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Effectiveness Factor

This document discusses the derivation of effectiveness factor (η) for heterogeneous catalytic reactions. It shows that η depends on the Thiele modulus (φs), which is a function of rate constant (k1), effective diffusivity (De), and pellet radius (rs) for a spherical pellet catalyst. It also describes how η varies with φs, with η approaching 1 for small φs when intraparticle diffusion effects are small, and η decreasing below 1 for large φs when diffusion limitations impact the reaction rate. The effectiveness factor expression is also provided for slab catalyst geometries.

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596 views13 pages

Effectiveness Factor

This document discusses the derivation of effectiveness factor (η) for heterogeneous catalytic reactions. It shows that η depends on the Thiele modulus (φs), which is a function of rate constant (k1), effective diffusivity (De), and pellet radius (rs) for a spherical pellet catalyst. It also describes how η varies with φs, with η approaching 1 for small φs when intraparticle diffusion effects are small, and η decreasing below 1 for large φs when diffusion limitations impact the reaction rate. The effectiveness factor expression is also provided for slab catalyst geometries.

Uploaded by

Basil Thampi
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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HETEROGENOUS CATALYTIC REACTION

EFFECTIVENESS FACTOR DERIVATION

HAJA SUHAIL M.R. , KAAVYA R. & DIVYA NANDHINI


IV year CHEMICAL
Effectiveness factor at isothermal conditions

For an irreversible first order reaction A → B , at isothermal condition the rate at


surface condition can be written as  . Then the actual global rate at outer surface
condition,  .

For a spherical catalyst pellet of radius ‘Rs', mass balance over a spherical shell
volume of thickness ∆R at steady state will be:

(Rate of diffusion of reactant into element) – (Rate of diffusion of reactant out of


element) = Rate of disappearance of reactant within element due to reaction
09/28/2022
Rate of reaction per unit mass of catalyst =  k1C
Rate of reaction per unit volume of catalyst = k1Cp .
Where  p is the density of pellet.
Then the mass balance equation over the element of thickness  can be
written as

If limit is taken as  ∆R→0 and assuming that effective diffusivity is


independent of concentration of reactant the above equation can be
written as

(7)
Boundary conditions:

At the center of the pellet, (8)

At the outer surface, C = Cs at R= Rs (9)

Solving the differential equation (7) with boundary conditions


(8) and (9) following relation is obtained

(10)

Where φs is a dimensionless group defined as


The  φs is called Thiele modulus for spherical pellet . Equation (10) gives
the concentration profile of A in the pellet.

This concentration profile is used to evaluate the rate of reaction rp for the
whole pellet. Calculating the diffusion rate of reactant into pellet at
position Rs per unit mass of catalyst pellet

                                                 

Substituting the value of mp in equation (12)


Differentiating   

and evaluating the derivative at  R= Rs and substituting in equation


(13), following relation for    can be obtained for isothermal
conditions.

Then substituting the    in the rate for whole pellet in terms of
concentration at outer surface rp = k1C1 , can be written as
Where for spherical pellets of radius rs , 
φs for a first-order reaction is given as

Where k1 is rate constant, ρp is pellet density; De is effective diffusivity.
Hence, to calculate Thiele modulus, both effective diffusivity De and rate constant
k1 need to be known.
the typical plot of η vs φs   .
As the figure shows, for small values of  φs , η →1.
Equation (13) shows that small values of  φs are obtained when the:

• pellets are small


• diffusivity is large
• reaction is intrinsically slow ( catalysts of low activity).

 For  φs > 5,  η can be approximated as             .

 For such large φs  , intra-particle diffusion has a large effect on the rate.
 At this condition, diffusion into the pellet is relatively slow and reaction
occurs before the reactant has diffused far into the pellet.

 When  η →1, rate for the whole pellet is the same as the rate at surface
concentration Cs and the entire catalyst surface is fully active.
 When  η << 1, the concentration within pellets drops from Cs to
nearly zero in a narrow region near rs.
 At this condition, only the surface near the outer periphery of the
pellet is effective and the catalyst surface in the central portion of the
pellet is not utilized.
 This situation can be caused by large particles, low De or high k1 ;
that is very active catalysts.
 Hence, low effectiveness factors are more likely with very active
catalysts. More active the catalyst, the more is the possibility that
intrapellet diffusion resistance will reduce global rate.
For flat plate or slab of catalysts, opened to reactant only from one side
with all other surface being sealed to reactant, the effectiveness factor is
given as

where L = thickness of plate.


If the slab is open to reactant on both side of the plate, the expression
remains similar with L becoming the half of the plate thickness.
Book Reference :
 
•  J. M. Smith, Chemical Engineering Kinetics , McGrawHill
Book Company, 1981
•  H. S. Fogler, Elements of Chemical reaction engineering ,
Prentice Hall of India., 1999
•  J.J. Carberry , Chemical and catalytic reaction Engineering,
Dover Publications, 2001
•  O. Levenspiel , Chemical reaction engineering, John Wiley &
sons, 1995

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