L22-1

Review: 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
C
Extn Ab
diff
of reactant consumption in/on the pellet
Intern
diff
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! M r external area internal area
A A
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
 L22-2
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 b V
ac: external surface area per reactor volume (m2/m3)
V: reactor volume (m3) : porosity of bed (void fraction)
-rA: rate of reaction per unit surface area (mol/m2s)
-rA: mol/g cats -rA: mol/volumes
Sa: surface area of catalyst per unit mass of catalyst (m2/g cat)
per b: bulk density, catalyst mass/ reactor volume b=c(1-
volume r ' A r '' A Sa rA r ' A c rA r '' A Sa c
per surface
per mass cat k 'n k ''n Sa k n k 'n c k n k ''n Sa c area

For a 1st order reaction, simplifies to:

k1k c ac CAb
MA WAr r R ac k c C Ab CAs ac rA Sa b rA
k c ac k1Sa b
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
 L22-3

Review: 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 b k c ac


rAb 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.
 L22-4

Review: Reaction Rate Variation vs

Reactor Conditions
D D
Ud
12

1 3
p
External diffusion r ' A k c AB Sh k c AB 2 0.6
dp dp
D AB

3 c k1Sa c k1Sa
Internal diffusion rA kr CAsSa R coth R 1
k S
2 c 1 a 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

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
 L22-5

L22: Nonideal Flow & Reactor Design

So far, the reactors we have considered ideal flow patterns
Residence time of all molecules are identical
Perfectly mixed CSTRs & batch reactors
No radial diffusion in a PFR/PBR

Goal: mathematically describe non-ideal flow and solve design

problems for reactors with nonideal flow
Identify possible deviations
Measurement of residence time distribution
Models for mixing
Calculation of exit conversion in real reactors

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
 L22-6

Nonideal Flow in a CSTR

Ideal CSTR: uniform reactant concentration throughout the vessel
Real stirred tank
Relatively high reactant concentration at the feed entrance
Relatively low concentration in the stagnant regions, called dead
zones (usually corners and behind baffles)
Short Circuiting

Dead Zone

Dead Zone
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
 L22-7

Nonideal Flow in a PBR

Ideal plug flow reactor: all reactant and product molecules at any given
axial position move at same rate in the direction of the bulk fluid flow
Real plug flow reactor: fluid velocity profiles, turbulent mixing, &
molecular diffusion cause molecules to move with changing speeds and
in different directions

channeling

Dead at
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois zones
Urbana-Champaign.
 L22-8

Residence Time Distribution (RTD)

Flow through a reactor is characterized by:
1. The amount of time molecules spend in the reactor, called the RTD
2. Quality of mixing
RTD E(t) residence time distribution function
RTD is measured experimentally by injecting an inert tracer at t=0 and
measuring the tracer concentration C(t) at the exit as a function of time
Tracer should be easy to detect & have physical properties similar to the
reactant
Measurement of RTD

(PBR or PFR)
This plot would
Pulse injection Detection have the same
shape as the
pulse injection
if the reactor
had perfect
plug flow
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
 L22-9

RTD Profiles & Cum RTD Function F(t)

Tracer Conc
Tracer Conc
Tracer Conc

Tracer Conc

t t
t t
Nearly Nearly ideal PBR w/ channeling CSTR with
ideal PFR CSTR & dead zones dead zones
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
 L22-10

Calculation of RTD
The C curve
RTD E(t) residence time distribution function
C(t) RTD describes the amount of time molecules have
spent in the reactor

t
C t tracer concentration at reactor exit between time t and t+t
E t
sum of tracer concentration at exit for an infinite time
C t dt
0
Fraction of material leaving the t2
reactor that has resided in the E t dt
reactor for a time between t1 & t2 t1

E(t)=0 for t<0 since no fluid can exit before it enters
E t dt 1 E(t)0 for t>0 since mass fractions are always positive
0
t1
Fraction of fluid element in the exit stream with age less than t1 is: E t dt
0
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
 L22-11

A pulse of tracer was injected into a reactor, and the effluent concentration as
a function of time is in the graph below. Construct a figure of C(t) & E(t) and
calculate the fraction of material that spent between 3 & 6 min in the reactor
t
min 0 1 2 3 4 5 6 7 8 9 10 12 14
C
g/m3 0 1 5 8 10 8 6 4 3 2.2 1.5 0.6 0

Tabulate E(t): divide C(t) by the total area under the

Plot C vs time:
C(t) curve, which must be numerically evaluated
12 10 14
10 C t dt C t dt C t dt
8
C(t) (g/m3) 0 0 10
6 XN
t
4 f x dx f0 4f1 2f2 4f3 2f4 ... 4fN1 fN
X0 3
2
0 10 1 0 4 1 2 5 4 8 2 10 4 8
C t dt
0 2 4 6 8 10 12 14

t (min) 0 3 2 6 4 4 2 3 4 2.2 1.5
10 g min
C t dt 47.4
0 m3
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
 L22-12

A pulse of tracer was injected into a reactor, and the effluent concentration as
a function of time is in the graph below. Construct a figure of C(t) & E(t) and
calculate the fraction of material that spent between 3 & 6 min in the reactor
t
min 0 1 2 3 4 5 6 7 8 9 10 12 14
C
g/m3 0 1 5 8 10 8 6 4 3 2.2 1.5 0.6 0

Tabulate E(t): divide C(t) by the total area under the

Plot C vs time:
C(t) curve, which must be numerically evaluated
12 10 14
10 C t dt C t dt C t dt
8
C(t) (g/m3) 0 0 10
6 X2
t
4 f x dx f0 4f1 f2
X0 3
2
0 14 2
C t dt 1.5 4 0.6 0 2.6
0 2 4 6 8 10 12 14
10 3
t (min)
g min g min
g min
C t dt 47.4 2.6 50
0 m3 m3 m3
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
 L22-13

A pulse of tracer was injected into a reactor, and the effluent concentration as
a function of time is in the graph below. Construct a figure of C(t) & E(t) and
calculate the fraction of material that spent between 3 & 6 min in the reactor
t
min 00 11 22 33 44 5 5 66 77 88 99 10 12
12 14
14
C
g/m3 00 11 55 88 1010 8 8 66 44 33 2.2
2.2 1.5 0.6
0.6 00

E(t) 0 0.02 0.1 0.16 0.2 0.16 0.12 0.08 0.06 0.044 0.03 0.012 0
g min
C t dt 50 Plot E vs time:
0 m3
Tabulate E(t): divide E t C t 0.25

C(t) by the total area 0.2
under the C(t) curve: C t dt E(t) 0.15
(min-1)
0
0.1
0 1
E t0 0 E t1 0.02 0.05
50 50
0
0 2 4 6 8 10 12 14
5 8
E t2 0.1 E t3 0.16
50 50 t (min)
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
 L22-14

A pulse of tracer was injected into a reactor, and the effluent concentration as
a function of time is in the graph below. Construct a figure of C(t) & E(t) and
calculate the fraction of material that spent between 3 & 6 min in the reactor
t
min 00 11 22 33 44 5 5 66 77 88 99 10 12
12 14
14
C
g/m3 00 11 55 88 1010 8 8 66 44 33 2.2
2.2 1.5 0.6
0.6 00

E(t) 0 0.02 0.1 0.16 0.2 0.16 0.12 0.08 0.06 0.044 0.03 0.012 0

E vs time: Fraction of material that spent between 3 & 6 min in

reactor = area under E(t) curve between 3 & 6 min
0.25
Evaluate numerically:
0.2
X3
E(t) 0.15
(min-1) 3
f x dx t f0 3f1 3f2 f3
0.1 X0 8
0.05
6 3
0
0 2 4 6 8 10 12 14
E t 1 0.16 3 0.2 3 0.16 0.12
3 8
t (min) 6
E t 0.51
3
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
 L22-15

Step-Input to Determine E(t)

Disadvantages of pulse input:
Injection must be done in a very short time
Can be inaccurate when the c-curve has a long tail
Amount of tracer used must be known

Alternatively, E(t) can be determined using a step input:

Conc. of tracer is kept constant until outlet conc. = inlet conc.

injection detection
Cin
Cout
C0 C0
The C curve
t t t t

t d C t
Cout C0 E t dt E(t)
0
dt C0 step

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
 L22-16

Questions
1. Which of the following graphs would you expect to see if a pulse
tracer test were performed on an ideal CSTR?
A B C D

Tracer Conc

Tracer Conc
Tracer Conc

Tracer Conc

t t
t t
2. Which of the following graphs would you expect to see if a pulse
tracer test were performed on a PBR that had dead zones?
A B C D

Tracer Conc
Tracer Conc
Tracer Conc

Tracer Conc

t t
t t
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
 L22-17

Cumulative RTD Function F(t)

F(t) = fraction of effluent that has been in the reactor for less than time t

F t 0 when t<0
t
F(t) E t dt F t 0 when t 0 1 F t E t dt
0 t
F 1

F(t)

0.8 80% of the molecules spend 40

min or less in the reactor

t
40

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
 L22-18

Relationship between E & F Curves

F(t) = fraction of effluent that has been in the reactor for less than time t
t
F(t) E t dt
0

C t
E t
C t dt
0
E(t)= Fraction of material leaving reactor that was inside for a time between t1 & t2
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
 L22-19

Boundary Conditions for the

Cum RTD Function F(t)
C(t) C(t) C(t) C(t)

t t
t t
Nearly Nearly ideal PBR with CSTR with
ideal PFR CSTR channeling & dead zones
t dead zones
F(t) E t dt F(t)=fraction of effluent in the reactor less for than time t
0
F(t)
F t 0 when t<0
0.8 80% of the molecules
F t 0 when t 0
spend 40 min or less in
F 1 the reactor

1 F t E t dt
t t (min)
40
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
 L22-20

Mean Residence Time, tm

For an ideal reactor, the space time is defined as V/0
The mean residence time tm is equal to in either ideal or nonideal
reactors

0 tE t dt V
tm
0 tE t dt 0
tm
0 E t dt
By calculating tm, the reactor V can be determined from a tracer experiment

2 0 t tm E t dt
2
The spread of the distribution (variance):

Space time and mean residence time tm would be equal if the following
two conditions are satisfied:
No density change
No backmixing

In practical reactors the above two may not be valid, hence there will be a
difference between them
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
 L22-21

RTD in Ideal Reactors

All the molecules leaving a PFR have spent ~ the same amount of time in the
PFR, so the residence time distribution function is:
E t t where = V 0

The Dirac delta function satisfies:

when x 0
x

x dx 1
g x x dx g
0 when x 0
but =1 over the
Zero everywhere
entire interval
but one point

tm t t dt=
0

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