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Prof Fogler’s Lecture 1- Revised and

Appended with Prof. Kraft's Lectures


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.

1
Lecture 1 –
 Introduction

 Definitions

 General Mole Balance Equation


 Batch (BR)
 Continuous Flow Stirred Tank Reactor (CSTR)
 Plug Flow Reactor (PFR)
 Packed Bed Reactor (PBR)

2
Chemical Reaction Engineering
 Chemical reaction engineering is at the heart of
virtually every chemical process. It separates the
chemical engineer from other engineers.

Industries that Draw Heavily on Chemical


Reaction Engineering (CRE) are:
CPI (Chemical Process Industries)
Examples like Dow, DuPont, Amoco, Chevron

3
Smog (Ch. 1)
Wetlands (Ch. 7 DVD-ROM)

Hippo Digestion (Ch. 2)

Oil Recovery Cobra Bites


(Ch. 7) (Ch. 8 DVD-ROM)

Lubricant Design Plant Safety


4
Chemical Plant for Ethylene Glycol (Ch. 5) (Ch. 9) (Ch. 11,12,13)
Materials on the Web and CD-ROM

http://www.umich.edu/~essen/
http://www.umich.edu/~elements/5e/index.
html

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Chemical Identity and Reactions
 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, and configuration of that
species’ atoms.
 There are three ways for a species to loose its
identity:

1. Decomposition CH3CH3  H2 + H2C=CH2


2. Combination N2 + O2  2 NO
3. Isomerization C2H5CH=CH2  CH2=C(CH3)2

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Reaction Rate
 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 of reactant: -rA
or as
 The rate of Formation (Generation) of product: rP
 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)

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Reaction Rate
Consider the isomerization
AB
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

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Reaction Rate
EXAMPLE: AB
If Species B is being formed at a rate of
0.2 moles per decimeter cubed per second, i.e.,
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

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Reaction Rate
Consider species j:
1. rj is the rate of formation of species j per unit volume
[e.g. mol/dm3s]
2. rj is a function of concentration, temperature,
pressure, and the type of catalyst (if any)
3. rj is independent of the type of reaction system
(batch, plug flow, etc.)
4. rj is an algebraic equation, not a differential equation
(e.g. -rA = kCA or -rA = kCA2)

10
Order of Reaction
• We use an algebraic equation to relate the
rate of reaction, -rA, to the concentration of
reacting species and to the temperature at
which the reaction occurs.
• Order of Reaction
 If -rA = kCA, the reaction is of first order
 If -rA = kCA2, the reaction is of second order
 If -rA = k, then the reaction is of what order?
 Reaction rate constant k is independent of
concentration, but depends on Temperature.
Chemical Reaction Engineering 11
Applications of Various Reactors
 Noncatalytic homogeneous  Ethylene polymerization
gas reactor (high pressure)
 Homogeneous liquid reactor  Mass polymerization of
 Liquid-liquid reactor styrene
 Gas-liquid reactor  Saponification of fats
 Non-catalytic gas-solid  Nitric acid production
reactor  Iron production
• Fixed bed  Chlorination of metals
• Fluidized bed  Ammonia synthesis
 Fixed bed catalytic reactor  Catalytic cracking (petroleum)
 Fluid bed catalytic reactor  Hydrodesulphurization of oils
 Gas-liquid-solid reactor
Types of Reactors
Reactors come in various sizes and
shapes, depending on the application
and scale.
Before attempting to design and analyze
real-life reactors, we analyze ideal
reactors (for homogeneous reactions)
Types of ideal reactors: Batch, CSTR &
PFTR.
Heterogeneous Reactions: Packed and
Fluidized Bed Reactors

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What type of reactor(s) to use?
in
Continuously Stirred
Tank Reactor (CSTR)

out

Plug flow reactor (PFR)


Well-mixed batch reactor
Building Block 1:
General Mole Balances
System
Volume, V

Fj0 Gj Fj

 Molar Flow  Molar Flow   Molar Rate   Molar Rate 


 Rate of    Rate of   Generation    Accumulation
       
 Species j in   Species j out  of Species j  of Species j 
dN j
Fj 0  Fj  Gj 
dt
 mole   mole   mole   mole 
          
 time   time   time   time 
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Building Block 1:
General Mole Balances
If spatially uniform:
G j  r jV

If NOT spatially uniform:

 V1
V2
rj1
rj 2
G j1  rj1V1
G j 2  rj 2 V2

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Building Block 1:
General Mole Balances
n
G j   rji Vi
i 1

Take limit
n
Gj   rjiVi   r dV
j
i1 lim V  0 n  

17
Building Block 1:
General Mole Balances
System
Volume, V

FA0 GA FA

General Mole Balance on System Volume V

In  Out  Generation  Accumulation


dN A
FA 0  FA   rA dV 
dt
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Reactor Types - Batch reactor

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L2-20

Batch Reactors Properties


• 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

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
L2-21

Examples of Batch Reactor


Lab-Scale
Typical Commercial Batch
Batch Reactor
Reactor

Motor for agitation

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
L2-22

Basic Mole Balance for Batch Reactor


No flow in
In - Out + Generation = Accumulation
or out!
V dN j
X X
Fj0 F j Fj F j   rjdV 
0 dt
0 0
V dN j
  rjdV  Batch Reactor
dt Design Equation

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


& therefore the reaction rate are spatially constant:
dN j Ideal Batch Reactor
rj V 
dt Design Equation
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
Ideal Batch Reactor – Features
 It is a well-mixed vessel (perfect mixing is
assumed).
 Reactants are fed into the vessel in the beginning.
 It is a Closed system (No inflow, nor outflow during
reaction).
 Concentration Cj and temperature (T) are
independent of position (Perfect Mixing)
 Cj(t) is a function of time
Reactant
Conc.

Nj

Reactants go in,
Time and you wait….
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Batch Reactor - Applications
 Applications
• Small scale operations
• Testing processes during development
• Expensive products (e.g. pharmaceuticals,
Biotech)
• Processes which are difficult to adapt to
continuous operations
 Advantage
• High conversion can be achieved
 Disadvantages
• High labor costs (setup time…)
• Difficult to use for high volume processing

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Batch Reactor - Mole Balances

Batch

dN A
FA0  FA   rAdV 
dt
FA0  FA  0

Well-Mixed  r dV
A  rAV
dN A
 rAV
25 dt
Batch Reactor - Mole Balances
dN A
Integrating dt 
rAV

t  0 N A  N A0
when
t  t NA  NA

N Ao
dN A
t 
NA
 rAV

Time necessary to reduce the number of moles of A from NA0 to NA.


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Batch Reactor - Mole Balances

NA

27 t
Continuous Stirred Tank Reactor L2-28

(CSTR) Properties
• Continuously add reactants and
remove products (open system)
• Inlet stream instantaneously mixes
with bulk of reactor volume
• Ideal CSTR- 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

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
L2-29

Examples of CSTRs

Laboratory-Scale Bioreactor

Pfaudler Inc.
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
L2-30

Basic Mole Balance for CSTR


Fj0 Fj
In - Out + Generation = Accumulation
V dN j CSTR is at steady state
Fj F j   rjdV  (SS), so no change in
0 dt
moles j with time!
0
V
 Fj F j   rjdV  0 Steady State CSTR
0 Mole Balance

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

rj is measured at Fj F j Ideal Steady


the outlet because
0  V State CSTR
 rj
Cj,exit = Cj,tank Design Equation
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
L2-31

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   
moles j  moles  volume 
  
time  volume  time 
Cj: concentration of j : volumetric flow rate
Ideal SS CSTR design equation in terms of concentration:
C j0   C j 
V
rj
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
Ideal Continuous Stirred Tank Reactor
(CSTR) - Features Products
out
Reactants
in

1. It is a well-mixed vessel (perfect mixing is assumed).


2. Reactants are fed into the vessel continuously and
products are removed continuously.
3. It is an open system (Continuous inflow and outflow
during reaction).
4. Concentration Cj and temperature (T) are independent
of position (Perfect Mixing).
5. Exit conditions are same as conditions within reactor!
i.e. if Cj(t) is the concentration in the reactor, the exit
stream concentration is also Cj(t)!

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CSTR - Applications
 When is it used?
• Usually for liquids
• When intense mixing is necessary
 Advantages
• Easy to maintain
• Good temperature control
 Disadvantages
• Conversion of reactant per unit volume is the lowest
of flow reactors
• Large reactors are necessary to obtain high
conversions

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Plug Flow Reactor (PFR): Battery of 2 Reactors.

Reactors
Furnace

Heat
exchangers

34
L2-35

Plug Flow Reactor (PFR) Properties


• 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

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
L2-36

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.
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
L2-37

Mole Balance – 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

FA0 FA
dN j
Fj0 - Fj + rjV =
dt
dN j Divide by V
Fj  Fj  rj V   Fj  Fj  rjV  0
V V V dt V V  V
V
0
 Fj lim
Fj Fj V  V F dFj
 V V V  r  0 
j V
 r V→0  rj
j j
V V dV
If we assume the PFR is ideal, the degree of completion Ideal SS PFR
is not affected by PFR shape, only by PFR volume Design Eq.
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
Ideal Continuous Plug Flow Tubular
Reactor (PFR or PFTR) - Features
Reactants in Products out

Reactant conc.
1. It is a Tubular Reactor like a
Cylindrical pipe.
2. As reactants flows down the
PFTR, they are mixed in the
radial direction,  Uniform
Volume
conditions in radial direction
3. But mixing does not occur in 5. Concentration Cj varies with
the axial direction. position (Total segregation).
4. Each plug of fluid is  Features 2 &3 of CSTR
considered a separate entity (slide 27) apply to PFTR as
as it flows down the pipe. well.
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PFTR - Applications
 When is it used?
• Usually for gases and for fast reactions
• Dehydrogenation of ethylbenzene for the
production of ethylene.
 Advantages
• Easy to maintain (no moving parts)
• Highest conversion per reactor volume of flow
reactors
 Disadvantages
• Difficult to control temperature
• Reaction rate and therefore temperature vary
along axial direction

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Plug Flow Reactor - Mole Balances
V

FA FA

V V  V
 

 In  Out  Generation
at V       0
  at V  V  in V 
FA V  FA V  V  rA V 0
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Plug Flow Reactor - Mole Balances
Rearrange and take limit as ΔV0

FA V  V  FA V
lim  rA
V 0 V

dFA
 rA
dV

This is the differential form of the General Mole Balance


over a PFR at steady state.

41
Plug Flow Reactor - Mole Balances
PFR

dN A
FA0  FA   rA dV 
dt
dN A
Steady State 0
dt

FA0  FA   rA dV  0
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Alternative Derivation
Plug Flow Reactor - Mole Balances
Differientiate with respect to V

0
dFA
 rA
dFA
 rA
dV dV
FA
dFA
The integral form is: V 
 FA 0
rA

This is the volume necessary to reduce the


entering molar flow rate (mol/s) from FA0 to the
exit molar flow rate of FA.
43
Reactors for Heterogenous
Reactions
Packed bed reactor (PBR)
Fluidized bed (FCC)

44
L2-45

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

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
Packed Bed Reactor - Mole Balances
W
PBR
FA FA

W W  W
 
FA W   FA W  W   rA W 
dN A
dt
Steady State dN A
0
dt
FA W  W  FA W
lim  rA
46
W 0 W
Packed Bed Reactor - Mole Balances
Rearrange:
dFA
 rA
dW
The integral form to find the catalyst weight is:
FA
 dFA
W 
FA 0
rA

PBR catalyst weight necessary to reduce the


entering molar flow rate FA0 to molar flow rate FA.
47
L2-48

Mole Balance- Packed Bed


Reactor (PBR)
dFj Similar to PFR, but we want to express it in terms
 rj
dV of catalyst weight instead of reactor volume

Units for the rate of a mol Units for the rate of mol
homogeneous rxn (rj) : s  m3 a catalytic rxn (rj’) : s  kg catalyst

So rewriting the PFR design equation in terms of catalyst


weight instead of reactor volume:

dFj
 rj ' where W is the weight of the catalyst
dW

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
PBR – Applications
 When is it used?
• Heterogeneous reactions
• E.g.catalytic converter
 Advantages
• Easy to maintain (no moving parts)
• High conversion per mass of catalyst
 Disadvantages
• Difficult to control temperature
• Can get channeling of packed bed
• Catalyst is difficult to replace

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L2-50

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
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
Reactor Mole Balances Summary
The GMBE applied to the four major reactor types
(and the general reaction AB)
Reactor Differential Algebraic Integral
NA
NA
dN A
Batch dN A
 rAV t 
dt rV
N A0 A
t
CSTR FA 0  FA
V
rA FA
FA
PFR dFA V 
dFA
 rA
dV FA 0
drA
V

FA FA
dFA dFA
PBR
 dW
 rA W 
FA 0
rA
51
W
Separations

Filtration Distillation Adsorption

These topics do not build upon one another.

52
Reaction Engineering

Mole Balance Rate Laws Stoichiometry

These topics build upon one another.

53
Heat Effects
Isothermal Design

Stoichiometry
Rate Laws
Mole Balance

CRE Algorithm

54
Mole Balance Rate Laws

Be careful not to cut corners on any of the


CRE building blocks while learning this material!

55
Heat Effects
Isothermal Design

Stoichiometry
Rate Laws

Mole Balance

Otherwise, your Algorithm becomes unstable.


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