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ITK-330

Chemical Reaction Engineering



Multiple Reactions

Dicky Dermawan
www.dickydermawan.net78.net
dickydermawan@gmail.com

Significance
SELDOM is the reaction of
interest the only ONE that
occurs in a chemical Reactor

Some reactions are Desired (D),
some are Undesired (U)

Goal: Maximize D, minimize U
SELDOM
ONE
Paralel reactions


Series or consecutive reactions


Mixed series paralel reactions
Classification
A + B
A + C
C + D
E
A
B
C
k
1
k
2
A B
C
k
1
k
2
Industrially Significant Examples
CH
2
CH
2
O

NH
3
HOCH
2
CH
2
NH
2
CH
2
CH
2
O

(HOCH
2
CH
2
)
2
NH (HOCH
2
CH
2
)
3
N
CH
2
CH
2
O

CH
2
=CH
2
+ O
2
2 CO
2
+ H
2
O
CH
2
CH
2
O

C
2
H
5
OH C
2
H
4
+ H
2
O
C
2
H
5
OH CH
3
CHO + H
2
C
2
H
4
+ CH
3
CHO C
2
H
6
+ H
2
O
Selectivity
Selectivity:

2 1
o o
= =
A
U
D
U
D
DU
C
k
k
r
r
S
A D Desired
A U
Undesired
k
D
k
U
1
o
A D D
C k r =
2
o
A U U
C k r =
Desired vs Undesired
Maximizing Selectivity
o
1
o
2

+ -
C
A
Keep it High Keep it Low
Inerts No Yes
Diluents No Yes
Recommended
Reactor
Batch, Plug Flow CSTR
2 1
o o
= =
A
U
D
U
D
DU
C
k
k
r
r
S
+
-
Recommendations
Other Definitions for selectivy
Overall Selectivity,

DU
S
~
) 12 6 (
~
= =
U of rate Flow Molar Exit
D of rate Flow Molar Exit
F
F
S
U
D
DU
Untuk reaktor Batch:

U
D
DU
N
N
S =
~
Yield
A A
D
D
N N
N
Y

=
0
~
Instantaneous Yield at a point:



Overall Yield:
Batch System:
Flow System:
A
D
D
r
r
Y

=
A A
D
D
F F
F
Y

=
0
~
Parallel Reactions Simple Example





















Senyawa A terdekomposisi menurut persamaan:
2 A R r
R
= 0.7. C
A
2
A S r
S
= 0,1.C
A


Suatu larutan yang mengandung A dengan
konsentrasi 2 mol/L diumpankan ke dalam reaktor
pipa dengan waktu tinggal 36 menit.

Tentukan konsentrasi A, R, dan S pada aliran yang
meninggalkan reaktor.

Simple Paralel Reactions:
Hand Calculation Solvable
min 3 . 0
min 06 . 0
min 002 . 0
3
3
2
3
1
2 2
3
1 1
= =
= =
= =

mol dm k C k r Y A
k C k r B A
dm mol k k r X A
A
Y
A B
x
P6-6
A

Consider the following system of gas-phase reactions:
min 3 . 0
min 06 . 0
min 002 . 0
3
3
2
3
1
2 2
3
1 1
= =
= =
= =

mol dm k C k r Y A
k C k r B A
dm mol k k r X A
A
Y
A B
x
B is the desired product, and X and Y are foul pollutants that are expensive to get rid of. The
specific reaction rates are at 27C. The reaction system is to be operated at 27C and 4 atm.
Pure A enters the system at a volumetric flow rate of 10 dm
3
/min.
a. Sketch the instantaneous selectivities (S
BX
, S
BY
, and S
B/XY
= r
B
/(r
x
+ r
y
) ) as a function of .
the concentration of C
A
.
b. Consider series of reactors. What should be the volume of the first reactor?
c. What are the effluent concentrations of A, B, X, and Y from the first reactor?
d. What is the conversion of A in the first reactor?
e. If 90% conversion of A is desired, what reaction scheme and reactor sizes should you use?
f. Suppose that E
1
= 10,000 cal/mol, E
2
= 20,000 cal/mol, and E
3
= 30,000 cal/mol.
What temperature would you recommend for a single CSTR with a space-time of 10 min
. and an entering concentration of A of 0.1 mol/dm
3
?
Paralel Reactions Economic Tradeoff
Series Reactions:
Hand Calculation Solvable
P6-7
B

Pharmacokinetics concerns the ingestion, distribution, reaction, and elimination reactions of
drugs in the body. Consider the application of pharmacokinetics to one of the major problems we
have in the united states, drinking and driving. Here we shall model how long one must wait to drive
after having a tall martini. In most states the legal intoxication limit is 1.0 g of ethanol per liter of
body fluid. (In Sweden it is 0.5 g/L, and in Eastern Europe and Russia it is any value above 0.0 g/L.)
The ingestion of ethanol into the bloodstream and subsequent elimination can be modeled as a
series reaction. The rate of absorption from the gastrointestinal tract into the bloodstream and body
is a first-order reaction with a specific rate constant of 10 h
-1
. The rate at which ethanol is broken
down in the bloodstream is limited by regeneration of a coenzyme. Consequently, the process may
be modeled as a zero order reaction with a specific rate of 0.192 g/h.L of body fluid.
How long would a person have to wait (a) in the united states; (b) in Sweden; and (c) in
Russia if they drank two tall martinis immediately after arriving at a party?
How would your answer change if (d) the drinks were taken hour apart; (e) the two drinks were
consumed at a uniform rate during the first hour?
(f) Suppose that one went to a party, had one and a half tall martinis right away, and then
received a phone call saying an emergency had come up and they needed to drive home
immediately. How many minutes would they have to reach home before he/she became legally
intoxicated, assuming that the person had nothing further to drink?
(g) How would your answers be different for a thin person? A heavy person? For each case
make a plot of concentration as a function of time.(Hint: Base all ethanol in the blood as a function
of time.) What generalizations can you make? What is the point of this problem?
Additional Information:
Ethanol in a tall martini: 40 g Volume of a body fluid: 40 L
2
1
Series Reactions:
Hand Calculation Solvable
The elementary liquid phase series reaction:

is carried out in a 500 dm
3
batch reactor. The initial concentration of A is 1.6
mol/dm
3
. The desired product is B and separation of the undesired
product C is very difficult and costly. Because the reaction is carried out
at a relatively high temperature, the reaction is easily quenched.

Additional information:
Cost of pure reactant A = $10/mol A
Selling Price of Pure B = $50/molB
Separation cost of A from B = $50/mol A
Separation cost of C from B = $30 (e
0.5Cc

1 )
k
1
= 0.4 hr
-1
, k
2
= 0.01 hr
-1
@ 100C

C B A
k k

2 1
P6-9
B
Series Reactions:
Hand Calculation Solvable (lanjutan)
a) Assuming that each reaction is reversible, plot the
concentrations of A, B, and C as a function of time
b) Calculate the time the reaction should be quenched to achieve
maximum profit
c) For a CSTR space-time of 0.5 h, what temperature would you
recommend to maximize B? (E
1
= 10000 cal/mol, E
2
= 20000
cal/mol)
d) Assume that the firs reaction is reversible with k
-1
= 0.3 h
-1
. Plot
the concentration of A, B, and C as a function of time
e) Plot the concentrations of A, B, and C as a function of time for
the case where both reactions are reversible with k
-2
= 0.005 h
-1

f) Vary k
1
, k
2
, k
-1
, and k
-2
. Explain the consequence of k
1
> 100 and
k
2
<0.1 with k
-1
= k
-2
= 0
Systematic Approach to handle
Multiple Reaction Problems
Mole Balances for Multiple Reactions
Use moles N
j
or molar flow rates F
j
rather than Conversion X.
Use differential form rather than integral form

Metode Penyelesaian Untuk Reaksi Jamak:
Lanjutan
Net Rates of Reaction for N Reactions Taking Place
Hukum Laju (Rate Law) untuk tiap reaksi dinyatakan
dalam konsentrasi tiap spesi yang bereaksi.
Stoichiometry: Relative Rates of Reaction

eg: a A + b B c C + d D (reaction i)
d
r
c
r
b
r
a
r
iD iC iB iA
= =

=
=
N
i
ij j
r r
1
species
Reaction number
Reactants
Metode Penyelesaian Untuk Reaksi Jamak:
Lanjutan
Stoichiometry: Concentrations
Liquid Phase,
0
u
j
j
F
C =
T
T
P
P
F
F
C
T
j
j
0
0
|
|
.
|

\
|
=
For Ideal Gasses:



Dengan:
0
0
u
T
F
0 T
C

=
=
n
j
j T
F F
1 0
0
0
RT
P
C
T
= dan
For


|
|
.
|

\
|
=
T
j
T j
F
F
C C
0
0
P
P
T
T
0
Isothermal System.
NO Pressure Drop,
Metode Penyelesaian Untuk Reaksi Jamak:
Lanjutan
Combining Step: Example for gas reaction in PFR
|
|
.
|

\
|
= = =
|
|
.
|

\
|
= = =

=
=
T
j
T
T
T j
q
i
ij j
j
T
j
T
T
T
q
i
i
F
F
C
F
F
C fn r r
dV
dF
F
F
C
F
F
C fn r r
dV
dF
0
1
0
1
0
1
0 1
1
1 1
1
..., ,
.
.
.
..., ,
Review on the Role of CSTR
& Net Rate of Reaction Principles
=
=
N
i
ij j
r r
1
CSTR Design for Multiple Reactions

=
=
N
i
ij j
r r
1
Mole Balances
0 V r F F
r
F F
V
A A 0 A
A
A 0 A
= +


=
0 r C C
A A 0 A 0
= t + u = u
All liquid reactions
& gas with all c = 0
Kinetic expression
Write down for
ALL species
Stoichiometry
d
r
c
r
b
r
a
r
iD iC iB iA
= =

Auxiliary
expressions:

=
=
n
j
j T
F F
1
0
0
0
RT
P
C
T
=
|
|
.
|

\
|
=
T
j
T j
F
F
C C
0
0
P
P
T
T
0
Combining equations form n nonlinear equation with n variables, i.e.
F
A
, F
B
, F
C
, or
CA
, C
B
, C
C
,.
n = number of species involved
The following liquid phase reactions are carried out
isothermally in a 50 L PFR:
A + 2 B C + D r
D1
= k
D1
.
C
A
.
C
B
2

2 D + 3 A C + E r
E2
= k
E2
.
C
A
.
C
D

B + 2 C D + F r
E3
= k
E3
.
C
B
.
C
C
2

P6-13
B

Maximizing Selectivity:
Semibatch Reactor
A + B D
A + B U
B
2
A 1 D
C C k r =
2
B A 2 D
C C k r =
B
A
2
1
U
D
U / D
C
C
k
k
r
r
S = =
Keep C
A
high, C
B
low
A
B
Semibatch Reactor Design
A
B
B
A
For the case P6-13B,
which one is better to maximize the production
of D?
A + 2 B C + D r
D1
= k
D1
.
C
A
.
C
B
2

2 D + 3 A C + E r
E2
= k
E2
.
C
A
.
C
D

B + 2 C D + F r
E3
= k
E3
.
C
B
.
C
C
2

Semibatch Reactor for Multiple Reaction

=
=
N
i
ij j
r r
1
Laju masuk laju keluar + laju pembentukan = laju akumulasi
Misalnya reaktor mula-mula hanya berisi A dengan volume V
0
dt
dN
V r 0 0
A
A
= +
B dialirkan ke reaktor dengan laju konstan u
o
dt
dN
V r 0 F
B
B 0 B
= +
C,D,E,F mula-mula tidak ada; tidak dialirkan

dt
dN
V r 0 0
C
C
= +
dt
dN
V r 0 0
D
D
= +
dt
dN
V r 0 0
E
E
= +
dt
dN
V r 0 0
F
F
= +
t u V V
0 0
+ =
Auxiliary equations:

0 B o 0 B
C u F =
V C N
j j
=
Kinetics:

Stoichiometry:

d
r
c
r
b
r
a
r
iD iC iB iA
= =

Performance equations:

Packed Bed Reactor Design
for Multiple Reactions

=
=
N
i
ij j
r r
1
d
r
c
r
b
r
a
r
iD iC iB iA
= =

Mole Balances
All liquid reactions follows exactly the same rule
as PFR Design
Kinetic expression
Write down for ALL species
Stoichiometry
Auxiliary
expressions:

=
=
n
j
j T
F F
1
0
0
0
RT
P
C
T
=
T
T
0
Combining equations form (n+1) ordinary differential equations with
(n+1) variables, i.e. F
A
, F
B
, F
C
, or
CA
, C
B
, C
C
,. AND P
n = number of species involved
j
j
' r
dW
dF
=
0
u = u
0 T
j
0 T j
P
P
F
F
C C
|
|
.
|

\
|
=
Pressure drop
0 T
T
0
0
0
F
F
P / P
P
T
T
2 dW
dP

o
=
Packed
Bed
Reactor
Design
for
Multiple
Reactions
P6-16C The following hydrodealkylation reactions occur
. over a Houdry Detol catalyst near 800 K and 3500 kPa:
(1) H
2
+ C
6
H(CH
3
)
5
C
6
H
2
(CH
3
)
4
+ CH
4
r
1
= k
1
.C
H2

.C
11

(2) H
2
+ C
6
H
2
(CH
3
)
4
C
6
H
3
(CH
3
)
3
+ CH
4
r
2
= k
2
.C
H2

.C
10

(3) H
2
+ C
6
H
3
(CH
3
)
3
C
6
H
4
(CH
3
)
2
+ CH
4
r
3
= k
3
.C
H2

.C
9

(4) H
2
+ C
6
H
4
(CH
3
)
2
C
6
H
5
(CH
3
) + CH
4
r
4
= k
4
.C
H2

.C
8

(5) H
2
+ C
6
H
5
(CH
3
) C
6
H
6
+ CH
4
r
5
= k
5
.C
H2

.C
7

k
5
= 2,1 (mol/L)
-
.s
-1
k
1
/k
5
= 17.6 k
2
/k
5
= 10 k
3
/k
5
=4.4 k
4
/k
5
= 2.7



6 , 17
5
1
k
k
=

10
5
2
k
k
=

4 , 4
5
3
k
k
=

7 , 2
5
4
k
k
=
The feed is equimolar in hydrogen and pentamethylbenzene.
(a) For an entering volumetric flowrate of 1 m
3
/s, what ratio of
hydrogen to pentamethylbenzene and what PFR reactor
volume would you recommend to maximize the formation
of C
6
H
4
(CH
3
)
2
?
. [Hint: Plot the overall selectivity as a function of reactor
volume]
P6-24C Methanol Synthesis
A new catalyst has been proposed for the synthesis of methanol from carbon
monoxide and hydrogen gas. This catalist is reasonably active between
temperatures of 330 K to about 430 K. The isothermal reactions involved in
the synthesis include:
CO + 2 H
2
CH
3
OH
CO + H
2
O CO
2
+ H
2
CH
3
OH CH
2
O + H
2
The reactions are elementary and take place in the gas phase. The reaction is
to be carried out isothermally and as a first approximating pressure drop will
be neglected. The feed consists of 7/15 hydrogen gas, 1/5 carbon monoxide,
1/5 carbon dioxide, and 2/15 steam. The total molar flow rate is 300 mol/s.
The entering pressure may be varied between 1 atm and 160 atm and the
entering temperature between 300 K and 400 K. Tubular (PFR) reactor
volumes between 0.1 m3 and 2 m3 are available for use.
a. Determine the entering conditions of temperature and pressure and reactor
volume that will optimize the production of methanol. (Hint: first try T
0
= 330 K
at P
0
= 40 atm, then try T
0
= 380 K and P
0
= 1 atm)
b. Vary the ratios of the entering reactant to CO
2
(i.e. thetaH
2
and thetaH
2
O) to
maximize methanol production. How do your results compare with those in
part (a)? Describe what you find.
Methanol Synthesis
( )
2
3
2
1
001987 . 0
298
1 1 620 , 30
exp
667 . 131
|
|
.
|

\
|
(

|
.
|

\
|

=
mol
dm
T
T R
K
(

|
.
|

\
|

=
298
1 1 834 , 9
exp
943 , 103
2
T R
K
CO + 2 H
2
CH
3
OH
CO + H
2
O CO
2
+ H
2
CH
3
OH CH
2
O + H
2
P6-24
C
K mol
cal
R K T dm V 987 . 1 , ] [ , 40
3
= = =
Data:
1
2
3
1
1
330
1 400 , 31
5 . 2 exp 933 . 0

|
|
.
|

\
|
(

|
|
.
|

\
|
|
.
|

\
|
= s
mol
dm
T R
k
s mol
dm
T R
k

|
.
|

\
|
=
3
2
1
300
1 000 , 18
exp 636 . 0
1
3
1
325
1 956 , 28
5 . 1 exp 244 . 0

(

|
|
.
|

\
|
|
.
|

\
|
= s
T R
k
Series Reactions
The elementary liquid phase series reaction:

is carried out in a 500 dm
3
batch reactor. The initial concentration of A is 1.6
mol/dm
3
. The desired product is B and separation of the undesired
product C is very difficult and costly. Because the reaction is carried out
at a relatively high temperature, the reaction is easily quenched.

Additional information:
Cost of pure reactant A = $10/mol A
Selling Price of Pure B = $50/molB
Separation cost of A from B = $50/mol A
Separation cost of C from B = $30 (e
0.5Cc

1 )
k
1
= 0.4 hr
-1
, k
2
= 0.01 hr
-1
@ 100C

C B A
2 1
k k

(b) Calculate the time the reaction should be quenched to
achieve the maximum profit.