Unit-2 Contd.

Solid Catalyzed Reactions

 Introduction
• With many reactions, the rates are affected by materials
which are neither reactants nor products.

• Such materials called catalysts, can speed a reaction by a

factor of a million or much more, or they may slow a reaction
(negative catalyst) .

• 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.
 Introduction (Contd…)

• The biochemical catalysts, called enzymes, are found

everywhere in the biochemical world and in living creatures.

• The man-made catalysts, mostly solids, usually aim to cause

the high-temperature rupture or synthesis of materials .

• These reactions play an important role in many industrial

processes, such as the production of methanol, sulfuric acid,
ammonia, and various petrochemicals, polymers, paints, and
plastics.
Representation of the action of a catalyst
 The Spectrum of Kinetic Regimes

Consider a porous catalyst particle bathed by reactant A.

The rate of reaction of A for the particle as a whole may depend
on:
• Surface kinetics, or what happens at the surfaces, interior or
exterior of the particle. This may involve the adsorption of
reactant A onto the surface, reaction on the surface, or
desorption of product back into the gas stream.

• Pore diffusion resistance which may cause the interior of the

particle to be starved for reactant.
 The Spectrum of Kinetic Regimes (Contd…)

• Particle ∆T or temperature gradients within the particle. This

is caused by large heat release or absorption during reaction.

• Film ∆T between the outer surface of the particle and the

main gas stream. For example, the particle may be uniform in
temperature throughout but hotter than the surrounding gas.

• Film diffusion resistance or concentration gradients across the

gas film surrounding the particle
 The rate equation for surface kinetics

For any surface of the catalyst, three steps are viewed to occur
successively.
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
Porous Catalyst Particles
 Porous Catalyst Particles

• The results for a single pore can approximate the behavior or

particles of various shapes (Spheres, cylinders etc.,). For these
systems the following apply:

1.

2. Proper measure of particle size

 Proper measure of particle size
To find the effective distance (L) penetrated by gas to get to all
interior surfaces, we define a characteristic size of particle of any
shape is defined as

• For flat plates without end effects (of thickness c)

• For cylinders (of radius R)

• For sphere (of radius R)

 Measures of reaction rates
• In catalytic reaction systems, the rate of reaction can be
expressed in a number of ways (using different bases-void
volume, weight of catalyst etc.,).
• For example, for first order kinetics the rate of reaction in its
various forms is:
 The relationship between ξ (effectiveness
factor) and MT (Thiele Modulus)
Effectiveness factor: It is defined as 'the ratio of the
real reaction rate of the catalyst particle to the
imaginary (ideal) reaction rate when the whole particle
is assumed to bathe in the surface reactant
concentration.

Thiele Modulus: It was developed to describe the

relationship between diffusion and reaction rate in
porous catalyst pellets with no mass transfer
limitations. This value is generally used in determining
the effectiveness factor for catalyst pellets.
 The relationship between ξ (effectiveness
factor) and MT (Thiele Modulus)

• The relation between ξ and MT are

for flat plates/slabs with

sealed edges
for cylinders with sealed ends
where I0 and I1 represent zero and first order (cylindrical catalyst pellets)
modified Bessel functions

For spheres (spherical catalyst

where pellets
Effectiveness factor versus MT for porous
particles of various shapes
 Finding pore resistance effects from
experiment
• To tell whether pore resistance is interfering or not to slow
the rate of reaction from the observed rate measurement for
a given catalyst pellets in a known environment, we define
Wagner-Weisz-Wheeler modulus Mw.
 Limits of pore resistance
• When reactant fully penetrates the particle and bathes all its
surfaces, then the particle is in the diffusion free regime. This
occurs when MT< 0.4 or Mw < 0.15.
• At the other extreme when the center of the particle is
starved for reactant and is unused then the particle is in the
strong diffusion resistance regime. This occurs when MT> 4 or
Mw > 4.
 Different size particles
• Comparing the behavior of particles of size R1 and R2 we find
in the diffusion-free regime

• In the regime of strong diffusion resistance

Thus the rate varies inversely proportional to the particle size.

 Pore diffusion resistance combined with
surface kinetics
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 taking place
at the walls of the pore, and
product diffusing out of the
pore.
Pore diffusion resistance combined with
surface kinetics (Contd…)
 Pore diffusion resistance combined with
surface kinetics (Contd…)
• A steady state material balance for reactant A for this
elementary section gives
Output – Input + Disappearance by Reaction = 0

On rearrangement

And taking limit as ∆x approaches zero

 Pore diffusion resistance combined with
surface kinetics (Contd…)
• The first-order chemical reaction is expressed in terms of unit
surface area of the wall of the catalyst pore; hence k" has unit
of length per time. In general, the interrelation between rate
constants on different basis given by

• Hence for cylindrical catalyst pore

• The above equation thus becomes

 Pore diffusion resistance combined with
surface kinetics (Contd…)
• This is a frequently met linear differential equation whose
general solution is

where
Distribution and average value of reactant concentration within
a catalyst pore as a function of the parameter m

This progressive drop in

concentration on moving
into the pore is seen to
be dependent on the
dimensionless quantity
mL, or MT called the
Thiele modulus.
Effectiveness Factor
Effectiveness factor as a function of Thiele
modulus
 Porous Catalyst

The results for a single pore can be applied for porous catalyst
particles of various shapes (Spheres, cylinders etc.,)

Proper diffusion coefficient: Here the molecular diffusion

coefficient D is to be replaced by the effective diffusion
coefficient of fluid in the porous solid De (m3/h.m.cat)
 Heat effects during reaction

• When reaction is so fast that the heat released (or absorbed)

in the pellet cannot be removed rapidly enough to keep the
pellet close to the temperature of the fluid, then non
isothermal effects intrude.
• In such a situation two different kinds of temperature effects
may be encountered:
– Within-particle ∆T. There may be a temperature variation within the
pellet.
– Film ∆T. The pellet may be hotter (or colder) than the surrounding
fluid.
• For exothermic reaction, heat is released and particles are
hotter than the surrounding fluid, hence the non isothermal
rate is always higher than the isothermal rate as measured by
the bulk stream conditions.

• However, for endothermic reactions the non isothermal rate

is lower than the isothermal rate because the particle is
cooler than the surrounding fluid.
• Thus our first conclusion: if the harmful effects of thermal
shock, or sintering of the catalyst surface, or drop in
selectivity, do not occur with hot particles, then we would
encourage non isothermal behaviour in exothermic reactions.
On the other hand, we would like to depress such behaviour
for endothermic reactions.
Performance Equations for reactors containing
porous catalysts
Performance Equations for reactors containing
porous catalysts (Contd…)
Performance Equations for reactors containing
porous catalysts (Contd…)

for first order catalytic reactions

For Mixed Flow
For a Reactor Containing a Batch of Catalyst
and a Batch of Gas
 Extensions of the Simple Performance
Equations
• There are numerous applications of catalytic reactions
where the fraction of solids f varies with height z in the
reactor.

• For these situations the performance equations could

more usefully be written differently. With uo as the
superficial gas velocity (velocity if solids are absent)
through the vertical reactor.
• A steady state material balance gives
• Input of A = output of A+ disappearance of A
• For the special case where εA = 0, f is constant, and the height
of catalyst bed is H, we have
 Experimental methods of finding rates
• Any type of reactor with known contacting pattern may be
used to explore the kinetics of catalytic reactions. Since only
one fluid phase is present in these reactions, the rates can be
found as with homogeneous reactions.
• The only special precaution to observe is to make sure that
the performance equation used is dimensionally correct and
that its terms are carefully and precisely defined.
• The experimental strategy in studying catalytic kinetics usually
involves measuring the extent of conversion of gas passing in
steady flow through a batch of solids.
• Any flow pattern can be used, as long as the pattern selected
is known; if it is not known then the kinetics cannot be found.
A batch reactor can also be used
 Experimental methods of finding rates contd.
• The following experimental reactors are used to
obtain kinetic data of catalytic reactions. This type of
data are required to determine the rate law
parameters, reaction order and rate constant i.e., to
obtain the complete rate equation for a given
catalytic reaction under consideration. Here the
experimental strategy is to measure the extent of
conversion of a gas passing in steady flow through a
batch of solid catalyst particles. In these reactions
only one fluid phase is present and hence the rates
can be found by a way similar to that adopted for
homogeneous reactions.
 There are different experimental reactors such as:

• Differential (flow reactor)

• Integral (plug flow) reactor
• Mixed flow reactor
• Batch reactor for both gas and solid
 Differential Reactor
A differential reactor is normally used to determine the rate of reaction as a function of
initial or entering concentration of reactant. It consists of a tube containing a very small
amount of catalyst, in the form of thin disk. Here the change in reactant concentration
through the bed of catalyst is extremely small and the reaction rate is considered to be
constant at all points within the reactor.

The performance equation for a differential reactor is

𝑊 𝑋𝐴𝑜𝑢𝑡 − 𝑋𝐴𝑖𝑛
=
𝐹𝐴0 (−𝑟𝐴′ )𝑎𝑣𝑔

From which the average rate is

ሺ𝑋𝐴𝑜𝑢𝑡 − 𝑋𝐴𝑖𝑛 ሻ 𝐹𝐴0 (ሺ𝑋𝐴𝑜𝑢𝑡 − 𝑋𝐴𝑖𝑛 ሻ 𝐹𝐴𝑖𝑛 − 𝐹𝐴𝑜𝑢𝑡

ሺ−𝑟𝐴′ ሻ = = =
𝑊/𝐹𝐴0 𝑊 𝑊

The average rate for each run – the rate at the average concentration in the reactor is
obtained by using the above equation. A series of runs gives a set of rate-concentration
data which can then be analyzed to obtain the rate law/rate equation.
 Differential Reactor contd…
The average concentration of reactant A within the reactor is given by

𝐶𝐴𝑖𝑛 + 𝐶𝐴𝑜𝑢𝑡
𝐶𝐴 𝑎𝑣𝑔 =
2
Step-wise procedure to obtain a rate equation:

i. Conduct a series of runs using different CAin.

ii. Treat the highest CAin as CA0 and use it as the basis for calculating F A0, XAin and XAout.
iii. Calculate FA0, W, XAin, XAout and CAavg for each run.
iv. Using the above equation calculate the reaction rate for each run.
v. Tabulate rate (-rA’) – concentration (CAavg) data.
vi. Apply the differential method of analysis of rate data to obtain a rate equation i.e.
to obtain kinetic/rate law parameters – order of reaction and rate constant.
 Integral Reactor

Here the variation in reaction rate within a reactor is large

owing to a significant change in the concentration of reactant
along a flow path through the reactor.

In this case we may adopt either integral or differential-

method of analysis.
Mixed Flow Reactor
Recycle Reactor
As with integral analysis of an integral
reactor, when we use a recycle reactor
we must put a specific kinetic equation to
the test.
The procedure requires inserting the
kinetic equation into the performance
equation for recycle reactors and
integrating.

Unfortunately such data would be

difficult to interpret when done using a
low or intermediate recycle ratio. So we
ignore this regime.
 Recycle Reactor (contd…)

• With a large enough recycle ratio mixed flow is approached, in

which case the methods of the mixed flow reactor (direct
evaluation of rate from each run) can be used. Thus a high
recycle ratio provides a way of approximating mixed flow with
what is essentially a plug flow device.
 Batch Reactor

• In this system we follow the changing composition with time and interpret
the results with the batch reactor performance equation.

• The procedure is analogous with the homogeneous batch reactor. To ensure

meaningful results, the composition of fluid must be uniform throughout the
system at any instant. This requires that the conversion per pass across the
catalyst be small.

• A recycle reactor without through-flow becomes a batch reactor.