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Lecture 1
Lecturer : 郭修伯
Syllabus
• Fundamentals of CRE • Non-ideal reactors
– Ideal reactor types and • Catalysis and catalytic
design equations reactors
• Interpretation of rate • External diffusion effects
data on heterogeneous
• Non-elementary reactions
homogeneous reactions • Diffusion and reaction in
• Non-isothermal reactors porous catalysts
• Multiple reactions • Residence time
distributions
What is Chemical Reaction Engineering (CRE) ?
Products
Raw Separation Chemical Separation
material Process process Process By products
CRE is the synthesis of all these factors with the aim of properly designing
and understanding the chemical reactor.
J. Wood at Bham Univ.
Text book and Recommended Books
• Elements of Reaction Engineering, 4th Edition.
H.Scott Fogler, Prentice Hall.
• Chemical Reaction Engineering, 3rd Edition. Octave
Levenspiel, John Wiley and Sons.
• Reactor Design for Chemical Engineers. J.M.
Winterbottom and M.B. King
Fundamentals
• Ideal Reactors :
– Perfectly mixed batch reactor (Batch)
– Continuous stirred tank reactor (CSTR) or Backmix reactor
– Plug flow reactor (PFR)
– Packed bed reactor (PBR)
• Chemical kinetics
– All reactions are presented as being homogeneous reactions.
• Multiple reactors
• Isothermal ideal Batch, CSTR, and PFR
Chemical reaction
• A detectable number of molecules of one or more species
have lost their identity and assumed a new form by a change
in the kind or number of atoms in the compound and/or by a
change in structure or configuration of these atoms.
– Decomposition
– Combination
– Isomerization
• Rate of reaction
– How fast a number of moles of one chemical species are being
consumed to form another chemical species.
Rate law for rj
• rA = the rate of formation of species A per unit volume [e.g.,
mol/dm3-s]
• -rA = the rate of a disappearance of species A per unit volume
• Rate law for rj is a function of concentration, temperature,
pressure, and the type of catalyst (if any)
• Rate law for rj is independent of the type of reaction system
(batch, plug flow, etc.)
• Rate law for rj is an algebraic equation, not a differential
equation
Ideal Reactor Types
• It has neither inflow nor outflow of reactants or
products which the reaction is being carried out.
• Perfectly mixed
• No variation in the rate of reaction throughout
the reactor volume
BATCH
Batch Reactor
• All reactants are supplied to the reactor at the outset. The reactor
is sealed and the reaction is performed. No addition of reactants
or removal of products during the reaction.
• Vessel is kept perfectly mixed. This means that there will be
uniform concentrations. Composition changes with time.
• The temperature will also be uniform throughout the reactor -
however, it may change with time.
• Generally used for small scale processes, e.g. Fine chemical and
pharmaceutical manufacturing.
• Low capital cost. But high labour costs.
• Multipurpose, therefore allowing variable product specification.
Example of a liquid phase batch reaction.
Sodium hydroxide + ethyl acetate = sodium acetate + ethanol
NaOH CH3COOC2H5
C2H5OH
CH3COONa
and
Unreacted NaOH
CH3COOC2H5
Typical Laboratory Glass
Batch Reactor
Typical Laboratory High
Pressure Batch Reactor
(Autoclave)
Typical Commercial Batch Reactor
Ideal Reactor Types
• Normally run at steady state.
• Quite well mixed
• Generally modelled as having no spatial
variations in cencentration, temperature, or
reaction rate throughout the vessel
FA0
(CA0) •Usually employed for
liquid phase reactions.
N.B.
In the case of a gas phase reaction, the pressure history of the reaction
must be noted in case the number of moles change during the reaction.
e.g. A B + C
dN i 1
ri S = interfacial area
dt S
(d) Based on unit mass of solid in fluid-solid reactor
dN i 1
ri ' W = mass of catalyst
dt W
Conversion
• Conversion is defined to answer the questions:
– How can we quantify how far a reaction has progressed?
– How many moles of product C are formed for every mole
reactant A consumed?
• The conversion XA is the number of moles of A that
have reacted per mole of A fed to the system:
moles of A reacted
XA
moles of A fed
Design equations for the ideal reactors:
dN j
Fj0 Fj Gj
dt
V
r dV
j
Fj0 Fj
Gj
System volume
Mole Balance - Batch Reactor
• No material enters or leaves the reactor.
• If composition in uniform (i.e. perfect mixing) -
material balance can be written over whole reactor.
• No flow in or out of reactor. Terms (1) and (2) = 0.
V
dN j
rj dV rjV V = Reactor volume, but really refers
dt to the volume of fluid in reactor.
N A1dN A
dt
dN A t1
N A0 r V
rAV A
Rate of accumulation of A,
[moles/time]
dN A
Where NA = moles of A in system
dt
dN A dX A
N A0
dt dt
Rate of disappearance of A,
[moles/time]
Rate of disappearance = (-rA) Vr where (-rA) = moles A reacting / (unit volume) (time)
Vr = Reactor volume, but really refers to the
volume of fluid in reactor.
dX A dX A
N A0 (rA )Vr N A0 (rA )Vr
dt dt
N A0
If system is constant volume, then C A0 Where CA0 is the initial concentration of A (mol/m3)
Vr
XA
dX A
Integrating the equation gives the design equation for the batch reactor t C A0 (rA )
0
Mole Balance - CSTR
CSTR (at steady state) - NO ACCUMULATION.
Accumulation = Input - Output + Generation by reaction
V
0 = Fj0 - Fj + r dV
j
No spatial variation:
r jV
Fj 0 Fj 0 C A 0 C A
0 F j 0 F j rjV V
rj rA
Mole Balance - CSTR
CSTR (at steady state) - NO ACCUMULATION.
FA = FA0 (1-XA)
FA0 XA = (-rA) Vr
FA0 = FA + (-rA)Vr
Vr XA
FA0 (rA )
Mole Balance – tubular reactor
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
Fj Fj dF j
Fj V Fj V V rj V 0 V V V
rj rj
V dV
dFA
FA
V
FA 0 r
A
Mole Balance - PFR
dVr
CA0 CAf
FA FA+dFA
FA0 FAf
XA XA+dXA
XA0= 0 XAf
INPUT OUTPUT
Input of A, moles/time = FA Output of A, moles/time = FA + dFA
Conversion of A = XA Conversion of A = XA + dXA
- dFA = (-rA)dVr
dVr dX A
FA0 (rA )
XA
Vr dX A
F A0
(rA )
0
Some issues
• Molar flow rates
Liquid phase FA0 C A0v0
PA0 y A0 P0 y A0 P0
Gas phase C A0 FA0 v0
RT0 RT0 RT0
• Space time
– Time necessary to process one reactor volume of fluid based
on entrance conditions
– Also called the holding time or mean residence time
V
v0
Some issues
• Space velocity
v0 1
SV SV
V
– Liquid-hourly space velocity (LHSV) v0 liquid @ 60 F or 75 F
LHSV
V
V
Factors Involved in Reactor Design
• Feedstock composition • Reactor type
– Single feedstock – Batch / continuous
– Reactant in a solvent – Semi batch / Semi continuous
– Multi-component feedstock
– Isothermal, non-isothermal,
• Scale of process adiabatic
– output of product – Single pass / recycle
• Process kinetics – Multiple reactors
– Effect of composition • Others
(concentration)
– Effect of temperature – Materials of construction
– Catalyst – instrumentation
– Thermodynamics – safety
Mole balances on 4 common reactors
Reactor Mole Balance Comment
dN j No spatial variation
Batch r jV
dt
F j0 F j
CSTR V No spatial variation,
rj
steady state
dF Steady state
PFR j
rj
dV
dF
PBR j
r j Steady state
dW
Design equations
• Batch:
– The conversion is a function of the time the
reactants spend in the reactor.
– We are interested in determining how long to leave
the reactants in the reactor to achieve a certain
conversion X.
dX
N A0 rAV
dt ?
?
Design equations
• CSTR:
– We are interested in determining the size of the
reactor to achieve a certain conversion X.
X
FA0 rA
V ? -1/rA
?
X
Design equations
• PFR:
– We are interested in determining the size of the
reactor to achieve a certain conversion X.
dX
FA0 rA
dV ?
?
-1/rA PBR
dX
Generally, the isothermal tubular reactor volume FA0 rA
is smaller than the CSTR for the same conversion dW
X
What is the relationship between X and rA ?
v C A0
V ln
k CA
dX
PFR design equation FA0 rA
dV
(b) Next, shade the area in Figure 2-2 that would give the PFR volume
necessary to achieve 80% conversion.
PFR design equation
dX
FA0 rA
dV
(c) Sketch the profile of –rA and X down the length of the reactor
For X=0.2, the corresponding reactor volume:
Example 2-4 From example 2-2 & 2-3, to achieve a conversion of 80% with
the entering molar flow rate FA0 = 0.4 mol/s and the same feed conditions,
The CSTR volume was 6.4 m3 and the PFR volume was 2.165 m3
For isothermal reactions greater than zero order, the CSTR volume will usually be greater
than the PFR volume for the same conversion and reaction conditions (temperature, flow
rate, etc.)
Example 2-5 For the two CSTRs in series, 40% conversion is achieved in
the first reactor. What is the volume of each of the two reactors necessary to
achieve 80% overall conversion of the entering species A?
(a) CSTR design equation
Example 2-6 calculate the reactor volumes V1 and V2 for the plug-flow
sequence when the intermediate conversion is 40% and the final
conversion is 80%. The entering molar flow rate is the same as in the
previous example, 0.4 mol/s.