CHEM ENG 3034/7051 Kinetics & Reactor Design

WEEK 2 – THEORY:
CONVERSION AND MULTIPLE
REACTORS
Dr Philip van Eyk
School of Chemical Engineering
[email protected]
Week 2 - Theory
Conversion and Multiple Reactors

Fogler, Chapter 2
• Conversion, X
• Levenspiel Plots
• Conversion for Reactors in Series

The University of Adelaide Slide 2

Conversion, XA
Conversion is convenient for relating: rj, V, υ, Nj, Fj, and Cj
a A + b B ⎯⎯→ c C + d D
Choose limiting reactant A as basis of calculation and normalize:
b c d
A+ B ⎯⎯→ C + D
a a a
moles A reacted
X A  conversion based on A 
moles A fed

BATCH
SYSTEM: “Moles A fed” is the amount of A at the start of the reactor (t=0)
FLOW
SYSTEM: “Moles A fed” is the amount of A entering the reactor

Usually pick the basis to be the limiting reagent

The University of Adelaide Slide 3
Conversion Example
A + 2B → 2C
Start with 1 mole of A & 1 mole of B

If A is the basis and at the end we have:

1 mole A, 1 mole B ↔ XA = 0/1 = 0 (no reaction)
½ mole A, 0 mole B ↔ XA = 0.5/1 = 1/2
0 mole A, -1 mole B ↔ XA = 1/1 = 1 (complete reaction)

Not possible!
The correct approach is to take B as the basis because B is the limiting
reagent
At the end we have:
1 mole A, 1 mole B ↔ XB = 0/1 = 0 (no reaction)
½ mole A, 0 mole B ↔ XB = 1/1 = 1 (complete reaction)
The University of Adelaide Slide 4
Expressing other Components in
Terms of Conversion of A (XA)
b c d moles A reacted
A+ B ⎯⎯→ C + D XA 
a a a moles A fed
Longer reactant is in reactor, more reactant is converted to product
BATCH
(until reactant is consumed or the reaction reaches equilibrium)
SYSTEM:
∴ Conversion (Xj) is a function of time (t) in the batch reactor
NA = NA 0 − NA 0 X A 
Moles A in Moles Moles A
reactor at time t
=
A fed
- consumed

reactant → NA = NA 0 (1 − X A ) product
b
NB = NB0 − (NA 0 X A ) c
NC = NC0 + (NA 0 X A )
a a
d
ND = ND0 + (NA 0 X A ) NI = NI0 (inert component )
a
The University of Adelaide Slide 5
Expressing other Components in
Terms of Conversion of A (XA)
b c d moles A reacted
A + B ⎯⎯→ C + D XA 
a a a moles A fed

d c b 
NT =  N j = NT0 +  + − − 1NA 0 X A
j a a a 
Total moles in Total total moles products formed
reactor at time t
=
moles fed
+ minus reactants consumed
j≡ stoichiometric coefficient; positive for products, negative for reactants
b c d
B = −  A = −1  c = d =
a a a
N j = N j0 +  jNA 0 X A
 
NT =  N j = NT0 +   j NA 0 X A
 j 
j  
The University of Adelaide Slide 6
Batch Reactor Design Equation with Xj
b c d moles A reacted
A + B ⎯⎯→ C + D XA 
a a a moles A fed
In terms of A: NA = NA 0 − NA 0 X A 
Ideal Batch Reactor dNA
Design Eq: = rA V
dt
Want to determine how long to leave reactants in reactor to achieve a desired value
for the conversion → take derivative of “NA” equation w/ respect to time
d d dNA dX A
(NA ) = (NA 0 − NA 0 X A ) → = 0 − NA 0
dt dt dt dt
dNA dX A
→ = − NA 0 ← Substitute into batch reactor design eq
dt dt
dX A XA
Ideal Batch Reactor dX A
NA 0 = −rA V  t = NA 0 
Design Eq with Xj:
0 − rA V
dt
The University of Adelaide Slide 7
Flow and Conversion
b c d moles A reacted
A+ B ⎯⎯→ C + D XA 
a a a moles A fed
For a given flow rate, the larger the reactor, the more time it takes
FLOW
the reactant to pass through the reactor, the more time to react
SYSTEM:
∴ Conversion (Xj) is a function of reactor volume (V)
FA = FA 0 − FA0 X A 
Molar flow
Molar flow rate that A Molar rate A is
leaves the reactor
= rate A is fed - consumed in reactor
to reactor
FA = FA 0 (1 − X A )
in general : Fj = Fj0 +  jFA 0 X A
 
FT =  Fj = FT0 +  j FA 0 X A

 j 
j  
The University of Adelaide Slide 8
CSTR Design Equation & Xj
FA 0 − FA
Ideal SS CSTR: V =
− rj

Substitute for FA
FA = FA 0 − FA 0 X A 

FA 0 − FA 0 − (FA 0 )(X A )

V=
− rA
FA 0 X A Ideal CSTR design eq
→V=
− rA in terms of XA
V ≡ CSTR volume required to achieve a specified conversion
Note: XA and –rA are evaluated at the exit of the CSTR

The University of Adelaide Slide 9

PFR Design Equation & Xj
dFA
Ideal SS PRF: = rA
dV
FA = FA 0 − FA 0 X A 
Want to determine the reactor volume required to achieve a desired amount
of conversion → take derivative of “FA“ expression with respect to volume
d
(FA ) = d (FA 0 − FA 0 X A ) →
dFA
= 0 − FA 0
dX A
dV dV dV dV
dFA dX A
→ = − FA 0 ← Substitute into PFR design eq
dV dV
XA
Ideal SS PFR dX dX A
F A = −r  V = FA 0 
0 − rA
Design Eq with Xj: A 0 A
dV
Applies for no pressure drop down PFR!
The University of Adelaide Slide 10
PBR Design Equation & Xj
dFA
Ideal SS PBF: = rA '
dW
FA = FA 0 − FA 0 X A 
Want to determine the weight of catalyst that is required to achieve a desired
amount of conversion → take derivative of FA expression with respect to W
dFA dX A
d
(FA ) = d (FA 0 − FA 0 X A ) → = 0 − FA 0
dW dW dW dW
dFA dX A
→ = − FA 0 ← Substitute into PBR design eq
dW dW
XA
Ideal SS PBR dX dX A
FA 0 A = −rA '  W = FA 0 
0 − rA '
Design Eq with Xj: dW
Applies for no pressure drop down PBR!
The University of Adelaide Slide 11
Reactor Mole Balances Summary

• The General Mole Balance in terms of conversion applied to the

four major reactor types (and the general reaction A → B )
Reactor Differential Algebraic Integral
X
dX X
Batch N A0
dX
= −r AV t = N A0 
dt 0
− rAV
t
FA 0 X
CSTR V=
−rA

Reactor Differential
dX Algebraic Integral X
FA0 dX X
PFR FA 0 = −rA V =
dV − rA
 0

X
V
dX FA0 dX X
FA 0 = − rA W =
PBR
 dW 0
− rA
W


The University of Adelaide Slide 12
Sizing CSTRs
We can determine the volume of the CSTR required to achieve a specific
conversion if we know how the reaction rate rj depends on the conversion Xj

Ideal SS Volume is
FA 0 X A  FA 0 
CSTR VCSTR = → VCSTR =   X A product of FA0/-
design eq. − rA  − rA  rA and XA
• Plot FA0/-rA vs XA (Levenspiel plot)
• VCSTR is the rectangle with a base of XA,exit and a height of FA0/-rA

Area = Volume of CSTR

FA 0
FA 0 
−rA V=  • X1
−rA  X
1

X X1

The University of Adelaide  Slide 13
 Sizing a CSTR with a Levenspiel Plot
XA 0 0.1 0.2 0.4 0.6 0.7 0.8
FA0/-rA 0.89 1.08 1.33 2.05 3.56 5.06 8

VCSTR for XA = 0.4?

9
8  FA 0 
7 VCSTR =  XA
 − rA 
FA0/-rA (m3)

6
5 Value of FA0/-rA for XA=0.4
4
3 VCSTR = (2.05 )0.4
2 = 0.82 m3
1
0
VCSTR for XA = 0.8?
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1 VCSTR = (8 )0.8
XA = 6.4 m3

The University of Adelaide Slide 14

 Sizing PFRs
We can determine the required volume of a PFR to achieve a specific
conversion if we know how the reaction rate rj depends on the conversion Xj
X A,exit X A,exit
Ideal PFR dX A  FA 0 
V = FA 0  → VPFR =   dX A
design eq. PFR − rA
0 0  − rA 
• Plot FA0/-rA vs XA (Experimentally determined numerical values)
• VPFR is the area under the curve FA0/-rA vs XA,exit

FA 0 Area = Volume of PFR

−rA X1  FA 0 
V= 0 
 −rA 
 dX

X1

The University of Adelaide  Slide 15
Sizing a PFR with a Levenspiel Plot
XA 0 0.1 0.2 0.4 0.6 0.7 0.8
FA0/-rA 0.89 1.08 1.33 2.05 3.56 5.06 8

VPFR for XA = 0.4?

X A,exit
 FA 0 
VPFR =   dX A
0  − rA 

We do not have an
expression for –rA(XA)

The University of Adelaide Slide 16

Sizing a PFR with a Levenspiel Plot
XA 0 0.1 0.2 0.4 0.6 0.7 0.8
FA0/-rA 0.89 1.08 1.33 2.05 3.56 5.06 8

VPFR for XA = 0.4?

X A,exit
 FA 0 
VPFR =   dX A
0  − rA 

We do not have an
expression for –rA(XA)

Numerically evaluate
Volume of PFR (Appendix A.4) to estimate
the area under the curve

The University of Adelaide Slide 17

Numerical Evaluation of Integrals
(Appendix A.4 Fogler)
Trapezoidal rule (2-point): Simpson’s one-third rule (3-point):
𝑋1 𝑋2
ℎ ℎ
න 𝑓 𝑥 𝑑𝑥 = 𝑓 𝑋0 + 𝑓 𝑋1 න 𝑓 𝑥 𝑑𝑥 = 𝑓 𝑋0 + 4𝑓 𝑋1 + 𝑓 𝑋2
2 3
0 0
𝑋2 − 𝑋0
ℎ = X1 − X 0 ℎ= X1 = 𝑋0 + ℎ
2

Simpson’s three-eights rule (4-point): X1 = 𝑋0 + ℎ X2 = 𝑋0 + 2ℎ

𝑋3
3
න 𝑓 𝑥 𝑑𝑥 = ℎ 𝑓 𝑋0 + 3𝑓 𝑋1 + 3𝑓 𝑋2 + 𝑓 𝑋3 𝑋3 − 𝑋0
8 ℎ=
0 3

Simpson’s five-point quadrature :

𝑋4
ℎ 𝑋4 − 𝑋0
න 𝑓 𝑥 𝑑𝑥 =
3
𝑓 𝑋0 + 4𝑓 𝑋1 + 2𝑓 𝑋2 + 4𝑓 𝑋3 + 𝑓 𝑋4 ℎ=
0
4

The University of Adelaide Slide 18

Sizing a PFR with a Levenspiel Plot
XA 0 0.1 0.2 0.4 0.6 0.7 0.8
FA0/-rA 0.89 1.08 1.33 2.05 3.56 5.06 8

VPFR for XA = 0.4? X A,exit

 FA 0 
VPFR =   dX A
0  − rA  XA increments
must be equal
Use Simpson’s one-third rule (3-point):
X2
h X 2 − X0
 f (x )dx = f (X0 ) + 4f (X1) + f (X2 ) h = X1 = X0 + h
0 3 2
0 .4 − 0
h= = 0.2 X1 = 0 + 0.2 = 0.2
2
h FA 0 FA 0 FA 0 
VP F R =  +4 + 
3  −rA ( X = 0 ) −rA ( X = 0. 2 ) −rA ( X = 0. 4 ) 
0. 2
VPF R = 0. 89 + 4 (1. 33 ) + 2. 05  = 0. 55 m3 = area under the curve
3
The University of Adelaide Slide 19
Reactors in Series
In practice, reactors are usually connected so the exit stream of one
reactor is the feed stream for the next reactor

Conversion up to point i total moles of A reacted up to point i

(no side streams): Xi =
Moles A fed into 1st reactor

FA1 FA2
V2
i=1 i=2
FA0
X1 X2
FA3
i=3 X3

V1 V3
FAi = FA 0 − FA 0 Xi

The University of Adelaide Slide 20

 2 CSTRs in Series
FA1, X1
Materials balance reactor 1:
FA0
X0 In - Out + Gen. = Accum.
FA2
X2
FA0 − FA1 + rA1V1 = 0

V1 V2 Need to express FA1 in terms of X1

FA1 = FA0 − FA0 X1

→ FA 0 − (F A0 - F A 0 X1 ) + rA1V1 = 0
→F A 0 X1 + rA1V1 = 0
 FA0 
  X1 = VCSTR1
 − rA1 
The University of Adelaide Slide 21
 2 CSTRs in Series
FA1, X1 Materials balance reactor 2:
In - Out + Gen. = Accum.
FA0
X0 FA1 − F A 2 + rA 2 V2 = 0
FA2
X2 FA1 − FA 2
VCSTR 2 =
− rA 2
V1 V2 Need to express FA2 in terms of X2
Materials balance reactor 1:
FA 2 = FA 0 − FA 0 X2
FA1 = FA 0 − FA 0 X1

VCSTR2 =
(FA 0 − FA 0 X1) − (FA 0 − FA 0 X2 )
 FA0 
  X1 = VCSTR1 − rA 2
 − rA1 
FA 0
VCSTR 2 = (X2 − X1)
− rA 2
Value of FA0/-rA at X2
The University of Adelaide Slide 22
 2 CSTRs in Series
FA1, X1=0.4 XA 0 0.4 0.8
FA0 FA0/-rA 0.89 2.05 8
X0 9
FA2 8
X2=0.8 7

FA0/-rA (m3)
6
V1 5
V2
4
VCSTR1 for XA1 = 0.4? 3
VCSTR1 = (2.05 )0.4 = 0.82 m3 2
1
VCSTR2 for XA2 = 0.4 to 0.8? 0
VCSTR 2 =
FA 0
(X2 − X1) 0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8
− rA 2 XA
VCSTR2 = (8 )(0.8 − 0.4 ) = 3.2 m3 VCSTR of single CSTR with XA = 0.8?
VCSTR1+ 2 = 0.82 m3 + 3.2 m3 = 4.02 m3 < VCSTR = (8 )0.8 = 6.4 m3
Usually for the same overall conversion, VTOTAL, 2 CSTRs IN SERIES < VSINGLE CSTR

The University of Adelaide Slide 23

 2 PFRs in Series FA1
FA0, X0 X1
FA2, X2
X2  F
 X1  F  X2  F 
VPFR =    A0
dX A    A 0 dX A +   A 0 dX A
0  − rA  0  − rA  X1  − rA 
XA 0 0.2 0.4 0.6 0.8 2 PFRs in series, X1=0.4 and X2=0.8
FA0/-rA 0.89 1.33 2.05 3.56 8
When XA1= 0.4, VPFR1 =0.55 m3 (slide 19)
VPFR2 for XA2 = 0.4 to 0.8?
h FA 0 4FA 0 FA 0 
V= + +
3  − rA (X = 0.4 ) − rA (X = 0.6 ) − rA (X = 0.8 )
0.2
VPFR2 = 2.05 + 4(3.56) + 8 = 13.61m3
3
VPFR1+ 2 = 0.55 m3 + 1.61 m3 = 2.17 m3
Same volume as 1 PFR with XA=0.8
The University of Adelaide Slide 24
Combinations of CSTRs & PFRs in
Series F , X F A1 FA2,
A1 1
FA2, X1 X2
FA0, X0
FA0 X2 V1
V2
X0
V2

V1

VCSTR1 VPFR2 VPFR1 VCSTR2

( )
VCSTR1 + VPFR2 ≠ VPFR1 + CCSTR2
The University of Adelaide Slide 25
Reactors in Series
F
If A0 is monotonically increasing, then
−rA

Vone PFR   VPFR(i) +  VCSTR( j) Vone CSTR

i j
for any combination of PFRs & CSTRs in series

In general, 1 PFR = any number of PFRs in series

1 PFR = ∞ number of CSTRs in series
Definitions:
𝑉
Space time (t): time necessary to process one reactor volume, 𝜏=
𝜐0
also called mean residence time or holding time
Space velocity (SV): inverse of space time, but vo may be 𝜐0 1
measured under different conditions than the space time 𝑆𝑉 = =
𝑉 𝜏

Liquid-hourly 𝐿𝐻𝑆𝑉 = 𝜐0 ȁ𝑙𝑖𝑞𝑢𝑖𝑑 @ 15°C 𝑜𝑟 25°C Gas-hourly 𝜐0 ȁ𝑆𝑇𝑃

𝑉 𝐺𝐻𝑆𝑉 =
space velocity space velocity 𝑉

u0| is the volumetric flow rate measured at specified condition

The University of Adelaide Slide 26
 Chemical Reaction Engineering (CRE)
Algorithm

1. Mole Balance (Week 1-2) Heat Effects

2. Rate Law (Week 3)
Isothermal Design
3. Stoichiometry (Week 3)
Stoichiometry
4. Combine (Week 4-5)
Rate Laws
5. Evaluate (Week 4-5)
6. Energy Balance (Week 8-9) Mole Balance

The University of Adelaide Slide 27

Week 2 – Theory: Summary

• From this lecture you should be able to:

1. Define the parameter conversion and rewrite the mole
balances in terms of conversion;
2. Size a number of reactors and reaction systems if given
–rA as a function of conversion X;
3. Arrange reactors in series to achieve the maximum
conversion for a given Levenspiel plot.

The University of Adelaide Slide 28