496 CHAPTER 11: FIXED BED CATALYTIC REACTORS

Figure 11.3-1
Multibed adiabatic reactor for catalytic reforming. After Smith [1959], from Froment
[1974].

Figure 11.3-2
Multibed adiabatic reactor for SO3 synthesis. After Winnacker and Kuechler [1970], from
Froment [1974].

The first and most elementary type of reactor to be considered is the

adiabatic reactor. In this case the reactor is simply a vessel of relatively large
diameter. Such a simple solution is not always applicable, however. Indeed, if the
reaction is very endothermic, the temperature drop may be such as to extinguish
the reaction before the desired conversion is attained  this would be the case
with catalytic reforming of naphtha or with ethylbenzene dehydrogenation into
styrene. Strongly exothermic reactions lead to a temperature rise that may be
prohibitive for several reasons: for its unfavorable influence on the equilibrium
 11.3 FACTORS INVOLVED IN THE PRELIMINARY DESIGN OF FIXED BED REACTORS 497

Figure 11.3-3
Multibed adiabatic reactor for NH3 synthesis. After Winnacker and Kuechler [1970],
from Froment [1974].
498 CHAPTER 11: FIXED BED CATALYTIC REACTORS

conversion, as in ammonia, methanol, and SO3 synthesis; or on the selectivity, as

in maleic anhydride or ethylene oxide synthesis; or on the catalyst stability, or
simply because it would lead to unsafe operation. A solution that can be applied
to endothermic reactions, although it is not without drawbacks, is to dilute the
reactant with a heat carrier. More often, however, the reactor is subdivided into
several stages, with intermediate heat exchange. An example of such a multibed
adiabatic reactor is shown in Figure 11.3-1 for an endothermic process-catalytic
reforming of naphtha into gasoline.
The exothermic SO3- and NH3-synthesis are carried out in reactors of the
type illustrated in Fig. 11.3-2 and Fig. 11.3-3, respectively. In ammonia- or SO3-
synthesis the intermediate cooling may be achieved by means of heat exchangers
or by injection of cold feed. With SO3 synthesis the heat exchangers are generally
located outside the reactor. Special care has to be taken to provide homogeneous
distribution over the bed underneath of the quench or the flow coming from an
intermediate heat exchanger.
The temperature-composition relationships in such a multibed adiabatic
reactor are illustrated in Fig. 11.3-4 for ammonia synthesis [Shipman and
Hickman, 1968]. The Γ e curve in this diagram represents the equilibrium
relation between composition and temperature. The maximum ammonia content
that could be obtained in a single adiabatic bed with inlet conditions
corresponding to A would be 14 mole-% as indicated by point B’, and this would
theoretically require an infinite amount of catalyst. The five-bed quench
converter corresponding to the reaction path ABCDEFGHIJ permits attaining a
much higher ammonia content. The reaction path ABCDEFGHIJ evolves around
the curves Γ m , which represents the conversion-temperature relationship that
ensures maximum reaction rate in each point of the reactor. Clearly, for each bed
the question is how close the adiabatic outlet condition will be allowed to
approach equilibrium and how far the reaction mixture will have to be cooled in
the heat exchanger before proceeding to the next stage. This is a problem of
optimization, requiring a more quantitative approach. For the specific case
considered here, another possibility is to depart from the adiabatic stages in order
to follow more closely the curve of optimum reaction rates, Γ m . The continuous
removal of excess heat implied by this is only possible in a multitubular reactor.
One way of achieving this in ammonia synthesis is shown in Fig. 11.3-5. Use is
made of the feed stream to remove the heat from the reaction section [Vancini,
1971]. How well the objective is met by a proposed design (i.e., how well the
actual trajectory approximates the Γ m curve) can only be found by a more
quantitative approach involving modeling, discussed further in Parts 2 and 3 of
this chapter. In modern reactors like that of Ammonia-Casale the continuous heat
exchange is achieved by plate heat exchangers.
 11.3 FACTORS INVOLVED IN THE PRELIMINARY DESIGN OF FIXED BED REACTORS 499

Figure 11.3-4
Mole percent ammonia versus temperature diagram. After Shipman and Hickman [1968].

With other very exothermic reactions, such as air oxidation of aromatic

hydrocarbons, the number of beds would have to be uneconomically large to
limit the temperature increase per bed, so that the multitubular reactor is
definitely preferred. Cooling the reactor with the incoming reactant would be
insufficient, however, and require too much heat exchanging surface. Such
reactors are therefore cooled by means of circulating molten salts that in turn
give off their heat to a boiler. The phthalic anhydride synthesis reactor shown in
Fig. 11.3-6 [Suter, 1972] may contain up to 20,000 tubes of 2.5 cm inside
diameter. The tube diameter has to be limited to such a small value to avoid
excessive overtemperatures on the axis, a feature that is discussed later in this
chapter. A different type of multitubular reactor has to be used in natural gas or
naphtha steam reforming into hydrogen or synthesis gas, an endothermic reaction
(Fig. 11.3-7). In this case the gases are gradually heated from 500° to 850°C. To
obtain the highest possible capacity for a given amount of catalyst, heat fluxes of
75.6 kJ/m² s are applied to tubes of 10 cm inner diameter. The tubes, 10 m long,
are suspended in two rows in a furnace that may contain as many as 300 tubes.
500 CHAPTER 11: FIXED BED CATALYTIC REACTORS

Figure 11.3-5
Ammonia synthesis reactor with tubular heat exchanger. From Vancini [1971].

In several cases effluent gases have to be recycled (e.g., in catalytic

reforming  hydrogen and light hydrocarbons; in ammonia synthesis  the
non-condensed fraction of the effluent, because of equilibrium limitations on the
conversion per pass). To limit the cost of recycling and get a maximum capacity
 11.3 FACTORS INVOLVED IN THE PRELIMINARY DESIGN OF FIXED BED REACTORS 501

Figure 11.3-6
Multitubular reactor for phthalic anhydride synthesis by o-xylene oxidation. After Suter
[1972], from Froment [1974].

Figure 11.3-7
Multitubular natural gas steam reformer with furnace. From Froment [1974], after “High
Performance Process Furnaces,” M. W. Kellogg Co.
502 CHAPTER 11: FIXED BED CATALYTIC REACTORS

Figure 11.3-8
Ammonia synthesis reactors.
(a) Radial H. Topsøe converter. After Finneran et al. [1972], from Froment [1974].

(b) Horizontal multibed Kellogg reactor. After Finneran et al. [1972], from Froment
[1974].
 11.4 MODELING OF FIXED BED REACTORS 503

out of the centrifugal recycle compressor, the pressure drop over the catalyst bed
has to be kept as low as possible. This requires limiting the bed depth, which
means, in conventional reactors at least, that the diameter would have to be
increased. This is no longer possible for the giant ammonia synthesis converters,
so that other solutions had to be sought. Figure 11.3-8 shows two ways of
increasing the flow area without increasing the bed depth [Finneran et al., 1972].
Radial flow has been applied for quite a number of years already in catalytic
naphtha reforming. Clearly, in all the decisions related to the above discussion,
the following elements had to be considered all the time: technology in all its
various aspects, the rate of reaction, reaction scheme, equilibrium, catalyst
composition and properties, heat transfer, and pressure drop, with constant
reference to safety, reliability, and economics.
The same factors will, of course, have to be considered in the next stage of
design, only more quantitatively and in a way accounting for their interaction.
This stage requires some degree of mathematical modeling of the reactor.

11.4 MODELING OF FIXED BED REACTORS

In this chapter it is not possible to concentrate on specific cases and processes.
Instead, general models and principles involved in the design and analysis of any
type of fixed bed reactor, no matter what the process, will be discussed.
The development of chemical reaction engineering as a recognized
discipline and the increasing possibilities of computers have led to extensive
exploration of reactor design and performance, both in the steady and nonsteady
state. Models now range from the very simple ones that could be handled before
1960 to some very sophisticated ones aiming at a more representative description
of the geometry and phenomena.
Reactor design and analysis groups are continuously confronted with the
degree of sophistication that is required and can be justified. This is a question
that cannot be answered in a general manner. The required degree of
sophistication depends in the first place on the process, that is, on the reaction
scheme and on its sensitivity to perturbations in the operating conditions. Of
equal importance is the degree of accuracy with which the kinetic and transport
parameters are known. Figure 11.4-1 shows the problems that have to be faced in
fixed bed reactor modeling and design. It relates the aspects on microscale,
already dealt with in Chapters 2 and 3, to the macroscale, to be dealt with in the
present chapter. The modeling of the macroscale, that is, the reactor, is mainly
determined by the hydrodynamics. Is plug flow a sufficient approximation or
not?