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6. Multiple Reactions;
Reaction Networks and Pathways
6a. Multiple Reactions (Fogler Ch 6, Ch 8.8)
Rate Law
(Module-1)
(rA) = kCAn
Design Algorithm
(Module-2)
1. GMBE, 2. Rate Law
3. Stoich 4.Combine
Output
Reactor Volume
Reaction Time
Rate Constant
Conversion
Product Composition
Multiple Reactions
(Module-6)
Selectivity, Yield
Energy Balance
Heat Transfer Rate
Equilibrium Reactions
Multiple Steady State
dT/dz = ?
Tin-Tout =?
Output
Temperature Profile
Heat Removal
Heating Requirement
Mole Balance
Net Rates of Reactions
Stoichiometry
Energy balances
Multiple Reactions
Types of Multiple Reactions
1. Series Reactions
k1
k2
A
B
C
2. Parallel Reactions
k1
A
B
k2
A
C
VERY IMPORTANT!!!
k1
A
B+C
k2
A+C
D
4. Independent
k1
A
C
k2
B
D
A+ B C+ D
Define
i = Fi 0 / FA0
(Limiting reagent A)
Species
Change within
Reactor
(mol/s)
FA0
FB 0 = B FA0
FC 0 = C FA0
FD 0 = D FA0
( FA0 X A )
b
( FA0 X A )
a
c
( FA0 X A )
a
d
( FA0 X A )
a
FA = FA0 (1 X A )
b
FB = FA0 ( B X A )
a
c
FC = FA0 (C + X A )
a
d
FD = FA0 ( D + X A )
a
FI = FI 0
I (inert)
Total
FIIf
I Fhave
0 =
A0
you
multiple reactions:
A + B C
FA0 X A
FT 0 = FA0 (1 + B + C
and
+ D +A
I )+ C D
then the consumption/generation rates of
A, B, C and D are not simply coupled
FT = FT 0 + FA0 X A
d c b
+ 1
a a a
Fogler 3.6
BATCH
DIFFERENTIAL
FORM
N A0
INTEGRAL
FORM
XA
dX
rAV
( rA )
CSTR
PFR
ALGEBRAIC
FORM
FA0
= (rA )
V = FA0
XA
dX
rA
PBR
dX A
= ( rA' )
FA0
dW
W = FA0
XA
dX
rA'
(well-mixed)
dN j
dt
Algebraic
Equation
= (rj )V
t=
V=
dF j
dV
N j0
(well-mixed
at steady-state)
= rj
dN j
Nj
CSTR
PFR
(steady-state flow;
well-mixed radially)
Integral
Equation
(rj )V
Remarks
Conc. changes with time
but is uniform within the
reactor. Reaction rate
varies with time.
Conc. inside reactor is
uniform. (rj) is constant.
Exit conc = conc inside
reactor.
Fj 0 Fj
( rj )
Fj
V=
Fj 0
dFj
( rj )
Liquid Phase
Semi-Batch
(B fed)
CSTR
PFR
PBR
ai A + bi B ci C + di D
The complex gas phase reactions take place in a PFR. The feed is equal molar in A
and B with FA0 = 10 mol/min and the volumetric flow rate is 100 dm3/min. The
reactor volume is 1,000 dm3, there is no pressure drop, the total entering
concentration is CT0 = 0.2 mol/dm3 and the rate constants are:
Example (contd)
2. Rate Laws
Species A
Species B
Species C
Species D
Example (contd)
3. Stoichiometry
4. Combine
Solution
N rxn
dT
=
dV
F C
i =1
pi
Fogler, 8.8.1
F (X )
but V = A 0 A
( rA )
i =1
i =1
i =1
Fogler, 8.8.2
Instantaneous
Selectivity
SDU =
Yield
YD =
Global
~ F
SDU = D
FU
rD
rU
rD
rA
YD =
FD
ND
=
FA0 FA NA0 NA
Reactor
System
FA
FD
FU
Fogler 6.1
Total Cost
FA
FU
Cost
FA0
S
E
P
A
R
A
T
O
R
Reactant Conversion
SDU = SDU
Y =Y
D
rD dFD
=
rA dFA
FD
Dformed
YD =
=
Areacted (FA0 FA)
YD =
YD =
CA
1
YDdCA
C
(CA0 CA) A0
Series Reactions
, t=0 CA=CA0
Series Reactions
See Appendix A3
Series Reactions
dC C
= k 2CB , t = 0 CC = 0
dt
You would have the same set of equations for an isothermal PFR, replacing t with
; see Fogler Ex. 6-4
Parallel Reactions:
Selectivity for Single Reactant Systems
Example (parallel reaction)
Desired Reaction:
kD
A
D
rD = kDCAD
Undesired Reaction:
kU
A
U
rU = kU CAU
S DU
rD
k D C A D
k D ( D U )
=
=
=
CA
U
rU
kU
kU C A
Parallel Reactions:
Selectivity for Single Reactant Systems
Case 1: D-U >0
rD kD (D U )
SDU = = CA
rU kU
High CA favors D
Parallel Reactions:
Selectivity for Single Reactant Systems
Case 2: D-U < 0
rD
kD
SDU = =
rU kU CA(U D )
Low CA favors D
CA0
CA
CSTR is preferred
CA
Reactant concentration
maintained at low level
Parallel Reactions:
Selectivity for Single Reactant Systems
Case 3: D-U = 0
Concentration cannot be used operating parameter for selectivity
maximization
What now?
rD kD
A D exp [ E D / RT ]
SDU = =
=
rU kU
AU exp [ E U / RT ]
AD
=
exp [ ( E D EU ) / RT ]
AU
(a) If ED > EU
Operate reactor at highest possible temperature
(b) If EU > ED
Operate reactor at lowest possible temperature
Parallel Reactions:
Selectivity for Two Reactant Systems
Example
kD
A + B
D
rD = kD CA1 CB1
k
Undesired Reaction: A + B
U
rU = kU CA2 CB2
Desired Reaction:
rD kD (1 2 ) ( 1 2 )
SDU = = CA
CB
rU kU
Parallel Reactions:
Selectivity for Two Reactant Systems
Case 1: 1>2; 1 > 2
S DU
Let, a = 1-2; b = 1 - 2
rD k D a b
=
=
C AC B
rU kU
Parallel Reactions:
Selectivity for Two Reactant Systems
Case 2: 1>2; 1 < 2
S DU
rD k D C Aa
=
=
rU kU CBb
Let, a = 1-2; b = 2 - 1
kD
A + B
D
rD = kD CA1 CB1
kU
A + B
U
rU = kU CA2 CB2
Parallel Reactions:
Selectivity for Two Reactant Systems
Case 3: 1<2; 1 < 2
S DU
Let, a = 2-1; b = 2 - 1
rD k D 1
=
=
rU kU C Aa CBb
Parallel Reactions:
Selectivity for Two Reactant Systems
Case 4: 1<2; 1 > 2
S DU
Let, a = 2-1; b = 1 - 2
rD k D CBb
=
=
rU kU C Aa
heat
A, B
Product C is continuously
removed
Higher conversion for reversible
reactions can be obtained
FB 0
dN B
0 + (rB ) V =
dt
V = V0 + v0t
Constant Flowrate
FB0
v0
[N A = V CA ]
dN A
0 0 + (rA ) V =
dt
(rA ) V =
d (V C A )
dC A
dV
=V
+ CA
dt
dt
dt
(rA ) V = V
dC A
+ v0C A
dt
FB 0
dN B
0 + (rB ) V =
dt
v
dCB
= (rB ) 0 (CB CB 0 )
dt
V
v
dC A
= (rA ) 0 C A
dt
V
[ FB 0 = v0 CB 0 ]
[ N B = V CB ]
Constant flow
and density
dV
= v0
dt
Mole Balance
Net Rates of Reactions
Stoichiometry
Energy Balances
Be able to derive the set of equations for the system
usually cannot be solved without computer programs
be able to sketch the expected qualitative behaviour