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Procedia Engineering 46 (2012) 172 – 177

1st International Symposium on Innovation and Technology in the Phosphate Industry

[SYMPHOS 2011]

The Operating experience of Nitrophosphate Plant

Iltifat Hussain*
Pak Arab Fertilizers Limited, Multan, Pakistan

Abstract

Pak Arab fertilizers private Limited has been operating its nitrophosphate plant based on the ODDA process since 1978. The technology
has been supplied by Stamicarbon Holland and engineering by Udhe Germany. Nitrophosphate route provides an interesting avenue for
producing an agronomically balanced complex fertilizer.
Numbers of improvements are made in original design since after installation to meet the performance guarantees. Rock Phosphate is the
main raw material for NP production. Plant was designed on Jordan rock and later Morocco, Egyptian and Algerian rock phosphates and
their blends are tested. The other bottle neck was CN separation centrifuges. Failure of this equipment kept the plant operation on low rate
hence these were replaced with Filter drums a slow moving unit. This helped to improved production quality and service period. To
improve environment, NOx abatement Urea solution is added to Dissolving reactor. Two new reactors added to system to control reaction
rate and anti foaming consumption was reduced drastically and it also helps in increasing production capacity of plant.
The main thrust of this paper is to present the operating experience of nitrophosphate plant, improvements made at this complex to
improve reliability of complex.

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Nomenclature
MTPD metric tonne per day
NP Nitrophosphate
PFL Pak Arab Fertilizers
CAN Calcium Ammonium nitrate
P 2O 5 Phosphorous pentoxide
0
C degree centigrade

* Corresponding author. Tel.: +92-300-3302402; fax: +92-333-2102402.

E-mail address: [email protected]

1877-7058 © 2012 The Authors. Published by Elsevier Ltd. Selection and/or peer-review under responsibility of the Scientific Committee of SYMPHOS 2011
Open access under CC BY-NC-ND license. doi:10.1016/j.proeng.2012.09.462
 Iltifat Hussain / Procedia Engineering 46 (2012) 172 – 177 173

1. Introduction

Pakarab Fertilizers is one of the largest fertilizer complex in Pakistan and is the only fertilizer manufacturing facility
producing compound fertilizer in the country. The company was established as a result of memorandum of understanding
concluded between West Pakistan Industrial Development Corporation of Pakistan and Abu Dhabi National Oil Company
on March 7, 1973 and a participation Agreement emerged on November 01, 1973 to establish a joint venture for the
expansion and modernization of the company predecessor - Natural Gas Fertilizer Factory, Multan. Thus the Company was
incorporated on November 12, 1973 with total authorized capital of Rs. 1000 Million.
Later West Pakistan Industrial Development Corporation of Pakistan share in the Company was assumed by National
Fertilizer Corporation of Pakistan as a result of reformation of public sector corporations and Abu Dhabi National Oil
Company share in the Company had been assumed by International Petroleum Investment Company, Abu Dhabi. On July
14, 2005, Pak Arab Fertilizers was privatized at a cost of 14.125 billion Pakistani Rupees by Reliance Export under the
umbrella of Fatima group and Arif Habib group.
Pak Arab Fertilizers complex operates with 960 MTPD ammonia, 1380 MTPD Nitric Acid, 280 MTPD Urea, 1500
MTPD Calcium ammonium nitrate, 1015 MTPD Nitrophosphate and 192 MTPD of Carbon di oxide.

2. Nitrophosphate Complex

The Nitrophosphate complex of PFL operates on basic ODDA process licensed by Stamicarbon, Holland and detailed
engineering by Udhe, Germany. NP plant was designed to get fertilizers product specification of Nitrogen 22.6 % and P2O5
22.6 %. At the time of start up product specification was not achieved so different modifications were made. Later on, more
modifications were done to achieve the desired product quality. In 1999, product specifications were revised to Nitrogen
22.5 ± 0.5 % and P2O5 20.0 ± 0.5 % due to

The Main Steps of NP process is as under

• Rock Phosphate Storage and Handling

• Dissolution of rock phosphate with nitric acid
• Crystallization of Dissolving solution and separation of calcium nitrate crystals from nitrophosphate acid
• Ammoniation (i.e. neutralization of nitrophosphate acid)
• Prilling of the slurry and conditioning of the product
Calcium Nitrate is produced as a by product in the process and sent to CAN plant where it is used for the production of
calcium ammonium nitrate fertilizer. Ammonium nitrate solution produced from CAN plant is used at NP plant for N2:P2O5
ratio correction.
Rock phosphate is weighed and added into the first dissolving reactor, fitted with an agitator, where it is mixed with the
proper amount of Nitric acid plus wash acid. The exothermic dissolution reactions raise the temperature of the mixture to
about 600C. In the second stage dissolving reactor (also fitted with an agitator), the reaction is completed and the dissolved
liquid flows over to the buffer tank via inerts removal settling tanks. Urea solution is also added in first dissolving reactor to
control NOx in off –gases.
In order to avoid foaming during the reactions, required quantities of antifoaming agent is sent to the first dissolving
reactor.
The phosphate solution is cooled to about 400C by means of cooling water. Solution is then pumped to over head tank,
and then solution is fed to the crystallization lines A, B, C, D, E and F. In the crystallizers calcium nitrate is crystallized out
as calcium nitrate tetra hydrate crystals and separated in Rotary drum vacuum filter. The mother liquor from filter drum is
pumped to the neutralizers. To obtain the proper NP ratio in the end product, a certain amount of ammonium nitrate
solution from the calcium nitrate conversion plant is recycled to this tank. This solution must be neutralized before
evaporation. The filtrate is pumped to the neutralizer. The neutralizer is also fed with a proper amount of ammonia in order
to effect adequate neutralization. Being exothermic, the neutralization reaction will cause the temperature to rise up to
1180C. The amount of ammonia is controlled by an automatic pH control which should be 3.5 ~ 4.5. Gases leaving the
neutralizer are washed in scrubber. After neutralization, the NP solution must be concentrated. Evaporation is effectuated in
circulation-type evaporators. The NP solution flows over from the neutralizer to evaporators; gases leaving the separators
are condensed in mixing condensers. In this evaporation stage, the solution is concentrated from about 75 % to 99.5 %. The
high concentrated solution flows over into a melt tank. From the melt tank the NP solution is pumped to the top of the
prilling tower. The concentrated NP melt is fed to the NP tank located on the prilling tower. From this tank, the NP solution
is fed to prilling bucket distributing the product in the form of droplets over the cross section of the prilling tower, in which
174 Iltifat Hussain / Procedia Engineering 46 (2012) 172 – 177

a rising air-flow is maintained by fans installed in the top part of the tower. During their fall the droplets solidify to prills.
The prills are removed from the bottom of the tower by means of a scraper at about 950C. Prills are conveyed by means of a
belt conveyor to a cooling unit, cooling is done by air induced by a blower. Cooled Product is sent to Handling plant for
Bagging and storage. The schematic diagram of NP process highlighting all the sections of ODDA process is shown in
figure 1.

Rock Phosphate Nitric Acid 60 % Antifoam Urea

P2O5 > 30 – 33 %

Rock Rock Rock Dissolving Innerts Buffer

Phosphate Phosphate Phosphate Reactors Removal Tank
Bulk Store Screening Bin

Grinders Ammonium Nitrate 60 %

Ammonia

Evaporators Mother Primary Crystallizers

Neutralizers
Liquour Tank Filter Drum Line A/B/C/D/F

To CAN Plant Secondary

CN Melt
Tank Filter Drum

NP Head
Prilling
Tank
Tower Fluidized Product
Bed Cooler Store

Fig. 1. Block diagram Nitrophosphate Plant

In order to keep plant in smooth operation a lot of in house modifications were carried out for debottlenecking of
problems some of which are discussed in this paper

2.1 Trial of Rock phosphates of different Origins

NP plant was designed on Jordan Rock Phosphate but then due to high cost and availability issues Morocco Rock
Phosphate started at plant in the year 1984. Later on, Egyptian and Algerian Rocks trial run also conducted at plant. The role
of main constituents of rock phosphate is discussed below

a) P2O5-Phosphorous Pentoxide

The most important constituent of rock phosphate is P2O5 as this is the element required for fertilizer production. The
ODDA section of our nitrophosphate plant is designed for a minimum P2O5 content of 33.4%. Hence any rock having P2O5
content lower than 33.4% is not suitable as it will increase the hydraulic load of the plant which has to be removed before
granulation. Higher P2O5 rocks are beneficial as the impurities level in these rocks will be lower.

b) Silica

The silica content of the rock is in two forms. The active silica (clay) is beneficial as it reacts with fluorides in the rock
and produces flousilicates which due to the low solubility, readily precipitates and finally reduces corrosion. The other silica
(quartz) is inert which will not affect the process chemistry, but causes erosion in the various equipments of digester section.
Hence the rock should have sufficient quantity of active silica to fix fluorides while the inert silica should be minimum. For
this, it is recommended to have active silica/fluoride ratio of 0.5 and the total silica should not exceed 3%.
 Iltifat Hussain / Procedia Engineering 46 (2012) 172 – 177 175

c) MgO (Magnesium oxide)

Acid soluble magnesium seems to be the main rock impurity that causes an increase in viscosity during ammoniation of
NP melt. It should be as minimal as possible. MgO content above 0.3% in rock is detrimental for the process.

d) Al2O3/Fe2O3 (aluminium/iron oxide)

A certain amount of these oxides are required for achieving good calcium nitrate crystal growth and favorable lime size
for filtration. However, higher amount of R2O3 causes very coarse lime which is not suitable for CAN plant and it also
increases viscosity of the nitrophosphate melt in ANP plant causing load reduction and small reduction of water solubility of
P2O5. R2O3 content of 0.4% ~ 0.8% is most favorable for ideal crystal growth of calcium nitrate as well as favorable lime
size distribution.

2.1.1 Methodology for rock phosphate processing and evaluation

For any rock phosphate, about 10 - 12 standard parameters are analyzed and based on the level of different impurities; a
broad prediction of its behavior is made. The analysis is compared with standard specification sheet (Table 1) and only
those rocks whose analysis is conforming to exactly as per our requirement are cleared for further trial.

Table 1. Phosphate Rock Analysis

Analysis PFL spec Morocco Egyptian Algerian

P2O5 34.35 32.03 30.59 28.95
Silica 1.97 1.1 6.12 1.6
MgO 0.2 0.4 0.4 0.8
Al2O3 0.25 0.3 1.31 0.3
Fe2O3 0.28 0.15 0.7 0.25

The actual trials in the plant are carried out in a phase-wise manner by blending of 10% of trial rock with the main rock.
The plant parameters are monitored and adjusted and the blend ratio is increased in steps of 10% after minimum observation
at least for one month. The changed parameters are recorded for future use. This practice is also followed internationally by
phosphatic fertilizer producers, while changing over the source of rock. Many a times blending of rocks helps in
maintaining other parameters and the blended rock is more suitable than the two original rocks, if used independently.

2.1.1 Morocco Rock Phosphate

• High P2O5 due to which low rock consumption / ton of NP production

• Low silica contents increases plant on- stream hours and less erosion
• Ideal particle size distribution
• No adverse affect observed while testing this rock phosphate

2.1.2 Egyptian Rock Phosphate

• Load reduction when 100 % Egyptian rock used due to its high bulk density
• High silica and fine contents reduce life of conveyor belts
• More time for inerts cleaning due to high silica contents

2.1.3 Algerian Rock Phosphate

• Due to low Al2O3/Fe2O3 ratio fine crystals of calcium nitrate crystals formation which causes blockage and load
reduction of rotary drum vacuum filters
• Nutrients in product could not be achieved due to low P2O5
• High MgO causes problems in ammoniation of NP solution and problems in evaporation system
176 Iltifat Hussain / Procedia Engineering 46 (2012) 172 – 177

2.2 Improvements in Inert Separation Section

In the design, three inert decanter centrifuges were installed; they had very high mechanical failure rate and operating
cost. Main problem was with Decanter screw which frequently got damage. Also, no standby decanter was available. So, in
case of problem in any centrifuge plant load had to be reduced and plant down time increases. Production of plant greatly
suffers. Lot of consumption of hydraulic oil due to very frequent leakages also increases the operating cost. In the year 1982
these decanters were replaced with the battery of settling tanks. Three settling tanks are installed which can be operated in
parallel or series as per requirement. That has reduced a lot of maintenance and operational

2.3 Improvement in CN separation

In the design, CN centrifuges were used for separation of CN crystals from mother liquor solution. But, again they have
very high failure rate due to which they have high maintenance and operational cost.
The common maintenance problems were damaging of the separation screens, damaging of solution pusher ring and oil
leakages due to vibrations. These screens were replaced with slow moving rotary filter drums. Double filtration technique
was adopted successfully in the year 1996 with Komline Sanderson filter drum of USA. Now, three filter drums with one
standby installed that has not only reduced greatly the maintenance cost but also has controlled slippage of P2O5 with CN.
P2O5 in CN is controlled < 0.5 %.

2.4 Installation of new refrigeration loop

Two additional compressors were installed in the year 1982 for cooling of Brine solution with two additional trains of
crystallizers. Which has not only improved quality of product but also reduce dependency on CAN plant for Ammonia
consumption. Molar ratio CaO/P2O5 decreases resulting increase in water solubility of NP product. Addition of two
crystallizer trains has increased plant capacity

2.5 Installation of separate discharge line for NP melt Pumps

In original plant design only one discharge line was available to pump NP melt from ground floor to top of prilling
tower. So in case of any blockage of line plant has to be shut down. This problem was removed by installing additional
separate discharge lines for NP melt pumps to prilling tower in the year 1996 that has increased plant reliability and smooth
operation.

2.6 Installation of new exhaust blower

In the design, one exhaust blower was installed, which was observed insufficient for exhaust gases discharge. This
problem was rectified by installing two additional blowers which have made working area comfortable by reducing NOx
and other gases in the year 1988.

2.7 Installation of Agitators in Neutralizers

In the design, there were no agitators in Neutralizers so pH of solution was not controlled and high pH causes decrease in
water solubility of product. So for proper mixing of Ammonia with Mother Liquor agitators were installed which enable us
to control pH. Also, two stages Neutralization pilot test run conducted successfully and its detail study for implementation is
in progress.

2.8 Addition of New train of Dissolving reactors

Initially one train with two dissolving reactors were installed. Two trains with two dissolving reactors each installed in
2004 for more residence time and better dissolution of Rock Phosphate in Nitric Acid. That has not only improved reaction
efficiency but also has improved production of plant. It has also reduced drastically antifoam consumption in dissolving
reactor. Overall production of plant increases from 900 MeT/day to 1100 MeT/day.
 Iltifat Hussain / Procedia Engineering 46 (2012) 172 – 177 177

2.9 Introduction of Urea control system to control NOx emissions

Urea solution addition started in the year 2005 in dissolving reactors to control NOx emission in stack. Now, NOx
emission in stack < 10 ppm before urea addition it was 200 ~ 300 ppm.

Conclusions

The Nitrophosphate Complex at PFL is unique in the sense that ammonium nitrophosphate and calcium ammonium
nitrate plants are integrated with each other. The quality of rock processed and all other parameters affects directly the slurry
behavior in the NP plant as well as the quality of byproduct lime from the NP plant which is used as raw material for the
CAN plant. The choice of rock phosphate and adjustment of parameters while processing it have to therefore delicately
balance the requirements of both.
While the operation of the Nitrophosphate Complex is well established over the years, we have been also successful in
blending other rocks in various proportions in a controlled and scientific manner. Efforts to establish plant operation will
continue in the future to achieve the best techno-economic benefits.