The Process

Technology of Agrochemicals
• Fertilizers
•Pesticides
By
Gizachew Shiferaw

Slide 1
 Synthetic chemical Rank Catalytic Process

Sulfuric acid (H2SO4) 1 SO2 oxidation to SO3 ; heterogeneous

Ethylene (CH2CH2) 2
Lime (CaO) 3
Ammonia (NH3) 4 N2 + H2 ; heterogeneous
Sodium hydroxide (NaOH) 5
Chlorine (Cl2) 6 Electrocatalysis; heterogeneous
Phosphoric acid (H3PO4) 7
Propylene (CH3CHCH2) 8
Sodium carbonate (Na2CO3) 9
1,2-Dichloroethane (ClCH2CH2Cl) 10 C2H4 + Cl2 ; homogeneous
Nitric acid (HNO3) 11 NH3 + O2 ; heterogeneous
Urea (CO(NH2)2) 12
Ammonium nitrate (NH4NO3) 13
Benzene (C6H6) 14 Petroleum refining; heterogeneous
Ethylbenzene (C6H5CH2CH3) 15 Alkylation of benzene; homogeneous
Carbon dioxide (CO2) 16
Vinyl chloride (CH2CHCl) 17 Chlorination of C2H4; heterogeneous
Styrene (C6H5CHCH2) 18 Dehydrogenation of ethylbenzene; heterog.
Terephthalic acid (1,4-(COOH)C6H4) 19 Oxidation of p-xylene; homogeneous
Methanol (CH3OH) 20 CO + H2; heterogeneous
 A chemical fertilizer or manure are
materials that contain one or more of the
essential plant nuitritional elements and are
applied to soils to increase crop productivity
and growth.
 The amount added is decided on after soil
analysis.
 chemical Fertilizers are mainly inorganic
and are manufactured materials.
 Manures are organic fertilizers(made from
plant and animal wastes).
 Most of the fertilizers contain N, P and K either singly or in
a combination.
 chemical Fertilizers are manufactured from the following:
 Air, Fossil hydrocarbons(Natural gas,crude oil,fuel oi,coal,etc)
 Mineral rock phosphates
 Natural potassium salts (potash)

 Fertilizers containing one nutrient element are called

Single nutrient fertilizers and those with a combination are
multi-nutrient or compound fertilizers.
 The most important straight fertilizers are Calcium
Ammonium Nitrate (CAN), Urea and Ground Rock
Phosphate.
 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

 OSU Soil Fertility 03 01

Anhydrous
+ + CO22
Sulfuric Ammonia
Acid
+
Nitric
acid

Ammonium Sulfate Ammonium Nitrate

Urea
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 A.N melts at 169o C.

Ammonium Nitrate is a nitrogenous fertilizer
representing 12.4% of the total nitrogen
consumption worldwide.
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: neutralization, evaporation,
solidification (prilling and granulation).
Individual plants vary widely in process detail.
Production of AN and related products
Anhydrous liquid ammonia is vaporized is allowed to react with nitric acd.
The stoichiometic 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. 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
Evaporation to Concentrate the A.N
The outlet from the neutralizer is received in an intermediate tank.
The solution should be made alkaline before being pumped (no need
for pumps in case of pressure neutralizers since the pressure will
maintain the flow) to the evaporation section (multi-effect) running
under vacuum.
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.

Mixing the Filling Material

In order to reduce the nitrogen content of A.N from 35% to 33.5%,
the proper filling material is added (about 4% by weight of powdered
limestone or dolomite or even kaolin)
3% clay can be added as a drying agent to prevent caking (34-0-0)
Prilling or Granulation
•The hot concentrated melt is either granulated (fluidize bed
granulation, drum granulation … etc) or prilled. Ammonium
nitrate is formed into droplets which then fall down a fall tower
(prill tower) where they cool and solidify. Granulation requires
more complicated plant than prilling and variety of equipment.
The main advantage of granulation with respect of environment is
that the quantity of air to be treated is much smaller and abatement
equipment is cheaper.
•.
 Final Cooling
The hot proper size granules, are then cooled (against cooled and
humid free air) down to 40C and treated with anti-caking
(usually amines) and then coated with an inert material (usually,
kaolin, limestone or dolomite) and then conveyed to the storage

Drying, Screening
The ammonium nitrate (prills or granules) is dried (usually in
drums) using hot air (steam heated), then screened to separate the
correct product size. The oversize and undersize will be recycled
either in the mixing tank (in case of prilling) or to the granulator .
 Percentage Composition
Element Ar
Let’s look at the nitrogen contents of:
Mg 24.3
Magnesium nitrate Mg(NO3)2 Na 23.1
Sodium nitrate NaNO3 N 14.0
Ammonium nitrate NH4NO3 O 16.0
H 1.0

% composition = ( nitrogen (by mass) / total mass (M r) ) x 100

Mg(NO3)2 NaNO3 NH4NO3

Mass N 28.0 14.0 28.0

Mr 148.3 85.1 80.0

% composition 18.9 16.5 35.0

 Colorless, crystalline salt
 Strong oxidizer that promotes
explosive reaction with
organic materials
 Decomposes when heated,
releasing nitrogen
 Main uses are gunpowder,
explosives, fireworks,
matches, and fertilizers
 Ammonium sulphate (A.S) 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
 Reaction of Ammonia and Sulphuric Acid:
 Liquid ammonia is evaporated in an evaporator using 16
bar steam and preheated using low pressure steam.
 The stiochiometric quantities of preheated gaseous
ammonia and concentrated sulphuric acid (98.5% wt/wt)
are introduced to the evaporator – crystalliser (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)

 Crystallization
The reaction takes place in the crystallizer where the
generated heat of reaction causes evaporation of water making
the solution supersaturated. The supersaturated solution
settles down to the bottom of crystalliser where it is pumped to
vacuum metallic filter where the A. S crystals are separated,
while the mother liquor is recycled to the crystalliser.

 Drying of the wet Ammonium Sulphate Crystals

The wet A.S 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.
 The take up in use of urea as a fertiliser at first was rather slow but
it has since become the most used solid nitrogen fertiliser in the
world, mainly because of its use for flooded rice.
 Urea is also used as a raw material for the manufacture
ofmelamine and for various urea/formaldehyde resins/adhesives
and as a cattle feed supplement,where it is an inexpensive source
of nitrogen for the build-up of protein.
 The annual global production has increased by approximately 30
Mtonnes in the last 10 years. Current world output amounts to
more than 100 Mtonnes/year.
 New urea installations vary in size of up to 3500 tonnes/day and
are typically 2000 tonnes/day units
 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
 Commercial Name Urea

 Chemical Name Carbamide or Carbonyl diamide



 Molecular Formulae CO (NH2)2



 Appearance White solid

 PH value solution 10% 9-10



 Melting point 133 C (decomposes)



 Bulk Density 700-780kg/m-3



 Solubility in water Soluble



 Total initial Nitrogen content 46%



 Content of biuret max 0.6%



 Content of moisture 0.5%



 Grain size


 0.5-3.5 mm min 90%



 Under 0.5 mm max 3 %



 Over 10 mm 0%

 Urea (carbamide) is a high-concentration nitrogenous fertilizer,
with a 46 % nitrogen content. It is produced from liquid
ammonia and gaseous carbon dioxide at about 170- 190º C and
135- 145 bar, according to the following reactions:

 CO2 + 2NH3 → NH2COONH4 (1)

 NH2COONH4 ↔ NH2CONH2 + H2O (2)

 The second reaction is dehydration of the carbamate to produce
liquid phase urea.
 Both reactions take place in the liquid phase in the same
reactor and are in equilibrium. The
yield depends on various operating parameters.
Reaction 1 is fast and exothermic and essentially goes to
completion under the industrial reaction conditions used.
Reaction 2 is slower and endothermic and does not go to
completion. The conversion (on a CO2 basis) is usually in
the order of 50 – 80 %. The conversion increases with
increasing temperature and NH3/CO2 ratio and decreases
with increasing H2O/CO2 ratio.
Several side reactions may occur in urea synthesis.
The most relevant equilibrium reactions are
 The hydrolysis reaction is the reverse reaction of the urea
formation and only takes place in the presence of water. Acids
or alkaline solutions can also accelerate the rate of hydrolysis.
In practice, residence times of urea solutions with low NH3
content at high temperatures must be minimised. Biuret must
be limited in fertiliser urea (preferably maximum of 1.2 %
EC), since biuret might cause crop damage, notably during
foliage spraying. In technical urea (e.g. used in the production
of synthetic resins), the biuret content is generally up to 0.3 –
0.4 % or much lower (even <0.15 %) depending on customer
requirements. Low NH3 concentrations and high
temperatures also favour the formation of isocyanic acid,
especially in the evaporation section of the plant, the reaction
equilibrium forming isocyanic acid is shifted to the right.
 NH4 NO3
NH4SO4
NH4 Cl
R s
e e
a p
C a
T r
O a
r-1 tor
Carbon dioxide is supplied from the ammonia plant and
compressed in the centrifugal CO2 compressor then
introduced into the bottom of the high pressure stripper,
which is a part of urea synthesis section. Liquid ammonia is
pumped from the storage tank to the urea plant and is
preheated to a temperature around 10º C. The high pressure
NH3 pump raises the pressure to 165 bars and delivers it to
the high pressure carbamate condenser. NH3 and CO2 are fed
to the synthesis section in the molar ratio of 2 for NH3/ CO2.
In the urea reactor most of the condensate carbamate is
converted to urea and water. The reaction mixture, leaving
the reactor from the overflow through internal down comer,
is distributed over the top of the stripper tubes. CO2 gas is
introduced in counter flow
The gases leaving the top of the stripper are led into the high
pressure carbamate condenser. Major parts of the stripper off-gases
are condensed gases and non-condensed NH3, CO2. They are
introduced into the bottom of the reactor where the conversion of
carbamate into urea takes place. Non-converted NH 3 and CO2 leave
the reactor to the high pressure scrubber, where major parts of NH 3
and CO2 are recovered and mixed with fresh NH3 feed through the
high pressure ejector.
The urea carbamate solution leaving the bottom part of the stripper
is sprayed on a bed of ball rings in a rectifying column. The urea
solution leaving the bottom part flows to a flash tank and then to
the urea solution storage tank (about 70- 80 % concentration). This
solution is further concentrated to a melt (98 % urea) by
evaporation under vacuum in two stages. The urea melt is pumped
to the prilling tower. The prills are received on conveyors and
transported to the bagging section.
The gases leaving the top of the stripper are led into the high
pressure carbamate condenser. Major parts of the stripper off-gases
are condensed gases and non-condensed NH3, CO2. They are
introduced into the bottom of the reactor where the conversion of
carbamate into urea takes place. Non-converted NH 3 and CO2 leave
the reactor to the high pressure scrubber, where major parts of NH 3
and CO2 are recovered and mixed with fresh NH3 feed through the
high pressure ejector.
The urea carbamate solution leaving the bottom part of the stripper
is sprayed on a bed of ball rings in a rectifying column. The urea
solution leaving the bottom part flows to a flash tank and then to
the urea solution storage tank (about 70- 80 % concentration). This
solution is further concentrated to a melt (98 % urea) by
evaporation under vacuum in two stages. The urea melt is pumped
to the prilling tower. The prills are received on conveyors and
transported to the bagging section.
The condensate containing NH3, CO2 and urea is pumped from the
NH3- water tank to the upper part of the first desorber, which is
stripped by the overhead vapours of the second desorber. The bottom
effluent of the first desorber is pumped to the hydrolyser column. In
the hydrolyser the urea is decomposed into NH3 and CO2 and fed to
the first desorber after separation in the second desorber. The
process condensate is discharged from the bottom of the second
desorber to the sewer system of the plant.
The desired temperature of the prills ranges from 60º C to 65º C. If
the temperature is 80º C- 85º C then the residual heat in the prills
causes some stretching and bursting for the polyethylene bags after
the bagging operation.
 At an economical conversion rate of NH3 and
CO2 to urea, the process design intends
nowadays to efficiently separate product urea
from the other reaction components, to recover
excess NH3,and to decompose residual
ammonium carbamate to NH3 and CO2 for
recycling into the process(“total recycling
processes”). This is usually realised by stripping
(still at high pressure) and subsequent
depressurisation/heating of the urea solution or
combinations of both
 Various strategies have been developed to realise “total recycling processes”, these
include:
 • conventional processes without stripping (older plants, provided by various
suppliers,
 • CO2 stripping processes, e.g. by Stamicarbon or Toyo’s ACES process
 • NH3 stripping processes, e.g. by Snamprogetti
 • the Isobaric Double Recycling process (IDR), applying stripping with NH3 and
CO2, by Montedison (see Section 8.4.4).
 Finally, the urea solution from the synthesis/recycling stages of the process is
concentrated via
 evaporation or crystallisation to a urea melt for conversion to a solid prilled or
granular product
 for use as a fertiliser or technical grade. In some cases, urea is produced solely for
melamine production.
 UAN solutions typically contain 28 to 32 % N but other
customised concentrations (including additional nutrients) are
produced.
 Plant capacities for the production of UAN solutions range
between 200 and 2000 tonnes/day. Most of the large scale UAN
production units are located within integrated plants where either
urea or ammonium nitrate or both are produced. Western
 Continuous and batch type processes are used for the production
of UAN. In both processes
 concentrated urea and ammonium nitrate solutions are measured,
mixed and then cooled. Figure 8.2 gives an overview.
 In the continuous process, the ingredients of the UAN solution
are continuously fed to and mixed in a series of appropriately
sized static mixers. Raw material flow as well as finished product
flow, pH and density are continuously measured and adjusted. The
finished product is cooled and transferred to a storage tank for
distribution.
 In the batch process, the raw materials are sequentially fed to a
mixing vessel fitted with an agitator and mounted on load-cells.
The dissolving of the solid raw material(s) can be enhanced by
recirculation and heat exchange as required. The pH of the UAN
product is adjusted prior to the addition of the corrosion
inhibitor.Solution AN (solid or in solution) mixing
Urea (solid or in solution) Process
 In the continuous process, the ingredients of the UAN
solution are continuously fed to and mixed in a series
of appropriately sized static mixers. Raw material flow
as well as finished product flow, pH and density are
continuously measured and adjusted. The finished
product iscooled and transferred to a storage tank for
distribution.
 In the batch process, the raw materials are
sequentially fed to a mixing vessel fitted with
anagitator and mounted on load-cells. The dissolving
of the solid raw material(s) can be enhanced by
recirculation and heat exchange as required. The pH
of the UAN product is adjusted prior to the addition of
the corrosion inhibitor.
Single supephosphate Fertilizer
 Fig (1) presents the block flow diagram for manufacturing of mono superphosphate
fertilizers and the related raw materials and pollution sources.

 The manufacturing process depends on reacting phosphate rock with sulfuric acid and
the fertilizer 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 accompanied by a rapid chemical
reaction on the particle
1) Phosphate weigh feeder
2) Feed tank for H2SO4
3 ) feed tank for water;
4) acid feeder;
5) mixer;
6) superphosphate den;
7)Single Superphosphe
(SSP);
8) Supephosphate storage site
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. The exhaust gases from the
reactor
 Multi-nutrient Compound fertilizers are made
from mixing straight fertilizers or by chemical
synthesis from the respective raw materials.
 Compound fertilizers are named by listing their

percentage content of N2, P205 and K20.

For example 10:10:20 contain 10% N2N, 10% P205
and 20% K20 .

Also called N PK Fertilizers

 For an overview of the nitrophosphate route, see Figure 7.2. The nitrophosphate process for
 producing NPK grades is characterised by the use of nitric acid for rock phosphate digestion and
 the subsequent cooling of the digestion solution in order to separate out most of the calcium
 ions from the solution as calcium nitrate crystals. The main difference to processes based on
 sulphuric acid is that it avoids the formation of gypsum. After filtration of the calcium nitrate
 crystals, the resultant NP solution is used for neutralisation and particulation as in other NPK
 processes. The final cooling temperature affects the range of NPK formulations possible with
 this process. The by-product calcium nitrate is converted into ammonium nitrate and calcium
 carbonate for CAN production or, after purification, marketed as CN fertiliser. Because of the
 required starting materials, the nitrophosphate route is usually realised integrated with ammonia,
 nitric acid and CAN production
 The remaining Fertilizers
percentage is made up of
chemicals and impurities 18 : 6 : 12

of various kinds.
27 : 2.5 : 5
 Each of the fertilizers is
designed for a particular 0 : 7 : 30

purpose.
0 : 10 : 20
 The nutrients are
balanced as to reflect the 10 : 10 : 20

uptake of the particular

24 : 2.5 : 10
crop.
Nitrophosphate
(NP) Fertilizers

NP
fertilizer