External Diffusion

Effects on
Heterogeneous
Reactions

Chapter 2
 Objectives
• Discuss Fick's Law and diffusion.

• Define the mass transfer coefficient, explain what it is

function of and how it is measured or calculated.

• Analyze PBRs in which mass transfer limits the rate of

reaction.

• Discuss how one goes form a region mass transfer

limitation to reaction limitation.

• Apply the shrinking core model to analyze catalyst

regeneration.
 Revision
7 steps in a catalytic reaction
 Revision
1. Mass transfer (diffusion) of the reactant(s) from the bulk fluid to
the external surface of the catalyst pellet

2. Diffusion of the reactant from the pore mouth through the catalyst
pores to the immediate vicinity of the internal catalytic surface

3. Adsorption of reactant A onto the catalytic surface

4. Reaction on the surface of the catalyst

5. Desorption of the products from the surface

6. Diffusion of the products from the interior of the pellet to the pore
mouth at the external surface

7. Mass transfer of the products from the external pellet surface to

the bulk fluid
 Diffusion
• Definition:
– the spontaneous intermingling or mixing of atoms or
molecules by random thermal motion. Mass transfer is
any process in which diffusion plays a role

• The molar flux is just the molar flow rate, FA, divided by
the cross sectional area, AC, normal to the flow.

FAz  AcWAz (1.1)

C Av
WAz 
Ac (1.2)
 FAy|y+y
y FAx|x+x
x+x, y+y, z+z

V=xyz
FAz|z+z
FAz|z
x+x, y, z+z FAz=WAzxy
x x, y, z x, y, z+z
FAy=WAyxz
FAx|x FAy|y
z FAx=WAxyz

Molar  Molar   Molar   Molar 

Flow rate  Flow rate   Flow rate    Flow rate  
       

 in 
z  out 
 z  Δz 
 in 
y  out 
 y  Δy
ΔxΔy W  ΔxΔy W  ΔxΔz W  ΔxΔz W 
Az z Az z  Δz Ay y Ay y  Δy

Molar   Molar 
Flow rate   Flow rate   Rate of   Rate of 
    
   
 Generation   Accumulation 


 in 
x  out 
 x  Δx
C
ΔyΔz W  ΔyΔz W  r ΔxΔyΔz  ΔxΔyΔz A
Ax x Ax x ruzinah A
Δx isha@gargoyle t
(1.3)
Divide by xyz for rectangular coordinates,

WAx WAy WAz C A

    rA 
x y z t (1.4)

For cylindrical coordinates, (rederive)

1  WAz C A
  rWAr    rA 
r r z t (1.5)
 Molar Flux
• Molar flux of A, WA (moles/time/area) with respect to fixed
coordinate system

WA = J A + B A (1.6)

• JA = diffusional flux of A with respect to bulk

motion
• BA = flux of A resulting from bulk flow
= CAV, where V=molar average velocity
 Binary Diffusion
• More than 1 species,

V=∑yiVi Vi= particle velocity of i

(1.7)
yi=mole fraction of i

• Thus for 2 species, A and B,

WA=JA+CAV
(1.8)
WA=JA+yA(WA+WB)
-in term of mole fraction of A
 Fick’s Law
• Adolph Fick made his entry into this world
in 1829 in Cassel, Germany.

• Talented in mathematics and physics

• Fick's first contribution as a physicist was

made in 1855 when he was just 26 years old

• Fick’s First Law

J A  cDAB y A
(1.9)
• Combine eq. 1.8:

WA  cDAB y A  y A (WA  WB )
(1.10)

• CONSTANT TOTAL concentration

WA   DAB C A  C AV
(1.11)
 Binary Diffusion
• 5 conditions

– Equimolar Counter Diffusion (EMCD)

– Dilute Concentrations
– Diffusion through a stagnant Gas

– Forced Convection

– Diffusion and convective transport

Equimolar Counter Diffusion
WA =-WB
A B

A B

Knowing :
WA  J A  y A [WA  WB ]  J A  [WA  (WA )]

Thus ,
WA  J A  cDAB y A (1.12)
 Dilute Concentration
• The diffusion of solutes in dilute concentration do not much differ.

• Thus,
WA  J A   DAB C A (1.13)

• For porous catalyst with small pore radii, Knudsen diffusion occurs
when mean free path of molecules is greater than catalyst pore
diameter,

WA  J A   DK C A (1.14)

Knudsen diffusivity
 Diffusion through a Stagnant Gas
• WB = 0
• Involve more than one phase where one
species readily diffuse to the other phase
(A) while another one cannot (B).

WA = JA + yAWA
 Forced Convection
JAz

JAx

• JAz is small in comparison with bulk flow contribution in that direction

J Az  0
Thus, WAZ  J AZ  BAZ
v FA
WAz  BAz  C AVz  C AU  CA  (1.15)
Ac Ac
U  Velocity of forced convection
 Diffusion and Convective Transport
Molar Flow rate

dC A
FAz  AcWAz  [ DAB  C AU Z ] Ac
dz (1.16)

Similar expression of eq 1.3

  2C A  2C A  2C A  C A C A C A C A
DAB  2   2 
U x U y U z  rA 
 x y z  x y z t
2

(1.17)
Simplified of eq 1.17 (assuming One Dimension at steady state):

 2C A C A
DAB U z  rA  0 (1.18)
z 2
z isha@gargoyle
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 Types of Boundary Conditions
1. Specify a concentration a boundary
              
   

2. Specify a flux at a boundary

Cross-section
a) No mass transfer across a boundary of a pipe
r=R
[E.g., at pipe wall]
           
      r =0

therefore
           
     
                
b) Reaction at a boundary is equal to the molar flux                                     
                                                        Cont’
                       

         =

c) Diffusion flux to a boundary (from z =  to z = 0) is equal to the convective flux

away from the boundary (at z = 0).
      

                                                      
e.g.,                                                          
                                                                                                                    
                                                      

at

ruzinah isha@gargoyle
=
 Cont’

        
                                                                
                                                   
3. Planes of Symmetry
[E.g., cylinder]
                      at                                     

Look at Table 11-2 for DAB values depends on temperature and pressure
 Modeling Diffusion Without
Reaction
Step 1: Perform a diffrential mole balance on a particular species A

Step 2: Substitute for FAz in terms of WAz

Step 3: Replace WAz by the appropriate expression for the

concentration gradient

Step 4: State the boundary conditions

Step 5: Solve for the concentration profile

Step 6: Solve for the molar flux

Look at Example 11-1!

 EXAMPLE 11-1 (Revision)
CAb at z = 0
FAz, WAz
CAs at z = 
• For species A which present in dilute concentration, it has been
found that concentration profile follows:
CA = CAb + (CAS – CAb) z/
 dC A 
• The molar flux can be determined by using equation: W Az   D AB  
 dz 
since the formula is applicable to dilute concentration.
• To obtain molar flux from concentration profile, apply
differentiation to get:
DAB DAB
WAz  (C Ab  C As )  kc (C Ab C As ); kc 
 
kc = Mass Transfer Coefficient

• EMCD also produces same molar flux equation as above.

Mass Transfer Coefficient (kc)
kc D
Sherwood Number Sh  = 2 + 0.6Re1/2Sc1/3
DAB

D = Diameter
DV V = Velocity
Reynold Number  v = kinematics
 viscosity
 = density
= viscosity

v
Schmidt Number 
DAB
 CASE STUDY 1:
MASS TRANSFER TO A SINGLE
PARTICLE
 Mass Transfer to Single Particle
with reaction on catalyst surface
Constitutive Equation for binary molar flux:
WA  cDABy A  y A (WA  WB ) (1.10)

Thus, B

Reaction on catalyst surface

Rate law on surface AB

 r  k r C AS
''
A
Boundary conditions (Cont’)

The rate of arrival of molecules on the surface equals the rate of

reaction on the surface

Thus,

Where,

Mass transfer coefficient

 IF…… (CONT’)

The flux to the surface is equal to the rate of reaction on the surface:
                                

                                                                             

                                                               

Solve for CAS

                                                         

Thus,
 Case 1(Rapid Reaction)
When kr >>> kc, then reaction is diffusion limited

C AS  0
Due to the rapid reaction on catalyst
surface (instantaneous reaction)!!

Thus,

 r  kcC Ab
'
A
In this case, to increase rate of reaction, one
must increase CAo and/or kc
 Case 1(Rapid Reaction) CONT’

• To increase kc, one must

 Increase velocity of fluid passing surface
 Decrease size (Diameter of object)

 DAB  12 13 *Assume that number 2

kc  0.6  Re Sc in the Sherwood Number
 D  is of negligible contribution
23 12
DAB V
 0.6  1 6  1 2
v D
-r”
Physical
Properties Condition of flow
(T, P) and size
V
 Case 2 (Slow Reaction)
When kc >>> kr, then reaction is reaction rate limited

C AS  C Ab slow surface reaction

-r”

Thus,
V
kr kc
Mass transfer effect
r 
"
C Ab  kr C AS
not important when
kr  kc
A
reaction rate is limiting

Reaction rate is independent of velocity and

particle size
At high velocities, kc >> kr and -rA is independent of velocity

(V/D)1/2
 Group Work
Based on the example 11.2, determine kc when the feed
velocity and catalyst particle size are varied as the
following table.

Comment the significance of the mass transfer effect

when these parameters are varied.
Group Parameter Group Parameter
Variation Variation
1 0.1 U1 6 0.1 dp1
2 0.3 U1 7 0.3 dp1
3 0.7 U1 8 0.7 dp1
4 2 U1 9 2 dp1
5 4 U1 10 4 dp1
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 CASE STUDY 2:
MASS TRANSFER LIMITED
REACTIONS IN INDUSTRIAL
PACKED BED REACTORS
Mass Transfer-Limited Reactions in
Packed beds

* Reaction happens as
it travels along the
packed bed

z z+z

molar  molar  molar rate  molar rate 

rate   rate   of   of 
       
in  out   generation  accumulati on 

FAz z  FAz z  z  rA" ac  Ac z   0

 Divided by Acz and taking the limit as z  0
1  dFAz  "
    rA ac  0
Ac  dz 

Axial diffusion is neglected as JAZ « BAZ

FAZ  AcWAz  Ac ( J AZ  BAZ )  Ac BAZ  (UC A ) Ac

** To simplify further the case studies,
Thus, assume constant U

d (C AU ) " dC A
  rA ac  U  rA" ac  0
dz dz

Differential equation describing flow

and reaction in a packed bed
Boundary condition (Assuming reaction is at steady state):
Thus  rA"  WAr  kc  C A  C AS 

Then,
dC A
U  kc ac  C A  C AS   0
dz

dC A Mass transfer limited

U  k c ac C A  0 CA >> CAS
dz
Integrating,

CA  ka 
 exp  c c z Analytical solution
C AO  U 
kc relationship (Packed Bed)
How the mass transfer coefficient varies with the physical properties:

Given by Thoenes and Kramers for

0.25<<0.5,40<Re’<4000, 1<Sc<4000

or
Given by Colburn J factor, valid for
Re>10 for gases and Re>0.01 for liquid.

Sh
JD  1
Sc Re
3

Colburn J factor
 Group Work
The irreversible gas phase reaction A→B is carried out over an isothermal
packed bed reactor of solid catalyst particles. The reaction is first order in the
concentration of A on the catalyst surface, where
-rAs’=k’CAs.

The feed consists of 50 mol% A and 50% inerts and enters the bed at a
temperature of 300 K. The entering volumetric flow rate is 10 dm3/s. The
pressure drop can be ignored. The entering concentration of A is 1.0M. Analyse
whether the reaction is surface reaction limited or mass transfer limited.
Then, calculate the catalyst weight necessary to achieve 60% conversion of
A for an isothermal operation.
Given information:
Kinematic viscosity: v=0.02 cm2/s Diffusivity of A: DAB= 10-2 cm2/s
Particle diameter: dp=0.1 cm k’(300K)= 0.01 cm3/s.gcat
Superficial velocity: U= 10 cm/s E= 4000 cal/mol
Catalyst surface area/mass of catalyst bed: a= 60 cm 2/g.cat
Porosity of the bed: = 0.013
 Shrinking Core model
~Applied in Catalyst Regeneration~

Mole balance
c on carbon C

C + O2  CO2
Reaction fast,
Diffusion slow

• Catalyst fully deactivated by coking (C).

The coke (C) deposit into the core of
catalyst through pores.
• O2 diffuse to the catalyst and reaction
happens to “clean” the catalyst incl. pores.
• The core is shrinking with time
Shrinking core model states that the time necessary for the
carbon solid interface to recede inward to a radius R is
O2
CO2

c R 2   R
2
 R 
3

t o c
1  3   2   R
6 DeC Ao   Ro   Ro  

RO

Shrinking core model states that the time needed to fully

regenerate a coked catalyst particle by consuming all carbon, tc

c R  2
tc  o c
6 DeC Ao
Thank you