AVP - Diffusion and Reaction in Porous Solid Spherical Catalyst Pellet

Chemical Reaction Engineering
Diffusion and reaction in porous solid spherical catalyst pellet

Dr. Anand V. Patwardhan
Professor of Chemical Engineering
Institute of Chemical Technology
Nathalal M. Parekh Road
Matunga (East), Mumbai-400019
av.patwardhan@ictmumbai.edu.in
Anand V. Patwardhan 1
DIFFUSION FUNDAMENTALS:
porous
catalyst
external C pellet
C diffusion As C r
Ab A
internal
diffusion
external
surface
Effective Diffusivity:
 The pores in any solid pellet are usually a series of
tortuous, interconnecting paths of pore bodies and
pore throats with varying cross-sectional areas.
 Therefore, we need to define an effective diffusion
coefficient to describe the average diffusion taking
place at any position r in the pellet.
 We consider only the radial variations in the
concentration.
 Therefore, the radial flux WAr is based on the total
area (voids and solid) perpendicular to diffusion
(4πr2), and NOT void area alone.
 This basis for WAr leads to the proper definition of
the effective diffusivity De.
 The effective diffusivity takes in to account:
1) Not all of the area perpendicular to the direction
of the flux is available diffusion of molecules.
2) The pore paths are tortuous.
3) The pores have varying cross-sectional areas.
 De is related to either the bulk or the Knudsen
diffusivity by the relation:
D  
A p
D 
e 
actual distance travelled by a molecule
  tortuosity 
shortest distance between the two points
void volume in a pellet
  pellet porosity 
p total volume of pellet  void+solid 
  constriction factor
 Constriction factor = accounts for the variation in

the cross-sectional area perpendicular to diffusion.
= f(ratio of maximum to minimum pore areas).
 When the two areas, A1 and A2, are equal, the
constriction factor = 1,
 When β = 10, constriction factor ≈ 0.5.
A A
1 2
A
 2 ;   f  
A
1
900
L L
 Typical values of the constriction factor (σ), the
tortuosity (τ), and the pellet porosity (Φp) are:
σ = 0.8
τ = 3.0
Φp= 0.40
Diffusion and reaction in porous solid spherical
catalyst pellet:
 Consider a chemical reaction occurring in a
catalytic reactor consisting of porous solid spherical
catalyst pellets.
 Consider single such pellet surrounded by reactant
‘A’.
 Reactant ‘A’ diffuses through the surface of pellet,
and reacts simultaneously.
 We are not considering the counter-diffusion of
product ‘B’ from within the catalyst porous matrix
to the exterior.
C
AS
'A' diffusing from

r  R to r  0
C C
AS AS
r dr
C
AS
k, s1
A  B
1st order, isothermal, irreversible
kmol kmol
 
r 
A s  kgCat
;C 
A kgCat
D  C 
A c A c k
r R
m2 kgCat kmol
m m s 1
s m3Cat m3Cat
Effective Concentration
molecular of ‘A’ in per Radius
First
diffusivity Density unit of
Radius order
of ‘A’ in of volume spherical
coordinate rate
catalyst catalyst of catalyst
constant
porous porous pellet
matrix matrix
 Taking mole rate balance, across a differential
volume, which in this case is, differential spherical
shell at a distance of ‘r’ from the sphere’s centre,
 rate of 'A' exiting    rate of 'A' entering 
 spherical shell at 'r '  spherical shell at 'r  dr '
 rate of 'A' reacting in 
 2dr 
 spherical shell of volume 4 r 


 D

d C 
A c 2




4r    D
d C 
A c

4r 2 
 
 A dr r  A dr  r  dr
 
OUT at r IN at r  dr
 r  4r 2dr
A c

 
Rate of reaction
 Note:
The flux does NOT have negative sign, because
diffusion of ‘A’ is taking place from r = R to r = 0,
and the ‘r-coordinate’ is from r = 0 to r = R.
Therefore, the sign of (dCA/dr) is already
POSITIVE, and we need not add a negative sign to
make it positive.
In other words: the direction of ‘r-coordinate’ and
the direction of diffusion are OPPOSITE to each
other.
 Dividing by differential spherical shell volume
(4r2.dr), and rearranging, for 1st order irreversible
reaction,
 2 dC   2 dC 
 r A   r A
D  dr r  dr  dr r
r2
A
dr 
A 
 r  kC
A
 2 dC   2 dC 
r A  r A
1  dr r  dr  dr r k
  C
A
r2 dr D
A
1 d  2 dCA  k 2 k
 r  C  C ; 
2 dr  dr  D A A D
r A A
 The above equation needs to be modified using
suitable substitution for analytical solution.
dy dC
Let y  C r  r A C
A dr dr A
dy y
dC dC 
dy A y A  dr r
 r  
dr dr r dr r
dC
r 2 A  r dy  y
dr dr
d  2 dC A  d 2y dy dy
 r r  
dr  dr  dr 2 dr dr
1 d  2 dCA  1 d 2 y
 r 
r 2 dr  dr  r dr 2
1 d2y 1 d 2y y d 2y
   2C   2   2y
r dr 2 A r dr 2 r dr 2
 Standard solution for the above equation:
 y  C e r  C e r
1 2
C and C to be evaluated using 2 boundary conditions
1 2
 Boundary conditions:
B.C.  1 : r  0, y  C r  y  0
A
B.C.  2  : r  R, y  C r  y  C R
AS AS
 Using the above 2 boundary conditions,
C R C R
C  AS ;C  AS
e R  e R e R  e R
1 2
C R C R
y AS sinh  r   C r  AS sinh  r 
sinh  R  A sinh  R 
C R  sinh  r  
C  AS
A sinh  R   r 
... concentration profile of 'A' from r  R to r  0
 Substituting r = R gives,
C C
A AS
 Substituting r = 0 should give the concentration of
‘A’ at the centre of spherical pellet.
 d 
C R   sinh r  
 
C  AS lim  dr ... L'Hospital rule
A sinh  R  r  0 d 
 r  
 dr 
  R  
 C C   ... concentration of A at r  0
A AS  sinh  R  
 Here, there are 2 extreme possibilities:
1) As rate constant decreases, αR decreases. In the
extreme:
   R   
C  lim C   
A R  0  AS  sinh  R   
  R  
C lim    C  1  C
AS R  0  sinh  R   AS AS
... hardly any reaction effected by catalyst
2) As the reaction rate constant increases, αR
increases. In the extreme:
   R   
C  lim C   
A R    AS  sinh  R   
  R  
C lim 
AS R    sinh  R  
C  0  0
AS
... complete reaction effected by catalyst
 Now, let us find out the actual total rate of reaction
within the spherical catalyst pellet.
 This can be obtained by finding the flux of reactant
‘A’ at the surface (r = R) and multiplying the
external surface area of spherical pellet.
Flux  D 

d C  
A c 

A dr r  R
C R d  sinh  r  
D  AS
A c sinh  R  dr  r 
rR
D C  R    r  cosh  r   sinh  r  
 A AS c  
 
sinh R  r 2  rR
D C  R    r  cosh  r   sinh  r  
 A AS c  
sinh  R   r 2  rR
D C  R  R cosh  R   sinh  R  
 A AS c  
sinh  R   R 2 
D C  R  1 1 
 A AS c 
R 
 tanh  R   R  
 1 1 
C  D k 
AS c A  tanh  R   R  
 Therefore, the rate of diffusion (with simultaneous
chemical reaction) from pellet surface into pellet’s
interior will be:
rate  surface area  flux
2  1 1 
 4R C  D k 
AS c A  tanh  R   R  
 Now, let us define ‘characteristic dimension’ of
spherical pellet as,
4
V R 3 R
p 3
 
S 4 R 2 3
p
 Therefore, we can rearrange the ‘rate’ as,
2  1 1 
rate  4R C  D k  
AS c A  tanh  R   R  
2  1 1 
 4R C  D k   
AS c A    
 tanh  R k   R k  
  D   D 
  A  A 
2  1 1 
 4R C  D k  
AS c A  R k   R k 
 tanh  3  3 
  3 D   3 D 
  A  A 
 1 1 
 4R 2C  D k 
AS c A  tanh  3   3  
R k
where   Thiele modulus  ... dimensionless
3 D
A
 If there were no diffusion resistance (mass transfer
resistance), then concentration of reactant ‘A’ will
be the same throughout pellet, instead of a
DECREASING profile from r = R till r = 0.
 Obviously, the reaction rate (in the case of
isothermal chemical reactions) will be maximum in
such a case.
 In fact, this rate will be like homogeneous reaction
rate with a concentration of.
 This rate (intrinsic kinetic rate) is given as:
intrinsic 4
kinetic  k  C   R 3
 AS c
rate 
   3 

   rate
concentration volume of
 kmol  constant
of ' A' spherical

 s 
  s1   kmol  catalyst
 3  pellet
 m Cat 
 m3Cat 
 Now we are in a position to define a dimensionless
factor, namely, effectiveness factor of catalyst pellet,
η.
actual rate of reaction

kinetic rate of reaction
 1 1 
4R 2C  D k 
AS c A  tanh  3   3  

4
k  C   R 3
AS c 3
3 D  1 1 
  A
R k  tanh  3    3  

1 1 1 
    
R k  tanh  3   3  
3 D
A
1 1 1 
   
  tanh  3   3  
 As k increases, Φ increases. In the extreme,

1
lim  
 
 This limiting expression holds true for porous solid
catalyst pellets IRRESPECTIVE of shape and size.
Interpretation of Thiele modulus:
k R k 2
R k
L    2 ... for spherical pellet,
D 3 D 9D
A A A
1st order irreversible isothermal reaction
 The above expression can be rearranged (with some
thinking) into the following expression:
4 3
2 k  C   R
2 R k AS c 3
  
9D C 
A D  AS c  4R 2
A  R 3
4 3
k  C   R
AS c 3

D 

C  0
AS c  4R 2 
A  R 3
 2 
kmol
kinetic rate of reaction of 'A' in speherical catalyst pellet,
s
kmol
maximum diffusion rate of 'A' in speherical catalyst pellet,
s
 CASc  0   concentration gradient of 'A'
 R 3
when diffusing (without reaction) from a
concentration of C
AS c
 
 kmol m 3Cat to ZERO ,
across a distance of  R 3 
 Now, consider the following:
2 kinetic rate of reaction
 
maximum diffusion rate

2 kinetic rate of reaction actual rate of reaction
  
maximum diffusion rate kinetic rate of reaction
2 actual rate of reaction
     Weisz modulus
maximum diffusion rate W
 Weisz modulus is useful in discerning kinetics of
unknown systems, where true (intrinsic) kinetics is
not known to start with.
 If the chemical reaction is nth order w.r.t. reactant
‘A’, then,
1 n
 1  kmol 
k,s  
 kgCat 
A  B
nth order, isothermal, irreversible
kmol kmol
 
r 
A s  kgCat
;C 
A kgCat
 In this case, the expressions for ‘Thiele modulus’
take the form: n 1

R n  1 k CAS

 
3 2 D
A
 As k ↑ (by raising T or by raising [catalyst] or by
changing to more effective catalyst, etc., Φ ↑:
 Kinetic rate of reaction tends to increase.
 However, diffusion rate remains almost constant.
 The increased kinetic rate capability of the
reaction system, is not realised.
 At very high k, (very high Φ): the overall rate
becomes diffusion controlled.
 This is quite distinctly from homogeneous systems,
wherein there is no question of diffusion resistance.
Reaction rate in porous catalyst pellet based on
‘catalyst surface area in porous matrix of catalyst’
k, m s
A  B
kmol
 rA    s    m2Catalyst surface area in porous matrix 
kmol
C 
A m 3Cat
D  S
A c k
r R
 m 2Cat 
m2 kgCat
  m
m
m  
s m3Cat  kgCat   s 
Effective Specific
First
molecular surface Radius
order
diffusivity Density area of
Radius surface
of ‘A’ in of in spherical
coordinate reaction
catalyst catalyst catalyst catalyst
rate
porous porous pellet
constant
Matrix matrix

 spherical shell at 'r'  spherical shell at 'r  dr'
 2 
 spherical shell of volume 4r dr 


 D
d C
A 
 4r

2




 D
d C
A 2
 4r 
  
 A dr  r  A dr  r  dr
A 
 r  S    4r 2dr
c
  2 dC   2 dC  
A A 


 1
r

 r
dr  r  dr  dr  r 
 A  
r  S  
c
 2 dr  D
r  A
kC    S  kS 
 A c  c C
D  D  A
A  A 
1 d  2 dCA   kSc  2C ;  
kS
c
  r     C  
r 2 dr  dr   D  A A D
 A  A
C R  sinh  r  
 C  AS
A sinh  R   r 
... concentration profile of A from r  R to r  0
Flux  D 

d C 
A  
A  dr  r  R
C R d  sinh  r  
D  AS
A sinh  R  dr  r 
rR
D C R  1 1 
 A AS  tanh  R    R  
R
k S  1 1 
D C c 
A AS D  tanh  R   R  

A
 1 1 
C D k S  
AS A c  tanh  R   R  
rate=surface area×flux
 1 1 
 4R 2  C D k S  
AS A c  tanh  R   R  
2  1 1 
 4R  C D k S   
AS A c  kS   kS 
 R c  R c
 tanh
 D   D 
  A   A  
2  1 1 
 4R  C D kS  
AS A c  kS    kS 
 3 R c  3 R c 
 tanh
 3 D   3 D 
  A   A  
2  1 1 
 4R  C D kS  
AS A c  tanh  3   3  
R kSc
where   Thiele mod ulus 
3 D
A
... DIMENSIONLESS
intrinsic 4
kinetic  k
  C  S
    R 3
rate AS  c 3 

   surface concentration specific
pellet volume
 kmol  reaction of
surface
density of
  rate area
 s  constant 'A' in  kgCat  spherical
 kmol  catalyst  3  catalyst
 
m  m Cat  pellet
   3  porous
 s   m Cat 
matrix  m3Cat 
 m2Cat 
kgCat

2  1 1 
4R  C D kS  
AS A c  tanh  3   3  

4
k C    S  R 3
AS c 3
 1 1 
 tanh  3    3  
   
R kcS
3 D
A
1  1 1 
  
 tanh  3   3  
R kSc  
3 D
A
1 1 1 
    
  tanh  3   3  
kS  R 2kS
R c 2 c
  
3 D 9D
A A
2 4 3
R kS kC  S R
2 c AS c 3
  
9D C
A D  AS  4R 2
A  R 3
4
kC  S R 3
2 AS c 3
 
D 
C 
AS
0
 4 R 2

A  R 3
 2 
kmol
s
kmol
s
 CASc  0  concentration gradient of 'A'

 R 3
concentration of C
AS

c
 kmol 
m 3Cat to ZERO ,
‘A’, then the units of ‘k’ will be:
1 n
 m   kmol 
  3
 s   m Cat 
take the form:
n 1

R n  1 kPS CAS

 
3 2 D
A
Reaction rate in porous catalyst pellet based on ‘mass
of catalyst’
1
 1  kgCat 
k, s  
 m 3
A  B
kmol
 
r 
A s  kgCat
kmol
C 
A m3
D  k
A c r R  1 
m2 kgCat 
 s 1 
kgCat  
m m 
s m3Cat   m 3  
Effective
First order
molecular Radius
reaction rate
diffusivity Density of
Radius constant
of ‘A’ in of spherical
coordinate based
catalyst catalyst catalyst
on catalyst
porous pellet
mass
Matrix
 spherical shell at 'r'  spherical shell at 'r  dr '
 2 
 spherical shell of MASS c 4r dr 
 
 D



d C
A  4r 2




 D
d C
A   
 4 r 2 
 A dr  r  A dr  r  dr
 
 r   4r dr
A c
2

 D
d C    
A  4r 2    D
d C 
A  4 r 2  
 A dr  r  A dr  r  dr
 
 r   4r 2dr
A c
  dC   dC  
 r 2 A  r 2 A 
  1  dr  r  dr  dr r 
 A
r  
c 
 2 dr  D
r  A
  dC   dC  
 r 2 A  r 2 A 
 k 
1  dr   dr 
 r  dr r    c C
 2 dr  D  A
r   A
1 d  2 dC A   kc  2
k
c
  r 
   C   C ; 
r 2 dr  dr   D  A A D
 A A
C R  sinh  r  
 C  AS
A sinh  R   r 
 Flux  D 

d C 
A 

A  dr  r  R
C R d  sinh  r  
D  AS
A sinh  R  dr  r  rR
D C R  1 1 
 A AS 
R 
 tanh  R   R  
k  1 1 
D C c 
A AS D  tanh  R   R  

A
 1 1 
C D k  
AS A c  tanh  R   R  
 rate  surface area  flux
 1 1 
 4R 2  C D k  
AS A c  tanh  R   R  
2  1 1 
 4R  C D k   
AS A c  k   k 
 R c  R c
 tanh
 D   D 
  A  A  
2  1 1 
 4R  C D k  
AS A c  k    k 
 3 R c  3 R c 
 tanh
 3 D   3 D 
  A  A  
 1 1 
 4 R 2  C D k  
AS A c  tanh  3   3  
R kc
where   Thiele modulus 
3 D
A
... DIMENSIONLESS
intrinsic 4
kinetic  k  C    R 3
 AS c
rate   3 

   reaction
concentration pellet
rate volume
 kmol  of 'A' density of
  constant
 s   km o l   kgCat  spherical
1 m  3
catalyst
   3   3 
 m   m Cat  pellet
 s kgCat 
 m3Cat 

2  1 1 
4R  C D k  
AS A c  tanh  3   3  

4 3
k C    R
AS c 3
 1 1 
 tanh  3    3   1  1 1 
    
k  k  tanh  3   3  
R c R c
3 D 3 D
A A
1 1 1 
   
  tanh  3   3  
2 4 3
R k kC  R
2 c AS c 3
  
9D C
A D  AS  4R 2
A  R 3
4
kC  R 3
AS c 3

D 
C
AS
0
 4R 2 
A  R 3
 2 
kmol
s
kmol
s
 CASc  0  concentration gradient of 'A'

 R 3
concentration of C
AS

c
 kmol 
m 3Cat to ZERO ,
‘A’, then the units of ‘k’ will be:
1 1 n
 1  kgCat   kmol 
s    3 
3
 m   m 
take the form:
n1

R n  1 kc CAS

 
3 2 D
A
 Reality check: check the concentration gradient of
‘A’ at the centre of spherical pellet.
C R  sinh  r  
C  AS
A sinh  R   r 
dC C R d  sinh  r  
 A  AS
dr sinh  R  dr  r 
dC C R  r    cosh  r   sinh  r  
 A  AS
dr 
sinh R   2 
r 
 This will give the form (ZEROZERO) if we
directly substitute r = 0. Therefore, applying
L’Hospital’s rule,
d
dC C R  r    cosh  r   sinh  r  
A  AS dr
dr sinh  R  d  2
r 
dr
C R   2  r  sinh  r  
 AS
sinh  R   2r 
C R 2
 AS  sinh  r  
2sinh  R 
dC C R 2
 A  AS sinh    0  
dr r  0 2sinh  R 
dC C R 2
 A  AS sinh  0
dr r  0 2sinh  R 
dC
 A 0
dr r  0
... as logically expected due to SYMMETRY of problem
C R  sinh  r  
A 
C 
sinh R    r 

AS


d C C
A AS 
 2
R sinh  r 
dr 2sinh  R 
... using L'Hospital rule
 Using the following data, let us construct plots.
–2
R = 1  10 m
3
CAS = 1 kmol/m
–5 –1
k = 1  10 s
–10 2 –1
DA = 1  10 m s
–1
α = 316.23 m
Φ= 1.05 -
η= 0.65 -
CA/CAS vs. r/R
1.2
1.0
0.8
0.6
0.4
0.2
0.0
0.0 0.2 0.4 0.6 0.8 1.0 1.2
r/R
d(CA/CAS)/dr vs. r/R
600
500
400
300
200
100
0
0.00 0.20 0.40 0.60 0.80 1.00 1.20
r/R

AVP - Diffusion and Reaction in Porous Solid Spherical Catalyst Pellet

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AVP - Diffusion and Reaction in Porous Solid Spherical Catalyst Pellet

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Chemical Reaction Engineering

Diffusion and reaction in porous solid spherical catalyst pellet

 Constriction factor = accounts for the variation in

'A' diffusing from

 As k increases, Φ increases. In the extreme,

 rate of 'A' exiting    rate of 'A' entering 

 CASc  0  concentration gradient of 'A'

... concentration profile of 'A' from r  R to r  0

 CASc  0  concentration gradient of 'A'

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