Monolith Reactors

Catalysis Engineering
June 2, 1999

1 Why monoliths
In the previous chapters we have used mass- and heat balances to describe mass and heat transport limitations
in catalytic reactors. In this process we have derived dimensionless numbers, such as the Thiele modulus and
the Carberry number Ca. All these numbers indicate that in most cases (i.e. when one doesnt want
limitations) it would be best to have the highest possible specific surface area, i.e. the shortest diffusional
lengths. In other words, it is often favorable to have small particles.

On the other hand, many of our calculations have focussed on particles sizes where mass or heat transfer
limitations did occur. The reason we often have such larger particles is that in reactor design also the
momentum balance is considered. Solving the momentum balances for a packed bed lead to equations such as
the Ergun equation for pressure drop in packed beds.
These pressure drop correlations have in common that for increasing surface area the pressure drop will rise.
In some applications high pressure drop is not a large issue. For instance, in a slow heterogeneously catalysed
process a large residence time will be required. The resulting low superficial velocities are not likely to pose
a large problem of pressure drop. On the other hand, fast reacting systems with high superficial velocities
benefit most from high surface areas. Here pressure drop may cause a problem.
It can be argued that the high pressure drop is not only caused by the size of the particles, but also by the
irregularity of the packing, i.e. the random way in which they are ordered geometrically in the column. For
instance, the friction factor for a regular structure like a pipe is significantly lower than for a packed bed.
Moreover, there are more phenomena which are difficult in packed column design that are caused by this
irregularity.

Maldistribution and incomplete wetting. Maldistribution in three phase reactors occurs when some
areas in the column have more liquid holdup (and thus less gas holdup) than other areas. In a severe
case of maldistribution, some catalyst particles are not wetted (completely) by the liquid. These
particles do not convert as much as completely wetted particles. Wall effects are also a form of
maldistribution.
Fouling and Attrition. Erosion can occur when particles are moving with respect to each other.
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All these considerations have led to the development of structured catalysts. There are several types of
structured catalysts, such as the Sulzer packing, the Three Levels of Porosity Reactor and the Bead String
Reactor. For more information on these types of reactors, as well as monolith reactors, the interested reader is
referred to Moulijn and Cybulski (1998).
All these catalytic reactor concepts have in common that a higher level of structuring is found relative to a
packed bed to overcome some of the before-mentioned limitations. In some cases, the distinction between
catalyst and reactor is lost, and the entire internal structure of the column is optimized to enhance mass and
heat transfer and to lower energy consumption (pressure drop). The regular structure itself is made up entirely
of catalytically active material or is coated on the surface with an active washcoat.
One type of common structured reactor, the monolith reactor, will be treated in more detail in this chapter.
The monolith reactor was developed for the cleaning of exhaust gases from combustion processes, both in
cars and large power plants. For these processes, the monolith reactor offers an irresistible combination of low
pressure drop (two to three orders of magnitude lower than in packed beds) and high surface area.
Recently, an effort is made, amongst others by Delft University, to use the monolith concept in other areas,
including three phase processes and counter current flow operations.

2 Geometry
The world monolith comes from Greek, and in interpreted here as made from one piece (of stone). Most
monolith reactors consist of one piece of ceramic material. This ceramic block contains a large number of
parallel channels extending over the entire length of the block, separated by thin walls. The channels usually
have a small diameter, resulting in large specific surface areas, combined with the pressure drop of a (small)
pipe. There are no open passages from one channel to neighboring ones, so the quality of distribution at the
entrance of the block is maintained throughout the entire length of the block.
The channels themselves can be square, hexagonal or triangular, etc. Another way of producing monoliths is
to use corrugated plates of metals. Ceramic monoliths are extruded to a (currently) maximum length of one
meter and a diameter of approximately 50 cm. Larger volumes of monolith structures are obtained by stacking
smaller building blocks.
Various channel geometries exist: square, hexagonal, triangular, finned channels, but also channel geometries
produced by wrapping up flat sheets with corrugated sheets in between. The monolith themselves have a
square, oval, racetrack (cf. Indy 500), triangular or round geometry, depending on the application of the
structure.

3 Engineering Correlations, single phase

Engineering correlations for pipes are readily available in the literature. These can be used for monoliths,
assuming the feed of each channel is the same. The monolith can then be regarded as a large number of
(parallel) tube reactors. For instance, the fanning equation for pressure drop in pipes (Bird et al., 1960)

is used successfully to model the pressure drop in monoliths. Off course this simple equation can be improved
to cover some other phenomena. In the entrance region, the flow pattern develops from an initially flat profile
to a parabolic one. (A similar phenomenon will be observed with mass and heat transfer later). This consumes
energy, and is accounted for by a term with a vanishing contribution for long channels. Also, the in- and
outlet effects can be included in a fashion, similar to the modeling of pipes

For mass and heat transfer, we can use the Chilton-Colburn analogies: for mass and heat transfer the equation
will have the same form

In Perry and Green (1984) we find for heat transfer for round tubes

which closely resembles the Sherwood correlation used for monoliths

The expressions for Sh and Nu contain a term for infinitely long channels and a contribution for entrance
effects. The length of the entrance effects depends on the flow properties (Re) and the fluid properties (Re, Sc,
Pr ). For a typical Re value of 100, a Sc value of 1 and 1000 for gases and liquids, respectively, and a channel
diameter of 1 mm the entrance length is 0.1 and 10 m, respectively. (Since mass transfer is enhanced by the
entrance effects, the fact that monoliths can only be extruded to a length of 1 m is less of a problem, if the
entrance effects are repeated every once in a while.)
So, we can conclude that well established solutions for the mass, heat and momentum balances can be used to
create a reactor model for monolith reactors with single phase feed. And, indeed, these models have been
applied successfully.