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Lecture 1 –
Introduction
Definitions
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Chemical Reaction Engineering
Chemical reaction engineering is at the heart of
virtually every chemical process. It separates the
chemical engineer from other engineers.
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Smog (Ch. 1)
Wetlands (Ch. 7 DVD-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:
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Reaction Rate
The reaction rate is the rate at which a species looses
its chemical identity per unit volume.
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Reaction Rate
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
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Reaction Rate
EXAMPLE: AB
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
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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)
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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
Fj0 Gj Fj
V1
V2
rj1
rj 2
G j1 rj1V1
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 rjiVi r dV
j
i1 lim V 0 n
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Building Block 1:
General Mole Balances
System
Volume, V
FA0 GA FA
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L2-20
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
L2-21
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
L2-22
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
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
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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
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L2-35
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
FA0 FA
dN j
Fj0 - Fj + rjV =
dt
dN j Divide by V
Fj Fj rj V Fj Fj rjV 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 ΔV0
FA V V FA V
lim rA
V 0 V
dFA
rA
dV
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
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L2-45
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
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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
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
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 AB)
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
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W
Separations
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Reaction Engineering
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Heat Effects
Isothermal Design
Stoichiometry
Rate Laws
Mole Balance
CRE Algorithm
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Mole Balance Rate Laws
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Heat Effects
Isothermal Design
Stoichiometry
Rate Laws
Mole Balance