CHEM ENG 3034/7051 Kinetics & Reactor Design

WEEK 5 - THEORY
ISOTHERMAL REACTOR DESIGN:
UNSTEADY STATE AND MULTIPLE
REACTIONS Dr Philip van Eyk
School of Chemical Engineering
[email protected]
Week 5 - Theory
Isothermal Reactor Design: Unsteady State and
Multiple Reactions
Fogler, Chapters 6 and 8
• Unsteady state isothermal reactor operation
o Start-up of a CSTR
o Semi-batch reactors

• Reactor design for multiple reactions

o Parallel reactions
o Series (consecutive) reactions
o CRE algorithm for multiple reactions

The University of Adelaide Slide 2

Introduction
• Last week: we used conversion to design a number of
isothermal reactors for single reactions.
• While in many situations writing the mole balances in
terms of conversion is an extremely effective strategy, there
are many instances where it is more convenient, and in
some cases absolutely necessary, to write the mole balance
in terms of moles (NA, NB) or molar flow rates (FA, FB).
• This week, we show how to make small changes in our
algorithm to analyse these situations.
• We first analyse unsteady state reactors and then look at
reactor systems with multiple reactions going on in the
same reactor.

The University of Adelaide Slide 3

Start-Up of a Fixed-Volume CSTR
Isothermal (unusual, but simple case), well-mixed CSTR
Unsteady state: concentrations vary with time & accumulation is non-zero
Goal: Determine the time necessary to reach steady-state operation

CA0u0 u0CA
In - Out + Generation = Accumulation
moles A in CSTR
dNA changes with
FA0 − F A + rA V =
dt time until steady
state is reached
Use concentration rather than conversion in the balance eqs
dNA → C A0u0 − C Au0 + rA V = dNA  1 
CA0u0 − C A u0 + rA V =  
dt V dt  V 
Divide by V to convert dNA to dCA

V C A0 CA dC A Multiply dCA
= → − + rA = CA0 − CA + rA = 
u0   dt by t dt

The University of Adelaide Slide 4

CSTR Start-Up: 1st Order Reaction
dCA dCA
CA0 − CA + rA =  Combine C − C − k C  = 
dt −rA = kCA A0 A A
dt
Integrate this eq to find CA (t) while 1st order rxn in CSTR is at unsteady-state:
Bring variables to dCA 1
one side & factor = ( CA0 − CA (1 + k ) )
dt 
dCA  1   CA0  Put like variables
→ =   (1 + k )  − CA 
   (1 + k )
dt with their integrals

  CA0 
CA t (1 + k )  − CA  
 (1 + k )
dCA
 C = dt
→    = 0 − (1 + k ) t
A0 − C  ln
 
0 0 CA0 
(1 + k ) A
 (1 + k ) − 0 
 
−
(1+k ) t
CA
=e 
( )
→ 1−  C 
→  A0  1 − e (
− t 1+k ) 
CA0 = CA
(1 + k )  1 + k 
The University of Adelaide Slide 5
CSTR Start-Up: 1st Order Reaction
dCA We integrated this eq to find CA (t) while
CA0 − CA + kCA = 
dt CSTR of 1st order rxn is in unsteady-state:

0
( A )
At steady state,  CA0  1 − e− t(1+k )  = C → CA0 = C
 is large and:  1 + k  1 + k  AS

Is this consistent with steady dCA No

CA0 − CA − kCA = 
state balance eq for CSTR? dt accumulation at
Yes, same! 0 steady state
CA0
→ CA0 − CA − kCA = 0 → = CAS Goal: combine start-up and SS eqs
(1 + k ) to estimate time to reach SS (ts)
In the unsteady state,  CA0 
when CA = 0.99CAS:
→
 1 + k   1− e

(
− t s (1+k ) 
)  CA 0 
= 0.99  
 1 + k 
Solve for ts to determine time to reach 99% of steady-state concentration
→ 1− e s(
− t 1+k ) 
= 0.99 → 0.01 = e s (
− t 1+k ) 
→ ln 0.01 = ln e s (
( ) (
− t 1+k ) 
)
 1 + k   time to reach 99% of steady-state
→ −4.6 = −t s  → 4.6 = ts
   1 + k concentration in terms of k

The University of Adelaide Slide 6

CSTR Start-Up: 1st Order Reaction
 CA0 
 1 + k 
 
(1 − e )
− t (1+k ) 
= CA

In the unsteady state, the time to 

t = 4.6
reach CA = 0.99CAS is: 1 + k

When k is very small When k is very big 4.6

t = 4.6 ts =
(slow rxn), 1>>k: s (fast rxn), 1<<k k

99% of the steady-state 

4.6 CA = 0.99CAS
concentration is achieved at: 1 + k

The University of Adelaide Slide 7

Better Selectivity in a Semi-Batch
Reactor
To enhance selectivity of desired product over side product
2
→ P rP = kpCA CB
kP
A + B ⎯⎯⎯ Desired product P
2
→ S rS = k SCA CB
kS
A + B ⎯⎯⎯ Undesired side product S

Instantaneous selectivity, SP/S, is the ratio of the relative

rates*: rP kPCA 2CB kPCA
SP/S = = =
rS k SCA CB2 k SCB
Higher concentrations of A favor formation of the desired product P
Higher concentrations of B favor formation of the undesired side product S
To maximize the formation of the desired product:
Slowly feed B into the reactor containing A
Commonly used in bioreactors, when the enzyme is inhibited by excess substrate
*We’ll look at this concept of instantaneous selectivity later in this lecture

The University of Adelaide Slide 8

Semi-Batch Reactor Design Equation
CBu0 Do a mole balance on A since it does not enter or leave the
reactor (assume the reactor is well-mixed)
In - Out + Generation = Accumulation
dNA
FA0 − F A + rA V =
dt
dNA
→ 0 − 0 + rA V =
dt
V0 + u0t
Use whatever units are most convenient (NA, CA, XA, etc)
Convert NA to CA using:
dC A V
NA
= CA → NA = CA V → rA V =
V dt

dCA dV 2 parts: how CA changes with

→ rA V = V + CA t and how V changes with t
dt dt

The University of Adelaide Slide 9

Semi-Batch Reactor Design Equation
CBu0 Do a mole balance on A since it does not enter or leave the
reactor (assume the reactor is well-mixed)
In - Out + Generation = Accumulation
dNA
0 − 0 + rA V ( t ) =
dt
dCA dV 2 parts: how CA changes with
→ rA V = V + CA
dt dt t and how V changes with t
V0 + u0t
Reactor volume at any time can be found with a mole balance
In - Out + Generation = Accumulation
d (  V ) u = u0 dV
0u0 − 0 + 0 = → u0 = → V0 + u0 t = V
dt  = 0 dt
dCA
Substitute: → rA V = V + CAu0 Rearrange to get in terms of dCA/dt
dt
dCA CAu0 dCA
→ rA V − CAu0 = V → rA − = Balance on A
dt V dt

The University of Adelaide Slide 10

Semi-Batch Reactor Design Equation
CBu0 Mole Balance on B
In - Out + Generation = Accumulation
dNB
FB0 − 0 + rB V =
dt
dNB
→ = rB V + FB0
dt
dVCB d
V0 + u0t → = ( CB V ) = rB V + FB0
dt dt

dV dCB dV
→ CB +V = rB V + CB0u0 u0 = Substitute
dt dt dt
dCB
→ CBu0 + V = rB V + CB0u0 Rearrange to get in terms of dCB/dt
dt

dCB u0 ( CB0 − CB )
→ = rB + Balance on B
dt V

The University of Adelaide Slide 11

Semi-Batch Reactor Design Equation: in
Terms of NA
In - Out + Generation = Accumulation
CBu0 dNA
0 − 0 + rA V =
dt
dNA
= rA V Substitute V = V0 + u0 t
dt
dNA Reactor design eq. provided
= rA ( V0 + u0 t )
dt that rA is a function of NA
 NA  NB NA NB
V0 + u0t -rA = kACACB → rA = − k  V  V → rA = −k
  ( V0 + u0 t )2
dNA dNA NA NB
→ = rA V → = −k
dt dt V0 + u0 t
dNB dNB NANB
NB comes from BMB: = −rA V + FB0 → = −k + FB0
dt dt V0 + u0 t
The design eq in terms of XA can be messy.
When using Nj or Cj gives multiple reactor design equations.

The University of Adelaide Slide 12

Improving Yields of Reversible Rxns
with Semi-Batch Reactors
Semi-batch
FD

A+B
A+B⇌C+D

V0 V0 - u0t Vf
To improve product yield in a reversible reaction: A l + B l ⇌ C l + D g
• Start with A(l) and B(l) in the reactor
• D(g) bubbles out of the liquid phase, pushing the equilibrium to the right
and forcing the reaction to go to completion Boil off water to
Common industrial reaction: produce high
MW polymer
+ n + H2O
n nylon

The University of Adelaide Slide 13

Improving Yields of Reversible Rxns
with Semi-Batch Reactors
Semi-batch
FD

A+B
A+B⇌C+D

V0 V0 - u0t Vf
To improve product yield in a reversible reaction: A l + B l ⇌ C l + D g
• Start with A(l) and B(l) in the reactor
• D(g) bubbles out of the liquid phase, pushing the equilibrium to the right
and forcing the reaction to go to completion

How do we account for the loss of product D in the material balance?

The University of Adelaide Slide 14

Loss of Mass in Semi-Batch Reactor
D(g) 𝐴 𝑙 + 𝐵 𝑙 ⇌ 𝐶 𝑙 + 𝐷 𝑔 elementary rxn u = u0  = 0
Overall Mass balance:
In - Out + Generation =Accumulation
m = 
dm g 
u0 − m + 0 =  gas leaving reactor
dt  time 
m m
= →V= ↑want in terms of dV/dt
V 
V0 + u0t u0 m dm  1  m dV
Divide mass balance by  − =   → u0 − =
  dt     dt
Relate ṁ to a rate: From stoichiometry, rD = -rA
moles Next, convert mass moles
−rA = Conversion 1: −rA ( V ) =
volume  time units to: time time
Conversion 2: mass
molesD =
massD
→ molesD (MWD ) = massD −rA ( V ) MW = =m
MWD time
rA V (MWD ) Substitute for ṁ
dV
= u0 + One of the diff. eq. that are simultaneously solved (by
dt  numerical methods)

The University of Adelaide Slide 15

Reactor Design for Multiple
Reactions

• Usually, more than one reaction occurs within a chemical reactor

• Minimization of undesired side reactions that occur with the desired
reaction contributes to the economic success of a chemical plant
• Goal: determine the reactor conditions and configuration that
maximizes product formation
• Reactor design for multiple reactions
• Parallel reactions
• Series reactions
• Independent reactions
• More complex reactions
• Use of selectivity factor to select the proper reactor that minimizes
unwanted side reactions

The University of Adelaide Slide 16

Classification of Multiple Reactions
1) Parallel or competing reactions

k1 B
A
k2 C
Desired product
2) Series reactions k1 k2
A B C
Desired product

3) Independent reactions Crude oil cracking

k1 k2
A B C D

4) Complex reactions A + B ⎯⎯→

k
1 C+D A + C ⎯⎯⎯
2 →E k

The University of Adelaide Slide 17

Parallel Reactions
Purpose: maximizing the desired product in parallel reactions
−ED
kD
D (desired) rD = kDCA1CB 1 → rD = AD e RT CA1CB 1
A+B −EU
kU 2 2 → r = A e RT C  2 C 2
U (undesired) rU = kUCA CB U U A B
−E
Rate of disappearance of A: −rA = rD + rU
k (T) = AeRT
−ED −EU
−rA = ADe RT C A1CB 1 + AUe RT C A2 CB2
Define the instantaneous rate selectivity, SD/U
− ED

rate of formation of D rD AD e RT
C A 1CB1
SD U = = sD U = − EU
rate of formation of U rU AUe RT
C A 2 CB2
−(ED −EU )
k
( )
SD U = D CA1−2 CB 1− 2 → SD U =
kU AU
AD
CA1−2 CB 1− 2
e RT ( )
Goal: Maximize SD/U to maximize production of the desired product
The University of Adelaide Slide 18
Maximizing SD/U for Parallel
Reactions: Temperature Control
−(ED −EU )

AU
SD U =
AD
e RT (CA1−2 ) CB1−2
What reactor conditions and configuration maximizes the selectivity?
Start with temperature (affects k):
a) If E > E b) If ED < EU
D U

−(ED −EU ) −(ED −EU )

ED − EU ED − EU
 0 → e RT 1  0 → e RT 1
RT RT
Specific rate of desired reaction kD
Specific rate of desired reaction increases less rapidly with
kD increases more rapidly with increasing T
increasing T
Use lower T to favor desired
Use higher temperature to favor product formation (not so low that
desired product formation the reaction rate is tiny)

The University of Adelaide Slide 19

Maximize SD/U for Parallel
Reactions using Temperature
kD D
−(ED −EU )
A AD
SD U = e RT CA1−2
AU
kU
U
What reactor temperature maximizes the selectivity?
ED = 20 kcal/mol, EU = 10 kcal/mol, T = 25 ◦C (298K) or 100 ◦C (373K)
T = 25 ◦C 
− 20,000
cal
−10,000
cal  a) ED > EU
 
(298K):  mol mol 
 cal 

( )
A  1.987 298K A
SD U = D e  molK  CA1−2 → SD U = D 4.6  10−8 CA1−2
AU AU
T = 100 ◦C  cal cal 
− 20,000 −10,000  kD/U
(373K):  mol mol 
 cal 

( )
AD  1.987 373K A
SD U = e  mol K  CA1−2
→ SD U = D 1.4  10−6 CA1−2
AU AU
SD/U is greater at 373K, higher temperature to favors desired product formation
The University of Adelaide Slide 20
Maximizing SD/U for Parallel
Reactions: Concentration
kD −(ED −EU )
D
A+B
kU
SD U =
AD
AU
e RT (CA1−2 ) CB1−2
U
What reactor conditions and configuration maximizes the selectivity?
Now evaluate concentration:
a) 1   2 → 1 −  2  0 b) 1   2 → 1 −  2  0

CA1−2 CA1−2
→ Use large CA → Use small CA

c) 1  2 → 1 − 2  0 d) 1  2 → 1 − 2  0
CB 1− 2 CB 1− 2
→ Use large CB → Use small CB
How do these concentration requirements affect reactor selection?
The University of Adelaide Slide 21
Concentration Requirements &
Reactor Selection
kD
D How do concentration requirements play
A+B into reactor selection?
kU CA0u0 CAu0
U
CB0u0 CBu0
CSTR:
PFR concentration is
PFR (or PBR): concentration is always at its
high at the inlet & progressively lowest value
drops to the outlet (that at outlet)
concentration
Semi-batch: concentration
Batch: CBu0
of one reactant (A as
concentration is shown) is high at t=0 &
CA(t)
CB(t) high at t=0 & progressively drops with
progressively drops increasing time, whereas
with increasing CA concentration of B can be
time kept low at all times
The University of Adelaide Slide 22
Different Types of Selectivity
rate of formation of D rD
instantaneous rate selectivity, SD/U SD U = =
rate of formation of U rU
overall rate selectivity, SD U
F Exit molar flow rate of desired product
SD U = D =
FU Exit molar flow rate of undesired product

N Final moles of desired product

SD U = D =
NU Final moles of undesired product

instantaneous yield, YD rate of formation of D r

YD = = D
(at any point or time in reactor) rate of consumption of A −rA
overall yield, YD

FD Evaluated ND Evaluated
flow YD = batch YD =
FA0 − FA at outlet NA0 − NA at tfinal

The University of Adelaide Slide 23

Series (Consecutive) Reactions
k1 k2
A D U Time is the key factor here!!!
(desired) (undesired)

Spacetime  for a flow reactor Real time t for a batch reactor

To maximize the production of D, use:

Batch CSTRs in series

or PFR/PBR or
n

and carefully select the time (batch) or spacetime (flow)

The University of Adelaide Slide 24

Concentrations in Series Reactions
k1 k2 -rA = k1CA
A B C rB,net = k1CA – k2CB
How does CA depend on ?
dFA dC A
= −k1C A → u0 = −k1C A → C A = C A0e −k1
dV dV
How does CB depend on ?
dFB
dV
= k1C A − k 2CB → u0
dCB
dV
= k1 C A0e −k1 − k 2CB ( ) Substitute
V
u0
=

→
dCB
d
(
= k1 CA0e−k1 − k 2CB →
dCB
d
)
+ k 2CB = k1 CA0e−k1 ( )
Use integrating
factor →
(
d CBek 2 ) =k C  e−k1 − e−k 2
(k 2 −k1) → CB = k1CA0 


1 A0 e  k 2 − k1
d  
CC = CA0 − CA − CB

The University of Adelaide Slide 25

Reactions in Series: Cj & Yield

B CA = CA0e−k1
A C
 e−k1 − e−k 2 
CB = k1CA0  
 k 2 − k1
 

CC = CA0 − CA − CB
opt
The reactor V (for a given u0) and  that maximizes CB occurs when dCB/dt=0
dCB  k1CA0 
= 
d  k 2 − k1 
−(
k1e −k1
+ k 2 e −k 2
)=0

1 k
 opt = ln 1
k1 − k 2 k 2
V
=  so Vopt = u0 opt
u0

The University of Adelaide Slide 26

CRE Algorithm for multiple reactions
New things for multiple reactions are:

1. Number Every Reaction

2. Mole Balance on every species
3. Rate Laws
(a) Net Rates of Reaction for every species
N
rA =  riA
i =1
(b) Rate Laws for every reaction
r1 A = −k1 AC AC B2
r2C = −k 2C C A2 CC3
(c) Relative Rates of Reaction for every reaction
For a given reaction i: (i) aiA+biB →ciC+diD:
riA riB riC riD
= = =
− ai − bi ci di
The University of Adelaide Slide 27
Gas phase reactions

Batch Flow
NB FB
CB = CB =
V u
NT P0 T0 FT P0 T0
V = V0 u = u0
NT 0 P T FT 0 P T
N B NT 0 P T0 FB FT 0 P T0
CB = CB =
NT V0 P0 T FT u0 P0 T
N B P T0 FB P T0
CB = CT 0 CB = CT 0
NT P0 T FT P0 T
The University of Adelaide Slide 28
Stoichiometry
𝑃
Concentration of Gas: 𝑦=
𝑃0
æ FA ö æ T0 ö
CA = CT 0 ç ÷ p𝑦ç ÷ FT = FA + FB + FC + FD
è FT ø è T ø
Note: For liquids we can just express the concentration as:

Flow: FA
CA =
u0
Batch: NA
CA =
V0

The University of Adelaide Slide 29

Example: Liquid Phase PFR

The complex liquid phase reactions follow

elementary rate laws:
(1) A + 2 B → C − r1A = k C C
1A A B
2

NOTE: The specific reaction rate k1A is defined with

respect to species A.

(2) 3C + 2 A → D − r2C = k2C CC3 C A2

NOTE: The specific reaction rate k2C is defined with

respect to species C.

The University of Adelaide Slide 30

Example: Liquid Phase PFR
Complex Reactions

1 𝐴 + 2𝐵 → 𝐶
2 2𝐴 + 3𝐶 → 𝐷
1) Mole Balance on each and every species
dFA dFB
(1) = rA (2) = rB
dV dV

dFC dFD
(3) = rC (4) = rD
dV dV

The University of Adelaide Slide 31

Example: Liquid Phase PFR
2) Rate Laws:
(5) rA = r1 A + r2 A (7) rB = r1B + r2 B
Net Rates
(6) rC = r1C + r2C (8) rD = 0 + r2 D

Rate Laws (9) r1 A = −k1 AC ACB2

(10) r2C = −k 2C C A2CC3
Relative Rates r1 A r1B r1C
Reaction 1 = =
−1 −2 1

(11) r1B = 2r1 A

(12) r1C = −r1 A

The University of Adelaide Slide 32

Example: Liquid Phase PFR
Relative Rates r2 A r2C r2 D
= =
Reaction 2 −2 −3 1
2
(13) r2 A = r2C
3
r2C
(14) r2 D = −
3
2
Hence, from rA = −k1 AC AC − k 2C C A2 CC3
2
B
Net Rates 3
rB = −2k1 AC AC B2
rC = k1 AC AC B − k 2C C A2 CC3
k 2C 2 3
rD = C ACC
3
The University of Adelaide Slide 33
Example: Liquid Phase PFR
3) Stoichiometry
Liquid
(15) 𝐶𝐴 = 𝐹𝐴 Τ𝜐0
(16) 𝐶𝐵 = 𝐹𝐵 Τ𝜐0
(17) 𝐶𝐶 = 𝐹𝐶 Τ𝜐0
(18) 𝐶𝐷 = 𝐹𝐷 Τ𝜐0

4) Parameters
(19) 𝑘1𝐴 = 10
(20) 𝑘2𝐶 = 25
(21) 𝐹𝐴0 = 200 mol/s
(22) 𝐹𝐵0 = 200 mol/s
(23) 𝐹𝐶0 = 0 mol/s
(24) 𝐹𝐷0 = 0 mol/s
(25) 𝜐0 = 100 dm3 /s

The University of Adelaide Slide 34

Example: Liquid Phase PFR
250

200
Molar Flowrate (mol/s)

150
FA
FB
100
FC
FD
50

0
0 300 600 900 1200 1500
PFR Reactor Volume (dm3)

The University of Adelaide Slide 35

Example: Liquid Phase PFR
1
0.9
0.8
Overall Selectivity D/C

0.7
0.6
0.5
𝑆ሚ𝐷/𝐶,𝑚𝑎𝑥 = 0.922 at V = 485 dm3
0.4
0.3
0.2
0.1
0
0 300 600 900 1200 1500
PFR Reactor Volume (dm3)

The University of Adelaide Slide 36

 Chemical Reaction Engineering (CRE)
Algorithm

1. Mole Balance (Week 1-2) Heat Effects

2. Rate Law (Week 3)
Isothermal Design
3. Stoichiometry (Week 3)
Stoichiometry
4. Combine (Week 4-5)
Rate Laws
5. Evaluate (Week 4-5)
6. Energy Balance (Week 8-9) Mole Balance

The University of Adelaide Slide 37

Week 5 – Theory: Summary

• From this lecture you should be able to:

1. Use the CRE algorithm to perform analysis of unsteady
state reactors, including:
o Start-up of a CSTR
o Semi-batch reactors
2. Describe the different types of multiple reactions (series,
parallel, independent, and complex) and to select a
reaction system that maximizes the selectivity.
3. Write down and use the algorithm for solving CRE
problems with unsteady state reactors and multiple
reactions using concentration rather than conversion.

The University of Adelaide Slide 38