Oct 22, 2018 1

FINAL YEAR PROJECT

PRODUCTION OF NITROPHOSPHATE
FERTILIZER

Supervised By:
Dr. Saleem Iqbal
Mr. Fazeel Ahmad

Presented By:

Shaharyar Abbasi UW-15-Ch.E-BSc-014

Khawaja Rehan Ahmed UW-15-Ch.E-BSc-016
Muhammad Mansoor UW-15-Ch.E-BSc-030
Abubaker Sufyan Amjad UW-15-Ch.E-BSc-034
 Final Year Project
Production of Nitro-phosphate Fertilizer
Outline
• Fertilizer • Manufacturing processes
• Nitro-phosphate (NP) • Process selection
• History of NP • Capacity selection
• Physical properties & thermodynamic data
• Chemical reactions
• Industrial applications
• Handling, storage & safety
• Shipping of NP
• World & Pakistan overview
• Market assessment
• Future trends
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Production of Nitro-phosphate Fertilizer
Fertilizer
• Includes two or more elements necessary for plant growth
• Organic or inorganic materials
• Absorbed by the roots and provide essential nutrients
• Elemental nitrogen (N), phosphorous pentoxide (P2O5) and potassium oxide (K2O).

P2O5 x 0.44 = P K2O x 0.83 = K Mg x 1.66 = MgO CaO x 0.71 = Ca

MgO x 0.60 = Mg SO3 x 0.40 = S S x 2.50 = SO3 P x 2.29 = P2O5
• Represented by a series of numbers separated by dashes called grade
• 20-22 NP = 20% N and 22% P2O5 NP
• Animal manure was used in ancient times for higher crop yields due to higher N-15
content.
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Production of Nitro-phosphate Fertilizer
Carbon
Major elements
Air & Water Hydrogen
(Macronutrients)
Oxygen
Nitrogen
Primary Nutrients Phosphorous
Potassium
Calcium
Secondary Nutrients Magnesium
Sulfur
Chlorine
Boron
Copper
Minor Elements
Molybdenum
(Micronutrients)
Zinc
Manganese
Iron
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Production of Nitro-phosphate Fertilizer

Nitro-phosphate
• Complex granulated fertilizer
• Consists of N and P2O5 with little amounts of Ca
• Acidic in nature with pH of 3.5
• Suitable for soils of higher pH
• 22-20, 20-20 and 18-18 grades of NP are mostly used

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Production of Nitro-phosphate Fertilizer
History of NP
• Process developed by Erling Johnson in 1928
• Named as Odda Process because invention was developed in the town of Odda,
Norway
• Norsk Hydro developed it on large scale in 1930
• After few years sulfuric acid was used to manufacture complex fertilizers
• high emissions of H2S and SOx
• gypsum as byproduct

Oct 22 2018 Erling Johnson 7

 Final Year Project
Production of Nitro-phosphate Fertilizer
Physical Properties
Property Nitric acid Ammonia Phosphate rock Nitro-phosphate
Molecular
HNO3 NH3 Ca5(PO4)3F NO6P-2
Formula
Molecular Weight
63.02 17.03 504.30 140.98
(g/mol)
Colorless White/grey granules
Appearance Colorless liquid Greyish Sedimentary rock
liquid/gas or prills
Smell Pungent Irritating - -
Boiling Point 86 oC -33.35 oC - -
Melting Point -41.59 oC -77.7 oC - -
47.8 mmHg at 10.2 atm at
Vapor Pressure - -
20 oC 25 oC
Density (g/cc) 1.529 0.77 1.69 1.1
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Production of Nitro-phosphate Fertilizer
Thermodynamic data
Property Nitric acid Ammonia Phosphate rock Nitro-phosphate
Standard Molar Enthalpy of
formation -174.1 -45.9 - -
(∆H) at 298.15K (KJ/mol)
Standard Molar Gibbs energy
of formation (∆G) at 298.15K -80.7 -16.4 - -
(KJ/mol)
Standard Molar Entropy at
155.6 192.8 - -
298.15K (J/mol-K)
Standard Molar heat capacity
109.9 80.8 - -
at 298.15K (J/mol-K)
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Production of Nitro-phosphate Fertilizer
Chemical Reactions
Ca3 PO4 2 + 4HNO3 → 2Ca NO3 2 + Ca H2 PO4 2 + 20.2 kcal
Ca H2 PO4 2 + 2HNO3 → Ca NO3 2 + 2H3 PO4 + 2.05 kcal
Overall
Ca3 PO4 2 + 6HNO3 → Ca NO3 2 + 2H3 PO4 + 22.25 kcal

2H3 PO4 + Ca NO3 2 + 4NH3 → CaHPO4 + NH4 2 HPO4 + 2NH4 NO3 + 66.67 kcal

CO2 g + NH3 g + H2 Ol → NH4 2 CO3 aq

𝐶𝑎 𝑁𝑂3 2 𝑎𝑞 + 𝑁𝐻4 2 𝐶𝑂3 𝑎𝑞 → 𝐶𝑎𝐶𝑂3 𝑠 + 2𝑁𝐻4 𝑁𝑂3 𝑎𝑞

HNO3 aq + NH3 aq → NH4 NO3 aq

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Production of Nitro-phosphate Fertilizer
Industrial applications
• applied on all types of soil
• mostly on soils of high pH or alkaline in nature
• applied at planting and early stages of growth of crops
• NP mainly constitutes of N and P2O5 hence, provide two plant macronutrients

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Production of Nitro-phosphate Fertilizer
Handling, storage & safety
Phosphate rock

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Production of Nitro-phosphate Fertilizer
Ammonia

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Production of Nitro-phosphate Fertilizer
Nitric acid

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Production of Nitro-phosphate Fertilizer
Nitro-phosphate (NP)

• Ammonium nitrate should be <70% by

weight
• Product checked for detonation ability
• Attracts moisture
• Packed in 50kg bags or bulk loading

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Production of Nitro-phosphate Fertilizer

Shipping of Product
• High mechanical resistance and low caking tendency
• Hydrophobic coated
• Bulk shipping in closed containers

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Production of Nitro-phosphate Fertilizer
World overview
210

200
Consumption 200.522 East Asia
193.882 South Asia
186.895 197.19 West Asia
190
190.732
180.079 Central Europe
MMT

180
170.845
183.175 N West Europe
176.784
170
161.829
fertilizer East Europe & Central Asia
North Africa
160
161.659 North America
150 Sub Saharian Africa
2008 2009 2010 2011 2012 2013 2014 2015 2016 2017 2018
Oceania
Year

South Aisa
East Asia
Central Europe
West Europe Source:
P East Europe & Central Asia
World fertilizer trends and
fertilizer Oceania
North Africa outlook 2018 by FAO
Sub Saharian Africa
North America

Oct 22 2018 Latin America & Caribbean

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 Final Year Project
Production of Nitro-phosphate Fertilizer
World
Production Consumption Oceania
(TMTA) (TMTA) East Asia
Country NP Country NP South Asia

Regions of the World

Russia 87,803 China 59,444
West Asia
China 28,624 India 26,939
Africa
Canada 27,094 USA 20,376
Latin America
USA 23,005 Brazil 16,597
North America
India 15,052 Indonesia 5,805
Eastern Europe & Central Asia
Belarus 8,842 Canada 3,975
Central Europe
Saudi Arabia 7,161 Russia 3,252
Western Europe
Morocco 6,485 France 3,043
0 50000 100000 150000 200000 250000 300000 350000
Indonesia 6,249 Vietnam 2,747 TMT
Total (NPK) K P N

Source:
World fertilizer trends and
outlook 2018 by FAO
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Production of Nitro-phosphate Fertilizer
Pakistan overview
700
700

600 Production 600 Consumption

500 500

TMT
TMT

400 400

300 300

200 200

100 100
1990 1993 1996 1999 2002 2005 2008 2011 2014 2017 1990 1993 1996 1999 2002 2005 2008 2011 2014 2017
Source: NFDC Year Year
Source: NFDC

1,200 MTPD 1,015 MTPD 130 MTPD

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Production of Nitro-phosphate Fertilizer

Market assessment & future trend

• Russia is the top producer of NP (20%)

• Russia is also the top exporter of NP (35%)
• China is the top consumer (45%)
• Currently Pakistan fulfill the demand by its production of NP
• Demand and consumption is increasing day by day
• In 2016 consumption is 651,000 MTPA
• In 2017 it reached 688,000 MTPA

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Production of Nitro-phosphate Fertilizer

Manufacturing Process

• Nitro-phosphate is manufactured commercially by two processes:

• Mixed Acid Process

• ODDA Process

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Mixed acid process

v
v

v
v

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Production of Nitro-phosphate Fertilizer
Description
• Phosphate rock is digested by nitric acid in the first reactor
• Temperature = 60-70oC
Ca3 PO4 2 + 6HNO3 → 3Ca NO3 2 + 2H3 PO4 + 22.25 kcal
• Acid gases like nitrous oxides and compounds of fluorine are formed
• Gases are removed by scrubbers
• Calcium nitrate stays in the reactor to provide two nutrients, calcium and nitrogen
• Neutralization is done in second reactor by ammonia.
• Sulfuric acid and phosphoric acid are also added to the reactor

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HNO3 + NH3 → NH4 NO3 + 22.27 kcal

H3 PO4 + 2NH3 → NH4 2 HPO4 + 33.52 kcal
2H3 PO4 + Ca NO3 2 + 4NH3 → CaHPO4 + NH4 2 HPO4 + 2NH4 NO3 + 66.67 kcal
Ca NO 3 + H2 SO4 → 2HNO3 + CaSO4 + 9.37 kcal

• Further neutralization is done in third reactor.

• pH of the solution reaches 5-6 to avoid HCl formation
• Buffer tank acts as a feed tank for spherodizer
• Water content 5-30% and temperature of 100-140oC
• Spherodizer includes granulator and dryer
• After screening, product reaches evaporator for moisture removal
• NP granules then get packed after coating

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ODDA Process

Raw Materials

• Phosphate rock
• Nitric acid
• Liquid ammonia

Flow sheet is shown on next slide

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Production of Nitro-phosphate Fertilizer
ODDA Process

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Production of Nitro-phosphate Fertilizer
Reactor
• Digestion reactor (R-01)
• Dissolution of phosphate rock in 60% nitric acid
• Stainless steel vessel, equipped with agitator
• Temperature = 60-70oC
Ca3 PO4 2 + 6HNO3 → Ca NO3 2 + 2H3 PO4 + 22.25 kcal
• Foaming occurs due to greater CO2 content, reduced by effective agitation
• Urea is used, 0.1-0.3% of rock feed, to suppress the emissions of NOx and HF

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Silica removal & Storage

• Silica particles are removed
• Hydro-cyclones S-03
• Clean overflow slurry is stored in storage tank T-05
• Sand is washed in washing drum
• Recover useful material and is conveyed to TK-05

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Production of Nitro-phosphate Fertilizer
Crystallization
• Slurry from (TK-05) is pumped via P-06
• Reached crystallizer (CR-07)
• Refrigeration cycle is provided to maintain crystallizer temperature
• Liquid ammonia enters evaporator (E-08)
• Hot stream from CR-07 also E-08 and exchange heat with liquid ammonia
• Ammonia gets vaporized and passed to neutralizer
• Slurry move towards heat exchanger (E-09) and is further cooled by water
• It is circulated back to crystallizer and to form crystals of calcium nitrate
• Temperature = -5oC to attain 85% P2O5-water solubility

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CN filter
• For further crystal growth slurry reaches filter feed tank (TK-10)
• Crystal size is 1 mm
• CN crystals are separated in belt or drum filter or centrifuge (F-11)
• Acidic slurry enters neutralizer reactor (R-13)
Neutralization
• Acidic slurry of nitro-phosphoric acid enters neutralizer (R-13)
• Ammonia is used as a neutralizing medium
• Temperature = 150-180oC
• Pressure = 1.5-2.5 bar
• NH4 NO3 is added to increase N content in final product
2H3 PO4 + Ca NO3 2 + 4NH3 → CaHPO4 + NH4 2 HPO4 + 2NH4 NO3 + 66.67 kcal
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Evaporation & Prilling
• Neutralizer product enters evaporator (E-15)
• Steam enters the evaporator to remove moisture from product
• Evaporator temperature = 150oC
• Then it enters prilling tower (T-16)
• Hot air is introduced from the bottom
• Slurry enters from the top of the tower
• Solid prills are formed and are scraped off from the bottom

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Formation of Ammonium Carbonate
• Ammonia gas enters absorption packed column (C-22) from evaporator (E-08)
• Carbon dioxide also enters the column
• Ammonium nitrate solution is also recirculated
• Pressure = 2 bar
• Heat of reaction is 36 kcal/moll.CO2
• Controlled by heat exchangers (E-24 & E-25)

CO2 g + NH3 g + H2 Ol → NH4 2 CO3 aq

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Conversion reaction

• Calcium nitrate melt and ammonium carbonate enter the tank reactor
• Form ammonium nitrate and calcium carbonate

𝐶𝑎 𝑁𝑂3 2 𝑎𝑞 + 𝑁𝐻4 2 𝐶𝑂3 𝑎𝑞 → 𝐶𝑎𝐶𝑂3 𝑠 + 2𝑁𝐻4 𝑁𝑂3 𝑎𝑞

• Heat of reaction is 7.5 kcal/mol.Ca

• Temperature = 70oC
• Solution contains little amounts of ammonia
• Neutralized by nitric acid

HNO3 aq + NH3 aq → NH4 NO3 aq

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Filter & Mixer

• Calcium carbonate is separated from ammonium nitrate solution in drum filter (F-28)
• Calcium carbonate is discharged to mixer
• Ammonium nitrate gets stored in TK-29
• Pumped via P-30 to absorber and neutralizer and absorber
• Ammonium nitrate enters mixer (M-31)
• Mixing of calcium carbonate and ammonium nitrate is done
• Calcium ammonium nitrate (CAN) is formed

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Evaporation & Prilling
• Mixer product enters evaporator (E-33)
• Steam enters the evaporator to remove moisture from product
• Evaporator temperature = 150oC
• Then it enters prilling tower (T-34)
• Hot air is introduced from the bottom
• Slurry enters from the top of the tower
• Solid prills are formed and are scraped off from the bottom

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Screening, Cooling & Coating

• Solid prills of NP and CAN are screened
• Oversize particles are crushed
• Required size of 1.65 mm
• Final prills are cooled and coated
• Product can be then bulk loaded or in packed in 50 kg bags.

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Production of Nitro-phosphate Fertilizer
Process Selection
Selected process for the manufacture of nitro-phosphate is ODDA PROCESS
because:

• It’s the oldest, simplest and widely used process all over the world.
• By-products are upgraded to commercial and useful products like AN, CAN and
CN.
• Process is sulfur independent.
• No solid waste and disposal difficulty.
• Product quality is fine due to removal of impurities at every step
• CO2 emissions from ammonia plant are used in the absorption column for the
formation of ammonium carbonate.
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Production of Nitro-phosphate Fertilizer
Capacity Selection
• Demand of nitro-phosphate fertilizer is increasing day by day
• Increasing demand of food with population growth
• Currently in Pakistan, Production of NP = Consumption of NP
• No import of NP after 2009-10
• After analyzing last 10 years
• Growth rate for consumption of NP is 9.6%
• Current consumption of NP is 688,000 MTPA
• Consumption after 5 years will be 992,040 MTPA
• Difference is 304,040 MTPA

Our selected capacity is 300,000 MTPA or 1,000 MTPD.

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References
1. Fertilizer processing manual by International Fertilizer Development Centre (IFDC)
2. Fertilizer processing manual by Francis T. Nielsson
3. World fertilizer statistics, International Fertilizer Development Centre (IFDC)
4. World fertilizer book by Food & Agriculture Organization of UN, 2018
5. The operating experience of nitro-phosphate plant by Iltifat Hussain, 2011
6. Fertilizer review by National Fertilizer Development Centre (NFDC), May 2017
7. Pakistan fertilizer statistics, National Fertilizer Development Centre (NFDC)

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