Understandably, the direct synthesis of ammonia from nitrogen in the air was attempted.

However, the difficulty in the synthesis of ammonia is that nitrogen is very stable and inert. This
can be understood from the data on the bond dissociation energy, the ionization enthalpy, and the
electron affinity of nitrogen (Table 6.1).
All values are very high. The bond dissociation energy is extremely high and, as a consequence,
dissociation is expected to be very difficult. Activation by ionizing the molecule is also expected
to be nearly impossible: the value for the electron affinity of nitrogen is exceptionally high, as
illustrated by comparison with the value for oxygen, which is about 1000 times lower.
The history of ammonia synthesis is very interesting because it was the first large-scale synthesis
in the chemical industry at high pressure (>100 bar) and high temperature (circa 700 K). It is
remarkable that scientists and engineers succeeded in realizing a safe and reliable process in a
short time, even to modern standards. The reaction to be carried out is:

N2 + 3 H22 NH3 H298 = 91.44 kJ/mol (6.1)

A crucial question concerned thermodynamics. Precise thermodynamic data were not known
and, as a consequence, a strong controversy existed as to where the equilibrium is located at the
conditions at which attempts to synthesize ammonia were made.
Around 1910 it was well documented that at atmospheric pressure in a mixture of nitrogen,
hydrogen and ammonia hardly any ammonia is present. For instance, Haber found that at 1290 K
the fraction of NH3 in an equilibrium mixture of N2, H2, and NH3 (N2/H2 = 1/3 mol/mol) was
only 0.01%. These data convinced many experts, in first instance including Haber, that industrial
synthesis based on nitrogen would never be economically feasible.
Meanwhile, more reliable thermodynamic data became available. Haber extrapolated these data
to lower temperatures and concluded that an industrial process was feasible, if suitable catalysts
could be developed.
Interestingly, Haber also pointed out that an industrial process is possible even if conversion is
not complete. He proposed a recycle loop under pressure and also suggested the use of a feed-
effluent heat exchanger. These concepts are still the basis of modern ammonia synthesis plants.
In the unbelievably short period of five years (19081913), Haber developed a commercial
process in operation (30 t/d) in cooperation with Bosch and Mittasch at BASF. The group at
BASF tested over 6500 (!) catalysts and discovered that a (multipromoted) iron-based catalyst
exhibits superior activity. The catalysts used today do not differ essentially from this catalyst,
although recently a new (noble-metal-based) catalyst has been commercialized by Kellogg [1].
In the early 2000s, the maximum attainable single-train capacity was 2200 t/d, and designs for
plants with sizes of 3000>4000 t/d are already available.

Commercial Ammonia Synthesis Reactors

Ammonia synthesis reactors are classified by flow type (axial, radial or cross flow) and cooling
method.
Temperature control is crucial in ammonia synthesis: the reaction is exothermic and the heat
produced needs to be removed. Two methods are applied: (1) direct cooling and (2) indirect
cooling:
1. In the case of direct cooling in so-called quench reactors, cold feed gas is added at different
heights in the reactor.
2. Indirect cooling is achieved with heat exchangers that are placed between the catalyst beds.
An example of a reactor with direct cooling is the ICI quench reactor [5, 6], which is shown in
Figure 6.4 together with the temperatureconcentration profile.
Part of the cold feed is introduced at the top and passes downward through the annular space
between the catalyst container and the converter shell. This is a feature used in most ammonia
converter designs. It serves to keep the reactor shell, which is made of carbon steel or a low-alloy
steel, at a relatively low temperature in order to prevent hydrogenation of the carbon in the steel,
which would result in embrittlement of the shell. The gas is then heated in the feed-effluent heat
exchanger before entering the catalyst bed. The remainder of the feed is injected at the inlet of
the second and third catalyst zones resulting in a reduction of the temperature.
The single catalyst bed consists of three zones separated only by gas distributors, facilitating
catalyst unloading. The effluent gas undergoes heat exchange with the feed and leaves the
reactor at approximately 500 K. An additional feature of this reactor is a separate inlet to which
preheated feed gas can be fed to start up the reactor.
Another quench reactor is the Kellogg vertical quench converter (Figure 6.5) [5, 6]. The Kellogg
vertical reactor consists of four beds held on separate grids. Quench gas distributors are placed in
the spaces between the beds. The feed enters the reactor at the bottom and flows upward between
the catalyst bed and shell to be heated in a feed-effluent exchanger located at the top of the
vessel. The product gas outlet is also located at the top.

It is attractive to employ catalyst particles that are as small as possible to increase the efficiency
of the catalyst. However, smaller particles increase the pressure drop in the catalyst beds.
Kellogg has designed a horizontal converter [5, 6] for plant capacities in excess of 1700 t/d
(Figure 6.5), in which the gas flows through two or more catalyst beds in a cross-flow pattern. A
larger cross-sectional area is possible than in axial flow reactors, providing a larger catalytic area
per unit volume of reactor and permitting the use of smaller catalyst particles without large
pressure drop. Another design achieving this effect is a radial flow reactor. An example is the
reactor designed by Haldor Topse [5, 7] (Figure 6.6), in which two annular catalyst beds are
used through which the gas flows in radial direction. After passing downward through the
annulus between shell and internals, then up again through a heat exchanger located at the
bottom, the feed gas passes up through a central pipe, from which it flows radially through the
top catalyst bed. The gas then passes downward around the bottom bed to flow inward
radially together with the quench gas. Both the Kellogg horizontal converter and the Haldor
Topse radial flow reactor are also available as indirectly cooled reactors.
Indirect cooling [1,5] has advantages (and disadvantages) compared to direct cooling. Figure 6.7
shows an example of an indirectly cooled reactor. The cooling medium can be the feed gas or
high-pressure steam can be generated. In the latter case, the catalyst beds and heat exchangers
are often not installed together inside a single pressure vessel, but the individual catalyst beds are
accommodated in separate vessels and have separate heat exchangers. Figure 6.7 shows a typical
temperature profile and a temperatureconcentration diagram. The advantage of this type of
reactor is that heat is recovered at the highest possible temperature. However, the investment cost
is higher than that of quench reactors due to the cost of the heat exchangers.