L21b-1

Review: Simultaneous Internal

Diffusion & External Diffusion
Goal: Derive a new rate eq that accounts for internal & external diffusion
• -r’A 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: M  W  a  V
A Ar c

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.
 L21b-2
Review: Basic Molar Balance at
Spherical Pellet Surface
Flux: Actual rxn
bulk to External rate per external +
x = x
external S.A. unit total internal S.A.
surface S.A.
MA  WAr r R ac V  rA  ac V  Sa rb V 
ac: external surface area per reactor volume (m2/m3)
V: reactor volume (m3) f: porosity of bed (void fraction)
-r’’A: rate of reaction per unit surface area (mol/m2·s)
-r’A: mol/g cat∙s -rA: mol/volume∙s
Sa: surface area of catalyst per unit mass of catalyst (m2/g cat)
per rb: bulk density, catalyst mass/ reactor volume rb=rc(1-f
volume r ' A  r '' A Sa  rA  r ' A rc  rA  r '' A Sa rc
per surface
per mass cat→ k 'n  k ''n Sa kn  k 'n rc kn  k ''n Sa rc area
Cancel out V & ac ≈0 since external surface area usually <<< internal surface
area (surface area of internal pores)
 MA  WAr r R ac  rA Sa rb
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
 L21b-3

Review: Overall Molar Rate of Reaction

MA  WAr r R ac  rA Sa rb
For external mass transport: WAr r R  kc  CAb  CAs 

Internal diffusion resistance is significant, so the reactant conc at the internal

surface is lower that the reactant conc at the external surface:
: internal effectiveness factor
r ''A observed rxn rate For a 1st order rxn:
     r ''As   r ''A
r ''As rxn rate if no internal diff limit -r’’A=-k1CAs

Plug flux & 1st order rxn rate back into the mass balance, solve for CAs:
k c CAb ac
MA  k c  CAb  CAs  ac  k1CAsSa rb  CAs 
k ''1 Sa rb  k c ac
Insert CAs into –r’’A=k1CAs:

k1k c ac CAb Overall 1st order rxn rate with

rA 
k c ac  k1Sa rb internal & external diffusion

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
 L21b-4

Review: Overall Effectiveness Factors

Remember, the internal effectiveness factor is based on CAs
actual overall rate of reaction

rate of rxn if entire interior surface were exposed to the external surface conditions

The overall effectiveness factor is based on CAb:

Omega
actual overall rate of reaction

rate of reaction if entire interior surface were exposed to the bulk conditions

k1CAb
rA 1  k1Sa rb k c ac 
  

rAb k1CAb 1  k1Sa rb 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.
 L21b-5

Review: Observed Rxn Rate Variation

vs FT0, dp & T
D AB   Udp    r  
12 13
External
r ' A  k c  C Ab  C As  kc   2  0.6     
diffusion limited: dp 
   r   D AB  

Internal diffusion r  k C S   3  rck1Sa  rck1Sa  

A r As a r k S
 R coth  R   1
D  De 
limited: R2 c 1 a  e 
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
Whether the rate varies when FT0 or particle size changes indicates tells us whether
external diffusion, internal diffusion, or the surface rxn is limiting (slowing down) the
observedEngr
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular rate
Dept, University of Illinois at Urbana-Champaign.
 L21b-6
Review: Rxn Rate Variation vs Reactor
Conditions
When the observed rate of a reaction is limited by external diffusion,
internal diffusion, or the surface rxn, the observed reaction kinetics are:
D AB   Udp    r  
12 13
Rate for external
r ' A  k c  C Ab  C As  k c   2  0.6     
diff limited rxn: dp 
   r   D AB   
kc: mass transfer coefficient DAB: diffusivity (m2/s) dp: diameter
U: free-stream velocity (m/s),  to flow rate (FT, FT0) for constant CA0
n: kinematic viscosity (m2/s); n/r r: fluid density (kg/m3) : viscosity

Rate for internal r  k C S   3  rck1Sa  rck1Sa  

A r As a r k S
 R coth  R   1
D  De 
diff limited rxn: R2 c 1 a  e 
De
R: radius at
actual  observed overall rate of rxn
particle surface 
De: effective diffusivity rate of rxn if entire interior surface were exposed to C As & Ts

Rate for surface reaction limited rxn: -r’A = kCA

Whether the rate varies when FT0 (at constant CT0) or particle size
changes indicates tells us whether external diffusion, internal diffusion,
orofthe
Slides courtesy Profsurface rxn is limiting
M L Kraft, Chemical (slowing
& Biomolecular down)
Engr Dept, the of
University observed rate
Illinois at Urbana-Champaign.
 L21b-7

Observed Rxn Rate vs FT0, dp & T

D AB   Udp    r  
12 13
Rate for external
r ' A  k c  C Ab  C As  kc   2  0.6     
diff limited rxn: dp 
   r   D AB  
dp: diameter U: free-stream velocity (m/s),  to flow rate (FT, FT0) for constant CA0

Rate for internal r  k C S   3  rck1Sa  rck1Sa  

A r As a r k S
 R coth  R   1
D  De 
diff limited rxn: R2 c 1 a  e 
R: radius at particle surface De
Rate for surface reaction limited rxn: -r’A= kCA
According to these equations, if we increase the flow rate (FT0) without
increasing the concentration of reactants in the feed, the observed rxn rate
will increase if the rxn is limited (slowed down) by:
a. External diffusion Free-stream velocity (U), which is  to flow rate for
b. Internal diffusion constant CA0, is only in rate eq for a external
diffusion limited reaction
c. The surface reaction
d. Either external & internal diffusion
e. Any of these (external diffusion, internal diffusion, or surface reaction)
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
The graph below shows the reaction rates obtained when the irreversible, liquid- L21b-8
phase, catalytic reaction A→B was carried out in a PBR using the indicated catalyst dp,
T, and FT0. CA0 was the same in each trial.
16 FT0=4000 mol/h, T=400K
14 FT0=4000 mol/h, T=300K
12 FT0=3500 mol/h, T=400K
-rA (mol/g cat*h)

FT0=3500 mol/h, T=300K

10
FT0=1000 mol/h, T=400K
8
FT0=1500 mol/h, T=400K
6
FT0=2000 mol/h, T=400K
4
2
0
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9
dp (cm)
Which, if any, of the conditions shown (flow rates, T, and dp) is the reaction limited by
external diffusion?
External diffusion limits the observed rate when increasing FT0 increases –r’A
• Need to find the points that have the same T and dp. If the rate increases when Fto
increases, the trial at the LOWER flow rate is limited by external diffusion
Trial with T = 400K, dp= 0.8 cm & FT0= 1000 mol/h has a lower rate than the trial with
T = 400K, dp= 0.8 cm & FT0= 1500 mol/h
Thus, rate is limited by external diffusion when T = 400K, dp= 0.8 cm & FT0= 1000 mol/h
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
The graph below shows the reaction rates obtained when the irreversible, liquid- L21b-9
phase, catalytic reaction A→B was carried out in a PBR using the indicated catalyst dp,
T, and FT0. CA0 was the same in each trial.
16 FT0=4000 mol/h, T=400K
14 FT0=4000 mol/h, T=300K
12 FT0=3500 mol/h, T=400K
-rA (mol/g cat*h)

FT0=3500 mol/h, T=300K

10
FT0=1000 mol/h, T=400K
8
FT0=1500 mol/h, T=400K
6
FT0=2000 mol/h, T=400K
4
2
ext diff lim
0
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9
dp (cm)
Which, if any, of the conditions shown (flow rates, T, and dp) is the reaction limited by
external diffusion?
External diffusion limits the observed rate when increasing FT0 increases –r’A
• Need to find the points that have the same T and dp. If the rate increases when Fto
increases, the trial at the LOWER flow rate is limited by external diffusion
Trial with T = 400K, dp= 0.8 cm & FT0= 1500 mol/h has a lower rate than the trial with
T = 400K, dp= 0.8 cm & FT0= 2000 mol/h
Thus, rate is limited by external diffusion when T = 400K, dp= 0.8 cm & FT0= 1500 mol/h
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
The graph below shows the reaction rates obtained when the irreversible, liquid- L21b-10
phase, catalytic reaction A→B was carried out in a PBR using the indicated catalyst dp,
T, and FT0. CA0 was the same in each trial.
16 FT0=4000 mol/h, T=400K
14 FT0=4000 mol/h, T=300K
12 FT0=3500 mol/h, T=400K
-rA (mol/g cat*h)

FT0=3500 mol/h, T=300K

10
FT0=1000 mol/h, T=400K
8
FT0=1500 mol/h, T=400K
6
FT0=2000 mol/h, T=400K
4 ext diff lim
2
ext diff lim
0
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9
dp (cm)
Which, if any, of the conditions shown (flow rates, T, and dp) is the reaction limited by
external diffusion?
External diffusion limits the observed rate when increasing FT0 increases –r’A
• Need to find the points that have the same T and dp. If the rate increases when Fto
increases, the trial at the LOWER flow rate is limited by external diffusion
Trial with T = 400K, dp= 0.8 cm & FT0= 2000 mol/h has a lower rate than the trial with
T = 400K, dp= 0.8 cm & FT0= 3500 mol/h
Thus, rate is limited by external diffusion when T = 400K, dp= 0.8 cm & FT0= 2000 mol/h
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
The graph below shows the reaction rates obtained when the irreversible, liquid- L21b-11
phase, catalytic reaction A→B was carried out in a PBR using the indicated catalyst dp,
T, and FT0. CA0 was the same in each trial.
16 FT0=4000 mol/h, T=400K
14 FT0=4000 mol/h, T=300K
12 FT0=3500 mol/h, T=400K
-rA (mol/g cat*h)

FT0=3500 mol/h, T=300K

10
FT0=1000 mol/h, T=400K
8 ext diff lim
FT0=1500 mol/h, T=400K
6
FT0=2000 mol/h, T=400K
4 ext diff lim
2
ext diff lim
0
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9
dp (cm)
Which, if any, of the conditions shown (flow rates, T, and dp) is the reaction limited by
external diffusion?
External diffusion limits the observed rate when increasing FT0 increases –r’A
• Need to find the points that have the same T and dp. If the rate increases when Fto
increases, the trial at the LOWER flow rate is limited by external diffusion
Trial with T = 400K, dp= 0.8 cm & FT0= 3500 mol/h has the same rate as the trial with
T = 400K, dp= 0.8 cm & FT0= 4000 mol/h
Rate is NOT limited by external diffusion when T = 400K, dp= 0.8 cm & FT0= 3500 mol/h
or T =courtesy
Slides 400K,ofdProf
p= 0.8
M L cm
Kraft,&Chemical
FT0= 4000 mol/h Engr Dept, University of Illinois at Urbana-Champaign.
& Biomolecular
The graph below shows the reaction rates obtained when the irreversible, liquid- L21b-12
phase, catalytic reaction A→B was carried out in a PBR using the indicated catalyst dp,
T, and FT0. CA0 was the same in each trial.
16 FT0=4000 mol/h, T=400K
14 FT0=4000 mol/h, T=300K
12 FT0=3500 mol/h, T=400K
-rA (mol/g cat*h)

FT0=3500 mol/h, T=300K

10
FT0=1000 mol/h, T=400K
8 ext diff lim
FT0=1500 mol/h, T=400K
6
FT0=2000 mol/h, T=400K
4 ext diff lim
2
ext diff lim
0
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9
dp (cm)
Which, if any, of the conditions shown (flow rates, T, and dp) is the reaction limited by
external diffusion?
External diffusion limits the observed rate when increasing FT0 increases –r’A
• Need to find the points that have the same T and dp. If the rate increases when Fto
increases, the trial at the LOWER flow rate is limited by external diffusion
For all remaining trials, increasing FT0 does not increase the reaction rate, so no other
trial conditions are external diffusion limited.

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
The graph below shows the reaction rates obtained when the irreversible, liquid- L21b-13
phase, catalytic reaction A→B was carried out in a PBR using the indicated catalyst dp,
T, and FT0. CA0 was the same in each trial.
16 FT0=4000 mol/h, T=400K
14 FT0=4000 mol/h, T=300K
12 FT0=3500 mol/h, T=400K
-rA (mol/g cat*h)

FT0=3500 mol/h, T=300K

10
FT0=1000 mol/h, T=400K
8 ext diff lim
FT0=1500 mol/h, T=400K
6
FT0=2000 mol/h, T=400K
4 ext diff lim
2 ext diff lim
0
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9
dp (cm)
Which, if any, of the conditions shown (flow rates, T, and dp) is the reaction limited by
internal diffusion?
Internal diffusion limits the observed rate when decreasing dp increases –r’A
• Need to find the points that have the same T. If the rate increases when dp
decreases but does not change with FT0, the trial at the larger dp is limited by
internal diffusion
Trial with T = 400K, dp= 0.8 cm & FT0= 3500 mol/h has a lower rate than the trial with
T = 400K, dp= 0.6 cm & FT0= 3500 mol/h
Thus, rate is limited by internal diffusion when T = 400K, dp= 0.8 cm & FT0= 3500 mol/h
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
The graph below shows the reaction rates obtained when the irreversible, liquid- L21b-14
phase, catalytic reaction A→B was carried out in a PBR using the indicated catalyst dp,
T, and FT0. CA0 was the same in each trial.
16 FT0=4000 mol/h, T=400K
14 FT0=4000 mol/h, T=300K
12 FT0=3500 mol/h, T=400K
-rA (mol/g cat*h)

FT0=3500 mol/h, T=300K

10
int diff lim FT0=1000 mol/h, T=400K
8 ext diff lim
FT0=1500 mol/h, T=400K
6
FT0=2000 mol/h, T=400K
4 ext diff lim
2 ext diff lim
0
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9
dp (cm)
Which, if any, of the conditions shown (flow rates, T, and dp) is the reaction limited by
internal diffusion?
Internal diffusion limits the observed rate when decreasing dp increases –r’A
• Need to find the points that have the same T. If the rate increases when dp
decreases but does not change with FT0, the trial at the larger dp is limited by
internal diffusion
Trial with T = 400K, dp= 0.8 cm & FT0= 4000 mol/h has a lower rate than the trial with
T = 400K, dp= 0.6 cm & FT0= 4000 mol/h
Thus, rate is limited by internal diffusion when T = 400K, dp= 0.8 cm & FT0= 4000 mol/h
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
The graph below shows the reaction rates obtained when the irreversible, liquid- L21b-15
phase, catalytic reaction A→B was carried out in a PBR using the indicated catalyst dp,
T, and FT0. CA0 was the same in each trial.
16 FT0=4000 mol/h, T=400K
14 FT0=4000 mol/h, T=300K
12 FT0=3500 mol/h, T=400K
-rA (mol/g cat*h)

int diff lim FT0=3500 mol/h, T=300K

10
int diff lim FT0=1000 mol/h, T=400K
8 ext diff lim
FT0=1500 mol/h, T=400K
6
FT0=2000 mol/h, T=400K
4 ext diff lim
2 ext diff lim
0
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9
dp (cm)
Which, if any, of the conditions shown (flow rates, T, and dp) is the reaction limited by
internal diffusion?
Internal diffusion limits the observed rate when decreasing dp increases –r’A
• Need to find the points that have the same T. If the rate increases when dp
decreases but does not change with FT0, the trial at the larger dp is limited by
internal diffusion
Trial with T = 400K, dp= 0.6 cm & FT0= 3500 mol/h has a lower rate than the trial with
T = 400K, dp= 0.2 cm & FT0= 3500 mol/h
Thus, rate is limited by internal diffusion when T = 400K, dp= 0.6 cm & FT0= 3500 mol/h
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
The graph below shows the reaction rates obtained when the irreversible, liquid- L21b-16
phase, catalytic reaction A→B was carried out in a PBR using the indicated catalyst dp,
T, and FT0. CA0 was the same in each trial.
16 FT0=4000 mol/h, T=400K
14 FT0=4000 mol/h, T=300K
12 FT0=3500 mol/h, T=400K
int diff
-rA (mol/g cat*h)

int diff lim FT0=3500 mol/h, T=300K

10 lim int diff lim FT0=1000 mol/h, T=400K
8 ext diff lim
FT0=1500 mol/h, T=400K
6
FT0=2000 mol/h, T=400K
4 ext diff lim
2 ext diff lim
0
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9
dp (cm)
Which, if any, of the conditions shown (flow rates, T, and dp) is the reaction limited by
internal diffusion?
Internal diffusion limits the observed rate when decreasing dp increases –r’A
• Need to find the points that have the same T. If the rate increases when dp
decreases but does not change with FT0, the trial at the larger dp is limited by
internal diffusion
Trial with T = 400K, dp= 0.6 cm & FT0= 4000 mol/h has a lower rate than the trial with
T = 400K, dp= 0.2 cm & FT0= 4000 mol/h
Thus, rate is limited by internal diffusion when T = 400K, dp= 0.6 cm & FT0= 4000 mol/h
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
The graph below shows the reaction rates obtained when the irreversible, liquid- L21b-17
phase, catalytic reaction A→B was carried out in a PBR using the indicated catalyst dp,
T, and FT0. CA0 was the same in each trial.
16 FT0=4000 mol/h, T=400K
14 FT0=4000 mol/h, T=300K
int diff lim FT0=3500 mol/h, T=400K
12 int diff
-rA (mol/g cat*h)

int diff lim FT0=3500 mol/h, T=300K

10 lim int diff lim FT0=1000 mol/h, T=400K
8 ext diff lim
FT0=1500 mol/h, T=400K
6
FT0=2000 mol/h, T=400K
4 ext diff lim
2 ext diff lim
0
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9
dp (cm)
Which, if any, of the conditions shown (flow rates, T, and dp) is the reaction limited by
internal diffusion?
Internal diffusion limits the observed rate when decreasing dp increases –r’A
• Need to find the points that have the same T. If the rate increases when dp
decreases but does not change with FT0, the trial at the larger dp is limited by
internal diffusion
Trial with T = 400K, dp= 0.2 cm & FT0= 3500 mol/h has a lower rate than the trial with
T = 400K, dp= 0.1 cm & FT0= 3500 mol/h
Thus, rate is limited by internal diffusion when T = 400K, dp= 0.2 cm & FT0= 3500 mol/h
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
The graph below shows the reaction rates obtained when the irreversible, liquid- L21b-18
phase, catalytic reaction A→B was carried out in a PBR using the indicated catalyst dp,
T, and FT0. CA0 was the same in each trial.
16 FT0=4000 mol/h, T=400K
14 FT0=4000 mol/h, T=300K
int diff lim int diff lim FT0=3500 mol/h, T=400K
12 int diff
-rA (mol/g cat*h)

int diff lim FT0=3500 mol/h, T=300K

10 lim int diff lim FT0=1000 mol/h, T=400K
8 ext diff lim
FT0=1500 mol/h, T=400K
6
FT0=2000 mol/h, T=400K
4 ext diff lim
2 ext diff lim
0
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9
dp (cm)
Which, if any, of the conditions shown (flow rates, T, and dp) is the reaction limited by
internal diffusion?
Internal diffusion limits the observed rate when decreasing dp increases –r’A
• Need to find the points that have the same T. If the rate increases when dp
decreases but does not change with FT0, the trial at the larger dp is limited by
internal diffusion
Trial with T = 400K, dp= 0.2 cm & FT0= 4000 mol/h has a lower rate than the trial with
T = 400K, dp= 0.1 cm & FT0= 4000 mol/h
Thus, rate is limited by internal diffusion when T = 400K, dp= 0.2 cm & FT0= 4000 mol/h
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
The graph below shows the reaction rates obtained when the irreversible, liquid- L21b-19
phase, catalytic reaction A→B was carried out in a PBR using the indicated catalyst dp,
T, and FT0. CA0 was the same in each trial.
16 FT0=4000 mol/h, T=400K
14 int diff lim FT0=4000 mol/h, T=300K
int diff lim int diff lim FT0=3500 mol/h, T=400K
12 int diff
-rA (mol/g cat*h)

int diff lim FT0=3500 mol/h, T=300K

10 lim int diff lim FT0=1000 mol/h, T=400K
8 ext diff lim
FT0=1500 mol/h, T=400K
6
FT0=2000 mol/h, T=400K
4 ext diff lim
2 ext diff lim
0
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9
dp (cm)
Which, if any, of the conditions shown (flow rates, T, and dp) is the reaction limited by
internal diffusion?
Internal diffusion limits the observed rate when decreasing dp increases –r’A
• Need to find the points that have the same T. If the rate increases when dp
decreases but does not change with FT0, the trial at the larger dp is limited by
internal diffusion
Trial with T = 400K, dp= 0.1 cm & FT0= 3500 mol/h has the SAME rate as the trial with
T = 400K, dp= 0.05 cm & FT0= 3500 mol/h
Rate israte
Thus, NOT is limited by internal diffusion when T = 400K, dp= 0.1 0.2 cm & FT0= 3500 4000 mol/h
or T =courtesy
Slides 400K,ofdProf
p= 0.05 cm Chemical
M L Kraft, & FT0= 3500 mol/h Engr Dept, University of Illinois at Urbana-Champaign.
& Biomolecular
The graph below shows the reaction rates obtained when the irreversible, liquid- L21b-20
phase, catalytic reaction A→B was carried out in a PBR using the indicated catalyst dp,
T, and FT0. CA0 was the same in each trial.
16 FT0=4000 mol/h, T=400K
14 int diff lim FT0=4000 mol/h, T=300K
int diff lim int diff lim FT0=3500 mol/h, T=400K
12 int diff
-rA (mol/g cat*h)

int diff lim FT0=3500 mol/h, T=300K

10 lim int diff lim FT0=1000 mol/h, T=400K
8 ext diff lim
FT0=1500 mol/h, T=400K
6
FT0=2000 mol/h, T=400K
4 ext diff lim
2 ext diff lim
0
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9
dp (cm)
Which, if any, of the conditions shown (flow rates, T, and dp) is the reaction limited by
internal diffusion?
Internal diffusion limits the observed rate when decreasing dp increases –r’A
• Need to find the points that have the same T. If the rate increases when dp
decreases but does not change with FT0, the trial at the larger dp is limited by
internal diffusion
For all remaining trials, decreasing dp does not increase the reaction rate, so no other
trial conditions are internal diffusion limited.

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
The graph below shows the reaction rates obtained when the irreversible, liquid- L21b-21
phase, catalytic reaction A→B was carried out in a PBR using the indicated catalyst dp,
T, and FT0. CA0 was the same in each trial.
16 FT0=4000 mol/h, T=400K
14 int diff lim FT0=4000 mol/h, T=300K
int diff lim int diff lim FT0=3500 mol/h, T=400K
12 int diff
-rA (mol/g cat*h)

int diff lim FT0=3500 mol/h, T=300K

10 lim int diff lim FT0=1000 mol/h, T=400K
8 ext diff lim
FT0=1500 mol/h, T=400K
6
FT0=2000 mol/h, T=400K
4 ext diff lim
2 ext diff lim
0
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9
dp (cm)
Which, if any, of the conditions shown (flow rates, T, and dp) is the reaction limited by
the surface reaction?
The surface reaction limits the reaction rate when the observed rxn rate increases
when we increase T, but it does not increase when we decrease dp or increase FT0
without increasing CT0
For all remaining trials, neither decreasing dp nor increasing FT0 increases the
reaction rate. Therefore, the surface reaction limits (slows down) the rates of the
remaining trial conditions.
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
The graph below shows the reaction rates obtained when the irreversible, liquid- L21b-22
phase, catalytic reaction A→B was carried out in a PBR using the indicated catalyst dp,
T, and FT0. CA0 was the same in each trial.
16 FT0=4000 mol/h, T=400K
14 int diff lim FT0=4000 mol/h, T=300K
int diff lim int diff lim FT0=3500 mol/h, T=400K
12 int diff
-rA (mol/g cat*h)

SRL int diff lim FT0=3500 mol/h, T=300K

10 lim int diff lim FT0=1000 mol/h, T=400K
8 ext diff lim
FT0=1500 mol/h, T=400K
6
FT0=2000 mol/h, T=400K
4 ext diff lim
2 ext diff lim
SRL
0
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9
dp (cm)
Which, if any, of the conditions shown (flow rates, T, and dp) is the reaction limited by
the surface reaction?
For all remaining trials, neither decreasing dp nor increasing FT0 increases the
reaction rate. Therefore, the surface reaction limits (slows down) the rates of the
remaining trial conditions. Surface reaction limited (SRL):
T = 400K, dp= 0.1 cm & FT0= 3500 mol/h, T = 400K, dp= 0.05 cm & FT0= 3500 mol/h,
T = 400K, dp= 0.1 cm & FT0= 4000 mol/h, T = 400K, dp= 0.05 cm & FT0= 4000 mol/h,
T = 300K, all dp tested, & FT0= 4000 mol/h & T = 300K, all dp tested, & FT0= 3500 mol/h
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
 The catalytic reaction A→B takes L21b-23

place in a fixed bed reactor containing

spherical porous catalyst X22. The

-r’A (mol/gcat·s)
overall rxn rates at a point in the
reactor are shown in the graph below.
For which, if any, of the conditions
shown (flow rates and temps) is the
reaction limited by external diffusion?
External diffusion limited where –r’A↑
linearly when T↑

Type of Variation of Reaction Rate with:

Limitation Superficial velocity Particle size Temperature
External U1/2 dp-3/2 Linear
Internal Independent dp-1 Exponential
Surface reaction Independent Independent Exponential
For FT0 = 10 mol/h, the rate of rxn increases approximately linearly with T over
the entire temperature range- external diffusion limited at FT0 = 10 and all T
For FT0 = 100 mol/h, the rate of rxn increases ~linearly with T when T > 360K.
The reaction is external diffusion limited when FT0 = 100 & T> 360K
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
 The catalytic reaction A→B takes Rxn rates ↑ exp
L21b-24

place in a fixed bed reactor containing with T but not

spherical porous catalyst X22. The FT0 for FT0 =

-r’A (mol/gcat·s)
100, 1000 &
overall rxn rates at a point in the 5000 mol/h at
reactor are shown in the graph below. T< 360K
For which, if any, of the conditions
shown (flow rates and temps) is the
ext diff lim
reaction limited by surface reaction
rate?
Surface rxn limited when –r’Aincreases
exponentially with T↑ but independent of superficial velocity (flow!)
Type of Variation of Reaction Rate with:
Limitation Superficial velocity Particle size Temperature
External U1/2 dp-3/2 Linear
Internal Independent dp-1 Exponential
Surface reaction Independent Independent Exponential
For conditions FT0 = 100, 1000 & 5000 mol/h at T< 360K, rxn rate is
independent of FT0 but exponentially dependent on T→ surface reaction limited

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
 The catalytic reaction A→B takes For FT0 = 1000
L21b-25

place in a fixed bed reactor containing & 5000 mol/h

spherical porous catalyst X22. The at T< 366K, rxn

-r’A (mol/gcat·s)
rates ↑ exp with
overall rxn rates at a point in the T but not FT0
reactor are shown in the graph below.
For which, if any, of the conditions
shown (flow rates and temps) is the
ext diff lim
reaction limited by surface reaction
rate?
Surface rxn limited when –r’Aincreases
exponentially with T↑ but independent of velocity
Type of Variation of Reaction Rate with:
Limitation Superficial velocity Particle size Temperature
External U1/2 dp-3/2 Linear
Internal Independent dp-1 Exponential
Surface reaction Independent Independent Exponential
For FT0 = 100, 1000 & 5000 mol/h at T< 360K → surface reaction limited

For conditions FT0 = 1000 & 5000 mol/h at T< 366K, rxn rate is independent of
FT0 but exponentially dependent on T→ surface reaction limited
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
 The catalytic reaction A→B takes Rxn rates ↑ exp
L21b-26

place in a fixed bed reactor containing with T but not

spherical porous catalyst X22. The FT0 for FT0=

-r’A (mol/gcat·s)
overall rxn rates at a point in the 1000 & 5000
mol/h at T>
reactor are shown in the graph below. 367K
For which, if any, of the conditions
shown (flow rates and temps) is the
ext diff lim
reaction limited by internal diffusion?

Internal diffusion limited when –r’Aincreases

exponentially with T↑ & is independent of velocity
Type of Variation of Reaction Rate with:
Limitation Superficial velocity Particle size Temperature
External U1/2 dp-3/2 Linear
Internal Independent dp-1 Exponential
Surface reaction Independent Independent Exponential

For FT0 = 1000 & 5000 mol/h at T> 367K, rxn rate is roughly independent of
FT0 but exponentially dependent on T. The reaction rate is internal diffusion
limited at T> 370K for FT0 = 1000 & 5000 mol/h
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
 The catalytic reaction A→B takes L21b-27

place in a fixed bed reactor containing

spherical porous catalyst X22. The

-r’A (mol/gcat·s)
overall rxn rates at a point in the
reactor are shown in the graph below.
For which, if any, of the conditions
shown (flow rates and temps) is the
ext diff lim
reaction limited by internal diffusion?

Internal diffusion limited when –r’Aincreases

exponentially with T↑ & is independent of velocity
Type of Variation of Reaction Rate with:
Limitation Superficial velocity Particle size Temperature
External U1/2 dp-3/2 Linear
Internal Independent dp-1 Exponential
Surface reaction Independent Independent Exponential

How do we know it’s not surface rxn limited at FT0=1000 & 5000 mol/h & T>367K?
As T↑, the specific rate constant k↑, the rate of the surface rxn & consumption of
reactant ↑. Thus the reactant is more likely to be consumed before it reaches the
core.
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
 The catalytic reaction A→B takes L21b-28

place in a fixed bed reactor containing

spherical porous catalyst X22. The

-r’A (mol/gcat·s)
overall rxn rates at a point in the
reactor are shown in the graph below.
For a flow rate of 10 g mol/h,
determine the overall effectiveness
factor  at 360K

actual overall rxn rate


rxn rate if entire interior surface were exposed to the bulk conditions

Rxn w/out diffusion limitations

rA
    0.26    0.37

rAb 0.70
What do we use for the rate of reaction if the interior was exposed to bulk conditions?

Use the rxn rate obtained under surface reaction limited conditions

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
 The catalytic reaction A→B takes L21b-29

place in a fixed bed reactor containing

spherical porous catalyst X22. The

-r’A (mol/gcat·s)
overall rxn rates at a point in the
reactor are shown in the graph below.
For FT0= 5000 g mol/h, estimate the
internal effectiveness factor  at 367K

actual overall rate of reaction


rate of rxn if entire interior surface were exposed to the external surface conditions

Rxn w/out internal diffusion limitations

r ''A
    1.2    0.86
r ''As 1.4
What do we use for the rate of reaction if the interior was exposed to the conditions at
the surface of the pellet?
Extrapolate the line for the surface reaction limited regime of the FT0 = 5000 mol/h plot
to estimate the rxn rate that would be obtained without internal diffusion
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
 L21b-30
Cl2 is removed from a waste stream by passing the effluent gas over a solid granular
absorbent in a tubular PBR. Presently 63.2% is removed and the reaction is external
diffusion limited. If the flow rate were increases by a factor of 4, the particle diameter
were decreased by a factor of 3, and the tube length (z) were increased by 1.5x, what
percentage of Cl2 would be removed (assume still external diffusion limited)? What
guidelines (T, CA, u) do you propose for efficient operation of this bed?
XA1=0.632 for dp, z, & u0 XA2=? for dp1/3, 1.5z1, and 4u0,1

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.
 L21b-31
Cl2 is removed from a waste stream by passing the effluent gas over a solid granular
absorbent in a tubular PBR. Presently 63.2% is removed and the reaction is external
diffusion limited. If the flow rate were increases by a factor of 4, the particle diameter
were decreased by a factor of 3, and the tube length (z) were increased by 1.5x, what
percentage of Cl2 would be removed (assume still external diffusion limited)? What
guidelines (T, CA, u) do you propose for efficient operation of this bed?
XA1=0.632 for dp, z, & u0 XA2=? for dp1/3, 1.5z1, and 4u0,1

Need to relate XA to reactor length in the presence of an external diffusion limit

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
 L21b-32
Review: Mass Transfer Limited Rxn in
PBR
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 out FAz z  FAz z z Take limit  1  dFAz   r '' a  0
 r ''A ac  0   A c
Acz: A c z as z→0: A c dz 
Put Faz and –rA’’ in terms of CA: FAz  WAz Ac  (JAz  BAz )Ac
Axial diffusion is negligible compared to bulk flow (convection)
FAz  BAz Ac  UCA Ac Substitute into the mass balance
d UCA   dCA dU  dCA
  r ''A ac  0    U  C A   r '' a
A c  0  U  r '' A ac  0
dz  dz dz  dz
0
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
 L21b-33
Review: Mass Transfer Limited Rxn in
PBR (continued)
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/d (s-1) d: boundary layer thickness
CAs: concentration of A at surface CA: concentration of A in bulk
dCA
U  k c ac  C A  C As   0 CAs ≈ 0 in most mass transfer-limited rxns
dz
dC Rearrange & integrate to find how CA and the r’’A
 U A  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 CA0 U
A0
CA  k a   k a   k a 
  exp   c c z   CA  CA0 exp   c c z  r ''A  k c CA0 exp   c c z 
CA0  U   U   U 
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
 L21b-34
Cl2 is removed from a waste stream by passing the effluent gas over a solid granular
absorbent in a tubular PBR. Presently 63.2% is removed and the reaction is external
diffusion limited. If the flow rate were increases by a factor of 4, the particle diameter
were decreased by a factor of 3, and the tube length (z) were increased by 1.5x, what
percentage of Cl2 would be removed (assume still external diffusion limited)? What
guidelines (T, CA, u) do you propose for efficient operation of this bed?
XA1=0.632 for dp, z, & u0 XA2=? for dp1/3, 1.5z1, and 4u0,1
ac: external surface
area of catalyst per a  6 1  f 
For an external diffusion
CA  k a 
limited rxn in a PBR, we  exp   c c z
found (L19): CA0  U  catalyst bed volume c dp
f: porosity of bed
In terms of XA: CA0 1  X A   k a  k c ac
 exp   c c z   ln 1  X A    z
CA0  U  U

Express XA at 2 ln 1  XA1  k c1ac1zU2 Relate U to u0 & ac to dp


reaction conditions ln 1  XA2  k c2ac2 1.5z  U1
as a ratio:
6 1  f  U=u0 Ac where Ac  cross-sectional area of PBR
ac1 dp1
 ac1 dp2 U1 u0,1 A c U1 u0,1
ac2 6 1  f   a  d   
c2 p1 U2 u0,2 A c U2 u0,2
dp2
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
 L21b-35
Cl2 is removed from a waste stream by passing the effluent gas over a solid granular
absorbent in a tubular PBR. Presently 63.2% is removed and the reaction is external
diffusion limited. If the flow rate were increases by a factor of 4, the particle diameter
were decreased by a factor of 3, and the tube length (z) were increased by 1.5x, what
percentage of Cl2 would be removed (assume still external diffusion limited)? What
guidelines (T, CA, u) do you propose for efficient operation of this bed?
XA1=0.632 for dp, z, & u0 XA2=? for dp1/3, 1.5z1, and 4u0,1
ln 1  XA1  k c1ac1zU2 ac1 dp2 U1 u0,1 How are kc1 and kc2
  
ln 1  XA2  k c2ac2 1.5z  U1 ac2 dp1 U2 u0,2 related?

DAB   Udp   n  
12 13
kc   2  0.6      Typically the 2 is negligible so
dp 
  n   DAB  
12
DAB  Udp   n 
13
DAB2 3 U1 2
 kc   0.6    D   k c  0.6
dp  n   AB  n 1 6 dp1 2

DAB 23 U11 2
k c1  U11 2  dp,2 
12 12
k c1 0.6 n 1 6 dp,1
    
k c2 0.6 DAB2 3 U21 2 k c2  dp,1  U2 
1 2 1 2
  
n 1 6 dp,21 2
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
 L21b-36
Cl2 is removed from a waste stream by passing the effluent gas over a solid granular
absorbent in a tubular PBR. Presently 63.2% is removed and the reaction is external
diffusion limited. If the flow rate were increases by a factor of 4, the particle diameter
were decreased by a factor of 3, and the tube length (z) were increased by 1.5x, what
percentage of Cl2 would be removed (assume still external diffusion limited)? What
guidelines (T, CA, u) do you propose for efficient operation of this bed?
XA1=0.632 for dp, z, & u0 XA2=? for dp1/3, 1.5z1, and 4u0,1
ln 1  XA1  k c1ac1zU2 ln 1  X A1  k c1  ac1   z  U2
     
ln 1  XA2  k c2ac2 1.5z  U1 ln 1  X A2  k c2  ac2   1.5z  U1

ac1 dp2 U1 u0,1 k c1  U11 2  dp,2 

12
    
ac2 dp1 U2 u0,2 k c2  dp,1  U2 

1 2

1 2

ln 1  X A1   U11 2  dp,2   dp2   z  u0,2
12
     
ln 1  X A2   dp,1  U2   dp1   1.5z  u0,1
1 2 1 2
  
ln 1  X A1   U 1 2 dp,23 2   1  u ln 1  X   u 1 2 dp,23 2   1  u
   11 2  
0,2
 A1
  0,1  
0,2
ln 1  X A 2   U2 dp,13 2   1.5  u0,1 ln 1  X A2   u0,21 2 dp,13 2   1.5  u0,1
   

1   ln 1  0.632    0,1  p,1    1 

 32  4u 1 2 d 3 3 2 
ln 1  X A1  u0,2 dp,2
12

      1.5 
ln 1  X A2   u0,11 2dp,13 2   1.5  ln 1  X A2   u0,11 2dp,13 2
   
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
 L21b-37
Cl2 is removed from a waste stream by passing the effluent gas over a solid granular
absorbent in a tubular PBR. Presently 63.2% is removed and the reaction is external
diffusion limited. If the flow rate were increases by a factor of 4, the particle diameter
were decreased by a factor of 3, and the tube length (z) were increased by 1.5x, what
percentage of Cl2 would be removed (assume still external diffusion limited)? What
guidelines (T, CA, u) do you propose for efficient operation of this bed?
XA1=0.632 for dp, z, & u0 XA2=? for dp1/3, 1.5z1, and 4u0,1


 4u 1 2 d 3 3 2 
ln 1  0.632   0,1

p,1  
 1   ln 1  0.632   2 1 3 3 2 0.667
ln 1  X A2   u0,11 2dp,13 2   1.5  ln 1  XA2 
 

ln  0.368  0.99967
  0.257   0.257
ln 1  XA2  ln 1  XA2 

 3.8898  ln 1  X A2   e3.8898  1  XA2  0.0204  1  XA2

 XA2  0.98

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
 L21b-38
Cl2 is removed from a waste stream by passing the effluent gas over a solid granular
absorbent in a tubular PBR. Presently 63.2% is removed and the reaction is external
diffusion limited. If the flow rate were increases by a factor of 4, the particle diameter
were decreased by a factor of 3, and the tube length (z) were increased by 1.5x, what
percentage of Cl2 would be removed (assume still external diffusion limited)? What
guidelines (T, CA, u) do you propose for efficient operation of this bed?
XA1=0.632 for dp, z, & u0 XA2=0.98 for dp1/3, 1.5z1, and 4u0,1

Hint for T: The conversion of 0.98 is dependent on the reaction still being external
diffusion-limited. How can we adjust the T, CA, and u to make sure that the process
is not instead slowed down by the surface reaction, but without slowing down
external diffusion?

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

• To keep the rate of Cl2 consumption (surface reaction) faster than external diffusion
(still in external diffusion limited regime), use high T

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
 L21b-39
Cl2 is removed from a waste stream by passing the effluent gas over a solid granular
absorbent in a tubular PBR. Presently 63.2% is removed and the reaction is external
diffusion limited. If the flow rate were increases by a factor of 4, the particle diameter
were decreased by a factor of 3, and the tube length (z) were increased by 1.5x, what
percentage of Cl2 would be removed (assume still external diffusion limited)? What
guidelines (T, CA, u) do you propose for efficient operation of this bed?
XA1=0.632 for dp, z, & u0 XA2=0.98 for dp1/3, 1.5z1, and 4u0,1

Hint: How does changing CA and u influence the rate of external diffusion and the
surface reaction?
• The mass transfer rate can be increased by increasing the concentration gradient,
which is achieved by increasing the bulk concentration of A

k c  0.6
DAB 23
u0,1 Ac 
12

n1 6 dp1 2
• Increasing the volumetric flow rate u0 increases the mass transfer coefficient but
reduces the spacetime, and therefore XA. The process also becomes reaction
limited instead of external diffusion limited. XA,mass x-fer a kc a u01/2 but XA,reaction a t a
u01 so the increase in u0 may be offset by a reaction-limited decrease in
conversion, assuming constant packed-bed properties. We would need the
parameters for the reaction to evaluate whether increasing u0 is a good idea.
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.