Lecture 2

Nitrogen Industries
Ammonia
Nitric Acid
Urea
Ammonium Nitrate

Ammonia
All processes for synthetic ammonia are based on the pressure catalytic
reaction of nitrogen and hydrogen
Industry

Use

Fertilizer

Production of
Ammonium sulfate
Ammonium Phosphate
Ammonium Nitrate
Urea

Chemicals

Synthesis of
Nitric acid
Sodium hydrogen carbonate (sodium bicarbonate), NaHCO3
Sodium carbonate, Na2CO3
Hodrogen cyanide, HCN
Hydrazine, N2H4 (used in rocket propulsion systems)

Explosives

Ammonium Nitrate

Fibers and Plastics

Nylon and other polyamides

Refrigeration

Used for making ice, large scale refrigeration plants, air conditioning units in
buildings and plants

Pharmaceuticals

Manufacture of drugs

Pulp and paper

Ammonium hydrogen sulfite, NH4HSO3, enables some hardwoods to be used

Production of Ammonia

All processes for synthetic ammonia are based on the pressure catalytic reaction of
nitrogen and hydrogen
In 1909 Fritz Haber established the conditions under which nitrogen, N2(g), and
hydrogen, H2(g), would combine using medium temperature ( around 500oC), very
high pressure (around 250 atmospheres, i.e. 25,500kPa) with a catalyst (a porous
iron catalyst prepared by reducing magnetite, Fe3O4)
Osmium (Os) is a much better catalyst for the reaction but is very expensive.
This process produces an ammonia, NH3(g), yield of approximately 10 - 20%.
The Haber synthesis was developed into an industrial process by Carl Bosch.
The reaction between nitrogen gas and hydrogen gas to produce ammonia gas is
an exothermic equilibrium reaction, releasing 92.4kJ/mol of energy at 298K
(25oC).

2N 2 + 3H 2

Fe, 500o C, High pressure

2NH 3

H O = - 22.0 Kcal/92.4 kJ/mol

Flowsheet of production of Ammonia

Nitric Acid
Industry

Use

Fertilizer

Production of
Ammonium Nitrate

Chemicals

Synthesis of
Sodium, Potassium and Calcium Nitrate

Explosives

Ammonium Nitrate and other nitro copmpounds

Fibers and Plastics

Nylon precurser, Adipic acid production

Solvents

Such as dinitrotoluene, nitrobenzene

Ammonia Oxidation Process for the production of Nitric Acid

Fundamental steps
1. Oxidation of NH3 to NO
2. Oxidation of NO to NO2
3. Absorption of NO2 in water
4. Concentration of HNO3

Flowsheet of for the production of Nitric Acid

Urea - CO(NH2)2
Urea
Mol wt.

60.05

M.P.

132.7oC

B.P.

Decomposes

Solubility

Fairly solubility in water (110gm per 100 gm at 20oC)

Uses

Used in solid fertilizer (51%), liquid fertilizer (31%), and other

applications such as animal food, formaldehyde resins and
adhesives

Production of Urea
Raw Materials: Carbon dioxide from synthesis gas
manufacturing unit and ammonia
Process: Carbon dioxide and ammonia are compressed and
reacted at 100-200 atm, and 170oC 190oC in an
autoclave to form ammonium carbamate. Urea is
formed by dehydration in a low pressure stripping
operation
Chemical Reactions:
CO 2 + 2NH 3 NH 4 iCOi NH 2

H O = - 37.4 Kcal

Ammonium carbamate
NH 4 iCOi NH 2 CO ( NH 2 )2 + H 2 O

H O = 6.3 Kcal

Undesirable side reaction:

2CO ( NH 2 )2 H 2 NCONHCONH 2 + NH 3
Biuret

Flowsheet of for the production of Urea

Process description

Ammonium Nitrate
Urea
Mol. Wt.

60.05

M.P.

170.0oC

B.P.

Decomposes at 200oC or higher

Solubility

Soluble in water (900gm/ 1 liter at 20oC)

Uses

Agricultural fertilizer due to high nitrogen content and

explosives manufacturing

Production of Ammonium Nitrate

Raw Materials:
60% nitric acid
Liquid ammonia
Clay e.g. kieselguhr, diatomaceous earth for coating end
product to prevent explosion
Chemical Reactions:
HNO3 + NH3 NH 4 NO3

H O = - 20.6 Kcal

Flowsheet of for the production of Ammonium Nitrate

Process description