Ammonia synthesis

Ammonia is synthesised from hydrogen (from natural gas)

and nitrogen (from the air).

Natural gas contains some sulfurous compounds which

damage the catalysts used in this process. These are removed by reacting them with zinc oxide,
ZnO + H2S

ZnS + H2O

 The methane from the natural gas is then converted to hydrogen gas by the following reactions:
CH4 + H2O 3H2 + CO

CH4 + 2H2O
CO + H2O

4H2 + CO2
H2 + CO2

Water, carbon monoxide and carbon dioxide (all of which poison the iron catalyst used in the ammonia synthesis) are removed. The carbon monoxide is converted to carbon dioxide which is removed and later used in the synthesis of urea:

CO + H2O

CO2 + H2

AMMONIA

Air is mixed in with the gas stream in a ratio of

hydrogen:nitrogen ratio of 3:1. The nitrogen and hydrogen are then reacted at high temperature and pressure using an iron catalyst to form ammonia:

The reaction

N + 3H
2

2NH

Manufacture of Nitric Acid.

There are three stages in the production of nitric acid i. The oxidation of ammonia, ii. The oxidation of nitrogen monoxide iii. The absorption of nitrogen dioxide in water.

Step 1 Oxidation of Ammonia

Oxidation of ammonia occurs in a catalytic reactor where The mixture of ammonia and air reacts to form nitrogen monoxide, on a Pt/Rh catalyst.
i. ii. iii. iv.

The catalyst gauzes are initially heated using a flaming bar, which uses hydrogen as the fuel to raise the temp to about 800c. Ammonia/air mixture containing about 10% ammonia is passed over the catalyst, the reaction is very rapid and exothermic. Thus no further external heating of the catalyst is necessary. Pressure should be maintained at 3 - 4 atm and the temperature at 800 C and 900 C. These conditions help prevent any side reactions and approximately 95% conversion of ammonia occurs.

 The main reaction

Pt/Rh catalyst

4NH3(g) + 5O2(g)

4NO(g) + 6H2O H = -903 kJ

T= 890C, P =3-4 atm

Parrarel reactions

4NH3 + 3O2 4NH3 + 4O2

2N2 + 6H2O 2N2O + 6H O

THE CATALYST
The catalyst typically consists of several woven or knitted gauzes

formed from wire containing about 90% platinum alloyed with rhodium for greater strength and sometimes containing palladium. Air pollution and contamination from the ammonia as well as poor ammonia-air mixing and poor gas distribution across the catalyst can poison the catalyst and may reduce the yield by 10%. Some of the platinum and rhodium vaporises during the reaction process and in most cases a platinum recovery system is installed below the catalyst. In this system a palladium alloy, known as a getter or catchment, allows a 60 to 80% recovery of the total catalyst losses.

Step 2 Oxidation of Nitrogen Monoxide

The nitrogen monoxide produced is passed through a heat exchanger to the condenser where nitrogen monoxide is converted to nitrogen dioxide.

The second reaction is the oxidation of nitrogen monoxide to nitrogen dioxide , secondary air is added to the gas mixture obtained from the ammonia oxidation to supply the oxygen required for oxidation
Oxygen content of the leaving stream should have content between 2 and 4% by volume to ensure maximum oxidation. The reaction

2NO(g) + O2(g) 2NO2(g)

H = -115 kJ

This reaction is also very exothermic releasing a lot of energy which is used to produce steam and/or to preheat the waste gas (tail gas). The heated waste gas is discharged to the atmosphere through a gas turbine for energy recovery. The combustion gas after this heat transfer for energy recovery has a temperature of 100 to 200C, depending on the process and it is then further cooled with water.

Step 3 Absorption of Nitrogen Dioxide into Water

The final reaction is the absorption of nitrogen dioxide in water in This

is carried out in an absorption tower, which has trays at different levels The absorber is operated with a counter-current flow of water Deionised water is brought in at the top of the tower and cascades down through the trays as the gas is drawn upwards. The absorption of the nitrogen dioxide and its reaction to nitric acid and nitric oxide take place simultaneously in the gaseous and liquid phases according to equations below.

3NO2(g) + H2O 2HNO3(aq) + NO(g)

H = -16 kJ

To maximize the yield of nitric acid, the temperature is kept low (50 C)

and the pressure high (9-10 atm) in the absorption tower. The absorption of nitrogen dioxide in water forming nitric acid is 99.9% efficient. Therefore the yield of nitric acid from ammonia is 95 x 0.999 = 94.9%.

Some of the uses of nitric acid

Manufacture of Calcium Ammonium Nitrate (CAN)

There are two stages in the production of calcium ammonium nitrate
Formation of Ammonium Nitrate Granulation

FEEDSTOCK Ammonia, Nitric acid Limestone/dolomite Reaction Gaseous ammonia and 60% w/w nitric acid react to produce an aqueous solution of ammonium nitrate (80%). NH3(g) + HNO3(aq) NH4NO3(aq) H = -92 kJ mol-1

Concentration of the Aqueous Ammonium Nitrate

The ammonium nitrate solution is also heated by steam in a heat exchanger which is operating at reduced pressure. This concentrates the ammonium nitrate solution by evaporating the water and a 96%-99% ammonium nitrate solution is formed.

Formation of Granules of CAN (Calcium Ammonium Nitrate)

To form granules of calcium ammonium nitrate, the hot

ammonium nitrate solution is mixed with ground limestone/dolomite at 180C, in a granulator. The granules formed have a moisture level of 3%, they are dried to a 0.2-0.3% moisture in a rotary dryer. This is done to prevent the final product from caking or sticking together. The granules size are reduced to the range of 2-4 mm. by crushing and screening the granules to remove the oversized and undersized product. The granules are then cooled and coated with oil and china clay because the uncoated granules are hygroscopic.