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CRE - Solid Catalyzed Reaction

1) Catalytic reactions occur in three steps - adsorption of reactants onto active sites on the catalyst surface, reaction of the adsorbed molecules, and desorption of products from the surface. 2) Kinetic models for catalytic reactions consider diffusion of reactants to and from the catalyst surface, as well as reaction rates. Film and pore resistances can limit the observed reaction rate. 3) Determining the controlling resistances and validating the assumed kinetic model involves experiments using different reactor configurations, catalyst amounts, and pellet sizes to examine the effects of mass transfer and temperature on the observed reaction rates.

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469 views47 pages

CRE - Solid Catalyzed Reaction

1) Catalytic reactions occur in three steps - adsorption of reactants onto active sites on the catalyst surface, reaction of the adsorbed molecules, and desorption of products from the surface. 2) Kinetic models for catalytic reactions consider diffusion of reactants to and from the catalyst surface, as well as reaction rates. Film and pore resistances can limit the observed reaction rate. 3) Determining the controlling resistances and validating the assumed kinetic model involves experiments using different reactor configurations, catalyst amounts, and pellet sizes to examine the effects of mass transfer and temperature on the observed reaction rates.

Uploaded by

andono kusuma jati
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© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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SOLID CATALYZED

REACTIONS
The most usefull of kinetic equations 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.

2
• 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)

3
• Step 3
Products are desorbed from the surface,
which then frees the site.

4
• Rate of reaction

For example, for the reaction :

5
Occuring in the presence of inert carrier material U, the rate
expression when adsorption of A control is :

We conclude that it is good enough to use the simplest available


correlating rate expression, hence first-order or nth-order kinetics,
to represent the surface reaction.

6
Single Cylindrical Pore, First-Order Reaction
First consider a single cylindrical pore. Reactant A diffusing into
the pore, and reacting on the surface by first-order reaction.

taking place at the walls of the pore, and product diffusing out of
the pore, as shown in the below figure

7
8
1. Use of the proper diffusion coefficient
D = molecular diffusion coefficient
De = gas and liquid in porous solid
(effective diffusion on porous)
2. Proper measure of particle size
Effective distance penetrated by gas to get to all in the interior surface, we
define a characterstic size of particle
3. Measure of reaction rate
First order kinetic reaction
For porous catalyst particles rate , based on the unit mass and unit volume
of particles, so we usually used r’ and r’’’

4. In a manner similar to what was done fo single cylindrical pore


5. Finding pore resistance effects from experiment
we use Mw as a Wagner-Weisz-Wheeler Modulus

6. Pore resistance limits


• Particles is in the diffusion free regime

• Particles is in strong pore resistance regime


7. Particles of Diffusion Sizes
•The diffusion –free regime

• The strong diffusion resistance regime


Extention
Summary- Diffusion Resistance in
Porous
In such a situation two different kinds of temperature effect may be encountered
For Plug Flow
At steady state a material balance for reactant gives :

in symbols

In differential form

Integrating over the whole reactor gives


Equation for homogenous reactions

So for first order catalytic reactions becomes


For mixed flow
Here we have, following the analysis for ɛA value
For a Reactor Containing a Batch of Catalyst and a
Batch of Gas

Extensions of the Simplest Performance Equations

There are numerous


applications of catalytic
reactions where the
fraction of solids f varies
with height z in the
reactor
Input of A = output of A + disappearance of A
For the first-order reactions this expression reduces to

For the special case where ɛA = 0, f is constant, and the


height of catalyst bed is H, we have
Experimental Devices
1 Differential (Flow) Reactor
• Consider the rate to be constant at all points within the
reactor
• Plug flow performance equation :
2 Integral (Plug Flow) Reactor
• When we use large variation in reaction rate within a reactor in the
method of analysis.
• Integral Analysis
A specific mechanism with its corresponding rate equation is tested by
integrating the basic performance equation to give

• Differential Analysis
More convenient to use with more complicated rate expressions.
3 Mixed Flow Reactor
• Requires a uniform composition of fluid throughout
• Experimental device :

• The performance equation:


Recycle Reactor
• Must put a specific kinetic equation to the test.
• Requires inserting the kinetic equation into the performance equation for recycle
reactors and integrating.

• Then plot the left vs right hand side of


the equation to test the linearity.
4 Batch Reactor for Both Gas and Solid

• Follow the changing composition with time and interpret the results with
the batch reactor performance equation

• The composition of fluid must be unfirom throughout the system at any


instant  the conversion per pass across the catalyst must be small.
Determining Controlling Resistances and the Rate Equation

1 Film Resistance

1. Using different amounts of catalyst in integral / differential


reactors for identical values for weight-time, by changing the
spinning rate in basket reactors / the circulation rate in recycle or
batch reactors.
2. If data are available, we can calculate whether film resistance to
heat trabsfer iis important and whether film resistance to mass
transport is important by comparing the observed first-order rate
constant based on the voulme of partiicle with the mass transfer
coefficient for that type of flow.
Determining Controlling Resistances and the Rate Equation

1 Film Resistance
For fluid moving past a single particle at relative velocity u Froessling
(1938) gives

while for fluid passing through a packed bed of particles Ranz (1952)
gives
Determining Controlling Resistances and the Rate Equation

1 Film Resistance

Thus to see whether film mass transfer resistance is important compare

If = gas film resistance affects the rate


If <<< the resistance to mass transport through the film may be
ignored
Determining Controlling Resistances and the Rate Equation

Nonisothermal Effects
2

The previous discussion indicates that for gas-solid systems, the most likely
effect to intrude on the rate will be the temperature gradient across the gas
film. Consequently, if experiment shows that gas film resistance is absent
then we may expect the particle to be at the temperature of its surrounding
fluid; hence, isothermal conditions may be assumed to prevail.
Determining Controlling Resistances and the Rate Equation

3 Pore Resistance
Based on unit mass of catalyst we have

The existence of pore resistance can be determined by


1.Calculation if is known.
2.Comparing rates for different pellet sizes.
3.Noting the drop in activation energy of the reaction with rise in
temperature,
4.coupled with a possible change in reaction order.
Decomposition of a Single Reactant by Two Paths
No resistance to pore diffusion. Consider the parallel-path decomposition

Here the instantaneous fractional yield at any element of catalyst surface is


given by

Strong resistance to pore diffusion.


Reactions in Series

When CA does not drop in the interior of catalyst particles, true


rates are observed, thus

Strong resistance to pore diffusion.

For mixed flow with CA going from CA0 to CAg with CR0 = 0 gives
For plug flow, integration with CR0 = 0 gives

For Plug Flow

For Mixed Flow


Extensions to Real Catalysts
So far we have considered catalyst pellets having only one size of pore. Real
catalysts, however, have pores of various sizes. A good example of this are
the pellets prepared by compressing a porous powder. Here there are large
openings between the agglomerated particles and small pores within each
particle.
If we define the degree of branching of a porous structure by α
where
α = 0 represents a nonporous particle
α = 1 represents a particle with one size of pore
α = 2 represents a particle with two pore size
Then every real porous pellet can be characterized by some
value of α
For strong diffusion in one size of pore

For strong diffusion in two sizes of pores


More generally for an arbitrary porous structure

These findings show that for large α, diffusion plays an increasingly


important role, in that the observed activation energy decreases to
that of diffusion and the reaction order approaches unity. So, for a
given porous structure with unknown α, the only reliable estimate of
the true k ratio would be from experiments under conditions where
pore diffusion is unimportant. On the other hand, finding the
experimental ratio of k values under both strong ang negligible pore
resistance should yield the value of α. This in turn should shed light
on the pore structure geometry of the catalyst.
THANK YOU

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