Chapter 18
Solid Catalyzed Reactions
There are two broad classes of catalysts: those that operate at close to ambient temperature with biochemical systems, and the
man-made catalysts that operate at high temperature.
The man-made catalysts, mostly solids play an important role in many industrial processes, such as the production of methanol,
sulfuric acid, ammonia, and various petrochemicals, polymers, paints, and plastics.
Although a catalyst can easily speed the rate of reactions a thousandfold or a millionfold, still, when a variety of reactions are
encountered (in Petroleum), the most important characteristic of a catalyst is its selectivity. By this we mean that it only changes
the rates of certain reactions, often a single reaction, leaving the rest unaffected.
The following are some general observations.
1. The selection of a catalyst to promote a reaction is not well understood; therefore, in practice extensive trial and error
may be needed to produce a satisfactory catalyst.
2. Duplication of the chemical constitution of a good catalyst is no guarantee that the solid produced will have any
catalytic activity
3. In terms of the transition-state theory, the catalyst reduces the potential energy barrier over which the reactants must
pass to form products
4. Though a catalyst may speed up a reaction, it never determines the equilibrium or endpoint of a reaction. This is
governed by thermodynamics alone.
5. Since the solid surface is responsible for catalytic activity, a large readily accessible surface in easily handled materials
is desirable. By a variety of methods, active surface areas the size of football fields can be obtained per cubic
centimeter of catalyst.
We wish to evaluate the kinetic behavior of reactants in the presence of this material and then use this information for design.
The Spectrum of Kinetic Regimes
18.1 THE RATE EQUATION FOR SURFACE KINETICS
The most useful for our purposes supposes that the reaction takes place on an active site on the surface of the catalyst. Thus
three steps are viewed to occur successively at the surface.
Step 1. A molecule is adsorbed onto the surface and is attached to an active site.
Step 2. It then reacts either with another molecule on an adjacent site (dual-site mechanism), with one coming from the main
gas stream (single-site mechanism), or it simply decomposes while on the site (single-site mechanism).
Step 3. Products are desorbed from the surface, which then frees the site.
Rate expressions derived from various postulated mechanisms are all of the form
Now, in terms of the contact time or space time, most catalytic conversion data can be fitted adequately by relatively simple
first- or nth-order rate expressions
18.2 PORE DIFFUSION RESISTANCE COMBINED WITH SURFACE KINETICS
Single Cylindrical Pore, First-Order Reaction
First consider a single cylindrical pore of length L, with reactant A diffusing into the pore, and reacting on the surface by a first-
order reaction
At steady state a material balance for reactant A for this elementary section gives
Rearranging gives
and taking the limit as x approaches
In general, the interrelation between rate constants on different bases is given by
Hence for the cylindrical catalyst pore
Thus in terms of volumetric units
…. 3
This is a frequently met linear differential equation whose general solution is
Where
where M1 and M2 are constants , evaluated with two boundary conditions
With the appropriate mathematical manipulations
Hence the concentration of reactant within the pore is
10
This progressive drop in concentration on moving into the pore is shown in Fig. 18.4, and this is seen to be dependent on the
dimensionless quantity called the Thiele modulus
To measure how much the reaction rate is lowered because of the resistance to pore diffusion, define the quantity called the
effectiveness factor as follows:
In particular, for first-order reactions because the rate is proportional to the concentration. Evaluating the average
rate in the pore from Eq. 10 gives the relationship
For small mL, or mL < 0.4, we see that = 1, the concentration of reactant does not drop appreciably within the pore; thus
pore diffusion offers negligible resistance. This can also be verified by noting that a small value for mL = L means either
a short pore, slow reaction, or rapid diffusion, all three factors tending to lower the resistance to diffusion.
For large mL, or mL > 4, we find that = 1/mL, the reactant concentration drops rapidly to zero on moving into the pore, hence
diffusion strongly influences the rate of reaction. We call this the regime of strong pore resistance.
18.3 POROUS CATALYST PARTICLES.
related with MT f or the various particle shapes as follows:
Where