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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
Hydrotreator...12
Primary & Secondary Reformer...13
Waste Heat boilers.14
HTS And LTS15
Carbon dioxide Removal16

Ammonia Production Process.19


Urea Production...21
General Process22
Structure of Urea..23

Uses of Urea24
Manufacturing of Urea28
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

UTILITIES SECTION38
REFERENCES39

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 six weeks span.

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
Engineer Muddassir (graduated from CIIT Lahore) for
all the guidance and support that he has given me to
complete our 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 head of the department Dr. ASADULLAH KHAN for
all the assistance and support given us to arrange this
industrial training. Without your support we may have not
come this far, so please accept our 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 industrial
processes.

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.

PLANT SECTIONS
There are two main sections in Pak American Fertilizers Limited, which are
enlisted 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

Brief introduction of Habers Process

be detected as low as 1 -5ppm. Ammonia can be

The Habers process combines nitrogen


from air with hydrogen derived mainly
from natural gas into ammonia. The
reaction is reversible and highly
exothermic. Increasing the pressure and
reducing the temperature shifts the
equilibrium to right.

highly toxic to a wide range of organisms.

N2 + 3H2

Ammonia vapor can be fatal. When dissolved in

Temperature (0C)
25
200
300
400
500

than air, with a density of approximately 0.6


times that of air at the same temperature. The
characteristic pungent odors of ammonia can

water, elevated levels of ammonia are also


toxic to a wide range of aquatic organisms.
Ammonia is highly soluble in water, although

2NH3 (G)

Keq
6400
.44
.0043
.00016
.000015

solubility decreases rapidly with increased


At around 200 0 C and above 750 atm
there is almost 100% conversion. Since
there is difficulty associated
produce ammonium (NH4)+ and hydroxide
(OH)- ions. with
containing larger amount of material at
high pressure,
base, and at room temperature only
about lower
1 inpressures
200 at around
200 atm are used industrially.

temperature. Ammonia reacts with water in a


reversible reaction to
Ammonia is a weak

molecules are present in the ammonium form (NH4)+. The formation of


hydroxide ions in this reaction increases the pH of the water, forming an
alkaline 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 800C or higher.
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

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,

Plastics

polyamides

Refrigeration

used for making ice, large scale refrigeration plants, air-

-[(CH2)4-CO-NH-(CH2)6-NH-CO]-,and

other

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

Component

Gas mole %

CH4

82.6

C2H6

8.5

C2H8

3.3

C4 + Higher 1.9
CO2

1.3

N2

2.4

Total

100.00

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 preparation
Synthesis gas purification
Purified synthesis gas compression and ammonia synthesis
Ammonia refrigeration system
Process condensate stripper
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Ammonia recovery system


Steam system
Other utilities

Raw Synthesis Gas Preparation:


Raw synthesis gas is produced from natural gas in the following four stages;
1.

Compression, preheating and final desulphurization of natural gas

feed.
2.

Partial reforming to intermediate level of hydrocarbons in the primary


reformer furnace.

3.

Final reforming in secondary reformer where sufficient air is


introduced to provide quantity of nitrogen required for synthesis.

4.

Conversion of carbon monoxide and steam in the reformed gas to


carbon dioxide and hydrogen in water shift reactors.

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

Natural gas contains proportion of


water and heavier hydrocarbon
molecules suspended in it.
Knockout drums employs de mister
pad to remove it.

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 compressor
over a wide range of operating conditions surge valves are provided.

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Fig. Knock out Drum

Fig. Demister pads

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, (A101-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 desulphurizers, (A-102DA/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). Reaction is;
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ZnO + H2S

ZnS + H2O

Operating variables for hydrotreator 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 stichiometric 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 0C 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 reacted
in 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.

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Fig. LTS & HTS

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 oC from the lean rich exchanger ( 111CA/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
1.1 kg/

and

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 Owners 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 ammonia
product 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 delayedrelease 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- CONH2) 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, ureaformaldehyde 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 of


one'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. Stamicarbons parent company
DSM 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 stiochiometric 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 stiochiometric 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 190C. 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 5256 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, thats 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/kgmol).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 prilling


tower.
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 strength

800

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 into
a 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.

UTILITIES SECTION
Raw Water Section
Cooling Water Section
Steam Generation
Power Generation
Fire Water Section
Water Treatment Section
Fuel Section
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RAW WATER SECTION


Intake
PAFL has its own water intake facility near river Indus. This facility is
comprises on the following:
Two 24 dia & 4500 meter long pipe from Banian Tree area to PAFL
plants

Storage
Raw water storage tank of 3000+1100 m3 capacity

Pumping
03 motor driven pumps of 580 m3/ hr capacity
01 diesel engine driven pump of 280 m3/ hr capacity

COOLING WATER SECTION


PAFL cooling tower is an induced draft type cooling tower with Counter
Flow design
Circulating water flow

15000 m3 / hr.

Hot (Inlet) water temperature

43 oC

Cold (Outlet ) water temperature

33 oC

Wet bulb temperature

30 oC

Drift losses (of circulated capacity)

0.01 %

Evaporation losses

1.66 %

Design wind load

44.4 m / Sec.

Design seismic load

9.0 seismic

Tower site

Ground level

Elevation above sea level

228.5 m

Tower exposure

Open

STEAM GENERATION
Babcocks & Wilcox boiler
Type
Capacity

Water tube
1550o0 Ib/hr
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Steam pressure

775 Psi (g)

water holding capacity

96,400 Ibs

Mitsui boiler
Type

Water Tube

Evaporation at peak

90,000 Kg/hr

Design pressures

60 Kg/cm2 G.

Steam temperature

450 + 5 oC

Pakage boiler
Type

Water Tube

Capacity

30000 Kg/hr

Design pressures

50 Kg/cm2 G.

Steam temperature

395 + 5 oC

POWER GENERATION
Steam Turbines
Out put (Rated)

11.5 MW

Steam press.(Max.)

770 psig (54 atg)

Steam Temp. (Max.)

850 oF (455 oC)

Normal speed

3000 rpm

Lube oil capacity

5 m3

Gas Turbine
Uses natural gas as fuel
Generates 7 MW of power
Plant, water pumping station and housing colony uses approximately
5.5 MW of power
Exhaust of turbine at 420 C is used to generate 70 Ton/Hr of steam

REFERENCES
Pak American Fertilizer Process Manual
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