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 Gas

HYDRODESULPHURISER (Sulphur Removal)

PRIMARY REFORMING (Steam Reforming)

SECONDARY REFORMING (Air Addition)

HIGH TEMP SHIFT (CO Conversion)

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

CH4 + H 2 O CO + H 2O

3H 2 + CO H 2+ CO 2

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

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

CO + H 2O

CO 2 + H 2

Catalyst: Iron/Chromium/Copper

Catalyst: Nickel Oxide

Catalyst: Nickel Oxide

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

K 2CO 3 + H 2O + CO 2

N 2+ 3H 2

2NH 3

CO + 3H 2 CO 2 +4H 2

CH 4 +H2 O CH 4+ 2H 2 O

CO + H 2O

CO 2 + H 2

Catalyst: Fused Promoted Magnetite Catalyst: Nickel Oxide

Catalyst: Copper/Zinc/Aluminium

Diagram 1

Simplified block diagram of typical 1000 tonne/day ammonia plant

Natural Gas Feed Hydrogen 400o C Steam Air
indicating KATALCO catalyst types and volumes required

KATALCO

550 C

350o C

200o C

290o C

400o C

41-6 10 M
3

KATALCO

KATALCO

KATALCO

KATALCO

CO2 Removal

KATALCO

KATALCO

KATALCO

57-4
3

54-8
3

71-5
3

83-3
3

11-4 25 M
3

35-4/8 65 M
3

59-3 10M
KATALCO

18 M 32-5 24 M
3

25 M

45 M

60 M

390o C

790o C

1000 C

420o C

220o C

330o C

470o C Ammonia Ammonia Synthesis Loop Volume % 63.4 9.5 24.9 <5ppm NH3 - 2.5

Purification

Primary Reforming

Secondary Reforming

High Temperature CO Shift

Low Temperature CO Shift

CO 2 Removal

Methanation

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 -

MUG Volume % 74.2 0.8 25.0 5ppm

Diagram 2

Simplified flowsheet for typical ammonia plant

Hydrodesulphuriser Air Primary Reformer Steam Secondary Reformer High Temperature Shift Low Temperature Shift

400oC H2 Natural Gas 30 bar

Steam

550oC

Cooling 350o C 200o C

Steam superheater

1000o C 390o C 790oC Preheater 290oC CO 2 Refrigeration Cooling 330o C Heat Recovery Steam 220 bar Steam raising

420oC Steam raising 150o C Quench Quench

220 C Heat Recovery Process Condensate 400o C

Reboiler

470o C Cooling Cooling Boiler Liquid Ammonia Purge Gas Carbon Dioxide Ammonia Synthesis

Cooling

Condensate

CO2 Removal

Methanator

Diagram 3