Chapter 5: Isothermal Reactor

5.1 Mole Balances in terms of Conversion

5.2 Pressure drop in PBR
5.2 Membrane reactor and Semibatch reactor

Building Block 4:
Combine
Fig 4-2 Algorithm for
isothermal reactor

5.1 Mole Balances in terms of Conversion

Algorithm for Isothermal Reactor Design
1. Mole Balances and Design Equation
2. Rate Laws
3. Stoichiometry
4. Combine
5. Evaluate (solution)
A. Graphically (Chapter 2 plots)
B. Numerical (Quadrature Formulas Chapter 2 and
appendices)
C. Analytical (Integral Tables in Appendix)
D. Software Packages (Appendix)

Chemical Plant for Ethylene Glycol

Design of CSTR
Damkhler Number (Da)
Measures the extent of reaction in a continuous flow reactor.

CSTR
Da = -rA0V/FA0 = reaction rate / convective rate

Da = k

(1st order reaction)

Da = kCA0

(2nd order reaction)

Single CSTR:
= 1/k (X/1-X)

X = k/(1+ k) = Da/(1+Da)
CA = CA0/(1+ Da)

If Da < 0.1, then X < 0.1

If Da > 10, then X > 0.9

First order

CSTR in Series:
t1 = 1/k1 (X1/1-X1)
X1 = t1k1/(1+ t1k1)= Da1/(1+Da1)
CA1 = CA0/(1+ Da1)
,
,
1
=1
1 +

First order

Ex 4-2: Producing ethylene glycol (EG) from ethylene

oxide (EO) in CSTR, P163
12.2 billion tons of ethylene glycol (EG) were produced in 2000, which ranked
it the 26th most production material in the nation. About one-half EG is used for
antifreeze while the other half is used in the manufacture of polyesters (88%
fibers and 12% bottles and films).
If 10 mol/min ethylene oxide at a 1 mol/L solution in water is fed to the reactor,
together with an equal volumetric water solution containing 0.9 wt% of catalyst
H2SO4. The specific reaction rate constant is 0.311 min-1.
a) If 80% is converted, determine the CSTR volume.
b) If 80% is converted with two equal-size CSTRs connected in series,
determine the CSTR volume.

Ex 4-2

Design of PFR
Design equation:

dX rA

dV
FA0

For a second order reaction, -rA=kCA2

For liquid phase, v=v0,
0
=
2
0

=
2
0 1

Dividing by v0 (=V/v0),

0
2
=
=
1 + 0 1 + 2

Da2= kCA0: Damkohler number for 2nd order reaction

10

Gas Phase reaction, and T=T0, P=P0:

CA

Substitute to design equation

0
=
2
0

FA0 1 X ) C A0 1 X )

0 1 X )
1 X )

1 + 2

2
1

From the integral equation from Appendix A.1,

=

11

0
[2
0

1 + ln(1 )+ 2X+

1+ 2
]
1

Second order

Ex 4-3 Producing C2H4 from C2H6 in PFR, P171

Ethylene ranks 4th as a chemical, and 1st as an organic chemical in US each year.
Over 25 million tons were produced in 2000, 65% in the manufacture of plastics,
20% for ethylene oxide, 16% for others.
The reaction is irreversible and follows an elementary law, with k=0.072 s-1 and
activation energy 82 kcal/g mol at 1000 K. The reactor is operated isothermally at
1100 K and at a pressure of 6 atm, with an 80% conversion. Determine the PFR
volume necessary to produce 180 million kilograms a year from cracking a feed
stream of pure ethane.

12

13

5.2 Pressure Drop

Liquid Phase Reactions:
Pressure Drop does NOT affect the reaction rate of liquid phase

Gas Phase Reactions:

The majority gas phase reactions are catalyzed by passing thought
a packed bed of catalyst particles.
The significant pressure drop will affect the concentration and
further the reaction rate.

Engineering Analysis of Pressure Drop

14

Equations in flow system

Concentration Flow System:
Gas Phase Flow System:
CA

15

FA

CA

FA

0 1 X )

FA0 1 X )
C 1 X ) T0 P
A0
T P0
1 X ) T P0
0 1 X )
T0 P

b
b

FA0 B X C A0 B X
F
a
a T0 P

CB B

1 X ) T P0
1 X ) T P0
0
T0 P

T P0
T0 P

Pressure Drop in PBRs

Sample Question:
Analyze the following second order gas phase reaction that occurs
isothermally in a PBR:
AB
1. Mole Balances
Must use the differential form of the mole balance to separate
dX
variables:
F
r
A0

dW

2. Rate Laws
Second order in A and irreversible:
3. Stoichiometry
Isothermal, T=T0
16

CA

FA

CA 0

rA kCA2
1 X ) P T0
1 X ) P0 T

CA CA 0

1 X ) P
1 X ) P0

4. Combine:

2
A0

dX kC

dW
FA0

1 X ) P
1 X )2 P0
2

Need to find (P/P0) as a function of W (or V if you have a PFR)

Ergun Equation:

dP
G 1 1501 )
3

1
.75
G

dz g c D p
D
p TURBULENT
LAMINAR

Constant mass flow:

m m 0

0 0
0
0

17

FT P0 T
0
FT 0 P T0
P0 T
0 (1 X )
P T0

http://dns2.asia.edu.tw/~ysho/YSHO-English/1000%20CE/1000%20CE.htm

18

Pressure Drop in PBRs

0

Variable Density
dP
G

dz 0 g c D p

P0 T FT
1 1501 )
3
1.75G
Dp

P T0 FT 0

Let

G
0 gc Dp

Catalyst Weight
Where

19

P T0 FT 0
P0 T FT

1 1501 )
3
1.75G
Dp

W zAc b zAc 1 )c
b bulk density
c solid catalyst density

porosity (a.k.a., void fraction)

(1 ) solid fraction

0
P0 T FT
dP

dW Ac 1 )c P T0 FT 0

Pressure Drop in PBRs

Let

2 0
1
Ac 1 ) c P0

dy
T FT

dW
2 y T0 FT 0

: Pressure drop parameter

y

P
P0

For single reaction, Ergun equation is expressed in terms of X.

d P P0 )
1 T
1 X )

dW
2 P P0 ) T0

FT
1 X )
FT 0

dy
T
1 X )

dW
2 y T0

20

dy

1 X )
dW
2y

Isothermal case

Pressure Drop in PBRs

dX kC 1 X ) 2

y
2
dW FA0 1 X )
2
A0

Mole balance and rate law

dX
dP
f X , P ) and
f X , P)
dW
dW

dy
f y, X )
or
dW

The two expressions are coupled ordinary differential equations.

We can only solve them simultaneously using an ODE solver
such as Matlab.
For the special case of isothermal operation and = 0, we can
obtain an analytical solution.
21

PBR with = 0
For 0

Or X<<1, =yA0

dy

(1 X )
dW 2 y
When W 0 y 1
dy dW
2

y 2 (1 W )
y (1 W )

1/ 2

CAUTION: Never use this form if 0.

22

PBR with = 0
Pressure Drop

Concentration Profile

Reaction Rate
P
rA kC k (1 X )
P0
2
A

Conversion

Flow Rate
0 1 X )

P0 T
P T0

For 0 :T T0
P
0 0
P

23

Example: Gas Phase Reaction in PBR for =0

Gas Phase reaction in PBR with = 0 (Analytical Solution)
A + B 2C
Equimolar feed of A and B: CA0=CB0=0.2 mol/dm3,
FA0=2mol/min

kA = 1.5dm6/mol-kg-min, = 0.0099 kg-1

Find X at 100 kg catalyst.

C A0
CB 0
24

X ?

Example: Gas Phase Reaction in PBR for =0

dX r ' A

dW
FA0

1) Mole Balance

r ' A kCACB

2) Rate Law
3) Stoichiometry
dy

dW
2y

C A C A0 1 X )y

CB C A0 1 X )y

2 ydy dW
y 1 W )

12

y 1 W

W 0 y 1

rA kCA2 0 1 X ) y 2 kCA2 0 1 X ) 1 W )
2

4) Combine
25

dX kCA2 0 1 X ) 1 W )

dW
FA0
2

Example: Gas Phase Reaction in PBR for =0

kCA2 0
dX
1 W )dW

2
1 X ) FA0
kCA2 0
X

1 X
FA0

W 2
W
2

W 0, X 0, W W , X X

X 0.6 with pressure drop)

X 0.75 without pressure drop, i.e. 0)

26

Example: Gas Phase Reaction in PBR for 0

The reaction
A + 2B C
is carried out in a packed bed reactor in which there is pressure drop.
The feed is stoichiometric in A and B.

Plot the conversion and pressure ratio y = P/P0 as a function of catalyst

weight up to 100 kg.
Additional Information: kA = 6 dm9/mol2-kg-min, = 0.02 kg-1
27

Example: Gas Phase Reaction in PBR for 0

A + 2B C
1) Mole Balance

dX rA

dW FA0

2) Rate Law

rA kCACB2

3) Stoichiometry: Gas, Isothermal

P
0 1 X ) 0
P

28

4)

1 X )
C A C A0
y
1 X )

dy

1 X )

dW
2y

B 2 X )
C B C A0
y
1 X )

Example: Gas Phase Reaction in PBR for 0

1 X )
5) f

0
y
1
2
6) y A0 [1 1 2] [2]
C A0

3
3
2, FA0 2, k 6, 0.02

Initial values: W=0, X=0, y=1

Final values: W=100

29

If 0, software must
be used to solve.

T = T0

Solve with software, e.g. Matlab

30

Engineering Analysis of Pressure Drop

Robert the Worrier wonders: What will the conversion change
if we increase the catalyst size by a factor of 2?

Turbulent dominant, Term 2 >> Term 1

dy

1 X )
dW
2y
Laminar dominant, Term 1 >> Term 2?

32

Impact of Catalyst diameter

Pack the catalyst into a larger diameter tube?

33

What is the impact of entering pressure, P0?

: 0 = 0 ,
0 = 0 =

0 =

0
=
0

0
0

20
150 1
=

+ 1.75

02 3

0
34

Ex 4-6 Producing
ethylene oxide from
ethylene in PBR,
P191

35

Ex 4-6

36

Pressure Drop - Summary

o Liquid Phase Reactions
Pressure Drop does not affect concentrations.

o Gas Phase Reactions

1)

d(P)/d(W)=
combine with d(X)/d(W) =
2) = 0 and isothermal
P=f(W)
Combine then separate variables (X,W) and integrate
3) Engineering Analysis of Pressure Drop
37

Design of a plant and the economics

38

Should the project go?

5.3 Membrane Reactors

Used for thermodynamically limited reactions, to achieve
conversions greater than the original equilibrium value, by removing
the reaction products and drive the reaction to the right.
A membrane permeable to that reaction product, but impermeable to
all other species, is placed around the reacting mixture.
Inert Membrane Reactor with Catalyst pellets on the Feed side
(IMRCF): membrane is inert and servers as a barrier
Catalytic Membrance Reactor (CMR): the catalyst is deposited
directrly on the membrane.

39

Membrane Reactors
Dehydrogenation Reaction:

C3H8 H2 + C3H6 A B + C

40

IMRCF for mole balance

Isothermal reaction
design algorithm for
mole balance

41

Membrane Reactors
sweep
FA0

W = bV = solids weight
b = (1-)C= bulk solids density

A,B,C
B

C = density of solids
=

H2

H2

CBS
CB

A,C stay behind since they are too big

42

Mole Balance:
Species A:

In out + generation = 0

FA V FA V V rA V 0
dFA
rA
dV

Species B:

In out out membrane + generation = 0

FB V FB V V RB V rB V 0
dFB
(rB RB )
dV

43

moles of B through sides

RB
volume of reactor

Neglected most of the time

RB kC CB CBS

mol
m3 s

Membrane Reactors: A B + C
Mole Balances: 1) dFA rA 2) dFB
dV

Rate Law:

4)

Relative Rates:
Net Rates:
Transport Law:
Stoichiometry:

44

Parameters:

dV

rB RB

3)

dFC
rC
dV

C C
rA k C A B C
KC

rA rB rC

1
1 1

5)
6)
7)

rA rB , rA rC

RB kC CB
FA
C A CT 0
(isothermal, isobaric)
FT
FB
8) CB CT 0
FT
9) CC CT 0 FC
FT
10) FT FA FB FC

Example 4-8, P211

The dehydrogenation reaction is carried out isothermally in a membrane reactor with
no pressure drop. The membrane is permeable to product hydrogen (kC=0.2 min-1),
but impermeable to all other species. The equilibrium constant is quite small at 227
0C, K = 0.05 mol/L. The specific reaction rate k= 0.7 min-1. The pure gaseous
C
propane enters the reactor at 8.2 atm and 227 0C at a rate of 10 mol/min.

Dehydrogenation Reaction:
C3H8 H2 + C3H6
AB+C

Inert Sweep Gas

H2 (B)

C3H8 (A)

Inert Sweep Gas

C3H6 (C)

For membrane reactors, we cannot use conversion. We have to work in terms of

the molar flow rates FA, FB, FC.
Reactor volume, rather than catalyst weight is chosen as independent variable,
which are easily related through the catalyst density.

45

Membrane Reactors: A B (H2) + C

Mole Balances: 1) dFA rA
dV

Rate Law:

4)

Relative Rates:
Net Rates:
Transport Law:
Stoichiometry:

46

2)

dFB
rB RB
dV

3)

dFC
rC
dV

C C
rA k C A B C
KC

rA rB rC

1
1 1

5)
6)
7)

rA rB , rA rC

RB kC CB
FA
C A CT 0
(isothermal, isobaric)
FT
FB
8) CB CT 0
FT
9) CC CT 0 FC
FT
10) FT FA FB FC

Combine: - Use Matlab or Polymath

Parameters: C
T0

mol
0.2 3
dm

k= 0.7 min-1
KC = 0.05 mol/L,
kC=0.2 min-1

Initial conditions for integration:

V=0: FA0 = 10 mol/min, FB0 = FC0 = 0

What is the conversion at V = 400L?

47

5.4 Semibatch Reactors (liquid phase)

Semibatch reactors can be very effective in maximizing selectivity

in liquid phase reactions.

One reactant is fed to the reactor, maintaining a low concentration.

48

Selectivity in Multiple Reactions

kD
A B
D

rD k DC A2CB

(Desired)

kU
A B
U

rU kU C ACB2

(Undesired)

Instantaneous

Selectivity
SD/U = rD/rU

YD rD / rA

Overall

D/U = FD/FU

YD FD /( FA0 FA )

S D /U
49

rD k DC A2CB k DC A

2
rU ku C ACB kU CB

Keep CA high and CB low. How?

Yield

Semibatch reactors, Ex4-9, P220: A + B C + D

B, v0

m
A
Initial V

dm

m
dt

1) Mass Balance:
dm
dV
0
00
dt
dt
50

dV
0
dt

V V0 0t

0 0
m

and

t 0 V V0

m V0

Semibatch Reactors
Mole Balance on Species A: [in] [out] + [gen] = [acc]
dN A
0 0 rAV
dt
dN A d [C AV ]
dC A
dV

V
CA
dt
dt
dt
dt

C
dC A
rA 0 A
dt
V

dV
0
dt

Mole Balance on Species B:

dN B d [CBV ]
dCB
dV

V
CB
dt
dt
dt
dt

51

CB 0 CB )0
dCB
rB
dt
V

dN B
FB 0 0 rBV
dt

FB 0 CB 00

dV
0
dt

1)

1) Mass and Mole

Balance Summary

2)
3)
4)
5)

2) Rate Laws
3) Stoichiometry
rA rB rC rD

1
1
1
1

6 =

7)
9)

rB rA

52

8)

rD rA

11)
4) Parameters

C
dC A
rA 0 A
dt
V
)B0 )
dC
dCBB r C0B(0CB 0CB C
rBB
dt
VV
dt
dCC
C
rC 0 C
dt
V
C
dC D
rD 0 D
dt
V
V V0 0t

rC rA
10)

N A0 C A0V0

C A0 , V0 , 0 , k , CB 0

N A0 N A
N A0

12)

N A C AV

Semibatch Reactors

53

Semibatch Reactors

54

Equilibrium Conversion in Semibatch Reactors with

Reversible Reactions

A B
C D

Consider the following reaction:

It allows to reach an equilibrium after feeding B for a time, t.

Everything is the same as for the irreversible case, except for the
rate law:

N 1 X )
C A0

C C
rA k A C ACB C D
KC

At equilibrium, rA 0

Where:

then

V
F t N A 0 X )
C B B0
V
N X
C C C D A0
V

CCeCDe N Ce N De
N A0 X e2
K C

C Ae CBe N Ae N Be 1 X e )FB 0t N A0 X e )
55

Xe changes with feeding time t.

0
2
=
( +
)
0
1

Semibatch Reactors
Three Forms of the Mole Balances applied to Semibatch Reactors:

1. Molar Basis

dN A
rAV
dt
dN B
FB 0 rBV
dt

0
dC A
rA C A
2. Concentration
dt
V
Basis
0
dCB
rB CB 0 CB )
dt
V

3. Conversion
56

dX rAV

dt
N A0

dN A
rAV
dt
dN B
FB 0 rBV
dt

Semibatch Reactors
Consider the following elementary reaction:
A+B C+D
-rA=kCACB

The combined Mole Balance, Rate Law, and Stoichiometry may

be written in terms of number of moles, conversion, and/or
concentration:
Conversion
(1 )(0 + 0 0 )
=

0 + 0

57

Concentration

No. of Moles

dC A
rA C A 0
dt
V

dN A
rAV
dt

dCB
rA CB 0 CB ) 0
dt
V

dN B
FA0 rBV
dt

End of Chapter 5
Practice:
P4-7, P4-13, P4-21, P4-23
Tutorial:

58