A variety of ammonia converters have been designed and used.

Zardi(1821)
gives diagrams of 17 diffrent types, plus four types of methanol synthesis
converts. Since the reaction is exothernic abd the gas volume decreases on
reaction, maximum conversion at equikibrium occurs at high pressure and low
temperature. As with methanol synthesis, the temperature profile through the
reactor must steer a compromise between inadequate rate if the temperature
es too low, and a thernodynamic limitation if the temperature es too high. The
maximum catalyst temperature is limited to about 500 C to avoid significant
decline in activity with time. The exit gas typically contains about 12 to
14%NH3, which is condensed before the renaining gas is recycled and added to
fresh gas .A very high degree of removal of NH3 is not justified economically,
so the gas mixture fed to the reactor will typically conatin in the range of 4%
NH3
In some of the more widely used designs the catalyst is held in two or three
baskets in series between which cold-shot or quench cooling (a supply of
additional synthesis gas at a lower temperature) is provided. Baskets may de
stacked above one another in a somewhat similar fashion to the reactor shown
in fig 10.7 except that cooling is provided by quench gas instead of cooling
coils. The exact design is dictated to a large extent by mechanical
consideration set by operation at a high pressure and temperature. In general
cold synthesis gas is passed between the inside of the pressure vessel and the
catalyst containers to prevent decarburization (hydrogen embrittlement) of the
pressure vessel that might occur at reaction conditions . An ICI quench
concerter is similar to that used in the ICI converter for methanol synthesis.
A radial-flow reactor may also de used . Because of the shorter path length
through the bed, smaller particle sizes e.g. 1.5 to 3 mm may de used without
excessive pressure drop. This results in a higher catalyst effectivenessfactor
and therefore a redustion in the total volume of catalyst required. Figure
10.12shows a schematic diagram of the design of a Topsoe two-bed radial flow
converter, which uses indirect cooling in a heat exchanger for interstage
cooling. The accompanying photograph is of a reactor having a capacity of
1500 tons of ammonia per day. The overhead derrick is for instalation and
removal of the catalyst basket. In the diagram, inlet gas enters at A, passes
through the narrow annulus to the bottom, where it is heated by exchange with
product gases leaving al D. This gas un then mixed with cold bypass gas, C
passes upward and A radial-flow reactor may also de used . Because of the
shorter path length through the bed, smaller particle sizes e.g. 1.5 to 3 mm
may de used without excessive pressure drop. This results in a higher catalyst
effectiveness factor and therefore a reduction in the total volume of catalyst
required. Figure 10.12 shows a schematic diagram of the design of a Topsoe
two-bed radial flow converter, which uses indirect cooling in a heat exchanger
for interstage cooling. The accompanying photograph is of a reactor having a
capacity of 1500 tons of ammonia per day. The overhead derrick is for

instalation and removal of the catalyst basket. In the diagram, inlet gas enters
at A, passes through the narrow annulus to the bottom, where it is heated by
exchange with product gases leaving al D. This gas un then mixed with cold
bypass gas, C passes upward and flows radially through the first (top) bed
fromthe outside toward the center. The product from this bed is cooled by heat
excange with inlet gas B and flows radially through the second, lower bed.
A horizontal converter may also be designedto achieve the same goals. Figure
10.13 shows a photograph of a Kellogg reactor , amd Fig. 10.14a shematic
drawing of a unit with three beds of catalyst Eschenbrenner & Wagner 1972)
The rate equation almost always used for correlation of data and prediction of
performance of industrial reactors is based on the formulation of Temkin and
Pyzhev (see temkin (1979)). The original form was derived by assuming that
the rate limiting step is the dissociative chemisorption of nitrogen to form
nitrogen atoms . These are assumed to be the main adbed species ,and their
surface concentration is determined by an equilibrium with hydrogen and
ammonia in the gas phase. (this is not the equilibrium with the actual
concentration of gaseous nitrogen , but instead with the partial pressure of
nitrogen that would exist if N2 were present in thermodynamic equilibrium
with the gaseous hydrogen and ammonia present. *The sites were further
assumed to have a linear distribution of the heat of adsorption of nitrogen. The
resulting expression for the rate of reaction is. FORMULA
The first term is for the rate of formation of ammonia and the second for the
rate of descomsition. and are both positive, and + =1 .In a
detailed review of kinetics of heterogeneous catalytic reactions ,
Temkin (1979) comments that Eq. (10.23) is unique in chemical
kinetics because it holds true for pressures varying from atm to 500
atm- a factor of 2000. No other reaction has been studied over such
wide range of pressure.
The expression has been modified in various ways .Since operation is
at high pressure; fugacities are usually substitutes for pressure. Other
derivations have used different assumptions concerning the energy
distribution of the sites and the nature of the principal absorbed
species .The net effect is that , in essence, the form of the TemkinPyzhev equation is retained , but then has a different mechanistic
interpretation .The sum of and remains 1 , but the numerical value of may vary .
Temkin proposed that =0.5 on all iron catalysts.
In various publications Boudart has commented on the kinetics and mechanism of the
synthesis .In a later review ( Boudart 1981) , he concludes that the likelythat likely ratedeterminig step is dissociative chemisorption of dinitrogen, N2 on a nonuniform iron
surface with N* as the most abundant reaction intermediate . in general accordance with
earlier views.This dissociative N2 chemisorption is followed by reaction with dissociative

hydrogen to form absorbed NH, NH2 and NH3 in succession , all in equilibrium . Ertl
(1987) has also evaluated evidence for this mechanism . Stoltse and norskov (1987)
derived a kineticexpression with parameters taken from ultrahigh vacuum conditions for
the reactants on single crystal surfaces and showed that this could describe the
observed synthesis kinetics at 375 to 500C and pressuresup to 30 MPa .Thisis interesting
in that rates surface science measurements could predict rates under industrial
conditions.
Careful experimentation with commercial iron catalysts under practical conditions has led
various researchers to the conclusion that the best correlation of the experimental data on
various individual catalysts was obtained by use of value of in the range from 0.4 to
0.75( Nielsen 1968; ; Nielsen et al . 1964 ;Guacci et al .1977). To expect that would vary
with catalyst composition is not unreasonable , but comparisons of correlations of
experimental data using values of from 0.5 to 0.75 show little or no significant
difference (Dyson & Simon 1986, Guacci et al . 1977)
Equation (10.23) clearly cannot be applicable at zero NH3 concentration.This is generally
unimportant for industrial operations , since the feed to the converter contains some NH3
from recycled gas . In tha absence of NH3 Temkin and coworkers (Temkin 1979) hace
established that the expression is of the form . FORMULA
Where K is the equilibrium constant for the reaction 1.5H2 + 0.5N2=NH3 and K2 is the
reaction rate constant for the reverse reaction .(The latter is , of course , proportional to the
constant for the forward reaction , K1) . The value of K2 seems to be independent of
pressure if fugacities instead of pressures are used in Eq.(10.25). K2 can be expressed in
the Arrhenius form , K2=Ae EIRT, but the value of E depends on the value of chosen .
Nielsen et al (1964) reported a value of E=177 kJ/mol for their (triply promoted) catalyst,
taking =0.64. Dyson and Simon (1989) calculate a value of 169 kJ/mol that is compared
to the normally quoted value of 159kJ/mol . Guacci et al ,in their analysis of the activity of
several commercial catalysts , aldo show how the comparison may vary depending on the
value of chosen and the temperature .
An extensive literature exists on ammonia synthesis , which is not surprising in view of its
central importance for the manufacture of fertilizer and explosives and the long-time study
devoted to it . The book by Nielsen (1968) gives an extensive treatment of industrial
catalysts.Composition , characterization , and detailed results of rate measurements under
industrial conditions are presented , with extensive references. In a more recent review
( Nielsen 1981), he discusses exploratory and applied research on he synthesis .Much of
the earlier understanding of the mechanism of ammonia synthesis is due to P.H. Emmett ,
who reviewed progress up to 1975 (Emmett 1975)
Surveys of various aspects of the subject may also be found in the book by Vancini
(1971).Mittash (1950)in a personal memoir describes the development of his early
concepts of promoter action and multicomponent catalysts , which led to the first
practicable catalyst composition. A detailed treatment of ammonia synthesis catalysts ,
focusing on promoters, poisons, kinetics, and thertmodynamics is givenby Jennings