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Chemical Reaction Engineering

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) ?

Understanding how chemical reactors work lies at the heart of almost


every chemical processing operation.

Products
Raw Separation Chemical Separation
material Process process Process By products

Design of the reactor is no routine matter, and many alternatives can be


proposed for a process. Reactor design uses information, knowledge and
experience from a variety of areas - thermodynamics, chemical kinetics,
fluid mechanics, heat and mass transfer, and economics.

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

CONTINUOUS STIRRED TANK REACTOR (CSTR)


BACKMIX REACTOR
Backmixed, Well mixed or CSTR

FA0
(CA0) •Usually employed for
liquid phase reactions.

FA •Use for gas phase usually


CA (CA)
CA in laboratory for kinetic
Vr, g Vr, l studies.
CA
Assumption: Perfect mixing occurs.
Schematic representation of a CSTR ?
Characteristics
• Perfect mixing: the properties of the reaction mixture are
uniform in all parts of the vessel and identical to the properties
of the reaction mixture in the exit stream (i.e. CA, outlet = CA, tank)
• The inlet stream instantaneously mixes with the bulk of the
reactor volume.
• A CSTR reactor is assumed to reach steady state. Therefore
reaction rate is the same at every point, and time independent.
• What reactor volume, Vr , do we take?
– Vr refers to the volume of reactor contents.
– Gas phase: Vr = reactor volume = volume contents
– Liquid phase: Vr = volume contents
Cutaway view of a Pfaudler
CSTR/ Batch Reactor
Ideal Reactor Types
• Normally operated at steady state
• No radial variation in concentration
• Referred to as a plug-flow reactor
• The reactants are continuously consumed as
they flow down the length of the reactor.

PLUG FLOW REACTOR (PFR), TUBULAR REACTOR


PFR, Tubular reactor
• There is a steady movement of materials along the length
of the reactor. No attempt to induce mixing of fluid
element, hence at steady state:
– At a given position, for any cross-section there is no pressure,
temperature or composition change in the radial direction.
– No diffusion from one fluid element to another.
– All fluid element have same residence time.

Used for either gas phase or liquid phase reactions.


The plug flow assumptions tend to hold when there is good radial mixing
(achieved at high flow rates Re >104) and when axial mixing may be
neglected (when the length divided by the diameter of the reactor > 50
(approx.))

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

As the reaction progresses the number of moles increases. Therefore at


constant pressure, fluid velocity must increase as conversion increases.
How can reaction rate be expressed ?
• Select one reaction component for consideration
and define the rate in terms of this component, i.
• If the rate of change in number of moles of this
component due to reaction is dNi/dt, then the
rate of reaction in its various forms is defined as
follows:
(a) Based on unit volume of reaction fluid
dNi 1 Ni : moles of i
ri 
dt V V : volume of fluid
e.g. CSTR (liquid) or Batch reactor (liquid)
(b) Based on unit volume of reactor
dNi 1
ri  Vr = reactor volume
dt Vr
(c) Based on unit interfacial surface area in two-fluid system or based on
per unit surface area of solids in gas-solid systems

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:

based on material balance


A Mole Balance on Species j
(isothermal)
Rate of flow of j Rate of flow of j Rate of generation of Rate of accumulation
into the system out of the system j by chemical rxn of j within the system
[moles/time] [moles/time] within the system [moles/time]
[moles/time]

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.

Rate of accumulation of Rate of generation of reactant A


reactant A in reactor = within by reactor duo to rxn
(4) (3)
V
dN j
dt
  r dV
j
Mole Balance - Batch Reactor

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

Where NA0 is the initial moles


NA = NA0 (1-XA) XA = fractional conversion of A = (NA0-NA)/NA0
dNA = -NA0 dXA NA = moles of A at conversion XA

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.

Accumulation = Input - Output - Disappearance by reaction


0 = FA0 - FA - (-rA)Vr

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

Disappearance of A by reaction, moles/time = (-rA) dVr


Accumulation = Input - Output - Disappearance by reaction
0 = FA - (FA+dFA) - (-rA)dVr

PFR (at steady state) - NO ACCUMULATION.

- dFA = (-rA)dVr

dFA = -FA0 (dXA)

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

– Gas-hourly space velocity (GHSV) v0


GHSV  STP

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 ?

We need only -rA = f (X) and FA0 to design a variety of reactors !


The heart of the design of an ideal reactor:

(-rA) as a function of conversion (concentration, partial pressure etc.)

We will discuss this issue in the later courses.


Reactors in series
• To achieve the same overall conversion, the total -1/rA
volume for two CSTRs in series is less than that
required for one CSTR.
X
• The overall conversion of two PFRs in series is the
-1/rA
same as one PFR with the same total volumn.

• CSTRs in series :A PFR can be modelled using a


X
number of CSTR in series
– useful in modelling catalyst decay in a packed-bed reactor
– modelling transit heat effects in PFRs.
Example Reactor Types
• Noncatalytic homogeneous gas • Ethylene polymerisation
reactor (high pressure)
• Homogeneous liquid reactor • Mass polymerisation of styrene
• Liquid-liquid reactor • Saponification of fats
• Gas-liquid reactor • Nitric acid production
• Non-catalytic gas-solid reactor
– Fixed bed • Iron production
– Fluidised bed • Chlorination of metals
• Fixed bed catalytic reactor • Ammonia synthesis
• Fluid bed catalytic reactor • Catalytic cracking (petroleum)
• Gas-liquid-solid reactor • Hydrodesulphurisation of oils
Battery of two tubular reactors.
Furnaces on the back. Heat exchangers on the front.
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 volumn (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
• Fluidised bed reactor (circulating fluidised bed CFB)
Example 1-1 Consider the liquid phase cis-trans isomerization of 2-
butenewhich we will write symbolically as AB. The first order (-rA=kCA)
reaction is carried out in a tubular reactor in which the volumetric flow rate,
v, is constant, i.e., v=v0. (a) Sketch the concentration profile. (b) Derive an
equation relating the reactor volume to the entering and exiting concentration
of A, the rate constant k, and the volumetric flow rate v.
PFR design equation CA0
dX
FA0  rA
dV
CA
FA0  C A0v
 rA  kCA  kV  0.1CA0
C A  C A0 exp   
d C A0 v X  v  0 V1 V
 kCA
dV
C A  C A0 (1  X ) V  vdCA v C A dC A v C A0
V  dV      ln
0 kCA k A0 C A
C k CA
Determine the reactor volume necessary to reduce the exiting concentration
to 10% of the entering concentration when the volumetric flow rate is 10
dm3/min (i.e., liters/min) and the specific reaction rate, k, is 0.23 min-1.

v C A0
V  ln
k CA

A reactor volume of 0.1m3 is necessary to convert 90% of species


A entering into product B for the parameter given.
Example 2-2 The reaction AB described by the data in Table 2-2 is to
be carried out in a CSTR. Species A enters the reactor at a molar flow
rate of 0.4 mol/s. (a) Using the data in Table 2-2, calculate the volume
necessary to achieve 80% conversion in a CSTR.

(a) CSTR design equation


(b) Shade the area in Figure 2-2 that would give the CSTR volume
necessary to achieve 80% conversion.

CSTR design equation


Example 2-3 The reaction described by the data in Table is to be carried
out in a PFR. The entering molar flow rate of A is 0.4 mol/s. (a) determine
the PFR reactor volume necessary to achieve 80% conversion.

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.

PFR design equation


dX
FA0  rA
dV
Example 2-7 The isomerization of butane:nC4H10iC4H10 was carried
out adiabatically in the liquid phase. The reactor scheme shown in Figure
E2-7.1 is used. Calculate the volume of each of the reactors for an entering
molar flow rate of n-butane of 50 kmol/hr.