L23b-1

Review: Nonideal Flow & Reactor Design

Real CSTRs Real PBRs
• Relatively high reactant conc at • fluid velocity profiles, turbulent
entrance mixing, & molecular diffusion
• Relatively low conc in stagnant cause molecules to move at
regions, called dead zones varying speeds & directions
(corners & behind baffles)
Short Circuiting channeling

Dead Zone

Dead zones

Dead Zone

Goal: mathematically describe non-ideal flow and solve design problems

for reactors with nonideal flow
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
 L23b-2

Residence Time Distribution (RTD)

RTD ≡ E(t) ≡ “residence time distribution” function
RTD describes the amount of time molecules have spent in the reactor
RTD is experimentally determined by injecting an inert “tracer” at t=0 and
measuring the tracer concentration C(t) at exit as a function of time
Measurement of RTD The C curve
Reactor X C(t)
↑ ↓
Pulse injection Detection
t
C t tracer conc at exit between t & t+t
E t   
0 C  t  dt sum of tracer conc at exit for infinite time

 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

Fraction of material leaving reactor that has  t2 E  t  dt


been inside reactor for a time between t1 & t2 t1
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
 L23b-3

E(t) E(t) E(t) E(t) Nice multiple

choice
question

 t t  t t
Nearly Nearly ideal PBR with CSTR with
ideal PFR CSTR dead zones dead zones

The fraction of the exit stream that has resided in the reactor for a period
of time shorter than a given value t:
F(t) is a cumulative distribution function
0 E  t  dt  F  t 
t


t E  t  dt  1  F  t 
0.8
F  t   0 when t<0 80% of the molecules
spend 40 min or less in
F  t   0 when t  0 the reactor
F    1
40
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
 L23b-4

Review: Mean Residence Time, tm

• For an ideal reactor, the space time  is defined as V/u0
• 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
The spread of the distribution (variance):  2  0  t  tm  E  t  dt

Space time t 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, Urbana-Champaign.
 L23b-5

Review: Complete Segregation Model

Mixing of different
‘age groups’ at the
last possible
moment

• Flow is visualized in the form of globules

• Each globule consists of molecules of the same residence time
• Different globules have different residence times
• No interaction/mixing between different globules
The mean conversion is the average conversion of the various globules in
the exit stream: X   X t E t t
A j A  j  j
Conversion achieved after Fraction of globules that spend
spending time tj in the reactor between tj and tj + Dt in the reactor

t 0
 X A   XA  t  E  t  dt
 XA(t) is from the batch
0 reactor design equation
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
 L23b-6

Review: Maximum Mixedness Model

In a PFR: as soon as the fluid enters the reactor, it is completely mixed
radially with the other fluid already in the reactor. Like a PFR with side
entrances, where each entrance port creates a new residence time:
 ∞ 0E( ) 0

u0
  

V=0  +Dl  V = V0
: time it takes for fluid to move from a particular point to end of the reactor
u():
l):volumetric flow rate at l, = flow that entered at l+Dl plus what entered
through the sides
u 0E(l)D l: Volumetric flow rate of fluid fed into side ports of reactor in interval
between  +  & 
Volumetric flow rate of fluid fed to reactor at :      0  E    d  0 1  F    
fraction of effluent that in reactor for less than time t
Volume of fluid with life expectancy between  +  & :V  0 1  F     
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
 L23b-7
For a pulse tracer expt, the effluent concentration C(t) & RTD function E(t) are given
in the table below. The irreversible, liquid-phase, nonelementary rxn A+B→C+D,
-rA=kCACB2 will be carried out isothermally at 320K in this reactor. Calculate the
conversion for (1) an ideal PFR and (2) for the complete segregation model.
CA0=CB0=0.0313 mol/L & k=176 L2/mol2·min at 320K
t min 0 1 2 3 4 5 6 7 8 9 10 12 14
C
0 1 5 8 10 8 6 4 3 2.2 1.5 0.6 0
g/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

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
 L23b-8
For a pulse tracer expt, the effluent concentration C(t) & RTD function E(t) are given
in the table below. The irreversible, liquid-phase, nonelementary rxn A+B→C+D,
-rA=kCACB2 will be carried out isothermally at 320K in this reactor. Calculate the
conversion for (1) an ideal PFR and (2) for the complete segregation model.
CA0=CB0=0.0313 mol/L & k=176 L2/mol2·min at 320K
t min 0 1 2 3 4 5 6 7 8 9 10 12 14
C
0 1 5 8 10 8 6 4 3 2.2 1.5 0.6 0
g/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
Start with PFR design eq & see how far can we get:
dX A rA dX A kCA CB2
   CA  CA0  1  XA  CB  CB0  1  XA 
dV FA0 dV CA00
3 2
dX A kCA0CB0  1  XA 
2 A X V kC
Get like terms dX A B0 dV
     
0 0
3
dV CA00 together & integrate 0  1  XA 

XA
1  kCB02  1 2 1
   V 2
 1  2kCB0   X A  1 
2
2  1  X A   0 0  1  X A  2kCB02  1

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
 L23b-9
For a pulse tracer expt, the effluent concentration C(t) & RTD function E(t) are given
in the table below. The irreversible, liquid-phase, nonelementary rxn A+B→C+D,
-rA=kCACB2 will be carried out isothermally at 320K in this reactor. Calculate the
conversion for (1) an ideal PFR and (2) for the complete segregation model.
CA0=CB0=0.0313 mol/L & k=176 L2/mol2·min at 320K
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
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
t*E(t) 0 0.02 0.2 0.48 0.8 0.8 0.72 0.56 0.48 0.396 0.3 0.144 0
For an ideal reactor, t =
1 How do we
XA  1  t tm  0 tE  t  dt
2kCB02  1 determine t? m
 10 14
Use numerical method tm   tE  t  dt   tE  t  dt   tE  t  dt
to determine tm: 0 0 10
10 1 0  4  0.02   2  0.2   4  0.48   2  0.8   4  0.8  
 tE  t  dt     4.57
0 3  2  0.72   4  0.56   2  0.48   4  0.396   0.3 
14 2
 tE  t  dt  0.3  4  0.144   0   0.584  tm  4.57  0.584  5.15min
10 3
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
 L23b-10
For a pulse tracer expt, the effluent concentration C(t) & RTD function E(t) are given
in the table below. The irreversible, liquid-phase, nonelementary rxn A+B→C+D,
-rA=kCACB2 will be carried out isothermally at 320K in this reactor. Calculate the
conversion for (1) an ideal PFR and (2) for the complete segregation model.
CA0=CB0=0.0313 mol/L & k=176 L2/mol2·min at 320K
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
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
t*E(t) 0 0.02 0.2 0.48 0.8 0.8 0.72 0.56 0.48 0.396 0.3 0.144 0

1 For an ideal PFR reactor, t = tm

XA  1  tm  5.15min  
2kCB02  1 tm  0 tE  t  dt

1
X A,PFR  1 
  2
L2 mol 
2  176
 2   0.0313   5.15min   1
 mol  min   L 

X A,PFR  0.40
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
 L23b-11
For a pulse tracer expt, the effluent concentration C(t) & RTD function E(t) are given
in the table below. The irreversible, liquid-phase, nonelementary rxn A+B→C+D,
-rA=kCACB2 will be carried out isothermally at 320K in this reactor. Calculate the
conversion for an ideal PFR, the complete segregation model and maximum mixedness
model. CA0=CB0=0.0313 mol/L & k=176 L2/mol2·min at 320K
t min 0 1 2 3 4 5 6 7 8 9 10 12 14
C
0 1 5 8 10 8 6 4 3 2.2 1.5 0.6 0
g/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

Segregation model: X A   X A  t  E  t  dt XA(t) is from batch reactor design eq
0
Numerical method
1. Solve batch reactor design equation to determine eq for XA
2. Determine XA for each time
3. Use numerical methods to determine X̄ A
Polymath Method
1. Use batch reactor design equation to find eq for XA
2. Use Polymath polynomial curve fitting to find equation for E(t)
3. Use Polymath to determine X̄ A

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
 L23b-12
For a pulse tracer expt, the effluent concentration C(t) & RTD function E(t) are given
in the table below. The irreversible, liquid-phase, nonelementary rxn A+B→C+D,
-rA=kCACB2 will be carried out isothermally at 320K in this reactor. Calculate the
conversion for an ideal PFR, the complete segregation model and maximum mixedness
model. CA0=CB0=0.0313 mol/L & k=176 L2/mol2·min at 320K
t min 0 1 2 3 4 5 6 7 8 9 10 12 14
C
0 1 5 8 10 8 6 4 3 2.2 1.5 0.6 0
g/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

Segregation model: X A   X A  t  E  t  dt XA(t) is from batch reactor design eq
0
Batch design eq: NA0  C A0 V
dX A dX A dX A 3
NA0  rA V  NA0  kCA0CB02  1  X A 
3
V  kCB02  1  XA 
dt dt dt
X A
XA t 
Stoichiometry: dX A 1
    kCB02dt    kCB0
2
t
rA  kC A CB 2 0  1  XA  3 0
2
2  1  X A   0

C A  CA0  1  XA  1 1
  1  2kCB02 t  X A  1 
CB  CB0  1  XA   1  XA  2 1  2kCB02 t

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
 L23b-13
For a pulse tracer expt, the effluent concentration C(t) & RTD function E(t) are given
in the table below. The irreversible, liquid-phase, nonelementary rxn A+B→C+D,
-rA=kCACB2 will be carried out isothermally at 320K in this reactor. Calculate the
conversion for an ideal PFR, the complete segregation model and maximum mixedness
model. CA0=CB0=0.0313 mol/L & k=176 L2/mol2·min at 320K
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

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
XA

Segregation model:
 1 1
X A   X A  t  E  t  dt XA  1   1
0 1  2kCB02 t 1  0.3429min1 t
Plug in each t & solve
Numerical method 1
XA 0   1  1
0
1  0.3429min  0
1
X A  1  1  1
 0.137
1  0.3429min  1min 
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
 L23b-14
For a pulse tracer expt, the effluent concentration C(t) & RTD function E(t) are given
in the table below. The irreversible, liquid-phase, nonelementary rxn A+B→C+D,
-rA=kCACB2 will be carried out isothermally at 320K in this reactor. Calculate the
conversion for an ideal PFR, the complete segregation model and maximum mixedness
model. CA0=CB0=0.0313 mol/L & k=176 L2/mol2·min at 320K
t min 0 1 2 3 4 5 6 7 8 9 10 12 14
C
0 1 5 8 10 8 6 4 3 2.2 1.5 0.6 0
g/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
XA 0 0.137 0.23 0.298 0.35 0.39 0.428 0.458 0.483 0.505 0.525 0.558 0.585

Segregation X   X t E t dt 1 1
A  A    XA  1   1
model: 0 1  2kCB02 t 1  0.3429min1 t
 10 14
Numerical method X A   X A  t  E  t  dt   X A  t  E  t  dt   X A  t  E  t  dt
0 0 10
0  4  0.137   0.02   2  0.23   0.1  4  0.298   0.16  
10 1 
 X A  t  E  t  dt   2  0.35   0.2   4  0.39   0.16   2  0.428   0.12   4  0.458   0.08  
3
0  2  0.483   0.06   4  0.505   0.044   0.525  0.03  
 
10
 X A  t  E  t  dt  0.35
0
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
 L23b-15
For a pulse tracer expt, the effluent concentration C(t) & RTD function E(t) are given
in the table below. The irreversible, liquid-phase, nonelementary rxn A+B→C+D,
-rA=kCACB2 will be carried out isothermally at 320K in this reactor. Calculate the
conversion for an ideal PFR, the complete segregation model and maximum mixedness
model. CA0=CB0=0.0313 mol/L & k=176 L2/mol2·min at 320K
t min 0 1 2 3 4 5 6 7 8 9 10 12 14
C
0 1 5 8 10 8 6 4 3 2.2 1.5 0.6 0
g/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
XA 0 0.137 0.23 0.298 0.35 0.39 0.428 0.458 0.483 0.505 0.525 0.558 0.585

Segregation X   X t E t dt 1 1
A  A    XA  1   1
model: 0 1  2kCB02 t 1  0.3429min1 t
 14
Numerical method X A   XA  t  E  t  dt  0.35   X A  t  E  t  dt
0 10
14 2
 X A  t  E  t  dt   0.525   0.03   4  0.558   0.012    0.585  0   0.0425
10 3

X A   X A  t  E  t  dt  0.35  0.04  XA  0.39
0
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
 L23b-16
For a pulse tracer expt, the effluent concentration C(t) & RTD function E(t) are given
in the table below. The irreversible, liquid-phase, nonelementary rxn A+B→C+D,
-rA=kCACB2 will be carried out isothermally at 320K in this reactor. Calculate the
conversion for an ideal PFR, the complete segregation model and maximum mixedness
model. CA0=CB0=0.0313 mol/L & k=176 L2/mol2·min at 320K
t min 0 1 2 3 4 5 6 7 8 9 10 12 14
C
0 1 5 8 10 8 6 4 3 2.2 1.5 0.6 0
g/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
XA 0 0.137 0.23 0.298 0.35 0.39 0.428 0.458 0.483 0.505 0.525 0.558 0.585

Alternative approach: segregation model by Polymath:

 1
dX A
X A   X A  t  E  t  dt  XA  t  E  t  XA  1 
0 dt 1  2kCB02 t

Need an equation for E(t) k=176

CB0=0.0313

Use Polymath to fit the E(t) vs t data in the table to a polynomial

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
 L23b-17
time E(t)

For the irreversible, liquid-

phase, nonelementary rxn
A+B→C+D, -rA=kCACB2
Calculate the XA using the
complete segregation model
using Polymath

Gave best fit

E(t) = 0 at t=0

Model: C02= a1*C01 + a2*C01^2 + a3*C01^3 + a4*C01^4

a1=0.0889237
a2= -0.0157181
a3= 0.0007926
a4= -8.63E-06
Final Equation: E= 0.0889237*t -0.0157181*t2 + 0.0007926*t3 – 8.63E-6*t4
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
Complete segregation model by Polymath L23b-18

A+B→C+D
-rA=kCACB2

Segregation model by Polymath: X A  0.36

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
 L23b-19
For a pulse tracer expt, the effluent concentration C(t) & RTD function E(t) are given
in the table below. The irreversible, liquid-phase, nonelementary rxn A+B→C+D,
-rA=kCACB2 will be carried out isothermally at 320K in this reactor. Calculate the
conversion for an ideal PFR, the complete segregation model and maximum mixedness
model. CA0=CB0=0.0313 mol/L & k=176 L2/mol2·min at 320K
t min 0 1 2 3 4 5 6 7 8 9 10 12 14
C
0 1 5 8 10 8 6 4 3 2.2 1.5 0.6 0
g/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

Maximum mixedness model: dX A  rA  E    X l=time

dF
E
d CA0 1  F    A d
F(l) is a cumulative distribution function
rA  kC A0CB02  1  XA 
3
C A0  CB0  0.0313mol L k  176 L2
mol2  min
Polymath cannot solve because l→0 (needs to increase)
Substitute l for z, where z=T̅-l where T̅=longest time interval (14 min)
dX A  rA E  T  z  dF E must be in terms of T̅-z.
   XA   E  T  z  Since T̅-z=l & l=t, simply
 C A0 1  F  T  z 
dz  
 dz substitute l for t
E(l)= 0.0889237*l-0.0157181*l2 + 0.0007926*l3 – 8.63E-6*l4
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
 L23b-20
Maximum Mixedness Model, nonelementary reaction A+B→C+D
-rA=kCACB2

dX A  rA E  T  z 
   XA 
 C A0 1  F  T  z 
dz  
dF 
 E  T  z 
dz Denominator
cannot = 0
z T  Tz

Eq for E describes RTD function only on

interval t= 0 to 14 minutes, otherwise E=0

XA, maximum mixedness = 0.347

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
 L23b-21
For a pulse tracer expt, C(t) & E(t) are given in the table below. The irreversible, liquid-
phase, nonelementary rxn A+B→C+D, -rA=kCACB2 will be carried out in this reactor.
Calculate the conversion for the complete segregation model under adiabatic conditions
with T0= 288K, CA0=CB0=0.0313 mol/L, k=176 L2/mol2·min at 320K, DH°RX=-40000
cal/mol, E/R =3600K, CPA=CPB=20cal/mol·K & CPC=CPD=30 cal/mol·K
t min 0 1 2 3 4 5 6 7 8 9 10 12 14
C
0 1 5 8 10 8 6 4 3 2.2 1.5 0.6 0
g/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
dX A dX A 3
Polymath eqs for segregation  XA  t  E  t   kCB02  1  X A 
dt dt
model:
E(t)= 0.0889237*t -0.0157181*t2 + 0.0007926*t3 – 8.63E-6*t4
Express k as L2   1 1 
k  T   176 exp  3600K   
function of T: mol2  min   320K T  
Need equations from energy balance. For adiabatic operation:
n
 HRX  TR   X A   iCp T0  XA CPTR
  i1
i
T
n 
   C
i pi  X A  CP
i1 
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
 L23b-22
For a pulse tracer expt, C(t) & E(t) are given in the table below. The irreversible, liquid-
phase, nonelementary rxn A+B→C+D, -rA=kCACB2 will be carried out in this reactor.
Calculate the conversion for the complete segregation model under adiabatic conditions
with T0= 288K, CA0=CB0=0.0313 mol/L, k=176 L2/mol2·min at 320K, DH°RX=-40000
cal/mol, E/R =3600K, CPA=CPB=20cal/mol·K & CPC=CPD=30 cal/mol·K
t min 0 1 2 3 4 5 6 7 8 9 10 12 14
C
0 1 5 8 10 8 6 4 3 2.2 1.5 0.6 0
g/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
n
 HRX  TR   X A   iCp T0  X A CP TR
Energy balance for   i1
i
T
adiabatic operation: n 
   C
i pi  X A CP Not zero!
n i1 
cal
 iCpi  Cp A  CPB  40 cal cal
i1 mol  K Cp   30  30  20  20   20
mol  K mol  K
cal cal dX A dX A
 XA  t  E  t 
3
1702 X A  576  kCB02  1  X A 
 T mol mol dt dt
cal  cal 
2  XA   L2   1 1 
mol  K  mol  K  k  T   176 exp  3600K   
mol2  min   320K T  
E(t)= 0.0889237*t -0.0157181*t2 + 0.0007926*t3 – 8.63E-6*t4
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
 L23b-23
Segregation model, adiabatic operation, nonelementary reaction kinetics
A+B→C+D
-rA=kCACB2

X A  0.93
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
 L23b-24

The following slides show how the same problem would be solved and
the solutions would differ if the reaction rate was still -rA=kCACB2 but the
reaction was instead elementary: A+2B→C+D

These slides may be provided as an extra example problem that the

students may study on there own if time does not permit doing it in class.

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
 L23b-25
For a pulse tracer expt, the effluent concentration C(t) & RTD function E(t) are given
in the table below. The irreversible, liquid-phase, elementary rxn A+2B→C+D,
-rA=kCACB2 will be carried out isothermally at 320K in this reactor. Calculate the
conversion for an ideal PFR, the complete segregation model and maximum mixedness
model. CA0=CB0=0.0313 mol/L & k=176 L2/mol2·min at 320K
t min 0 1 2 3 4 5 6 7 8 9 10 12 14
C
0 1 5 8 10 8 6 4 3 2.2 1.5 0.6 0
g/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

Start with PFR design eq dX A rA dX A kCA CB2 dX A kCA CB2

    
& see how far can we get: dV F dV CA00 d C A0
A0
b 2
C A  CA0  1  XA  b = =  CB  CB0  1  2XA 
a 1

dX A kCA0CB0  1  X A   1  2XA 
2 2 dX A 2
    kCB02  1  X A   1  2XA 
d CA0 d

CB0 = 0.0313 k = 0.0313

Could solve with Polymath if we knew the value of t

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
 L23b-26
For a pulse tracer expt, the effluent concentration C(t) & RTD function E(t) are given
in the table below. The irreversible, liquid-phase, elementary rxn A+2B→C+D,
-rA=kCACB2 will be carried out isothermally at 320K in this reactor. Calculate the
conversion for an ideal PFR, the complete segregation model and maximum mixedness
model. CA0=CB0=0.0313 mol/L & k=176 L2/mol2·min at 320K
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
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
t*E(t) 0 0.02 0.2 0.48 0.8 0.8 0.72 0.56 0.48 0.396 0.3 0.144 0

dX A For an ideal reactor, t =

2 How do we
 kCB02  1  X A   1  2XA  t tm  0 tE  t  dt
d determine t? m
 10 14
Use numerical method tm   tE  t  dt   tE  t  dt   tE  t  dt
to determine tm: 0 0 10
10 1 0  4  0.02   2  0.2   4  0.48   2  0.8   4  0.8  
 tE  t  dt     4.57
0 3  2  0.72   4  0.56   2  0.48   4  0.396   0.3 
14 2
 tE  t  dt  0.3  4  0.144   0   0.584  tm  4.57  0.584  5.15min
10 3
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
 L23b-27
For a pulse tracer expt, the effluent concentration C(t) & RTD function E(t) are given
in the table below. The irreversible, liquid-phase, elementary rxn A+2B→C+D,
-rA=kCACB2 will be carried out isothermally at 320K in this reactor. Calculate the
conversion for an ideal PFR, the complete segregation model and maximum mixedness
model. CA0=CB0=0.0313 mol/L & k=176 L2/mol2·min at 320K
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
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
t*E(t) 0 0.02 0.2 0.48 0.8 0.8 0.72 0.56 0.48 0.396 0.3 0.144 0

dX A For an ideal reactor, t =

2
 kCB02  1  X A   1  2XA  tm t    tE  t  dt
d m 0 tm  5.15min  
Final XA
corresponds to
t=5.15 min

X A,PFR  0.29

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
 L23b-28
For a pulse tracer expt, the effluent concentration C(t) & RTD function E(t) are given
in the table below. The irreversible, liquid-phase, elementary rxn A+2B→C+D,
-rA=kCACB2 will be carried out isothermally at 320K in this reactor. Calculate the
conversion for an ideal PFR, the complete segregation model and maximum mixedness
model. CA0=CB0=0.0313 mol/L & k=176 L2/mol2·min at 320K
t min 0 1 2 3 4 5 6 7 8 9 10 12 14
C
0 1 5 8 10 8 6 4 3 2.2 1.5 0.6 0
g/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

Segregation model X   X t E t dt  dX A  X  t  E  t  XA(t) is from

A  A    A batch reactor
with Polymath: 0 dt
design eq
Batch reactor dX A dX A 2
design eq: N A0  rA V  NA0  kCA0CB0 2  1  XA   1  2XA  V
dt dt
NA0  CA0 V
dX A 2
Stoichiometry:   kCB02  1  X A   1  2XA 
dt
rA  kC A CB2
Best-fit polynomial line
C A  CA0  1  XA  k=176 CB0=0.0313 for E(t) vs t calculated
by Polymath (slide 19)
CB  CB0  1  2XA 
E(t)=
Slides courtesy of Prof M L Kraft, 0.0889237*t
Chemical -0.0157181*t
& Biomolecular
2
+ 0.0007926*t
Engr Dept, University
3
– 8.63E-6*t
of Illinois, Urbana-Champaign.
4
 L23b-29
Segregation model, isothermal operation, elementary rxn: A+2B→C+D

X A,seg  0.27
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
 L23b-30
For a pulse tracer expt, the effluent concentration C(t) & RTD function E(t) are given
in the table below. The irreversible, liquid-phase, elementary rxn A+2B→C+D,
-rA=kCACB2 will be carried out isothermally at 320K in this reactor. Calculate the
conversion for an ideal PFR, the complete segregation model and maximum mixedness
model. CA0=CB0=0.0313 mol/L & k=176 L2/mol2·min at 320K
t min 0 1 2 3 4 5 6 7 8 9 10 12 14
C
0 1 5 8 10 8 6 4 3 2.2 1.5 0.6 0
g/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

Maximum mixedness model: dX A  rA  E    X dF

l=time d  E
d CA0 1  F    A

Polymath cannot solve r  kC C 2  1  X   1  2X  2

A A0 B0 A A L2
because l→0 (must k  176
increase) C A0  CB0  0.0313mol L mol2  min

Substitute l for z, where z=T̅-l where T̅=longest time interval (14 min)
dX A  rA E  T  z  dF E must be in terms of T̅-z.
   XA   E  T  z  Since T̅-z=l & l=t, simply
 C A0 1  F  T  z 
dz  
 dz substitute l for t
E(l)= 0.0889237*l-0.0157181*l2 + 0.0007926*l3 – 8.63E-6*l4
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
Maximum Mixedness Model, elementary reaction A+2B→C+D, -rA=kCACL23b-31
B
2

dX A  rA E  T  z 
   XA 
dF
dz 
 C A0 1  F  T  z  

 E  T  z 
dz Denominator
cannot = 0
z T   Tz
Eq for E describes RTD function only on
interval t= 0 to 14 minutes, otherwise E=0

XA, maximum mixedness = 0.25

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
 L23b-32
For a pulse tracer expt, C(t) & E(t) are given in the table below. The irreversible, liquid-
phase, elementary rxn A+2B→C+D, -rA=kCACB2 will be carried out in this reactor.
Calculate the conversion for the complete segregation model under adiabatic conditions
with T0= 288K, CA0=CB0=0.0313 mol/L, k=176 L2/mol2·min at 320K, DH°RX=-40000
cal/mol, E/R =3600K, CPA=CPB=20cal/mol·K & CPC=CPD=30 cal/mol·K
t min 0 1 2 3 4 5 6 7 8 9 10 12 14
C
0 1 5 8 10 8 6 4 3 2.2 1.5 0.6 0
g/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
Polymath eqs for dX A dX A 2
segregation model: dt  X A  t  E  t   kCB0
2
 1  X A   1  2X A 
dt
E(t)= 0.0889237*t -0.0157181*t2 + 0.0007926*t3 – 8.63E-6*t4
Express k as L2   1 1 
k  T   176 exp 3600K   
function of T: mol2  min   320K T  
Need equations from energy balance. For adiabatic operation:
n
 HRX  TR   X A   iCp T0  X A CPTR
  i1
i
T
n 
   C
i pi  X A CP
i1 
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
 L23b-33
For a pulse tracer expt, C(t) & E(t) are given in the table below. The irreversible, liquid-
phase, elementary rxn A+2B→C+D, -rA=kCACB2 will be carried out in this reactor.
Calculate the conversion for the complete segregation model under adiabatic conditions
with T0= 288K, CA0=CB0=0.0313 mol/L, k=176 L2/mol2·min at 320K, DH°RX=-40000
cal/mol, E/R =3600K, CPA=CPB=20cal/mol·K & CPC=CPD=30 cal/mol·K
t min 0 1 2 3 4 5 6 7 8 9 10 12 14
C
0 1 5 8 10 8 6 4 3 2.2 1.5 0.6 0
g/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
Adiabatic EB:
 HRX  TR   X A   iCp T0  XA CP TR Cp   30  30  2  20   20   0
n
  i 1
i
T n cal
 n  
 i pi
C  C  C  40
  iCpi  X A CP 
pA PB
i1 mol  K
i1 
dX A dX A 2
T  288K  1000X A  XA  t  E  t   kCB02  1  X A   1  2XA 
dt dt
L2   1 1 
k  T   176 exp  3600K   
mol2  min   320K T  
E(t)= 0.0889237*t -0.0157181*t2 + 0.0007926*t3 – 8.63E-6*t4
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.