Topic 11 - Theory

Diffusion effects in catalysis

Fogler, Chapters 14-15

• External Diffusion Effects
o Mass Transfer
o Rapid reaction at catalyst surface
o Mass transfer vs reaction rate limited reactions
• Internal Diffusion Effects
o Diffusion and reaction in a spherical catalyst particle
o Effectiveness Factor

Slide 2
Mass Transfer

• Diffusion: spontaneous intermingling or mixing of atoms or molecules

by random thermal motion
• External diffusion: diffusion of the reactants or products between bulk
fluid and external surface of the catalyst
• Molar flux (W)
o Molecules of a given species within a single phase will always
diffuse from regions of higher concentrations to regions of lower
concentrations
o This gradient results in a molar flux of the species, (e.g., A), WA
(moles/area•time), in the direction of the concentration gradient
o A vector:

WA = iWAx + jWAy + kWAz

Slide 4
Molar Flux W & Bulk Motion BA
Molar flux consists of two parts
•Bulk motion of the fluid, BA
•Molecular diffusion flux relative to the bulk motion of the fluid
produced by a concentration gradient, JA
•WA = BA + JA (total flux = bulk motion + diffusion)
Bulk flow term for species A, BA: total flux of all molecules relative to fixed
coordinates (SWi) times the mole fraction of A (yA):
BA = y A  Wi
Or, expressed in terms of concentration of A & the molar average velocity V:
mol mol m
BA = CA V → BA = CA  yi Vi 2
= 3 
m s m s
The total molar flux of A in a binary system composed of A & B is then:
WA = JA + CA V ←In terms of concentration of A
WA = JA + CA  yi Vi
WA = JA + y A ( WA + WB ) ←In terms of mol fraction A
Slide 5
Diffusional Flux of A, JA & Molar Flux, W
WA = JA + BA (total flux = diffusion + bulk motion)
WA = JA + CA V
WA = JA + CA  yi Vi
WA = JA + y A ( WA + WB )
Diffusional flux of A resulting from a concentration difference, JA, is related
to the concentration gradient by Fick’s first law:
mol
2
JA = −cDABy A
m s
c: total concentration DAB: diffusivity of A in B yA: mole fraction of A
  
 =i + j +k gradient in rectangular coordinates
x y z
Putting it all together:
WA = −cDABy A + y A  Wi General equation
WA = −cDABy A + y A ( WA + WB ) molar flux of A in binary system of A & B
i

Effective diffusivity, DAe: diffusivity of A though multiple species

Slide 6
Simplifications for Molar Flux
WA = JA + BA (total flux = diffusion + bulk motion)

General equation: WA = −cDABy A + y A  Wi

i
WA = −cDABy A + y A ( WA + WB )
Molar flux of A in binary system of A & B

• For constant total concentration: cDAB∇yA = DAB∇CA

• When there is no bulk flow:  Wi = 0
i
• For dilute concentrations, yA is so small that: 𝑦𝐴 ෍ 𝑊𝑖 ≃ 0
𝑖

For example, consider 1M of a solute diffusing in

water, where the concentration of water is 55.6 mol
water/dm3
𝐶𝐴 1
𝑦𝐴 = = → 𝑦𝐴 = 0.018 ≃ 0
𝐶𝐴 + 𝐶𝑊 1 + 55.6

Slide 7
Evaluation of Molar Flux
Type 1: Equimolar counter diffusion (EMCD)
• For every mole of A that diffuses in a given direction, one mole of B
diffuses in the opposite direction
• Fluxes of A and B are equal in magnitude & flow counter to each other:
WA = - WB WA = −cDABy A + y A ( WA + WB )
0 bulk motion ≈ 0
→ WA = −cDABy A or for constant total concentration: WA = −DABCA
Type 2: Dilute concentration of A: 𝑦𝐴 ෍ 𝑊𝑖 ≃ 0
𝑖
WA = −cDABy A + y A ( WA + WB ) → WA = −cDABy A or constant Ctotal :
0 WA = −DABCA
Type 3: Diffusion of A though stagnant B: WB=0
−1
WA = −cDABy A + y A ( WA + WB ) → WA = cDABy A
0 1− yA
Type 4: Forced convection drives the flux of A. Diffusion in the direction
of flow (JA) is tiny compared to the bulk flow of A in that direction (z):
 volumetric flow rate
WA = −cDABy A + CA Vz → WA = CA Vz → WA = CA
0 diffusion ≈ 0 A c cross-sectional area
Slide 8
Boundary Conditions
Boundary layer
•Hydrodynamic boundary layer thickness: distance from a solid object to
where the fluid velocity is 99% of the bulk velocity U0
•Mass transfer layer thickness: distance  from a solid object to where the
concentration of the diffusing species is 99% of the bulk concentration
Typically diffusive transport is modelled by treating the fluid layer next
to a solid boundary as a stagnant film of thickness 
CAb


CAs

CAs: Concentration of A at surface CAb: Concentration of A in bulk

In order to solve a design equation that accounts for external
diffusion limitations we need to set the boundary conditions

Slide 9
Correlation for Convective Transport
Across the Boundary Layer
For convective transport across the boundary layer, the boundary condition is:
WA boundary = k c ( CAb − CAs )
The mass transfer coefficient for a single spherical particle is calculated from the
Frössling correlation:
DAB
kc = Sh
dp
kc: mass transfer coefficient DAB: diffusivity (m2/s)
dp: diameter of pellet (m) Sh: Sherwood number (dimensionless)

Sh = 2 + 0.6Re1 2 Sc1 3
Udp 
Reynold's number Re= Schmidt number: Sc =
 D AB
: kinematic viscosity or momentum diffusivity (m2/s);  = m/r
r: fluid density (kg/m3) m: dynamic viscosity (kg/m·s)
U: free-stream velocity (m/s) dp: diameter of pellet (m)
DAB: diffusivity (m2/s)

Slide 11
Rapid Reaction on Catalyst Surface
• Spherical catalyst particle in PBR CAb= 1 mol/L
• Liquid velocity past particle U = 0.1 m/s 0.01m
• Catalyst diameter dp= 1 cm = 0.01 m
• Instantaneous rxn at catalyst surface CAs≈0
CAs=0
• Bulk concentration CAb= 1 mol/L
•  ≡ kinematic viscosity = 0.5 x 10-6 m2/s Determine the flux of A to
• DAB = 1x10-10 m2/s the catalyst particle
The velocity is non-zero, so we primarily have convective mass transfer to the
catalyst particle: WA boundary = k c ( CAb − CAs )
Compute kC from k = D AB Sh Udp 
c 1
Sh = 2 + 0.6 Re Sc2 1 3 Re= Sc =
Frössling correlation: dp  D AB
0.1m s ( 0.01m ) 0.5  10 −6 m2 s
Re = → Re = 2000 Sc = → Sc = 5000
−
0.5  10 −6 m2 s 1 10 10 2
m s
Sh = 2 + 0.6 ( 2000 ) ( 5000 )
12 13
→ Sh = 461
1 10 −10 m2 s −6 m
kc = 461 → k c = 4.61 10
0.01m s
Slide 12
Rapid Reaction on Catalyst Surface
• Spherical catalyst particle in PBR CAb= 1 mol/L
• Liquid velocity past particle U = 0.1 m/s 0.01m
• Catalyst diameter dp= 1cm = 0.01m
• Instantaneous rxn at catalyst surface CAs≈0
CAs=0
• Bulk concentration CAb= 1 mol/L
• n ≡ kinematic viscosity = 0.5 x 10-6 m2/s Determine the flux of A to
• DAB = 1x10-10 m2/s the catalyst particle
The velocity is non-zero, so we primarily have convective mass transfer to the
catalyst particle: WA boundary = k c ( C Ab − C As )
Computed kC from DAB m
kc = Sh k c = 4.61 10 −6
Frössling correlation: dp s
m  mol  1000L   −3 mol
WA boundary = 4.61 10−6 1 − 0 → W = 4.61  10
s  L  m3  

A boundary
m2  s
Because the reactant is consumed as soon as it reaches the surface
mol
WA boundary = −rAs '' = 4.61 10 −3 2
m s
Slide 13
Non-instantaneous Reaction on
Catalyst Surface
For the previous example, derive an equation for the flux if the reaction were not
instantaneous, and was instead at steady state (WA|surface =-rA”) and followed the
kinetics: -rAS’’=krCAs (Observed rate is not diffusion limited)

k c ( CAb − CAs ) = WA boundary −rAs '' = kr CAs

Because the reaction at the surface is at the steady state & not instantaneous:

CAs  0 WA boundary = −rAs '' = kr CAs

So if CAs were in terms of measurable species, we would know WA,boundary
Use the equality to put CAs in terms of measurable species (solve for CAs)
k c ( C Ab − CAs ) = k r CAs → k c C Ab − k c CAs = k r CAs → k c C Ab = k r CAs + k c CAs
k c C Ab
→ k c CAb = CAs ( k r + k c ) → = C As Plug into -r’’As
kr + k c
k r k c C Ab
WA boundary = −r '' As = kr C As → WA boundary = −r '' As =
kr + k c

Slide 14
Special Cases for Reactions on
Catalyst Surface
Rapid rxn, kr>>kc→ kc in kk C
−r '' As = r c Ab
denominator is negligible kr + k c
kr k c CAb→ −r '' = k C
→ −r '' As = As c Ab
kr Diffusion limited

Slow rxn, kr<<kc→ kr in kk C

−r '' As = r c Ab
denominator is negligible kr + k c
kk C
→ −r '' As = r c Ab→ −r ''As = kr CAb
kc Reaction limited

Slide 15
 Mass Transfer & Rxn Limited Reactions
b c d
A+ B→ C+ D
a a a
A steady state mole balance on reactant A between z and z + z :
6 (1 − f )
FAz z − FAz z +z + r ''A ac (A c z) = 0 where ac =
dp
ac: external surface area of catalyst per volume of catalytic bed (m2/m3)
f: porosity of bed, void fraction dp: particle diameter (m)
r’’A: rate of generation of A per unit catalytic surface area (mol/s·m2)
Divide FAz z − FAz z +z Take limit− 1  dFAz  + r '' a = 0
+ r '' A ac = 0   A c
out Acz: A c z as z→0: A c  dz 
Put Faz and –rA’’ in terms of CA: FAz = WAz A c = (JAz + BAz )A c
Axial diffusion is negligible compared to bulk flow (convection)
FAz = BAz A c = UCA A c Substitute into the mass balance
d (UCA )  dCA dU  dCA
− + r ''A ac = 0 → −  U + CA  + r ''A ac = 0 → −U dz + r ''A ac = 0
dz  dz dz 
0
Slide 17
Mass Transfer Limited Rxn in PBR
b c d dCA
A+ B→ C+ D −U + r '' A ac = 0
a a a dz
At steady-state:
Molar flux of A to particle surface = rate of disappearance of A on the
surface −r ''A = WAr = k c ( CA − CAs ) Substitute
mass transfer coefficient kc =DAB/ (s-1) : boundary layer thickness
CAs: concentration of A at surface CA: concentration of A in bulk
dC
−U A − k c ac ( CA − CAs ) = 0 CAs ≈ 0 in most mass transfer-limited rxns
dz
dCA Rearrange & integrate to find how CA and the r’’A
→ −U − k c ac CA = 0
dz varies with distance down reactor
CA CA k c ac
dCA dCA z k c ac → = −
→ −U = k c ac C A →  = − dz ln z
dz C CA 0 U C A0 U
A0
CA  k c ac   k a   k a 
→ = exp  − z  → CA = C A0 exp  − c c z  −r ''A = k c CA0 exp  − c c z
CA0  U   U   U 
Slide 18
Reaction Rate Variation vs
Reactor Conditions
DAB   Udp   m r  
12 13
DAB
External diffusion −r ' A  k c = Sh → k c =  2 + 0.6     
dp dp   m r   DAB  
 
3  rck1Sa  rck1Sa  
Internal diffusion −rA = kr CAsSa  =  R coth  R  − 1
2 rc k1Sa  De  De  
R
De
Surface reaction -r’A=kCA
Variation of Reaction Rate with:
Type of Limitation
Superficial velocity Particle size Temperature

External U1/2 dp-3/2 Linear

Internal Independent dp-1 Exponential

Surface reaction Independent Independent Exponential

Slide 27
Topic 11 – Theory: Summary

• From this lecture you should be able to:

o describe the regimes and conditions under which
mass transfer–limited reactions occur and when
reaction rate-limited reactions occur,
o perform calculations of the rates of reaction and
mass transfer for each mass transfer and reaction
rate limited cases;
o understand the differential equations describing
diffusion and reaction;
o identify the regions of external and internal mass
transfer limitations and reaction-rate limitations
Slide 28