CHAPTER - 6

biuret

Fertilizers and Phosphoric acids

 Fertilizers and Essential elements for plant growth
■ A fertilizer is a material that furnishes one or more of the chemical elements
necessary for the proper development and growth of plants.
■ The most important fertilizers are chemical or mineral fertilizers, manures,
and plant residues.
■ Plant Nutrients: are chemical elements that are essential for the proper
development and growth of plants (sixteen)
Chemistry of manufacture of phosphoric acid
■ Phosphorus is an essential plant nutrient taken up by plant roots,
usually as the dihydrogen phosphate ion (H2PO4- ) derived from
phosphoric acid, H3PO4.

■ About 90% of the phosphoric acid produced is used to make 

fertilizers and other are used in soft drinks and as a supplement in
feed given to cattle, pigs and poultry

■  It is mainly converted into three phosphate salts which are used as
fertilizers:
 Triple superphosphate (TSP),
 Diamonium hydrogen phosphate (DAP)
 Monoammonium dihydrogen phosphate (MAP
 Manufacture of phosphoric acid
■ Phosphoric acid is made by two processes:
a) the 'wet' process
b) thermal process
■ The thermal method normally produces a more concentrated and purer
product, but is energy intensive (because of the manufacture of phosphorus
 itself.
■ Acid produced by the 'wet' route is less pure but is used in the manufacture of
fertilizers.
A) Wet process
■ In this method fluorapatite (phosphate rock, 3Ca3(PO4)2.CaF2 reacted by
(93%) sulfuric acid in a series of well-stirred reactors.
■ This results in phosphoric acid and calcium sulfate (gypsum) plus other
insoluble impurities.  
■ Water is added and the gypsum is removed by filtration along with other
insoluble materials (e.g. silica).
■  Fluoride, as H2SiF6, is removed at a further stage by evaporation.
Cont.…….
■ Although the reaction takes place in stages involving calcium dihydrogen
phosphate, the overall reaction can be represented as:

■ However, there are side reactions; for example with calcium fluoride and
calcium carbonate present in the rock:

■ Fluorosilicilic acid is an important by-product and from the manufacture of

hydrogen fluoride.
■ It can be neutralized with sodium hydroxide to form sodium
hexafluorosilicate which is used to make aluminum fluoride for
manufacture of aluminum.
■ The product from the 'wet process' is impure but can be used for fertilizer
without further purification
■  Alternatively it can be evaporated further to ca 70% P2O5, a solution called
superphosphoric acid which is used directly as a liquid fertilizer.
Cont.…….
■ To make industrial phosphates, the acid is purified by solvent extraction
using methyl isobutyl ketone (MIBK) in which the acid is slightly soluble
and concentrated to give 60% P2O5 content.
■ This acid can be further purified using solvents to extract it from heavy
metals and defluorinated (by evaporation) to produce a product of food
grade quality
B) Thermal process
■ The raw materials for this process are phosphorus and air:

■ Initially, phosphorus is sprayed into the furnace and is burnt in air at about
1800-3000 K.
■ Most processes uses undried air and many involve the addition of steam to
the phosphorus burner to produce and maintain a film of condensed
polyphosphoric acids to protect the stainless steel burner tower (externally
water cooled)
■ The products from the burner tower pass directly into a hydration tower
where the gaseous phosphorus oxide is absorbed in recycled phosphoric acid:
Flow diagram of Conversion of Phosphate rock to Phosphoric Acid
Manufacture of nitrogenous fertilizers
Urea

■ Is the main N2 fertilizer and used as cattle feed supplement

(protein food supplements)
■ it is cheap and used as an ingredient in the manufacture of
melamine plastics and various adhesives (Urea
Formaldehye,urea melamine formaldehyde)
■ It is used in the manufacture of resins and coatings
■ Textiles anti-shrink agents and ion exchange resins
■ intermediate in the manufacture of ammonium sulfamate,
sulfamic acid and pthalocyanines
■ Reaction of ammonia and carbon dioxide at high pressure
forming ammonium carbamate, which is then dehydrated by
applying heat, forming urea and water
■ 2 NH3 + CO2 NH2COONH4(l) CO(NH2)2+ H2O
■ Both reactions take place in the liquid phase in the same reactor
and are in equilibrium.
■ Reaction 1 is fast and exothermic and essentially goes to
completion under the industrial reaction conditions used
2 NH3 + CO2 NH2COONH4(l)
■ Reaction 2 is slower and endothermic and does not go to
completion
NH2COONH4 CO(NH2)2(l)+ H2O
 Manufacturing process of Urea
■ Urea is produced from ammonia and carbon dioxide in two
equilibrium reactions:
• 2NH3 + CO2 NH2COONH4 ammonium carbamate
• NH2COONH4 NH2CONH2 + H2O urea
■ The urea manufacturing process is designed to maximize these
reactions while inhibiting biuret formation:
•2NH2CONH2 NH2CONHCONH2 + NH3 biuret
■ This reaction is undesirable, not only because it lowers the yield
of urea, but because biuret burns the leaves of plants.
■ This means that urea which contains high levels of biuret is
unsuitable for use as a fertilizer.
■ Urea solution from the process is concentrated via evaporation
or crystallization to a urea melt for conversion to a solid prilled
or granular product.
solid Urea
 Ammonium nitrate
■ Its also nitrogenous fertilizers that contains 33.5 to 34.5 %
nitrogen
■ is produced by neutralizing 50 to 70 wt-% aqueous HNO3 with
gaseous NH3
NH3 + HNO3 NH4NO3
■ The reaction is highly exothermic and proceeds rapidly and 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: neutralization, evaporation and solidification
(prilling or granulation).
■ Neutralization is carried at low pH in the first stage (acidic
condiions) neutral pH in the second stage.
Cont.……
 Potash Fertilizer
■ Fertilizers that supplies potassium commonly added to improve the yield and
quality of plants growing in soils that are lacking of essential nutrient
■ Potassium is an essential plant nutrient and is required in large amounts for
proper growth and reproduction of plants.
■ Potassium found to occur very commonly in the combined form as naturally
occurring minerals.
 Classification of potassic fertilizers
■ Natural: Potassic minerals, Wood ash and Sea weeds
■ Processed: Murate of potash (KCl) and Sulphate of potash
(K2SO4)
■ Synthetic: Potassium nitrate(KNO3) and Potassium
orthophosphate (KHPO4)
Manufacturing of potassium fertilizer
■ KCl is commercially manufactured using any one of the minerals;

1. Sylvinite or sylvite and

2. Carnallite.
 Two main steps involved in the manufacture of this fertilizer.
1. Mining of the K mineral
2. Separation of the main ingredient and purifying.
 Cont.…..
1. Mining of the K mineral
• The ore (650 to 2,500 feet below the earth’s surface) is mined and
brought over to the surface by electrically operating elevators and
machineries.
2. Separation of the main ingredient and purifying that involves
the following process:
A. Grinding: potassic ore ground to fine size and screened to get
only the ore of required size.
B. Lixiviation/solutioning or converting the ore into solution form
 Dissolving of the ore in hot water and NaCl solution (brine) for
obtaining a mixture of KCl + NaCl
 Sylvinite (KCl) is separated from NaCl through increasing the
temperature of the reaction that will increase the formation of
more KCl and the solubility of NaCl will stop after a stage.
■ The process is continued till a saturated solution of KCl is
obtained.
 Cont.…..

C. Crystallization

■ The saturated solution containing both KCl and NaCl is

suddenly cooled in a vacuum and the KCl separates out as
crystals while NaCl remains in the solution

D. Separation

■ Crystallized KCl can be separated out by mechanical means and

it is dried, powdered and used.
 Manufacture of super phosphate and triple super phosphate fertilizers
Manufacturing of super phosphate or single superphosphate
(Ca(H2PO4)2)
■ Is the first chemically manufactured commercial fertilizers that are
produced as a combination of rock phosphate and concentrated sulfuric
acid.
■ The production of superphosphate consists of three distinct steps.
Step 1 - Phosphate rock blending and grinding
■ Phosphate rock from different sources have different phosphate,
fluoride and silica contents.
■ These rocks are mixed in the blending plant to produce a product with a
total phosphate concentration of 15%.
■ The phosphate rock mixture is passed through a hammer mill which
reduces the particle size to 0.5cm or less.
■ The coarsely ground rock is then passed through an air swept roller mill
(Bradley Mill) to attain a rock grist of approximately 75% less than 75
microns.
 Cont.…..
Step 2 - Superphosphate manufacturing
■ The ground rock and sulfuric acid are reacted in a horizontal
mixer with the feed rate of 25tonne/hr. of phosphate rock and
14.5tone/hr. of 98.0% sulfuric acid to form partially matured
super phosphate in Bradfield den
■ Then matured superphosphate cake is cut out with a rotating
cutter wheel after a retention time of approximately 30 minutes.
Reactions

Ca3(PO4)2 + 2H2SO4 + 4H2O CaH4(PO4)2 + 2(CaSO4.2H2O)

CaF2 + H2SO4 + 2H2O CaSO4.2H2O + 2HF

4HF + SiO2 SiF4 + 2H2O

3SiF4 + 2H2O SiO2 + 2H2SiF6

Overall reaction
CaF2.3Ca3(PO4)2 + 7H2SO4 + 3H2O 3CaH4(PO4)2.H2O + 2HF +
7CaSO4 Single super phosphate
 Cont.…..
Step 3 - Granulation
■ The granulation process is card out in granulation
circuit consists of a pulveriser, granulation drum and
classifier.
■ The pulveriser breaks up any lumps in the product
before it is fed to the granulation drum.
■ The granulation drum rolls and agglomerates the
superphosphate to form granules.
■ The granules are passed out of the end of the drum and through a
classifier (wire screen).
■ The superphosphate continues to cure in the store for
about two weeks and the product is dressed (oversize is
passed through a hammer mill after screening) before
dispatch.
 Cont.….

■ If sulfuric acid is used, single or normal, superphosphate

(SSP) is produced, with a phosphorus content of 16–21 %
as phosphorous pentoxide (P2O5).

■ -If phosphoric acid is used to acidulate the phosphate rock,

triple superphosphate (TSP) is produced with a phosphorus
content of 43–48 % as P2O5.