Chapter 5-6

Isothermal Reactor DesignHeterogeneous Reactions- Pressure Drop

Chemical Reaction Engineering

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

4.1 Design structure for isothermal reactors

Algorithm for isothermal reactor design
1. Mole balance and design equation
2. Rate law
3. Stoichiometry
4. Combine
5. Evaluate
We can solve the equations in the
combine step either
A. Graphically (Chapter 2)
B. Numerical (Appendix A4)
C. Analytical (Appendix A1)
D. Software packages (polymath)

Algorithm for Isothermal Reactors

Pressure Drop in Reactors

In liquid-phase reactions
- the concentration of reactants is insignificantly affected by even
relatively large change in the total pressure =>
- Hence, the effect of pressure drop on the rate of reaction can be ignored
when sizing liquid-phase chemical reactors
In gas-phase reactions,
the concentration of the reacting species is proportional to the total
pressure
- the effects of pressure drop on the reaction system are a key factor
in the success or failure of the reactor operation
- that is, pressure drop may be very important for gas-phase reactions

Pressure Drop and Rate Law

For an ideal gas,

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

- determine the ratio P/P0 as a function of V or W

- combine the concentration, rate law, and design equation
- the differential form of the mole balance (design equation) must be used

Pressure Drop and Rate Law

For example, the second order isomerization reaction in a packedbed reactor
2A B + C
-the differential form of the mole balance

FA 0
- rate law

dX
rA
dW

gmoles

g catalyst min

rA kCA2
-from stoichiometry for gas-phase reactions

1 X
C A C A0
1 X

P T0

P0 T

Pressure drop and the rate law

Then, the rate law

1 X P T0
rA k C A0

X
P
T

(5-20)

- the larger the pressure drop from frictional losses, the

smaller the reaction rate
Combining with the mole balance and assuming isothermal
operation (T=To) in a Packed-bed reactor,

FA 0
Dividing by FA0

dX
C A0 (1 X )
k

dW
1

dX kCA0

dW
v0

P
0

1 X P

X
P

Pressure Drop and Rate Law

For

isothermal operation (T =T0), a function of only conversion

and pressure

dX
f ( X , P)
dW

(5-21)

-Another equation is needed to determine the conversion as a

function of catalyst weight, - that is, we need to relate the
pressure drop to the catalyst weight

P f (W )

Flow Through a Packed Bed

The majority of gas-phase reactions are catalyzed by
passing the reactant through a packed of catalyst particles
Ergun equation: to calculate pressure drop in a packed
porous bed
dP
G

dz
g c D p

150 (1 )

1.75G

Dp

laminar

(4-22)

turbulent

G= u=superficial mass velocity [g/cm2s]; u=superficial velocity [cm/s];

Dp=diameter of particle in the bed [cm]; =porosity=volume of void/total
bed volume; 1- =volume of solid/total bed volume

The gas density is the only parameter that varies with

pressure on the right-hand side. So, calculate the pressure
drop through the bed

Flow through a Packed Bed

Equation of continuity

0 m
m
m
o = m
0 v0 v

- steady state the mass flow rate at any point is equal to the entering
mass flow rate
Gas-phase volumetric flow rate

P
v v0 0
P
Then,

T
0

FT

F
T0

v0
P T0 FT 0
0

v
P0 T FT

(3-41)

(4-23)

Pressure Drop in a Packed Bed Reactor

then, Ergun equation

dP
G (1 )

dz
0 g c D p 3
Simplifying

We need

150 (1 )
P0 T FT

1.75G

Dp

P T0 FT 0

P0 T FT
dP

dz
P T0 FT 0

(4-24)

G (1 ) 150 (1 )
0
1.75G

3
Dp
0 g c D p

dP
dW

(4-25)

The catalyst weight,

(1 ) Ac z c
Volume of
solid

dW

Density of
solid catalyst

c (1 ) Ac dz

(4-26)

Pressure Drop in a Packed Bed Reactor

then, Ergun equation

Simplifying

Let y=P/Po

0
P0 T FT
dP

dW
Ac (1 ) c P T0 FT 0
dP
T P0

dW
2 T0 P / P0

FT

F
T0

(4-27)

P0T
dP
dy T F
(1 X )
2y
To
dW
2 T0 P F
/P
0

(4-28)

2 0
Ac c (1 ) P0

(4-29)

F
FT FT 0 FT 0 X FT 0 1 A0 X
FT 0

FT
1 X
FT 0

FA0
y A0

FT 0

Pressure drop in a packed bed reactor

dP
T P0
dy

(1+X)(1 X )
2y
dW
2 T0 P / P0

(4-30)

< 0, the pressure drop (DP) will be less than that for = 0
> 0, the pressure drop (DP) will be greater than that for = 0
For isothermal operation
dP
f ( X , P)
dW

and

dX
f ( X , P)
dW

(4-31)

The two expressions are coupled ordinary differential equations. We can

solve them simultaneously using an ODE solver such as Polymath.
For the special case of isothermal operation and = 0, we can obtain an
analytical solution.
Polymath will combine the mole balance, rate law and stoichiometry

Pressure Drop in a Packed Bed Reactor

dP
T P0
dy

(1+X)(1 X )
2y
dW
2 T0 P / P0

(4-30)

Analytical Solution
If = 0 or X 1, we can obtain an analytical solution to Eq. (4-30) for isothermal
operation (i.e., T=T0). For isothermal operation with = 0, Eq. (4-30) becomes

dy
dP
P0

2y
dW
2 ( P / P0 )

Isothermal (T=To)
with = 0

dy
2y
dW = -

At W=0, y=1 (P/Po=1)

y2= 1- w

dy2
dW = -

Pressure Drop in a Packed Bed Reactor

If = 0 or X 1, we can obtain an analytical solution to Eq. (4-30) for isothermal
operation (i.e., T=T0). For isothermal operation with = 0, Eq. (4-30) becomes
Pressure ratio
only for = 0

P
1 W
y=
P0

(4-33)

2 0

Ac (1 ) c P0

Pressure as a
function of
reactor length, z

(1 ) Ac z c

(4-26)

y=

2 z
P
1 0 =f (z)
P0
P0

(4-34)

Pressure Drop in Pipes

Pressure drop along the length of the pipe
dP
d 2 fG 2
G

dL
dL
D

P dP
2 fG 2
2 dP
0
G

0
P0 dL
PdL
D

Integrating with P=P0 at L=0, and assuming that f = constant

0

P02 P 2
P
P
L
G2 0 2 f
ln 0
2
0
D
P

Rearranging, we get
P0
1 pV
P

4 fG 2
p
0 P0 Ac D

Example 4-4: 1 schedule 40 x1000-ft L (p=0.018), P<10%

Analytical Solution for Reaction with Pressure Drop

Conversion as a function of catalyst weight
2nd-order isothermal reaction

Mole balance:

F A0

dX kCA2 0

(1 X ) 2 1 W 1/ 2
dW
FA0

Separating variable and Integrating

dX
rA
dW

Rate law:

Stoichiometry: Gas-phase isothermal with =0

C A C A0 (1 X )

FA0
kCA2 0

dX
(1 X )

1 W dW

at X 0, W 0 and FA0 C A0 v0

rA kCA2

y=

Combining

P
P0

P
1 W
P0

C A C A0 (1 X )(1 W )1/ 2

v0 X
W

W 1

2
kCA0 1 X

kCA0W
W
1

v0
2
X
kC W
W
1 A0 1

v0
2

(4-38)

Reaction with Pressure Drop

Conversion as a function of catalyst weight
kCA0W
W
1

v0
2
X
kC W
W
1 A0 1

v0
2

(4-38)

Catalyst weight for 2nd-order isothermal reaction in PFR with P

1 1 (2v0 ) / kCA0 X /(1 X ) 1/ 2

W

(4-39)

Reaction with Pressure Drop

Conversion as a function of catalyst weight
For gas phase reactions, as the pressure drop increases, the concentration
decreases, resulting in a decreased rate of reaction, hence a lower conversion
when compared to a reactor without a pressure drop.

Spherical Packed-Bed Reactors

Spherical Ultraformer Reactor (Amoco) for dehydrogenation reaction such as

Paraffin

Aromatic + 3 H2

Spherical reactor
- minimize pressure drop
- inexpensive
- the most economical shape for high
pressure

Coordinate system and variables

used with a spherical reactor

Synthesizing a Chemical Plant

Always challenge the assumptions, constraints, and
boundaries of the problem
The profit from a chemical plant will be the
difference between income from sales and the cost to
produce the chemical

Profit = (value of products) (cost of

reactants)
(operating costs) (separation
costs)
The operating cost: energy, labor, overhead, and

Production of Ethylene Glycol

402 million
lbC2H6 /yr
1
O2, C2H4, N2, C2H4O

H2, C2H4
C2H6 C2H4 + H2

V=81 ft3, X=0.8

C2H6

separator

Ag

C2H4+ O2 C2H4O
6

C2H4O

3
4

separator
H2O

C2H4

W=45,440 lb, X=0.6

8

H2O, 0.9wt% H2SO4

C2H4O(aq)
9
V=197 ft3, X=0.8
absorber
Cat.

C2H4O + H2O

CH2OH
CH OH

200 million
lb EG/yr

Air

Synthesizing a Chemical Plant

Ethylene glycol = $0.38/lb (2x108 lb/yr)

Ethane = $0.04/lb (4x106 lb/yr)
Sulfuric acid = $0.043/lb (2.26x108 lb/yr)
Operating cost = $8x106/yr

Profit = ($0.38/lb x 2x108 lb/yr) ($0.04/lb x 4x108 lb/yr)

-($0.043/lb x 2.26x106 lb/yr) ($8x106/yr)
= $52 million
How the profit will be affected by conversion, separation, recycle stream,
and operating costs?

Using CA (liquid) and FA (gas)

in the mole balance and rate laws
More convenient to work in terms of the number of moles or molar
flow rate rather than conversion.

Membrane reactor, multiple reaction, and unsteady state

Must write a mole balance on each species when molar flow

rates (Fi) and concentrations (Ci) are used as variables
A

b
c
d
B C D
a
a
a

rC rD
rA
rB

a b c
d
rA k AC A C B

Liquid Phase

or liquid-phase reaction with no volume change

oncentration is the preferred variable
aA bB cC dD
b
c
d
A B
C D
a
a
a

Mole balance for liquid-phase reactions

Batch

dC A
rA
dt

dC B b
rA
dt
a

CSTR

v0 (C A0 C A )
V
rA

v0 (C B 0 C B )
V
(b / a )rA

PFR

dC A
v0
rA
dV

dC B b
v0
rA
dV
a

PBR

dC A
v0
rA
dW

dC B b
v0
rA
dW
a

Gas Phase
For gas phase reactions
need to be expressed in terms of the molar flow rates

dF j
dV

rj

(1-11)
y

F j P T0


C j CT 0

FT P0 T
dy
- FT
=
dW
2y FTo

(3-42)

(4-28, T=To)

Total molar flow rate

n

FT

F
j 1

= FA + FB + FC + FD + FI

Algorithm for Gas Phase Reaction

aA bB cC dD
Mole balances:
Batch

CSTR

PFR

dN A
rAV
dt

FA 0 FA
V
rA

dFA
rA
dV

dN B
rBV
dt

F FB
V B0
rB

dFB
rB
dV

dN C
rCV
dt

F FC
V C0
rC

dFC
rC
dV

dN D
rDV
dt

F FD
V D0
rD

dFD
rD
dV

Algorithm for Gas Phase Reaction

Rate law:

rA

k AC A C B

Stoichiometry:
Relative rate of reaction:

r
rA
r
r
B C D
a b c
d
b
rB rA
a

Concentration:

Total molar flow rate:

c
rC rA
y a

d
rD rA
a

C A CT 0

FA P T0
FT P0 T

C B CT 0

FB P T0
FT P0 T

CC CT 0

FC P T0
FT P0 T

C D CT 0

FD P T0
FT P0 T

FT FA FB FC FD

Algorithm for Gas Phase Reaction

Combine:
dFA
FA

k ACT 0
dV
FT

dFC c
FA

k ACT 0
dV
a
FT

FB

FT

FB

FT

dFB
b
FA

k ACT 0
dV
a
FT
dFB d
FA

k ACT 0
dV
a
FT

FB

FT

FB

FT

- Specify the parameter values: kA, CT0, T0, a, b, c, d

- Specify the entering number: FA0, FB0, FC0, FD0, and final value: Vfinal

Use an ODE solver