L21-1

Review: Heterogeneous Catalyst

We have looked at cases where
1) Adsorption, surface reaction, or desorption is rate limiting
2) External diffusion is rate limiting
3) Internal diffusion is rate limiting
Next goal: Derive an overall rate law for heterogeneous catalyst where the
rate limiting step as any of the 7 reaction steps. This new overall reaction
rate would be inserted into the design equation to get W, XA, CA, etc

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
 L21-2

Review: Internal Diffusion Effects in

Spherical Catalyst Particles
Internal diffusion: diffusion of reactants or products from particle surface
(pore mouth) to pellet interior
Concentration at the pore mouth will be higher than that inside the pore

Step 1) Mole balance over the shell thickness r is:

Internal IN - OUT + GEN = ACCUM
CAb
diffusion
WAr 4r 2 r WAr 4r 2 r r rA 4rm2r c 0

CAs R Volume of shell

External r
diffusion rA: rxn rate per mass of catalyst
c: catalyst density
rm: mean radius between r and r - r

Divide by -4/r & take

d WAr r 2 r r 2 Differential BMB in
limit as r 0 A c 0 spherical catalyst particle
dr
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
 L21-3
Review: Diffusion & Rxn in Spherical
CAs Catalyst

d WAr r 2 r r 2 0 (step 1, BMB)
A c
R dr
r
r+r System at steady state, so EMCD: WB = -WA
(otherwise A or B would accumulate)
dy A dC
WA cDe De A
dr dr

Rate law:
mol n mol catalyst surface area
r ''A k C
n A -r ' A r ''A S A SA
2
m s g cat s mass of catalyst

Insert diffusion eq & d dCA 2 2 n Solve for CA(r) & get

D r r S k "C 0
rate eq into BMB: dr e dr C A n A WAr(r) from diffusion eq

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
 L21-4

Review:Dimensionless Variables
d dCA 2 2 n
D e r r C A n A 0 Put into dimensionless form
S k " C
dr dr
n 2 n1
r CA k " S R C k " S R C
n2 n a c As n2 n a c As
R CAs De CAs 0 R De
d2 2 d 2 n Boundary Conditions:

n 0
d 2 d =1 at =1 =finite at =0
Thiele modulus for rxn of nth order n "a" surface rxn rate
n2
Subscript n = reaction order "a" diffusion rate
n is small: surface reaction is rate limiting
n is large: internal diffusion is rate limiting small 1
CA
The solution for C A 1 sinh 1
CAs sinh 1 medium 1
C As
a 1st order rxn:
large 1
small 1: surface rxn control, significant amount of reactant
diffuses into pellet interior w/out reacting R r=0
large 1: surface rxn is rapid, reactant is consumed very closed to the external surface of
pellet (A waste of precious metal inside of pellet)
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
 L21-5

Review: Internal Effectiveness Factor,

actual observed overall rate of rxn

eta rate of reaction if entire interior surface were exposed to CAs & Ts
rA r ''A r 'A mass of catalyst

rAs r ''As r 'As mass of catalyst

Effectiveness factor vs n
2 knR2Sac CAsn1
1 n
0.8 Reaction limited De
0.6
As particle diameter ,
0.4 n , 1, rxn is
surface rxn limited
0.2
Internal diffusion limited As particle diameter ,
0.1 n , 0, rxn is
0.2 1 2 4 6 8 10 diffusion limited
1
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
 L21-6

Review: Effectiveness Factor & Rxn Rate

ck1Sa
rA rAs
k1CAs Sa
3
1 coth 1 1 1 R
De
12
R 1 1 surface-reaction-limited
3 3 De
when 1 ,( 30) can be simplified to: , 1
1 R k1c Sa
1 is large, diffusion-limited reaction inside the pellet (external diffusion will have a
negligible effect on the overall rxn rate because internal diffusion limits the rxn rate)
rA 3 3 De
1 coth 1 1 When internal-diffusion-limited:

rAs 12 R k1c Sa
3 De 3 De Sak1
rA k1CAs Sa rA k1CAs Sa -rA
c
CAs
R k1c Sa R
Overall rate for 1st-order rxn
To increase the overall rate of a rxn limited by internal diffusion
(1) decrease the radius R (3) increase the concentration of A
(2) increase the temperature (4) increase the internal surface area
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
 L21-7

L21: Simultaneous Internal

Diffusion & External Diffusion
Goal: Derive a new rate eq that accounts for internal & external diffusion
-rA is a function of reactant concentration
Reactant conc is affected by internal & external diffusion
Express reactant conc in terms of diffusion-related constants & variables
Use mole balance
At steady-state: transport of reactants from bulk
CAs fluid to external catalyst surface is equal to net rate
CAb of reactant consumption in/on the pellet

C(r) Molar rate of mass transfer from bulk fluid to

external surface: MA WAr ac V

molar flux reactor volume

external surface area per unit reactor volume
This molar rate of mass transfer to surface is equal to net rxn rate on & in pellet!
MA rA external area internal area
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
 L21-8

Basic Molar Balance at Pellet Surface

Flux: Actual rxn
bulk to External rate per external +
x = x
external S.A. unit total internal S.A.
surface S.A.

WAr r R ac V
rA ac V Sa bV
ac: external surface area per reactor volume (m2/m3)
V: reactor volume (m3)
-rA: rate of reaction per unit surface area (mol/m2s)
Sa: surface area of catalyst per unit mass of catalyst (m2/g cat)
b: bulk density, catalyst mass/ reactor volume b=c(1-
: porosity of bed (void fraction) c: catalyst density
MA WAr r R ac V rA ac V Sa b V
MA WAr r R ac rA ac Sa b
Typically external surface area <<< internal surface area
MA WAr r R ac rA Sa b
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
 L21-9

Overall Molar Rate of Reaction

Overall rxn rate = flux to surface = rxn rate on & in pellet
MA WAr r R ac rA Sa b
For external mass transport: WAr r R kc CAb CAs
Since internal diffusion resistance is also significant, the reactant conc at the
internal surface is lower that the reactant conc at the external surface:
r ''A
r ''As r ''A For a 1st order rxn: -rA=-k1CAs
r ''As
actual observed overall rate of rxn
where the internal
effectiveness factor: rxn rate if entire interior surface were exposed to C As & Ts
Plug flux & 1st order rxn rate back into the mass balance:
MA k c CAb CAs ac k1CAsSa b Solve mass balance for CAs
kcCAbac kcCAsac k1CAsSa b kcCAbac k1CAsSa b kcCAsac
k c CAbac
k c CAbac CAs k1Sa b k c ac CAs
k1Sa b k c ac
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
 L21-10

Overall Effectiveness Factors

k c ac CAb
CAs Finally insert CAs into rA
k c ac k1Sa b
k1k c acC Ab Overall rxn rate with internal
rA k1CAs rA
k c ac k1Sa b & external diffusion

Is this the overall rxn rate that we ALWAYS use for a

surface reaction that has internal & external?
(a) Yes, we should always use this rate equation for a surface reaction
(b) No, we should only use this rate eq for processes that use spherical
catalyst pellets
(c) No, we should only use this rate eq for processes that that involve
catalyst particles that have a constant density & even catalyst loading
on the surface
(d) No, we should only use this rate eq for 1st order irreversible reactions
(e) b, c, & d
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
 L21-11

Overall Effectiveness Factors

k c ac CAb
CAs Finally insert CAs into rA
k c ac k1Sa b
k1k c ac CAb Overall rxn rate with internal
rA k1CAs rA
k c ac k1Sa b & external diffusion

Remember, the internal effectiveness factor (based on CAs) is:

actual overall rate of reaction

rate of rxn if entire interior surface were exposed to the external surface conditions
The overall effectiveness factor (based on CAb) is defined as:
Omega
actual overall rate of reaction

rate of reaction if entire interior surface were exposed to the bulk conditions
rA k1CAb


rAb 1 k1Sa b k c ac

k1CAb 1 k1Sa b k c ac
rAb
r ''A Put into design eq to account for internal & external diffusion
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
 L21-12

Rxn Rate Variation vs Reactor

Conditions
D D Ud
12

13
r 'A k c AB Sh k c AB 2 0.6
p
External diffusion
dp dp
DAB

3 ck1Sa ck1Sa
Internal diffusion rA kr CAsSa R coth R 1
2 ck1Sa De De
R
De
Surface reaction -rA=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

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
 L21-13
Consider an isothermal catalytic reaction in a PBR where there is no pressure
drop and the catalyst pellets are uniformly packed & spherical. The kinetics
are 1st order, and k, all physical parameters, and the inlet conditions (pure A
in feed, A products) are given. Derive an equation for XA, taking into
account the diffusion to and within each catalyst particle, but ignore diffusion
down the length of the reactor.
dX A Rate must account for diffusion &
PBR design eq: F A0 r ' A
dW be in terms of catalyst surface area

1. Put rate in terms of the unit surface area: -r 'A r ''A Sa

2. Account for diffusion limitations in rate eq: r ''A rAb
-r 'A r ''Ab Sa

3. Rate is 1st order: r ''Ab kCAb -r 'A kCAbSa

dX A
4. Put into design eq: FA0 kCAb Sa
dW
dX A
5. Put Cab in terms of XA: CAb CAb0 1 X A FA0 kSaCAb0 1 X A
dW
6. Integrate: dXA kSaCAb0 1 XA XA
dXA W kS C
a Ab0 dW
dW FA0 0 1 X A 0 FA0
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
 L21-14
Consider an isothermal catalytic reaction in a PBR where there is no pressure
drop and the catalyst pellets are uniformly packed & spherical. The kinetics
are 1st order, and k, all physical parameters, and the inlet conditions (pure A
in feed, A products) are given. Derive an equation for XA, taking into
account the diffusion to and within each catalyst particle, but ignore diffusion
down the length of the reactor.

XA
dXA W kS C kSaCAb0 W
6. Integrate: a Ab0 dW ln 1 X A
0 1 X A 0 FA0 FA0

kSaCAb0 W kSaCAb0 W
7. Solve for XA: ln 1 X A FA0
FA0 1 XA e

kSaCAb0 W kSa W
FA0 0
XA 1 e XA 1 e

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
 L21-15
XA for 1st
order rxn executed in an isothermal PBR packed with spherical
catalyst particles with internal & external diffusion limitations
kSa W
0
XA 1 e
For same conditions, eq derived in Fogler (12-71) for XA at end of reactor of
length L is:
kSa bL
XA 1 e U

catalyst mass kg 0
where : b = 3 L= z U=superficial velocity=
reactor volume m Ac
Are these equations the same?
kSa W kSa bL
They differ in the exponent: ?
0 U

W bL W b L A c L A c V W b V W W V V W W
? ? ? ?
0 0 0 0 0 0 0 0 0 0
Ac kSa W kSa bL
0
XA 1 e 1 e U XA
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.