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 800C 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
(Sulphur Removal)

Gas

RSH + H2
RH + H 2S
HCI + NaAlO 2
Al0OH + NaCL
H2 S + ZnO
ZnS + H 2O
Catalyst: CoMo/NiMo
Modified Alumina
Zinc Oxide

PRIMARY REFORMING
(Steam Reforming)

CH4 + H 2 O
CO + H 2O

3H 2+ CO
H 2+ CO 2

Catalyst: Nickel Oxide

SECONDARY REFORMING
(Air Addition)

CH4 + H 2O
2H 2 + [O 2+ N 2]

3H 2+ CO
2H 2O + N 2

HIGH TEMP SHIFT

(CO Conversion)

CO + H 2O

CO 2+ H 2

Catalyst: Iron/Chromium/Copper

Catalyst: Nickel Oxide

CO 2 Removal
Ammonia

AMMONIA SYNTHESIS
(Ammonia Formation)

N 2+ 3H 2

2NH 3

METHANATOR
CO/CO 2 Polishing

CO + 3H 2
CO 2 +4H 2

CH 4+ H 2O
CH 4+ 2H 2O

Catalyst: Fused Promoted Magnetite

K 2CO 3 + H 2O + CO 2
2KHCO3

2KHCO 3

K 2CO 3 + H 2O + CO 2

LOW TEMP SHIFT

(CO Conversion)

CO + H 2O

CO 2+ H 2

Catalyst: Copper/Zinc/Aluminium
Catalyst: Nickel Oxide

Diagram 1

Simplified block diagram of typical 1000 tonne/day ammonia plant

Natural Gas Feed

Air

Steam

indicating KATALCO catalyst types and volumes required

Hydrogen
400o C
o

350o C

550 C

KATALCO

200o C

290o C

400o C

10 M

KATALCO

59-3 10M

KATALCO

KATALCO

KATALCO

57-4

54-8

71-5

CO2 Removal

41-6
KATALCO

83-3

18 M

25 M

45 M

60 M

KATALCO

KATALCO

KATALCO

11-4

35-4/8

25 M

65 M

32-5 24 M

390o C

Purification

790o C

Primary Reforming

1000 C

Secondary
Reforming

420o C

High Temperature
CO Shift

220o C

Low Temperature
CO Shift

330o C

CO 2
Removal

Exit Gas Composition

N2
CO
CO2
CH4
N2 + A
CO + CO2

Volume %
69.8
9.3
10.5
10.4
-

Volume %
56.5
12.9
7.5
0.3
22.8
-

Volume %
60.3
3.0
15.6
0.3
20.8
-

Volume %
61.4
0.3
17.8
0.2
20.3
-

Volume %
74.6
0.4
0.1
0.3
24.6
-

470o C
Ammonia

Methanation

Ammonia
Synthesis

MUG
Volume %
74.2
0.8
25.0
5ppm

Loop
Volume %
63.4
9.5
24.9
<5ppm
NH3 - 2.5

Diagram 2

Simplified flowsheet for typical ammonia plant

Hydrodesulphuriser

Primary
Reformer

Air

Secondary
Reformer

High
Temperature
Shift

Low
Temperature
Shift

Steam

400oC

Cooling

550oC

Steam

350o C

H2

200o C

Steam
superheater

Natural
Gas
30
bar

1000o C
Steam
raising

790oC

390o C

220 C

420oC

Preheater

Steam
raising

Heat
Recovery

150o C

Process
Condensate

290oC
CO 2

Quench
Refrigeration

Cooling

Reboiler

Cooling

CO2 Removal

330o C
Heat
Recovery

Steam

220 bar
470o C
Cooling
Cooling

Condensate

Methanator

400o C

Quench

Boiler
Liquid Ammonia
Purge Gas
Carbon Dioxide
Ammonia Synthesis

Diagram 3