6

AMMONIA SYNTHESIS

The ammonia synthesis reaction is:

In most processes the reaction takes place on an iron catalyst. The reaction
pressure is normally in the range of 150 to 250 bar‚ and temperatures are in the
range of 350°C to 550°C. At the usual commercial converter operating
conditions‚ the conversion achieved per pass is only 20% to 30%53. In most
commercial ammonia plants‚ the Haber recycle loop process is still used to give
substantially complete conversion of the synthesis gas. In the Haber process the
ammonia is separated from the recycle gas by cooling and condensation. Next
the unconverted synthesis gas is supplemented with fresh makeup gas‚ and
returned as feed to the ammonia synthesis converter74.
Synthesis loop arrangements differ with respect to 1) the points in the loop
at which the make-up gas is delivered‚ 2) where the ammonia is taken out and 3)
where the purge gas is taken out53 (see Figure 6.1). The best arrangement is
shown in Figure 6.1 (A). After the gas leaves the ammonia synthesis converter‚
ammonia is condensed/removed by cooling and the recycle gas is returned to the
recycle compressor. This represents the most favorable arrangement from a
minimum energy point of view. It results in the lowest ammonia content at the
entrance to the converter and the highest ammonia concentration for
condensation74.

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 164 SYNTHETIC NITROGEN PRODUCTS

74
Figure 6.1. Schematic flow diagrams of typical ammonia synthesis loops.
(Reproduced by permission of Wiley-VCH)

When the makeup gas contains water or carbon dioxide‚ the condensation
stage is located partially or wholly between the makeup gas supply point and the
converter [see Figure 6.1 (B)]. This arrangement is used because water and
carbon dioxide are completely absorbed by condensing ammonia. The
disadvantages of this arrangement are 1) the ammonia concentration for
condensation is reduced by dilution with the makeup gas‚ 2) at equal condensing
temperatures‚ a higher ammonia concentration exists at the inlet to the converter
and 3) the ammonia produced in the vapor of the gas must be compressed with
the recycle gas in the recycle compressor74.
The design in Figure 6.1 (C) avoids the energy expenditure in Figure 6.1
(B). With this arrangement‚ recycle compression follows directly after the
ammonia is condensed and separated. Therefore it is possible to cool the recycle
gas using cooling water or air immediately before admixing the makeup gas