RXN Ch..4
RXN Ch..4
Multiple Reactions
Objectives
Independent rxns
k1
A B+C
k2
D E+F
8.1.1 Examples of Multiple Reaction
Parallel rxns (Oxidation of ethylene to ethylene oxide)
k1 2CO2 + 2H2O
CH2=CH2 +O2
k2
CH2-CH2
Series rxns (rxn of EO with NH3) O
Monoethanolamine
O
CH2-CH2 + NH3 HOCH2CH2NH2
EO EO
(HOCH 2CH2)2NH
Diethanolamine (HOCH 2CH2)3N
Triethanolamine
C2H5OH C2 H4 + H 2 O
C2H5OH CH3CHO + H2
C2H4 + CH3CHO C4 H6 + H 2 O
D Total cost
cost
Reaction cost
A separation
Separation cost
reaction
A, U Low High
kD D (Desired Product)
A
kU U (Undesired Product)
Selectivity tells us
how one product is
The rate laws are favored over another
rA k D C A1 kU C A 2 when we have
multiple reactions.
rD k D C A1
rU kU C A 2
r k Rate of formation of D
S D /U D D C A1 2 =
rU kU Rate of formation of U
Overall Selectivity, ~SDU
~
Mission: Develop a relationship between SD/U and SD/U in a CSTR
Solution rD
SD/U =
kD D (Desired Product) rU
A
kU U (Undesired Product) ~ FD
SD/U =
FU
Mole balance of D and U yields FD=rDV and FU=rUV, respectively
~ FD rDV rD
SD/U = = = = SD/U
FU rUV rU
~
SD/U = SD/U
8.1.3 Yields
).
~ FD
For a flow system: YD = F -F
Ao A
8.3 Parallel Reactions
kD D (Desired Product)
A
kU U (Undesired Product)
kD D (Desired Product) rD k D 1 2
S D /U CA
A rU kU
kU U (Undesired Product)
Maximize SD/U
- keeping the concentration of reactant A as high as possible during the rxn
- in gas phase rxn, we should run it with inert and at high pressures to keep CA high
- in liquid phase rxn, the use of diluents should be keep to a minimum.
- use a batch or plug-flow reactor
8.3.2 Maximizing the Desired Product for One Reactant
kD D (Desired Product) rD k D 1 2
SDU CA
A rU k U
kU U (Undesired Product)
Maximize SD/U
- keeping the concentration of reactant A as low as possible during the rxn
- in gas phase rxn, we should run it with inerts and at low pressures to keep CA low
- in liquid phase rxn, the use of diluents should be keep to a maximum
- use a CSTR or recycle reactor (product stream act as a diluent)
Maximizing SDU for one reactant
Whether the reaction should be run at high or low T?
rD k D 1 2
SDU CA
E D EU rU k U
k D AD
S D /U ~ e RT
kU AU
ED EU
Case 3: ED > EU S D /U
- kD (rD) increases more rapidly with increasing temp. than does the kU.
ED EU
Case 4: EU > ED
S D /U
- keeping the temperature as low as possible to maximize SDU
- not so low that the desired rxn does not proceed to any significant extent.
T
Ex 8-1: Maximizing SB/XY for the Trambouze Reaction
CA SB/(X+Y) rB k 2C A
SB/(X Y)
0 0
rX rY k1 k 3C 2A
0.025 0.357143
0.05 0.625
0.075 0.775862
SB/(X+Y)=(0.0015*CA)/(0.0001+0.008*CA2)
0.1 0.833333
0.125 0.833333
1
rB k 2C A
0.15 0.803571
0.84 SB/(X Y)
rX rY k1 k 3C 2A
0.175 0.76087
0.8
0.2 0.714286
0.225 0.668317
0.6
0.25 0.625
SB/(X+Y)
0.275 0.585106
0.3 0.54878
0.4
0.325 0.515873
0.35 0.486111 0.2
0.375 0.459184
0.4 0.434783 0 0.112
0.425 0.412621
0 0.1 0.2 0.3 0.4 0.5
0.45 0.392442
0.475 0.374016
0.5 0.357143 CA (mol/dm3)
Maximizing SB/XY for the Trambouze Reaction
k3 0.008(dm 3 /mol s)
k1 k1
k2 k2
rB k 2C A* k3 k3 k2
SB/XY 0.8385
r X rY k1 k 3C A*2
k1
2
2k1 2 k1k 3
k1 k 3
k3
Maximizing SB/XY for the Trambouze Reaction
We now calculate this CSTR volume and conversion. The net rate of formation of
A from reactions (1), (2), and (3) is
rX k1
- rA k1 k 2C A k 3C 2
A rB k 2 C A
rY k 3C 2A
0 [C A0 C*A ] 0 [C A0 C*A ]
V 1567.6 dm 3 CSTR volume for
maximum selectivity
rA [k1 k 2 C*A k 3C*A2 ]
k1 0.0001 mol/dm 3 s
V CA0 C *
C A0 C *
A
783.8s
A
k 2 0.0015 s 1
0 rA
*
k1 k 2C A k 3C A
* *2
k 3 0.008 dm 3 /mol s
0 2.0 dm 3 /s
C A0 0.4 mol/dm 3
C A* 0.112 mol/dm 3
Maximizing SB/XY for the Trambouze Reaction
C A0 - C A* 0.4 - 0.112
X
*
0.72
C A0 0.4
If greater than 72% conversion of A is required, then the CSTR operated with a
reactor concentration of 0.112 mol/dm3 should be followed by a PFR because the
concentration and selectivity will decrease continuously from C*A as we move down
the PFR to an exit concentration CAf. Hence the system
υ0 C X υ0 C X
Species X: V C X k1τ (0.0001)(783) 0.0783mol / dm 3
rX k1
υ0 C B υ0 C B
Species B: V *
C B k 2 τC *A (0.0015)(0.112 )(783) 0.132mol / dm 3
rB k2 C A
υ0 CY υC
Species Y: V 0 *Y2 CY k3 τC *A2 (0.008)(0.112 ) 2 (783) 0.0786mol / dm 3
rY k3 C A
Let’s check to make sure the sum of all the species in solution equals the initial
concentration CA0 = 0.4.
CA+CX+CB+CY=0.112+0.0783+0.132+0.0786=0.4
8.3.3 Reactor Selection and Operating Conditions
Rate selectivity rD k1 1 2 1 2
SD / U CA CB
parameter rU k 2
Selectivity
Yield
Temperature control
Safety
Cost
Figure 8-2
Different reactors and schemes for maximizing the desired product
A B A
B
A
B A
B A B
(a) CSTR (b) tubular reactor (c ) batch (d) semi-batch 1 (e) semi-batch 2
A A
B B
(f) Tubular reactor with side streams (g) Tubular reactor with side streams
B
A
The two reactors with recycle shown in (i) and (j) can be used for highly
exothermic reactions. Here recycle stream is cooled and returned to the
reactor to dilute and cool the inlet stream thereby avoiding hot spots and
run-away reactions. The PFR with recycle is used for gas-phase
reactions, and the CSTR is used for liquid-phase reactions.
A
B
A
B
D
(k) Membrane reactor
(l) Reactive distillation
Example 8-2: Minimizing unwanted products for two reactants
For the parallel reactions, consider all possible combinations of reaction orders and select
the reaction scheme that will maximize SD/U.
k1
D (Desired Product)
A+B
k2
U (Undesired Product)
To maximize the SDU, maintain the concentration of both A and B as high as possible
a tubular reactor (Figure 8-2 (b))
a batch reactor (Figure 8-2 (c))
high pressures (if gas phase), and reduce inerts
Example 8-2: Minimizing unwanted products for two reactants
rD k1C Aa
S DU
the rate selectivity parameter rU k 2C Bb
Case III : 1 < 2, 1 < 2, a = 2-1 > 0, b = 2-1 > 0
rD k1
S DU
the rate selectivity parameter
rU k 2C Aa C Bb
To maximize the SDU, maintain the concentration of both A and B as low as possible
a CSTR (Figure 8-2(a))
a tubular reactor in which there is a large recycle ratio (Figure 8-2(i))
a feed diluted with inert material
low pressures (if gas phase)
Example 8-2: Minimizing unwanted products for two reactants
rD k1C Bb
S DU
the rate selectivity parameter rU k 2C Aa
To maximize the SDU, maintain the concentration of both A and B as high as possible
a semibatch reactor in which A is slowly fed to a large amount of B (Figure 8-2(e))
a membrane reactor or tubular reactor with side stream of A (Figure 8-2(g))
a series of small CSTRs with fresh A fed to each reactor
8.4 Maximizing the desired product in series reaction
k1 k2
A B C
k1 k2
A B C
Desired Product
k1 k2
A→ B→ C
Determine the concentration of desired product as a function of space-
time in packed bed reactor?
Solution
kk11ττ
C C e
CAA CAA00 e
eekk11ττ eekk22ττ
CAA00
CBB kk11C
C
kk22 kk11
Reaction paths for different ks in series reaction
k1 k2
A B C
For k1/k2>1, a
B k1
1
Large quantity of B
Can be obtained k2
k1
~1
k2
For k1/k2<1, a
Little quantity of B 2'
Can be obtained 3' k1
1 1st rxn is slow
'
1 k2 2nd rxn is fast
A C
Long rxn time in batch or long tubular reactor
B will be converted to C
Relationship for Multiple Rxns Occuring in a PFR
For equations for species j and reaction i that are to be combined when we have q reactions and n species
dF j
Mole Balance: rj
dV
Rate laws: rij kij f i (C1 , C j , Cn )
q
rj rij
i 1
riA r r r
iB iC iD
ai bi ci di
n
Stoichiometry: FT F j
j 1
F j P T0
(gas-phase) C j CT 0
FT P0 T
(liquid-phase)
Fj
Cj
0
Multiple reactions
Reaction 1: 4NH3 + 6NO 5N2 + 6H2O r1NO k1NO C NH 3 C 1NO
.5
Reaction 2: 2NO N2 + O2 r2 N 2 k 2 N 2 C NO
2
The rates for rxns 1, 2 and 3 are given in terms of species NO, N 2, and O2, respectively.
Consequently, to relate each reacting species in each rxn to its rate law more clearly, we divide
each rxn through by the stoichiometric coefficient of the species for which the rate law is given.
2: 2NO N2 + O2
r3O2 k 3O2 C N 2 C O22
3: O2 + 1/2N2 NO2
3 3
5 5
r1N 2 (r1NO ) k1NO C NH 3 C 1NO .5
6 6
r1H 2O (r1NO ) k1NO C NH 3 C 1NO
.5
Reaction 2:
2
r2 N 2 k 2 N 2 C NO
2
r2 NO 2r2 N 2 2k 2 N 2 C NO
2
r2O2 r2 N 2 k 2 N 2 C NO
2
Reaction 3:
3
1 1
r3O2 k3O2 C N 2 CO22 r3 N 2 (r3O2 ) k3O2 C N 2 CO22
2 2
r3 NO2 r3O2 k3O2 C N 2 CO22
3
0
Net rate of formation NO: rNO riNO r1NO r2 NO r3 NO
i 1
5 1
rN 2 k1NO C NH 3 C 1NO
.5
k 2 N 2 C NO
2
k3O2 C N 2 CO22
6 2
3
0
Net rate of formation O2: rO2 riO2 r1O2 r2O2 r3O2
i 1
rO2 2k 2 N 2 C NO
2
k3O2 C N 2 CO22
Multiple reactions in a PFR
For gas-phase rxns, concentration of species j is
Fj FT 0 F j P T0 Fj P T0 Fj
Cj CT 0 T=P=0 C j CT 0
0 0 FT P0 T FT P0 T FT
For gas-phase rxns, concentration of species j is
n
FT F j FNO FNH 3 FN 2 FH 2O FO2 FNO2
j 1
dFNO
rNO k1NO C NH 3 C 1NO
.5
2k 2 N 2 C NO
2
dV
1.5 2
2.5 NH 3 FNO
dFNO F 2 FNO
k1NO CTO
F 2k 2 N 2 CTO
dV FT T FT
(2) Mole balance on NH3:
dFNH 3 2 2
rNH 3 r1NH 3 r1NO k1NOC NH 3 C 1NO
.5
dV 3 3
1.5
2.5 NH 3 FNO
dFNH 3 2 F
k1NOCTO
dV 3 FT FT
dFH 2O
rH 2O r1H 2O r1NO k1NO C NH 3 C 1NO
.5
dV
1.5
2.5 NH 3 FNO
dFH 2O F
k1NO CTO
dV FT FT
(4) Mole balance on N2:
dFN 2 5 1
rN 2 k1NO C NH 3 C 1NO
.5
k 2 N 2 C NO
2
k3O2 C N 2 CO22
dV 6 2
1.5 2 2
2.5 NH 3 FNO 2 FNO 3 N2 FO2
dFN 2
5 F 1 F
k1NOCTO k 2 N 2 CTO k3O2 CTO
dV 6 FT FT FT 2 FT FT
2 2
2 FNO 3 N2 FO2
dFO2 F
k 2 N 2 CTO k3O2 CTO
dV FT FT FT
2
3 N2 FO2
dFNO2 F
rNO2 r3 NO2 r3O2 k3O2 CTO
dV FT FT
Hydrodealkylation of Mesitylene in a PFR
1,3,5-trimethylbenzene
CH3 CH3
k1
+ H2 + CH 4
CH3 CH3 CH3
CH3 CH3
k2
+ H2 + CH 4
CH3
The bulk density of the catalyst has been included in the specific reaction rate (i.e., k 1=k1’ b)
1. Mole balances:
dFH
Hydrogen
r1H r2 H
dV
dFM
Mesitylene r1M
dV
dFX
Xylene r1 X r2 X
dV
dFT
Toluene r2T
dV
dFMe
Methane r1Me r2 Me
dV
2. Rate laws: r1H k1C H0.5CM
r2T k 2C H0.5C X
Relative Reaction rates:
Reaction 1: -r1H = -r1M = r1X = r1Me
Reaction 2: -r2H = -r2X = r2T = r2Me
2.0
1.5 CH
Ci 1.0 H2
opt
CM CX
0.5
0.0 (hr)
0.0 0.1 0.2 0.3 0.4 0.5
Multiple reactions in a CSTR
For a CSTR, a coupled set of algebraic eqns analogous to PFR differential eqns must be solved.
Fj0 Fj
V
rj
q
After writing a mole balance on each species in the reaction set, we substitute for concentrations
in the respective rate laws.
For =0.5, the exiting concentrations are CH=0.0089, CM=0.0029 and CX=0.0033.
The overall conversion is
FH 0 FH C H 0 C H 0.021 0.0089
Hydrogen : XH 0.58
FH 0 CH 0 0.021
FM 0 FM CM 0 CM 0.0105 0.0029
Mesitylene : XM 0.72
FM 0 CM 0 0.0105
0.020
0.015 CH
Ci 0.010
0.005 CX
0.000
CM
0.0 1.0 2.0
CSTR
Hydrodealkylation of Mesitylene in a CSTR
The moles of hydrogen consumed in reaction 1 are equal to the moles of mesitylene consumed.
Therefore, the conversion of hydrogen in reaction 1 is
C M 0 C M 0.0105 0.0029
X 1H 0.36
CH 0 0.021
The conversion of hydrogen in reaction 2 is
The yield of xylene from mesitylene based on molar flow rates exiting the CSTR for =0.5 is
~ F C CX 0.00313
S XT X X
FT CT C M 0 C M C X 0.0105 0.0029 0.00313
mole xylene produced
0.7
mole toluene produced