ITK-330

Chemical Reaction Engineering

Multiple Reactions

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

Significance
SELDOM is the reaction of
SELDOM
interest the only ONE
ONE that
occurs in a chemical Reactor
Some reactions are Desired (D),
(D)
some are Undesired (U)
Goal: Maximize D, minimize U

Classification

Paralel reactions
A

k2

Series or consecutive reactions

A

k1

k1

k2

Mixed series paralel reactions

A+B
A+C

C+D
E

Industrially Significant Examples

Selectivity
Desired vs Undesired

Selectivity:

A
A

kD
kU

D Desired
U Undesired

SDU

rD k DC A

rU kUC A

rD k D 1 2

CA
rU kU

Maximizing Selectivity
SDU
1

rD k D 1 2

CA
rU kU

CA

Keep it High

Keep it Low

Inerts

No

Yes

Recommended
Reactor

Batch, Plug Flow

CSTR

Recommendations
Diluents
No
Yes

Other Definitions for selectivy

~

Overall Selectivity,
~

S DU

S DU

FD Exit Molar Flow rate of D

FU Exit Molar Flow rate of U

Untuk reaktor Batch:

~

S DU

ND

NU

(6 12)

Yield
Instantaneous Yield at a point:
rD
YD
rA

Overall Yield:
Batch System:
Flow System:

YD

ND
N A0 N A

FD
YD
FA0 FA
~

Parallel Reactions Simple Example

Simple Paralel Reactions:

Hand Calculation
Solvable
P6-6
A

Consider the following system of gas-phase reactions:

A X

rx k1

A B

rB
k 2Cthe
k 2desired
0.06 min 1product,
B is
A

AY

k1 0.002 mol dm 3 min

A X

rx k1

k1 0.002 mol dm3 min

AB

rB k 2C A

k 2 0.06 min 1

AY

rY k3C A2

k3 0.3 dm 3 mol min

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 dm3/min.

rY k3C 2A

k3 0.3 dm 3 mol min

a. Sketch the instantaneous selectivities (SBX, SBY, and SB/XY = rB/(rx + ry) ) as a function of
.
the concentration of CA.
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 E1 = 10,000 cal/mol, E2 = 20,000 cal/mol, and E3 = 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/dm3?

Paralel Reactions Economic Tradeoff

Series Reactions:

Hand
Calculation
Solvable
Pharmacokinetics concerns the ingestion, distribution, reaction, and elimination reactions of

P6-7B

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?
1
How would your answer change if (d) the drinks were taken hour apart; (e) the two drinks were
2
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

Series Reactions:

Hand Calculation Solvable

P6-9B

The elementary liquid phase series reaction:

A k1 B k 2 C

is carried out in a 500 dm3 batch reactor. The initial concentration of A is 1.6
mol/dm3. 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 (e0.5Cc 1 )
k1 = 0.4 hr-1, k2 = 0.01 hr-1 @ 100C

Series Reactions:
a)
b)
c)

d)

e)

f)

Hand
Calculation
Solvable
Assuming
that each
reaction is reversible,(lanjutan)
plot the
concentrations of A, B, and C as a function of time
Calculate the time the reaction should be quenched
to achieve maximum profit
For a CSTR space-time of 0.5 h, what temperature
would you recommend to maximize B? (E1 = 10000
cal/mol, E2 = 20000 cal/mol)
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
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
Vary k1, k2, k-1, and k-2. Explain the consequence of
k1 > 100 and k2 <0.1 with k-1 = k-2 = 0

Systematic Approach to handle

Multiple Reaction Problems
Mole Balances for Multiple Reactions
Use moles Nj or molar flow rates Fj 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
N

r j rij
i 1

species
Reaction number

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)

riC riD
riA
riB

a b c
d
Reactants

Metode Penyelesaian Untuk Reaksi Jamak:

Lanjutan
Stoichiometry: Concentrations
Liquid Phase,
Fj

Cj

0
For Isothermal System.
NO Pressure Drop,

For Ideal Gasses:

FT 0
Cj
0

Fj

FT

P T0

P0 T

Fj
C j CT 0
FT

CT 0

Dengan:
n

FT Fj
j 1

dan

CT 0

P0
RT0

P T0

P0 T

Metode Penyelesaian Untuk Reaksi Jamak:

Lanjutan
Combining Step: Example for gas reaction in
q
Fj

dF1
F1
r1 ri 1 fn1 CT 0 ,..., CT 0
dV
FT
FT
i 1

.
.
.
dFj

Fj
F1
r j rij fn j CT 0 ,..., CT 0
dV
FT
FT
i 1

PFR

Review on the Role of CSTR

& Net Rate of Reaction Principles

r j rij
i 1

CSTR Design for Multiple Reactions

Mole Balances

F FA
V A0
FA 0 FA r A V 0
rA

0 C A 0 C A rA 0
Kinetic expression

r j rij
i 1

Auxiliary
expressions:

Write down for

ALL species
All liquid reactions
& gas with all = 0

CT 0

P0
RT0
n

Stoichiometry

riA
r
r
r
iB iC iD
a b c
d

FT Fj
j 1

Fj
C j CT 0
FT

P T0

P0 T

Combining equations form n nonlinear equation with n variables, i.e.

FA, FB, FC, or CA, CB, CC,.
n = number of species involved

P6-13B

The following liquid phase reactions are

carried out isothermally in a 50 L PFR:
A+2BC+D
rD1 = kD1.CA.CB2
2D+3AC+E
rE2 = kE2.CA.CD
B+2CD+F
rE3 = kE3.CB.CC2

Maximizing Selectivity:
Semibatch Reactor

A+BD
A+BU

SD / U

rD
k1 C A

rU k 2 C B

Keep CA high, CB low

rD k 1 C A 2 C B
rD k 2 C A C B 2

Semibatch Reactor Design

For the case P6-13B,
which one is better to maximize the production
of D?

A+2BC+D
kD1.CA.CB2
2D+3AC+E
kE2.CA.CD
B+2CD+F

rD1 =
rE2 =
rE3 =

Semibatch Reactor for Multiple Reaction

Misalnya reaktor mula-mula hanya berisi A dengan volume V0

B dialirkan ke reaktor dengan laju konstan uo

V V0 u 0 t

C,D,E,F mula-mula tidak ada; tidak dialirkan

Performance equations: Laju masuk laju keluar + laju pembentukan = laju akumulasi

FB0 0 rB V

0 0 rA V

dN A
dt

dN C
dt
dN D
0 0 rD V
dt
0 0 rC V

dN E
0 0 rE V
dt
dN F
0 0 rF V
dt

dN B
dt

Kinetics:

r j rij
i 1

Stoichiometry:

riA
r
r
r
iB iC iD
a b c
d
Auxiliary equations:

FB0 u o CB0
Nj Cj V

Packed Bed Reactor Design

for Multiple Reactions
Mole Balances

dFj
dW

r' j

0
Kinetic expression

Write down for ALL species

All liquid reactions follows exactly the same rule
as PFR Design

r j rij
i 1

Stoichiometry

Pressure drop

r
riA
r
r
iB iC iD
a b
c
d
P
F
dP
T

0 T
dW
2 T0 P / P0 FT0

Auxiliary
expressions:

CT 0

P0
RT0
n

FT Fj
j 1

Fj

T
P 0
F P
0 T
T

C j C T0

Combining equations form (n+1) ordinary differential equations with

(n+1) variables, i.e. FA, FB, FC, or CA, CB, CC,. AND P
n = number of species involved

Packed
Bed
Reactor
Design
for
Multiple
Reactions

P6-16C The following hydrodealkylation reactions occur

.
over a Houdry Detol catalyst near 800 K and 3500
(1) H2 + C6H(CH3)5 C6H2(CH3)4 + CH4
r1 = k1.CH2.C11
kPa:
(2) H2 + C6H2(CH3)4 C6H3(CH3)3 + CH4
(3) H2 + C6H3(CH3)3 C6H4(CH3)2 + CH4
(4) H2 + C6H4(CH3)2 C6H5(CH3) + CH4
(5) H2 + C6H5(CH3) C6H6 + CH4

1
5

17,6

2
5

10

4,4

4
5

2,7

k5 = 2,1 (mol/L)-.s-1
k1/k5 = 17.6

k2/k5= 10

r2 = k2.CH2.C10
r3 = k3.CH2.C9
r4 = k4.CH2.C8
r5 = k5.CH2.C7

k3/k5=4.4

k4/k5 = 2.7

The feed is equimolar in hydrogen and pentamethylbenzene.

(a) For an entering volumetric flowrate of 1 m3/s, what ratio of
hydrogen to pentamethylbenzene and what PFR reactor
volume would you recommend to maximize the formation
of C6H4(CH3)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 H2

CH3OH

CO + H2O

CO2 + H2

CH3OH

CH2O + H2

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 T0 = 330 K
at P0 = 40 atm, then try T0 = 380 K and P0 = 1 atm)
b. Vary the ratios of the entering reactant to CO2 (i.e. thetaH2 and thetaH2O) to
maximize methanol production. How do your results compare with those in
part (a)? Describe what you find.

P6-24C
V 40 dm 3 , T [] K , R 1.987

Data:
K1

exp

131.667
0.001987T 2
30,620 1
1

R
T 298

K2

exp

Methanol Synthesis

cal
mol K
dm 3

mol

103,943
9,834 1
1

R T 298

31,400 1 1
k1 0.933 exp 2.5

R 330 T

dm 3 1

s
mol

18,000 1
1
k 2 0.636 exp

300 T
R

dm 3
mol s

28,956 1
1
k3 0.244 exp 1.5

R
325 T

s 1

CO + 2 H2

CH3OH

CO + H2O

CO2 + H2

CH3OH

CH2O + H2

Series Reactions
The elementary liquid phase series reaction:
k

A 1B

k2

is carried out in a 500 dm3 batch reactor. The initial concentration of A is 1.6
mol/dm3. 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 (e0.5Cc 1 )
k1 = 0.4 hr-1, k2 = 0.01 hr-1 @ 100C
(b) Calculate the time the reaction should be quenched to
achieve the maximum profit.