L3-1

Review: Batch Reactor Basic Molar Balance

No material enters or leaves the reactor
In ideal reactor, composition and temperature are spatially
uniform (i.e. perfect mixing)
No flow in or out of reactor. Fj0 and Fj = 0.

Rate of generation of reactant Rate of accumulation of

=
A in reactor due to rxn reactant A in reactor
V dN j Batch Reactor
rjdV
dt Design Equation
Ideal (perfectly mixed)
dN j Ideal Batch Reactor
reactor: spatially uniform r V
j Design Equation
temp, conc, & reaction rate dt

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
 L3-2

Review: CSTR Basic Molar Balance

Continuously add reactants and remove products F Fj
j0
In an ideal reactor, composition and temperature
are spatially uniform (i.e. perfect mixing)
At steady state- no accumulation
Accumulation = In - Out + Generation
by rxn V
0 = Fj0 - Fj + rjdV
No spatial variation:
rj V
Ideal Steady State CSTR Design Equation:
Fj0 Fj 0C A 0 C A
in terms V
r j

F j C j V
rA
in terms of
of flow concentration
(upsilon)
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
 L3-3

Review: Molar Balance PFR

Flow reactor operated at steady state (no accumulation per )
Composition of fluid varies down length of reactor (material
balance for differential element of volume V
V

FA0 FA
dN j
Fj0 - Fj + rjV =
dt
lim Fj V V Fj V
Fj Fj rjV 0 rj
V V V V 0 V

dFj Ideal SS PFR

rj
dV Design Eq.
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
Review: Molar Balance- Packed L3-4

Bed Reactor (PBR)

Heterogeneous rxn: reaction occurs at catalyst particle surface
Concentration gradient of reactant and product change down
length of the reactor
Rxn rate based on the mass of catalyst W, not reactor volume V

dFj Similar to PFR, but expressed in terms of

rj
dV catalyst weight instead of reactor volume

Units for the rate of a mol Units for the rate of mol
homogeneous rxn (rj) : s m3 a catalytic rxn (rj) : s kg catalyst

So in terms of catalyst weight instead of reactor volume:

dFj
rj ' where W is the weight of the catalyst
dW
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
 L3-5

L3: Conversion and Reactors in Series

FA1, X1
FA1, X1
FFA2
A2,,
FFA0
A0 FFA0
A0 XX22
V2
X
X00 X
X00
FA2
X2

V1 V2 V1

VCSTR1 VPFR2

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
 L3-6

Conversion, XA
Conversion is convenient for relating: rj, V, , Nj, Fj, and Cj
a A bB c C dD
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

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
 L3-7

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)
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)
mole A, 0 mole B XB = 1/1 = 1 (complete reaction)
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
 L3-8
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 c
NB NB0 NA 0 X A NC NC0 NA 0 X A
a a
d
ND ND0 NA 0 X A NI NI0 inert component
a
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
 L3-9
Expressing other Components in Terms of
Conversion of A (XA)
b c d moles A reacted
A B C D X A
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
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
 L3-10

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 dN A

rA V
Design Eq: 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 dN A dX A
NA d NA 0 NA 0 X A 0 NA 0
dt dt dt dt
dN A dX A
NA 0 Substitute into batch reactor design eq
dt dt
dX XA
Ideal Batch Reactor N A r V dX A
A0 A t NA 0
Design Eq with Xj: dt 0 rA V
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
 L3-11

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 FA 0 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
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
 L3-12

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
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
 L3-13

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 A dX A
F rA V FA 0
Design Eq with Xj: A 0 dV 0 rA

Applies for no pressure drop down PFR!

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
 L3-14

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
d d dFA dX A
FA 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 A dX A
FA 0 rA ' W FA 0
Design Eq with Xj: dW 0 rA '

Applies for no pressure drop down PBR!

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
 L3-15

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 FA 0 Volume is
FA 0 X A
CSTR VCSTR VCSTR X A product of FA0/-rA
design eq. 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

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
 L3-16

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?

FA 0
VCSTR XA
rA
Value of FA0/-rA for XA=0.4

VCSTR 2.05 0.4

0.82 m3
VCSTR for XA = 0.8?
VCSTR 8 0.8
6.4 m3
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
 L3-17

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
VPFR FA 0 VPFR dX A
design eq.
0 rA 0 rA
Plot FA0/-rA vs XA (Experimentally determined numerical values)
VPFR is the area under the curve FA0/-rA vs XA,exit

Area = Volume of PFR

FA 0
rA X1 FA 0
V 0 dX
rA

X1
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
 L3-18

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

We do not have an
expression for rA(XA)

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
 L3-19

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
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
 L3-20

Numerical Evaluation of Integrals (A.4)

Trapezoidal rule (2-point): Simpsons one-third rule (3-point):
X1 X2
h h
f x dx f X0 f X1 f x dx f X0 4f X1 f X2
0 2 0 3
h X1 X0 X 2 X0
h X1 X0 h
2

Simpsons three-eights rule (4-point):

X1 X0 h X2 X0 2h
X3
3
f x dx h f X0 3f X1 3f X2 f X3 h
X3 X 0
0 8 3
Simpsons five-point quadrature :
X4 X 4 X0
h
f x dx f X0 4f X1 2f X2 4f X3 f X 4 h
0 3 4
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
 L3-21

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
X A,exit
VPFR for XA = 0.4? FA 0
VPFR dX A
0 rA XA increments
must be equal
Use Simpsons one-third rule (3-point):
X2 X 2 X0
h
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 FR 4
3 rA X 0 rA X 0.2 rA X 0.4

0.2
VPFR 0.89 4 1.33 2.05 0.55 m3 = area under the curve
3
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
 L3-22

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 total moles of A reacted up to point i

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

FFA1
A1 FFA2
A2
V
V22
FFA0 i=1
i=1 i=2
i=2
A0
XX11 XX22
FFA3
A3
i=3
i=3
XX33
V
V11 V
V33

FAi FA 0 FA 0 Xi
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
 L3-23

2 CSTRs in Series
FA1, X1
Materials balance reactor 1:
FFA0
A0
X
X00 In - Out + Gen. = Accum.
FA2
X2 FA 0 FA1 rA1V1 0

V1 V2 Need to express FA1 in terms of X1

FA1 FA0 FA0 X1

FA 0 F A 0 - F A 0 X1 rA1V1 0
F A 0 X1 rA1V1 0

FA 0
X1 VCSTR1
rA1
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
 L3-24

2 CSTRs in Series
FA1, X1 Materials balance reactor 2:
In - Out + Gen. = Accum.
FFA0
A0
X
X00 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:
FA1 FA 0 FA 0 X1 FA 2 FA 0 FA 0 X2
FA 0
X1 VCSTR1 VCSTR 2
FA 0 FA 0 X1 FA 0 FA 0 X2
rA1 rA 2
FA 0
VCSTR 2 X2 X1
rA 2
Value of FA0/-rA at X2
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
 L3-25

2 CSTRs in Series
FA1, X1=0.4 XA 0 0.4 0.8
FFA0 FA0/-rA 0.89 2.05 8
A0
X
X00
FA2
X2=0.8

V1 V2
VCSTR1 for XA1 = 0.4?
VCSTR1 2.05 0.4 0.82 m3
VCSTR2 for XA2 = 0.4 to 0.8?
F
VCSTR 2 A 0 X2 X1
rA 2
VCSTR 2 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
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
 L3-26

2 PFRs in SeriesFF
A1
A1
FFA0
A0,, X
X00 X
X11
FFA2
A2,, X
X22
X2
FA 0 X1 F X2 F
VPFR 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 L3-20)
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 3.61 m3
3
VPFR1 2 0.55 m3 1.61 m3 2.17 m3
Same volume as 1 PFR with XA=0.8
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
 L3-27

Combinations of CSTRs & PFRs in Series

FFA1
A1 X
X11 FFA2
FA1, X1 A2,, X
X22
FFA2
A2,, X
X22 FFA0
A0,, X
X00
FFA0
A0 V1
V2
X
X00
V2

V1

VCSTR1 VPFR2 VPFR1 VCSTR2

( )
V CSTR1 + V PFR2 V PFR1 +C
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, CSTR2
University of Illinois at Urbana-Champaign.
 L3-28

Reactors in Series
FA0
If is monotonica lly 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 (): time necessary to process one reactor
0
volume, also called mean residence time or holding time
Space velocity (SV): inverse of space time, but vo may be SV 0 1
measured under different conditions than the space time V
Liquid-hourly 0 liquid @ 60F or 75F Gas-hourly 0 STP
space LHSV space GHSV V
V
velocity velocity
0| is the volumetric flow rate measured at specified condition
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.