Introduction to Ammonia Manufacture

Ammonia is generally manufactured from natural gas using the steam reforming process. Other feedstocks and
processes are used but these are not described here. There are several reaction stages and catalysts are key to the
economic operation of modern ammonia production plants. Diagram 1 illustrates the chemistry of the ammonia
process and the basic materials of the catalysts used.

The first stage is purification where impurities, mainly sulphur compounds, are removed from the gas stream.

Steam reforming is performed in two stages. In the primary stage, the endothermic reactions take place at
pressures around 30 bar and temperatures of 800°C or higher. This is followed by an exothermic secondary
reformer where air is added to the partially reformed gas stream.

The carbon monoxide in the gas leaving the secondary reformer is converted to carbon dioxide in the shift reactors
and then removed by scrubbing from the gas stream. Any residual carbon oxides are then converted back to
methane by methanation before compression of the hydrogen and nitrogen to ammonia synthesis pressure.

The final reaction stage is ammonia synthesis where the hydrogen and nitrogen combine to form ammonia. This
reaction stage takes place at high pressure (100-350 bar) and is highly exothermic.

Diagram 2 shows a simplified block diagram of a typical 1000 tonne/day ammonia plant including details of
operating temperatures, catalyst volumes, KATALCO catalyst and gas compositions.

The economics of ammonia production require careful energy management as illustrated by the flowsheet in
Diagram 3 which shows many heat exchangers are necessary to optimised heat recovery as well as to generate the
steam required for process purposes.
 CHEMISTRY OF AMMONIA PROCESS

Natural
HYDRODESULPHURISER PRIMARY REFORMING SECONDARY REFORMING HIGH TEMP SHIFT
Gas (Sulphur Removal) (Steam Reforming) (Air Addition) (CO Conversion)

RSH + H2 RH + H 2S CH4 + H 2 O 3H 2+ CO CH4 + H 2O 3H 2+ CO CO + H 2O CO 2+ H 2

HCI + NaAlO 2 Al0OH + NaCL CO + H 2O H 2+ CO 2 2H 2 + [O 2+ N 2] 2H 2O + N 2
H2 S + ZnO ZnS + H 2O Catalyst: Iron/Chromium/Copper
Catalyst: CoMo/NiMo Catalyst: Nickel Oxide Catalyst: Nickel Oxide
Modified Alumina
Zinc Oxide

CO 2 Removal
Ammonia K 2CO 3 + H 2O + CO 2 2KHCO 3
AMMONIA SYNTHESIS METHANATOR LOW TEMP SHIFT
(Ammonia Formation) CO/CO 2 Polishing (CO Conversion)
2KHCO3 K 2CO 3 + H 2O + CO 2

N 2+ 3H 2 2NH 3 CO + 3H 2 CH 4+ H 2O CO + H 2O CO 2+ H 2
CO 2 +4H 2 CH 4+ 2H 2O
Catalyst: Fused Promoted Magnetite Catalyst: Copper/Zinc/Aluminium
Catalyst: Nickel Oxide

Diagram 1
 Simplified block diagram of typical 1000 tonne/day ammonia plant
Natural Gas Feed Steam Air
indicating KATALCO catalyst types and volumes required
Hydrogen

400o C
o
KATALCO 550 C 350o C 200o C 290o C 400o C
41-6

CO2 Removal
3 KATALCO KATALCO KATALCO KATALCO KATALCO KATALCO
10 M
KATALCO 57-4 54-8 71-5 83-3 11-4 35-4/8
3
59-3 10M 3 3 3 3 3 3
18 M 25 M 45 M 60 M 25 M 65 M
KATALCO
3
32-5 24 M

o
390o C 790o C 1000 C 420o C 220o C 330o C 470o C
Ammonia

Purification Primary Reforming Secondary High Temperature Low Temperature CO 2 Methanation Ammonia
Reforming CO Shift CO Shift Removal Synthesis

Exit Gas Composition

MUG Loop
Volume % Volume % Volume % Volume % Volume % Volume % Volume %
N2 69.8 56.5 60.3 61.4 74.6 74.2 63.4
CO 9.3 12.9 3.0 0.3 0.4 - -
CO2 10.5 7.5 15.6 17.8 0.1 - -
CH4 10.4 0.3 0.3 0.2 0.3 0.8 9.5
N2 + A - 22.8 20.8 20.3 24.6 25.0 24.9
CO + CO2 - - - - - 5ppm <5ppm
NH3 - 2.5

Diagram 2
 Simplified flowsheet for typical ammonia plant
Hydrodesulphuriser Primary Secondary High Low
Reformer Reformer Temperature Temperature
Air Shift Shift
Steam

Cooling
Steam 550oC
400oC 350o C
200o C

H2
Steam
Natural superheater
Gas
30 o
220 C
bar 1000o C 420oC
Steam Heat
790oC Steam
Recovery
390o C raising raising
Preheater
150o C Process
290oC Condensate

CO 2 Quench
400o C
Quench
Refrigeration
Cooling
330o C Steam
220 bar
Heat 470o C
Reboiler Recovery
Cooling Boiler

Cooling Liquid Ammonia

Cooling Condensate Purge Gas
Carbon Dioxide
CO2 Removal Methanator Ammonia Synthesis

Diagram 3