperatures in the Catalyst bed are usually in the order of 360oC to 520oC.
At the inlet to each Catalyst bed, a certain minimum temperature of 360
380oC is required to ensure a sufficient reaction rate. If the temperature at
catalyst inlet is below 360oC, the reaction rate may become so low that the heat
liberated by the reaction becomes too small to maintain the temperature in the
converter. And the reaction will quickly extinguish itself if proper process
adjustments (lowering the gas circulation and / or closing the cold shot) are not
made immediately. On the other hand, it is desirable to keep the catalyst
temperatures as low as possible to prolong the catalyst life. It is therefore
recommended that the catalyst inlet temperature be kept as close as practically
possible to the minimum temperature without extinguishing the reactor. The
Synthesis gas entering the converter at 252oC is heated in inter bed heat
exchanger by the hot gas coming out of the 1st bed. Before entering the 1st bed,
the temperature of thisgas is controlled to about 370-380oC by mixing withcold
shot. As the gas passes through the catalyst bed, the temperature increases to a
maximum temperature at the outlet from the 1st catalyst bed, which is normally
the highest temperature in the converter, called the "hot spot".The temperature of
the hot spot may be up to 520oC, but should not exceed 530oC. The gas from the
1st bed is cooled in the inter bed heat exchanger by the main part of the cold
inlet gas to the 1st bed in order to obtain a temperature of approx. 380oC before
entering the 2nd bed. In the 2nd bed the gas outlet temperature is about 439oC.

The capacity of the synthesis loop with regard to Ammonia production riseswith
increasing circulation rate. However, the Ammonia production per cubicmeter of
circulation gas which is proportional to the temperature differencebetween
converter exit and converter inlet, will decrease.
 The Synthesis loop is designed for a maximum pressure of 155 Kg/Cm2 g
and it is foreseen that the Synthesis loop can operate at a pressure of 142
Kg/Cm2 g when operating at design production rate, design inert level and design
gas composition. The actual operating pressure isnot directly controlledand is
dependent on the other process conditions, notably production rate, inertlevel,
ammonia concentration at converter inlet, H2/N2 ratio and Catalyst Activity. The
production rate increases with rising pressure and for a given set
of process conditions, the pressure will adjust itself so that the production rate
corresponds to the amount of Makeup gas fed into the loop. The loop pressure
will be increased by increasing the Makeup gas flow to the loop, by decreasing
the circulation rate, increasing the inert level or the concentration of Ammonia at
converter inlet and by changing the H2/N2 ratio away from the optimum. The
decreases in Catalyst activity will also increase the operating pressure.

The refrigeration section is used to liquefy gaseous Ammonia and consists

of a compressor unit, a condenser, an accumulator and number of chillers. Liquid
NH3 flows from the NH3 accumulator, Vessel, to the NH3 heater, which serves to
heat Ammonia sent to the Urea Plant. Then the liquid NH3 flows partly to make up
gas chiller, partly to the 1st NH3 chiller and partly to theinert gas chiller. In chillers,
the liquid NH3 is evaporated at 6.9 Kg/Cm2g corresponding to a temperature of
17oC. Part of the liquid from 1st chiller and 2nd chiller is transferred to the 2nd NH3
chiller, where it is expanded to 1.9 Kg/Cm2 g corresponding to a temperature of
-10oC and from exchanger part ofthis Ammonia is sent to the flash vessel. The
refrigeration compressor compresses vaporized NH3 from the chillers and flash
vessel, which is
three-stage steam driven centrifugal compressor. The suction pressure
corresponds to the pressures in the vessel and chillers. After compression, the
vapour NH3 is condensed with cooling water in the NH3condensers and
collected in the Accumulator, Vessel. Non-condensable’s are purged and sent to
ammonia absorption unit.

Ammonia produced in the Ammonia Synthesis Converter is separated from the

unreacted gas mixture in Ammonia Separator, Vessel. Due to high pressure and
low temperature in Vessel, the loop gases are dissolved in liquid ammonia to a
certain extent depending on their respective solubility. These gases are
removed from liquid ammonia by successfully flashing the Ammonia liquid from
132 Kg/Cm2 g to 25 Kg/Cm2 g in the Letdown vessel and further to near
atmospheric pressure in the Flash vessel. The vapors from the Letdown vessel,
which contain 15.35% (Vol.) Ammonia are sent to Ammonia Absorption unit to
recover Ammonia. While the vapors from flash vessel are sent to Refrigeration
Compressor and after compression along with other Ammonia vapors from the
refrigeration circuit are condensed in NH3 condenser and sent to Ammonia
accumulator. The uncondensed gases from Ammonia Accumulator are again
cooled in Inert gas chiller for recovering some Ammonia and the inert gases
which also contain about 48.51% (Vol.) NH3 are sent to Ammonia absorption
unit to recover balance Ammonia. The inert and Letdown gases are sent to the
bottom of Ammonia absorber, where they are contacted with water flowing
down in the packed beds. The Ammonia is absorbed in water while the gas
mixture containing H2, N2, Ar, and CH4 is sent as off gas to be burnt in Auxiliary
steam super heater. The Ammonia water mixture along with aqueous NH3 from
PGR is sent to the distillation column, where Ammonia is separated from water.
The water is again circulated to the absorber, and partly to the absorber in PGR
unit. The overhead Ammonia gases from the distillation column are condensedin
Condenser and NH3 liquid is sent to flash vessel.

In order to maintain the inerts (CH4 + Ar) concentration in the Synthesis loop ata
constant value a continuous purge is taken from the downstream of 2nd coldHeat
Exchanger, where the inerts concentration is the maximum. Typically purge gas
is about 6% of the makeup synthesis gas. If H2 from this purge gas can be
recovered and used for NH3 synthesis, increase in Ammonia productionto an
extent of 5-7% is possible without proportionately increasing the NG feed.Normally
a purge rate sufficient to maintain the acceptable inerts level in the Synthesis
loop is maintained. But, since there is a Purge gas recovery unit in NFCL, a higher
purge rate is taken during normal level. This higher purge rate reduces the inert
level in the Synthesis loop, which has a dual effect. Firstly, conversion per pass
increases due to increased partial pressure of H2& N2.
Secondly, sensitivity of Synthesis loop operation due to CH4 slip from secondary
reformer and CO slip from LTS converter is greatly reduced. In the
PGR unit, cryogenic cooling in cold box separates hydrogen, where CH4, Ar and
most of N2 are condensed. So, more process Air (N2 + O2) must be introduced to
secondary reformer in order to maintain H2:N2 ratio as 3:1 in the Synthesis loop.
The increased Process Air results in greater combustion in Secondary Reformer,
which means, more CH4 slip from Primary Reformer can be allowed.Consequently,
Primary Reformer duty is decreased marginally, resulting in better tube life and
overall less energy consumption.
The purge gas is sent at 133 Kg/Cm2 g and 13oC to PGR Ammonia absorber,
where Ammonia is absorbed in water. The Ammonia - water mixture (Aqueous
Ammonia) from PGR absorber is sent to the Distillation column, for separationof
Ammonia. The Purge gas, which contains traces of Ammonia and water is
letdown to 70 Kg/Cm2 g and sent through the adsorption unit where molecular
sieve is used to adsorb traces of ammonia and water. The dry gas now
containing only H2, CH4, N2 and Ar is sent to the cold box where the gas is cooled
to below -180oC where almost all the CH4 and argon and some of the N2are
condensed. The uncondensed Hydrogen along with some quantity of Nitrogen
and small percentages of CH4 and Argon is sent back to the 3rd stagesuction of
the Synthesis gas compressor.
The gases while leaving the cold box cool the incoming feed gas. The low
temperature in the cold box is maintained by the flashing of condensed CH4 to5
Kg/Cm2 g which is removed as off gas and along with off gas from Ammonia
absorber is used for burning in Auxiliary Steam Super heater.
As the number moles increases with the reaction Low pressure is favorable, for
reforming.
Reforming pressure is fixed by an optimal balance between the reaction
equilibrium on one hand and compression power and heat recovery on theother
hand.

CH4 composition increase

CO composition decrease
CO2 composition increase
H2 composition decrease

On decreasing reforming temperature, the effects are reversed there is a

theoretical risk of carbon formation according to

• The above reaction is taking place below 700 C and the rate of reaction is
too slow.

With many reactions, the rates are affected by materials which are neither
reactants nor products and such materials are called catalysts.
A compound which reducesactivation energy for a reaction selectively
and accelerates reaction and remains unaltered after completion of
Reaction.
In simple, catalyst accelerates the rate of reaction to attain equilibrium
faster by without taking part in the reaction

Conversion inside the reactor filled with the catalyst based on:
Gas composition
Space velocity
Pressure
Catalyst temperature
Catalyst activity

Good catalytic activity

Good mechanical crushing strength
Highly Inert
High temperature Resistance

–is easily oxidized

– is not stable in metallic state at H2O/H2 ratios present in
reforming condition
- too expensive being noble

Should with stand to high temperature

Should with stand to high steam partial pressure
Should provide more surface area
Should be inert with the catalyst metal and tube metal.

◈ Cement type
◈ Ceramic type

Crush strength low.

Volatile impurities, Like silica.
Significant interaction with nickel.

Good crush strength.

Almost inert with catalyst.
High temperature resistance.
 Decay, isdefined as lossof catalyst activity.
Different causes:
Sintering
Carbon formation or Fouling
Sublimation
Retardation
Ageing
Poisoning
Ruby formation
Carbon formation may due to cracking reaction
2CO = C + CO2 (Boudard reaction)
CH4 = C + 2H2 (Methane cracking)
Formation of whiskers inside the pores, when there is a complete loss of
steam (Whisker-carbon formation)
These deposits can be removed partially or completely by controlled
burning or steaming.

It is severe poison for reforming catalyst

Source- Natural gas,Naphtha.
E.g. - Ni+H2S à Ni-S+H2

1.A conc. Of 50-100 ppm effects the activity

Reformer tube also picks up As,(as forms alloy with Nickel) which will
transfer to subsequent new catalyst and poisons them.
Source – GV solution, ZnO Bed

Improper Filtration i.e. escape of carbon fines; catalyst dust any rust particles
and organic degraded substances to the GV circulating systemBypassing of
Activated Carbon filter
Increased Pressure Dropsacrossthe towersSolutioncarryover to
OH systemIncrease in solution holdup in packing
 -to uniformly distribute liquid over the entire crosssectional area
with minimum disruption of vapor flow.

-to prevent the entry of packing into the liquid distributor.

to limit the expansion of packing due to upward thrust by gas

No. of beds-7
Height (m) volume (m3)
Bottom bed (7) 11
1st stage (1,2,3 beds) 18 193
2ndstage (4, 5, 6beds) 18.6 106.5
Material of construction of packing: S.S.
Design temp./Operating pressure: 150oC/27K.Sc
Shell and heads: C.S
Design pre.: 31 k.sc.

No. of beds – 5
height (m) volume(m3)
2ndstage (1) 51
1st stage (2,3,4) 19 195
Top bed (5) 31
Material of construction of beds: S.S.
Material of const. of Shell and head: C.S.
Design temp./Operating pressure: 1500c/1.07 k.sc
Design pressure: 3 k. SC
Vacuum breaker (1 no.): -200MMWC

No. of beds: 3
h(m) volume(m3)
1,2,3 beds 19 149
Design temp./op. pre.: 1500c/0.1k.sc
Design pre.: 3k.sc.
Material of construction of packing and beds: S.S.
Material of construction of shell and head: C.S.
vacuum breaker (2no.): -200mmw

Insufficient heat supply to the solution

Too high flow rates
Incorrect rich solution sharing between two regenerators.
Too low temperature at absorber bottom
Too low pressure in HP regenerator
Too high pressure in HP regenerator
Too high pressure in LP regenerator
Foaming

Copper Liquor Scrubbing

Cryogenic Purification
▷Sabatier and Sendereus first produced Methane in 1902 by passing
mixture of CO, CO2 and H2 over finely divided metals.
▷Methanation method was first used commercially in 1947 in US for high
purity hydrogen generation plant using Nickel catalyst,
▷Methanation was first used in ammonia synthesis gas preparation in1953.
▷This process was widely used after 1960s due to low operating,
installation cost and simplicity operation comparing to CLS.

▷The Carbon Monoxide (CO) and Carbon Dioxide (CO2) content in the
process gas is around 0.2% and 0.1% during normal plant condition.
▷The CO & CO2 in synthesis gas are having great affinity to poison theAmmonia
Synthesis Convertor Catalyst.
▷So, CO & CO2 from Synthesis are to be reduced to minimum acceptable
limits before feeding to Ammonia Synthesis Section.
Pressure : 31 Kg/Cm2g
Temperature 450 °C

Pressure : 25.0 Kg/Cm2g

Temperature 295 / 320 (In/out) °C

SIZE: 5mm rings

BULK DENSITY:0.6 gm/lt
Catalyst composition: NiO> 29%
Al2O3: Balance
Operating temperature range: 190-450c

Iron studied originally

Ruthenium good at low temperature (ultra-methanation)
Nickel conventionally used
Promoters are used to reduce sintering
Long life proven in service
Low temperature Methanation catalysts available.

Lower Temperature operability, therefore COx slip < 5 ppm

Pre-reduced for higher activity, controlled reduction at shop end will give
higher Ni surface area.
Lower Pressure drop i.e. 50% reduction comparing conventional catalysts
High Thermal Resistance i.e.up to 700°C and long life even at mild
temperature excursions.
Good resistance towards poisoning.

+ 206 KJ/mole
 CO2 +4H2 CH4 + 2H2O + 160 KJ/mole

Each 1 % rise in composition of

CO Rise in temperature will be 74 °C
CO2 Rise in temperature will be 60 °C
O2 Rise in temperature will be 175 °C

Inlet / Outlet / Bed Temperatures

Reactor DP
Reactor DT
Outlet CO & CO2 concentration from analyzers
Catalyst Bed Temperature Profile

Colorless liquid at ambient temperature

Extremely Toxic (OEL 1.0 ppb) US OSHA
Very low boiling point (41.5°C at 1 atm)

• HABER REACTION:
•

Topsoe’s S-300 converter is the latest development in Topsoe’sammonia

converter portfolio and is the recommended converterdesign for all new plants.
The advantages of the S-300 radialflow converter are proven by more than 50
installations worldwide,making it the benchmark within the ammonia
industrytoday.
Compared to the S-200 converters, the presence of threecatalyst beds offers
higher conversion into ammonia and henceincreased production efficiency.
Alternatively, the catalyst volumecan be reduced, which lowers investment costs
compared to theprevious generation of converter design. When the S-300basketis
installed in an existing ammonia converter pressure shell aspart of a revamp
project, significant energy savingscan beachieved. These advantages
can be obtained in connection withthe revamp of both Topsoe and non-Topsoe
designed convertertypes.
Two versions of the S-300 converter are available: One versionhas an integral
feed-effluent heat exchanger at the exit of thethird catalyst bed, allowing the
heat of reaction to be used forpreheating boiler feed water downstream of the
ammonia converter.The second version isdesigned without a feed-effluentheat
exchanger, meaning that the outlet gas from the third bedcan go directly to a
boiler for the production of high-pressuresteam.
With the number of ammonia converter basket installationsconstantly increasing,
Topsoe hasachieved an unequaled referencesituation. With over 60yearsof
experience in the ammoniaindustry, Topsoe provide flexible and highly efficient
ammoniaconverter solutions.

Topsoe isa leading supplier of both state-of-the-art catalyst andtechnology forthe

ammonia industry. Topsoe has achieved thisposition through a unique business
model which integrates allaspects from fundamental knowledge to practical
implementation.Today, the majority of the world’s ammonia is produced
withTopsoe’s KM1 ammonia synthesis catalyst.
TYPE KM1 KM1R
VOLUME 26.9 68.4 M3
WEIGHT 59720 194940 KG
COMPOSITION Fe3O4, oxides of Ca, Al and K

KM1 is an iron-based ammonia synthesis catalyst containing anumber of

carefully selected promoters, essential for obtainingthe optimum catalyst
properties. KM1 is available in a wide rangeof sizes, making it suitable for
operation in all converter designs.

The unreduced KM1 and the prereduced KM1R.

High and unmatched stable activity, excellent poison resistance.

Magnetite has a spinel structure, consisting of cubic packing oxygen ions, inthe
interstices of which Fe2+ and Fe3+ ions are distributed. During reduction, all
the oxygen is removed, but no shrinkage occurs.
• Catalyst is activated by reducing the iron oxide surface layer to free iron.
This reduction is normally carried out with circulating syn gas.

• Main component has remained iron since the catalyst was first
introduced in1914 by BASF in Germany. (osmium & uranium have been
tried).
• Reaction does not take in absence of catalyst because of high stability of
the N2 molecule.
• The catalyst function by forming a nitrogen compound on the catalyst
surface which is hydrogenated to ammonia.
• Iron chemisorbs nitrogen rapidly, and it is this adsorption which is
generally considered to be the step which controls the rate of overall
synthesis process.

• In the manufacture of catalyst, some of the alumina and magnesia

promoters dissolve in the magnetite as they have similar ionic
dimensions.
• During reduction, the dissolved Al2O3& MgO comes out of solution and
separatesin the poresbetween the iron crystallites, hindering their further
growth during the reduction and in subsequent use.
• Thus, Al2O3 assist in both the formation and preservation of small iron
crystals of high surface area.

• Potash
• It increases the intrinsic activity of the iron surface, but also tends to
decrease the iron surface area.
• Calcium oxide
• it enhances the action of Al2O3 in stabilizing the iron surface area and
preventing sintering.
• It also makesthe catalyst more resistant to poisoning by Sulphur and
chlorine.
 • OXYGEN COMPOUNDS
• CHLORINE
• SULFUR

The refrigeration section is used to liquefy gaseous Ammonia and consists

of a compressor unit, a condenser, an accumulator and number of chillers. Liquid
NH3 flows from the NH3 accumulator, Vessel, to the NH3 heater, which serves to
heat Ammonia sent to the Urea Plant. Then the liquid NH3 flows partly to make up
gas chiller, partly to the 1st NH3 chiller and partly to theinert gas chiller. In chillers,
the liquid NH3 is evaporated at 6.9 Kg/Cm2g corresponding to a temperature of
17oC. Part of the liquid from 1st chiller and 2ndchiller is transferred to the 2nd NH3
chiller, where it is expanded to 1.9 Kg/Cm2 g corresponding to a temperature of
-10oC and from exchanger part ofthis Ammonia is sent to the flash vessel. The
refrigeration compressor compresses vaporized NH3 from the chillers and flash
vessel, which is
three-stage steam driven centrifugal compressor. After compression, the vapour
NH3 is condensed with cooling water in the NH3condensers and collected in the
Accumulator, Vessel. Non-condensablesare purged and sent toammonia
absorption unit.
For refrigeration, we use vapour compression cycle of thermodynamics

A liquid evaporating at constant pressure provides a means for heat

absorption at low temperature.
The vapor produced is compressed to high pressure, and is then cooled,
condensed with rejection of heat at high temperature level
Liquid from the condenser returnsto its original pressure by an expansion
process.
Example: Ammonia refrigeration Compressor.
vapor absorption chiller (VAM) is a refrigerating machine to produce chilledwater
using heat source such as steam, hot water, gas, and oil.

“maintaining the temperature below that of the surrounding”

In this process of extracting heat from a low temperature medium andtransferring
it to a high temperature heat sink.
Common Refrigeration cycles:
Vapor compression cycle
Vapor Absorption cycle

It is the amount of heat required to remove, from one short ton of water at 0° Cto
produce ice at 0° C in 24hrs
One Short ton = 2000lb = 907.18kgs
Latent heat of ice=334.9 KJ/Kg
One Ton of ref = (334.9*907.18)/ (24*3600)
=3.516KW
= 200Btu/ min
In vapor Absorption machine the vapor generated in a evaporator is absorbedby a
solvent, which is regenerated by using heat source.

For Synthesis Gas Compressor suction chilling in Ammonia-II (550 tonsof

Refrigeration)
For Process Air Compressor suction chilling in Ammonia-I (440 tons of
Refrigeration)

The first principle is that water boilsat 5deg C at low-pressure vacuum

conditions of 6.5 mmHg.
The second principle is “Evaporation resultsin cooling

Lithium Bromide, LiB(Absorbent)

Water (Adsorbate/refrigerant)
Lithium molybdenite(corrosion inhibitor)
(Li2MoO4)
Octyl alcohol (Activator)
DM water (Chilled water)
Lithium Hydroxide
Hydrogen bromide
Cooling Water (for refrigerant cooling)
Steam (3ksc) (for regeneration)

Absorbent is a material that has great affinity with Adsorbate(water). The

vapour absorption machine uses an aqueous absorbent Lithium Bromide
(Li Br).
(LiBr) is a salt and having similar properties of NaCl, but having higher
Absorption Capacity.
 Chemical Formula :
Molecular Weigh t: 86.856°
Component: = 7.99% / Br = 92.01%
Specific Gravity : 3.464 at 25°C (77°F)
Melting Point : 549°C (1,020.2°F)
Boiling Point t: 1,265°C (2,309°F)
Li Br isa non-toxic aqueous solution but very corrosive in oxygen.
Absorbent in the ammonia based absorption machine is water.

Li Br has a corrosive action to metals in oxygen. But, as the absorptionchiller

is a vacuum vessel, almost no oxygen is present in it.
However, to safeguard and have a complete protection, corrosion inhibitor
Lithium Molybdenite is added in the absorbent and alkalinity isadjusted.
Excess Addition of Inhibitor causes the LiBr to precipitates and degradesthe
Machine

At Generator Outlet: shows concentrated and heated state of lithium bromide

solution (65% lithium bromide by weight) and temperature 103 deg. C and
corresponding vapor pressure of 75 mm mercury Absolute.
At Absorber Inlet: Lithium bromide concentration remaining unchanged i.e.
65% but solution temperature coming down to 61 degC (after pas sing through
heat-exchanger) and vapor pressure 13 mm mercury Absolute.
At Absorber Outlet: Lower solution concentration of 60.3% reached after
dilution and cold solution temperature of approx. 38.5 deg C
Inlet of Generator: Solution concentration remaining unchanged i.e. 60.3% (as
in 3above) but higher solution temperature of approx. 78 deg C attained due to
pre-heating in the heat-exchanger.

The inside of the absorption machine is always kept in vacuum. Thereare 4

main components of the VAM namely
Evaporator
Absorber
Generator
Condenser
 The single effect absorption cycle uses water as the refrigerant
and lithium bromide as the absorbent. It is the strong affinity that these two
substances have for one another that makes the cycle work. The entire process
occurs in almost a complete vacuum.
Solution Pump: A dilute lithium bromide solution (63 % concentration) is
collected in the bottom of the absorber shell. From here, a hermetic solutionpump
moves the solution through a shell and tube heat exchanger for preheating.

The refrigerant liquid moves from the condenser in the upper shell down
to the evaporator in the lower shell and is sprayed over the evaporatortube
bundle.
Due to the extreme vacuum of the lower shell [6 mm Hg (0.8 kPa)
absolute pressure], the refrigerant liquid boils at approximately 3.9°C, creating
the refrigerant effect. (This vacuum is created by hygroscopic action - the
strong affinity lithium bromide hasfor water - in the Absorberdirectly below.)

As the refrigerant vapor migrates to the absorber from the evaporator, the
strong lithium bromide solution from the generator is sprayed over the topof
the absorber tube bundle.
The strong lithium bromide solution actually pullsthe refrigerant vapor
into solution, creating the extreme vacuum in the evaporator. The
absorption of the refrigerant vapor into the lithium bromide solution also
generates heat which is removed by the cooling water.
The now dilute lithium bromide solution collects in the bottom of the
lower shell, where it flows down to the solution pump. The chilling cycle isnow
completed and the process begins once again.

:
After exiting the heat exchanger, the dilute solution moves into the upper
shell.
The solution surrounds a bundle of tubes which carries either steam or
hot water.
The steam transfers heat into the pool of dilute lithium bromide solution.
The solution boils, sending refrigerant vapor upward into the condenserand
leaving behind concentrated lithium bromide.
The concentrated lithium bromide solution moves down to the heat
exchanger, where it is cooled by the weak solution being pumped up tothe
generator.

:
The refrigerant vapor migratesthrough mist eliminators to the condenser
tube bundle.
The refrigerant vapor condenses on the tubes. The heat is removed by the
cooling water which moves through the inside of the tubes.
As the refrigerant condenses, it collects in a trough at the bottom of the
condenser.

Synthesismake-up gascontains H2,N2and some Ar,CH4(inert

components) in the Ammonia synthesis reaction.
These components get accumulated in the Syn. loop.
Therefore, a purge stream has to be drawn off to prevent buildup of Ar &
CH4 content in the loop.
The amount of Syn. gas purged results in H2 loss.
Hence H2 has to be recovered from the purge gas stream and to be
recycle back to the syn loop.
In the process an NH3, H2 and an off-gas fractions are obtained.

In general PGR unit, can be divided into two major sections. The NH3 and
H2 recovery section.
The NH3 recovery section consists mainly of purge gas absorber and the
wash water regeneration system.
The H2 recovery section consists of the absorber station with
regeneration gas heater and the cold box with the blow down system.

Comp: H2 61.66
N2 20.54
Ar 2.34
CH4 7.55
NH3 7.91
Pressure 134 KSC
Temp 13C
Purge gas from plant only is feeding in the Cold box the refrigeration
which is produced by expansion of the liquid phase of the H2 separator is
not enough to maintain required temp. And the amount of off gas would be
very low for the regeneration of the Absorbers.

High pressure purge gas heated against lean solution in Feed gas
Preheater lean water is cooled.
Afterwards purge gas enters the purge gas absorber and Ammonia is
scrubbed-out by lean water.
The pre-purified Purge gas leavesexchanger over top.
Bottom product of the exchanger an ammonia water solution with
17%(By wt.) is expanded at the operating pr. of the Wash water
regeneration system.

The rich solution from column and Flash gas absorber are heated in Rich
solution Preheater.
Where as in ammonia plant Steam flow is controlled according to the
Temp. of the Column
The temp. Difference between the bottom and the top of the first filling of
pall rings in the Regenerator Column is used to modify the set point of the
steam Pressure controller of the Regenerator Column.
The regenerated solution from the column bottom at boiling conditions
cooled in cooler against rich solution.
Regeneration column top product ammonia with product quality
condensed in Condenser and Liquid flows into the reflux accumulator.
In the accumulator, uncondensed inert components (H2,N2,CH4 and Ar)
as well as NH3 were separated and sent to exchanger. Via columnpressure
control valve.
Inert components soluted in the wash water due to the high operating
pressure of the Purge gas absorber.

The pre-purified Purge gas from the NH3 recovery section containswater
at saturated condition and traces of NH3.
Water and NH3 traces are to be removed from purge gas before entering
the gas into Cryogenic section.
Before entering the absorber unit purge gas is let down to 84 KSC.
Pre-purified purge gasnow entersone of the two interchangeable
absorbers where NH3 and water are caught on Molecular sieve.
Of the two absorbers one is in line and the other is on regeneration.
Regeneration of the Absorber
The loaded absorber is depressurized to <7.0KSC
A part of the off gas from the cold box is heated in exchanger to 230C,
And Deactivates the molecular sieve bed by passing heated off gas.
Water and NH3 leaves the molecular sieve bed with the regeneration gas
The reactivation of the molecular sieve in the bed is done by by-passing
the heater Exchanger and cooling down the bed.
In the regeneration gas outlet line of the absorber a fast closing valve is
installed to act if the pressure in the off-gas line has reached a certain set
point.Regenerationsequence time is 6hr.

The bed in off-line isdepressurized from operating pr.

(82KSC) to Off gas header pr. (3.0KSC)
After heating Mol. Sieve bed is heated up to 200°C with the off
gas from cold box.
After heating bed is cooled with the same off gas to 13°C by

Cooling will be continued.

Regenerated bed is now pressurized to the operating pr.
Regenerated bed will come into service and the bed in
service will be regenerated.
Between each step Pressure, Temperature and valve opening contacts
were checked and alarm will be annunciated.
◈
◈ Throttling process
when a fluid flow through a restriction, such as an orifice, a partly closed
valve, or a porous plug, without any appreciable change in kinetic energy,
the primary result of the process is a pressure drop in the fluid and the
process occurs at constant enthalpy
◈ This resultant joule-Thompson effect leadsto a temperature drop.
◈The temperature of gases must of course decrease during expansion, the
exception being hydrogen and helium which increase in temperature upon
throttling unless the initial temperature isbelow about 100 k for hydrogen and20 k
for helium.
The purified purge gas is cooled from13°c to -185°c in the plate fin exchangers
against cold separation products.
Most of the CH4, AR, major part of N2 and some H2 condense and separatedin
flash vessel
The first heat exchanger (the warm part) provides cooling/heating of gas
streams only.
Condensation/evaporation takes place in the second heat exchanger (cold
part).
H2 rich gas from the separator heated in exchanger and will be fed to the
Synthesismake up gas compressor.
The liquid phase of the separator vessel is expanded to the Off-gas pressure bya
level control valve.
To reduce the partial pressure of the CH4 in the Off gas fraction a part of the
top product of vessel is injected into the Off gas.
Insulation for the cold box is perlite.
Wet perlite has poor insulation qualities and hence ingress of rain water shouldbe
prevented.
For safety purpose, a Nitrogen purging through cold box is provided to dilute the
gas in case of leak.

o H2 - 91.41 mole% H2 - 18.16 mole%

o N2 - 7.79 mole % N2 - 51.28 mole%
o Ar - 0.47 mole % Ar - 6.68 mole%
o CH4 - 0.33 mole % - 23.88 mole %