1

Fertilizers
 2
Fertilizers

• However, many soils do not provide all the nutrients in quantities needed by crops.
• Soil nutrients removed by continuous cropping must be replaced through the addition of
nutrient sources, such as fertilizers
 3
Fertilizers
“any material, as manure, chemicals, etc., put on or in
the soil to improve the quality or quantity of plant
growth”
 4
Fertilizers

??????
• Ammonium nitrate (33.5-0-0),
• Urea (46-0-0),
• Sodium nitrate (16-0-0)
• liquid nitrogen (30-0-0).
• Phosphorus 0-46-0
• Potash as 0-0-60 or 0-0-50
 5
Fertilizers
Compost: Organic matter that has been decomposed & recycled as a fertilizer &
soil amendment
• With the proper mixture of water, oxygen, carbon, and
nitrogen, micro-organisms are able to break down organic
matter to produce compost
• Most common microorganisms are
• Bacteria→ Depending on the phase of compositing material, mesophilic or
thermophilic microorganisms may predominate
• Actinobacteria→ breaking down paper products e.g., newspaper..
• Protozoa→ consume bacteria, fungi and micro organic particulates
• Rotifiers → help control populations of bacteria and small protozoans.
 6
Fertilizers
Fertilizer

Chemical
Organic Manure
Fertilizer

vermicomposting
 7
Fertilizers Classification
Fertilizer
Number of nutrients

ght ound
ra i m p
St Co
fertilizer having only one of the fertilizer having at least two of
primary plant nutrients, i.e. N, P the plant nutrients, i.e. N, P or
or K K
Fertilizer
Type of combination

Mixed Fertilizers Complex Fertilizers

physical mixtures of two or more two or more nutrients are chemically
single-nutrient or multi-nutrient combined (e.g. nitrophosphates,
fertilizers ammonium phosphates).
 8
Fertilizers Classification
Fertilizer
Physical condition

ol i d quid se s
S Li G a
crystalline, powdered, prilled or solutions & liquid under pressure,
granular of various size ranges suspensions e.g. ammonia

Fertilizer
Number of nutrients

l e te l e t e
m p m p
co nc o
I
Containing all 3 primary Do not have all 3 primary
nutrients i.e., 10-15-10 nutrient i.e., 10-0-15
 9
Fertilizers Classification
Fertilizer
Nutrient Release

c t i ng l e as e
k- a re
quic trol l e d
Con
water-soluble and g by coating d
ac t i n i z e
- i l
immediately available sl o w St ab
transformation into soluble form by inhibitors
required, e.g. direct application of
phosphate rock
 10
Fertilizers Manufacturing
 11
Fertilizers Production World Wide
 12
Fertilizers Production Companies in Pakistan
 13

UREA
• Urea (carbamide) is a high quality nitrogenous fertilizer with 46% N content
• It is called carbamide because it has two groups of NH2.
 14
UREA
USES:
 15
UREA Production Processes
1. Once Though Process

2. Solution Recycle Process

3. Internal Carbamate Recycle Process

 Snam Progetti Process

 Stamicarbon (Holland)
 16
UREA PRODUCTION
4 H2O is removed from carbamate
2 NH3, CO2, H2O,
carbamate & urea formed

4
2 5

1 NH3 & CO2 are

pumped to synthesizer
5 Granulation is done

3 • Carbamate is decomposed into

NH3 and CO2
• NH3 & CO2 , are separated from
top Total Recycle Process
• H2O & carbamate remaining
 17
UREA PRODUCTION Total Recycle Process
1- Ammonia and compressed CO2 pumping
Liquid ammonia is pumped from the multistage pump which maintain the reaction pressure in the
synthesis reactor. CO2 is compressed through a compressor up to the urea synthesis reactor pressure

2- Synthesis: (Urea Synthesis Tower)

The process consists of two main equilibrium reactions with incomplete conversion of the reactants

1- carbamate formation: the fast exothermic reaction of NH3 & CO2 with the mole ratio of 2:1 is
achieved at high temperature and pressure to form ammonium carbamate
o
190 C
2NH3  CO2      NH2COONH4 H   117 KJ/ mol

2- urea conversion: the slower endothermic decomposition of ammonium carbamate into urea
and water NH2COONH4  140
    
175 bar
 NH2CONH2  H2O H   15 KJ/ mol

(78% conversion of CO2 to urea is achieved).

 18
Total Recycle Process
2- Synthesis: (Urea Synthesis Tower)

• The overall conversion of NH3 and CO2 to urea is exothermic, the reaction heat from the first
reaction driving the second.
• Like all chemical equilibria, these reactions behave according to Le Chatelier`s principle, and
the conditions that most favor carbamate formation have an unfavorable effect on the urea
conversion equilibrium so the process condition are “a compromise”
• Synthesis Tower is lined with film of oxides to protect form corrosion
• Plug flow operation take places and molten urea is removed from the top of the tower
• Since the urea conversion is incomplete, the product must be separated from unchanged
ammonium carbamate
 19
UREA PRODUCTION Total Recycle Process
3- Decomposition & Purification (Stripper)
• The major impurities in the mixture at this stage are water from the urea production reaction
and unconsumed reactants i.e., NH3, CO2 & ammonium carbamate.
• The pressure is reduced in 3 stages and solution is heated which causes ammonium
carbamate to decompose into NH3 and CO2

 reduc
NH2COONH4  ApplyLe ed
 press
 ure
    2NH3  CO2
Chatelier`s principle

• NH3 and CO2 are stripped off and a solution of urea dissolved in water and free from other
impurities remains.
• The excess NH3 is purified and recycled as a feed stock.
 20
UREA PRODUCTION Total Recycle Process
4- Concentration (Evaporator)
• 75% of urea solution is heated under vacuum to evaporate some of water resulting increase in urea
concentration from 68% w/w to 80% w/w.
• At this stage some urea crystals are also formed which are dissolved by heating the solution from 80-
110 oC. In the evaporation stage, molten urea (99% w/w) is produced at ~140 oC
5- Granulation (Granulator/ Prilling Tower)
• Urea is sold for fertilizer as 2-4 mm diameter granules and this is done by sprinkling the molten urea
from top of the tower onto seed granules and air is passed from the bottom.
• All the moisture is removed while urea is removed from bottom.
• Classification of granules is done through screens and oversized granules are crushed and combined
with undersized ones to use as seed.
• All dust and air from the granulator is removed by a fan into dust scrubber which removes urea with a
water solution then discharge the air to atmosphere.
 21
UREA PRODUCTION
Side Reactions
• Hydrolysis of urea:
The hydrolysis reaction takes place in the presence of water. Acids or alkaline
solutions accelerate hydrolysis
CO(NH2 )2  H2O  NH2COONH4  NH3  CO2
• Formation of biuret:
2 CO(NH2 )2  NH2CONHCONH2  NH3
• Formation of isocyanic acid:

CO(NH2 )2  NH4NCO  NH3  HNCO

 22
UREA PRODUCTION

NH3
CO2
synthesis
Urea, excess NH3,
CO2, carbamate, H2O
NH3 & CO2 Cooling
Decomposition Recovery

Urea, H2O
Heat H2O
Concentration

Heat Granulation

Urea Granule
 23
UREA PRODUCTION
 24
UREA
Influence of Temperature on NH3 and CO2 conversion
 25
UREA
Influence of Temperature on Urea Concentration
 26
UREA
Urea Finishing Processes
• Urea solution from the synthesis/recycling stages of the process is concentrated via evaporation or

crystallization to a urea melt for conversion to a solid prilled or granular product for use as a
fertilizer or technical grade.

Prilling → Spinning bucket, shower head

• All prilling tower have dust problem

• Inline cooling or fluidized bed cooling.

Granulation → Sprinkling through nozzle

• Less dust problem, uniform size,

• better crushing and impact,

• transport and handling strength.

 27
Major Engineering Problems
1) Autoclave variables
The objective of autoclave reaction is to produce the optimum economic yield. The conditions which
affects rate of reactions are temperature, pressure, NH 3/CO2 ratio and feed rate. The urea production
rate can be varied as follows
1. Increase with increasing pressure
2. Increase with temperature to maximum at 175-180 0C, then falls of sharply.
3. Use no excess ammonia.
Reasons for not operating at maximum temperature and pressure without excess ammonia
Increased pressure increases capital and operating cost of compression and reaction equipment.

At higher temperature urea decomposed to biuret, which is detrimental to germinating seeds and

toxic to animals.
 28
Major Engineering Problems
2) Corrosion:
 This has been the major reason why the NH3-CO2 process was slow to develop.

 Minimum pressure and temperature conditions with excess NH3 are desirable to
reduce the severe corrosion rates.
 Under these conditions, stainless steel can be used in the autoclave.

3) Production of granular urea:

 Problem again is biuret formation. Vacuum evaporation of urea from 80% to

about 99%, spraying to air cool and solidification must be done just above the
melting point of urea (i.e., 133 oC) and with a minimum residence time in the
range of several seconds.
 29
Major Engineering Problems
4) Carbamate decomposition and recycle
 It is optimized by short residence times in a stripping column operating at low
pressure and high temperature. Later should be below 110 0C if hold up time
exceeds 1-2 seconds to avoid biuret formation. Use of millisecond contact time in a
flash evaporator allows 140 0C operating temperatures in the high recycle design.
 30
UREA Manufacturing Process
2- Once through process
NH3, CO2 & H2O
steam

Reactor175-190 0C
Gas Liquid
Let down Separator
valve
Decomposer 85-90% Urea Solution

Liquid NH3
Compressed CO2 Once through urea process
 31
UREA Manufacturing Process
2- Once through process
• The reactor effluent is let down in pressure to about 2 atm and the carbamate decomposed and
stripped from the urea-product solution in a heat exchanger.
• The moist gas, separated from the 85-90 % urea product solution, & containing about 0.6
tons of gaseous NH3 per ton of urea produced is usually sent to an adjacent ammonium
nitrate or ammonium sulfate producing plant for recovery.
• An average conversion of carbamate to urea of about 60 % is attained..
• NH3 to CO2 feed mole ratio of 2/1 or 3/1
• Simplest and least expansive (both capital and operating cost)
• Least flexible and cannot be operated unless some provision is made to utilize large amount of
ammonia and off-gas
 32
UREA Manufacturing Process
Snam Progetti process (Italy)
NH3 & CO2

190 0C
18 4.5
atm atm
162
atm
162 atm
 33
UREA Manufacturing Process
Snam Progetti Process (Italy):
• The basic difference between the Snam process & the conventional urea processes is that
in this case the unconverted carbamate is stripped and recovered from the urea synthesis
reactor, condensed to an aqueous solution in a steam producing high pressure condenser, &
recycle back to the reactor by gravity.
• Part of the liquid NH3 reactor feed, vaporized in a steam heated exchanger, is used as inert
gas to decompose & strip ammonium carbamate in the steam heated high pressure stripper.
• The urea product solution, leaving the stripper & still containing 2-3 % of residual
unreacted carbamate, is further degassed in a low pressure decomposition-absorption
system.
 34
UREA Manufacturing Process
Stamicarbon
Process (Holland):
 35

Ammonium Nitrate
• Ammonium nitrate contains 33.5 - 34.5 % nitrogen
• Quick acting Nitrate & slow-acting Ammonical Nitrogen
• Military explosive (mixed with oil) & for mining
• The world production of ANs is estimated to be 40 - 45 Mtonnes/year
 36
Ammonium Nitrate
neutralisation
Production Process

evaporation solidification

NH3 (g) + HNO3 (aq)  NH4NO3 (aq) ∆H = -86.2 kJ

 37
Ammonium Nitrate
Production Process:
AN is produced by neutralizing 60% aqueous HNO3 with gaseous NH3

NH3 (g) + HNO3 (aq)  NH4NO3 (aq) ∆H = -86.2 kJ

Highly exothermic reaction and proceeds rapidly.

The heat produced is often used to generate steam.

The obtained AN solution can be concentrated by evaporation.

Most applied production processes comprise three main operations:

 38
Ammonium Nitrate
 HNO3 NH3

Ammonium Nitrate
 40

CAN is preferred to ammonium nitrate in acid soils

Calcium Ammonium Nitrate (CAN)

• 26% N (Dual Nitrogen) - 13% Nitrate and 13% Ammonical other than Nitrogen.
• Supplies additional 5 elements required for plant growth:

K - 0.9%, Ca - 10%, Mg- 0.05%, S- 0.4%, Cu - 0.001%

 41
Calcium Ammonium Nitrate
Uses:
I. Valuable source of Nitrogen & Calcium.

II. As a fertilizer can be applied for all types of soil and all plants.

III. Nitrogen fertilizer supplying nutritive elements (N as NH4+ and NO3-,

Mg and Ca as carbonates).

IV. Suitable for blending with other granulated fertilizers

V. Commonly used on fruit, process and vegetable crops

 42
Calcium Ammonium Nitrate
1 2

3 1 Neutralization,
evaporation, NH4NO3
formation

2 Reaction with CaCO3

3 Granulation,
Screening
4
4 Nitrochalk Formation
5

5 Scrubbing &
Recycling
 43
Calcium Ammonium Nitrate
Production Process:

Raw Materials Sources:

I. Ammonia→ Haber – Bosch
II. Nitric acid → Ostwald‘s process
III. Lime stone → mineral calcite or aragonite, which can be used after removal of clay,
slit and sand (silica).
 44
Calcium Ammonium Nitrate

 CAN is obtained by reaction of limestone with concentrated HNO3 by

 the addition of ammonia to neutralize excess of acid,
 evaporation of the resulting solution,
 and finally prilling or flaking
 The resulting product is a double salt Ca(NO3)2NH4NO3 called calcium ammonium
nitrate.
 Granules are coated with thin layer of protective coating (soap stone powder) which
prevents the absorption of moisture during storage and transportation
 45

Ammonium Phosphate
• Salt of ammonia and phosphoric acid
• Two major types of ammonium phosphate are
 Monoammonium phosphate (MAP)
 Diammonium phosphate (DAP)
 46
Ammonium Phosphate
1. Monoammonium phosphate (MAP)
• Produced by adding anhydrous NH3 to liquid H3PO4

• Fertilizer (intermediate) with high P2O5 content of about 55% and 11-12% N.

2. Diammonium phosphate (DAP)

• With more NH3, DAP containing 16 -18% N and 20-21 % P (46% P2O5) is formed.

Sources of raw material

× NH3 →Haber – Bosch,

× H3PO4 →electric arc furnace, blast furnace or wet process

 47
evaporation, NH4NO3
Ammonium Phosphate
exothermic reaction →130°C
1 Neutralization,

2
Granulation
formation

16 - 20% H2O
1 1 1 2 3 3 Drying

4
NH3 + H3PO4  NH4H2PO4
4 screening
NH3 + NH4H2PO4 (NH4)2HPO4
 48
Ammonium Phosphate
The two principal steps are Reaction
NH3 + H3PO4  NH4H2PO4
 Neutralization
 Granulation
NH3 + NH4H2PO4 (NH4)2HPO4

Neutralizer
0.6
MAP Granulator
1.0
Ratio of
NH3/H3PO4 Neutralizer
1.4
DAP Granulator
1.0
Ca3(PO4 )2  2H2SO4  H2O  Ca(H2PO4 )2.H2O  2CaSO4
 49
Ammonium Phosphate
Neutralization:
exothermic reaction →130°C.

Unreacted and excess NH3 vapour is collected from the top and recharged for reducing NH 3
losses (less than 3%).
The hot slurry containing about 16 to 20% water is pumped into the granulator, where more
ammonia is added to increase the molar ratio to approximately 2.0.
 50
Ammonium Phosphate
Granulation:
Slurry from neutralizer is mixed with KCl and absorbed in a bed of dry recycle
fertilizer moving through a rotating drum granulator.
Drier reduces the moisture to less than 1%, with 10 minute contact time with air
initially at 150 oC.
Dried product is separated into three fractions on a double deck screen.
A portion of the product from the deck of the lower screen is sent to bagging
operations and oversize and fines, is returned to the granulator.
The weight ratio of recycle to product is 6:1-15:1 depending on the grade produced.
 51
Ammonium Phosphate
Uses:

P/N,P/P,K/NPK compound
fertilizer manufacturing of yeast, vinegar, yeast
foods, fermentation agent & bread
improvers

Used as a fire prevention agent for fabric, timber and paper, as well as a
fire prevention coating & dry powder for fire extinguisher
 52

Thanks
 53
MAP & DAP
Production
 54

Ammonium Nitrate

evaporation
Second
175 oC
evaporation
First
125 oC
97% NH4NO3
HNO3, 55% solution
Reactor

Solution
Tanks
5.6 ml H2SO4

Solution
Tanks
CaCO3
Solution Tanks
(Limestone)
NH3, 22 oC,

Prilling
Tower
74-83% ammonium nitrate
solution
 55
Ammonium Nitrate

nitric acid (55% concentration wt/ wt)