L9-1

Review: Isothermal Reactor Design

1. Set up mole balance for In - Out +Generation = Accumulation
specific reactor V dN j
Fj0  F j   rjdV 
dt

Batch CSTR PFR

2. Derive design eq. in FA0 XA XA dX
XA
terms of XA for each dXA V= A
t = NA0  -rA V = FA0 
reactor 0 -rA V 0 -rA

3. Put Cj is in terms of C j0   jCA0 X A  P   T0   Z0 

rA  kC jn Cj     
XA and plug into rA 1   XA  P0   T   Z 
Reaction order
(We will always look n
needs to be  C j0   jC A0 X A  P   T0  
conditions where Z0=Z)
determined. rA  k     
 1  X A  P0   T  
4. Plug rA into design eq & solve for the time
(batch) or V (flow) required for a specific XA Be able to rearrange
equations & integrate for Q2
or the XA obtained for given V , 0, time, etc
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
 L9-2

Review: Analysis of Rate Data

Goal: determine reaction order, a, and specific reaction rate constant, k
• Data collection is done in the lab so we can simplify BMB, stoichiometry,
and fluid dynamic considerations
• Want ideal conditions → well-mixed (data is easiest to interpret)
• Constant-volume batch reactor for homogeneous reactions: make
concentration vs time measurements during unsteady-state operation
• Differential reactor for solid-fluid reactions: monitor product concentration
for different feed conditions during steady state operation
 Method of Excess
 Differential method
 Integral method
 Half-lives method
 Initial rate method
 Differential reactor
 More complex kinetics
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
 L9-3

Review: Method of Excess

A + B → products Suspect rate eq. -rA = kCAaCBb

1.Run reaction with an excess of B so CB ≈ CB0

2.Rate equation simplifies to –rA = k’CAa where k’=kACBb ≈ k’=kACB0b and a
can be determined
3.Repeat, but with an excess of A so that CA ≈ CA0
4.With excess A, rate simplifies to –rA = k’’CBb where k’’=kACAa ≈ k’’=kACA0a
5.Determine kA by measuring –rA at known concentrations of A and B, where

 
rA 3    1  1 
kA   dm mol  
C A CB  s

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
 L9-4

Review: Differential Method

d dC j alpha power
Fj0  Fj  rj V  Nj  rj
dt Where –rA = kCAa
0 0 dt
Average slope
1. Plot DCA/Dt vs t
Curved line
2. Determine dCA/dt from plot by
represents
graphical or numerical methods –dCA/dt
a) Draw rectangles on the graph.
Then draw a curved line so that
the area above the curve that is
cut off of each rectangle
approximately fills the unfilled
area under the curve
b) -dCA/dt is read using the value
where the curve crosses a  dCA dt
Slope of line = α k
specified time C A
 dCA 
3. Plot ln(-dCA/dt) vs ln CA ln    lnk   lnCA Insert α, –dCA,p/dt, &
 dt  corresponding CA,p
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
 L9-5

Review: Integral Method

• A trial-and-error procedure to find reaction order

• Guess the reaction order → integrate the differential
equation
• Method is used most often when reaction order is known
and it is desired to evaluate the specific reaction rate
constants (k) at different temps to determine the activation
energy
• Looking for the appropriate function of concentration
corresponding to a particular rate law that is linear with time

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
 dC A L9-6
For the reaction A  products  rA
dt
For a zero-order reaction -rA = k dCA
 k
dt
Plot of CA vs CA
t is a straight
line CA  CA0  kt
t
For a first-order reaction - r A = k CA dCA
 kCA
ln (CA0/CA) dt
Plot of ln(CA0/CA)
vs t is a straight CA0
line
ln  kt
t CA

dCA
For a second-order reaction - rA = k CA2  kCA 2
dt
1/CA

Plot of 1/CA vs t 1 1
  kt
is a straight line CA C A0
t
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
 L9-7

Review: Method of Half-lives

Half-life of a reaction (t1/2): time it takes
for the concentration of the reactant to A  products  dCA  kC 
 A
drop to half of its initial value rA  kCA dt

ln (t1/2)
1  1 1 
t   1  
k    1  C A CA0 1

Slope = 1- 
1
CA  CA0 at t = t1 2
2

2 1  1  1 
t1 2   
k    1  CA0 1 
ln CA0
Plot ln(t1/2) vs ln CA0. Get a straight 2 1  1
line with a slope of 1-α
 
ln t1 2  ln
k    1
  1    lnCA0

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
 L9-8

Review: Method of Initial Rates

• When the reaction is reversible, the method of initial rates
can be used to determine the reaction order and the
specific rate constant
• Very little product is initially present, so rate of reverse
reaction is negligible
– A series of experiments is carried out at different initial
concentrations
– Initial rate of reaction is determined for each run
– Initial rate can be found by differentiating the data and
extrapolating to zero time
– By various plotting or numerical analysis techniques relating -rA0
to CA0, we can obtain the appropriate
 rate law:
rA0  kCA0
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
 L9-9

Review: Differential Catalyst Bed

Conversion of reactants r’A: rate of reaction per unit mass of catalyst
& change in reactant
concentration in the bed flow in - flow out + rate of gen = rate of accum.
is extremely small

L FA0  FAe  rA W  0

FA0  FAe 0CA0   CAe

rA  
W W
FA0 FAe
When constant flow rate, u0 = u:
CA0 Cp
Fp 0  CA0  CAe  0 Cp Product
rA   concentration
W W
The reaction rate is determined by measuring
W product concentration, Cp
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
 L9-10

L9: 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

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
 L9-11

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

k k
4) Complex reactions 1 CD
A  B  2 E
A  C 
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
 L9-12

Parallel Reactions
Purpose: maximizing the desired product in parallel reactions
ED
kD
D (desired) rD  kDCA1CB 1  rD  AD e RT C A1CB 1
A+B EU
kU
U (undesired) rU  kUC A 2 CB 2  rU  AUe RT CA 2 CB 2
E
k  T  AeRT Rate of disappearance of A: rA  rD  rU
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 ADe RT

C A 1CB1
SD U   sD U   EU
rate of formation of U rU A Ue RT
C A 2 CB2
 ED EU 
SD U 
kD
kU
 
CA1 2 CB 1 2  SD U 
AU
AD
e RT  CA12  CB12
Goal: Maximize SD/U to maximize production of the desired product
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
 L9-13

Maximizing SD/U for Parallel

Reactions: Temperature Control
 ED EU 
SD U 
AD
AU
e RT  
CA12 CB 1 2

What reactor conditions and configuration maximizes the selectivity?

Start with temperature (affects k):
a) If ED > EU b) If ED < EU

 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)
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
 L9-14

Maximize SD/U for Parallel Reactions

using Temperature
kD D
 ED EU 
A AD
SD U  e RT CA12
AU
U kU
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 
1.987 298K
 
A  A
SD U  D e  molK  C A1 2  SD U  D 4.6  108 C A1 2
AU AU
 cal cal 
T = 100 ◦C  20,000 10,000  kD/U
(373K):  mol mol 
 cal 
1.987 373K
 
AD  A
SD U  e  mol K  C A1 2
 SD U  D 1.4  106 C A12
AU AU
SD/U is greater at 373K, higher temperature to favors desired product formation
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
 L9-15

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?
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
 L9-16

Concentration Requirements &

k
Reactor Selection
D
D How do concentration requirements play
A+B into reactor selection?
kU
U CA0u0 CAu0
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)
high at t=0 & progressively drops with
CB(t)
progressively drops increasing time, whereas
with increasing time CA concentration of B can be
kept low at all times
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
 kD L9-17
D High C favors desired High CA favors undesired
A+B a1 > a 2 A a1 < a 2
product formation product formation
kU
U (keep CA low)
b1 > b 2 PFR/PBR
Batch reactor
Side streams feed low CA
High CB CA
When CA & CB are low (end time Semi-batch
favors or position), all rxns will be slow reactor slowly feed ←High CB
desired A to large amt of B
product PFR/PBR CA CA CA
formation High P for gas-phase rxn, do not CSTRs in
add inert gas (dilutes reactants) series
CA0u0 CAu0
CB0u0 CBu0
b1 < b 2 CSTR
PFR/PBR w/ side streams feeding
High CB low CB CB
favors Semi-batch
undesired reactor, slowly ←High CA PFR/PBR
product feed B to large amount of A PFR/PBR w/ high
formation CB CB CB recycle
CSTRs in • Dilute feed with inerts that are
(keep CB series
easily separated from product
low) B consumed
Slides courtesy of Prof before&leaving
M L Kraft, Chemical CSTR
Biomolecular Engr • Low P if gas phaseUrbana-Champaign.
n Dept, University of Illinois,
 L9-18

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,S DU

F Exit molar flow rate of desired product

S D U  D 
FU Exit molar flow rate of undesired product

N Final moles of desired product

S D 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, Y D

  FD Evaluated ND Evaluated
Y
flow D F  F batch Y D 
A0 A at outlet NA0  NA at tfinal
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
 L9-19

Series (Consecutive) Reactions

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

Spacetime t 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)

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
 L9-20

Concentrations in Series Reactions

k1 k2 -rA = k1CA
A B C rB,net = k1CA – k2CB
How does CA depend on t?
dFA dC A
 k1C A  0  k1CA  C A  C A0e k1
dV dV
How does CB depend on t?
dFB
dV
dC
 k1C A  k 2CB  0 B  k1 C A0e k1  k 2CB
dV
  Substitute
V
0



dCB
d

 k1 CA0 ek1  k 2CB 
dCB
d

 k 2CB  k1 CA0 ek1  
Use integrating
factor (reviewed 

d CBek 2  k C e
 ek1  ek 2
 k 2 k1   CB  k1CA0 


1 A0  k 2  k1
on Compass) d  

CC  CA0  CA  CB
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
 L9-21

Reactions in Series: Cj & Yield

B CA  CA0 ek1
A C
 ek1  ek 2 
CB  k1CA0  
 k 2  k1
 

CC  CA0  CA  CB
topt
The reactor V (for a given u0) and t that maximizes CB occurs when dCB/dt=0
dCB  k1CA0 
d
 
 k 2  k1 
k1
e k1
 k 2 e k 2
0 
1 k
 opt  ln 1
k1  k 2 k 2

V
  so Vopt  0 opt
0

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