Review: Nonideal Flow in A CSTR

L23-1
Review: 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.
Review: 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.
Review: Residence Time Distribution
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 C curve
Reactor X C(t)
↑ ↓
Pulse injection Detection
t
C (t ) tracer conc at exit between t & t+Δt
RTD = E ( t ) = =
∫0 C ( t ) dt sum of tracer conc at exit for infinite time
∞
∞ E(t)=0 for t<0 since no tracer 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
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
To tabulate E(t): divide C(t) by the total area under
Plot C vs time:
the C(t) curve, which must be numerically evaluated
12 as shown below:
10 ∞ 10 14
8 ∫ C ( t ) dt = ∫ C ( t ) dt + ∫ C ( t ) dt
C(t) (g/m3)
6 0 0 10
XN
4 Δt
2 ∫ f ( x ) dx = ( f0 + 4f1 + 2f2 + 4f3 + 2f4 ... + 4fN−1 + fN )
X 3
0
0
X2
0 2 4 6 8 10 12 14 Δt
t (min)
∫ f ( x ) dx = ( f0 + 4f1 + f2 )
X0 3
∞ g ⋅ min g ⋅ min g ⋅ min
→→ ∫ C ( t ) dt = 47.4 + 2.6 = 50
3 3
0 m m m3
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
0 m3 Plot E(t):
Tabulate E(t): divide E t = C ( t ) 0.25
() ∞
C(t) by the total area 0.2
∫ C ( t ) dt
E(t) (min-1)
under the C(t) curve: 0.15
0
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)
Review: RTD Profiles & Cum RTD
Function F(t)
E(t) E(t) E(t) E(t)
τ t τ t
t t
Nearly Nearly ideal PBR with CSTR with
ideal PFR CSTR channeling & dead zones
dead zones
t
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
L23-7
Review: Relationship between E & F

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
L23-8
Review: Mean Residence Time, tm

•  For an ideal reactor, the space time τ is defined as V/υ0
•  The mean residence time tm is equal toτ 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
L23-9
Significance of Mixing
• RTD provides information on how long material has been in the reactor
• RTD does not provide information about the exchange of matter within the
reactor (i.e., mixing)!
• For a 1st order reaction: dX
= k (1 − X )
dt
• Concentration does not affect the rate of conversion, so RTD is sufficient

to predict conversion
• But concentration does affect conversion in higher order reactions, so we
need to know the degree of mixing in the reactor
• Macromixing: produces a distribution of residence times without specifying

how molecules of different age encounter each other and are distributed
inside of the reactor
• Micromixing: describes how molecules of different residence time

encounter each other in the reactor
L23-10
Quality of Mixing
• RTDs alone are not sufficient to determine reactor performance
• Quality of mixing is also required
Goal: use RTD and micromixing models to predict conversion in real reactors
2 Extremes of Fluid Mixing
Maximum mixedness: molecules are
free to move anywhere, like a
microfluid. This is the extreme case
of early mixing
L23-11
Quality of Mixing
• RTDs alone are not sufficient to determine reactor performance
• Quality of mixing is also required
Goal: use RTD and micromixing models to predict conversion in real reactors
2 Extremes of Fluid Mixing
Maximum mixedness: molecules are Complete segregation: molecules of
free to move anywhere, like a a given age do not mix with other
microfluid. This is the extreme case globules. This is the extreme case of
of early mixing late mixing
L23-12
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 Δt ( j) ( j)
A j A
Conversion achieved after Fraction of globules that spend
spending time tj in the reactor between tj and tj + Δt in the reactor
∞
Δt →0
→ XA = ∫ XA ( t ) E ( t ) dt
⎯⎯⎯⎯ XA(t) is from the batch
0 reactor design equation
L23-13
Complete Segregation Example

First order reaction, A→Products
Batch reactor dX A dX A
NA0 = −rA V → NA0 = kCA V
design equation: dt dt
dX A dX A
→ NA0 = kCA0 (1 − X A ) V → NA0 = kNA0 (1 − X A )
dt dt
dX A
→ = k (1 − X A ) → XA ( t ) = 1 − e−kt
dt
To compute conversion for a reaction with a 1st order rxn and complete
segregation, insert E(t) from tracer experiment and XA(t) from batch reactor
design equation into: ∞
XA = ∫ XA ( t ) E ( t ) dt & integrate
0
L23-14
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:
λ →∞ υ0E(λ )Δλ λ → 0
υ0
υλ +Δλ υλ
V=0 λ +Δλ λ V = V0
λ: time it takes for fluid to move from a particular point to end of the reactor
υ(λ): volumetric flow rate at λ, = flow that entered at λ+Δλ plus what entered
through the sides
υ0E(λ)Δλ: Volumetric flow rate of fluid fed into side ports of reactor in interval
between λ + Δλ & λ
Volumetric flow rate of fluid fed to reactor at λ: υ ( λ ) = υ0 ∫λ∞ E ( λ ) dλ = υ0 ⎡⎣1 − F ( λ )⎤⎦
fraction of effluent in reactor for less than time t
Volume of fluid with life expectancy between λ + Δλ & λ: ΔV = υ0 ⎡⎣1 − F ( λ )⎤⎦ Δλ
L23-15
Maximum Mixedness & Polymath

residence time distribution function
Mole balance on dX A r E (λ )
A gives: = A + XA
dλ CA0 1 − F ( λ )
fraction of effluent in reactor for less than time t
• E(t) must be specified
• Often it is an expression that fits the experimental data
• 2 curves, one on the increasing side, and a second for the decreasing
side
• Use the IF function to specify which E is used when
See section 13.8 E1 E2

E
in book
t
Also need to replace λ because Polymath cannot calculate as λ gets smaller
z = T − λ where T is the longest time measured
dXA rA E (T − z) Note that the sign on
=− − XA
dz CA0 1 − F ( T − z ) each term changes
Review: Nonideal Flow & Reactor
Real CSTRs
Design
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
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+Δt
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
E(t) E(t) E(t) E(t) Nice multiple
choice
question
τ t t τ 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
t
∫0 E ( t ) dt = F ( 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
L22-19
Review: 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
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 Δt ( j) ( j)
A j A
Conversion achieved after Fraction of globules that spend
spending time tj in the reactor between tj and tj + Δt in the reactor
∞
Δt →0
→ XA = ∫ XA ( t ) E ( t ) dt
⎯⎯⎯⎯ XA(t) is from the batch
0 reactor design equation
L22-21
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:
λ →∞ υ0E(λ )Δλ λ → 0
υ0
υλ +Δλ υλ
V=0 λ +Δλ λ V = V0
λ: time it takes for fluid to move from a particular point to end of the reactor
υ(λ): volumetric flow rate at λ, = flow that entered at λ+Δλ plus what entered
through the sides
υ0E(λ)Δλ: Volumetric flow rate of fluid fed into side ports of reactor in interval
between λ + Δλ & λ
Volumetric flow rate of fluid fed to reactor at λ: υ ( λ ) = υ0 ∫λ∞ E ( λ ) dλ = υ0 ⎡⎣1 − F ( λ )⎤⎦
fraction of effluent that in reactor for less than time t
Volume of fluid with life expectancy between λ + Δλ & λ: ΔV = υ0 ⎡⎣1 − F ( λ )⎤⎦ Δλ
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/
0 1 5 8 10 8 6 4 3 2.2 1.5 0.6 0
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
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
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 dXA kCA CB2
= → = CA = CA0 (1 − XA ) CB = CB0 (1 − XA )
dV FA0 dV CA0υ0
2 3 XA V kC 2
dXA kCA0CB0 (1 − XA ) Get like terms dXA B0 dV
→ = → ∫ 3
= ∫
dV CA0υ0 together & integrate 0 (1 − X A ) 0 υ0
X
A
1 ⎤ kCB02 → 1 2 1
→ ⎥ = V 2
− 1 = 2kCB0 → X A = 1 −
τ
2
2 (1 − X A ) ⎥⎦ 0 υ0 (1 − XA ) 2kCB02τ + 1
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
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, τ = tm
1 How do we
XA = 1 − tm = ∫0∞ tE ( t ) dt
2
2kCB0 τ + 1 determine τ?
∞ 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
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
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, τ = tm

XA = 1 − tm = 5.15min = τ
2kCB02τ + 1 tm = ∫0∞ tE ( t ) dt
1
X A,PFR = 1 −
2
⎛ L2 ⎞ ⎛ mol ⎞
2 ⎜ 176 ⎟⎟ ⎜ 0.0313 ⎟ (5.15min ) + 1
⎜ 2 L
⎝ mol ⋅ min ⎠ ⎝ ⎠
XA,PFR = 0.40
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/
0 1 5 8 10 8 6 4 3 2.2 1.5 0.6 0
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: XA = ∫ XA ( 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 X̄A
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 X̄A
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
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: XA = ∫ XA ( t ) E ( t ) dt XA(t) is from batch reactor design eq
0
Batch design eq: NA0 = CA0 V
dX A dX A dX A 3
NA0 = −rA V → NA0
2 3
= kCA0CB0 (1 − X A ) V → = kCB02 (1 − X A )
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
CA = CA0 (1 − XA ) 1 1
→ − 1 = 2kCB02 t → XA = 1 −
CB = CB0 (1 − XA ) (1 − X A )2 1 + 2kCB02t
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
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
XA = ∫ XA ( t ) E ( t ) dt XA = 1 − = 1−
0 1 + 2kCB02t 1 + 0.3429min−1 t
Plug in each t & solve
Numerical method 1
XA (0 ) = 1 − −1
=0
1 + 0.3429min (0 )
1
XA (1) = 1 − −1
= 0.137
1 + 0.3429min (1min)
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
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 ∞ 1 1
XA = ∫ XA ( t ) E ( t ) dt XA = 1 − = 1−
model: 0 1 + 2kCB02t 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 )⎥
0 3
⎢ +2 ( 0.483 )(0.06 ) + 4 (0.505 )(0.044 ) + 0.525 (0.03 ) ⎥
⎣ ⎦
10
∫ X A ( t ) E ( t ) dt = 0.35
0
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
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 ∞ 1 1
XA = ∫ XA ( t ) E ( t ) dt XA = 1 − = 1−
model: 0 1 + 2kCB02t 1 + 0.3429min−1 t
∞ 14
Numerical method X A = ∫ X A ( 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 → X A = 0.39
0
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
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:

∞
dX A 1
XA = ∫ XA ( t ) E ( t ) dt = XA ( t )E ( t ) XA = 1 −
0 dt 1 + 2kCB02t
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

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
Complete segregation model by Polymath
A+B→C+D
-rA=kCACB2
Segregation model by Polymath: X A = 0.36

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
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 ( λ ) X dF
λ=time =E
dλ CA0 1 − F ( λ ) A dλ
F(λ) is a cumulative distribution function
−rA = kCA0CB02 (1 − XA )
3
CA0 = CB0 = 0.0313mol L k = 176 L2
mol2 ⋅ min
Polymath cannot solve because λ→0 (needs to increase)
Substitute λ for z, where z=T̅-λ where T̅=longest time interval (14 min)
⎛ rA E (T − z) ⎞ dF E must be in terms of T̅-z.
dXA
= − ⎜ + XA ⎟ = −E ( T − z ) Since T̅-z=λ & λ=t, simply
dz ⎝ CA0 1 − F ( T − z )
⎜ ⎟
⎠ dz substitute λ for t
E(λ)= 0.0889237*λ-0.0157181*λ2 + 0.0007926*λ3 – 8.63E-6*λ4
Maximum Mixedness Model, nonelementary reaction A+B→C+D
-rA=kCACB2
dXA ⎛ rA E (T − z) ⎞
= − ⎜ + XA ⎟
dz ⎝ CA0 1 − F ( T − z )
⎜ ⎟
dF ⎠
= −E ( T − z )
dz Denominator
cannot = 0
z =T−λ →λ = T−z
Eq for E describes RTD function only on

interval t= 0 to 14 minutes, otherwise E=0
XA, maximum mixedness = 0.347
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, ΔH°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 g/
0 1 5 8 10 8 6 4 3 2.2 1.5 0.6 0
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 model: = X A ( t ) E ( t ) = kCB02 (1 − X A )
dt 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: 2
mol ⋅ min ⎣ ⎝ 320K T ⎠ ⎦
Need equations from energy balance. For adiabatic operation:
n
⎡ −ΔHoRX ( TR )⎤ X A + ∑ ΘiCp T0 + X A ΔCPTR
⎣ ⎦ i
T= i=1
⎡ n ⎤
⎢ ∑ Θ C
i pi + X A ΔCP ⎥
⎣i=1 ⎦
phase, nonelementary rxn A+B→C+D, -rA=kCACB2 will be carried out in this 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
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
⎡ −ΔHoRX ( TR )⎤ X A + ∑ ΘiCp T0 + X A ΔCPTR
Energy balance for ⎣ ⎦ i=1
i
T=
adiabatic operation: ⎡ n ⎤
⎢ ∑ Θ C
i pi + X A ΔCP ⎥ Not zero!
n ⎣i=1 ⎦
cal
∑ ΘiCpi = CpA + CPB = 40 cal cal
i=1 mol ⋅ K ΔCp = (30 + 30 − 20 − 20 ) = 20
mol ⋅ K mol ⋅ K
cal cal dX A dX A 3
1702 X A + 576 = XA ( t )E ( t ) = kCB02 (1 − X A )
→ T= mol mol dt dt
cal ⎛ cal ⎞
2 + X A ⎜ ⎟ 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
Segregation model, adiabatic operation, nonelementary reaction kinetics
A+B→C+D
-rA=kCACB2
X A = 0.93
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.
in the table below. The irreversible, liquid-phase, elementary rxn A+2B→C+D,
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
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 dXA kCA CB2 dXA kCA CB2
= → = → =
& see how far can we get: dV FA0 dV CA0υ0 dτ CA0
b 2
CA = CA0 (1 − XA ) νb = = → CB = CB0 (1 − 2XA )
a 1
2 2 dXA 2
→
dXA kCA0CB0 (1 − XA )(1 − 2XA )
= → = kCB02 (1 − XA )(1 − 2XA )
dτ CA0 dτ
CB0 = 0.0313 k = 0.0313
Could solve with Polymath if we knew the value of τ

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
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
dXA For an ideal reactor, τ = tm

2 How do we
= kCB02 (1 − XA )(1 − 2XA ) tm = ∫0∞ tE ( t ) dt
dτ determine τ?
∞ 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
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
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
dXA For an ideal reactor, τ = tm

2
= kCB02 (1 − XA )(1 − 2XA ) tm = ∫0∞ tE ( t ) dt
dτ tm = 5.15min = τ
Final XA
corresponds to
τ=5.15 min
XA,PFR = 0.29
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
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 ∞ dX A XA(t) is from
XA = ∫ XA ( t ) E ( t ) dt → = XA ( t )E ( t ) batch reactor
with Polymath: 0 dt
design eq
Batch reactor dX A dXA 2 2
design eq: NA0 = −rA V → N A0 = k C C
A0 B0 (1 − X A )(1 − 2X A V
)
dt dt
NA0 = CA0 V
Stoichiometry: dXA 2
→ = kCB02 (1 − XA )(1 − 2XA )
dt
−rA = kC A CB2
Best-fit polynomial line
CA = CA0 (1 − XA ) k=176 CB0=0.0313 for E(t) vs t calculated
by Polymath (slide 19)
CB = CB0 (1 − 2XA )
Slides courtesy of Prof M L Kraft,E(t)= 0.0889237*t -0.0157181*t + 0.0007926*t – 8.63E-6*t
2 3 4
Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
Segregation model, isothermal operation, elementary rxn: A+2B→C+D
X A,seg = 0.27
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
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 ( λ ) X dF

A λ=time =E
dλ CA0 1 − F ( λ ) dλ
Polymath cannot solve −r = kC C 2 1 − X 1 − 2X 2
A A0 B0 ( A )( A) L2
because λ→0 (must k = 176
increase) CA0 = CB0 = 0.0313mol L mol2 ⋅ min
Substitute λ for z, where z=T̅-λ where T̅=longest time interval (14 min)
⎛ rA E (T − z) ⎞ dF E must be in terms of T̅-z.
dXA
= − ⎜ + XA ⎟ = −E ( T − z ) Since T̅-z=λ & λ=t, simply
dz ⎝ CA0 1 − F ( T − z )
⎜ ⎟
⎠ dz substitute λ for t
E(λ)= 0.0889237*λ-0.0157181*λ2 + 0.0007926*λ3 – 8.63E-6*λ4
Maximum Mixedness Model, elementary reaction A+2B→C+D, -rA=kCACB2
dXA ⎛ rA E (T − z) ⎞
= − ⎜ + XA ⎟
dz ⎝ CA0 1 − F ( T − z )
⎜ ⎟
dF ⎠
= −E ( T − z )
dz Denominator
cannot = 0
z =T−λ →λ = T−z
Eq for E describes RTD function only on
interval t= 0 to 14 minutes, otherwise E=0
XA, maximum mixedness = 0.25
phase, elementary rxn A+2B→C+D, -rA=kCACB2 will be carried out in this 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
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 2
segregation model: dt = X A ( t ) E ( t ) = kCB0 (1 − X A )(1 − 2X A )
dt
E(t)= 0.0889237*t -0.0157181*t2 + 0.0007926*t3 –
8.63E-6*t4 L2
Express k as ⎡ ⎛ 1 1 ⎞ ⎤
k ( T ) = 176 exp ⎢ 3600K ⎜ − ⎟
function of T: mol2 ⋅ min ⎣ ⎝ 320K T ⎠ ⎥⎦
Need equations from energy balance. For adiabatic operation:
n
⎡ −ΔHoRX ( TR )⎤⎦ XA + ∑ ΘiCpi T0 + XA ΔCPTR
⎣ i=1
T=
⎡ n ⎤
⎢ ∑ Θ C
i pi + X A ΔCP ⎥
⎣i=1 ⎦
phase, elementary rxn A+2B→C+D, -rA=kCACB2 will be carried out in this 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
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:
n
⎡ −ΔHoRX ( TR )⎤ X A + ∑ ΘiCp T0 + X A ΔCPTR ΔCp = ( 30 + 30 − 2 ( 20 ) − 20 ) = 0
⎣ ⎦ i
T= i =1
n cal
n
⎡
∑ Θ C + X ΔC
⎤ ∑ ΘiCpi = CpA + CPB = 40
⎢ i pi A P ⎥ i=1 mol ⋅ K
⎣i=1 ⎦
dX A dX A 2
T = 288K + 1000X A = XA ( t )E ( t ) = kCB02 (1 − X A )(1 − 2X A )
dt dt
L2 ⎡ ⎛ 1 1 ⎞ ⎤
k ( T ) = 176 2
exp ⎢3600K ⎜ − ⎟ ⎥
mol ⋅ min ⎣ ⎝ 320K T ⎠ ⎦
E(t)= 0.0889237*t -0.0157181*t2 + 0.0007926*t3 –
8.63E-6*t
Slides courtesy 4
of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
Segregation model, adiabatic operation, elementary reaction kinetics
A+2B→C+D
-rA=kCACB2
Because B is completely
consumed by XA=0.5
X̅A = 0.50
Why so much lower
than before?

Review: Nonideal Flow in A CSTR

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L23-1

Review: Nonideal Flow in a CSTR

∞ E(t)=0 for t<0 since no tracer can exit before it enters

Fraction of material leaving reactor that has = t2 E ( t ) dt

Review: Relationship between E & F

Review: Mean Residence Time, tm

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

• Concentration does not affect the rate of conversion, so RTD is sufficient

• Macromixing: produces a distribution of residence times without specifying

• Micromixing: describes how molecules of different residence time

Complete Segregation Model

• Flow is visualized in the form of globules

Complete Segregation Example

Maximum Mixedness Model

Maximum Mixedness & Polymath

See section 13.8 E1 E2

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

∞ E(t)=0 for t<0 since no fluid can exit before it enters

Fraction of material leaving reactor that has = t2 E ( t ) dt

Review: Mean Residence Time, tm

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

• Flow is visualized in the form of globules

Review: Maximum Mixedness Model

1 For an ideal PFR reactor, τ = tm

Alternative approach: segregation model by Polymath:

Need an equation for E(t) k=176

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

For the irreversible, liquid-

Gave best fit

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

Segregation model by Polymath: X A = 0.36

Eq for E describes RTD function only on

XA, maximum mixedness = 0.347

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

CB0 = 0.0313 k = 0.0313

Could solve with Polymath if we knew the value of τ

dXA For an ideal reactor, τ = tm

dXA For an ideal reactor, τ = tm

Maximum mixedness model: dX A = rA + E ( λ ) X dF

XA, maximum mixedness = 0.25

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• Concentration does not affect the rate of conversion, so RTD is sufficient

• Macromixing: produces a distribution of residence times without specifying

• Micromixing: describes how molecules of different residence time

•  Flow is visualized in the form of globules

•  Flow is visualized in the form of globules

Model: C02= a1C01 + a2C01^2 + a3C01^3 + a4C01^4