Chapter 1 PDF

Dr.
Shaker Haji, University of Bahrain 2/19/2012
CHEMICAL REACTOR DESIGN

CHENG 323 Dr Shaker Haji
What are the Core Subjects of Chemical

Engineering?
CHENG 323 1
Dr. Shaker Haji, University of Bahrain 2/19/2012
What Does Chemical Reaction Engineering

Involve?
3
Chemical kinetics is the study of chemical reaction

rates and mechanisms.
The study of chemical reaction engineering (CRE)

combines the study of chemical kinetics with the design
of the reactors in which the reaction occur.
It is primary the knowledge of chemical kinetics &

reactor design that distinguishes the chemical
engineer from other engineers.
What Does Chemical Engineering Thermodynamics

Involve?
4
Calculations of heat and work requirements for physical

and chemical processes.
Determination of equilibrium compositions/conditions in

cases of:
chemical reactions
transfer of chemical species between phases
CHENG 323 2
What Thermodynamics Cannot Predict?
1. Thermodynamic consideration do not establish the rates

of chemical and physical processes.
Rates depend on:
driving force
Thermodynamics tells you where the ball would stop, but does not tell you how fast
resistance does it reach there. You need transport phenomena/chemical kinetic sciences to
determine how long you need to wait or how big your equipment should be to reach
equilibrium or where you want to be.
Although driving forces are thermodynamic variables,

resistances are not.
2. Neither can thermodynamics, reveal the microscopic
mechanisms of physical and chemical processes.
What each science enables you to know?

same material, same mass, insulated container.
6
T0=50oC T0=100oC Tf=75oC Tf=75oC
after infinite time
Thermodynamics Tfinal = Tequilibrium = 75oC
Heat Transfer It takes 3 minutes to reach this

temperature
CHENG 323 3
What each science enables you to know?
7
Batch Reactor Charged with A, B, & C
A + B C A + B C
1 mole 1.5 mole 0.1 mole 0.3 mole 0.8 mole 0.8 mole
yA0=0.38 yB0=0.58 yC0=0.04 yA=0.16 yB=0.42 yC=0.42
after infinite time

Thermodynamics Final/equilibrium composition is:
yA= 0.16, yB= 0.42, & yC=0.42;
equilibrium conversion of A is 70%.
Chemical Kinetics It takes 10 minutes to reach this

equilibrium composition/conversion.
1 Mole Balances
CHENG 323 4
In this Chapter
9
Introduction
Definitions
General Mole Balance Equation
Batch, CSTR, PFR, PBR
Chemical Reaction Engineering

10
Chemical reaction engineering is at the heart of virtually

every chemical process.
Industries that draw heavily on Chemical Reaction
Engineering (CRE) are called CPI (Chemical Process
Industries).
Examples of CPI?
GPIC; SABIC: Ibn Sina, Yansab, Ibn Rushd;
Dow; DuPont; Shell; Chevron; Bapco
CHENG 323 5
Areas of Applications
11
In addition to the more traditional areas of the

manufacturing of chemicals & pharmaceuticals, the
Chemical Reaction Engineering (CRE) principles can also
be applied in areas such as
waste treatment
microelectronics
nanoparticles
living systems
12
CHENG 323 6
Materials on the Web and CDROM

13
http://www.engin.umich.edu/~cre CD-ROM
Lets Begin CRE

14
Chemical Reaction Engineering (CRE) is the field that

studies the rates and mechanisms of chemical
reactions and the design of the reactors in which
they take place.
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Chemical Identity
15
A chemical species is said to have reacted when it

has lost its chemical identity.
The identity of a chemical species is determined

by the
kind,
Number, &
Configuration
of that species atoms.
Chemical Identity
16
A chemical species is said to have reacted when it

has lost its chemical identity.
There are three basic ways a species may lose its
chemical identity:
1. Decomposition
2. Combination
3. Isomerization
CHENG 323 8
Reaction Rate
17
During a chemical reaction, some species are

consumed while others are generated.
In this classical approach to chemical change, it is

assumed that the total mass is neither created no
destroyed.
Reaction Rate
18
The reaction rate is the rate at which a species

looses its chemical identity per unit volume.
The rate of a reaction (mol/dm3/s) can be
expressed as either
the rate of Disappearance (Consumption): rA

or as
the rate of Formation (Generation): rA
CHENG 323 9
Reaction Rate
19
Consider the isomerization AB
rA = the rate of formation of species A per unit volume
-rA = the rate of a disappearance of species A per unit volume
rB = the rate of formation of species B per unit volume
Reaction Rate
20
EXAMPLE: AB
If Species B is being formed at a rate of
0.2 moles per decimeter cubed per second, ie,
rB = 0.2 mole/dm3/s
CHENG 323 10
Reaction Rate
21
EXAMPLE: AB
rB = 0.2 mole/dm3/s
Then A is disappearing at the same rate:

rA= 0.2 mole/dm3/s
The rate of formation (generation of A) is

rA= 0.2 mole/dm3/s
Reaction Rate
22
The reaction rate is the rate at which a species looses

its chemical identity per unit volume (mol/dm3/s).
For a catalytic reaction, we refer to rA', which is the

rate of disappearance of species A on a per mass of
catalyst basis (mol/gcat/s).
The heterogeneous reaction rate can also be

expressed on a per catalyst surface area, where it is
referred to as rA" (mol/m2/s).
CHENG 323 11
Mathematical Definition of Reaction Rate

23
The mathematical definition of a chemical reaction rate

has been a source of confusion in the literature.
The confusion stems from laboratory bench-scale
experiments that were carried out, in batch reactors, to
obtain reaction rate data.
The reactants were mixed together at t = 0 & the
concentration of one of the 1.2
1
reactants, CA, was measured at
0.8
CA, mole/l
various times t. 0.6
0.4
0.2
0
0 20 40 60 80
t, second
Mathematical Definition of Reaction Rate

24
The rate of reaction was determined from the slope of a

plot of CA vs. t.
Therefore, the reaction rate was reported as:
This definition is wrong! dCA/dt is not the rate of reaction.
It is simply the mole balance for a constant volume batch
system. 1.2
It does not apply to any continuous 1
0.8
flow reactor operated at steady
CA, mole/l
0.6
state (e.g. CSTR where CA f(t)) 0.4
0.2
0
0 20 40 60 80
t, second
CHENG 323 12
Reaction Rate
25
Consider species j:
rj is the rate of formation of species j per unit volume
rj is a function of concentration, temperature, pressure,
and the type of catalyst (if any)
rj is independent of the type of reaction system
(batch, plug flow, etc.)
rj is an algebraic equation, not a differential equation
For example for A B, the reaction rate could be:
or or
1.2 The General Mole Balance Equation

26
Perform a mole balance on species j in the system volume

shown below:
-r = f (V)
Note: j
If all the system variable (e.g. T, Cj, P, cat activity) are

spatially uniform throught the system volume then Gj = rj.V.
However this is not the case, i.e. rj = f (V).
In Out + Generation = Accumulation
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General Mole Balance

27
V
dN A
Fj 0 Fj r j dV
0
dt
From this general mole balance equation we can develop

the design equations for the various types of industrial
reactors: batch, semibatch, & continuous-flow.
Upon evaluation of these equations we can determine the
time (batch) or reactor volume (continuous-flow) necessary
to convert a specified amount of reactants to products.
1.3 Batch Reactors

28
A batch reactor has neither inflow nor

outflow of reactants or products while
a reaction is being carried out.
The reaction takes place during that
time.
A typical batch reactor consists of a
tank with an agitator and integral
heating/cooling system.
CHENG 323 14
1.3 Batch Reactors

29
In the batch reactor, it is assumed that the reaction

mixture is perfectly mixed.
Therefore, there is no variation in the rate of reaction
throughout the reactor volume.
Mixing patterns in a batch reactor or CSRT

[Encyclopedia of Equipment]
1.3 Batch Reactors

30
A batch reactor is used for:

Small-scale operation
Testing new processes that have not been fully developed
Processes that are difficult to convert to continuous operations
Manufacturing expensive products
Batch reactor symbol [wiki]
CHENG 323 15
1.3 Batch Reactors

31
Advantages of batch reactors

High conversions through leaving the reaction mixture in the
reactor for long periods of time.
Disadvantages of batch reactor:

High labor costs per batch
The variability of products from batch to batch
Difficulty of large scale production
Batch reactor symbol [wiki]
1.3 Batch Reactors

32
Starting from the general mole balance

equation, derive the batch reactor mole
balance.
design equation of
batch reactor.
CHENG 323 16
1.3 Batch Reactors

33
Starting from the batch reactor mole balance, find the time,
t1, necessary to reduce the initial number of moles of A
from NA0 to a final desired number NA1.
AB
Differential form of batch
reactor mole balance
Integral form of batch

reactor mole balance
How Long the RXN Takes?

34
CDP1-A:
A 200-L constant-volume batch reactor is pressurized to 20
atm with a mixture of 75% A and 25% inert. The gas-
phase reaction is carried out isothermally at 227oC.
Assuming that the ideal gas law is valid, how many moles of
A are in the reactor initially? What is the initial
concentration of A? (R = 0.08206 L.atm/mol.K)
If the reaction is first order, rA=kCA with k = 0.1 min1,
calculate the time necessary to consume 99% of A.
NA0 = 73.1 mol, CA0 = 0.365M, t = 46 min
CHENG 323 17
1.4 Continuous-Flow Reactors

35
Continuous flow reactors are almost always

operated at steady state.
We will consider three type:
Continuous Stirred Tank Reactor (CSTR)
Plug Flow Reactor (PFR)
Packed Bed Reactor (PBR)
1.4.1 Continuous-Stirred Tank Reactor

36
CSTR is used primarily for liquid

phase reactions and is normally
operated at steady state.
It is assumed to be perfectly mixed. CSTR symbol [wiki]
Therefore, T & Cj are the same at the

exit point as they are elsewhere in the
tank.
CHENG 323 18

37
Starting from the general mole balance

equation, derive the CSTR mole balance
equation.
CSTR mole balance equation.
The CSTR design equation gives the reactor volume V

necessary to reduce the entering flow rate of species j, from
Fj0 to the exit flow rate Fj, when species j is disappearing at
a rate of rj.

38
The molar flow rate of FA can be written in

terms of CA & as: FA C A
Hence the design equation can be rewritten as:
CHENG 323 19
1.4.2 Plug Flow Tubular Reactor

39
Tubular Reactor consists of cylindrical pipes

and is normally operated at steady state.
It is used most often for gas-phase
reactions.
In the tubular reactor, the

reactants are continually
consumed as they flow down
the length of the reactor and
hence the reaction rate varies
axially (except for the zero-
order reaction)

40
The fluid flow through the tubular reactor may be modeled as

a flow of a series of infinitely thin coherent "plugs", each with
a uniform composition.
The plugs are viewed to be traveling in the axial direction of
the reactor, with each plug having a different composition
from the ones before and after it.
The key assumption is that as a
plug flows through a PFR, the
fluid is perfectly mixed in the
radial direction but not in the
axial direction (forwards or
backwards). Schematic diagram of a Plug Flow
Reactor (PFR) [wiki]
CHENG 323 20

41
Each plug of differential volume is considered as a separate

entity, effectively an infinitesimally small batch reactor,
limiting to zero volume.
Plugs of reactants are continuously

fed into the reactor.
Schematic diagram of a Plug Flow

Reactor (PFR) [wiki]

42
As the plug flows down the reactor the reaction takes place,
resulting in an axial concentration gradient.
Operation of a PFR & the reactants & products concentration profile [Encyclopedia of Equipment]
CHENG 323 21

43
PFR can also be viewed and modeled as large number of

CSTRs in series.
Every segment, which is small, can be viewed as a CSTR.
Why?

44
GMBE
The PFR design equation can be derived from the GMBE
in two ways:
1. By differentiating the GMBE with respect to volume, V
2. From a mole balance on species j (e.g. A) in a

differential segment of the reactor volume V
The V is chosen sufficiently small such
that there are no spatial variation in
reaction rate within this volume.
CHENG 323 22

45
dFA
Differential form of PFR
rA
mole balance dV
Find the volume, V1, necessary to reduce the entering

molar flow rate from FA0 to the exit molar flow rate of FA.
FA dF A
V
FA 0 rA
Integral form of PFR

mole balance

46
dFA
Differential form of PFR rA
mole balance dV
CHENG 323 23
1.4.2 Packed-Bed Reactor

47
PBR
The fluid-solid heterogeneous rxns take place on the surface

of the catalyst.
Consequently, the rxn rate is based on mass of solid catalyst,
W, rather than on reactor volume, V.
The rate of rxn of a substance A is, therefore, defined as:
The mass of solid catalyst is used because the amount of the

catalyst is what is important to the rate of product formation.
48
CHENG 323 24
1.4.2 Packed-Bed Reactor

49
PBR
FA0 FA rdW dNdt

A
A
FA dFA
The integral form to find the catalyst weight is: W
FA 0 rA
How Large is the Reactor?

50
Example 1-1:
Consider the liquid phase cis trans isomerization of 2-butene shown
above which can be written symbolically as AB.
The first order (-rA = kCA) rxn is carried out in a tubular reactor in
which the volumetric flow rate, , is constant.
1. Derive an equation relating V to CA0, CA, , & k.

2. Determine the reactor volume necessary to reduce CA to 10%
of CA0 when the is 10 L/min and the specific rate constant,
k, is 0.23 min-1. C
V 0
ln A0 100 L
k CA
CHENG 323 25
How Large is the Reactor?

51
Problem 1-6:
For the same conditions & requirements of Example 1-1 (PFR),
calculate the volume of a CSTR.
Which volume is larger, the PFR or the CSTR? Explain why.
1.5 Industrial Reactors

52
Be sure to view actual photographs of industrial

reactors on the CD-ROM and on the Web site.
CHENG 323 26
1.5.1 Liquid-Phase Reactions

53
Semibatch reactors and CSTRs are used primarily for liquid-

phase rxns.
A semibatch reactor has essentially the same disadvantages as
the batch reactor.
However, it has the advantages of:
- T control by regulation of the feed rate
- the capability of minimizing unwanted side rxns through the
maintenance of a low conc. of one of the reactants.
The semibatch reactor is also used for two-phase rxns in which

a gas usually is bubbled continuously through the liquid.
1.5.1 Liquid-Phase Reactions

54
A CSTR is used when intense agitation is required.
CHENG 323 27
The CSTR can either be used by itself or as part of a series or

battery of CSTRs.
Advantage: Easy to maintain good T control with a CSTR; why?

Because it is well mixed.
Disadvantage: The concentration of reactant per volume of
reactor is the smallest of the flow reactors. So?
So, very large reactors are necessary to obtain high conversion.
If you are not able to afford to purchase a new reactor, it may
55
be possible to find a used reactor that may fit your needs.
1.5.2 Gas-Phase Reactions

56
The tubular reactor is relatively easy to maintain (no moving

parts).
It usually produces the highest conversion per reactor volume
of any of the flow reactors.
The disadvantage of the tubular reactor is that it is difficult to
control T within the reactor & hot spots can occur when the rxn
is exothermic.
Most homogeneous liquid-phase flow reactors are CSTRs,
whereas most homogeneous gas-phase flow reactors are
tubular.
CHENG 323 28
1.5.2 Gas-Phase Reactions

57
The tubular reactor is commonly found either in the form of

one long rube or as one of a number of shorter reactors
arranged in a tube bank.
www.hydrocarbonprocessing.com
http://www.stamixco-usa.com/
The cost of PFRs and PBRs (without catalyst) are similar to the
costs of heat exchangers.
A packed-bed (also called a fixed-bed) reactor is essentially
a tubular reactor that is packed with solid catalyst particles.
58
Fixed Bed Reactor, by GERHART EIGENBERGER
CHENG 323 29
This heterogeneous reaction system

is most often used to catalyze gas
reactions.
Disadvantages:
This reactor has the same
difficulties with T control as the
other tubular reactors.
The catalyst is usually troublesome to replace.
Channeling of the gas flow occurs, resulting in ineffective use
of part of the reactor bed.
Advantage of the packed-bed reactor:

For most reactions PBR gives the highest conversion per
59
weight of catalyst of any catalytic reactor.
Another type of catalytic reactor in common use is the

Fluidized-bed reactor.
The fluidized-bed reactor is analogous to the CSTR in that its
contents, though heterogeneous, are well mixed.
60 D. Kunii and O. Levenspiel, Fluidization Engineering
CHENG 323 30
The fluidized-bed reactor is analogous to the CSTR in that its

contents, though heterogeneous, are well mixed.
Which results in an even T distribution throughout the bed, thus
avoiding hot spots.
The fluidized-bed reactor can only be approximately modeled
as a CSTR; for higher precision it requires a model of its own.
This type of reactor can handle large amounts of feed & solids
and has good T control; thus it is used in a large number of
applications.
Advantages: the ease of catalyst replacement or regeneration.
61
The advantages of the ease of catalyst replacement or

regeneration are sometimes offset by the high cost of the
reactor and catalyst regeneration equipment.
62
Bapcos
Fluidized-Bed Catalytic Reactor Fluidized Catalytic Cracking Unit, FCCU
CHENG 323 31
63
In this chapter, and on the CD-ROM, we've introduced each

of the major types of industrial reactors: batch, semibatch,
stirred tank, tubuIar, fixed bed (packed bed), and fluidized
bed.
Many variations and modifications of these commercial
reactors are in current use.
64
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Dr.

Shaker Haji, University of Bahrain 2/19/2012

CHEMICAL REACTOR DESIGN

What are the Core Subjects of Chemical

What Does Chemical Reaction Engineering

Chemical kinetics is the study of chemical reaction

The study of chemical reaction engineering (CRE)

It is primary the knowledge of chemical kinetics &

What Does Chemical Engineering Thermodynamics

Calculations of heat and work requirements for physical

Determination of equilibrium compositions/conditions in

What Thermodynamics Cannot Predict?

1. Thermodynamic consideration do not establish the rates

Although driving forces are thermodynamic variables,

What each science enables you to know?

T0=50oC T0=100oC Tf=75oC Tf=75oC

after infinite time

Thermodynamics Tfinal = Tequilibrium = 75oC

Heat Transfer It takes 3 minutes to reach this

What each science enables you to know?

after infinite time

Chemical Kinetics It takes 10 minutes to reach this

Chemical Reaction Engineering

Chemical reaction engineering is at the heart of virtually

In addition to the more traditional areas of the

Materials on the Web and CDROM

Lets Begin CRE

Chemical Reaction Engineering (CRE) is the field that

A chemical species is said to have reacted when it

The identity of a chemical species is determined

of that species atoms.

A chemical species is said to have reacted when it

During a chemical reaction, some species are

In this classical approach to chemical change, it is

The reaction rate is the rate at which a species

the rate of Disappearance (Consumption): rA

Consider the isomerization AB

rA = the rate of formation of species A per unit volume

-rA = the rate of a disappearance of species A per unit volume

rB = the rate of formation of species B per unit volume

Then A is disappearing at the same rate:

The rate of formation (generation of A) is

The reaction rate is the rate at which a species looses

For a catalytic reaction, we refer to rA', which is the

The heterogeneous reaction rate can also be

Mathematical Definition of Reaction Rate

The mathematical definition of a chemical reaction rate

Mathematical Definition of Reaction Rate

The rate of reaction was determined from the slope of a

It does not apply to any continuous 1

state (e.g. CSTR where CA f(t)) 0.4

1.2 The General Mole Balance Equation

Perform a mole balance on species j in the system volume

If all the system variable (e.g. T, Cj, P, cat activity) are

In Out + Generation = Accumulation

General Mole Balance

From this general mole balance equation we can develop

1.3 Batch Reactors

A batch reactor has neither inflow nor