L22-1

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
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 ) ΔV
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 = −rAʹ′ʹ′ ( external area + internal area )
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
 Review: Basic Molar Balance at
L22-2

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 ΔV = −rAʹ′ʹ′ (ac ΔV + Sa ρbΔV )
ac: external surface area per reactor volume (m2/m3)
ΔV: reactor volume (m3) φ: 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 ρb: bulk density, catalyst mass/ reactor volume ρb=ρc(1-φ)
volume −r 'A = −r ''A Sa − rA = −r 'A ρc − rA = −r ''A Sa ρc
per surface
per mass cat→ k 'n = k ''n Sa kn = −k 'n ρc kn = k ''n Sa ρc area

For a 1st order reaction, simplifies to:

ηk1k c ac CAb
→ MA = WAr r =R ac → k c ( CAb − CAs ) ac = −rA Sa ρb
ʹ′
ʹ′ →→ −rAʹ′
ʹ′ =
k c ac + ηk1Sa ρb
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
η=
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
Ω=
rate of reaction if entire interior surface were exposed to the bulk conditions

ηk1CAb
−rAʹ′ʹ′ 1 + ηk1Sa ρb k c ac η
Ω= →Ω= →Ω=
−rAb
ʹ′ʹ′ k1CAb 1 + ηk1Sa ρb k c ac

→ Ω ( −rAb
ʹ′ʹ′ ) = −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 12 13
DAB DAB ⎛ ⎛ Ud ⎞ ⎛ µ ρ ⎞ ⎞
p
External diffusion −r 'A ∝ k c = Sh → k c = ⎜ 2 + 0.6 ⎜ ⎟ ⎜ ⎟ ⎟
dp dp ⎜ ⎝ µ ρ ⎠ ⎝ DAB ⎠ ⎟⎠
⎝
3 ⎛ ρck1Sa ⎛ ρck1Sa ⎞ ⎞
Internal diffusion −rAʹ′ = ηkr CAsSa η = ⎜⎜ R coth ⎜ R ⎟ − 1⎟⎟
ρ k S De De ⎠ ⎠
R2 c 1 a ⎝ ⎝
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 atzones
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois 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

τ t τ 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+Δt
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/
0 1 5 8 10 8 6 4 3 2.2 1.5 0.6 0
m3
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
Δt
4 ∫ f ( x ) dx = ( f0 + 4f1 + 2f2 + 4f3 + 2f4... + 4fN−1 + fN )
X0 3
2
0 10 1 ⎡0 + 4 (1) + 2 (5 ) + 4 (8 ) + 2 (10 ) + 4 (8 )⎤
0 2 4 6 8 10 12 14 ∫ C ( t ) dt = ⎢ ⎥
0 3 ⎣ +2 ( 6 ) + 4 ( 4 ) + 2 ( 3 ) + 4 ( 2.2 ) + 1.5 ⎦
t (min)
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/
0 1 5 8 10 8 6 4 3 2.2 1.5 0.6 0
m3
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
Δt
4 ∫ f ( x ) dx = ( f0 + 4f1 + f2 )
X0 3
2
0 14 2
0 2 4 6 8 10 12 14 ∫ C ( t ) dt = ⎡⎣1.5 + 4 (0.6 ) + 0 ⎤⎦ = 2.6
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/
00 11 55 88 1010 8 8 66 44 33 2.2
2.2 1.5 0.6
0.6 00
m3
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) (min-1)
0 0.15
0.1
0 1
E ( t0 ) = = 0 E ( t1 ) = = 0.02 0.05
50 50
0
5 8 0 2 4 6 8 10 12 14
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/
00 11 55 88 1010 8 8 66 44 33 2.2
2.2 1.5 0.6
0.6 00
m3
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
3
E(t) (min-1)

0.15 ∫ f ( x ) dx = Δt ( f0 + 3f1 + 3f2 + f3 )

0.1 X0 8
0.05 6 3
0 ∫ E (t ) = (1) (0.16 + 3 (0.2) + 3 (0.16 ) + 0.12)
3 8
0 2 4 6 8 10 12 14
6
t (min) → ∫ 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) = ⎜ ⎟
dt ⎝ C0 ⎠step
0

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 τ 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 τ 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.
 Boundary Conditions for the
L22-19

Cum RTD Function F(t)

C(t) C(t) C(t) C(t)

τ t τ 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 τ is defined as V/υ0
•  The mean residence time tm is equal to τ in either ideal or nonideal
reactors
∞
∫0 tE ( t ) dt ∞ V
= τ = tm
tm = ∞ = ∫0 tE ( t ) dt = τ
∫0 E ( t ) dt υ0

By calculating tm, the reactor V can be determined from a tracer experiment

2
The spread of the distribution (variance): σ 2 = ∫0∞ ( t − tm ) E ( t ) dt

Space time τ 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 ) = δ ( t − τ ) where τ =V υ0

The Dirac delta function satisfies:

⎧∞ when x = 0
δ ( x ) = ⎨ ∫
∞
−∞ δ ( x ) dx = 1
∞
∫−∞ g ( x ) δ ( x − τ ) dx = g (τ )
⎩ 0 when x ≠ 0
…but =1 over the
Zero everywhere
entire interval
but one point
∞
tm = ∫ tδ ( t − τ )dt=τ
0

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