L9-1

Review: Isothermal Reactor Design

1. Set up mole balance for In - Out + Generation = Accumulation
specific reactor V dNj
Fj0 F j rjdV
dt

Batch CSTR PFR

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

3. Put Cj is in terms of C j0 jCA0 XA P T0 Z0

rA kC jn Cj
XA and plug into rA 1 XA 0
P T Z
Reaction order
(We will always look n
conditions where Z0=Z)
needs to be
C j0 jC A0 X A P T0
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
or the XA obtained for given V , 0, time, etc equations & integrate for Q2
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 = kCAa 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 = kCBb where k=kACAa k=kACA0a
5.Determine kA by measuring rA at known concentrations of A and B, where

rA 3 a b 1 1
kA a b
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 alpha power
Fj0 Fj rj V N j j
rj Where rA = kCAa
dt dt
0 0
Average slope
1. Plot DCA/Dt vs t
2. Determine dCA/dt from plot by Curved line
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 = k
specified time C Aa
3. Plot ln(-dCA/dt) vs ln CA dCA
ln lnk a lnCA Insert , 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
dCA
For a first-order reaction - rA = k CA kCA
ln (CA0/CA) dt
Plot of
ln(CA0/CA) vs t CA0
is a straight 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
is a straight line kt
t CA CA0
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
a A
drop to half of its initial value rA kCA dt

ln (t1/2)
1 1 1
t a 1
k a 1 CA CA0a 1

Slope = 1- a
1
CA CA0 at t = t1 2
2

2a 1 1 1
t1 2
k a 1 CA0a 1
ln CA0
2a 1 1
Plot ln(t1/2) vs ln CA0. Get a straight
line with a slope of 1-
ln t1 2 ln
k a 1
1 a 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 kCA0a
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 rA: 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

DL FA0 FAe rA DW 0

FA0 FAe 0 CA0 CAe

rA
DW DW
FA0 FAe
When constant flow rate, 0 = :
CA0 Cp
Fp 0 CA0 CAe 0Cp Product
rA concentration
DW DW
The reaction rate is determined by measuring
DW 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 A B
1 CD A C
2 E

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 kDCAa1CB b1 rD AD e RT CAa1CB b1
A+B EU
kU
U (undesired) rU kUCAa 2 CB b2 rU AUe RT CAa 2 CB b2
E
k T AeRT Rate of disappearance of A: rA rD rU
ED EU
rA ADe RT C Aa1CB b1 AUe RT C Aa2 CB b2
Define the instantaneous rate selectivity, SD/U
ED

rate of formation of D rD AD e RT
C A a1CBb1
SD U sD U EU
rate of formation of U rU A Ue RT
C A a2 CBb2
ED EU
k

SD U D CAa1a2 CB b1 b2 SD U
kU AU
AD
CAa1a2 CB b1 b2
e RT
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 CAa1a2 CBb1b2
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
D
kD ED EU
AD
e RT CAa1a2
A
SD U
AU
UkU
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 cal cal a) ED > EU
20,000 10,000
(298K): mol mol
cal

AD 1.987 298K AD
SD U e molK CAa1a2 SD U 4.6 108 CAa1a2
AU AU
cal cal
T = 100 C 20,000 10,000 kD/U
(373K): mol mol
cal

AD 1.987 373K AD
SD U e mol K CAa1a2 1.4 106 CAa1a2
SD U
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
CAa1a2 CB b1 b2
U
What reactor conditions and configuration maximizes the selectivity?
Now evaluate concentration:
a) a1 a2 a1 a2 0 b) a1 a2 a1 a2 0

CAa1a2 CAa1a2
Use large CA Use small CA

c) b1 b2 b1 b2 0 d) b1 b2 b1 b2 0
CBb1b2 CBb1b2
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
ReactorD
Selection
D How do concentration requirements play
A+B into reactor selection?
kU
U CA00 CA0
CB00 CB0
CSTR:
PFR concentration is
PFR (or PBR): concentration is always at its
high at the inlet & progressively lowest value
drops to the outlet concentration (that at outlet)

Semi-batch: concentration
Batch: CB0
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 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 a2 A a1 a2
product formation product formation
kU (keep CA low)
U

b1 b 2 Batch reactor
PFR/PBR
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
CA00 CA0
CB00 CB0
b1 b2 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
(keep CB CSTRs in Dilute feed with inerts that are
series easily separated from product
low)
B consumed
Slides courtesy of Prof before&leaving
M L Kraft, Chemical CSTR
Biomolecular Engr Low
n Dept, P if gas
University phaseUrbana-Champaign.
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, 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 ND
flow YD F F
Evaluated
batch YD Evaluated
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 k1C A C A C A0e k1t
dV dV
How does CB depend on t?
dFB
dV
k1C A k 2CB 0
dCB
dV
k1 C A0e k1t k 2CB Substitute
V
0
t

dCB
dt

k1 CA0ek1t k 2CB
dCB
dt
k 2CB k1 C A0ek1t
Use integrating
factor (reviewed

d CBek 2t k C ek1t ek 2t
k 2 k1t CB k1CA0


1 A0 e k 2 k1
on Compass) dt
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 CA0ek1t
A C
ek1t ek 2t
CB k1CA0
k 2 k1

CC CA0 CA CB
topt
The reactor V (for a given 0) and t that maximizes CB occurs when dCB/dt=0
dCB k1CA0
dt

k 2 k1
k1
e k1t
k 2 e k 2t
0
1 k
t opt ln 1
k1 k 2 k 2

V
t so Vopt 0t opt
0
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.