CEB2093

REACTION ENGINEERING II

Fluid-Particle Reaction
Slide prepared and edited by: AP Dr Suriati Sufian
Acknowledgement to: Dr Mohd Hizami Mohd Yusoff Prof Ir Dr Suzana Yusup
Main Reference from:
i. Fogler H. S., Elements of Chemical Reaction Engineering, 4th Ed., Prentice Hall, 2006.
ii. Levenspiel O., Chemical Reaction Engineering, 3rd Ed., John Wiley, 1999.

1
 Topics
• Introduction of models

• Shrinking-core model (with ash layer)

1) Diffusion through gas film controls
2) Diffusion through ash layer controls
Levenspiel,
3) Chemical reaction controls
chapter 25

• Shrinking-particle model (no ash layer)

1) Diffusion through gas film controls
2) Chemical reaction controls

• Summary of shrinking-core model and shrinking

particle model

• General expression of shrinking core model

Levenspiel, O., Chemical Reaction Engineering 3rd ed., John Wiley & Sons (1999).
 Introduction to Models
Shrinking-particle model
A(g) + b B(s) → gas product + solid product
Shrinking-core model

Representative reactions:
C(s) + O2(g) → CO2(g)
C(s) + CO2(g) → 2CO(g)
C(s) + H2O(g) → CO(g)+H2(g)
Representative reactions:
Coal + O2 → CO2(g) + ash layer
Fe(s) + 0.5O2 → FeO(s)
2ZnS(s)+3O2→2ZnO(s)+2SO2(g)
Fe2O3(s)+4H2→3Fe(s)+2H2O(g)
Ash in the last three reactions means Progressive-conversion
solid product.
model
 Shrinking-Core Model
Shrinking unreacted core containing B
General description
Surface Reaction:
Gas film of
particle
A (gas) + bB(solid) → product
Reaction interface
moving inward as the Ash Step 1:
reaction progresses
Diffusion of A through the film
Step 2:
Diffusion of A through the ash
Step 3:
Reaction of A with B
Step 4:
Diffusion of gaseous product through the ash
C Ag Step 5:
gaseous reactant A
Concentration of

C As Diffusion of gaseous product through the film

CA

C Ac
CA: Concentration of the reactant A [mol/m3]
CAg: CA at the gas bulk [mol/m3]
CAs: CA at the surface of the particle [mol/m3]
R rc 0 rc R CAc: CA cat the reaction interface [mol/m3]
R: Radius of the solid particle [m]
r r: Radial distance [m]
Radial distance rc: Radius of the unreacted core [m]
 Shrinking-Core Model
1) Diffusion through gas film controls
Reaction rate of A per external surface
Reaction
interface area of particle = Mass transfer rate of
Shrinking
unreacted core
Gas film
Surface
A through the film [mol/m2 s]
Surface of
of
containing B particle
particle
(volume=V)
1 dN A
− = k g (C Ag − C As ) (2.1.1)

Ash
4R dt
2

dN B
gaseous reactant A

dN A =
Concentration of

C Ag Concentration
in bulk gas b
C As  C Ag

CAs=C Ac 1 dN B
R rc 0 rc R − = bk g C Ag (2.1.2)
Radial distance 4R dt
2

Reaction:
N: Amount [mol], C: Concentration [mol/m3], kg:
A (gas) + bB(solid) → product Mass transfer coefficient [m/s], t: Time [s], b:
Stoichiometric coefficient of B
 Shrinking-Core Model
1) Diffusion through gas film controls
1 dN B
− = bk g C Ag (2.1.2)
4R dt
2

4
− dN B = −  B dV = −  B d (  rc3 ) = −4 B rc2 drc
3
 r drc
2 Molar density of B [mol/m3]
 B rc3 − R 3
− B c
2
= bk g C Ag (2.1.3)
t=−
R dt bk g C Ag R 2 3
 B rc 2 t
 B R   rc  
 3
− 2  rc drc = bk g C Ag  dt = 1 −   
(2.1.4)
R R 0
3bk g C Ag   R  

 B rc3 − R 3 (2.1.6)
− 2 = bk g C Ag t
R 3 (2.1.5)
 Shrinking-Core Model
1) Diffusion through gas film controls

Relationship of t vs. rc

 B R   rc  
 3

t= 1 −    (2.1.6)
3bk g C Ag   R  
Completion time 
B R
 = t r =0 = (2.1.7)
c
3bk g C Ag
Dimensionless time t/ vs. core size rc or conversion XB
3
t  rc 
= 1−   = X B (2.1.8)
 R
XB: Conversion of B (dimensionless)
 Shrinking-Core Model
2) Diffusion through ash layer controls
Shrinking unreacted core Reaction rate of A = Flux of A through
containing B
the ash x area [mol/s]
Gas film
dN A dC A
Reaction
interface
− = 4 r De
2
(2.2.1)
dt dr
Ash
Integrating throughout the ash layer
dN A rc dr C Ac

dt  R r 2 CAs
Surface of particle
− = 4 De dC A
(2.2.2)
gaseous reactant A
Concentration of

C As= C Ag
dN A  1 1 
CA −  −  = 4 De (C As − C Ac )
dt  rc R 
C Ac =0
R rc 0 rc R = 4 DeC Ag (2.2.3)
r
Radial distance

Reaction: De: Effective diffusion coefficient of A in ash layer

A (gas) + bB(solid) → product [m2/s]
 Shrinking-Core Model
2) Diffusion through ash layer controls
dN A  1 1 
−  −  = 4 DeC Ag (2.2.3)
dt  rc R 
dN B
dN A =
b
4 3
dN B =  B dV =  B d (  rc ) = 4 B rc drc
2

3
4 B rc2 drc  1 1 
−  −  = 4 DeC Ag dt (2.2.4)
b  rc R 
Integrating from R to rc (0 to t)

 B R   rc   rc  

2 2 3

t= 1 − 3  + 2   (2.2.5)
6bDeC Ag   R   R  
 Shrinking-Core Model
2) Diffusion through ash layer controls
Relationship of t vs. rc

 B R   rc   rc  

2 2 3

t= 1 − 3  + 2   (2.2.5)
6bDeC Ag   R   R  

Completion time 
B R2
= (2.2.6)

6bDeC Ag
Dimensionless time t/ vs. core size rc or conversion XB

2 3
t  rc   rc 
= 1 − 3  + 2  = 1 − 3(1 − X B ) 2 / 3 + 2(1 − X B ) (2.2.7)
 R R
 Shrinking-Core Model
3) Chemical reaction controls Reaction rate of A per external surface area of
Gas film core = Intrinsic reaction rate of A [mol/m2 s]
Shrinking
1 dN A
− = kC Ac = kC Ag (2.3.1)
Ash unreacted core
Reaction
containing B
4 rc dt
interface 2

dN B
Surface of
particle
dN A =
b
1 dN B
− = kbC Ag
gaseous reactant A

(2.3.2)
4 rc dt
Concentration of

2
C Ac=CAs=CAg
dN B = 4 B rc2 drc
drc
− B = kbC Ag (2.3.3)
R rc 0 rc R
dt
rc t
Radial distance
−  B  drc = kbC Ag  dt (2.3.4)
R 0
Reaction:
A (gas) + bB(solid) → product  B ( R − rc ) = kbC Ag t (2.3.5)

k: Reaction rate constant [m/s]

 Shrinking-Core Model
3) Chemical reaction controls
Relationship of t vs. rc
B R rc
t= (1 − ) (2.3.6)
kbC Ag R

Completion time 

B R
= (2.3.7)
kbC Ag

Dimensionless time t/ vs. core size rc or conversion XB

t rc
= 1 − = 1 − (1 − X B )1/ 3 (2.3.8)
 R
 Shrinking-Particle Model
1) Diffusion through gas film controls
Shrinking unreacted particle consisting of B
(volume=V) Reaction rate of A per external surface
area of particle = Mass transfer flux of A
through the film [mol/m2 s]

1 dN A
− = k g (C Ag − C As ) (3.1.1)
4R dt
2
Gas film
dN B
dN A =
gaseous reactant A

b
Concentration of

C Ag

CAs=C Ac
C As  C Ag
1 dN B
− = bk g C Ag (3.1.2)
R 0 R
Radial distance
4R dt
2

Initially R0, finally 0 The equations are the same as those in the section
2. 1). In the section 2. 1), R does not change with
Reaction: time. In this case, R changes with time.
A (gas) + bB(solid) → product (without ash layer)
 Shrinking-Particle Model
1) Diffusion through gas film controls
1 dN B
− = bk g C Ag (3.1.2)
4R dt
2

4 3
dN B =  B dV =  B d ( R ) = 4 B R 2 dR
3
dR
−  B = bk g C Ag (3.1.3) Diffusion coefficient of A
dt
D k g 2R
kg = = 2 + 0.6 Re1/ 2 Sc1/ 3 = 2
R D
dR D
−  B = b C Ag
At low Re number
(3.1.4)
dt R

 R   R  
 2
2
R bDC Ag t 1 2 2 bDC Ag
−  RdR =  dt ( R0 − R ) = t t= B 0
1 −   
R0 B 0 2 B 2bDC Ag   R 0  
 
(3.1.5) (3.1.6) (3.1.7)
 Shrinking-Particle Model
1) Diffusion through gas film controls
Relationship of t vs. R

 R   R  
 2
2
t= 1 −   
B 0
(3.1.7)
2bDC Ag   R 0  
 
Completion time 
 B R02
= (3.1.8)
2bDC Ag

Dimensionless time t/ vs. particle size R or conversion XB

2
t R
= 1 −   = 1 − (1 − X B ) 2 / 3 (3.1.9)
  R0 
 Shrinking-Particle Model
2) Chemical reaction controls
The behavior is identical to that of the shrinking-core model in the section 2. 3).
Shrinking core → Shrinking particle
R → R0
rc →R Gas film
Shrinking
Ash unreacted core
Reaction
containing B
interface

Surface of
particle

gaseous reactant A
Concentration of
C Ac=CAs=CAg

R rc 0 rc R
Radial distance
 Shrinking-Particle Model
2) Chemical reaction controls
Relationship of t vs. R

 B R0 R
t= (1 − ) (3.2.1)
kbC Ag R0
Completion time 

 B R0
= (3.2.2)
kbC Ag
Dimensionless time t/ vs. particle size R or conversion XB

t R
= 1 − = 1 − (1 − X B )1/ 3 (3.2.3)
 R0
 Summary

Controlling Shrinking-core Shrinking-particle

step
3
 rc 
2
t
= 1−   = X B t R
Gas film
 = 1 −   = 1 − (1 − X B ) 2 / 3
R   R0 
2 3
t  rc   rc 
= 1 − 3  + 2 
Ash layer  R R Ash layer does not exist
in this model.
= 1 − 3(1 − X B ) 2 / 3 + 2(1 − X B )

t rc t R
Reaction = 1 − = 1 − (1 − X B )1/ 3 = 1 − = 1 − (1 − X B )1/ 3
 R  R0
 Summary
2
R
rc/R (or R/R0) vs. t/ Shrinking particle model
t
= 1 −  
  R0 
Gas film diffusion controls

t R
= 1−
 R0

3
t r 
rc/R
= 1−  c  Shrinking core model
 R
t r
=1 − c
 R
2 3
t r  r 
= 1 − 3 c  + 2 c 
 R R

t/
 Summary
t
= XB
1-XB vs. t/ Shrinking core model 
t
= 1 − (1 − X B )1/ 3

t
= 1 − 3(1 − X B ) 2 / 3 + 2(1 − X B )

Shrinking particle model
t
Gas film diffusion controls
= 1 − (1 − X B ) 2 / 3

1-XB

t
= 1 − (1 − X B )1/ 3


t/
General expression of shrinking-core model
Shrinking unreacted core containing B
Surface
Gas film of
particle
Reaction interface
moving inward as the
General description
Ash
reaction progresses
Reaction:
A (gas) + bB(solid) → product

Step 1:
Diffusion of A through the film
Step 2:
C Ag Diffusion of A through the ash
gaseous reactant A
Concentration of

C As Step 3:
CA Reaction of A with B
C Ac

1 dN A C Ag
R rc 0 rc R − =
4R dt
2
1 R2 1 1 R2
Radial distance
r + ( − )+ 2
k g De rc R rc k
Conversion-Time Expression