Reactors1 9

CSTRs are used for the saponification of fats and for suspension and emulsion
polymerizations. Gas-liquid mixers are used for the oxidation of cyclohexane. Gas
homogeneous CSTRs are extremely rare.
ADVANTAGES-DISADVANTAGES. The advantages for CSTRs include (1) steady-

state operation, (2) back mixing of heat generated by exothermic reactions, which
increases the reaction rate and subsequent reactor performance, (3) avoidance of reactor
hot spots for highly exothermic reactions, making temperature easier to control, (4)
favoring lower-order reactions in parallel reaction schemes, (5) economical operation
when large volumes require high contact time, and (6) enhancement of heat transfer by
mixing.
For the kinetics of decreasing rate with increasing conversion (most reactions),
isothermal CSTRs have lower product composition than plug flow reactors. Additional
disadvantages of CSTR are that larger reactor volumes are usually required, compared
with other reactor schemes, and that energy for agitation is required in the tank,
increasing operating costs .
D. PLUG FLOW
DESCRIPTION. This reactor has continuous input and output of material through a
tube. Assumptions made for the plug flow reactor (PFR) are (1) material passes through
the reactor in incremental slices (each slice is perfectly mixed radially but has no forward
or backward mixing between slices; each slice can be envisioned as a miniature CSTR),
(2) composition and conversion vary with residence time and can be correlated with
reactor volume or reactor length, and (3) the reactor operates at steady state.
The PFR can be imagined as a tube, but not all tubular reactors respond as PFRs. The
assumptions need to be verified with experimental data.
CLASSIFICATION. The plug flow reactor is the second primary type of ideal flow
reactor. It is also erroneously referred to as a tubular reactor.
DESIGN PARAMETERS. The parameters for PFRs include space time, concentration,
volumetric flow rate, and volume. This reactor follows an integral reaction expression
identical to the batch reactor except that space time has been substituted for reaction
time. In the plug flow reactor, concentration can be envisioned as having a profile down
the reactor. Conversion and concentration can be directly related to the reactor length,
which in turn corresponds to reactor volume.
APPLICATIONS. For normal reaction kinetics the plug flow reactor is smaller than the
continuous-stirred tank reactor under similar conditions. This gives the PFR an
advantage over CSTR for most reactions. These conditions are best met for short
residence times where velocity profiles in the tubes can be maintained in the turbulent
flow regime. In an empty tube this requires high flow rates; for packed columns the flow
rates need not be as high. Noncatalytic reactions performed in PFRs include high-
pressure polymerization of ethylene and naphtha conversion to ethylene. A gas-liquid
noncatalytic PFR is used for adipinic nitrile production. A gas-solid PFR is a packed-bed
reactor (Section IV). An example of a noncatalytic gas-solid PFR is the convertor for
steel production. Catalytic PFRs are used for sulfur dioxide combustion and ammonia
synthesis.
ADVANTAGES-DISADVANTAGES. The advantages of a PFR include (1) steady

state operation, (2) minimum back mixing of product so that concentration remains
higher than in a CSTR for normal reaction kinetics, (3) minimum reactor volume in
comparison with CSTR (since each incremental slice of the reactor looks like an
individual CSTR, we can operate at an infinite number of points along the rate curve), (4)
application of heat transfer in only those sections of the reactor where it is needed
(allowing for temperature profiles to be generated down the reactor), and (5) no
requirement for agitation and baffling.
The plug flow reactor is more complex than the continuous-stirred tank alternative with
regard to operating conditions. There are a few other disadvantages associated with the
PFR. For the kinetics where rate increases with conversion (rare), an isothermal plug
flow reactor has lower product composition than a CSTR. For highly viscous reactants,
problems can develop due to high-pressure drop through the tubes and unusual flow
profiles.
E. FLUIDIZED BED
DESCRIPTION. Fluidization occurs when a fluid is passed upward through a bed of fine
solids. At low flow rates the gases or liquids channel around the packed bed of solids,
and the bed pressure drop changes linearly with flow rate. At higher flow rates the force
of the gas or liquid is sufficient to lift the bed, and a bubbling action is observed. During
normal operation of a fluidized bed the solid particles take on the appearance of a boiling
fluid. The reactor configuration is usually a vertical column. The fluidized solid may be
either a reactant, a catalyst, or an inert. The solid may be considered well mixed, while
the fluid passing up through the bed may be either plug flow or well mixed depending on
the flow conditions. Bubble size is critical to the efficiency of a fluidized bed. [See
FLUIDIZED BED COMBUSTION.]
CLASSIFICATION. Fluidized reactors are the fifth type of primary reactor

configuration. There is some debate as to whether or not the fluidized bed deserves
distinction into this classification since operation of the bed can be approximated with
combined models of the CSTR and the PFR. However, most models developed for
fluidized beds have parameters that do not appear in any of the other primary reactor
expressions .
DESIGN PARAMETERS. In addition to the usual reactor design parameters, height of

the fluidized bed is controlled by the gas contact time, solids retention time, bubble size,
particle size, and bubble velocity.
APPLICATIONS. Fluidized beds are used for both catalytic and noncatalytic reactions.
In the catalytic category, there are fluidized catalytic crackers of petroleum, acrylonitrile
production from propylene and ammonia, and the chlorination of olefins to alkyl
chlorides. Noncatalytic reactions include fluidized combustion of coal and calcination of
lime.
ADVANTAGES-DISADVANTAGES The fluidized bed allows for even heat

distribution throughout the bed, thereby reducing the hot spots that can be observed in
fixed-bed reactors. The small particle sizes used in the bed allow high surface area per
unit mass for improved heat and mass transfer characteristics. The fluidized
configuration of the bed allows catalyst removal for regeneration without disturbing the
operation of the bed. This is particularly advantageous for a catalyst that requires
frequent regeneration.
Several disadvantages are associated with the fluidized bed. The equipment tends to be
large, gas velocities must be controlled to reduce particle blowout, deterioration of the
equipment by abrasion occurs, and improper bed operation with large bubble sizes can
drastically reduce conversion.
III. Generalized Reactor Design
Design of a chemical reactor starts with a knowledge of the chemical reactions that take
place in the reactor. The ultimate product of the design is the reactor and the supporting
equipment such as piping, valves, control systems, heat exchangers, and mixers. The
reactor must have sufficient volume to handle the capacity required and to allow time for
the reaction to reach a predetermined level of conversion or yield.
A. APPROACH, CONSIDERATIONS, AND METHODS
1. Use of the Reaction Coordinate or Molar Extent of Reaction
In chemical reactor design, an understanding of the reactions and mechanisms involved is

required before a reactor can be built. In general, this means the chemical reaction
equilibrium thermodynamics must be known before the reactor is even conceptualized.
Any chemical reaction can be written as
aA + bB + ... = rR + sS + ...
where A and B are the reactants, R and S the products, and a, b, r, s are defined as the
stoichiometric coefficients. In general, these stoichiometric coefficients are given a value
of vi (stoichiometric numbers). An arbitrary sign convention is given to the
stoichiometric numbers to make them consistent with thermodynamics: positive signs for
products, negative signs for reactants.
An example for the reaction of methane with ethylene to give butane plus hydrogen is
written as
2 CH4 + C2H4 → C4H10 + H2

Here the stoichiometric number of methane is -2, ethylene -1, butane +1, and hydrogen
+1. If we look at the change in the number of moles of one component, there is a direct
relationship between stoichiometry and the change in the number of moles of any other
component.
∆N 1 N2 ∆N i
= =L=
v1 v2 vi
For a differential amount
dN 1 dN 2 dN
= = L = i = dε
v1 v2 vi
where ε is the reaction coordinate or molar extent of reaction.

Note that
dN i
≡ dε (i = 1, 2, ..., n )
vi
This equation, with the boundary conditions.
N = N i0 for ε = 0
N = Ni for ε = ε
on integration gives
N i = N i 0 + v i ε (i = 1, 2 , ..., n )
The reaction coordinate provides a relationship between the initial number of moles
Ni0, the reaction coordinate ε, and the number of moles Ni at any point or stage in the
reaction Since the units of the stoichiometric numbers vi are dimensionless, the reaction
coordinate has the same units as Ni (for example, mol, kg mol, or kg mol/sec).
Example. For the gas phase reaction,
2A + B = R + S
seven moles of A are reacted with four moles of B in a batch reactor. A gas-mixture
analysis after reaction showed the final mixture contained 20 mol% R. Calculate the
mole fractions of the other components.
Knowns:

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CSTRs are used for the saponification of fats and for suspension and emulsion

ADVANTAGES-DISADVANTAGES. The advantages for CSTRs include (1) steady-

ADVANTAGES-DISADVANTAGES. The advantages of a PFR include (1) steady

CLASSIFICATION. Fluidized reactors are the fifth type of primary reactor

DESIGN PARAMETERS. In addition to the usual reactor design parameters, height of

ADVANTAGES-DISADVANTAGES The fluidized bed allows for even heat

III. Generalized Reactor Design

A. APPROACH, CONSIDERATIONS, AND METHODS

1. Use of the Reaction Coordinate or Molar Extent of Reaction

In chemical reactor design, an understanding of the reactions and mechanisms involved is

2 CH4 + C2H4 → C4H10 + H2

For a differential amount

where ε is the reaction coordinate or molar extent of reaction.

This equation, with the boundary conditions.

Example. For the gas phase reaction,

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