Topic 1:

Reaction and Reactor Fundamentals

Outline:
1. Introduction

2. Type of Reactors: Batch, Continuous

3. Definition of Rate of Reaction, - rA

4. The General Mole Balance Equation

5. Mole Balances for

I. Batch Reactor
II. Continuous Stirred Tank Reactor (CSTR)
III. Plug Flow (Tubular) Reactor (PFR)
IV. Packed Bed Reactor (PBR)

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Reaction & Reactor Fundamentals Introduction

The Place of Reactor Design in Chemical Engineering

Physical Chemical Physical

Raw treatment treatment Products
Reactions
materials steps steps

Recycle
Typical chemical process

Chemical treatment steps are carried out in chemical reactors.

Reactor design based on information, knowledge and experience from a

variety of areas:
Thermodynamics Heat Transfer
Chemical kinetics Mass Transfer
Fluid Mechanics Economics

Knowledge of chemical kinetics and reactors design distinguishes the

chemical engineer from both chemists and other engineers
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Reaction & Reactor Fundamentals Introduction

Types of Reactors
Batch Reactors

Description
Reactants are charged into the vessel, react for a
specific period of time. Products are discharged after
the reaction.

Applicability
Relatively Small Scale (a few thousands of tons per
year)
Advantages Disadvantages
High Flexibility High demands in manpower
Low Cross- Lower efficiency of services
contamination (heating & cooling)
Short Period for Complicated automatic
Reactor Start-up control

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Reaction & Reactor Fundamentals Introduction

Types of Reactors
Reactants
Continuous
Continuous Reactors Stirred Tank
Reactor
Products
Description (CSTR)

Reactants flow continuously into the vessel, and

products flow continuously out of the reactor

Applicability
Large Tonnage Production (tens or hundreds of
thousands tons per year)

Advantages Disadvantages Tubular or

Steady-State Long Start-up Plug Reactor
Operation Flow
High cost of halting
Lower demands in operation
manpower
Low flexibility
Easy automatic
control
Efficient services
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Reaction & Reactor Fundamentals Introduction

Reactor Technology Revolution

Microreactor Technology (MRT)
Description
MRT or microstructured reactor is an advanced
continuous process based plug flow reactor in which
chemical reactions take place in a microchannel (100
500 m).
Microchannel in a
Applicability microreactor
Suitable or KILOGRAM-SCALE SYNTHESES in continuous
mode (reduce production area from 100 to 1000 times).

Advantages
Higher yield and selectivity
Inherently safer processes
Straight forward scaling up
Continuous production possible
Improved reactor control
Enables numerous chemical synthesis MIcroreactor
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Reaction & Reactor Fundamentals Introduction

Plug flow microreactor

Example:

Catalytic microreactor for partial oxidation of methane

to carbon monoxide and hydrogen.
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Reaction & Reactor Fundamentals Definition of rate of reaction

Definition of rate of reaction

(Homogeneous reaction systems) Consider the reaction: A B

Rate of reaction, - rA, is the rate of disappearance of species A per unit volume or
it is the number of moles of species A reacted per unit time per unit volume

Rate of reaction, rB, is the rate of formation of species B per unit volume or it is the
number of moles of species B formed per unit time per unit volume
- r A = rB Units: moles
volume time
Definition of rate of reaction
Consider the reaction: A B
(Heterogeneous reaction systems)
over a catalyst

Rate of reaction, - rA, is the number of moles of species A reacted per unit time per
unit mass of catalyst (or per unit surface area of catalyst), (or per unit volume of
catalyst)
- rA = rB
Units:
moles moles moles
mass catalyst time surface area catalyst time volume catalyst time 7
Reaction & Reactor Fundamentals Definition of rate of reaction

Source of confusion Consider the reaction: A B

A Constant volume batch reactor
C
dC A B
rA
dt
A

Time
CH3COOC2H5 + NaOH CH3COONa + C2H5OH
Perfect mixing and steady-state operation
result in identical concentration of each
NaOH CH3COOC2H5 species in any point:
dCA
0 Wrong for continuous
C2H5OH dt systems
CH3COONa
unreacted: In flow system the differential form :
CH3COOC2H5 dC A
NaOH rA
dt
does not represent the rate of reaction
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Reaction & Reactor Fundamentals The rate law

The chemical reaction rate:

An intensive quantity
Depends on the properties of the reacting materials (concentration, temperature,
pressure, type of catalysts) at a point in the system
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:

k1C A
rA kCA rA kC A2 rA The rate law
1 k 2C A

The reaction rate is essentially an algebraic equation involving

concentration, not a differential equation.

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Reaction & Reactor Fundamentals Mole Balance

General Mole Balance Equation

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 volume is defined as the volume enclosed by physical boundaries
of the reactor. System
Volume

Fj0 Gj Fj

Focus on species which are able to 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
rate of flow rate of flow rate of accumulation
of j into of j by chemical of j out of j within
reaction within
the system the system the system
the system
(moles / time) (moles / time) (moles / time) (moles / time)

in + generation out = accumulation
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Reaction & Reactor Fundamentals Mole Balance

General Mole Balance

rate of generation
rate of flow rate of flow rate of accumulation
of j into of j by chemical
reaction within of j out of j within
the system the system the system
the system
( moles / time) (moles / time) ( moles / time) ( moles / time)

in + generation out = accumulation

dN j
Fj 0 G j Fj (1)
dt

If all the system variables are spatially uniform throughout the system volume, the
rate of generation of species j, Gj:
(2)
G j rj V
moles moles
volume
time volume time
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Reaction & Reactor Fundamentals Mole Balance

General Mole Balance

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
dependant on the location within the system volume.
V Consider indefinitely small volumes, Vi,
V1
so that the rate of reaction
rj1 V2 rj1 in V1; rj2 in V2 rji in Vi

Using equation (2):

rj2
G ji r ji Vi (3)

Total rate of generation within the system Returning to the equation of mole
divided into M sub-volumes : balance (1):
M M
G j G ji r ji Vi (4) V
dN j
i 1 i 1 F j 0 F j r j dV (6)
Let M and V0: 0
dt
V
G j r j dV (5) General Mole Balance Equation
12
0
Reaction & Reactor Fundamentals Mole Balance (Batch Reactor)

Mole Balance for Batch Reactors

A batch reactor has neither inflow nor outflow of reactant or products in the
course of reaction
V
dN j
F j 0 F j r j dV
0
dt

General mole balance on species j:

V
dN j
r j dV (7)
dt 0

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

dN j
r jV (8)
dt
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Reaction & Reactor Fundamentals Mole Balance (Batch Reactor)

Mole Balance for Batch Reactors NA

NA0
Consider the reaction: A B dN A
rAV
dt
Question:
NA1
Time, t1 necessary to reduce the initial number of moles
t
from NA0 to a final desired number NA1? t1

dN A (8)
rAV
dt
Rearranging, dN A
dt
rAV
Integrating with limits at t=0, then NA=NA0, and t=t1, then NA=NA1,

Time, t1 necessary to reduce the number of moles from NA0 to NA1 is:
N A0
dN A
t
rV
N A1 A
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Reaction & Reactor Fundamentals Mole Balance (Batch Reactor)

Batch Reactor
Constant Volume or Constant Pressure: dN A
rAV
Does it make a difference? dt

Consider the reaction:

(CH3)2O CH4 + H2 + CO
A M + H + C
dN A 1 dN A
Constant volume Constant pressure rAV rA
dt V dt
Perfectly mixed No spatial variation of rate

Constant-volume batch reactor

1 dN A d ( N A / V ) dCA
rA
Constant-pressure batch reactor V dt dt dt
N A C AV
1 dN A 1 d (C AV ) dCA C A dV dCA C Ad (lnV )
rA rA
V dt V dt dt V dt dt dt 15
Reaction & Reactor Fundamentals Mole Balance (CSTR)

Mole Balance for CSTR

The CSTR is a well mixed reactor operated continuously
Reactants There are no spatial variations in concentration,
temperature, or reaction rate throughout the tank
V
dN j
Products
F j 0 F j r j dV
0
dt

CSTR are operated at steady state: Using equations (9) and (10):
dN j
0 (9) Fj 0 Fj Vrj 0 (11)
dt
and rj = const Design equation for a CSTR

Fj0 Fj
V

r j dV Vr j
(12)
(10) V
0 rj

The molar flow rate Fj is just the product of concentration Fj C j v

of species j and the volumetric flow rate v moles moles volume

time volume time 16
Reaction & Reactor Fundamentals Mole Balance (PFR)

Mole Balance for Tubular Reactors V

dN j
Tubular reactors consist of a cylindrical pipe and are F j 0 F j r j dV dt
normally operated at steady state 0

General mole balance for the

F V F,
subvolume:
j0 j exit
F j (V ) F j (V V ) r j V 0
Fj(V) - the molar flow Fj(V+V) the molar flow
rate of species j into rate of species j out of
(14)
subvolume V the subvolume After rearranging:
Fj(V) V Fj(V+V) F j (V V ) F j (V )
rj (15)
Highly turbulent flow V
No radial variations in taking the limit as V0
concentrations F j (V V ) F j (V ) dFj
lim (16)
Model of a plug-flow reactor (PFR) V 0
V dV
In spatially uniform subvolume V: General Mole Balance Equation
V
G j rj dV rj V
Fj
(13) dF j dF j (17)
rj

or
0 dN j
V (18)
- steady state operation: 0
dV rj
Fj0
dt 17
Differential Integral
Reaction & Reactor Fundamentals Mole Balance (PFR)

Mole Balance for Packed-Bed Reactors W

dN j
Packed-Bed Reactors are designed to carry out F j 0 F j r dV
'
j
heterogeneous reaction. 0
dt
W PBR Features
Fj0 W Fj,exit Reactor volume is filled with
catalysts
Reaction kinetics is dependant
W on a quantity of catalyst
moles A
rj'
Fj(W) Fj(W+W) mass of catalyst time
Replacing volume coordinate with the If the limit is W0
catalyst weight coordinate and assuming Differential form of the general mole
that there are no radial gradients in balance for PBR:
concentration, temperature, or reaction dF j
rate: r j (20)
dW
F j (W ) F j (W W ) r jW 0 (19) Integral form of the general mole
balance for PBR: Fj
After rearranging: dF j
F j (W W ) F j (W )
r j
W rj (21)
18
W
Fj 0
Reaction & Reactor Fundamentals Mole Balance

Mole Balance for Different Types of Reactors

Reactor Type Differential Algebraic Integral

NA
dN A dN A
Batch rAV t
dt rV
N A0 A

FA0 FA
CSTR V
rA
FA 0
dFA dFA
PFR
dV
rA V
FA
rA

dFA dFA
FA 0
PBR rA W
F r
dW A
A

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Reaction & Reactor Fundamentals Mole Balance (Example 1-3)

AB

Calculate the time to reduce the number of moles by a factor of

10
N A0
A
N
10

in a batch reactor for the above reaction with

rA kCA , when k 0.046 min 1

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Reaction & Reactor Fundamentals Mole Balance (Example 1-3)

Assume well mixed batch reactor

Mole Balance: N A0 dN A
t
NA rAV
In - Out Generation Accumulation
N A0 dN A
dN A
0 0 rAV NA kN A
dt
1 N A0
Boundary Conditions: ln
k NA
t 0, N A N A0 and t t , N A N A
1 N A0
Rate Law: ln
rA kCA k N A0

NA 10
rA k
ln10
V 1
1
rAV kN A 0.046 min
50 min
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Reaction & Reactor Fundamentals Mole Balance (Example 1-3)

PFR Mole Balance

In Out Generation Accumulation
dN A

FA0 FA rA dV
dt
dN A
Steady State 0
reactants products dt

FA0 FA rA dV 0
Differenti ate with respect to V
This is the volume dFA
necessary to reduce the 0 rA 0
dV
entering molar flow rate
dFA
(mol/s) from FA0 to the rA
exit molar flow of FA. dV
FA dF
V
FA 0 rA
A

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Reaction & Reactor Fundamentals Mole Balance (Example 1-3)

PBR Mole Balance

In Out Generation Accumulation
dN A

FA0 FA r ' A dW
dt
catalysts, W dN A
Steady State 0
reactants products dt

FA0 FA r ' A dW 0
Differenti ate with respect to W
dFA
0 r' A 0
dW
The integral form is to
dFA
find the catalyst weight. r' A
dW
FA dF
W A
FA 0 r ' A

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Reaction & Reactor Fundamentals Mole Balance (Example 1-5)

Reactants Products
AB

The first order rA kCA reaction is carried out in a tubular

reactor at constant volumetric flow rate,

Calculate the reactor volume necessary to reduce the exit

concentration to 10% of the entering concentration when
10dm3 / min and k 0.23min1

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Reaction & Reactor Fundamentals Mole Balance (Example 1-5)

Assume steady state tubular reactor 0 CA dC A

k C A 0 C A
Mole Balance: V

In - Out Generation Accumulation 0 C A0

ln
FA FA0 rA dV 0 k CA
0 C A0
dFA
rA ln
k 0.1C A0
dV
Boundary Conditions: 10dm3 / min
1
ln 10
V 0, C A C A0 and V V , C A 0.1C A 0.23 min
100dm3
Rate Law: rA kCA
Reactor Sizing: r dFA d (C A ) d (C A0 ) dC A
kC A
A 0
dV dV dV dV
0 dC A
dV
k CA
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Reaction & Reactor Fundamentals Mole Balance (Example 1-3)

CSTR Mole Balance

In Out Generation Accumulation
reactants
dN A

FA0 FA rA dV
dt
dN A
Steady State 0
dt
Well mixed r dV r V
A A

FA0 FA rAV 0
F A 0 FA
V
rA
products

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Reaction & Reactor Fundamentals Mole Balance (Example 1-4)

dm 3
10 (3) Stoichiometry
min
F F
CA0 FA = CA CA A A
0
FA0 = CA0 CA = 0.1 CA0
3
(4) Combine
0 CA0 CA
dm
10
min V
kC A
= 0, FA= 0CA
(5) Evaluate
C A 0.1C A0
(1) Mole balance
dm 3
FA0 FA 0CA0 0CA 0 CA0 CA 10 C A0 0.1C A0
V
V
min
rA rA rA

0.23min1 0.1CA0
(2) Rate Law
rA kC A 101 0.1

0.230.1
391dm 3
If FA = 10 mol/min, then CA = 1 mol/dm3
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Nexts Lecture Topic 2
Definition of Conversion X

Design Equations in terms of X

Relative Rate

Reactor Sizing and Reactor in Series

Space Time, Space velocity

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