Lecture on

Non-Isothermal Catalyst Pellets (Internal Heat Transfer

Limitations)

Instructor

Prof. Bishnupada Mandal

Room No. 102, Block - K
Department of Chemical Engineering
Indian Institute of Technology Guwahati

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 Lecture 9: Internal Heat Transfer Limitations

Lecture Outline
• Recap on previous lecture
• Non-Isothermal Catalyst Pellets (Internal Heat Transfer
Limitations)
 Internal Heat Transfer Limitations

 In principle, there can also be temperature gradients inside the

particle.

 In the same way that reactants must diffuse in and products diffuse
out of the particle, the heat produced or consumed by reaction
must be conducted in or out of the particle.

 In practice, concentration gradients are more likely to occur within

the particle (it would be very rare to have external diffusion
limitations without also having internal diffusion limitations), but
temperature gradients are most likely to occur outside the particle.
 Internal Heat Transfer Limitations
 The difference is that diffusion coefficients are approximately the
same within the catalyst pores and in the gas outside the catalyst,
and if there is a difference, they tend to be lower within the pores.

 However, heat is primarily conducted in the solid portion of the

catalyst, which generally has a thermal conductivity that is very much
higher than the thermal conductivity of the fluid in the pores, at least
if the fluid phase is a gas.

 Under practical conditions, it is unlikely that temperature gradients

inside the particle will be important.

 However, there has been substantial theoretical work on the problem,

and it is one of the “classic” problems of chemical engineering, so we
will briefly consider it here.
 Internal Heat Transfer Limitations
 For simultaneous diffusion and reaction d  dC A 
in a catalyst pore, the governing  eA
D   r CA , T 
dx  dx 
equations are d  dT 
 e   H rxn r  C A , T 
s dx  dx 
 Where DeA  DA

 DeA is the effective diffusion coefficient for diffusion in the pores, and
λe is the effective thermal conductivity of the catalyst pellet. r(CA,T) is
the reaction rate, which depends both on the reactant concentration
and the temperature. The boundary conditions are

 At x = 0: CA = CAs and T = Ts
dC A dT
 At x = l 0 0
dx dx
 Internal Heat Transfer Limitations
 We have d  dC A   BCs: At x = 0: CA = CAs and T = Ts
 eA
D   r CA , T 
dx  dx 
dC A dT
d  dT   At x = l 0 0
 e   H rxn r  C A , T  dx dx
dx  dx 

 Due to the nonlinear dependence of the reaction rate on temperature,

in general it will be necessary to solve these coupled ODE’s
numerically.
 However, since the concentration gradient and temperature gradient
are driven by the same reaction, we can derive a relationship between
the concentration and the temperature by combining the above
equations.
 This is similar to what we did previously considering only external
temperature gradients.
 Internal Heat Transfer Limitations
 We have d  dC A   BCs: At x = 0: CA = CAs and T = Ts
 eA
D   r CA , T 
dx  dx 
dC A dT
d  dT   At x = l 0 0
 e   H rxn r  C A , T  dx dx
dx  dx 

 Dividing the energy equation by (-∆Hrxn)

d  dC A e dT 
and adding it to the reactant continuity  eA
D  0
dx  dx H rxn dx 
equation gives:

 Integrating this once and using the dC A e dT

DeA  0
boundary conditions at x = l gives: dx H rxn dx

 Integrating again, assuming constant

properties, and using the boundary
conditions at x = 0, gives:
 Internal Heat Transfer Limitations
 Integrating again, assuming constant
properties, and using the boundary
conditions at x = 0, gives:
 so that:

 For an exothermic reaction, ∆Hrxn is negative, and the temperature

inside the pellet is greater than the temperature at its surface. The
maximum possible temperature rise is obtained for complete
conversion of the reactant (CA = 0), i.e.  H rxn  DeAC As
Tmax 
e
 The potential for temperature gradients
inside the particle is therefore generally Tmax  H rxn  DeAC As
characterized by a dimensionless  
Ts eTs
parameter β, defined as
 Internal Heat Transfer Limitations
 We have  H rxn  DeAC As Tmax  H rxn  DeAC As
Tmax   
e Ts eTs

 The extent to which the reaction rate depends on temperature can be

characterized by a second dimensionless parameter (a dimensionless
activation energy, ) defined by Ea

RTs

 The relationship between T and CA d  dC A 

derived above can be used to eliminate  eA
D   r CA , T 
dx  dx 
CA in the energy balance, leaving a d  dT 
single equation for the temperature.  e   H rxn r  C A , T 
dx  dx 
 Internal Heat Transfer Limitations
 We have d  dC A 
 DeA   r CA , T 
dx  dx 
d  dT 
 BCs: At x = 0: CA = CAs and T = Ts  e   H rxn r  C A , T 
dx  dx 
dC A dT
 At x = l 0 0
dx dx
d 2    1  
 If that entire equation is made   1      exp   
2

d 2
   
dimensionless, using dimensionless
variables ξ = x/l and θ = T/Ts it  BCs: At ξ = 0: θ = 1
becomes. d
 At ξ = 1: 0
d

 In this equation, the Thiele modulus is

S g c A exp  Ea / RTs 
defined based on the rate constant at  l
the pellet surface temperature as: DeA
 Internal Heat Transfer Limitations
 We have d 2    1    BCs: At ξ = 0: θ = 1
  2
1      exp   
d 2
    d
0
 At ξ = 1: d

 This nonlinear equation can be integrated numerically to determine

the temperature and concentration profiles and the effectiveness
factor for particular values of the three dimensionless parameters (β,
θ, and ξ).
 For exothermic reactions, the temperature inside the pellet will be
greater than the bulk temperature, which increases the reaction rate
above what it would be at bulk conditions. This means that the
effectiveness factor can be greater than one.
 Internal Heat Transfer Limitations
 For highly exothermic
reactions with high activation
energies, there are a range of
values of  for which there
are multiple steady state
temperature and
concentration profiles for the
catalyst particle – and
corresponding multiple
values of the effectiveness
factor.
 This is seen in the figure
below for values of  between
about 0.2 and 0.5 on the
upper curves (β = 12).