Lecture 6

Fluid-solid catalytic reactions: external diffusion and heat transfer

effects
Introduction:
Having considered the rates and mechanisms of reactions at solid surfaces, we will now investigate
how those chemical rate processes are coupled to the physical rate processes that transport
reactants to the active sites on the surface and transport products away from those sites.

As discussed in the previous section, for a catalytic reaction occurring in a porous catalyst pellet,
we can envision the overall reaction as a series of seven sequential steps:

(1) Transport of reactants to the surface of the pellet.

(2) Transport of reactants to active sites inside the pores.
(3) Adsorption of reactants onto the surface at active sites.
(4) Reaction on the surface.
(5) Desorption of products from the surface.
(6) Transport of products out of the pores to the pellet surface.
(7) Transport of products from the pellet surface to the bulk fluid.

For the generic catalytic reaction A→B, this can be illustrated schematically as

We have already considered steps (3)-(5), the reaction steps. Now we will consider steps (1), (2),
(6), and (7) – the transport steps.
For a spherical catalyst particle, we expect that transport limitations lead to a profile of reactant
concentration that qualitatively looks like the curve labeled (c) in the picture shown below.

Far from the catalyst pellet, there is some bulk concentration of reactant (CAb). This is the variable
that we would like to use in our reactor design equations, and is generally the concentration in
which we are interested (at the end of the reactor, this is what comes out). There is, in general,
some concentration drop across a boundary layer near the external surface of the particle, so that
the concentration at the external surface of the particle (CAs) differs from the bulk concentration.
If the concentration at the particle surface were exactly the same as that in the bulk, there would
be no driving force for transport of reactant from the bulk to the surface. The concentration drop
across the boundary layer is usually described in terms of a mass transfer coefficient, kg. The flux
of A across the boundary layer (moles per area per time) is given by NA = kg(CAb – CAs). The
reactant concentration decreases further within the particle, as the reactant simultaneously diffuses
into the pores and reacts on the pore walls. If there were no concentration gradient, there would
be no driving force for transport of reactant into the particle. The coupled diffusion and reaction
inside the particle has been the subject of much study, and will be discussed in detail later on. In
general, we want to model the simultaneous reaction and diffusion in the pores to obtain a total
reaction rate for the whole particle as a function of the concentration at the particles exterior
surface, and we want to model the transport across the boundary layer so that, finally, we obtain
the reaction rate in terms of the bulk concentration.

There are 3 limiting cases for the concentration profiles. These are illustrated above, as labeled in
the plot. If external mass transfer (diffusion from the bulk to the exterior surface of the particle)
is rate limiting, then the majority of the concentration drop will be across the external boundary
layer, as shown in curve (d). The reaction rate, in terms of the bulk concentration, will be
approximately given by kgCAb (moles per time per external particle surface area). If internal mass
transfer (pore diffusion) is the rate limiting step, then the majority of the concentration drop will
be inside the catalyst pellet, as illustrated in curve (b). The reaction rate will depend on factors
like the pellet size and pore geometry. If there are no transport limitations (reaction is rate-
limiting) then the concentration will be nearly equal to the bulk concentration throughout the pellet,
as illustrated in curve (a). If resistances to reaction, external mass transfer, and internal mass
transfer are all comparable, then a concentration profile like curve (c) will be observed.

External Mass Transfer Limitations:

Before analyzing the more complicated diffusion and reaction inside the pellet, we will consider
the external mass transport to the particle surface.

Diffusion across a boundary layer with reaction at a solid surface is illustrated schematically above.
If the reactant is consumed in a 1st order reaction at the solid surface, then the reaction rate is r″ =
kr CAs. The mass transfer rate across the boundary layer is NA = kg(CAb – CAs). Both of these rates
are in moles (or molecules) per area per time. At steady state, these two rates must be equal
(otherwise there would be accumulation or depletion of A at the surface). This allows us to
eliminate the unknown concentration at the surface (CAs) and write the rate in terms of the bulk
concentration (CAb). Doing this gives

kr CAs = kg(CAb – CAs)

from which

and the rate is

k g kr
r ''  N A  CAb  keff CAb
kr  k g
where the effective rate constant is
The two limiting cases of this expression are (1) a reaction-limited situation, where kr << kg, and
therefore keff ≈ kr, and (2) a mass transfer limited situation where kr >> kg, and therefore keff ≈ kg.

Note the similarity of this expression to the one for the effective rate constant for a pressure
dependent unimolecular reaction and the effective rate constant for a solution phase reaction that
is affected by diffusion of the reactants to each other. In all three of these cases, two processes
occur in series (sequentially). For unimolecular reactions, activation by collision must first occur,
followed by reaction to give products. For liquid-phase reactions, diffusion of the reactants to
each other must first occur, followed by reaction to give products. For the heterogeneous reaction
considered here, transport to the surface must first occur, followed by reaction to give products.
In all of these cases, we observe that the effective rate constant is the geometric (or harmonic)
mean of the first order rate constants for the processes that are occurring in series.

If, instead of a 1st order reaction at the surface we had an nth order reaction at the surface, then the
rate would be related to the bulk concentration by

n
 r '' 
r ''  kr  CAb  
 kg
 

Except for special cases (i.e. n = 0, 1, 2) this can’t be easily solved to give the rate explicitly in
terms of CAb, but it can always be solved iteratively.

External Heat Transfer Limitations:

So far, we have dealt almost exclusively with reactions occurring at constant temperature
(isothermally), and have written equations to describe changes in concentrations, but not changes
in temperature. However, since heat transfer limitations near and within a catalyst particle are
closely related to mass transfer limitations, it makes sense for us to treat them together in this set
of notes. We will pay much more attention to equations describing changes in temperature (energy
balances) and will very often deal with non-isothermal reactions and reactors.

It is often the case that temperature changes across the external boundary layer are more important
than concentration changes. These are correlated in the same way, using a heat transfer coefficient.

q = hf (Tb – Ts)

where q is the heat flux (energy per area per time) to the particle surface, hf is a heat transfer
coefficient, and Tb and Ts are the bulk and surface temperatures, respectively. An energy balance
at the surface shows that this flux must be equal to the rate at which energy is consumed by
reaction. This is the reaction rate multiplied by the heat of reaction, ∆Hrxn r″. But this is not as
simple as the analysis of mass transfer, because the reaction rate is strongly and nonlinearly
dependent on the temperature (where as it depends linearly on concentration for the assumed 1st
order reaction). For combined heat and mass transfer limitations, we can write the coupled balance
equations:

kr C As  k g  C Ab  C As 
H rxn kr C As  h f Tb  Ts 

Including the Arrhenius dependence of the rate constant on temperature, this is

 E 
A exp  a  C As  k g  C Ab  C As 
 RTs 
 E 
H rxn A exp  a  C As  h f Tb  Ts 
 RTs 

Eliminating CAs from the equations using

hf
CAs  CAb  Tb  Ts 
H rxn k g

gives

 E  hf 
H rxn A exp  a  C Ab  Tb  Ts   h f Tb  Ts 
 RTs   H rxn k g 

This can’t readily be solved analytically, but can be solved numerically. We can show graphically
that this equation can lead to multiple steady states (multiple solutions of this equation) for the
temperature in the catalyst when ∆Hrxn is negative (exothermic reaction). The above equation can
be rearranged to give

 E 
k g A exp  a  C Ab
h f Ts  Tb    H rxn   RTs 
 E 
k g  A exp  a 
 RTs 
The term on the left-hand-side can be identified as the heat transfer rate (flux of heat away from
the particle) while the term on the right-hand-side can be identified as the heat release rate by the
chemical reaction. It is the effective rate constant (the harmonic mean of the reaction rate constant
and the mass transfer coefficient) multiplied by the heat of reaction and the bulk concentration of
reactant. When plotted vs. Ts, the left-hand-side is a straight line, and the right-hand-side is a
sigmoidal (s-shaped) curve. These curves can intersect at 1 or three points, depending on the
values of the parameters. This is illustrated in the plot shown below, where they intersect at 3
points (3 steady states possible). For slightly different parameter values, there would be a single
intersection at a low temperature or a single intersection at a high temperature. This is similar to
the multiple steady states that can be observed in a continuous stirred tank reactor (CSTR). It can
lead to ‘ignition’ and ‘extinction’ phenomena in catalyst particles, where they suddenly jump from
the low-reaction-rate steady-state to the high-reaction-rate steady-state. For this situation, the
middle steady state is unstable. We will return to the issue of stability when we discuss CSTR’s.
Similar phenomena can result from internal heat transfer limitations, and this will be discussed
below.