Lecture 6 External Diffusion PDF

Catalytic
Reaction Engineering
Yongdan Li
Professor of Industrial Chemistry
Department of Chemical and Metallurgical Engineering
School of Chemical Technology
Aalto University
Email: yongdan.li@aalto.fi Nov-Dec, 2017
Kemistintie 1, E404
6. External diffusion
2
Part 6-1 Diffusion and Molar flux
Steps of heterogeneous reaction

Reactant:
external (film) diffusion
Active
Active site
site • internal
In principle, all steps
(pore) diffusion
can affectonthe
adsorption reaction
active site
rate
•chemical reaction
The slowest step (RDS,
rate determining step)
Product:
determines the reaction
desorption
rate almost alone
internal diffuusion
external diffusion
3
What is diffusion?
• Driving force?
4
Definition of diffusion and mass transfer
 Diffusion: Spontaneous mixing of atoms or molecules due to

thermal motion
Driving force of diffusion is the concentration gradient
(movement from higher concentration to lower one)
The gradient causes a molar flux WA in the
direction of concentration gradient
 Mass transfer: Transfer of a mass species through the

bulk of a fluid or a solid matrix
Diffusion is a kind of mass transfer
5
Molar flux
• Flux is a vector: WA = i WAx + j WAy + k WAz
molar amount mol

[WA ]   2 y
WA
area  time m s
x
WAy
WAx
z
WAz
• Molar flux of A can be divided into two components:
1) Molecular diffusion flux JA
2) Flux due to motion of the fluid BA
WA = JA + BA (1)
6
Molar flux: case 1
xoxoxoxoxoxoxo
oxoxoxoxoxoxox U
xoxoxoxoxoxoxox
• A (x) and B (o) completely mixed

• No concentration gradient => no molecular diffusion JA= 0
• Flux of A only due to motion of bulk flow:
WA=BA (2)
7
Molar flux: case 2
Flux due to concentration gradient and bulk flow:
WA = JA + BA eq (1) in page 6
x o o o o
x x o o o
J U
x x x o Ao
x x x x o
8
• Overall flux:
WA = JA + BA eq (1) in page 6 BA = yA Wtotal =yA Wi (2)
• Bulk flow:
BA =CAU (3)
 WA = JA + CAU (4)
• For a binary system:
BA = yA (WA + WB )  WA = JA + yA (WA + WB ) (5)
WA = Molar flux for A, mol/(m2∙s) WB = Molar flux for B, mol/(m2∙s)

JA = Diffusion flux, mol/(m2∙s) BA = Bulk flow, mol/(m2∙s)
CA = Bulk concentration, mol/m3 U = Average molar velocity, m/s
yA = Mole fraction of A
9
Analogy of heat and mass transfer
• Heat transfer: Fourier’s law • Mass transfer: Fick’s law

• Heat flux due to • Diffusion flux due to
temperature gradient concentration gradient
q   kt T J A  cDAB y A (6)
• As one dimensional • As one dimensional

dC A
q Z   kt
dT J AZ   DAB (7)
dZ dZ
  
i j k Diffusivity of A in B
Thermal conductivity x y z (molecular diffusion coefficient)
10
Part 6-2 Binary Diffusion
Molar flux dependency on concentration gradient
• Molar flux
WA = JA + yA (WA + WB)
 WA = - c DAB yA + yA (WA + WB) (8)
Typically a multicomponent solution

• Diffusion of every component can be treated as a binary
mixture
11
Three special cases of binary diffusion

Equimolar counter-diffusion
• Diffusion of 1 mol A in a given direction and diffusion of 1

mol B in opposite direction
• Fluxes of A and B equal in value with opposite signs
A B
AB
12
• Derivation
WA = - WB
= JA + yA (WA - WA) = JA
WA = JA = - c DAB yA (9)
• Assuming constant total concentration:
WA = - DAB CA (10)
13
Diluted solutions
• Molar fraction of diffusing component very low

• Motion of bulk in the direction of diffusion is small
=> second term can be neglected.
WA  JA = - DAB CA (11)
14
Strong (forced) convection
• Assumption: diffusion flux in the direction of flow is small,

JA, compared to the bulk flow, BA,
JA  0
WA=BA=yA(WA+WB)=CAU (12)
15
Part 6-3 External diffusion limitation
External diffusion limitation
Diffusion of reactants to the catalyst

particle outer surface is slow
• Diffusion resistance can cause a
concentration gradient => bulk
concentration ≠ concentration on the
outer surface
A single catalyst particle is first examined

Reaction happens only on the catalyst surface
16

Catalyst particle Gas or liquid film
Gas or liquid bulk,

Concentration on the
concentration CAb
active sites inside the
catalyst pore CAS
Concentration gradient
Concenration on the
over gas or liquid film
outer surface CAs
17

 Diffusion resistance almost exclusively exists in a narrow
layer around the catalyst particle
 Fluid layer around the particle can be treated as stagnant film
(boundary layer) with thickness 
• If film thinkness is much smaller than the radius of the
particle => curvature of the particle can be neglected
WA = -DABCA eq (11) in page 14
• This equation can be solved applying appropriate boudnary
conditions (stagnant gas or liquid film)
18
Diffusion through a stagnant film
kc (mass transfer coefficient)

DAB
WA  (CAb  CAs ) (13)
δ
19
Reaction and external diffusion resistance Outer surface Centre
cAb
• Elementary reaction A  B
cAs cAs
rAs  kr CAs  rAs  kr CAs
'' ''
• In steady state: molar flux to catalyst outer surface = generation

rate of A on the catalyst
kc (C Ab  C As )  kr C As CAb = Bulk (gas or liquid) concentration
kc CAb CAs = Concentration at the outer surface
C As  (14) = Concentration inside the pore
k r  kc kc= Mass transfer coefficient
kr= Reaction rate constant
20
Reaction and external diffusion resistance
rAs''  kr CAs
kc kr CAb
kc CAb r 
''
(15)
C As  k r  kc
As
k r  kc
Fast chemical reaction: kr >> kc 
rAs''  kc CAb (overall rate depens only on the mass transfer)
Slow chemical reaction: kr << kc 

rAs
''
 kr CAb (overall rate depends only on the reaction)
21
Part 6-4 The Mass Transfer Coefficient
Heat transfer coefficient
Heat transfer coefficient can be determined using dimensionless

numbers (Nusselt, Reynolds, Prandtl)
hd p Uρd p μC p μ ρC p 
Nu  (16) Re  (17) Pr    (18)
kt μ kt ρ kt t
The empirical formula of Nusselt number for spherical particles:

Nu = 2 + 0.6 Re1/2 Pr1/3 (19)
h = Heat transfer coefficient, J/m2∙s∙K ρ = Density, kg/m3

dp = Particle diameter, m μ = Dynamic viscosity, kg/m∙s
Cp = Heat capacity, J/kg/K
kt = Heat conductivity J/K∙m∙s
 = μ/ρ = Kinematic viscosity, m2/s
U = Free-stream velocity, m/s
t = Thermal diffusivity, m2/s
22
Mass transfer coefficient

• Correspondingly for mass transfer coefficient
kc d p
• Nusselt  Sherwood Sh  (20)
DAB

• Prandtl  Schmidt Sc  (21)
DAB
• Frössling correlation: Sh = 2 + 0.6 Re1/2 Sc1/3 (22)
• Valid for external mass transfer around spherical particles
kc = Mass transfer coefficient

dp = Particle diameter, m
 = μ/ρ = Kinematic viscosity, m2/s
23
Rapid Reaction
• Re>> 25 => Sh = 2 + 0.6 Re1/2 Sc1/3 =>

 DAB  12 13
kc  0.6   Re Sc
 d
 p 
 DAB   Ud p 
1/ 2 1/ 3
 ν 
kc  0.6 
 d   ν   
 p   AB 
D
 DAB 2 / 3   U 1/ 2 
kc  0.6  1/ 6   1/ 2  (23)
 ν 
 p 
d 
I II
What does parts I and II describe?

24
 DAB 2/3   U 1/2 

kc  0.6  1/6   1/2 
    d p 
Physical System
properties properties
• DAB increases with the increase of T • kc increases with the decrease of

(both for gases and liquids) the catalyst particle size or with
• Kinematic viscosity, for gases:  the increase of the bulk flow
T3/2, for liquids viscosity decreases velocity.
with the increase of T
25
Part 6-4 The Mass Transfer Coefficienton
Example 6.1 Rapid Reaction on the Surface of a Catalyst
Calculate the molar flux, WAr, of reactant A to a single catalyst pellet 1 cm in

diameter suspended in a large body of liquid B. The reactant is present in dilute
concentrations, and the reaction is
considered to take place =1M
instantaneously at the external pellet ≈0
surface (i.e., CAs ≈ 0). The bulk
concentration of the reactant A is 1.0
M, and the free-stream liquid velocity
passing the sphere is 0.1 m/s. The
kinematic viscosity, v, (i.e., v =μ/ρ) is
0.5 centistoke (cS; 1 centistoke = 10-6
m2/s), and the liquid diffusivity of A in
B is DAB = 10-10 m2/s, at 300 K. DAB = 10-10 m2/s
U=0.1m/s
v=0.5 centistoke
26
Solution
According to the Equation (13), For dilute concentrations of the solute, the
radial flux is
WAr  kc (C Ab  C As ) (E1-1)
Because reaction is assumed to occur instantaneously on the external surface
of the pellet, CAs=0. Also, CAb is given as 1 mol/dm3. The mass transfer
coefficient for single sphere is calculated from the Frössling correlation
kc d p
Sh   2  0.6 Re1/2 Sc1/3 eq (22) in page 23
DAB
 d pU d pU (0.01m)(0.1m/s)
Re  =   2000
 v 6
0.5 10 m /s
2
 5 107 m 2 / s
Sc   10 2
 5000
DAB 10 m / s
27
Substituting these values into the Equation (22), it gives us
Rearranging the Equation (20) gives us
Substituting for kc and CAb in the equation(E1-1), the molar flux to the
surface is
WAr=(4.61×10-6) m/s (103-0) mol/m3 =4.61×10-3 mol/m2∙s
28
Part 6-5 The Mass Transfer in a Packed bed
Example: External diffusion limitation in a packed bed reactor

Ac External diffusion limits
the reaction rate in a
packed catalyst bed
z z+z
 Molar   Molar   Molar rate of   Molar rate of 
 rate in  -  rate out  +  generation    accumulation 
       
FAz z - FAz z z
 r a (Ac Δz ) 
''
A c 0
r’’A= Rate of generation of A per unit of catalytic surface area, mol/s∙m2
ac = Catalyst outer surface area/catalyst bed volume m2/m3
Volume of solid Surface area
ac    (1-  )  d p2 / ( d p3 / 6) 
Volume of bed Volume of solid
 6(1   ) / d p for packed beds, m 2 /m 3
ϕ = Void of the bed
Ac = Cross-sectional area of tube containing the catalyst 29
Part 6-5 The Mass Transfer in a Packed Bed
Balance equation in differential form

1 dFAz
  rA'' ac  0 (24)
Ac dz
We now need to express FAz and r’’A in terms of concentration.
The molar flow rate of A in the axial direction is
𝐹 Az = Ac WAz = Ac(JAz + BAz)
Often diffusion in axial direction is negligible in packed beds compared to convection
of bulk (plug flow): JAz << BAz
𝐹 Az = Ac BAz = Ac CA U
where U is the superficial average molar velocity through the bed (m/s). Substituting for
FAz in the Equation (24) gives us
1 d (CAU ) '' d (CAU ) ''

  Ac  rA ac  0    rA ac  0
Ac dz dz
30
For the case of constant superficial velocity U

dCA
U  rA'' ac  0
dz
For reactions at steady state, the molar flux of A to the particle surface, WAr,
is equal to the rate of disappearance of A on the surface
-rA''  WAr  k（
c CA - CAs）
rA''
Substituting for
dCA
U  kc ac (CA  CAs )  0
dz
In most mass transfer–limited reactions, the surface concentration is negligible with respect
to the bulk concentration, (i.e., CA>> CAs )
dCA
U  kc acCA
dz
Integrating with the limit, at z=0, CA=CA0
kc ac
 ln (CA / CA0 )   z (25)
U 31
The concentration and conversion profiles down a reactor of length L
Figure 6-1 Axial concentration (a) and conversion (b) profiles in a packed bed.
To determine the reactor length L necessary to achieve a conversion X, we
combine the definition of conversion
CA0  CAL CAL
X  1
CA0 CA0
thus
kc ac kc ac 1 kc ac
X  1  exp (  L)  ln (1  X )   L  ln  L (26)
U U 1 X U
32
Thoenes & Kramers correlation

0.25< ϕ < 0.5, 40< Re’ <4000, and 1< Sc <4000
Sh '  1.0(Re ')1/2 (Sc)1/3 (27)
 1  Ud p  
1/ 2 1/ 3
kc d p  μ 
   
DAB (1 -  ) γ  μ(1 -  )γ    DAB 
where
Re dp = Particle diameter (equivalent diameter of a sphere of
Re'  (28) the same volume), m
(1 -  )γ
= [(6/π) (volume of pellet)]1/3, m
Sh
Sh'  (29) ϕ = Void fraction of packed bed
(1 -  )γ γ = Shape factor (external surface area divided by  d p )
2
and
U, ρ, μ, v and DAB are as previously defined
For constant fluid properties and particle diameter
kc  U1/2
33
Colburn J factor
Colburn J factor can also be applied for the determination of external
mass transfer coefficients
Sh
J D  1/3 (30)
Sc Re
Following equation is valid when Re > 10 (gases) and Re > 0.01
(liquids) in a packed bed :
0.765 0.365
 J D  0.82  0.386 (31)
Re Re
Uρd p dp = Particle diameter (equivalent diameter of a
Re 
μ sphere of the same external surface area), m
34
Example 6.2 Mass Transfer Effects in Maneuvering a Space Satellite

Hydrazine has been studied extensively for use in monopropellant thrusters for
space flights of long duration. Thrusters are used for altitude control of
communication satellites. Here, the decomposition of hydrazine over a packed
bed of alumina-supported iridium catalyst is of interest. In a proposed study, a
2% hydrazine in 98% helium mixture is to be passed over a packed bed of
cylindrical particles 0.25 cm in diameter and 0.5 cm in length at a gas-phase
velocity of 150 m/s and a temperature of 450 K. The kinematic viscosity of
helium at this temperature is 4.94×10-5 m2/s. The hydrazine decomposition
reaction is believed to be externally mass transfer–limited under these conditions.
If the packed bed is 0.05 m in length, what conversion can be expected? Assume
isothermal operation
Additional information:
DAB =0.69×10-4 m2/s at 298 K
Bed void ϕ : 40%
35
Solution
The following solution is detailed and a bit tedious, but it is important to know the details
of how a mass transfer coefficient is calculated.
Rearranging the Equation (26) gives us
(a) Using the Thoenes–Kramers correlation to calculate the mass transfer coefficient, kc
1. First we find the volume-average particle diameter
2. Surface area per volume of bed
36
3. Mass transfer coefficient

(3.61103 m)(150 m/s)
4
 10942
4.94 10 m / s
2
For cylindrical pellets
Correcting the diffusivity to 450 K using Table 6-1 gives us Go to Table 6-1
37
Substituting Re’ and Sc into the Equation (27) yields
Sh’ = (15173.92)1/2(0.35)1/3 = (123.18)(0.70) = 86.66

Rearranging the Equation (20) and (29) gives us
kc = 6.15 m/s
The conversion is
= 1-0.13 = 0.87
We find 87% conversion.
38
(b) Colburn JD factor to calculate kc. To find kc, we first calculate the surface-area-average
particle diameter.
For cylindrical pellets, the external surface area is
=11996.04
39
eq (31) in 35
=3.5×10-4 + 9.7×10-3 = 0.010
JD = 0.010/0.4 = 0.25
Rearranging the Equation (20) and (30) gives us
Sh = Sc1/3Re(JD) = (0.35)1/3(11996)(0.025) = 212
Then
= 0.9
40
Summary
Molar Flux WA For a binary system: WA = JA + yA (WA + WB )

Diffusion
dC A
Molecular Diffusion Coefficient DAB J AZ   DAB
dZ
Equimolar counter-diffusion
Binary Diffusion Three special cases Diluted solutions
Strong (forced) convection
Mass Transfer Coefficient kc

Reaction and external diffusion resistance
External Diffusion Limitation Heat transfer coefficient: Nu, Re, Pr
Mass transfer coefficient: Sh, Sc
a catalyst pellet
Example: Rapid Reaction on the Surface of a Catalyst
41
Summary
1 kc ac
Conversion X ln  L
1 X U
The Mass Transfer in a Packed bed Thoenes & Kramers correlation
Sh '  1.0(Re ')1/2 (Sc)1/3

External diffusion
Colburn J factor
limitation in a
0.765 0.365
packed bed reactor  JD  0.82
 0.386
Re Re
Example: mass transfer effects in a packed bed
42
Catalytic
Reaction Engineering
Yongdan Li
Professor of Industrial Chemistry
Department of Chemical and Metallurgical Engineering
School of Chemical Technology
Aalto University
Email: yongdan.li@aalto.fi Nov-Dec, 2017
Kemistintie 1, E404
43
Supporting Information
Table 6-1 Diffusivity relationships for gases, liquids, and solids
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Catalytic

Steps of heterogeneous reaction

Definition of diffusion and mass transfer

 Diffusion: Spontaneous mixing of atoms or molecules due to

 Mass transfer: Transfer of a mass species through the

molar amount mol

Molar flux: case 1

• A (x) and B (o) completely mixed

Molar flux: case 2

Flux due to concentration gradient and bulk flow:

WA = Molar flux for A, mol/(m2∙s) WB = Molar flux for B, mol/(m2∙s)

Analogy of heat and mass transfer

• Heat transfer: Fourier’s law • Mass transfer: Fick’s law

• As one dimensional • As one dimensional

Molar flux dependency on concentration gradient

Typically a multicomponent solution

Three special cases of binary diffusion

• Diffusion of 1 mol A in a given direction and diffusion of 1

• Fluxes of A and B equal in value with opposite signs

• Assuming constant total concentration:

WA = - DAB CA (10)

• Molar fraction of diffusing component very low

Strong (forced) convection

• Assumption: diffusion flux in the direction of flow is small,

External diffusion limitation

Diffusion of reactants to the catalyst

A single catalyst particle is first examined

External diffusion limitation

Gas or liquid bulk,

External diffusion limitation

Diffusion through a stagnant film

kc (mass transfer coefficient)

Reaction and external diffusion resistance Outer surface Centre

• In steady state: molar flux to catalyst outer surface = generation

Reaction and external diffusion resistance

Slow chemical reaction: kr << kc 

Heat transfer coefficient

Heat transfer coefficient can be determined using dimensionless

The empirical formula of Nusselt number for spherical particles:

h = Heat transfer coefficient, J/m2∙s∙K ρ = Density, kg/m3

Mass transfer coefficient

kc = Mass transfer coefficient

• Re>> 25 => Sh = 2 + 0.6 Re1/2 Sc1/3 =>

What does parts I and II describe?

 DAB 2/3   U 1/2 

• DAB increases with the increase of T • kc increases with the decrease of

Example 6.1 Rapid Reaction on the Surface of a Catalyst

Calculate the molar flux, WAr, of reactant A to a single catalyst pellet 1 cm in

Substituting these values into the Equation (22), it gives us

Rearranging the Equation (20) gives us

WAr=(4.61×10-6) m/s (103-0) mol/m3 =4.61×10-3 mol/m2∙s

Example: External diffusion limitation in a packed bed reactor

Balance equation in differential form

1 d (CAU ) '' d (CAU ) ''

For the case of constant superficial velocity U

The concentration and conversion profiles down a reactor of length L

Thoenes & Kramers correlation

Sh '  1.0(Re ')1/2 (Sc)1/3 (27)

Example 6.2 Mass Transfer Effects in Maneuvering a Space Satellite

2. Surface area per volume of bed

3. Mass transfer coefficient

For cylindrical pellets