SKKK 3223

Chemical Reaction Engineering

CHAPTER 1
Mole Balances

Mohd Asmadi
Assoc. BinMukhlis
Prof. Dr Mohammed Yussuf
A Rahman
Faculty of Chemical
FACULTY Engineering
OF ENGINEERING
Universiti
SCHOOL Teknologi Malaysia,
OF CHEMICAL 81310 UTM
ENGINEERING
UNIVERSITI
Johor, JohorTEKNOLOGI MALAYSIA
Bahru, Malaysia

Chemical Reaction Engineering Group, Universiti Teknologi Malaysia

 Contents
Learning Outcomes

General mole balance equation

Batch reactor

Continuous-stirred tank reactor (CSTR)

Plug-flow reactor (PFR)

Packed-bed reactor (PBR)

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 Learning Outcomes

Week Topic Learning Outcome

1 Rate Law & Mole Balances It is expected that students are able to:

• Basic definitions • Write rate law, define reaction order

and activation energy for elementary
• General mole balance reactions.
equation
• Define the rate of chemical reaction for
• Batch, continuous and basic chemical reactor.
industrial reactors
• Write the mole balance equation to a
batch reactor, CSTR, PFR, and PBR.

• Describe reactors used in industries.

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General Mole Balance Equation

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General Mole Balance Equation
System volume, V

G
Fin Fout

[Rate flow in] + [Generation] – [Rate flow out]=[accumulation]

Unit: moles/time

dN
Fin + G - Fout =
dt
moles/time moles/time moles/time moles/time

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 General Mole Balance Equation
If the system is uniform throughout its entire volume, then:

Gj = rjVj

moles/time moles/(time.volume) volume

Generally, the rate of reaction varies

from point to point in the reactor:

V
G j = ò rjdV

The general mole balance equation:

dN
Fin + ò r.dV - Fout =
dt
From here, design equation
for different types of the
moles moles moles moles
.volume reactors can be developed.
time time.volume time time
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 GENERAL MOLE BALANCE
Fj0 Fj
Gj

System volume
Rate of flow Rate of flow Rate of Rate of
of j into - of j out of + generation of j by - decomposition = Rate of
system system chemical rxn of j accumulation

dNj
Fj0 - Fj + Gj =
dt
æ mol ö æ mol ö æ mol ö d
ç s ÷ ç s ÷ ç s ÷ (mol)
è ø è ø è ø dt

If the system is uniform throughout its entire volume, then:

Gj = ( rj ) ( V )
Moles j generated Moles generated per
per unit time (mol/s) = unit time and volume Volume
(mol/s•m3) (m3)
 Fj0 Fj
Gj

System volume

In - Out + Generation = Accumulation

dNj
Fj0 - F j +G j =
dt
ti on dNj
ua
ee
q Fj0 - F j +rj V = uniform rate in V
l anc dt
ba
ol e
ral
m V dNj
ne Fj0 - F j + ò rjdV = nonuniform rate in V
Ge dt

Next: Apply general mole balance equation to ideal batch, CSTR, & PFR reactors
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 Types of Reactors
Depending on loading/unloading of the reactor

Batch Semi-batch Continuous flow

Continuous stirred tank reactor (CSTR)

Plug flow reactor (PFR)/ Tubular

Packed bed reactor (PBR)

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Types of Reactors (Cont.)
Continuous Flow

Batch CSTR

Continuous Flow Continuous Flow

catalyst

Tubular/Plug Flow
Packed bed
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Batch Reactor
• Reactants are placed in the reactor,
and the reaction is allowed to proceed
for some amount of time
• Closed system- no addition of reactants
or removal of products during the
reaction
• Unsteady-state conditions- the
composition changes with time
• Ideal batch reactor- vessel is perfectly
mixed
• Concentration and temperature are
spatially constant, but NOT constant in
TIME
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 Examples of Batch Reactor

Lab-Scale Typical Commercial Batch

Batch Reactor Reactor

Motor for agitation

Pfaudler’s Batch reactor

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 Batch Reactor

For small-scale operation.

Testing new processes.
Manufacturing expensive products.
Processes difficult to convert to
continuous operation.

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 Basic Mole Balance for Batch Reactor

No flow in
In - Out + Generation = Accumulation
or out! V
dN j

X X
Fj0 F j 0 - F j + ò r j dV =
Fj dt

0 0
V dN j Batch Reactor Design
® ò rjdV = Equation
dt

If the reactor is perfectly mixed, the temperature, concentration, &

therefore the reaction rate are spatially constant:
Ideal Batch Reactor dNj NA0 dNA
Design Equation rj V = or t1 = ò
dt
NA1 - rA V
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Continuous Flow Reactors

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1. Continuous-stirred Tank Reactor

Laboratory-Scale Bioreactor

Pfaudler’s CSTR reactor

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1. Continuous Stirred Tank Reactor (CSTR)
• Continuously add reactants and
remove products (open system)
• Inlet stream instantaneously mixes
with bulk of reactor volume
• Ideal batch reactor- assume perfect
mixing occurs in vessel
• Temperature and concentration
are uniform throughout space
• Composition of the exit stream
is the same as that inside
reactor (CA,outlet = CA, tank)
• Steady-state conditions- the reaction
rate is the same at every point and
does not change with time

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 Basic Mole Balance for CSTR
In - Out + Generation = Accumulation Fj0 Fj
V
dN j CSTR is at steady state (SS), so
F j 0 - F j + ò r j dV = no change in moles j with time!
dt
0
V Steady State CSTR
® Fj -F j + ò rjdV = 0 Design Equation
0

A perfectly mixed CSTR has no spatial variations in reaction rate

® Fj -F j +rj V = 0 Rearrange to put in terms of V
0

Fj 0 -F j
rj is measured at the outlet = V Ideal Steady State
because Cj,exit = Cj,tank - rj CSTR Design Equation

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 Ideal SS CSTR Design Equation
Fj -F j
V= 0
- rj
Reactor volume required to reduce the entering flow rate of species j
from Fj0 to Fj at the outlet (and in the tank)

How do we determine the molar flow rate, Fj (units = mol/time)?

Fj = ( C j ) (u )
moles j æ moles öæ volume ö
=ç ÷ç ÷
time è volume øè time ø
Cj: concentration of j u: volumetric flow rate

Ideal SS CSTR design equation in terms of concentration:

C j0 u - C j u
V=
-rj

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Continuous-stirred Tank Reactor

V dN j
Fj0 - Fj + ò ridV =
dt

=0, operation in a steady mode

Assuming perfect mixing, so

Ø Reaction rate is the same through the volume.
Ø Conditions of exit stream are the same as in the reactor.

Fj0 - Fj v jC j0 - vC j
Fj0 - Fj = -rj V V= or
- rj - rj

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2. Plugged Flow Reactor (PFR)
• Also called a tubular reactor
• Cylindrical pipe with openings at
both ends
• Steady movement of material
down length of reactor
• Reactants are consumed as they
flow down the length of the
reactor
• Operated at steady state:
• No radial variation in
temperature, concentration,
or reaction rate
• All fluid/gas elements have
the same residence time

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2. Tubular /Plugged Flow Reactor

Usually operates in steady state

Primarily used for gas reactions
Easy to maintain, no moving parts
Produce highest yield
Temperature could be difficult to
control, hot spots might occur

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 Industrial PFRs

Polyethylene reactor:
• 16 inch inner diameter
• Operates at 35,000 psi & 600 °F
• Has a vertical orientation when in use

Courtesy of Autoclave Engineers of Snap-tite, Inc.

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2. Tubular /Plugged Flow Reactor

No radial variations in velocity,

concentration temperature, or reaction rate

Reactants Products

Reaction continuously progresses along the length of the

reactor, so the concentration and consequently the reaction rate
varies in axial direction.

In the model of PFR the velocity is considered uniform and there

are no variation of concentration (and reaction rate) in the radial
direction.

If it cannot be neglected we have a model of Laminar Flow Reactor.

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2. Tubular /Plugged Flow Reactor

No radial variations in velocity,

concentration temperature, or reaction rate

Reactants Products

V dN j
Fj0 - Fj + ò rjdV =
dt
No accumulation 0

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 Basic mole balance for PFR
In a plug flow reactor the composition of the fluid varies from point to point along a
flow path. Consequently, the material balance for a reaction component must be
made for a differential element of volume ΔV
ΔV

Fj0 Fj
dN j
Fj0 - Fj + r j DV =
dt
dNj
Fj - Fj + rj DV = ® Fj - Fj + rjDV = 0
V V +DV dt V V + DV Divide by DV
DV
0
Fj - Fj Fj V + DV -Fj V dFj
® V V +DV + rj = 0 ® = rj lim = rj
DV DV DV→0 dV
If we assume the PFR is ideal, the degree of completion is not Ideal SS PFR
affected by PFR shape, only by PFR volume Design Eq.
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 Design Equation for PFR
For every slice of volume:

Fj|V + ΔV - Fj|V dFj

Fj0 - Fj + ri DV = 0 ri = ri =
ΔV dV

From here, a volume required to produce given molar flow rate of

product can be determined.

dFj dFj Fj dFj Fj0 dFj

rj = dV = V=ò =ò
dV rj Fj0 rj Fj - rj

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3. Packed Bed Reactors (PBR)
• Cylindrical shell, vertically oriented
• Often gravity-driven flow
• Heterogeneous reaction: fixed bed of catalyst
inside
• Reactants enter top and flow through the packed
bed of catalyst
• Concentration gradient of reactant and product
down the length of the reactor
• Reaction occurs on the surface of the catalyst
pellets
• Reaction rate is based on the mass of the solid
catalyst, W, not reactor volume V

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3. Packed-bed Reactor (PBR)

Here the reaction takes place on

the surface of catalyst.

Reaction rate defined per unit

area (or mass) of catalyst.

–rA = mol A reacted/ s. g catalyst

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3. Packed-bed Reactor (PBR)

W – catalyst weight coordinate

As in the PFR case, we can calculate design equation now in terms

of catalyst weight coordinate.

FA|W - FA|W+ DW ' dFA

FA|W - FA|W + DW + ri DW = 0 ri = rA =
DW dW

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 Basic mole balance for PBR

dFj Similar to PFR, but we want to express it in terms of catalyst

= rj weight instead of reactor volume
dV
Units for the rate of a mol Units for the rate of a mol
homogeneous rxn (rj) : s × m3 catalytic rxn (rj’) : s × kg catalyst

So rewriting the PFR design equation in terms of catalyst weight

instead of reactor volume:
dF j The integral form to find the catalyst weight is:
= rj '
dW dFA
FA
where W is the weight W=ò
FA 0 rA¢
of the catalyst The catalyst weight necessary to reduce the
entering molar flow rate, Fj0 to a flow rate Fj

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 Packed Bed Reactor (PBR) Mole Balance

ò rA¢ dW =
dNA
PBR: FA0 - FA +
dt

The integral form to find the catalyst weight is:

dFA
FA
W=ò
FA 0 rA¢

The catalyst weight necessary to reduce the

entering molar flow rate, FA0 to a flow rate FA

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Reactor Mole Balance: Summary

Mole Balance Algebraic Integral

Reactor Comment
Differential Form Form Form
Batch •No spatial variations
dNA NA0 dNA
•Fin = Fout =0 = rA V t1 = ò
•V = constant dt NA1 - rA V

CSTR •No spatial variations

•Well mixed - const. FA0 - FA
C, T, rxn rate. ― V= ―
•No accumulation - rA
•Steady state
PFR •Steady state dFA FA0 dFA
= rA V1 = ò
dV FA1 - rA
PBR •Steady state dFA FA0 dFA
= rA' W1 = ò
dW FA1 - rA'

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 Selection of Reactors
Batch
• small scale
• production of expensive products (e.g. pharmacy)
• high labor costs per batch
• difficult for large-scale production

CSTR: most homogeneous liquid-phase flow reactors

• when intense agitation is required
• relatively easy to maintain good temperature control
• the conversion of reactant per volume of reactor is the smallest of the
flow reactors - very large reactors are necessary to obtain high
conversions

PFR: most homogeneous gas-phase flow reactors

• relatively easy to maintain
• usually produces the highest conversion per reactor volume (weight of
catalyst if it is a packed-bed catalyze gas reaction) of any of the flow
reactors
• difficult to control temperature within the reactor
• hot spots can occur Chemical Reaction Engineering Group, Universiti Teknologi Malaysia
 Tutorial 1
The reaction
A →B
Is to be carried out isothermally in a continuous-flow reactor.
Calculate both CSTR and PFR reactor volume necessary to consume
99% of A (i.e., CA = 0.01CA0) when the entering molar flow rate is 5
mol/h, assuming the reaction rate –rA is:
(a) –rA = k with k = 0.05 mol/h.dm3
(b) –rA = kCA with k = 0.0001 s-1
(c) –rA = kCA2 with k = 3 dm3/mol.h
The entering volumetric flow rate is 10 dm3/h.
[Note: FA = CAν. For a constant volumetric flow rate v = v0, then FA = CAν0.
Also, CA0 = FA0 /ν0 = (5 mol/h)(10 dm3/h) = 0.5 mol/dm3.]

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