L6-1

Review: Logic of Isothermal Reactor Design

1. Set up mole balance for
specific reactor

2. Derive design eq. in

terms of XA for each
reactor

3. Put Cj is in terms of
XA and plug into rA
(We will always look
conditions where Z0=Z)

In - Out +Generation = Accumulation

V
dN j
Fj0 F j rjdV
dt
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

4. Plug rA into design eq and solve for the

time (batch) or volume (flow) required
for a specific XA

Examples of combining rates &

design eqs follow!

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

L6-2

Review: Batch Reactor Operation

A B

-rA = kCA2

2nd order reaction rate

Be able to do these 4 steps, and

then integrate to solve for time
for ANY REACTION

Calculate the time required for a conversion of XA in a constant V batch reactor

dX A
rA V
dt

Mole balance

NA0

Rate law

rA kC A 2

Stoichiometry (put CA in
terms of X)

C A C A0 (1 X A )

Combine

dX A
2
NA0
k CA 02 1 X A V
dt
Batch Volume is constant, V=V0

Integrate this equation in

order to solve for time, t

NA0

dX A
2
k CA02 1 X A V0
dt
1 XA

kC A0 1 X A

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

L6-3

Review: CSTR Operation

A B

-rA = kCA

1st order reaction rate

Calculate the CSTR volume required to get a conversion of XA

FA 0 X A
rA

Mole balance

Rate law

rA kCA

Stoichiometry (put CA in
terms of X)

C A C A0 (1 X A )

Combine

FA0 X
kCA0 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
Be able to do these steps for any order reaction!
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.

L6-4

Review: Scaling CSTRs

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 rxn:
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 must be proportional to the volumetric flow rate 0

0 X A
Separate variables we will
V
k 1 X A vary from those held constant
Eq is for a 1st order rxn only!

V 0

XA
k 1 XA

XA
V

0 k 1 X A

Space time (residence time) required to

achieve XA for 1st order irreversible rxn
Be able to do this for any order rxn!

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

L6-5

Review: Damkhler Number, Da

Da

rA0 V rate of reaction at entrance

reaction rate

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:
Da

kCA0 V
rA0 V kCA 0 V
Da

Da kC A0
0
FA 0
CA00

2nd order
irreversible
reaction

How is XA related to Da in a first order irreversible reaction in a flow reactor?

k
Da
From
XA
XA
slide L6-7:
1 k
1 Da

If Da < 0.1, then XA < 0.1

If Da > 10, then XA > 0.9

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

L6-6

Review: Sizing CSTRs for 2nd Order Rxn

AB

-rA = kCA2

Liquid-phase 2nd order reaction rate

Calculate the CSTR volume required to get a conversion of XA

FA0 X 0CA0 X

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?
Eq is for a 2nd order
liquid irreversible rxn

Da kC A0

Be able to do these steps!

In terms of space time?

V
X

2
or 0
kC 1 X
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.

L6-7

Review: 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

Rate of disappearance of A in the nth reactor:

C A0
rAn kCAn k
1 k n
How is conversion related to the # of CSTRs in series?
CA0
Put CAn in terms of XA
1
C A0 1 X A

A
n
(XA at the last CSTR):
1 k
1 k n
1

1 k

X A or 1

1 Da

XA

1st order irreversible liquid phase

rxn run in n CSTRs with identical
V, and k

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

L6-8

Review: Isothermal CSTRs in Parallel

Mole Balance
X Subscript i
Vi FA0i Ai
rAi denotes reactor i

FA01
FA0
FA02

same T, V,
FA01 = FA02 = FA0n

X A

rA

V FA0

V total volume of all CSTRs

Vi
n
# of CSTRs
Volume of each CSTR
FA0i

FA0 total molar flow rate

n
# of CSTRs

Molar flow rate of each CSTR

X1 =X 2 =... =Xn =X
rA1 rA2 ... rAn rA

V FA0 X Ai

n
n rAi

X A

r
A

V FA0

Conversion achieved by any one of the reactors in parallel is the

same as if all the reactant were fed into one big reactor of volume
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular
V Engr Dept, University of Illinois at Urbana-Champaign.

L6-9

Be able to do these 4 steps,

integrate & solve for V for ANY
ORDER RXN

Liquid Phase Reaction in PFR

LIQUID PHASE: Ci f(P) no pressure drop
2A B -rA = kCA2 2nd order reaction rate
Calculate volume required to get a conversion of XA in a PFR
dX A rA

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

See Appendix A for integrals

frequently used in reactor design

dV
0

k C A02 1 X A

FA0

k CA02

FA0

XA
1 X V

Liquid-phase 2nd order reaction in PFR

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

L6-10

Liquid Phase Reaction in PBR

Be able to do these 4 steps, integrate
& solve for V for ANY ORDER RXN

LIQUID PHASE: Ci f(P) no pressure drop

2A B -rA = kCA2 2nd order reaction rate
Calculate catalyst weight required to get a conversion of XA in a PBR
dX A r ' A

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

Liquid-phase 2nd order reaction in PBR

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

L6-11

Isobaric, Isothermal, Ideal Rxns in

Tubular Reactors

Gas-phase reactions are usually carried out in tubular reactors (PFRs & PBRs)
Plug flow: no radial variations in concentration, temperature, & -rA
No stirring element, so flow must be turbulent

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

Stoichiometry for basis species A:

C A0 1 X A
C A0 CA0 X A
CA
CA
1 XA
1 XA
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.

L6-12

Isobaric, Isothermal, Ideal Rxn in PFR

GAS PHASE: Ci = f() no P, T, or Z
2A B -rA = kCA2 2nd order reaction rate
Calculate PFR volume required to get a conversion of XA
dX A rA

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

Integral A-7 in appendix

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

L6-13

NTf NT0 Change in total # moles at X A 1

NT0
total moles fed

: expansion factor, the fraction of change in V per mol A reacted

0: volumetric flow rate
varies if gas phase & moles product 1 X Z T P0

0
A
moles reactant, or if a P, T, or Z occurs
Z0 T
0 P
No P, T, or Z occurs, but moles product moles reactant
0 1 X A
= 0 (mol product = mol reactants): : constant volumetric flow rate as XA
increases
< 0 (mol product < mol reactants): volumetric flow rate decreases as
XA increases
Longer residence time than when
Higher conversion per volume of reactor (weight of catalyst) than if 0
> 0 (mol product > mol reactants): with increasing XA
Shorter residence time than when
Lower conversion per volume of reactor (weight of catalyst) than if 0
Slidescourtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.

L6-14

Pressure Drop in PFRs & PBRs

GAS PHASE:

C j0 jCA0 X A P T0
Cj

1 XA
P0 T

Considering ideal gas

phase behavior (Z0=Z)

Concentration is a function of P so pressure drop is important in gas phase

rxns
Why? Take a 1st order reaction A B in a PBR with rA = kCA
C CA0 X A
Substitute concentration
r 'A k A0
of A into the rate law:
1 XA

P T0

P0 T

If P drops during the reaction, P/P0 is less than one, so CA & the rxn rate
Use the differential forms of the design equations to address pressure drop
PFR
PBR
For tubular
reactors:
dX A
moles
dX A
moles
FA0
rA
F

r
'
A0
A
dV
dW
dm3 min
g catalyst min

Pressure drops are especially common in reactions run in PBRs

we will focus on PBR applications
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.

L6-15

Pressure Drop in PBRs

GAS PHASE: A B

-rA = kCA2

2nd order reaction rate

Calculate dXA/dW for an isothermal ideal gas phase reaction with P

dX A
Mole balance
FA0
r ' A
dW
Rate law
r 'A kCA 2
Stoichiometry (put CA in
terms of X)
Combine

CA0 1 X A P
CA

1 X A P0
dX A

dW

k C A02
FA0

1 XA 2
2
1 XA

P0

This eq. is solved simultaneously

2
2
1

P
with an eq. that describes how the dX A kCA0
A
pressure drops as the reactant
dW
0 1 X 2 P0

A
moves down the reactor
Function of XA and pressure

We need to relate P/P0 to W

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

L6-16

Ergun Equation relates P to W

dP
T P0

1 X A This equation can be simplified to:
dW
2 T0 P P0
Differential form of Ergun equation
for pressure drop in PBR:
y

P
P0

NTf NT0
y A0
NT0

T
dy

1 XA
dW
2y
T0

20
A c c 1 P0

volume of solid
1 : fraction of solid in bed =
total bed volume
AC: cross-sectional area

C: particle density

: constant for each reactor, calculated using a complex

equation that depends on properties of bed (gas density,
particle size, gas viscosity, void volume in bed, etc)
: constant dependant on the packing in the bed
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.

L6-17

Gas Phase Reaction in PBR with P

GAS PHASE: A B

-rA = kCA2 2nd order reaction rate

Calculate dXA/dW for an isothermal ideal gas phase reaction with P

dX A
Mole balance
FA0
r ' A
dW
Combine with rate law
and stoichiometry
Relate P/P0 to W

dX A kC A0 1 X A P

dW
0 1 X 2 P0

dP
T P0

1 XA
dW
2 T0 P P0

Ergun Equation can be simplified by using y=P/P0 and T=T0:

dy

1 XA
dW
2y
Simultaneously solve dXA/dW and dP/dW (or dy/dW) using Polymath
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.

L6-18

Analytical Solutions to P/P0

Sometimes P/P0 can be calculated analytically. When T is constant and = 0:
dy
T
1 XA
dW
2y T0
0
1

From no pressure change

2

P
1 W
P0

dy

Evaluate
dW
2y

To pressure change

2ydy dW

P
y
P0

2ydy dW

P
1
P0

1 W
P0

2 P P0
y
1

Only for isothermal

rxn where =0

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

L6-19

Pressure Drop Example

GAS PHASE: A B -rA = kCA2 2nd order reaction rate
This gas phase reaction is carried out isothermally in a PBR. Relate the
catalyst weight to XA
dX A
N NT0 1 1
FA0
r ' A Tf

0
dW
NT0
1
CA

CA0 CA0 X A
1 XA
0

P T0

P0 T
1

P
1 W
= 0 and isothermal, so:
P0
Plug into PBR
design eq:

P0

C A C A0 1 X A
Plug
into CA

CA CA0 C A0 X A 1 W

2
dX A
dX A
2
FA0
kCA FA 0
k CA0 1 X A 1 W
dW
dW

Simplify, integrate, and solve for XA in terms of W or W in terms of XA:

FA0
dX A
2
2

FA0
kC A0 1 X A 1 W
dW
kC A02

XA

dX A

1 XA

1 W dW
0

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

L6-20

Pressure Drop Example

AB

-rA = kCA2

2nd order gas phase rxn non-elementary rate

This gas phase reaction is carried out isothermally in a PBR. Relate the
catalyst weight to XA
W
A0 X A
FA0 XA dX A
W

W
1

1 W dW

1 X
2
2
k
C
2

kC A0 0 1 X A

A0
A
0
XA
W kCA0

W
1

1 X
Solve for XA
2

A
0

W kCA0
W

kC A0
XA W 1

W 1
XA
2 0
2
0

W kC A0
W

kC A0
XA W 1

X A W 1
2 0
2
0

W kCA0

2 0

20 X A
XA
1 1
1 X
Rearrange
W kC A0

kC

A0
A
1 1

eq.
for
W:
2 0

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

L6-21

Next Time
Startup of a CSTR under isothermal conditions
Semi-batch reactor

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