ADDIS ABABA UNIVERSITY

ADDIS ABABA INSTITUTE OF TECHNOLOGY

SCHOOL OF CHEMICAL AND BIO ENGINEERING

CBEg 3151: Chemical Process Industries

Lecture 5: Process Technology of Agrochemicals

(Fertilizers )

BY: Yeayneabeba Tadesse

May 5, 2021
OUTLINE
 Introduction to fertilizers
 Advantage of fertilizers
 Type of fertilizers
 Nitrogen based fertilizers
 Phosphate fertilizers
 Potash fertilizers
 Multi nutrient fertilizers

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Introduction to fertilizers
 Fertilizers are chemical substances which provides
plants with nutrients they need for growth and
development by improving soil fertility.
 Fertilization implies the supply of one or more
nutrient to the soil as chemical elements are
necessary for normal plant growth.
 Plants can take oxygen, carbon, hydrogen essentially
and easily from the soil through roots or from the
atmosphere through leaves, while nitrogen,
phosphorus and potassium can be naturally obtained
to a certain extent from soil but not adequate.

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 Nitrogen, phosphorous and potassium minerals
are required by plants in large amount and are
called primary nutrients.
 Calcium, magnesium and sulfur which are
needed relatively in smaller but still in
appreciable quantity are secondary nutrient.
 The other elements (Mn, Mo, Zn, Bo, Fe, Cu, and
Cl) which are generally available in soil at
reasonably sufficient levels for healthy plant
growth are called Micro-nutrient.
 Fertilizers containing one nutrient element are
called single nutrient fertilizer and those with a
combination are multi-nutrient or compound
fertilizers
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Advantage of fertilizer
 Enhance soil activity
 Increase crop yield by 20-30%
 Enhance root growth due to better soil structure
 Activate the soil biologically
 Restore natural soil fertility
 Stimulate plant growth

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Types of fertilizer
1. Chemical fertilizers
 Are mainly inorganic and are manufactured
materials
2. Manure or organic fertilizer
 Made from plant and animal waste
3. Bio-fertilizers
 Is a product containing living micro organisms
and that are agriculturally useful in terms of
 Nitrogen fixation
 Phosphorous solubilization
 Nutrient mobilization
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Chemical fertilizers
 chemical Fertilizers are manufactured from the
following raw materials:
 Air, Fossil hydrocarbons(Natural gas, crude oil,
fuel oil, coal, etc )
 Mineral rock phosphates

 Natural potassium salts (potash)

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Types of chemical fertilizers

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Nutrient (N,P2O5,K20) Content in Fertilizer
products

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CO2

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Ammonia based fertilizers
H2SO4 (NH4)2SO4 20%N
ammonium sulfate

HNO3 NH4NO3 33%N

ammonium nitrate
NH3 + CO2 (NH2)2CO 45%N
urea

H3PO4 NH4H2PO4 11-18%N

ammoniated phosphates
11-48-0
18-46-0

HNO3/rock phosphate nitric phosphates

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Nitrogen based fertilizers

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1. Ammonium nitrate
 Colorless, crystalline salt of ammonia
and nitric acid
 Strong oxidant that reacts with
combustible and reducing material
 Contains 34% nitrogen, all of which is
usable by plants
 Pure solid ammonium nitrate melts
at 169o C.
 Ammonium nitrate is a nitrogenous
fertilizer representing 12.4% of the
total nitrogen consumption
worldwide.
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 It is more readily available to crops than urea.
 Ammonium nitrate’s powerful oxidizing
properties is used as commercial explosive
with proper additives.
 The production process comprises three main
unit operations:
 1. Neutralization
 2. Evaporation
 3. Solidification (prilling, cristalilization
and granulation).
 Individual plants vary widely in process detail

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Production of AN and related products

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NH3

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Purpose of each unit operation
1. Neutralization:
 Anhydrous liquid ammonia is vaporized and
allowed to react with nitric acid.
 The stoichiometric quantities of nitric acid (55-
65% concentration wt/ wt) and gaseous ammonia
are introduced by an automatic ratio controller
to a neutralizer.
 The reaction between Ammonia and nitric acid
produces ammonium nitrate solution according
to the following exothermic reaction.
NH3 + HNO3 NH4 NO3
 Neutralization can be performed in a single
stage or in two stages.

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 The neutralizer can be carried out at
atmospheric in normal neutralizers where the
temperature does not exceed 105C or at
elevated pressure of almost 4 atmospheres.
 The normal neutralizers are usually followed
by flash evaporation in order to increase A.N
concentration to 70%.
 In case of pressure neutralizers the
temperature will be in the range of 178C and
the steam generated from the heat of reaction
will be utilized in the subsequent step namely
concentration of A.N solution

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2. Evaporation
 The outlet from the neutralizer is received in an
intermediate tank.
 The solution is then pumped to the multi effect
evaporation section running under vacuum for
flash evaporation.
 There is no need for pumps in case of pressure
neutralizers since the pressure will maintain the
flow.
 The solution will be steam heated in the multi
effect evaporation section and will be
concentrated up to 97.5-99.5% (normally over 99
%) depending on whether ammonium nitrate will
be granulated or prilled.
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3. Prilling/ crystallization/granulation
 The hot concentrated ammonia nitrate melt is
either prilled or crystallized or granulated.
 Prilling
 AN melt is atomized into droplets to fall down
along the prill tower where they cool and solidify.
 Crystallization
 The evaporation process proceeds in a higher
degree of saturation after which it is dropped
into crystallizer.
 The solution that contain the ammonium crystal
are then separated by centrifuge for subsequent
drying operation.

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 Granulation
 It require more complicated plant and Varity
of equipment such as fluidized bed
granulation, drum granulation etc. than that
of prilling.
 The main advantage of granulation over
prilling is that the quantity of exhaust air to
be treated is much smaller and pollution
abatement equipment is cheaper.
4. Cooling

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5. Mixing the filling material
 AN is highly hydroscopic material and can be
easily caked when it comes in to a moist
environment or when exposed to humid air
during transportation or storage.
 It is necessary to dust the prill or crystal or
granules with inert material.
 To prevent intimate contact and possibility of
caking.
 To avoid the possibility of explosion that could
take place when stored in fine particulate state
and get in contact with explosive agent.

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 The mixing of filling material such as clay,
limestone, dolomite, or even kaolin with AN
product and subsequent dusting reduce the
nitrogen content of AN from 35% to about 33%.
 The quantity of filling material added is about 4%
by weight.
 The anti caking chemical usually amines can be
added as coating material.

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6. Drying/screening

 The ammonium nitrate (prills, crystal or granules)

is dried (usually in drums) using hot air and is
screened to get the correct product size.
 The oversize and undersize will be recycled either
in the mixing tank (in case of prilling), to
crystallizer or to the granulator.
 The proper size prill, crystals or granules are then
cooled down, packed and stored.

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2. Ammonium sulphate
 Ammonium sulphate (AS) is a nitrogenous
fertilizer with an additional source of soluble
sulphur which is a secondary plant nutrient.
 The majority of its production is coming from
coking of coal as a byproduct.
 Ammonium sulphate is produced by the direct
reaction of concentrated sulphuric acid and
gaseous ammonia and proceeds according to
the following steps.
2NH3(g) + H2SO4(aq) [NH4]2[SO4]
ammonium sulfate

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Purpose of each unit operation
Neutralization
 Liquid ammonia is evaporated in an evaporator and
preheated using low pressure steam.
 The stoichiometric quantities of preheated gaseous
ammonia and concentrated sulphuric acid (98.5%
wt/wt) are introduced to the reactor – crystallizer
(operating under vacuum).
 These quantities are maintained by a flow recorder
controller and properly mixed by a circulating
pump (from upper part of the crystalliser to the
evaporator)
2NH3(g) + H2SO4(aq) [NH4]2[SO4]
ammonium sulfate
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 Crystallization and filtration
 The reaction takes place in the reactor-
crystallizer where the generated heat of reaction
causes evaporation of water making the solution
supersaturated.
 The supersaturated solution settles down to the
bottom of crystallizer where it is pumped to
vacuum metallic filter where the AS crystals are
separated, while the mother liquor is recycled to
the crystallizer.

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Drying

 The wet AS crystals are conveyed (by belt

conveyors) to the rotary dryer to be dried
against hot air (steam heated) and then
conveyed to the storage area where it naturally
cooled and bagged.

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3. Urea production
Urea fertilizer: 46 %N2

 Colorless, crystalline compound

 Strong oxidizer promotes
explosive reaction with organic
materials
 Decomposes to produce carbon
dioxide and ammonia
 Many uses, including
 Fertilizers,
 Plastics,
 Drugs and cosmetics
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 It is also known as carbamide or carbonyl diamide,
is a high concentration nitrogen fertilizer, with a
46% nitrogen content.
 85% percent of urea produced is used in fertilizer
mixtures, with 3% going to animal feed
supplements and 12% is used for plastics and
other uses.
 Urea is marketed as a solution or in solid form.
 Most solids are produced as prills and granules

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Main advantages with urea application
 Can be applied as solid or solution and on certain
crops as spray.
 It’s usage involved little or no fire or explosion
hazard.
 Urea’s high 46% nitrogen helps reduce handling
and transportation costs.
 Urea manufacture release less pollutant to
atmosphere.
 When properly applied, increases crop yield
significantly.

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Urea production process

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 The second reaction
 Is dehydration of formed ammonium
carbamate and produce the required urea
and water solution.
 Slow and endothermic
 Incomplete conversion. The conversion (on
CO2 basis) is usually in order of 50-80%.
 The urea reactor demand high pressure system
implying that the ammonia must be in
pressurized liquid state. The CO2 has to be
compressed to optimum pressure
 The finishing process can operate at atmospheric
pressure.

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 The urea plant consists of high and low pressure
section.
 The high pressure section is composed of:
 Urea synthesis including the high stripper
and condenser.
 The low pressure section is composed of:
 Evaporation
 Recovery
 Prilling

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 The urea production process must be designed
to maximize the urea formation reactions while
inhibiting the side reactions. Such as
 Hydrolysis of urea

 Formation of biuret

 Formation of isocyanic acid

 The biuret formation reaction is undesirable,

not only because it lower the yield of urea, but
because biuret burns the leaves of the plant.
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 This means that urea which contains high
levels of biuret is undesirable for use as
fertilizer.

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Major unit operations employed in urea
plant

Urea synthesis

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Carbamate decomposition and recycle system

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Evaporation or crystallization and melt formation
 The urea solution (68-70%w/w) coming from
synthesis and purification/recovery units is heated
under vacuum, which evaporates the water,
increasing the urea concentration to 98-99% w/w.
 At this stage some urea crystals can be formed.
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Granulation
 Urea melt is transferred from the urea melt plant
to the granulator by a means of urea melt pump.
 In the suction line of the pump formaldehyde is
added.
 Formaldehyde is used as granulation additive and
anti-caking agent. It also improves the granule
crushing strength and reduce dust formation
during handling.
 Granules are formed by spraying molten urea
onto seed granules which is supported on a bed
of air.
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 Dry, cool granulates are classified using screens
 The oversized granules are crushed and combined
with undersized ones for use as seed.
 All dust and air from the granulator is removed by
a fan in to a dust scrubber, which removes the
urea with solution than discharge the air to the
atmosphere.
 The final product is cooled in air, weighted and
conveyed to bulk storage ready for sale.

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PHOSPHATE FERTILIZER
 Are fertilizer that contain one of the basic macro
nutrient, which is phosphorous.
 There are different types of phosphate fertilizer
 Phosphoric acid
 Superphosphate
 Ammonium phosphate

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1.Phospheric acid
 It is also known as ortho-phospheric acid
 The modern manufacturing methods of phosphoric
acid are
1) Using phosphate rock and blast furnace
2) Using phosphate rock and electric furnace
3) Oxidation and hydration of phosphorous
4) Wet process or from sulfuric acid and
phosphate rock.
 The process that use strong mineral acid to digest
phosphate rock are called wet process and they are
the most economically feasible alternative
technology to produce phosphoric acid.
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 Even if the thermal process produce higher quality
phosphoric acid, it fails to compete the wet process
because of the high energy consumption or cost
required per ton of acid.

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Wet process
 Phosphoric acid is produced from phosphate
rock/ore by the action of strong mineral acids such
as sulphuric acid, nitric acid, and hydrochloric acid.
 Sulphuric acid is the only acid which forms an
insoluble precipitate of sulphate with the calcium of
the phosphate rock/ ore, thus allowing the
phosphoric acid to be separated directly by filtration.
 The chloride and nitrate of calcium of phosphate
rock/ore are both soluble that demand costly
separation techniques like solvent extraction or
cooling crystallization.

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 The acidulation process by nitric acid and
hydrochloric acid is determined by
1) The type of technology used
2) Availability and price of acid
3) Local production condition
 The use of nitric acid produce calcium nitrate
(nitrogenous fertilizer) as a by product along with the
phosphoric acid.
 Main unit operation of wet process
1) Size reduction and grinding
2) Digestion/acidulation (reaction and
crystallization)
3) Filtration and
4) Evaporation

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Grinding
 Depending on the phosphate rock properties and
the process applied, grinding of the phosphate rock
can be necessary.
 This is usually carried out using ball or rod mills.
Both types of mills can operate with wet or dry
rock.
 Some grades of commercial rock do not need
grinding, their particle size distribution already
being acceptable for the dehydrate reaction section.
 Most other phosphate rocks require particle size
reduction.

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 The particle size of phosphate rock should be less
than 200 mesh size for effective high yield solid-
liquid reaction.
 The energy requirements for grinding depends on
the type of phosphate rock.

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2. Digestion: reaction and crystallization

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 There are two processes i.e. dihydrate and
hemihydrates (CaSO4.2H2O and CaSO4.1/2H2O)
are used for production of phosphoric acid.

 The dihydrate process is the most popular due

to simplicity and ability to use a wide variety of
phosphate rocks in the process.
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3. Filtration

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4. Evaporation
 Currently, almost all evaporators are of the forced
circulation design. The forced circulation evaporator
consists of a heat exchanger, vapor or flash chamber,
condenser, vacuum pump, acid circulating pump and
associated pipe work. Acid scrubber is usually included
with the system.
 All the evaporators in this service are generally of the
single-effect design because of the corrosive nature of
phosphoric acid and the very high boiling point of the
process. The heat exchangers are fabricated from graphite
or stainless steel with the rest of the equipment made from
rubber-lined steel. A multiple effect evaporation system
may be used depending on the concentration needed.

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2. Superphosphate

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2.1. Single superphosphate fertilizer
 The manufacturing process depends on reacting
phosphate rock with sulfuric acid and the
fertilizer accompanied by a rapid chemical
reaction on the particle
 contains about (16- 20 %) P2O5. The net reaction
proceeds as follows:
 Ca F2. 3Ca3 (PO4)2 + 7H2SO4 + 14H2O
→3Ca(H2PO4)2 + 7Ca SO4 . 2H2O + 2HF
 The process can be divided into two stages as
follows: The first stage represents the diffusion of
sulfuric acid to the rock particles

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 Major unit operation and process flow
diagram

1. Phosphate weigh feeder

2. Feed tank for H2SO4
3. Feed tank for water;
4. Acid feeder;
5. Mixer;
6. Superphosphate den;
7. Single Superphosphate (SSP);
8. Superphosphate storage site

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 2.2. Triple superphosphate fertilizer
 This type of fertilizers is much more concentrated than the
ordinary superphosphate, containing 45- 46 % of available
P2O5. Triple superphosphate is manufactured by the action of
phosphoric acid on phosphate rock. The main reaction is:
CaF2. 3Ca3 (PO4)2 + 14H3PO4 → 10Ca (H2PO4)2 + 2HF ↑
(Phosphate Rock) (Triple Superphosphate)
 A process similar to single superphosphate production is
used, in which pulverized phosphate rock is mixed with
phosphoric acid in a two-stage reactor. The resultant slurry
is sprayed into the granulator. The slurry is sprayed into the
drum granulation co-current with flue gases of fired fuel
(natural gas or fuel oil and air). The product is screened and
off-size is recycled back to the granulator. The on-size
product is cooled and stored ready for being bagged.

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POTASH FERTILIZER
 Are fertilizers that contain one of the basic macro
nutrient, which is potassium.
 There are different type of potash fertilizer
1. Potassium chloride
2. Potassium sulphate
3. Potassium nitrate

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1. Potassium chloride
 Potassium chloride (KCl) is a metal halide salt
composed of potassium and chlorine.
 It is odorless and has a white or colorless vitreous
crystal appearance, with a crystal structure that
cleaves easily in three directions.
 White potash or soluble potash is usually higher in
analysis and is used primarily for making liquid
starter fertilizers. It occurs naturally as the mineral
sylvite and in combination with sodium chloride as
sylvinite.

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Raw materials
 Potash mineral or brine
 Potash mineral or sylvinite contain potassium
chloride and sodium chloride

Process technology

 Potassium chloride is obtained by following

methods
1. Leaching process
2. Flotation process

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1. Leaching process
 The solubility of potassium chloride and sodium
chloride increases as the temperature increases.
 Individually both are much more soluble in hot
water than in cold water. But in solutions saturated
with both sodium and potassium chloride, the
concentration of NaCl diminishes as temperature
rises, while the concentration of potassium chloride
increases.
 These solubility characteristics are used to extract
potassium chloride from sylvinite.

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 Crushed ore is mixed with sufficient quantity of
recycle brine which is already saturated with NaCl
and heated almost to hilling to dissolve KCl.
 The KCl rich brine on clarification and then
cooling by vacuum evaporation produces KCl
crystals which are centrifuged, washed, dried and
packed.
 The filtrate (brine) is recycled for leaching more
ore.

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2.Flotation process
 Floatation process for extraction of potassium chloride is
much cheaper than leaching process and hence is used
more extensively in the industry.
 In this process, the ore is crushed to +10 mesh size then
washed to remove clay slimes.
 To render it inert to amines, washed crushed ore is
treated first with starch and then with an amine acetate
which selectively coats KCl particles. Air is then bubbled
through the slurry.
 The air bubbles attach themselves to the coated particles
and float them to the surface while the uncoated particles
sink. The floated KCl is centrifuged, dried and packed.

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4. MULTI-NUTRAINT COMPOUND
FERTILIZER

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Ammonium phosphate

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 The two principal steps are
a) Neutralization
b) Granulation
a) Neutralization
 Quantities of phosphoric acid and ammonia in the
neutralization step are different form mono
ammonium phosphate (MAP) and diammonium
phosphate (DAP).
 To manufacture mono ammonium phosphate,
ammonia to phosphoric acid ratio is 0.6 in the
neutralizer and then 1.0 in the granulator. While for
diammonium phosphate, the ratios are 1.4 and 1.0 in
the neutralizer and granulator respectively.

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 Phosphoric and ammonia are added to the first of
three continuous mixed reactors, anhydrous
ammonia is added beneath the slurry level in the
first neutralizer in an amount equivalent to 80%
neutralization.
 Further ammonia is added in the 2nd and 3rd tanks
to obtain conversion to the di ammonium salt if a
higher nitrogen containing fertilizer is needed.

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 The exothermic reaction heats the slurry nearly
to the boiling point (130°C).
 Unreacted and excess ammonia vapor is
collected from the top of each tank and
recharged below the liquid level for reducing
ammonia 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.

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b) Granulation

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THANK YOU!

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