Chapter-5

AGRO CHEMICAL INDUSTRIES

By:
Yonas D. (MSc.)
Department of Chemical Engineering
Kombolcha Institute of Technology, Wollo University, Ethiopia

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 FERTILIZERS

 Substances which are added to the soil to increase its fertility are
called Fertilizers.
 Many natural substance like leaves, cow dung, bone meal compost
etc are used to make up the deficiency of nitrogen , phosphorus
and potassium in soils. These substance are known as natural
fertilizers.
 Since the demand for fertilizers cannot be met by natural
fertilizers alone, many compounds are manufactured to provide
nitrogen, potassium and phosphorous to plants.
 These chemicals are known as artificial or chemical fertilizers.

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  A complete fertilizer contains all three
elements (nitrogen, phosphorus and
potassium), while an incomplete fertilizer
contains just one or two.
 Straight fertilizers supply only one primary
plant nutrient, either N or P or K. Example
Ammonium Sulphate (AS)
 Mixed fertilizers are physical mixtures of the
straight fertilizers.

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 Fertilizers Factories in Ethiopia

A) The plant, named :Dire Dawa

Fertilizer Complex B)Yayu Fertilizer Factory under construction

C) Moroccan Fertilizers Industry

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 Nitrogen Fertilizers
Pertinent properties of Urea:
Chemical formula : NH2.CO.NH2
Molecular weight : 60.05
Boiling point :Decomposes
 Melting point : 132.7oC
Specific gravity : 1.335
Solubility : Soluble in water
Grades : i)Fertilizer – Granular coated with non-hygroscopic dust such as
phosphate rock or limestone(40-42% Nitrogen)
ii) Liquor – Mixtures of Urea in NH3 solution( 45% total N, 30% as free
Ammonia, 15% as Urea)
iii) Slow release – contains low molecular weight polymers.

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Methods of Production:
Classification of Processes:
Ammonium carbamate decomposition
i) Ammonia and CO2 are compressed and reacted at 100-200 atm pressure and 170-
190oC in an autoclave to form ammonium carbamate ( NH4.COO.NH2 ).
ii) Urea is formed by dehydration in a low –pressure stripping operation.
iii) Process modifications occur in recycle of unreacted NH3-CO2 and percentage
excess NH3 in reactants.
Chemical Reactions:

i) CO2 + NH3 NH4.COO.NH2 ΔH= - 37.4 Kcal

ii) NH4.COO.NH2 NH2.CO.NH2 + H2O ΔH= + 6.3 Kcal

Ammonium carbamate Urea

Undesirable side reaction:

2NH2.CO.NH2 NH2.CO.NH. CO.NH2 + NH3

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Biuret
 Manufacture of Urea( Montecatini Process)
Raw Materials:
CO2 from synthesis gas
NH3
Quantitative Requirements:
Basis: 1 ton of Urea (99%)
Plant capacity: 100-1500 tons/day

Content Once -through Partial Recycle Total Recycle

NH3 , tons 1.15 0.88 0.60

CO2 , tons 1.47 0.91 0.77

Power, KWH 210 70 110
Cooling water, 120 70 110
tons
Steam, tons 1.8 2.0 2.4

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Process Description:
1) Ammonia and CO2 are compressed separately and added to the high
pressure autoclave.
2) It must be water-cooled due to the highly exothermic nature of the
reaction.
3) The average residence time in the autoclave is 1.5-2 hours.
4) A mixture of Urea, Ammonium carbamate, water and unreacted
NH3+CO2 results.
5) This liquid is fed to a special flash evaporator containing a gas-liquid
separator and condenser at 140OC and 27 atms pressure.
6) Unreacted NH3,CO2 and H2O as a solution are removed and recycled
(partial recycle option)
7) An aqueous solution of carbamate-Urea is passed to the atmospheric
flash drum where further decomposition of carbamate takes place. 8
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 Cont…d

8. The off-gases from this step can either be recycled (total recycle
option) or sent to NH3 processes for making chemical fertilizer.
9. The 80% aqueous urea solution can be sent to a vacuum
evaporator to obtain molten urea containing less than 1% water.
10. The molten mass is then sprayed into a granular solidification
tower.

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 Manufacture of Urea

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Major Engineering Problems:
 Autoclave variables
Urea production rate is varied by the following variables.
Temperature
Pressure
NH3/CO2
Feed rate
i) Urea production rate is increased by increasing pressure.
ii) Urea production rate is increased with increasing temperature to a
maximum at 1750C -1800C and then reduced sharply.
iii) Use no excess ammonia.

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Uses of Urea:
Urea is used as solid fertilizer about 53%.
It is also used as liquid fertilizer around 31%
It is used as animal feed.
It is used to produce Urea-Formaldehyde resins, Melamine-
Formaldehyde resins and adhesives.
The very popular nitrogen fertilizer is a Urea-Ammonium
nitrate solution.
Urea-Formaldehyde resins is used as a plywood adhesive

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 Phosphate Fertilizers

Important phosphate fertilizers are

1) Super phosphate of lime ( Calcium super phosphate)
2) Triple super phosphate
End Uses:
It is used as Fertilizers(42%)
It is also used as soaps and Detergents (37%)
It is used as Food chemicals (12%)

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 Phosphoric acid(H3PO4)
Pertinent Properties:
i)Molecular weight: 98 ; ii)Melting point :42.4oC ; iii)Boiling point :Loses
of hydration of water at 213oC
iv)Solubility : Soluble in water
v)Grades: White solid ; vi)Density : 1.83 gm/cc at 20oC
Methods of Production: Wet process
1) Wet process Raw Materials:
 strong sulfuric acid leaching
 Hydrochloric acid leaching Phosphate rock contains gypsum
2) Electric furnace process Sulfuric acid
 Direct conversion at plant site
 Oxidation and hydration of Quantitative Requirements:
Basis: 1 ton of 100 % H3PO4
Phosphorus  Phosphate rock( 32 % P2O5) : 2.5 tons
3) Blast furnace process  Sulfuric acid (93-98%) : 2 tons

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 Manufacture of Phosphoric acid

Chemical Reactions:
1) Ca3(PO4)2 +3H2SO4 ---------------- 2H3PO4 + 3(CaSO4.2H2O)

Side Reactions:
2) CaF2 + H2SO4 + 2 H2O ---------------- 2HF + CaSO4.2H2O
3) 6 HF + SiO2 ---------------------------- H2SiF6 + 2 H2O

Process description:
1) Phosphate rock is ground to 65% and 200 mesh size fed to a chute and weak
phosphoric acid is used to clean the reactor tank.
2) Strong sulfuric acid is passed to maintain the acid and rock ratio at the desired
level.
3) A single reactor is used to convert 9 % conversion in 4- hours.
4) A series of 4-5 continuous mixing tanks are used to control the backmixing.
5) The gypsum-Phosphoric acid is passed to a pan vacuum filter where 40 % acid is
removed and cake is washed with water.
6) The gypsum is reacted with ammonium carbonate and gives ammonium sulfate.
7) Filtrate thickness is measured as 2 inches and collected in the form of Potash
crystals.
8) Most of the wet process acid is converted to high concentration chemical fertilizers.
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 Calcium Phosphates (Superphosphate & Triple superphosphate)

Superphosphate: It is made by reacting phosphate rock with sulfuric acid and contains 16-
20% P2O5.
Triple superphosphate: It is made by reacting phosphate rock with phosphoric acid contains
42-50 % P2O5.
Quantitative Requirements:
Raw Materials:
Basis: 1 ton of superphosphate
i)Phosphate rock
Phosphate rock : 0.5-0.6 tons
ii) Dilute sulfuric acid
Sulfuric acid : 0.3- 0.4 tons
iii) Phosphoric acid
Phosphoric acid : 0.3-0.7 tons
Super phosphate Chemical reactions:

Chemical Reactions:
1) [Ca3(PO4)2]3 . CaF2 +7 H2SO4------------------ 3 CaH4 (PO4)2 . 7CaSO4 +2HF

Silica impurity removal:

2) 4HF + SiO2 ------------------ SiF4 + 2H2O
3) 3SiF4 + 2H2O ---------------------2H2SiF6 + SiO2
4) H2SiF6 + NaCl ------------- Na2SiF6 +2HCl
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Superphosphate Process Description:
i) Phosphate rock lumps are crushed in a aw crusher and ground to 100 mesh
size.
ii) Dilute sulfuric acid and phosphate rock are passed to continuous blender of
12 m length.
iii) Then it is passed to Den where granules are formed and stored for 24 hours.
iv) This granules are passed to Rotary granulator for further granulation.
v) Then it is passed to the Rotary dryer and finally superphosphate is collected
vi) SiF4 and HF are scrubbed with water and then removed with silica.
Triple superphosphate
Triple superphosphate: It is made by reacting phosphate rock with phosphoric acid contains
42-50 % P2O5

Chemical Reactions:

[Ca3(PO4)2]3 . CaF2 +14 H3PO4------------------ 10 CaH4 (PO4)2 +2HF)

Quantitative Requirements:
Basis: 1 ton of Triple superphosphate
Phosphate rock : 0.45 tons ( 32 % P2O5)
Phosphoric acid : 0.62 tons ( 56 % P2O5)
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Triple Superphosphate Process Description:
i) The acid at 60oC- 70oC is mixed with ground rock in a continuous mixer.
ii) Then it is passed to continuous belt where the reaction is completed in 15-20
minutes.
iii) The product is next granulated , dried and bagged.

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Superphosphate and Triple super Phosphate Process flow Sheet

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 Potassium Nitrate (KNO3)
(Saltpeter)
Pertinent Properties:
i)Molecular weight: 101.1 ; ii)Melting point :334oC ; iii)Boiling point :Decomposes at 400oC
iv)Solubility : Soluble in water , glycerol and Ammonia
v)Grades: White solid ; vi)Density : 2.109 gm/cm3

End Uses:
Raw Materials:
Ammonium nitrate i) Potassium nitrate is used as food preservative of
Potassium chloride salted meat ;
Potassium hydroxide ii) It is used as thickening agent in soups okra soup in
Nitric acid west African cuisine
iii)It is used as fertilizers
iv) It is used as toothpaste for sensitive teeth
Chemical Reactions: v)It is also used as kidney tablets in Thailand.

NH4NO3 + KCl KNO3 +NH4Cl

ii) KOH + NH4NO3--------- KNO3 + NH4Cl

iii)HNO3 + KCl ------------- KNO3 + HCl

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 Mixed Fertilizers

 A fertilizer which contains more than one plant nutrients is called mixed
fertilizer.
 Mixed fertilizer Containing nitrogenous, phosphatic and potash fertilizers
in definite proportions. Such fertilizers are called NPK fertilizers

NPK Value:-
 The efficiency of a fertilizer is expressed in terms of NPK Value. N,P,K
stands for Nitrogen, Phosphorous and Potassium.
 It expresses the nitrogen, phosphorous and potassium contents in terms
of elementary nitrogen, P2O5, and K2O respectively .
 Example: NPK Value of 10:5:20 for a mixed fertilizer means that the
particular fertilizer contains 10% nitrogen, 5% P2O5 and 20% K2O.

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 Pesticides
 Pesticides are chemical compounds useful in killing pests.

 Generally, a pesticide is a chemical compound or even a biological

agent such as a bacteria, virus, antimicrobial, or disinfectant that
prevents, incapacitates, or kills pests.

Classification
• Insecticides – Insects
• Herbicide – Plants
• Rodenticides – Rodents (rats & mice)
• Bactericides – Bacteria
• Fungicides – Fungus
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Larvicides – Larvae 22
 Dichloro-diphenyl-trichloroethane (DDT) Manufacture

Raw Materials:
i) Ethanol
ii) Benzene
 Ethanol is converted to chloral by oxidation with chlorine and
acetaldehyde
 Benzene is chlorinated to Monochlorobenzene.

Chemical Reaction:

CCl3CHO + 2 C6H5Cl ------------- (C6H4Cl)2 CHCCl3 + H2O

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 Process Description of Dichloro-diphenyl-trichloroethane (DDT)

 Dry chlorine is first absorbed into ethanol at room temperature conditions. Then
the alcohol turns to a syrupy fluid.
 The operation occurs in a chlorination tank which produces chloral hydrate and
HCl.
 From the chlorination tank, HCl is separated by using partial condenser.
 The incondensable HCl is sent for gas recovery using scrubbing.
 The liquid stream from the partial condenser is sent back to the chlorinator.
 The condensate from the chlorination tank is sent to a still, where distillation is
facilitated in the presence of sulphuric acid which acts as a desiccant.
 Then still is operated at high temperature and for this purpose, steam is used for
heating purposes.
 After the reaction, the batch still produces the waste acid as a product at the bottom
and the clear chloral liquid at the top along with the vent gases.
 Cont…d
 The purified crude chloral is further sent to distillation to remove chloral
hydrates present in the stream.
 Chloral is produced from the distillation unit and chloral hydrate is recycled
back to the chloral hydrate converter to chloral.
 Then purified chloral, monochlorobenzene, oleum are allowed to enter the
DDT condensation unit.
 After condensation, the organic layer and spent acid are withdrawn. The
organic layer consists of DDT and monochlorobenzene. This is first
neutralized with soda ash.
 After reaction, the organic layer is sent to a dryer where the vapors
generated from dryer enters total condenser followed with gravity settling
separator. The gravity settling unit separates monochlorobenzene from other
organic impurities.
 The dryer produces DDT powder which is sent for casting/pelletization
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process to obtain the DDT in either flakes or in pellets for sale.
 Manufacture of DDT

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 Benzene Hexachloride (BHC) Manufacture
Raw Materials:
i) Benzene
ii) Chlorine
Process Description:
i) Benzene and chlorine are passed into a cooled reactor containing a Ultra violet
light level is well
ii) Then it is passed through the tubular reactor with a fluorescent lamp mounted
on the axis of the reaction tube in a protective glass tube.
iii) After the reaction is completed the molten BHC is obtained at the bottom.
iv) Benzene is taken as overhead and recycled.

Chemical Reaction:
C6H6 + 3Cl2 ----------------- C6H6Cl6

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