H83RED Reactor Design

Topic 4 Mole Balances

Binjie Hu
Dept of Chem & Env Eng
Binjie.Hu@nottingham.edu.cn

Recap
Discuss chemical reactions
Define basic terms required in subsequent
derivations

Source of confusion (1)

Consider the reaction: A B

Constant volume batch reactor

Is this equation always valid?

Time

Constant volume

Source of confusion (2)

CH3COOC2H5 + NaOH CH3COONa + C2H5OH

NaOH

CH3COOC2H5

Perfect mixing and steady-state

operation, therefore result in
identical concentration of each
species in any point:

CH3COONa
C2H5OH

Wrong for continuous system

Unreacted
CH3COOC2H5
NaOH

does not represent the rate of reaction

The rate law

The chemical reaction rate is an intensive quantity and
depends on the properties of the reacting materials
(concentration, temperature, pressure, type of catalysts) at a
point in the system and is independent of the type of
system (i.e. batch or continuous flow) in which the reaction is
carried out.

Consider the reaction:

A products
Different forms of the dependencies of the reaction rate on
concentration:

Outline
Derive general mole balance in an unsteady, open
system
Adopting the general mole balance equation to
derive design equations for

Batch Reactor
Continuous Stirred Tank Reactor
Plug Flow Reactor
Packed Bed Reactor

MOLE BALANCE

General Mole Balance Equation (1)

Main Task of Reactor Design:
To determine the degree of conversion of a
particular reactant, or,
To determine the reactor volume to achieve a
particular conversion.
The system/reactor volume is defined as the
volume enclosed by physical boundaries of the
reactor.
System
volume

Fjo

Gj

Fj

General Mole Balance Equation (2)

Focus on species which participate in a chemical
reaction or are generated as a result of it. Molar
fluxes of such components must be balanced
A mole balance on species j at any instant of time, t:

Rate of generation
of j by chemical
reaction within
the system
(moles / time)

Rate of flow
of j into
the system
(moles / time)

In

generation

Rate of flow
of j out
the system
(moles / time)

out

Rate of accumulation
of j within
the system
(moles / time)

accumulation

 Molar flowrate of species j flowing into the system

Fjo

[moles/time]

Molar flowrate of species j flowing out of the system

Fj

[moles/time]

The rate of generation of species j within the system

Gj

[moles/time]

Number of moles of species j within the system at any time

Nj

[moles/time]

General Mole Balance Equation (3)

Rate of generation
of j by chemical
reaction within
the system
(moles / time)

Rate of flow
of j into
the system
(moles / time)

In

generation

Rate of flow
of j out
the system
(moles / time)

out

Rate of accumulation
of j within
the system
(moles / time)

accumulation

(1)
If all the system variables are spatially uniform throughout the
system volume, the rate of generation of species j, Gj:
(2)

General mole balance (1)

The rate of reaction could vary through the system volume due to
variation of concentration, temperature, etc..
This means that rate of generation of species j is dependent on the
location within the system volume.
Consider indefinitely small volumes, Vi, so that concentration within
them is uniform.

The rate of reaction for species j within the volume Vi at location i, is

rji.
rj1 in V1; rj2 in V2 ... rji in Vi
V

V1
V2

rj1*

Vi
rj2

VM

Using equation (2), the rate of generation of

species j in volume i, Gji is given by:

rji*

rjM*

Gji = rji Vi

(3)

General Mole balance (2)

Total rate of generation of species j within the system divided
into M sub-volumes:
M

i 1

i 1

G j G ji r ji Vi

(3)

Let M and V0

(1)

(4)
Replace Gi in the equation of mole balance (1)

(5)

General Mole
Balance Equation

Mole balance (Batch reactor)

A batch reactor has neither inflow not outflow of
reactant or products in the course of reaction.
General mole balance on species j:

General mole balance on species j:

(7)

If the reaction mixture is perfectly mixed (rj=const)

(8)

Mole balance (Batch reactor)

Consider the reaction: A B
NA

dN j
dt

rjV
A

Batch reactor
Constant volume or Constant pressure:
Does it make a difference?

Time

Mole balance (batch reactor)

Constant volume Constant Pressure

dN j
dt

rjV

Consider the reaction:

(CH3)2O CH4 + H2 + CO
AM+H+C

Perfectly mixed No spatial variation of rate

dC A
rA
dt

Constant-volume batch reactor

Constant-pressure batch reactor

dC A
dt

+C A

( ) =r

d lnV
dt

Mole balance (CSTR)

Reactants

The CSTR is a well mixed reactor operated

continuously. There are no spatial variations in
concentration, temperature, or reaction rate
throughout the tank
Products

CSTR are operated at steady state

except for start-up and shutdown:
(9)

Using equations (9) and (10):

(11)

Design equation for a CSTR

and rj = const
(10)

(12)

Mole Balance (CSTR) contd

Design equation for a CSTR

(12)

The molar flow rate Fj is just the product of concentration

of species j and the volumetric flow rate v

Mole Balance (PFR)

Mole Balance for Tubular Reactors
Tubular flow reactors consist of a cylindrical pipe and are normally operated
at steady state.
V
The molar flow rate
of species j into
subvolume V

Highly turbulent flow

No radial variations in concentration

In spatially uniform subvolume V:

- steady state operation

The molar flow rate

of species j jout of
subvolume V

Model of a plug-flow reactor (PFR)

(13)

General mole balance for the subvolume:

(14)

After rearranging:

(15)

taking the limit as V --> 0

(16)

General Mole Balance Equation

Differential:

(17)

Integral:

V=

Fj

Fjo

dFj
rj

(18)

Mole Balance (PFR)

Mole Balance for Packed-Bed Reactors
Packed-Bed Reactors are designed to carry out heterogeneous reaction.
Reactor volume is filled with catalysts. Reaction kinetics is dependent on
the quantity of the catalyst.
It is assumed that there are no radial gradients in concentration,
temperature, or reaction rate. Furthermore PBR operates at steady state.
W
The molar flow
rate of species j
into subvolume
V

W
W

PBR Features
Reactor volume is filled with catalysts
Reaction kinetics is dependent on the quantity of catalyst

The molar flow

rate of species j
out of
subvolume V

Replacing volume coordinate with the catalyst weight coordinate and

assuming that there are no radial gradients in concentration, temperature,
or reaction rate:
(19)

After rearranging:

If the limit is W0
Differential form of the general mole balance for PBR:

(20)
Integral form of the general mole balance for PBR:

W=

Fj

Fjo

dFj
rj

(21)

Mole Balance for Different Types of

Reactors

Mole Balance (Example 1-3)

The first-order reaction A B is carried out in a
tubular reactor in which the volumetric flow rate, v, is
constant.
Derive an equation relating the reactor volume to
the entering and exiting concentrations of A, the
rate constant k, and the volumetric flow rate v.
Determine the reactor volume necessary to reduce
the exiting concentration to 10% of the entering
concentration when the volumetric flow rate is 10
dm3/min and the specific reaction rate, k, is 0.23
min-1.

Mole Balance (Example P1-3)

Summary
Derive general mole balance in an unsteady, open
system
Adopting the general mole balance equation to
derive design equations for

Batch Reactor
Continuous Stirred Tank Reactor
Plug Flow Reactor
Packed Bed Reactor

30

Homework
Finish reading Chapter 1
1.5 Industrial reactors, pages 16 25
Questions and problems

From P1-1 to P1-14