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Lecture Slides – Part 1
Objectives:
Highlight important concepts in kinetics and design of
chemical reactors for heterogeneous systems
Point out the two complicating factors in (i) the rate
expression, and (ii) the contacting patterns for two-phase
systems
Professor Jibril, Baba El-Yakubu
Chemical Engineering Department
Ahmadu Bello University, Nigeria
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Introduction
Homogeneous vs Heterogeneous system
Two complications factors while using
Heterogeneous
• Complication of the rate expression, and
• Complication of the contacting patterns for
two-phase systems
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The Complications of the Rate Equation
• Since more than one phase is present, the movement
of material from phase to phase must be considered
in the rate equation.
• The rate expression in general will incorporate mass
transfer terms in addition to the usual chemical
kinetics term.
• These mass transfer terms are different in type and
numbers in the different kinds of heterogeneous
systems; hence, no single rate expression has general
application.
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Solution:
At least two steps are involved – O2 transfer and chemical reaction
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Solution:
There are up to seven possible resistance steps, only one involving
the reaction. How many you choose to consider depends on you
and on the situation.
To get an overall rate expression, write the individual rate steps on
the same basis
or
or
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Now put all the mass transfer and reaction steps into the same rate
form and then combine. Thus
or
and if the steps are in series, as in Examples 17.1 and 17.2
If they are in parallel
Please, note:
Consider steps in series. In general, if all the steps are
linear in concentration, then it is easy to combine them.
However, if any of the steps are nonlinear, then you will
get a messy overall expression.
Therefore, you may try to bypass this nonlinear step in
one of various ways. Approximating the r, versus C, curve
by a first-order expression is probably the most useful
procedure.
Another point: in combining rates we normally do not
know the concentration of materials at intermediate
conditions, so these are the concentrations that we
eliminate in combining rates.
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Solution:
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Note: There are additive resistances. It so happens that the
addition of resistances to obtain on overall resistance is
permissible only when the rate is a linear function of the
driving force and when the processes occur in series.
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Contacting Patterns for Two-Phase Systems
There are many ways that two phases can be contacted, and for
each the design equation will be unique.
Design equations for these ideal flow patterns may be developed
without too much difficulty.
However, when real flow deviates considerably from these, we can
do one of two things: we may develop models to mirror actual flow
closely, or we may calculate performance with ideal patterns
which "bracket" actual flow.
Fortunately, most real reactors for heterogeneous systems can be
satisfactorily approximated by one of the five ideal flow patterns
of Fig. 17.1.
Notable exceptions are the reactions which take place in fluidized
beds. There special models must be developed.
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Final Thoughts on Flow Modeling
• In reactor design and scale-up, it is essential to select a
flow model which reasonably represents our setup.
• A simple reasonable model is much better than a
precise and detailed model which does not represent the
contacting.
• Often the choice of a good flow model and the
knowledge of how the flow pattern changes with scale-
up spells the difference between success and failure.
• This guides us in our approach to heterogeneous
reaction, which we will consider in the rest of the
course. 15
Solid Catalyzed Reactions
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.
Production of methanol, sulfuric acid, ammonia, and various petrochemicals,
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polymers, paints, and plastics.
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Important in the modern industrial development – more
than 80% of chemicals are affected by a catalyst.
Although a catalyst can easily speed the rate of reactions
(or conversion) a thousandfold or a millionfold, still,
when a variety of reactions are encountered, the most
important characteristic of a catalyst is its selectivity.
By selectivity, it means that, in the presence of an
appropriate catalyst, products containing predominantly
the materials desired can be obtained from a given feed.
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The following are some general observations.
1. The selection of a catalyst to promote a reaction is not
well understood; 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. - physical or crystalline structure
somehow imparts catalytic activity to a material.
3. Therefore, heating a catalyst above a certain critical
temperature may cause it to lose its activity, often
permanently. Thus, present research on catalysts is
strongly centered on the surface structure of solids.
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The following are some general observations.
4. To explain the action of catalysts, it is thought that
reactant molecules are somehow changed, energized, or
affected to form intermediates in the regions close to the
catalyst surface. Various theories have been proposed
to explain the details of this action.
- In one theory, the intermediate is viewed as an
association of a reactant molecule with a region of the
surface; in other words, the molecules are somehow
attached to the surface.
- In another theory, molecules are thought to move down
into the atmosphere close to the surface and be under the
influence of surface forces. In this view the molecules
are still mobile but are nevertheless modified.
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- In still a third theory, it is thought that an active
complex, a free radical, is formed at the surface of the
catalyst.
- This free radical then moves back into the main gas
stream, triggering a chain of reactions with fresh
molecules before being finally destroyed.
- In contrast with the first two theories, which consider
the reaction to occur in the vicinity of the surface, this
theory views the catalyst surface simply as a generator
of free radicals, with the reaction occurring in the main
body of the gas.
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5. In terms of the transition-state theory, the catalyst
reduces the potential energy barrier over which the
reactants must pass to form products.
Figure 18.1 Representation of the action of a catalyst.
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6. Though a catalyst may speed up a reaction, it never
determines the equilibrium or endpoint of a reaction.
This is governed by thermodynamics alone. Thus with or
without a catalyst the equilibrium constant for the
reaction is always the same.
7. 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.
Though there are many problems related to solid
catalysts, we consider only those which are related to the
development of kinetic rate equations needed in design.
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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:
1. 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.
2. Pore diffusion resistance which may cause the interior of the
particle to be starved for reactant.
3. Particle DT or temperature gradients within the particle. This is
caused by large heat release or absorption during reaction.
4. Film DT 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.
5. Film diffusion resistance or concentration gradients across the
gas film surrounding the particle.
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Particle DT
Surface kinetics and
Film DT
pore diffusion
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The Spectrum of Kinetic Regimes -summary
Consider a porous catalyst particle bathed by reactant A. The rate of
reaction of A for the particle as a whole may depend on:
1. Surface kinetics- adsorption, reaction, desorption
2. Pore diffusion resistance.
3. Particle DT or temperature gradients within the particle.
4. Film DT - outer surface of the particle and the main gas stream.
5. Film diffusion resistance.
For gas/porous catalyst systems slow reactions are
influenced by (1) alone, in faster reactions (2) intrudes to
slow the rate, then (3) and/or (4) enter the picture, (5)
unlikely limits the overall rate.
In liquid systems the order in which these effects intrude
is (1), (2), (5), and rarely (3) and/or (4).
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Factors which Influence the Rate of Reaction of Particles
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Factors which Influence the Rate of Reaction of Particles
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Thank you
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Parallel-bundle model for a supported FCC catalyst
G. Thomson and R. Mann, Application of stochastic pore networks to interpret adsorption
isotherms, in Adsorption: Science and Technology, E.A. Rodrigues, ed., Kluwer Academic
Publishers, Dordrecht, The Netherlands, 1989, p. 63. 29
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