FOAMING

ISSUE IN AN
STORAGE
TANK (17-2009)
NITRO-PHOSPHATE PLANT
 PREPARED BY
MUHAMMAD ZEESHAN
INTERN

FATIMA FERTILIZER COMPANY LIMITED, SADIQABAD, PAKISTAN

 CONTENTS

Preface (2)
Process description (8)
Acknowledgement (3)
Ammonium nitrate (15)
Fatima Fertilizer Company (4) Uses in Nitro-phosphate plant (15)
Introduction (4)
Seven sins of AN (15)
Company’s overview (4) Foaming (16)

Vision and mission (5) Causes (16)

Production facilities (5) Effects (17)

Fertilizers (5) Rectification of foaming (17)

Introduction (5) Using membranes (17)

Nitro-Phosphate Plant (6) Using mechanical foam breakers (19)

Introduction (6) References (19)

Block flow diagram (7)

Nitro-Phosphate Plant 1
 Preface: -
This report describes the internship program at Fatima fertilizer Company Limited (FFCL),
located at Mukhtargarh, Sadiqabad, Pakistan. There are five production facilities i.e. ammonia,
nitric acid, urea, calcium ammonium nitrate (CAN) and nitro-phosphate (NP) at the plant. The
company is contributing a lion's share in country's fertilizer's demand. Nitrophosphate is a source
of nitrogen (22%) and phosphate (20%) for the plants. Raw materials for the production of
nitrophosphate are nitric acid, rock phosphate and ammonia. Rock phosphate is imported from
Egypt and Morocco while ammonia and nitric acid are produced in the plant. Major chemical
reactions take place in two parallel trains of dissolving reactors and each train comprises of two
reactors in series. After removing inert by seven centrifuges operating in parallel, the dissolving
slurry is fed to two trains of eight crystallizers. Needle-like crystals of calcium nitrate tetra-
hydrate (CNTH) are separated from phosphoric acid by two trains of rotary vacuum drum filters.
Mother liquor from rotary vacuum drum filter is neutralized with ammonia in three neutralizers
operating in series. NP solution from neutralizers is evaporated in two thermosyphon natural
evaporators installed in parallel. Concentrated NP melt is converted into prills and conveyed to
the product handling section for packing. CNTH crystals are transformed into calcium carbonate
(Lime) and ammonium nitrate and are exported to CAN plant. Due to presence of lime in AN,
foaming is produced which results in poor temperature, pressure and capacity control of tanks.
Membranes, antifoaming agents and mechanical foam breakers can be employed to minimize
foaming.

Nitro-Phosphate Plant 2
 Acknowledgement: -
I am very thankful to Allah Almighty above all, The Creator of whole universe, who gave me
the ability to learn. Millions of blessings of Allah Almighty on Hazrat Muhammad (PBUH),
whose life is a permanent source of guidance for the people of every generation. I am in debt of
the kindness of my parents who are a source of constant support for me. I am very grateful to the
Fatima Fertilizer Company Limited for giving me an opportunity to gain a professional and
practical knowledge. I am very obliged Sir Naveed Ahmad (DM) and Sir Muhammad Asif (UM)
of NP operation whose guidance helped me to gain maximum knowledge during my stay at NP
operation. I am very grateful to my mentors Sir Saad Ahmad and Sir Salman Sarwar who guided
me every day to complete my learning at NP plant. I shall try my best to keep working on the
things which I have learned from them. I can never pay back the support and knowledge which I
have gained from sir Usman Ahmad, sir Usman Iftikhar, sir Tahir Mehmood, sir Umar Rehmani,
sir Shams Raza and sir Amir Rafique. I am also thankful to sir Muhammad Faisal and sir Muiz
Shahab for supporting me.

Nitro-Phosphate Plant 3
 Fatima Fertilizer Company limited: -
Introduction: -
Fatima Group contributes significantly to the economic development of Pakistan. It was
established in 1936 with trading of commodities and gradually entered into the manufacturing of
various products. The Group has a success story spread over seven decades, expanding its
horizon from trading to manufacturing. Today, the Group is engaged in trading of commodities,
manufacturing of fertilizers, textiles, sugar, mining and energy.
Fatima Fertilizer Company Limited is a joint venture of Fatima Group and Arif Habeeb Group.
Fatima Fertilizer Company Limited is the first and the only green field project which has
materialized under the 2001 Fertilizer Policy of the Government of Pakistan, aiming to
encourage investors in this field, in view of growing demand of fertilizer in the Country.
Company’s overview: -
The fertilizer complex is a fully integrated production facility, capable of producing two
intermediate products, i.e., Ammonia and Nitric Acid and four final products which are Urea,
Calcium Ammonium Nitrate (CAN), Nitro Phosphate (NP) and Nitrogen Phosphorous Potassium
(NPK) at Sadiqabad, Rahim Yar Khan.
The Complex has a 56MW captive power plant in addition to off-sites and utilities. The
Complex has been allocated 110 MMCFD of gas from the dedicated Mari Gas fields.
Foundation stone was laid on April 26, 2006 by the then Prime Minister of Pakistan. The
construction of the Complex commenced in March 2007 and is housed on 950 acres of land. The
Complex, when completed, is designed to produce:
• 500,000 Metric Tons of Urea per Annum
• 420,000 Metric Tons of Calcium Ammonium Nitrate (CAN) per Annum
• 360,000 Metric Tons of Nitro Phosphate (NP) per Annum
The Complex, during its construction phase engaged over 4,000 engineers and technicians from
Pakistan, China, USA, Japan and Europe.
The Complex provides modern housing for its employees with all necessary facilities. This
includes a school for children of employees and the local community, a medical centre and sports
facilities.
The Company is listed on Pakistan Stock Exchange, through a successful initial public offering
(IPO) in February 2010. 200 million ordinary shares were offered to the public bringing the
issued Share Capital from 1,800 million to 2,000 million shares.

Nitro-Phosphate Plant 4
 Vision and mission
Vision: -

To be a world class manufacturer of fertilizer and ancillary products,

with a focus on safety, quality and positive contribution to national
economic growth and development. We will care for the environment
and the communities we work in while continuing to create
shareholders' value.
Mission: -

 To be the preferred fertilizer company for farmers, business associates and suppliers by
providing quality products and services.
 To provide employees with an exciting, enabling and supportive environment to excel in,
be innovative, entrepreneurial in an ethical and safe working place based on meritocracy
and equal opportunity.
 To be a responsible corporate citizen with a concern for the environment and the
communities we deal with.
Production facilities: -
Fatima Fertilizer Company Limited is the largest fertilizer manufacturing complex that
processes natural minerals and nitrogen into vital products for farmers and industrial customers.
The major products of the plant are: -
 Ammonia
 Nitric acid
 Urea
 Calcium ammonium nitrate (CAN)
 Nitro-phosphate (NP)

Fertilizers
Introduction: -
A fertilizer is any material of natural or synthetic origin (other
than liming materials) that is applied to soils or to plant tissues to
supply one or more plant nutrients essential to the growth of
plants.
The rapid increase in world’s population has alarmingly increase the demand of food. There are
two possible ways to increase the production of food either by increasing the cultivation area or
by increasing the production of food per unit area. Due to immense transformation of cultivation

Nitro-Phosphate Plant 5
 area into domestic and commercial colonies, the chances to increase the cultivation area has
faded in recent time. Therefore, the necessity of increasing the production per unit area has
become crucial. Therefore, the use of fertilizers has become indispensable. Moreover, due to
repeated cultivation of soil, it has become life-and-death to provide nutrients to plants by external
source like fertilizers.

Nitro-phosphate plant
Introduction: -
Nitro Phosphate (NP) plant is based on modern European technology. The Plant has been
designed to use low grade different grades of rock phosphate without compromising on product
quality in order to maximize profitability. The designed production capacity of the Plant is 1,200
MTPD of NP. However, due to rapid increase in the demand of NP, the capacity of the Plant has
accrued to 1450MTPD. NP is a prilled fertilizer in which each prill has evenly distributed
Raw materials: -

The raw materials for the production of NP are: -

 Rock Phosphate
 Nitric acid
 Ammonia
Rock phosphate is imported from East Asian countries such as Morocco, Egypt, Jordan, Syria
etc. by sea ships. However, rock phosphate is currently imported from Morocco and Egypt. Rock
from sea port is transported to the Plant through trains and containers. While nitric acid and
ammonia is produced in the plant. Other chemicals required for the smooth and better operation
of Plant are Urea, anti-foaming agent, lube oils etc.
Product composition: -

1. Nitrogen (N) 22%

 Phosphorus (P2O5) 20%

 P2O5 relative water solubility >60%

 Moisture content <0.5w/w%
 Prill size: 95% between 1-3.5mm
 Temperature 95oC
 Bulk density approx. 1000 kg/m3

Nitro-Phosphate Plant 6
 Block flow diagram: -

Rock Off gas scrubber

Phosphate

Nitric Acid
Dissolving tank Inert separation

Inerts
Antifoam

NH3 crystallizer

Neutralization CN filtration

Evaporator

Prilling

CN startup tank
NH 3 CO 2 AN

AC Reactor

CN Conversion

Pressure Filter

Evaporators LDU

Nitro-Phosphate Plant 7
 Process description
Rock storage: -

Rock imported from Egypt and Morocco is transported to the Plant site by trains and containers.
Rock is stored in specified areas in the form of heaps. In order to tackle the disturbation caused
by rain, a concrete rock bulk storage with an upholding capacity of 10000 metric tons has built.
Rock from heaps is fed to the belt conveyor through a screen to remove foreign materials such as
plastic bags, bricks etc. This belt pours the rock on a Y-type flapper valve which diverts the rock
either to the rock storage or to the Plant site.
Rock conveying: -

Rock from bulk storage and the one diverted by Y-type flapper valve is conveyed by belt
conveyor to the bucket elevator installed at the Plant site. Y-type flapper valve has an adjustment
range from 0 to 100%. In order to operate the belt conveyor under smooth process and to deal
with any emergency situation some securities has attached with the belt conveyor. Some of them
are: -
 Plug chute
 Pull cart
 Miss alignment switch
 Speed sensor
 Take-up weight
 Emergency stop
An independent feed hopper is also installed outside the rock storage to feed rock directly on
the belt conveyor if the rock storage feeding hopper is out of order.
Screening: -

Bucket elevator dumps the rock on a vibrator which evenly distribute rock on the vibrating
screens. The average diameter of the screen opening is 1.5mm. Rock particles coarser than
1.5mm are separated and stored in the coarse concrete bin having a storage capacity of 85 metric
tons. While particles finer than 1.5mm are stored in fine concrete bin with a storage capacity of
190 metric tons.
Grinding: -

Rock stored in coarse concrete bin is conveyed by a screw conveyor to hammer mill for
grinding. Two hammer mills in parallel are installed to collaborate continuous running of the
Plant without any disturbation. Both hammer mill consist 8 rods connected to the rotor via discs.
Numbers of hammers per rod is 9. One side of the hammer is fixed with the rod while other side
is free to rotate. Grinding of the rock is caused by the force imparted by the hammer. Four sides
of the hammer are used for the grinding. Grinding efficiency of the mill is 30-40%.

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 Dosing: -

Rock from the fine concrete bin is fed to the feed hopper whose capacity is 12 metric tons per
hour. Rock flow to each hopper is controlled by the manual adjustment of a Y-type diverter
installed at the outlet chute of the bucket elevator. Each hopper consists of a Loss-In-Weight
feeding hopper (LIWH). LIWH consists of a butterfly valve, storage bin, load cells, agitator, bag
filters, screw conveyor and controller. The storage capacity of bin is 1000kg. Butterfly valve,
load cells and screw conveyor are connected to the controller. Controller is continuously
measuring the weight lost per hour from the hopper and compare it with the set value given to it.
Depending upon the error, the controller generates the signal and send it to the VFD motor which
then changes the speed of motor rotating the screw conveyor accordingly. Depending upon the
rock stored inside the hopper, controller operates the butterfly valve to meet the set point of
1000kg.
Rock phosphate dissolution
Chemistry: -

NP fertilizer is a compound fertilizer. It is produced by nitric acid route i.e. rock phosphate is
dissolved in nitric acid to produce phosphorus acid. Calcium nitrate is produced as by-product.
Rock phosphate mainly consists of 3Ca3(PO4)2.CaX2. where X is one of the following elements
and/or groups: F, Cl, OH, 1/2 CO 3. Rock phosphate is dissolved in nitric acid to convert its
available water insoluble phosphorus (P2O5) content into water and citrate soluble phosphorus.
Only water and citrate soluble phosphorus content is available to plants for their use. Rock
dissolution into nitric acid results in phosphoric acid and calcium nitrate as major products and
calcium sulphate, metals, nitrates, calcium fluorosilicate, hydrogen fluoride and carbon dioxide
as minor products. The residue is acid insoluble or inerts which are around 2~4% (wt) of the rock
phosphate.
Chemical reactions involved in rock phosphate dissolution with nitric acid are
CaCO3 + 2 HNO3 Ca(NO3) + H2O + CO2
CaF2 + 2HNO3 Ca(NO3) + 2HF

Ca(NO3) + SiO2 + 6HF CaSiF6 + 2HNO3+ 2H2O

Ca3(PO4) + 6HNO3 3Ca (NO3) + 2H3PO4

Important side reactions are

Fe2O3 + 6HNO3 2Fe(NO3) + 3H2O

AI2O3+ 6HNO3 2Al(NO3) + 3H2O

Process: -

Two trains of continuous stirred tank reactors (CSTR) are used for the dissolving of the rock in
nitric acid. Each train operating in parallel consists of two reactors connected in series to achieve
adequate residence time for rock dissolution in nitric acid which is around 85 minutes. Each

Nitro-Phosphate Plant 9
 reactor is equipped with anchor type agitator which is used to mix and dissolve rock phosphate in
nitric acid. Agitators have VFD motors to change their speed as per requirement. Its maximum
speed is 34 revolutions per minute. Each reactor consists of four baffles to enhance agitation.
Rock phosphate is fed into the first reactor of each train under ratio control with battery limit
(fresh) nitric acid. Nitric acid ratio against master flow rock phosphate is controlled to maintain
desired free acid ratio (0.4 to 0.6) in final digesting slurry. Part of total nitric acid required to
dissolve rock phosphate in dissolving reactors comes from CN filtration section. Nitric acid used
for CN cake repulping and CN cake washing in CN filtration section is recycled to dissolving
reactors, called as "wash acid". Wash acid is fed into dissolving reactors under ratio control with
rock flow. In cascade control rock phosphate being master flow, controls ratio of both fresh nitric
acid and wash acid to dissolving reactors. Digesting slurry from first dissolution reactor
overflows to second dissolution reactor under gravity. Exothermic dissolution reactions tend to
raise the operating temperature of dissolution reactors up to 80°C. To reduce the NOx produced
in the reactors, urea is fed to the first reactors of each train. Due to CO 2 foaming is produced in
the first reactor, therefore to overcome this issue antifoaming agent is used.
Inerts separation: -
Digesting slurry from reactors is fed to the decanter tank where two strainers one for each
reactor is installed to remove foreign material, scaling pump, metal pieces etc. Carrying over of
these heavy particles to decanter centrifuges may result in their wear &tear, unbalance and
vibration. To remove acid insoluble seven screw decanter centrifuges are installed. All operate in
parallel to each other. Each centrifuge capacity is 12.5 m3 per hour (max) at operating speed
1000 G. About 50%wt of total inerts in digesting slurry is removed by these centrifuges. The
digesting slurry from decanter centrifuges after inert separation is collected in buffer tank.
Decanter centrifuges discard sludge to sludge screw conveyor which is then carried to the waste
place.
CNTH crystallization: -
To produce NP fertilizer with maximum water & citrate soluble phosphorous it is necessary to
remove as much as possible calcium present in phosphate solution. NP Product water or citrate
solubility is measured in terms of molar ratio CaO/P 2O5. This molar ratio depends on the quality
of rock phosphate and concentration of nitric acid used. In rock phosphate (Egyptian) molar
ratio, CaO/P2O5 is about 4.29, whereas in NP product for its water solubility up to 80% this ratio
should be around 0.79. To remove maximum calcium from digesting slurry two trains of batch
type crystallizers are installed. Calcium is crystallized out as Ca(NO 3).4H2O (Calcium Nitrate
Tetra Hydrate) by chilling the phosphate solution in crystallizers. Each crystallizer is equipped
with three bundles of cooling coils and agitator to increase the rate of heat and mass transfer.
Phosphate solution at 45°C is fed to each crystallizer to dissolve deposited scaling on cooling
coils. Both trains operate in parallel; each train contains eight crystallizers in series to achieve
residence time of eight hours for each crystallizer. Total cycle time is nine hours. Each
crystallizer fills in half hour and also drains in half hour. Each crystallizer in both trains receives
coolant from its preceding crystallizers for seven hours and fresh chilled coolant from
refrigeration systems for one hour to cool down phosphate solution up to its final temperature

Nitro-Phosphate Plant 10
 -5°C. 25%wt ammonia/water solution is used as coolant to cool down phosphate solution in
crystallizers. The coolant is chilled in two different refrigeration systems from 22°C to -15°C. In
one system, coolant is chilled by liquid ammonia evaporation in kettle type ammonia vaporizers
whereas in second system coolant is chilled in ammonia vapor compression unit. Chilled coolant
from both refrigeration systems is combined into one common header for its distribution to
crystallizers, wash acid cooler, and dehumidifier (of product bulk flow cooler). The coolant, after
passing through crystallizers, wash acid cooler, and dehumidifier is recycled back to its storage
tank.
CNTH filtration: -
Two parallel trains of rotary vacuum drum filters are installed to separate CNTH crystals from
crystal suspension slurry. Each train consists of two drum filters in series, first drum filter called
as primary drum filter whereas second drum filter as secondary drum filter. Each drum filter
main drive has variable speed control. Drum speed may be varied from local panel as per
requirement. Normally CN crystals are filtered in two stages. In first stage crystal suspension
slurry is separated into filtrate mainly phosphoric acid (mother liquor) and calcium nitrate cake.
Filtrate is collected in 1st mother liquor tank and then pumped to 2nd mother liquor tank through
filtrate coolers to cool down nitric acid. CN cake is repulped with chilled nitric acid (-10°C) in
primary drum filter crystal mixing screw conveyor and repulper tanks fitted with propeller type
agitators. From repulper tank CN cake flows to secondary drum filter under gravity. In secondary
drum filter the repulped CNTH cake is washed by spraying chilled nitric acid (-10°C) to recover
entrained phosphoric acid. Wash nitric acid separated in second stage filtration is recycled to
dissolution reactors and CN cake containing around 0.35% phosphoric acid & about 7.5% nitric
acid as entrainment is collected in CN melt tank. CN melt tank is equipped with low pressure
steam (14°C & 4 kg/cm2a) heating coil and ammonia gas injection distribution ring. In CN melt
tank CN cake is heated up to 75°C to release or evolve four molecules of water attached as water
of crystallization. Part of CN melt is recycled through pumps to secondary drum filter chutes as
flushing carrying over fluid for CN cake. Ammonia gas is injected in CN melt tank to neutralize
50%wt entrained nitric acid in the CN cake. Agitator is installed in CN melt tank for effective
mixing and heat transfer. CN melt solution with a concentration of 62%wt is pumped to CN
conditioning section.
Neutralization
Chemistry: -

Neutralization is an exothermic reaction which tends to increase the temperature of neutralized

solution. Solution temperature at the outlet of 3rd stage neutralizer is 118°C. Each neutralizer
operates at slight sub atmospheric pressure (0.1 kg/cm2g) induced by gas scrubbing system.
Water base antifoam solution is used to control foaming inside neutralizers. Gases produced
during neutralization reaction are treated in basic gas scrubbing system.

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 Main neutralization reactions are
CaSiFs + 2Ca(NO3)2 + 2H2O + 4NH3 3CaF2 + SiO2 + NH4NO3

Al(NO3)3 + H3PO4 + 3NH3 AlPO4 + 3NH4NO3

Fe(NO3)3 + H3PO4 + 3NH3 FePO4 + 3NH4NO3

Ca(NO3)3 + H3PO4 + 3NH3 Ca(H2PO4)2 + 2NH4NO3

Ca(NO3)2 + H3PO4 + 2NH3 CaHPO4 + NH4NO3

H3PO4 + NH3 NH4H2PO4

HNO3+ NH3 NH4NO3
Process: -

Mother liquor which mainly contains phosphoric acid, calcium nitrate, nitric acid and water is
neutralized in three stage neutralization process. Three stages neutralization is adopted for
gradual neutralization. Gradual and slow neutralization is favorable for water and citrate soluble
compounds. A measured quantity of 62.5% ammonium nitrate is added to mother liquor before
sending it to neutralizers to achieve the required nitrogen content in NP.
NP solution evaporation: -
Two thermosyphon natural recirculation evaporators are installed which operate in parallel to
each other. These evaporators concentrate neutralized NP solution (mother liquor) from 75%wt
to 99.5%wt.
Evaporation: -

NP melt evaporators operate under sub atmospheric pressure or vacuum (0.3 kg/cm2 abs) and
temperature 175°C. Evaporators operating pressure and temperature control is very important to
achieve natural circulation and required end product concentration. High operating pressure or
poor vacuum results in high moisture content of product and on the other hand too low pressure
or high vacuum causes to overload the evaporators. Vacuum pumps are used to create the
required vacuum for evaporators. Exhaust gases from vacuum pumps are directed to atmosphere.
Evaporator's pressure is controlled by self-controlling pressure control valve open to atmosphere
installed at evaporators' outlet gases common header to vacuum pumps. Desuperheated steam
(16 kg/cm2& 201°C) is supplied to NP melt evaporators for evaporation. Evaporator temperature
is controlled by regulating steam supply flow and pressure. Low pH increases solution viscosity
and also lowers its crystallization point. High pH decreases solution viscosity, but at the same
time increases the crystallization point. Evaporator feed solution pH is controlled around 4.5 to
5.1 and at the outlet of NP melt evaporators' pH declines to, 3.5 to 4.0. At low pH (lower than
3.0) the melt becomes highly viscous.AN solution (62.5%wt) is added to decrease melt viscosity.
Ammonia gas and antifoam solution injection provision is incorporated for troubleshooting
purposes. Medium pressure steam coils are installed inside NP melt tank to maintain temperature
of NP melt. Steam supply to steam coils is regulated by a control valve according to the

Nitro-Phosphate Plant 12
 prevailing melt temperature inside NP melt tank. Agitator is also installed in the tank.
Concentrated NP melt, from evaporators flows to NP melt tank through seal pot under gravity.
NP melt is pumped from NP melt tank to another melt tank through steam jacketed line at the top
of prilling tower for its prilling.
Evaporator Fouling: -

The performance of evaporator is highly dependent on degree of internal fouling of heat

exchangers tubes. The capacity of evaporator decline as this degree of fouling increases and
finally falls below the design capacity. At this stage evaporator is cleaned to remove the
deposition the inner walls of the heat exchangers. The fouling of evaporator is highly dependent
on operating conditions and increases rapidly when evaporator is operated on low load or is
taken out on hold for long intervals. Particularly during first startup period, risk of rapid fouling
prevails.
Evaporator Cleaning: -

Evaporator is cleaned with 30%wt (approx.) nitric acid solution for one hour at 101°C. To
ensure effective liquid circulation through the whole evaporator, it is filled up with cleaning
solution up to its overflow level.
NP prilling: -
NP prilling section consists of a NP melt tank, induced draft fans, prilling bucket, prilling tower
and scrapper. The draft can be created by any of the following three types: -
 Natural draft
 Induced draft
 Forced draft
Induced draft tower is installed at NP Plant. Six induced draft fans are installed at the top of the
tower. The fan is placed over grating and is driven by a motor. Hot air coming from the bottom
also carry dust with it which results in the choking of grating. In this situation the efficiency of
the prilling decreases. To overcome this issue, grating is cleaned continuously. NP melt from the
melt tank enters into a prilling bucket connected with inner shaft being rotated by a belt
connected with the smaller pulley of the motor. Two metal rods (also known as “scrapper”) are
placed inside the bucket connected with the outer shaft being rotated by a belt connected with the
larger pulley of the motor. Due to differential in the speed of scraper and prilling bucket, the
scraper tends to scrap out the NP melt from the bucket and impart a force as a result of which NP
prills are spread towards the whole diameter of tower. While coming downwards NP prill
exchange mass as well as heat transfer with the air.
Product handling: -
NP prills after cooling from 95°C to 45°C are sent to the product handling section where they
are packed in bags and are supplied to the whole country.

Nitro-Phosphate Plant 13
 CN conditioning: -
CN melt from CN melt tank is fed to the CN start-up or buffer tank where 62.5% ammonium
nitrate and process condensate to makeup the water content for its easy conveying. An agitator is
installed inside the tank for proper mixing. CN melt is neutralized with ammonia in two pre
neutralizer tanks connected in series. The neutralization is an exothermic reaction which results
in the increase of temperature. That’s why to control the temperature within desire limits coils
with cooling water flow is placed in the 1st pre neutralizer. Neutralized CN from pre-neutralizers
flows under gravity to the CAN slurry tanks.
CN Conversion: -
CN is converted to ammonium nitrate and lime in CAN Slurry tanks. This conversion takes
place in two steps. In first step, ammonium carbonate is produced by the reaction of ammonia
and carbon dioxide in AC reactor. While in second step, ammonium carbonate is mixed with the
neutralized CN in CAN Slurry tanks to synthesis lime and ammonium carbonate.
Ammonium carbonate production: -
Ammonium carbonate is produced by the reaction of ammonia and carbon dioxide in the presence of
ammonium nitrate in AC reactor. The reactor consists of two packing beds to enhance the contact time
between ammonia and carbon dioxide. Ammonium nitrate is poured from the top of the 1 st packing while
both the reactants are introduced from the bottom. The product is a mixture of ammonium carbonate and
ammonium nitrate also known as “CAN Slurry”. This CAN Slurry is cooled with cooling water in a Plate
and frame heat exchanger. A part of this cooled CAN Slurry is recycled back to the AC reactor while a
major portion is launched to the CAN Slurry tanks.
Calcium Carbonate precipitation: -

Two CAN Slurry tanks for the conversion of ammonium carbonate and CN melt into lime and
ammonium nitrate are placed in series for giving a required residence time. pH of the solution is
maintained at 7.6 to 7.8 by controlling the ratio of AC and CN and controlling the injection of
ammonia. Average grain size of lime is 100microns.
Ammonium nitrate filtration
Lime and ammonium nitrate slurry is injected to the pressure filter for the filtration.
Pressure filter: -

Pressure filter consists of plate packs, flexible diaphragm for squeezing or pressing filter cake,
quick action cylinder, propylene grating, filter cloth, cloth driving motors, feed slurry hoses and
pressing air hoses. Plates are packed over one another in such a way that they form a
compartment. Filter cloth is placed over propylene grating (total 30 pieces of grating per plate).
Lime and ammonium nitrate slurry is fed to the upper part of the cloth through a common feed
header. Ammonium nitrate permeates through the cloth while lime is retained over the cloth. The
cake is then washed with the vapor condensate to filter out the entrained ammonium nitrate in
filter cake. This lime cake retained over the cloth is then pressed with the diaphragm by a stream
of pressing air (10 to 12 kg/cm2). After pressing cake is again washed with the fresh process

Nitro-Phosphate Plant 14
 condensate and ammonium nitrate separated by is stored in weak ammonium nitrate solution
tank and is pumped to the filter cake for the washing of lime in first part.

Ammonium nitrate
Ammonium nitrate is a salt of ammonia and nitric acid. Its molecular
formula is NH4NO3. It contains 34.5% nitrogen which is available to
the plant. That is why ammonium nitrate is used as a fertilizer. It is an
odorless crystalline sloid. Its crystals are usually of trigonal structure.
Uses: -
Ammonium nitrate is used: -
 As a solvent
 In manufacturing fertilizer
 To balance nitrogen content in Nitro Phosphate
 In manufacturing explosives
Seven sins of ammonium nitrate
1. High temperature: -

Decomposition of ammonium nitrate is an exponentially function of temperature. At elevated

temperatures density of ammonium nitrate also decreases.
2. Low pH: -
Acidic conditions favor the decomposition of ammonium nitrate at a given temperature.
3. Low density: -

Ease in decomposition of ammonium nitrate is an inverse function of its density. As the density
of ammonium nitrate decreases, decomposition of ammonium nitrate becomes easy for a given
concentration at a given temperature.
4. Contamination: -

Contamination in ammonium nitrate decreases the temperature required for decomposition at a

given condition. Contamination is of two types: -
 Catalytic contamination
 Organic contamination
5. Confinement: -

If decomposition takes underway confinement, temperature increase takes place rapidly and the
explosion take place.

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 6. Time: -

Self-acidic decomposition of ammonium nitrate takes place with the passage of time. Longer we
store it, larger will be the chances of explosion.
NH4NO3 NH3 + HNO3
7. Concentration: -

Ammonium nitrate solution sensitivity to explosion decreases when concentration of it is

lowered. Water retards the decomposition reaction when present in excess and provides a source
of heat removal.

Foaming
In physical chemistry, foaming is defined as a colloidal system (i.e. suspension of particles in a
homogeneous medium) in which particles are gas bubbles and the medium is a liquid.
Causes: -
The foaming in ammonium nitrate is due to the following
reasons: -
 Lime slippage into AN
 High surface tension of AN
 Reaction of lime with nitric acid Foaming Phenomena
Lime slippage: -

Lime slippage in AN may be due to cloth damage (i.e. holes in cloth due to a sudden force of
pull attracted on cloth during cake discharge cycle by the
cloth driving motors or due to the friction between cloth and
propylene grating). There is large variation in grain size of
lime due to which fine particles of lime are able to pass
through the cloth into AN collector. There are also some
design limitations of Pressure Filter (i.e. in first cycle of
filtration upper part of cloth is used as a filtration medium.
AN permeates through the cloth while lime is retained over
the upper part of the cloth. As 100% removal of lime cake
from the cloth is not possible, a part of it is retained over the
cloth. When in 2nd cycle of filtration lower part of cloth is
used for filtration, lime retained over the upper part during
1st cycle is able to flow into AN collector).

Pressure Filter

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 Reaction of lime with nitric acid: -

In order to maintain pH of AN and to convert lime into CN, nitric acid is added to the AN
storage tank. As a result of reaction, water, CN and carbon dioxide is produced.
HNO3 + CaCO3 H2O + CO2 + CaNO3
Carbon dioxide being a gas tends to rise up the tank but high surface tension of AN makes it
difficult for the carbon dioxide to evolve from the system. This force of attraction of AN result in
the production of forming.
High surface tension: -

AN possesses very high surface tension as a result of which AN molecules exert a strong force
of attraction on CO2 and forming is produced.

AN Molecules

Effects of foaming: -
Foaming can cause trouble in the process by the following mentioned ways: -
 Decrease in utilizable storage volume of tank for AN
 Overflow issue of AN
 Poor temperature control as foaming act as a perfect insulator

Rectification of foaming
The major cause of foaming is the presence of lime in AN solution. This issue can be resolved
by limiting the flow of lime into AN. Following measures can be taken to terminate foaming: -

solid particles from the liquids. “Membrane made of synthetic polymer (i.e. polycarbonate) is used”. Size of pores is uniform. S

Nitro-Phosphate Plant 17
 opening size of pore are retained over the
membrane and are removed while liquid
permeate through the membrane.
Design of membrane: -
A spiral-wound module design can be
used in the present case. Some features of
this module are as follows: -
 Flat sheets of membranes are
fabricated into spiral-wound modules.
 It consists of two membrane sheets
separated by spacers for the flow of the
feed and permeate, is wound around a
central, perforated collection tube to
form a module that is inserted into a
pressure vessel.
 Feed flows axially in the channels
created between the membranes by
porous spacers.
 Permeate (AN) passes through the
membrane, traveling inward in a spiral
path to the central collection tube.
 A typical spiral-wound module is 0.1–
0.3 m in diameter and 3 m long.
 Six such modules may be installed in
series in a single tube.
 Two parallel tubes each having six modules in series should be used to keep the process
continued during the cleaning of membranes to dechoke membranes pores.

Pictorial representation of process

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 Packing density (m2/m3) 200 to 800
Membrane fouling Moderate
Ease of cleaning Fair
Relative Cost Low

Features of spiral wound module

Membrane cleaning: -
Membranes pores can choke due to high flowrate of AN solution. As a result of which
performance of membrane goes down the desired value. In order to overcome this issue, cleaning
(backwashing) of membrane is required. This can simply be done by flowing distilled water
through the membrane. time. Symptoms of membrane cleaning would include one or all of the
following conditions:
 AN flow has decreased by 10-15% from start-up (reference) conditions.
 Lime rejection has decreased significantly over time.
 Delta P, or pressure drop over a stage or the system, has increased by 10-15%.

Mechanical deformers: -
Mechanical deformers which are usually rotors can also be used
to lower the foaming produced in AN storage tank. These rotors
are connected with the shaft of agitators. Due to their higher speed
of rotation they lower the surface tension and make an easier way
for carbon dioxide to evolve from the tank.

References: -
 Process description of Nitro-Phosphate Plant (accessed on 25-28 of July, 2019).
 http://fatima-group.com/ffcl/ (accessed on 25-28 of July, 2019).
 https://www.chemicalprocessing.com/assets/Media/MediaManager/Larox_PF_C_series.pdf
(accessed on 25-28 of July, 2019)

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