CHEMICAL REACTION Class of 2020, Fall 2022

Department of Chemical

ENGINEERING Engineering
TUBULAR REACTOR
In the tubular reactor, the reactants are continuously consumed as
they flow down the length of the reactor. In modeling the tubular
reactor, we assume that the concentration varies continuously in the
axial direction through the reactor. Consequently, the reaction rate,
which is a function of concentration for all but zero-order reactions,
will also vary axially.
The general mole balance equation is given by equation:
V
dN j
F j − F j +∫ r j dV =
0
0 dt
To develop the PFR design equation we shall divide (conceptually)
the reactor into a number of sub-volumes so that within each sub-
volume ∆V, the reaction rate may be considered spatially uniform.
We let Fj (y) represent the molar flow rate of species j into volume
∆V at y and Fj (y + ∆y) the molar flow of species j out of the
volume at the location (y + ∆y).
In a spatially uniform sub-volume ∆V, general mole balance
equation is given by equation:
∆V
Gj=∫ r j dV =r j ∆V
0
For a tubular reactor operating at steady state
dN j
=0
dt
The general mole balance equation becomes:
F 𝑗 ( 𝑦 ) − F j ( 𝑦 +∆ 𝑦 )+r j ∆ V =0
The volume ∆V is the product of the cross-sectional area A of the
reactor and the reactor length ∆y.
∆ V = A ∆ y
Then
F j ( y )− F j ( y +∆ y )
=− r j A
∆ y
The term in brackets resembles the definition of the derivative

lim
∆ x →0 [ f ( x+ ∆ x ) − f ( x )
∆ x
=¿
df
dx
¿
]
Then
d F j
− =− r j A
dy
Or
d F j
=r j A
dy
It is usually most convenient to have the reactor volume V rather
than the reactor length y as the independent variable. Accordingly,
we shall change variables using the relation dV = A dy to obtain
one form of the design equation for a tubular reactor:
d F j
=r j
dV
 ∆V
Gj=∫ r j dV =r j ∆V
0
After accounting for steady-state operation
F j (V )− F j (V + ∆ V )+r j ∆ V =0
F (V )− F j (V + ∆ V )
j
=− r j
∆V
d F j
=r j
dV
PACKED BED REACTOR
The principal difference between
reactor design calculations
involving homogeneous reactions
and those involving fluid-solid
heterogeneous reactions is that for
the latter, the reaction rate is based
on mass of solid catalyst, W, rather
than on reactor volume, V.
For a fluid-solid heterogeneous system, the rate of reaction of a
substance A is defined as
′ g . mole A reacted
−r A=
g . catalyst . sec
The derivation of the design equation for a packed-bed catalytic
reactor will be carried out in a manner analogous to the
development of the tubular design equation. To accomplish this
derivation, simply replace the volume coordinate with the catalyst
weight coordinate W.

As with the PFR, the PBR is assumed to have no radial gradients in

concentration, temperature, or reaction rate. The generalized mole
balance on species A over catalyst weight AW results in the
equation
′
F A ( W ) − F A ( W +∆ W ) +r A ( W ) =0
 ′
F A ( W ) − F A ( W +∆ W ) +r A ( W ) =0
The dimensions of the generation term are:
′ Moles of A Moles of A
r A (W )= ( Mass of Catalyst )=
( time )( Mass of Catalyst ) time

Then
F A (W ) − F A (W + ∆ W ) ′
=−r A
∆W
The term in brackets resembles the definition of the derivative

lim
∆ x →0 [ f ( x+ ∆ x ) − f ( x )
∆ x
=¿
df
dx
¿
]
Then
d FA ′
− =− r A
dW
Or
d F A ′
=r A
dW
Use differential form of design equation for catalyst decay and
pressure drop.
When pressure drop through the reactor (see Section 4.4) and
catalyst decay are neglected, the integral form of the packed-
catalyst - bed design equation can be used to calculate the catalyst
weight.
F A
d F
W =∫
A
′
F A0
r A
PROBLEM 1
The first-order reaction A→B is carried out in a tubular reactor in
which the volumetric flow rate, 𝜐, is constant.
(a) Derive an equation relating the reactor volume to the entering
and exiting concentrations of A, the rate constant k, and the
volumetric flow rate 𝜐.
(b) Determine the reactor volume necessary to reduce the exiting
concentration to 10% of the entering concentration when the
volumetric flow rate is 10 (i.e., liters/min) and the specific reaction
rate, k, is 0.23 .
Solution
Part (a)

For a tubular reactor, the mole balance on species A is shown to

be

For a first-order reaction, the rate law is

Then
The flowrate of specie A can be written in terms of volumetric
flowrate and concentration as

Then eq. (A) becomes

Since the volumetric flowrate is constant

Or
Rearranging it we get

Using the conditions at the entrance of the reactor that when V =

0, then CA = CA0,

This gives
Part (b)
From data provided in question

Substituting all these values in eq. (B)

We have

𝟑 𝟑
𝐕 =𝟏𝟎𝟎 𝐝𝐦 =𝟏𝟎𝟎 𝐋=𝟎 . 𝟏 𝐦
PROBLEM 2
(a) Calculate the volume of a CSTR for the conditions used to
calculate the plug-flow reactor volume in previous problem.
(b) Calculate the time to reduce the number of moles of A to 1 % of
its initial value in a constant-volume batch reactor for the reaction
and data in previous problem.
PROBLEM 3
What is the difference between the rate of reaction for a
homogeneous system, -rA, and the rate of reaction for a
heterogeneous system, -rA’?
Use the mole balance to derive an equation for a fluidized CSTR
containing catalyst particles in terms of the catalyst weight, W and
other appropriate terms.
PROBLEM 4
The first-order reaction A→B is to be carried out isothermally in a
continuous-flow reactor.
Calculate both the CSTR and PFR reactor volumes necessary to
consume 99% of A (i.e., ) when the entering molar flow rate is 5
mol/h, assuming the reaction rate is:
(a)
(b)
(c)
The entering volumetric flowrate is 10 for a constant volumetric
flowrate , then .
Also
Solution

Part (a)

CSTR
The mole balance equation of continuous flow reactor is

Substituting the values, we get

𝟑
𝐕=𝟗𝟗𝐝𝐦
PFR
The mole balance equation of continuous flow reactor is

or

Rearranging and integrating it at boundary conditions, we get

We get

Substituting the values, we get

𝟑
𝐕=𝟗𝟗 𝐝𝐦
Part (b)
CSTR
The mole balance equation of continuous flow reactor is

As we know that , the above equation becomes

or
Substituting the values, we get

𝟑
𝐕=𝟐𝟕𝟓𝟎𝐝𝐦
PFR
The mole balance equation of continuous flow reactor is

As we know that , the above equation becomes

Rearranging and integrating it at boundary conditions, we get

CA V
υ  0 d CA
− ∫
k C CA
=∫ dV
A0 0
We get

Substituting the values, we have

𝟑 𝟑
𝐕=𝟏𝟐𝟕. 𝟗 𝐝𝐦 =𝟏𝟐𝟖 𝐝𝐦
Part (b)

CSTR
The mole balance equation of continuous flow reactor is

As we know that , the above equation becomes

or
Substituting the values, we get

or

𝟑
𝐕=𝟔𝟔, 𝟎𝟎𝟎𝐝𝐦
PFR
The mole balance equation of continuous flow reactor is

As we know that , the above equation becomes

Rearranging and integrating it at boundary conditions, we get

CA V
υ  0 d CA
− ∫
k C CA 2
=∫ dV
A0 0
We get

Substituting the values, we have

Or

𝟑
𝐕=𝟔𝟔𝟎𝐝𝐦
 PROBLEM 5
The gas phase reaction A→B+C is to be carried out isothermally in
a 20 constant-volume batch reactor. Twenty moles of pure A is
initially placed in the reactor. The reactor is well mixed
(a) If the reaction is first order:

Calculate the time necessary to reduce the number of moles of A in

the reactor to 0.2 mol.
(b) If the reaction is second order:

Calculate the time necessary to consume 19.0 mol of A.

(c) If the temperature is 127 °C, what is the initial total pressure?
What is the final total pressure assuming the reaction goes to
completion? Use gas constant with a value of 0.082 .