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Isothermal Design
Stoichiometry
Rate Laws
Mole Balance
Rate Laws
Mole Balance
Stoichiometry
Review
Lecture 2
Building Block 1: Mole
Balances
in terms of conversion, X
Reactor
Batch
Differential
N A0
PBR
dX
t N A0
rAV
0
V
dX
FA 0
rA
dV
dX
FA 0
rA
dW
Integral
X
dX
r AV
dt
CSTR
PFR
Algebraic
X
t
FA 0 X
rA
X
dX
V FA0
rA
0
X
W FA0
0
X
dX
rA
Review Lecture 3
rA kC C
2 A B 3C
order in A
order in B
Overall Rection Order
rA k AC C B
2
A
Review Lecture 4
Building Block 3:
Stoichiometry
L5-7
Feed rate
(mol/time)
FA0
Change in reactor
(mol/time)
-FA0XA
FA
FB
Out
FC
FD
FI
Effluent rate from
reactor (mol/time)
FA = FA0 (1XA)
FB0 = FA0
BFA0XA
FB = FA0 (+ BXA)
FC0 = CFA0
CFA0XA
FD0 = DFA0
DFA0XA
FI0 = IFA0
---
FI =FI0
Species
In
FT0
Total
Fj0
C j00
C j0
y j0
J
b
c
d
B C D
a
a
a
FA0XA
FT = FT0 + FA0XA
d c b
j stoichiometric coefficient
= 1
for products, for reactants
a a a
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
Review Lecture 5
Review Lecture 5
Building Block 4:
Combine
Objectives
Describe the algorithm that allows the reader to
solve chemical reaction engineering problems
through logic rather than memorization.
Sizing batch reactors, semi-batch reactors, CSTRs,
PFRs, and PBRs for isothermal operation given the
rate law and feed conditions.
Studying a liquid-phase batch reactor to determine
the specific reaction rate constant needed for the
design of a CSTR.
Design of a tubular reactor for a gas-phase reaction.
Account for the effects of pressure drop on
conversion in packed bed tubular reactors and in
packed bed spherical reactors.
The principles of unsteady operation and semi-batch
reactors.
Fig. 5-1
Isothermal
Reaction
Design
Algorithm
for Conversion
L5-14
3. Put Cj is in terms of
XA and plug into rA
(We will always look
conditions where Z0=Z)
Batch
t =NA0
XA
dX A
0 -rA V
rA kC jn
CSTR
F X
V = A0 A
-rA
PFR
X A dX
A
V =FA0
0 -rA
C j0 jCA0 X A P T0 Z 0
Cj
1 XA
Z
P0 T
C j0 jCA0 X A P T0 Z 0
rA k
P T Z
1
X
0
A
This week!
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
L5-15
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
L5-16
-rA = kCA2
Mole balance
NA0
Rate law
rA kC A 2
Stoichiometry (put CA in
terms of X)
C A C A0 (1 X A )
Combine
NA0
dX A
2
k CA 02 1 X A V
dt
dX A
2
k C A02 1 X A V0
dt
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
L5-17
-rA = kCA2
dX A
2
NA 0
kC A 02 1 X A V0
dt
dX A
dX A
2 1
2 V0
2
kC A02 1 X A
kC A0 1 X A
dt
CA 0
dt
NA0
dX A
2
Rearrange to get like variables together
kCA0 1 X A
dt
dX A
1 XA
Integrate
kC A0dt
XA
dX A
1
k is constant for an
dt
2
isothermal reaction
kC
A0 1 X A
dX A
1
2
kC
A0
0 1 XA
Time required to
1 XA
t achieve XA for
dt
kC A0 1 X A
0
2nd order rxn
t
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
L5-18
-rA = kCA
dX A
NA0
rA V
dt
Rate law
rA kCA
Stoichiometry (put CA in
terms of X)
C A C A0 (1 X A )
Combine
dX A
NA0
kC A 0 1 X A V
dt
N
kC A 0 1 X A V0
Mole balance as a function of conversion
A0
dt
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
L5-19
-rA = kCA
kC A0 1 X A
dt
NA0
dX A
k 1 XA
dt
dX A
kdt
1
dX A
1
kC A0 1 X A
dt
CA0
dX A
1
k is constant for an
dt
isothermal reaction
k 1 X A
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
L5-20
-rA = kCA
1
- ln 1 X A
k
XA
0
t
0
ln 1 X A
k
1
ln 1 0 t 0
k
0=ln(1)
1
1
1
ln 1 X A t ln
t
k
k
1
A
1
Remember: ln ln a
a
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
Batch Operation
Algorithm for isothermal reactor design
1. Mole balance and
design equation
2. Rate law
3. Stoichiometry
4. Combination
1 dN A
rA
V dt
1 dN A d N A / V0 dC A
rA
V0 dt
dt
dt
5. Analytical
Evaluation
rA kCA2
A B
dC A
kCA2
dt
dC A
kCA2
dC A
C A0
C A2
CA=CAo(1-X)
dX
CAo
=kCAo2(1-X)2
dt
dt
CA
1 1
1
k C A C A0
t
X dX
1
kCAo 0 (1-X)2 = dt
0
dt
1
t=
kCAo
X
1-X
r
dX
AV
dt
N A0
Second order
Rate law
Stoichiometry (V=V0)
rA kCA2
CA
NA
C A0 (1 X )
V0
Combine
dX
kCA0 (1 X ) 2
dt
Integration
X
kCA0 (1 X )
1
1
ln
k 1 X
1
1
ln
k 1 0.9
2.3
2.3
10
4 1
X
kCA0 (1 X )
0 .9
kCA0 (1 0.9)
9
kCA0
9
10 3 s 1
23,000 sec
9,000 sec
6.4hr
2.5hr
2nd-order
kCA0 (s-1)
Reaction time
tR
10-4
10-3
Hours
10-2
10-1
Minutes
10
Seconds
1,000
10,000
Milliseconds
k C A C A0
2nd order
Isothermal
Liquid-phase
Batch reaction
tt = t f + t e + t R + t c
1.
2.
3.
4.
Activity
Time (h)
1.5-3.0
1.0-2.0
Varies (5-60)
0.5-1.0
3.0-6.0
L5-26
Isothermal CSTR
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
L5-27
-rA = kCA
Mole balance
Rate law
rA kC A
Stoichiometry (put CA in
terms of X)
C A CA0 (1 X A )
Combine
FA0 X
kC A0 1 X A
Put FA0 in
terms of CA0
Volume required
C A00 X A
0 X A
V
V
to achieve XA for
kC A0 1 X A
k 1 XA
1st order rxn
(at
)
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois
Urbana-Champaign.
L5-28
Scaling CSTRs
Chemical engineers are involved in scaling up a laboratory scale reaction
to the pilot plant scale or full-scale reactor
If one knows the volume of the pilot-scale reactor required to achieve X A,
how is this information used to achieve XA in a larger reactor?
Suppose for a 1st order irreversible liquid-phase reaction:
0 X A
0 X A
known: Vsmall
want: Vbigger
k 1 XA
k 1 XA
Want XA in the small reactor to be the same as XA in the bigger reactor
k in the small reactor is the same as k in the bigger reactor
0 in the small reactor must be different from 0 in the bigger reactor
So the reactor volume V must be proportional to the volumetric flow rate 0
XA
V
0 X A
How?
Separate variables we will
V
0 k 1 X A
k 1 X A vary from those held constant
V 0
XA
k 1 XA
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
L5-29
XA
k 1 XA
-rA = kCA
XA
1 k
XA
k 1 XA
k X A kX A
XA
1 XA
k XA 1 k
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
L5-30
Damkhler Number, Da
rA0 V rate of reaction at entrance
reaction rate
Da
FA0
entering flow rate of A
convection rate
Estimates the degree of conversion that can be obtained in a flow reactor
First order irreversible reaction:
r V kC A0 V
kV
Da
Da A0
0
FA0
C A00
1st order
Da k irreversible
reaction
V 0 Substitute
Second order irreversible reaction:
nd
2
order
kC
V
rA0 V kCA 0 V
A
0
Da
Da
Da kC A0 irreversible
0
FA 0
CA00
reaction
A
A
previous
1 k
1 Da
slide:
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
L5-31
Damkhler Number, Da
rA0 V rate of reaction at entrance
reaction rate
Da
FA0
entering flow rate of A
convection rate
Estimates the degree of conversion that can be obtained in a flow reactor
Relate XA to Da for a 1st
order irreversible rxn in
a flow reactor:
XA
1 k
Da k
1 order
irreversible rxn
st
XA
Da
1 Da
If Da=0.1 for this 1st order irreversible rxn in a flow reactor, then
Da
0.1
XA
XA
0.091
1 Da
1 0.1
If Da=10 for this 1st order irreversible rxn in a flow reactor, then
XA
Da
10
XA
0.91
1 Da
1 10
L5-32
-rA = kCA2
rA
rA
Mole balance
Rate laws
rA kCA 2
Stoichiometry
C A CA0 (1 X)
Combine
0CA0 X
kCA 02 1 X
In terms of conversion?
2nd order liquid
irreversible reaction
Da kC A0
1 2 kC A0
In terms of XA as a
function of Da?
1 4 kC A0
2 kC A0
1 2Da
1 4Da
2Da
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
0.88
0.67
60
L5-34
CSTRs
in
Series
C
A0 0
CA1
CA2
A first order reaction is carried out isothermally using 2 CSTRs that are the
same size, and and k are the same in both reactors (& k1 = k2 = k)
Determine V1 for 1st CSTR using our standard procedure. For 2nd CSTR:
FA1 FA2
1. Mole balance CSTR2 V
rA2
2. Rate law CSTR2
rA2 kC A2
CA1 CA2
kCA2
0 CA1 CA2
C A1 C A2
V
or =
kC A2
kC A2
kC A2 C A1 C A2 kC A2 C A2 C A1
C A2 k 1 CA1 CA2
C A1
k 1
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
L5-35
CSTRs
in
Series,
C
A1
C
A0 0
CA1
CA2
A first order reaction is carried out isothermally using 2 CSTRs that are the
same size, and and k are the same in both reactors (& k1 = k2 = k)
What is CA1 in terms of and k?
XA
st
k Put XA for 1 C C (1 X ) CA1 1 X X 1 CA1
A1
A0
A1
A1
A1
CSTR in
CA0
CA0
1 k
terms of CA1:
CA1 Solve
C A1
k
k
1 k
Substitute:
A1
1 k
1 k
CA0 for CA1:
C A0
C A1 CA1
C A1
C A1 CA1
k 1 k
1
1 k 1
CA0 C A0
C A0
C A0 CA0
C A1
1
C A0 1 k
C A1
C A0
1 k
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
L5-36
CA1
CA2
Effluent of reactor 1 is
input for reactor 2
A first order reaction is carried out isothermally using 2 CSTRs that are the
same size, and and k are the same in both reactors (& k1 = k2 = k)
CA0
C A1
& CA1
Relate CA2 to k & CA2
k 1
1 k
Substitute
CA2
CA0
CA 0 1
CA 2
k 1
1
1 k 2
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
L5-37
n CSTRs in Series
CA00
CA1
CA2
1st order irreversible liquid-phase rxn run in n CSTRs with identical V, and k
For n identical CSTRs, then: C An
CA0
1 k n
1 k
X An or 1
1 Da
X An
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
CSTRs in Series
Solving for CA2, the concentration exiting the second reactor, we get
C A2
C A0
C A1
1 2 k 2 1 2 k 2 1 1k1
C An
C A0
1 k n
C A0
1 Da n
The conversion and the rate of disappearance of A for these n tank reactors
in series would be
X 1
1 k
X= 1-CA/CAo
1
=1(1+Da)n
rAn kCAn
kCA0
1 k n
Da=k=0.1
L5-40
FA01
FA0
FA02
same T, V,
FA01 = FA02 = FA0n
X A
rA
V FA0
n
# of CSTRs
X1 =X 2 =... =Xn =X
rA1 rA2 ... rAn rA
V FA0 X Ai
n
n rAi
X A
r
A
V FA0
CSTRs in Parallel
A balance on any reactor i, gives the individual
reactor volume
FA0
Xi
Vi FA0i
rAi
FA0 i
-rA1, V1, X1
X1 X 2 X n X
-rAi, Vi
n
-rAn, Vn
CSTRs in Parallel
Substituting these values into Eq (4-12) yields
F
FA 0 i A0
n
V
Vi
FA0
Xi
Vi FA0i
rAi
FA01
FA0i
-r-rA1, ,VV1, X1
A1
V F A0 X i
n
n rAi
V
FA0n
-r-rAiAi, ,VVi,i Xi
FA 0 X i FA 0 X
rAi
rA
-r-rAn, ,VVn, Xn
An
Isothermal PFR/PBR
L6-44
Mole balance
dV
FA0
Rate law
rA kC A 2
Stoichiometry (put CA in
terms of X)
C A C A0 (1 X A )
dX A
dV
Combine
FA0
k C A0
XA
dX A
1 XA
dV
0
k C A02 1 X A
FA0
k CA02
FA0
XA
1 X V
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
L6-45
Mole balance
dW
FA0
r 'A kCA 2
Rate law
CA C A0 (1 X A )
Stoichiometry (put CA in
terms of X)
dX A
dW
Combine
FA0
k CA0
XA
dX A
1 XA
dW
0
k CA02 1 X A
FA0
k CA02
FA0
XA
1 X W
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
L6-46
FA0
FA
C j0 jCA0 X A
C j0 jCA0 X A P T0 Z 0
Cj
GAS PHASE: C j
1 XA
1 XA
Z
P0 T
1
L6-47
Mole balance
dV
FA0
rA kC A 2
Rate law
Stoichiometry (put CA in
terms of X)
C A0 1 X A
CA
1 X A
2
Combine
V
V
FA0
k CA0
FA0
k CA0
XA
1 X A dX
A
2
1 XA
2 1 ln 1 X A
dX A k C A0 1 X A
dV
1 X 2 F
A
A0
1 2 X
A
2XA
1 X A
Gas-phase 2nd
order rxn in PFR
no P, T, or Z
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
Effect of on and XA
L6-48
NT0
total moles fed
Tubular Reactors
- 2nd-order gas-phase reaction
- Turbulent
- No dispersion
- No radial gradients in T, u, or C
PLUG-FLOW REACTOR
PFR mole balance
FA 0
dX
rA
dV
V FA 0
dX
rA
Rate law
V FA0
dX
kCA2
V FA0
dX
1
V/vo= = kC
Ao
X=
= FAo
kCA2
kCAo2(1-X)2
vo
=
kCAo
X
1-X
dX
X
1-X
Da2
kCAo
=
1+kCAo 1 + Da2
V FA0
dX
kCA2
v (1 0.5 X )v0
the reactant spends more time
v (1 2 X )v0
the reactant spends less time
V(m3)
The volumetric flow rate decreases with increasing conversion, and the reactant
spends more time in the reactor than reactants that produce no net change in the
total number of moles.
Fi
FA 0 i vi X
Ci
v v0 (1 X )( P0 / P )(T / T0 )
(4-18)
i vi X
C i C A0
1 X
P To
P0 T