Lec 2 - Heterogeneous Catalysis - Part 1

Heterogeneous Catalysis: Kinetic in Porous
Catalyst Particles
Prof. Zayed Al-Hamamre
1
Chemical Engineering Department | University of Jordan | Amman 11942, Jordan
Tel. +962 6 535 5000 | 22888
Content
 Introduction
 Diffusion Mass Transfer
 External Resistance to Mass Transfer
 Mass Transfer-Limited Reactions in Packed Beds
 Diffusion through a Spherical Catalyst Pellets
 Thiele Modulus
 Effectiveness Factor
 Combining External Mass Transfer with Diffusion
Giving up is the ultimate tragedy
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Introduction
 Heterogeneous reactions are distinguished from homogeneous ones by the different phases
present during reaction.
 For the design of heterogeneous chemical reactors a special consideration should be taken for
 The transfer of matter between phases,
Transport processes play a critical role, capable to have strong influence on the degree of
conversion and the selectivity. The heat and mass transfer coefficient as well as the
exchange area are the parameters that describe the transport rate,
 The fluid dynamics and chemistry of the system.
 Additional complexity enters into the problem

 Complication of the rate expression, and
 Complication of the contacting patterns for two-phase systems
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Introduction
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
 Thus, in addition to an equation describing the rate at which the chemical reaction proceeds,
one must also provide a relationship or algorithm to account for the various physical processes
which occur.
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Examples
 Burning of carbon particle in air
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Examples
 Aerobic fermentation : Air bubble pass thorough liquid tank to the microbial cell to form
product material.
 There are up to seven possible resistance steps, only one involving the reaction
 If the steps are in series
 If the steps are in parallel 6

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Diffusion Mass Transfer
 Diffusion is the spontaneous intermingling or mixing of atoms or molecules by random
thermal motion.
 It gives rise to motion of the species relative to motion of the mixture.
 In the absence of other gradients (such as temperature, electric potential, or gravitational
potential), molecules of a given species within a single phase will always diffuse from regions
of higher concentrations to regions of lower concentrations.
 The mass transfer flux law is given according to Ficks law by
 The molar flux of A. WA is the result of two contributions:

i. JA the molecular diffusion flux relative to the bulk motion of the fluid produced by a
concentration gradient, and
ii. BA the flux resulting from the bulk motion of the fluid,
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Or
where the molar average velocity is
hence
and
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 Since the flux of A must be constant through

the stagnant film (conservation of mass), the
derivative of the flux with respect to
distance in the film must vanish
With boundary conditions:
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Equimolar Counter Diffusion
For constant total concentration
Dilute Concentrations
 When the mole fraction of the diffusing solute and the bulk motion In the direction of the
diffusion are small
<<
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Diffusion Through a Stagnant Gas
Forced Convection,
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 In a tubular flow reactor
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External Resistance to Mass Transfer
Mass Transfer to a Single Particle
where
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Example
For dilute concentrations of the solute the radial flux is
Because reaction is assumed to occur instantaneously on the external surface of the pellet,
also
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Example
 For the isomerization reaction
 If the temperature is sufficiently high, then we have very weak adsorption (i.e., low surface
coverage) of A and B: thus
 At steady state
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Example Cont.
Or where
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Example Cont.
Rapid Reaction:
 The rate of mass transfer to the surface limits the overall rate of reaction.
And the surface centration of reactant approaches zero,
 kc can be found using several correlations such as
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Example Cont.
Slow Reaction
And the surface concentration approaches the bulk fluid concentration.
 The external resistance decreases as

 The velocity across the pellet is
Increased,
 The particle size is decreased.
 The boundary layer becomes smaller and
the mass transfer coefficient (mass transfer
rate) increases,
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Diffusion from the Bulk to the External Transport
: The diffusion coefficient

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Reactant Concentration Profiles

 Reactant concentration profiles around a catalyst
pellet for reaction control and for external mass
transfer control
kr
kr
kr
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Interphase effectiveness factor
 An interphase effectiveness factor, is defined as the reaction rate based on surface conditions
divided by the rate that would be observed in the absence of diffusional limitations:
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Example
Dilute A diffuses through a stagnant liquid film onto a plane surface consisting of B, reacts there
to produce R which diffuses back into the mainstream. Develop the overall rate expression for the
L/S reaction
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Example Cont.
 The flux of A to the surface is
 Reaction is first order with respect to A
 At steady state the flow rate to the surface is equal to the reaction rate at the surface (steps in
series).
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Definitions
 The individual rate steps on the same basis (unit surface of burning particle, unit volume of
fermenter, unit volume of cells, etc.).
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Definitions
And
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Mass Transfer-Limited Reactions in Packed Beds

 For the mass transfer-limited reaction
Curried out in PBR
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The molar flow rate of A in the axial direction is
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 If the flow rate through the bed is very large, the axial diffusion can be neglected,
Or
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Hence
At steady state
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 In most mass transfer-limited reactions, the surface concentration is negligible with respect to
the bulk concentration
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To determine L the reactor length necessary to achieve a conversion X
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Diffusion through a Spherical Catalyst Pellets

 The pores in the pellet are not straight and
cylindrical;
 They are a series of tortuous, interconnecting
paths of pore bodies and pore throats with
varying cross-sectional areas.
 Effective diffusion coefficient is used to describe the average diffusion taking place at any
position r in the pellet
where
accounts for the variation in the cross-sectional area that is

normal to diffusion
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Diffusion
 Effect of pore size on the diffusivity of gas molecules
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 For the reaction
 The material balance is
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Diffusion Through a Spherical Catalyst Pellets
But
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The boundary conditions are
where
Thiele modulus
 φ21 is a measure of the ratio of "a" surface reaction rate to "a" rate of diffusion through the
catalyst pellet.
 When the Thiele modulus is large, internal diffusion usually limits the overall rate of reaction;
when φn is small, the surface reaction is usually rate-limiting.
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Reactant concentration
gradients in a sphere for a
first-order reaction.
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Reaction rate limitations.
Moderate effect of diffusion on the average rate
the concentration at the center is almost zero, and the reaction rate will be very
low in the central part of the catalyst (regime of diffusion controlled reaction)
Pore diffusion limitation

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Reactant concentration profiles around and
within a porous catalyst pellet for the cases
of reaction control, external mass transfer
control, and pore diffusion control. Each of
these situations leads to different reaction
rate expressions.
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Quiz: If the initial concentration of species A is doubled, how will the Thiele modulus
change? Tel. +962 6 535 5000 | 22888
 For large pellets, it takes a long time for the reactant A
to diffuse into interior compared to the time it takes for
the reaction to occur on the interior surface
 The reactant is only consumed n the exterior surface of
the pellet and the catalyst near the center of the pellet
wasted catalyst
 For very small pellets it takes very little time lo

diffuse into and out of the pellet interior and, as a
result, internal (fusion no Longer limits the rate of
reaction.
The rare of reaction
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Remarks
 For a first order reaction take place within a spherical catalyst pellet
 In the Thiele modulus,

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The Rate of Reaction
 At steady state, the amount of reactant entering the particle must equal that consumed by the
reaction
The overall rate is the diffusion flux into the pellet:
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Effectiveness Factor
 To measure how much the reaction rate is lowered because of the resistance to pore diffusion,
define the quantity the effectiveness factor as
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 The internal effectiveness factor for a first-order reaction in a spherical catalyst pellet
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Generally
For 1st order reaction

The characteristic length a
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Thiele Modulus
 We observe that as the particle diameter becomes very small, φn decreases, so that the
effectiveness factor approaches 1 and the reaction is surface-reaction- limited.
For small value of φn
o The concentration of reactant does not drop appreciably within the pore;
o Pore diffusion offers negligible resistance.
o It means either a short pore, slow reaction, or rapid diffusion, all three factors tending to
lower the resistance to diffusion
For large value of φn
o when φn is large (about 30), the internal effectiveness factor η is small ( η << 1) and the
reaction is diffusion- limited within the pellet
o The reactant concentration drops rapidly to zero on moving into the pore,
o Diffusion strongly influences the rate of reaction (regime of strong pore resistance).
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 For large values of the Thiele modulus,
the effectiveness factor for a first order reaction can be written as
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Other Catalyst Shapes
In which B.Cs
The characteristic length a
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Other Catalyst Shapes
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Spherical pellet
Spherical pellet
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 The overall rate of reaction in terms of φn and η
i. Decrease the radius of reaction be R (make pellets smaller);

ii. Increase the temperature;
iii. Increase the concentration; and
iv. Increase the internal surface area 54
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Nth Order Reaction

 For a reaction to take place within a spherical catalyst pellet, with
shell balance equation on A
then
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Nth Order Reaction
 For large values of the Thiele modulus, the effectiveness factor is
An approximate value for the Thiele modulus can be given as
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Nth-Order Reaction with Other Catalyst Shape

For the reaction
The reaction-diffusion equation
In which The characteristic

length a
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Summary
 The equation for the effectiveness factor in

a slab is the simplest and will be used for
all pellet shapes with the appropriate
Thiele modulus.
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Summary
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External Resistance to Mass Transfer
 If the external mass-transfer rate is low, the concentrations in the bulk fluid and external
catalyst surface are Significantly different.
 At steady state, the molar flux to the boundary equal to convective transport across the
boundary layer
Internal diffusion External mass transfer
Multiply by
in which is the Biot number or dimensionless mass-

transfer coefficient
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Combining External Mass Transfer with Diffusion

 For finite external mass transfer, the dimensionless model and boundary conditions for a
spherical catalyst pellet are
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1st order reaction in a spherical pellet with φ=1
Biot number
 With decreasing B, corresponding to slower external mass transfer the concentration profile in the pellet
becomes more uniform and the dimensionless surface concentration decreases. The lower concentration
leads to lower reaction rates.
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First-order reaction in a spherical pellet.
 As B goes to infinity, then the reaction proceeds without external mass-transfer limitations
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The controlling mechanisms for pellet reaction rate given finite rates of internal
diffusion and external mass transfer.
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Example
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Example Cont.
 Assuming the porosity and tortuosity to be 0.5 and 4, respectively
0.745 cm
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Example
Use the production rate and pellet parameters for the 0.3 cm pellet to find the unknown values
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Example Cont.
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Example Cont.
The smaller pellet is half the radius of the larger pellet,
 Decreasing the pellet size increases the production rate by almost 60%.
 This is possible only when the pellet is in the diffusion-limited regime.
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Reactor Containing Porous Catalyst
 The pellet volume consists of both

void and solid. The pellet void
fraction (or porosity) is
Expanded views of a fixed-bed reactor
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Plug Flow
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Mixed Flow
For a Reactor Containing a Batch of Catalyst
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Example
Use the data presented in the previous example to
the Thiele modulus
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Example Cont.
For an ideal gas mixture
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Example Cont.
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Overall Effectiveness Factor
 At steady state, the transport of the reactant.(s) from the bulk fluid to the external surface of
the catalyst is equal to the net rate of reaction of the reactant within and an the pellet.
 For the case when the external and internal resistance to mass transfer to and within the pellet
are of the same order of magnitude
And
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Overall Effectiveness Factor
Also
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Example
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Example Cont.
 If the flow rate through the bed is very large, the

axial diffusion (dispersion) can be neglected, i.e., if
Then
But
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Example Cont.
For
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Example Cont.
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Lec 2 - Heterogeneous Catalysis - Part 1

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Lec 2 - Heterogeneous Catalysis - Part 1

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Heterogeneous Catalysis: Kinetic in Porous

Prof. Zayed Al-Hamamre

Giving up is the ultimate tragedy

 Additional complexity enters into the problem

 If the steps are in parallel 6

 The molar flux of A. WA is the result of two contributions:

Diffusion Mass Transfer

where the molar average velocity is

 Since the flux of A must be constant through

With boundary conditions:

Diffusion Mass Transfer

For constant total concentration

Diffusion Mass Transfer

 In a tubular flow reactor

For dilute concentrations of the solute the radial flux is

And the surface centration of reactant approaches zero,

 kc can be found using several correlations such as

And the surface concentration approaches the bulk fluid concentration.

 The external resistance decreases as

: The diffusion coefficient

Reactant Concentration Profiles

 Reaction is first order with respect to A

Mass Transfer-Limited Reactions in Packed Beds

Curried out in PBR

The molar flow rate of A in the axial direction is

Mass Transfer-Limited Reactions in Packed Beds

Mass Transfer-Limited Reactions in Packed Beds

Diffusion through a Spherical Catalyst Pellets

accounts for the variation in the cross-sectional area that is

 The material balance is

Diffusion Through a Spherical Catalyst Pellets

Diffusion Through a Spherical Catalyst Pellets

Reaction rate limitations.

Moderate effect of diffusion on the average rate

Pore diffusion limitation

Diffusion Through a Spherical Catalyst Pellets

 For very small pellets it takes very little time lo

The rare of reaction

 In the Thiele modulus,

For 1st order reaction

Other Catalyst Shapes

The characteristic length a

i. Decrease the radius of reaction be R (make pellets smaller);

Nth Order Reaction

shell balance equation on A

An approximate value for the Thiele modulus can be given as

Nth-Order Reaction with Other Catalyst Shape

The reaction-diffusion equation

In which The characteristic

 The equation for the effectiveness factor in

Internal diffusion External mass transfer

in which is the Biot number or dimensionless mass-

Combining External Mass Transfer with Diffusion

Combining External Mass Transfer with Diffusion

First-order reaction in a spherical pellet.

 Assuming the porosity and tortuosity to be 0.5 and 4, respectively

 The pellet volume consists of both

Expanded views of a fixed-bed reactor

Reactor Containing Porous Catalyst

For a Reactor Containing a Batch of Catalyst

the Thiele modulus

For an ideal gas mixture