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Internship Report
AGRITECH LIMITED, FORMERLY PAK AMERICIAN FERTILIZER.

Mirza Danish Baig | BSC Chemical Engineering | 27-07-2022

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Contents
Topic Page No.

Preface ............................................................................................................ 3
Acknowledgements .........................................................................................4
Introduction .....................................................................................................5
Plant Sections…………………………………….……,. 6
Uses Of Ammonia........................................................................................... 9
Detailed Process Description ........................................................................ 10
Raw Synthesis Gas Preparation ..................................................... 11

Knock Out Drums ........................................................................... 11

Hydrotreater ..................................................................................... 12
Primary & Secondary Reformer ..................................................... 13
Waste Heat boilers............................................................................ 14
HTS And LTS................................................................................... 15
Carbon dioxide Removal ................................................................... 16
Ammonia Production Process ...................................................................... 19
Urea Production ........................................................................................... 21
General Process ............................................................................................ 22
Structure of Urea .......................................................................................... 23
Uses of Urea ................................................................................................. 24
Manufacturing of Urea ................................................................................. 28
UREA Process .............................................................................................. 30

Detailed Process Description ........................................................................ 31

UREA SECTIONS.........................................................................................31
High pressure CO2 Compressor ................................................................... 32

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UREA REACTOR: ....................................................................................... 34

Concentration Section ............................................................................. 35
Prilling tower ......................................................................................... 36
Recovery Section ...........................................................................................37
Process Condensate Treatment Section ........................................................ 37
REFERENCES .............................................................................................. 39

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PREFACE

This report is about the learning outcomes of internship in Pak American Fertilizers Limited
(PAFL) Iskandrabad, Mianwali currently known as AGRITECH covering details of its
environment, process, operations and other technical information. Most of the Information was
collected from Engineers and other technical staff of every department and is written according
to internship schedule provided by PAFL. This helps to understand various steps involved in
achieving certain efficiency or the quality of the product. Undoubtedly there is so much to
learn from this industry and this is a small effort to compile as much information that has been
collected in four weeks span.

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ACKNOWLEDGEMENTS

I express gratitude and praise to ALMIGHTY ALLAH, the creator of universe, who is
beneficent and merciful, guided me in difficult and congeal circumstance, who endowed me
with the will to complete this Internship. Great respect our Holy Prophet Hazrat Muhammad
(PBUH), who taught me to learn till lap to grave.

I would like to grant my heartiest gratitude to the Engr. Hannan Qureshi & Engr. Jazib
Yaseen for all the guidance and support that they has given me to complete my Industrial
training. Dear Sir, please accept my sincere thanks for your kind hearted support and genuine
friendly attitude shown towards my work. Thank you very much for spending your precious
time to share your knowledge & experience with us.

Then again, I must not forget all the staff members of Chemical & Process Engineering
department, including the Internship Incharge Dr. Muhammad Athar for all the assistance
and support given to me to arrange this industrial training. Without your support I may have
not come this far, so please accept my sincere thanks.

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INTRODUCTION

On August 01, 2014 I was granted the unique opportunity for an industrial training at PAK-
AMERICAN FERTILIZERS LTD as a part of an internship program for BS(Chemical
engineering). I was lucky enough to have four weeks of vigorous training that broadened our
knowledge of various industrialprocesses.
INTRODUCTION TO COMPANY
Pak American Fertilizers Limited (PAFL) is located at Iskanderabad (Daudkhel), Distt:
Mianwali and produces 1050 metric tons of urea per day. PAFL is the subsidiary of National
Fertilizer Corporation of Pakistan (NFC). Japan Bank of International Cooperation (JBIC)
provided loan for setting up the fertilizer plant. The plant was commissioned in 1999. The old
plant was closed down in 1997 and a new Ammonia/Urea Plant commenced commercial
production in 1999. The new plant is designed to produce 600 Ton/Day Ammonia and 1,050
Ton/Day urea using natural gas as feed and fuel. Both plants have been designed by TOYO
Engineering Japan. Ammonia plant is under license from Kellogg International, USA, while
urea plant is TEC's own. The plants are latest in design and most modern. The company
possesses over 11,481 Kanals of land, comprising 6,432 for Factory, 2,818 for Housing Colony
and 2,230 for experimental farm.

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PLANT SECTIONS
There are two main sections in Pak American Fertilizers Limited, which areenlisted below:
• Ammonia Production
• Urea Production
AMMONIA PRODUCTION
INTRODUCTION:
Ammonia, NH3, is a comparatively stable, colorless gas at ordinary temperatures, with a
boiling point of –33C. Ammonia gas is lighter than air, with a density of approximately 0.6
times that of air at the same temperature. The characteristic pungent odors of ammonia can
be detected as low as 1 -5ppm. Ammonia can behighly toxic to a wide range of organisms.
Ammonia vapor can be fatal. When dissolved in water, elevated levels of ammonia are also
toxic to a wide range of aquatic organisms. Ammonia is highly soluble in water, although
solubility decreases rapidly with increasedtemperature. Ammonia reacts with water in a
reversible reaction to produce ammonium (NH4)+ and hydroxide (OH)- ions. Ammonia is a
weak base, and at room temperature only about 1 in 200 molecules are present in the
ammonium form (NH4)+. The formation of hydroxide ions in this reaction increases the pH
of the water, forming analkaline solution.

AMMONIA MANUFACTURING:
Ammonia is generally manufactured from natural gas using the steam reforming process.
There are several reaction stages and catalysts are key to the economic operation of ammonia
production plants.

Diagram 1 illustrates the chemistry of the ammonia process and the basic materials of the
catalysts used. The first stage is purification where impurities, mainly sulfur compounds, are
removed from the gas stream. Steam reforming is performed in two stages. In the primary
stage, the endothermic reactions take place at pressures around 30 bar and temperatures of
800°C or higher.

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This is followed by an exothermic secondary reformer where air is added to the partially
reformed gas stream. The carbon monoxide in the gas leaving the secondary reformer is
converted to carbon dioxide in the shift reactors and then removed by scrubbing from the gas
stream. Any residual carbon oxides are then converted back to methane by methanation before
compression of the hydrogen and nitrogen to ammonia synthesis pressure. The final reaction
stage is ammonia synthesis where the hydrogen and nitrogen combine to form ammonia. This
reaction stage takes place at high pressure (100-350 bars) and is highly exothermic.

DIAGRAM 1: Chemistry Of Ammonia Process

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Diagram 2 shows a simplified block diagram of a typical 1000 tone/day ammonia plant
including details of operating temperatures, catalyst volumes, and catalyst and

gas compositions.

DIAGRAM 2: Simplified block diagram for (1000 T/day) ammonia plant

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USES OF AMMONIA:

Chemicals synthesis of:

• nitric acid, HNO3, which is used in making explosives
such as TNT (2,4,6-trinitrotoluene), nitroglycerine which
is also used as a vasodilator (a substance that dilates blood
vessels) and PETN (pentaerythritol nitrate).
• sodium hydrogen carbonate (sodium bicarbonate),
NaHCO3
• sodium carbonate, Na2CO3
• hydrogen cyanide (hydrocyanic acid), HCN
• hydrazine, N2H4 (used in rocket propulsion systems)
Explosives ammonium nitrate, NH4NO3
Fibers & Nylon -[(CH2)4-CO-NH-(CH2)6-NH-CO]-,and other
Plastics polyamides
Refrigeration used for making ice, large scale refrigeration plants, air-
conditioning units in buildings and plants
Pharmaceutical used in the manufacture of drugs such as sulfonamide
which inhibit the growth and multiplication of bacteria that
require p-aminobenzoic acid (PABA) for the biosynthesis
of folic acids, anti-malarials and vitamins such as the B
vitamins nicotinamide (niacinamide) and
thiamine.
Pulp & Paper ammonium hydrogen sulfite, NH4HSO3, enables
some
hardwoods to be used
Mining & used in nitriding (bright annealing)
steel,
Metallurgy
used in zinc and nickel extraction
Cleaning ammonia in solution is used as a cleaning agent such as in
'cloudy ammonia'

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DETAILED PROCESS DESCRIPTION

The ammonia process is the low energy natural gas reforming process. The ammonia plant
design is based upon producing 600 MTPD of anhydrous liquid ammonia. Feedstock is
natural gas and at battery limit has the following composition;
Table: Composition of Feedstock

Conditions for Feedstock:

▪ Pressure at battery limit, 7.5 Kg/cm2a

▪ Temperature at battery limit, 28 0C
▪ Lower heating value, 9606 Kcal/NM2
▪ Sulphur, H2S, 10 ppmv
▪ Sulphur, Organic, 13 ppmv

PROCESS:

The process is as follows;

• Raw synthesis gas preparationSynthesis gas purification.

• Purified synthesis gas compression and ammonia synthesisAmmonia refrigeration system.
• process condensate stripper.
• Ammonia recovery steam system.
• other utilities.

Raw Synthesis Gas Preparation:

Raw synthesis gas is produced from natural gas in the following four stages;

• Compression, preheating and final desulphurization of natural gasfeed.

• Partial reforming to intermediate level of hydrocarbons in the primaryreformer furnace.
• Final reforming in secondary reformer where sufficient air isintroduced to provide quantity of
nitrogen required for synthesis.
• Conversion of carbon monoxide and steam in the reformed gas tocarbon dioxide and
hydrogen in water shift reactors.
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Knock Out Drums:

Natural gas is used as feedstock and fuel. The natural gas at 7.5 Kg/cm2a passes through a feed
gas knockout drum, (A-120-F), consisting of demister pad to remove suspended liquids and
solids. The natural gas is split in to two streams feed gas and fuel. Thee feed gas portion is
compressed to 46.0 Kg/cm2a in a steam driven 2-stage centrifugal natural gas compressor, (A-
102-J). After the first discharge it passes through an inter stage cooler, (A-135-C), and an inter
stage knockout drum, (A-121-F), to remove any moisture. In order to maintain a 2% level of
hydrogen in gas a hydrogen rich stream is introduces from (A-104-F). To protect the
compressorover a wide range of operating conditions surge valves are provided.

Hydrotreator:
The compressed natural gas then flows to the convection section of primary reformer where it
is heated to 399 0C. It then flows to the hydrotreater, (A- 101-D), where the hydrogenation of
sulfur compounds to H2S takes place. Hydrotreater consists of 8.6 m3 cobalt-molybdenum
catalyst through which the feed gas flows and conversion of sulfur to hydrogen sulfide takes
place. Reaction is;
S + H2 H2S
After passing through the hydrotreater it passes into desulfurizers, (A-102- DA/DB), which
contains a 21 m3 layer of zinc oxide catalyst. The hydrogen sulfide produced is absorbed by the
zinc oxide catalyst as a result of which the gas becomes free of sulfur, ( S < .01 ppm).

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ZnO + H2S ZnS + H2O

Operating variables for hydrotreater are

• Hydrogen/ Fee gas ratio (0.02 mol H2/ mol
feed gas)
• Temperature (371 0C-399 0C)
• Pressure (46.0 Kg/cm2)
Temperature of exiting stream is 388 0C.

De sulfurized natural gas

21 m3 of catalyst

Feed

After the sulfur compounds have been removed, it is essential to reform he feed gas under
conditions that will produce H2. This is done by contacting the gas and steam with nickel
catalyst in suspended tubes at elevated temperatures and pressure

Primary & Secondary Reformer:

This stream is mixed with 44.0 Kg/cm2a and 390 0C, high pressure steam, in the ratio of 3.5
moles of steam per mol of organic carbon. The steam mixed gas then goes to the convection
section of primary reformer where its gets heated to 621 0C. After heating it is distributed to
the catalyst tubes suspended in radiant section of primary reformer. The catalyst is in the form
of rings or cylinders that are filled in to the tubes. The entering gas is split in to three

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streams each having 52, catalyst filled, tubes suspended in furnace. Here the following
reactions take place;
2CH4 + 3H2O CO + CO2 + 7H2
The partially reformed gas from the primary reformer enters the secondary reformer, (A-103-
D), lower combustion chamber nozzle with water jacketed transfer line, (A-107-D). The
temperature at the secondary inlet will be about 833 0C. Here it is mixed with stoichiometric
nitrogen requirements of ammonia synthesis reaction. The air supply for combustion in
secondary reformer is provided by steam turbine driven air compressor, (A-101-J). The air is
preheated in the convection zone of primary reformer to about 621 0C. The exit temperature
from secondary reformer is about 1013 0C.

Fig. Primary reformer and convection section.

“Catalyst bed consists of 18.0 m3 of nickel catalyst. The catalyst is supported on a bed of 19-25
mm spheres laid on a bed of 50 mm dia low silica alumina refractory spheres. The spheres and
catalyst are supported by an arched brick dome located over the exit chamber of secondary
reformer.

Waste Heat boilers

Raw synthesis gas at 1013 0C leaves the bottom of secondary reformer and passes through the
tube side of reformed gas waste heat boiler, (A-101-C). The gases are cooled to about 640 0C.
The process stream is further cooled in steam super heater, (A-102-C), to a temperature of 371
0
C before entering high temperature shift converter, A-104-DA. High temperature shift effluent
is cooled from 434 oC to 216 0C before entering low temperature shift converter, (A-104-DB),
by heating boiler feed water on shell side of exchanger.

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HTS And LTS:

HTS (High temperature shift converter), is constructed as a single bed vessel having iron oxide
as a catalyst. Catalyst volume is 29.2 M3. Raw synthesis gas enters at 371 0C where a large
percentage of CO content will be reactedin accordance with the following reaction:
CO + H2O CO2 + H2
The reaction is a reversible one, with “shifting” of CO favored by low temperature. However,
the rate of reaction is favored by high temperature. To attain a specified CO conversion, the
principal operating variables are temperature and steam gas ratio. The steam gas ratio is
usually maintained constant.
If the reaction is near equilibrium, a decrease in temperature will likely improve conversion,
and if not near equilibrium, a temperature decrease will reduce shifting reaction. The
temperature conditions selected for shift converters are based on a higher temperature for HT
converter to take advantage of higher conversion rates for high CO content and low
temperature for LT converter, to take advantage of favorable equilibrium conditions for
low CO concentrations in this section of converter.

LTS (Low temperature shift converter), consists of a bed of Cu-ZnO catalyst and is operated at
a temperature of 216 0C. However, lower temperature is permissible and desirable. The
temperature at the inlet to LTS is controlled by heat exchange which takes place in (A-103-C)
exchangers. HTS effluent passes through these exchangers giving heat to BFW for HP steam
generation,which cools the stream to 216 0C. Max permissible temperature in LTS is 260
0
C.

Fig.LTS&HTS
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After the synthesis gas has been prepared it is purified off carbon dioxide and carbon
monoxide to yield a high purity nitrogen hydrogen synthesis gas.

Carbon dioxide Removal:

Absorber and Stripper:

The new configuration consists of 1 stage absorber , LP-flash column and a stripper . In the
absorption side only the bulk absorber part will be used . While for regeneration, additional
flashing column is installed in order to reduce vapor load and energy requirement on the old
stripper.

The feed gas from 102-F at and 29.6 kg/ enters the absorber at the bottom . The lean
aMDEA solution at 50 C from the lean rich exchanger (111- CA/CB ) and lean cooler (109
CA/CB ) enters the absorber from the middle inlet via semi lean circulation pump ( 107J/JA)
(518 kg/ ) . While the two streams flow counter current through the absorber, the lean
solution gradually absorbs the C present in the feed gas, and leaves the absorber bottom as rich
solution stream at to LP flash column (104-E). the treated gas at exists the
absorber from the top , on specification . Mist carry-over to the down stream equipment is
minimized by the packing in thr previous lean absorption section which is now
performing as “demister”.

Regeneration takes place in two steps i.e. flashing in 104-E and stripping in 102-E . The rich
solution at is flashed in the newly installed LP-flash column ( 104-E ) at
0.9 kg/ , via LV1201-A/B . Liquid from 104-E bottom is pumped through 113 J/JA to lean
rich exchanger ( 111-CA/CB ) where it is heated before going to the stripper

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102-E through FT-1234 ( 537 /hr ) and LC-1208, which is used to control104-E level. Part
of the solvent will be directed to the bottom section of 102-E via FC-1210, and boiled in the
reboiler ( A-105 )at . Most of the solvent from the middle section of 102-E is sent to
114-C and then 117-F through LC-1203 and stripped directly by SL steam in 114-C. Steam for
this purpose is produced in A-113-C and provision is made to control steam supply from SH
and SL headers . Regenerated solution leaves 114-C ( LIA-1282 ) and goes to 117-F by gravity
flow . 117-F is used as holding tank to provide residence time for 107-J/JA . The lean solution
at from 117-F is then cooled down sequentially in lean rich exchanger ( 111-CA/CB )
and lean cooler ( 109 CA/CB ) to with 50 % concentration , prior to recycle into the
absorber.

Acid off gas from 105-C , 117-F and 114-C leaves 102-E from the top at and
1.1 kg/ is directed to 104-E to aid in flashing section . The gas is cooled down in the direct
contact condenser ( 104-E top bed ) where a large part of saturated water is reclaimed for reuse
in the system (FC-1206=65 app. ) .
The cooled acid off gas at and 0.9 kg/ is ready to be sent to down stream unit . Water
balance in the system is slightly positive , which means that some of water should be drained
from the condenser intermittently , in order to maintain solvent strength.

Polished water is directly supplied to 113-C for steam generation . Steam condensate from
114-C is directed to condensate vessel ( 118-F ) from where it is sent to 101-J/JA and de-super
heated via condensate transfer pump 115-J/JA and LIC- 1209 . SL steam to 114-C is provided
from 113-C , SL header and SH to SL letdown PC-1656. SL flow is controlled by FICA-1235
(HV-1200 old) . PC-1203 will act as vent.

Anti-foam:

BASF recommends the use of as antifoam. is produced by the

Drew Ameroid Company . It is widely used in many aMDEA plants. This antifoam agent can
also be purchased through BASF.

Typical dosage rate of 1500 for ammonia plant is 380 ml/day for a plant of Owner’s
capacity.

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Fig. Stripper & absorber

AMMONIA PRODUCTION SYSTEM

Compression of Synthesis Gas and Water Removal:

The purified gas is compressed from 31.2kg/cm2a to about 78.2 kg/cm2a in the first case of the
Synthesis Gas Compressor, A-103-J, and then chilled in two steps: first, by heat exchange to
cooling water in the Synthesis Gas Compressor Inter stage Cooler, A-116-C, to 410C, then
ammonia refrigeration in the Synthesis Gas Compressor Interstate Chiller, A-129-C. This
chiller cools the gas to 4.40C, dropping the water in the Synthesis Gas Compressor First Stage
Separator, 105-F.
The low moisture content synthesis gas leaving A-105-F goes to the Molecular Sieve Driers, A-
109-DA/DB, where all the water is removed. These are regenerated by dry synthesis gas exit
the driers. The synthesis gas then goes to the second case of A-103-J, and pressure is increased
to about 146 kg/cm2a to enter the synthesis loop. At an intermediate point (last wheel suction)
of the second case of A-103-J, the synthesis gas is joined by the synthesis of recycle gas.

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Synthesis (Conversion) of Synthesis Gas to Ammonia:

The synthesis converter A-105-D contains 31.6 M3 of promoted in catalyst. The catalyst is
contained in an international basket designed which has three separate catalyst beds within
horizontal reactor. The catalyst beds are divided into four sections. The first bed contains 228
catalysts to limit the temperature rise. Fresh feed can be injected above the first bed to control
the temperature of the produced gas. The first bed effluent is passed through the interchanger
A-122-C before being passed through the second bed, and the second effluent passes through
interchanger A-122-C followed by beds 3A in series.
Separation of Anhydrous Liquid Ammonia from Synthesis Gas: The ammonia produced in
the synthesis reaction would quickly build a level to interfere with the reaction so it has to
be continuously removed from the synthesis recycle gas stream going to the converter. This
is done by chilling the recycle stream via a series of cooler chillers to condense the net
ammoniaproduct that is produced in each pass through the converter.

The temperature of the recycle gas stream is -17.80C by the time it reaches the Ammonia
Product Separator, A-106-F. Condensing and sub cooling the ammonia in the synthesis gas
loop to -17.80C at 136.7 kg/cm2a pressure will reduce the ammonia in the recycle gas stream
from 15.8 to 2.793. The resulting chilled ammonia liquid collects in the Ammonia Product
Separator, A-106-F, which is level controlled (LICA-1351). The liquid ammonia leaving A-
106-F is fed to the Ammonia Letdown Drum, A-107-F, for the final product purification step
of the process.

Ammonia Production Purification (Removal of Absorbed Gases): As previously noted, the

liquid ammonia that is separated from the synthesis gas will contain a certain amount of
absorbed gases that would result in a contaminated product.

The purpose of the refrigeration system in the product purification step is twofold: first,
flash and re flash of liquid ammonia at lower pressure levels to

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release all absorbed gases and direct them to the fuel gas system; second, as an integral part of
the refrigeration system, the process chillers remove heat from the synthesis gas in the
synthesis gas loop to sub cool the recycle gas to - 17.80C for the satisfactory separation and
removal of the net ammonia make from the synthesis loop. These chillers are so located in the
refrigeration system to take full advantage of the various pressures (and temperature) levels at
which it is operated.

Fig. Simplified flow sheet for typical ammonia plant

Ammonia storage:
Anhydrous ammonia is usually stored as a liquid in refrigerated tanks at – 33.3C and
atmospheric pressure, often in doubled-walled tanks with the capacity for hundreds or
thousands of tonnes. The low temperature is usually maintained by the venting of ammonia
gas. The vented gas is re-liquefied for recycling, or absorbed in water to make aqueous
ammonia. Relatively small
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quantities of anhydrous ammonia are sometimes stored under pressure in spherical vessel at
ambient temperature. Ammonia is corrosive to alloys of copper and zinc and these materials
must never be used in ammonia service.
Iron and steel are usually the only metals used in ammonia storage tanks, piping and fittings.

UREA PRODUCTION
INTRODUCTION:
Urea was first identified in 1773 when it was isolated by crystallization from urine. It was first
was first prepared synthetically in 1828 by Wohler from ammonia and cyanuric acid.
NH3 + HCNO → CO(NH2)2

This preparation was a milestone in science since urea became the first organic compound
prepared by synthesis from inorganic materials previously it was believed that organic
compounds could be produced only by living organisms. The present method of synthesizing
urea from ammonia and carbon dioxide has been known in principle since 1868, but
commercial production by this method started in 1922 in Germany, in 1922 in the United
States, and in 1935 in England. However, there was some commercial production in Canada
(by DuPont) starting in 1920 using calcium cyan amide according to the reaction:

CaCN2 + 3 H2O→ CO (NH2)2 + Ca(OH)2

Use of urea as a fertilizer developed rather slowly at first, partly because early processes
were cumbersome and expensive partly because of some doubt about its agronomic suitability.
Urea has been considered a slow release fertilizer in Europe since it must undergo to
transformation in the soil before it becomes available to most crops. The first transformation is
hydrolysis.

CO(NH2)2 +H2O→ 2NH3 +CO2

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The second transformation is nitrification in which ammonia is oxidized in the soil by

microbiological means, first to nitrite and then to nitrate gives reaction to precede rapidly warm
moist soil, but they are quite slow in cool soil which is the characteristic of temperature
climate in a spring season.

GENERAL PROPERTIES:
Under some circumstances urea can be phototoxic, and many cases of severe damage to crops
have occurred, especially when the urea was placed close to the seeds.
Aside from toxicity, poor agronomic results may be caused by loss of ammonia to the
atmosphere when urea is applied on the surface of the soil or as topdressing to growing crops.
This loss is caused by the formation of ammonia by hydrolysis under such conditions that part
of it escapes to the atmosphere rather than being absorbed by the soil.

Urea is generally satisfactory for rice and preferable to nitrates for flooded rice since nitrates
are reduced to NO to N2 in the anaerobic zone of the rice paddy and hence lost to the
atmosphere. Also the rice plant, unlike most other crops, can utilize the ammonium form of
nitrogen efficiently. In tropical, subtropical, and warm temperature zones, the hydrolysis and
nitrification (in aerobic soil conditions) are rapidly completed; thus, there is no delayed-
release effect. For these reasons and because of its high concentration and favorable
production cost, it has become the most popular nitrogen fertilizer in Asia and in many
countries on other continents. An excellent discussion of the agronomic effects of urea has
been presented by Tomlinson who concludes that urea can be used efficiently, but its use
requires a higher degree of understandings than is the case with simple inorganic salts.

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Structure of Urea:

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USES OF UREA
Agricultural use

Urea is used as a nitrogen release fertilizer as it hydrolyses back to ammonia and carbon
dioxide, but its most common impurity (biuret,NH2-CONH- CO- NH2) must be present at
less than 2% as it impairs plant growth. It is also used in many multi-component solid
fertilizer formulations. Its action of nitrogen release is due to the conditions favoring the
reagent side of the equilibriums which produce urea. Urea is usually spread at rates of between
40 and 300 kg/ha, but actual spreading rates will vary according to farm type and region. It is
better to make several small to medium applications at intervals to minimize leaching losses
and increase efficient use of the N applied compared with single heavy applications. During
summer, urea should be spread just before, or during rain to reduce possible losses from
volatilization (process where nitrogen is lost to the atmosphere as ammonia gas). Urea should
not be mixed for any length of time with other fertilizers as problems of physical quality may
result. Because of the high N concentration in urea, it is very important to achieve an even
spread. Make sure that the application equipment has been correctly calibrated and is properly
used. Do not drill on contact with or close to seed, due to the risk of germination damage. Urea
dissolves in water for application as a spray or through irrigation systems.

Industrial use
Urea has the ability to form 'loose compounds' with many organic compounds. The organic
compounds are held in channels formed by interpenetrating helices comprising of hydrogen
bonded urea molecules. This behavior can be used to separate mixtures and has been used in
the production of aviation fuel and lubricating oils. As the helices are interconnected all helices
in a crystal must have the same 'handedness'. This is determined when the crystal is nucleated
and can thus be forced by seeding. This property has been used to separate raceme mixtures

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Further commercial uses

• A component of fertilizer and animal feed, providing a relatively cheap source of nitrogen to
promote growth
• A raw material for the manufacture of plastics, to be specific, urea- formaldehyde resin A raw
material for the manufacture of various glues (urea-formaldehyde or urea melamine-
formaldehyde);the latter is waterproof and is used for marine plywood
• An alternative to rock salt in the de-icing of roadways and runways, it does not promote metal
corrosion to the extent that salt does
• An additive ingredient in cigarettes, designed to enhance flavor
• A browning agent in factory-produced pretzels
• An ingredient in some hair conditioners, facial cleansers, bath oils,and lotions
• A reactant in some ready-to-use cold compresses for first-aid use, due to the endothermic
reaction it creates when mixed with water
• A cloud seeding agent, along with salts, to expedite the condensation of water in clouds,
producing precipitation
• An ingredient used in the past to separate paraffin, due to the ability of urea to form catharses
(also called host-guest complexes, inclusion compounds, and adducts)
• A flame-proofing agent (commonly used in dry chemical fire extinguishers as Urea-potassium
bicarbonate)
• An ingredient in many tooth whitening products
• A cream to soften the skin, especially cracked skin on the bottom ofone's feet
• An ingredient in dish soap.
• To make potassium cyanate
• A melt agent used in re-surfacing snowboarding half pipes and terrain park features
• A raw material for melamine production More than 95% of all melamine production is based
on urea. Stamicarbon¶s parent companyDSM is the largest melamine producer in the world.

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• A supplementary substitute protein source in feedstuffs for cattle and other ruminants. Because
of the activity of micro-organisms in their cud, ruminants are able to metabolize certain
nitrogen containing compounds, including urea, as protein substitutes. In the USA this
capability is exploited on a large scale. Western Europe, in contrast, uses little urea in cattle
feed.

Laboratory use:
Urea is a powerful protein denaturant. This property can be exploited to increase the solubility
of some proteins. For this application, it is used in concentrations up to 10 M. Urea is used to
effectively disrupt the non-covalent bonds in proteins. Urea is an ingredient in the synthesis of
urea nitrate. Urea nitrate is also a high explosive very similar to ammonium nitrate, however it
may even be more powerful because of its complexity.

Medical use:
Drug use
Urea is used in topical dermatological products to promote rehydration of the skin. If covered
by an occlusive dressing, 40% urea preparations may also be used for nonsurgical debridement
of nails. This drug is also used as an earwax removal aid. Like saline, urea injection is used to
perform abortions. It is also the main component of an alternative medicinal treatment referred
to as urine therapy.

iagnostic use
Isotopically-labeled urea (carbon- 14 - radioactive, or carbon- 13 - stable isotope) is used in the
urea breath test, which is used to detect the presence of the bacteria Helicobacter pylori (H.
pylori) in the stomach and duodenum of humans. The test detects the characteristic enzyme
urease, produced by H. pylori, by a reaction that produces ammonia from urea. This increases
the pH (reduces acidity) of the stomach environment around the bacteria. Similar bacteria
species to H. pylori can be identified by the same test in animal.

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Textile use
Urea is a raw material for urea-formaldehyde resins production in the adhesives and textile
industries. A significant portion of urea production is used in the preparation of Urea
formaldehyde resins. These synthetic resins are used in the manufacture of adhesives, molding
powders, varnishes and foams. They are also used for impregnating paper, textiles and leather. In
textile laboratories they are frequently used both in dyeing and printing as an important
auxiliary, which provides solubility to the bath and retains some moisture required for the
dyeing or printing process.

MANUFACTURING OF UREA

Process Operating Variable:

1. Temperature
Conversion of ammonium carbamate to urea in the absence of excess ammonia increases with
temperature to a maximum of about 50% at 170% at 170 to 190 degree C when the pressure is
sufficiently high to keep the reactant in the liquid state. The rate of reaction is increases with
temperature. it is slow at 150C and below(with stiochiometric ratio of NH3 and CO2)and quit
rapid at 210C a satisfactory approach to equilibrium can be obtain in the temperature with
excess ammonia. Corrosion difficult increases with temperature and a range of 180-210C is
generally accepted as optimum for most process.

2. Pressure
At constant temperature conversion increase with pressure up to the critical point with is the
point at which the vapor phase substantially eliminated and the reactants are in the liquid state.
A further increase in pressure is not beneficial. The critical temperature is the complex
function of the temperature and composition of the reactor content .For example At 150C the
pressure is

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at 100atm might be near optimum for a stoichiometric NH3 and CO2 ratio, but at this
temperature of 180-210C pressure of 140-240atm are commonly used.

3. Mole Ratio Of Ammonia And Carbon dioxide

Excess ammonia above the stoichiometric mole ratio of 2 favors the rate of the reaction. The
percentage of carbon dioxide converted to urea is increased but, of course, the percentage of
ammonia converted to urea is decreased. Because recycling of excess ammonia is relatively
simple, most process used 50% or more excess ammonia (a molar ratio of 3.1)

4. Other Factors
The presence of water decreases the conversion there most process are design to minimized the
amount of water recycled to the reactor the presence of small amount of oxygen decreasing the
corrosion and all process are used to minimized the corrosion.

5. Optimum Condition
It is generally not economical to maximize the percentage conversion in the reactor because
this would require an excessive retention time. The aim therefore is to attain maximum
quantity of urea production per unit of time with regard to the cost of recycling unrelated
carbon dioxide and ammonia and the cost of increased reactor size and corrosion difficulties
which increase with temperature .typically operating condition are temperature 180-140C and
the pressure is about 140-250atm NH3-CO2 ratio is 3.1 and 4.1 and the reaction time is 36
minutes.

Raw materials of urea manufacturing:

The PAK AMERICAN Fertilizer plant uses gaseous CO2 and liquid ammonia from ammonia
plant, as a raw material for urea synthesis. This plant is designed to yield 1050 MT/D of urea
of specified quality.

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UREA Process:

Toyo Engineering-ACES Process:

The synthesis section of the Toyo Engineering-ACES (Advanced Process for Cost and Energy
Saving) . In this process the synthesis section operates at 175 bars with an ammonia and carbon
dioxide molar ratio of 4.0 and a temperature of 185 to 190°C. Liquid ammonia is fed directly
into the reactor while gaseous is sent from the centrifugal compressor at the bottom of the
stripper the reactor effluent is stripped at essentially reactor pressure using as the stripping
agent. The overhead gas mixture from the stripper is fed to two carbamate condensers in
parallel. Here the gases are condensed and recycled under gravity to the reactor along with
absorbent solutions from the HP scrubber and absorber. The heat generated in the first
carbamate condenser is used to generate 5.0 bar steam, and the heat from the second condenser
is used to heat the solution leaving the stripper bottom after pressure reduction The ACES
stripper uses a ferrite-austenite stainless steel as do the carbamate condensers. The reactor and
scrubber are constructed with 316L urea-grade stainless steel The urea solution that leaves the
stripper bottom is further purified in HP (17.5 bar) and LP (2.5 bar) decomposers. The urea
solution is first concentrated to 88.7% in a vacuum concentrator and then to the required
concentration for prilling or granulating.

Chemical Reactions:
2NH3+CO2 = NH4COONH2 +HEAT (ammonium carbamate)

NH4COONH2+HEAT=NH2CONH2+H2O (urea)
Introduction:
Mitsui Toatsu Total recycle process (now Toyo Aces Process) is mostly commercially used for
the production of urea. In Pakistan, Pak American urea fertilizer used this process. Toyo Koatsu
developed of this process.

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Detailed Process Description:

In this process all unconverted ammonia, carbon dioxide, and carbamate are recycled to the
urea reactor. (Conversion is about 99%) this is the more flexible of urea process because it
depends only on the CO2 and NH3 supply from its supporting ammonia plant for operation.

Fig. Urea Manufacturing Process Flow Block diagram

UREA SECTIONS
⚫ Synthesis Section
⚫ Purification Section
⚫ Concentration Section
⚫ Prilling Section
⚫ Recovery Section
⚫ Process Condensate Treatment Section
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1. Synthesis Section:
Equipment and machinery Involved in Synthesis:
• High pressure carbon dioxide compressor
• High pressure ammonia feed pump
• High pressure carbamate feed pump
• Reactor
• Ammonia preheater
• Carbamate preheater
• Carbamate heater

High pressure CO2 Compressor

Both CO2 compressor are interchangeable and can feed CO2 to any reactor. But at a time only
one compressor can feed to reactor. These compressors have two different cooling systems
for cylindrical jacket and intercooler
.mostly using the cooling water (tempered water).temped water is deminerlized water treated
with sodium di-chromate and caustic soda.
Special precautions are taken to maintain temperature at fifth stage suction knock out drum.
Temperature is maintained between 52–56 C.

High Pressure ammonia Feed Pump

Ammonia feed pump increase the pressure of ammonia more than the reactor so that it can be
feed to the rector about 3000-3300psig. These feed pumps operate parallel. These feed pumps
are equipped variable speed drive which enables flow control at different load condition.

High Pressure Carbamate Feed Pump

These pumps increase the pressure of recycle carbamate more than the reactor abut 3000-
3300psig.these pumps equipped with the variable speed driven which enable flow/level control
at different load condition. At 100% load approximate flow of carbamate to reactor is 185-
195gpm each.
Pump speed is controlled through a fluid drive (Gyrole) which consists of a pump, a heat
exchanger and a speed controller.

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Ammonia Pre-Heater
It is a shell and tube heat exchanger with heating medium process gas on shell side and NH3 in
tube side. Ammonia pre heater recover process heat from liquid distributer off gases and
preheat ammonia from 80F up to 185-200F.
A bypass control valve is installed on ammonia line to preheat which can bypass ammonia
flow to control temperature

Ammonia Heater
There are two sets of shell and tube heat exchanger with counter current flow of steam.
Ammonia flows in the tube at a pressure of 3000-3300psig counter current to heating medium.
Two heating source are available i.e. process condensate and 100psig steam. Temperature of
ammonia is controlled by the regulating the flow of heating medium through control valve.
Maximum temperature of ammonia is 270F which is maintained through control valve above
270F flashing of ammonia take place which is undesirable.

Carbamate Heater:
These are u tube heat exchanger in which carbamate temperature is increased and controlled
at 260-265F before entering the reactor(temperature of carbamate is controlled at this level
because higher temperature create corrosion in the pipe line and valves). Process condensate is
the heating medium in the shell side. Temperature is manually controlled by manipulating
condensate outlet and bypass valve.

Carbamate Preheater:
This is the simple shell and tube type heat exchanger in preheater increased the temperature of
the carbamate from 190 to 225-235F the carbamate in the tubes is at the pressure of 3000-
3300psig and the heating medium in the shell side at the pressure of 300psig.

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UREA REACTOR:
Plug Flow Reactor
All the raw material (ammonia carbamate and carbon dioxide are introduced in the reactor).
Reactor unique design is presented by IVO Maverick and manufactured by Neuter Corporation
2NH3 + CO2 NH4COONH2 (Exothermic reaction)
NH4COONH2 NH2CONH2 + H2O

In synthesis section raw material ammonia and carbon dioxide and recycle carbamate solution
are pumped to the reactor at sufficient pressure and temperature to promote the reaction.

All feeds are maintained at their specified levels to get maximum conversion efficiency of
reactor. After the formation of ammonium carbamate urea is formed due to the dehydration of
ammonium carbamate .This chemical reaction takes place in the plug flow reactor. The molar
ratio of ammonium carbamate and carbon dioxide is adjusting 4:1 higher the ratio of
ammonium and carbon dioxide means higher the conversion.

2. Purification/Decomposition section
The solution taking from the reactor is passed from the pressure relief valve and decreases the
pressure from 3200psig to 300psig.
Now this solution is pumped at a temperature of 377F in the first decomposer this solution
contain the unconverted ammonium carbamate, that’s why it should decomposed in to
ammonia and carbon dioxide. The reactor effluent solution enter in the decomposer it suddenly
reduced the pressure, due to the reduction of pressure temperature is also decreases. For the
decomposition of ammonium carbamate there is the following reaction is take place:

NH2CO2NH4 ↔ CO2 +2NH3

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This reaction is the reverse of the first step of the synthesis process and is strongly endothermic
(37.7kcal/kg mol).This energy is provided by steam.
In the decomposition section using the steam for the heating purposes, steam flows in shell
side and urea solution in tube side, so urea containing dissolved gases its separate and leaving
from the top of the decomposer.

The urea solution taking from the bottom of the first decomposer at the temperature of 343F it
enters the second decomposer but before it pass in the pressure relief valve and reduced the
pressure 15psig. Then enter in the second decomposer same process is happened just like as
the first decomposer. In second decomposer further remove the dissolved gases formed the
urea and un-decomposed carbamate solution is decomposed. The urea solution taking from the
bottom of the low pressure decomposer it enters in the concentrator for improving the
concentration of urea solution.

3. Concentration Section:
Concentrator:
The urea solution coming from the second decomposer enters in the concentrator. Using the
steam for the heating purposes in concentrator we increased the concentration of the urea
solution by evaporating the water. This system is design to concentrate urea product .heat is
providing by 55psig steam controlled by the steam valve. the gases (ammonia and carbon
dioxide, water vapor) are separated from the top of the concentrator. These gases are
condensed. A 72-73 wt% urea solution is separated from the gases and concentrated under low
vacuum in the Urea Concentrator to an 88 wt% solution and is then sent to evaporation before
prilling or granulation. Vacuum is maintained in the Urea Concentrator by a single stage
vacuum system using a very small amount of steam, only about 10 to 18 inches of hg (in the
aspirator part of concentrator). The condensed overhead vapors are condensed. After it urea
solution comes out in the urea filter.

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Urea filter:
One of the two filter remains in service for 24hrs the filter is designed to reduced oil and iron
in the product solution. It consists of filter leaves which are coated with filtering medium
diatomaceous earth which absorbed the oil and removes iron partial. After filtration, urea
solution flows to vacuum evaporator.

Evaporator:
Filling film type evaporator is used for these purposes. An atmospheric air swept falling film
Evaporator, with heat being supplied by low pressure steam, evaporates the 88 wt% urea
product to a 99.7 wt% urea melt product, ready for prilling or granulation.

4. Prilling tower:
It is the natural draft prilling tower, the height of the prilling tower is 73 meterandinner
diameter is 17 meters. There are the 16 window at the bottom of the prilling tower for the
entry of air and lovers are installed in the windows to control air flow and prevent prills from
falling out similarly there are 16 window at the top for exiting hot air out. Louvers are also
installed at the top windows for exiting air and preventing rain water into the prills tower.

Scrapper:
Scrapper rotates at speed of 2 rpm with the help of motor through gear. Scrapper consists of
two arms with inclined blades which direct urea prills to the central discharge cone. Scrapper
motor speed in indicated in local panel for smooth operation of scrapper.

1. Spinning bucket assembly is installed in bucket room at the top of prillingtower.

2. There are independent spinning buckets at a time only one bucket is in service while other is
standby
3. Bucket speed control is provided locally in substation and in control room.

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4. Bucket speed control to maintained the product quality

Air enter from bottom louvers and exits from top louvers. Air flow is naturally established due
height and temperature difference. At the bottom of the cooling tower there is a conical
scrapper floor with a scrapper on the top of it to collect and transport the falling prills to the
center of the conical floor for delivery to rotating dispebser and to conveyor for delivery to
vibrating screen
.after screening the product is either treated with anticaking spray.

Flow of air in Prilling tower:

Air flows through prilling tower shaft s controlled by adjusting lower window louvers rubber
mats are also placed on walk way grating around the lower window to control the air flow. Air
flow regulation depends on plant load and weather condition or example humidity and air
temperature. Air flows counter current to falling urea prills and exits from top windows louvers.
Opening of top window louvers remain fixed and is never altered.

Contant Quantity
Biuret 1.25 max
Moisture 0.6 max
Fines 3.0 max
Size 2.2 max
Crushing 800
strength

5. Recovery Section:
The gases produced from the top of the second decomposer are introduced at the bottom side
of a unit name as second absorber. At the top of the second absorber quantity of water is
introduced at the top of the second absorber the solution collected at the bottom of the absorber
is recycled into the unit so the concentration of the carbamate formally become seasonable.

Most of the carbon dioxide coming from the second decomposer is fixed up carbamate
solution. Unabsorbed ammonia is recovered at the top side of the second absorber. Since the
absorption of the ammonia and the carbon dioxide

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is the exothermic in nature. There by the continuous heat is recovered during this exothermic
reaction.
To utilize this heat we use this hot dilute carbamate solution from second absorber in a second
decomposer in second decomposer the decomposition unrecompensed carbamate is carried out.

After decomposing the carbamate solution the ammonium carbamate solution along with gases
is transfer into a unit name as first absorber and finally concentrated carbamate solution
containing small quantity of water is led intoa reactor.

The gaseous ammonium is recovered at the top of the first and second absorber is compressed
and liquefies and finally returns in to the ammonia storage tank.

In the first absorber we concentrate the ammonium carbamate into concentrated ammonium
carbamate. This ammonium carbamate is sent back in to the reactor through ammonium
carbamate heater and pump which we discussed previous in detail.

6. Process Condensate Treatment Section:

The process condensate leaving the system is purified to 1ppm of urea and 1ppm of NH3. The
gas effluent from prilling tower (or granulator) is scrubbed through a packed bed scrubber to
reduce the urea dust content of the effluent to 30mg/Nm3-air.

REFERENCES

Pak American Fertilizer Process Manual

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