1.

Catalytic

Reactions that require the presence of a catalyst to obtain the rate conditions necessary
for that particular reactor design.

2. Noncatalytic

Reactions that do not include either a homogeneous or heterogeneous catalyst.

3. Autocatalytic

Reaction scheme whereby one of the products increases the overall rate of reaction.

4. Biological

Reactions that involve living cells (enzymes, bacteria, or yeast), parts of cells, or
products from cells required for the reaction scheme.

5. Polymerization

Reactions that involve formation of molecular chains, whether on a solid support or in

solution.

D. COMBINATION OF TERMS

Any combination of the above classifications can be used to describe a reactor: for
example, a heterogeneous-catalytic-batch reactor.

II. Primary Reactors

There are five primary reactor designs based in theory: batch, semibatch, continuous-
stirred tank, plug flow, and fluidized bed. The operating expressions for these reactors
are derived from material and energy balances, and each represents a specific mode of
operation. Selected reactor configurations are presented in Fig. 1.

A. BATCH

DESCRIPTION. Batch processes are the easiest to understand since they strongly
relate to "cookbook" technology. You put everything in at the beginning and stop the
reaction at some time later. This cookbook technology allows for immediate production
of a new product without extensive knowledge of the reaction kinetics. [See BATCH
PROCESSING (CHEMICAL ENGINEERING) .]
The reactor is characterized by no addition of reactant or removal of product during the
reaction. Any reaction being carried out with this constraint, regardless of any other
reactor characteristic, is considered batch. The assumptions for batch operation are (1)
the contents of the tank are well mixed, (2) reaction does not occur to any appreciable
degree until filling and startup procedures are complete, and (3) the reaction stops when
quenched or emptied. The reactor can be operated with either a homogeneous or
heterogeneous reaction mixture for almost any type of reaction.

CLASSIFICATION. The batch reactor, one of the five primary reactor configurations,
is the oldest reactor scheme.

DESIGN PARAMETERS. The design parameters for a batch reactor can be as simple
as concentration and time for isothermal systems. The number of parameters increases
with each additional complication in the reactor. For example, an additional reactant
requires measurement of a second concentration, a second phase adds parameters, and
variation of the reaction rate with temperature requires additional descriptors: a
frequency factor and an activation energy. These values can be related to the reactor
volume by the equations in Section III.

FIG. 1. Selected reactor configurations: (a) batch, (b) continuous stirred-tank reactor, (c)
plug flow reactor, (d) fluidized bed, (e) packed bed, (f) spray column, and (g) bubble
column.

APPLICATIONS. Application of the batch reactor design equations requires integration

over time. Along with the simplicity of cookbook chemistry, this is one of the major
advantages of the batch reactor: concentrations are not averaged over time. Initially,
when concentrations are at their highest, the corresponding rates of reaction are also high.
This gives the greatest amount of conversion in the shortest time. The integral reactor
design form makes the batch reactor attractive for higher-order reactions. Batch is also
good for reactions in series (if the reaction can be quickly quenched), where large
amounts of an intermediate can be produced quickly before it has time to react away to a
by-product.
The batch reactor is extremely flexible compared with continuous reactor
configurations. For example, temperature can easily be made a function of reaction time.
Once the reactor is put into service, operational alternatives are still available. The tank
can be operated half-full without affecting product quality, or the reaction time can be
modified easily. Both of these changes may cause heat and mass transfer problems in
fixed-volume continuous equipment. This flexibility is worthwhile for products that are
made in various grades, have seasonal demand, or have subjective specifications such as
the taste of beer.
Batch reactors are used extensively in industries where only small quantities of product
are made, such as pharmaceuticals. For small amounts, the economy of scale hurts flow
reactors, which typically have a higher initial investment for controls and plumbing.

ADVANTAGES-DISADVANTAGES. The primary advantages of the batch reactor

are simplicity of design, which allows for tremendous flexibility, and integration of the
performance equation over time. The simplicity of design, usually a stirred tank, makes
operation and monitoring easy for the majority of reactions. The integrated form of the
performance equation has varied significance depending on the particular reaction
scheme being performed. For example, molecular weight distributions in polymerization
reactions can be controlled more precisely in batch reactors.
One of the traditional disadvantages of the batch reactor has been the labor required
between runs for emptying and filling the tank. With recent advances in computer
control, this disadvantage no longer exists. If the advantages of batch are significant, the
capital expense of computer control is essentially negligible. Due to computer control,
the batch reactor should no longer be looked upon as something to be avoided. If the
kinetics and design parameters indicate that batch is a competitive design, then use it.
The major disadvantage of batch reaction now is the hold-up time between batches.
Although the actual reaction time necessary to process a given amount of feed may be
substantially less than for a time-averaged reactor such as a CSTR, when the hold-up
time is added, the total process time may be greater. Other disadvantages of the batch
reactor are dependent on the particular type of reaction being considered, such as whether
the reaction is in parallel or serles.

B. SEMIBATCH

DESCRIPTION. The semibatch reactor is a cross between an ordinary batch reactor

and a continuous-stirred tank reactor. The reactor has continuous input of reactant
through the course of the batch run with no output stream. Another possibility for
semibatch operation is continuous withdrawal of product with no addition of reactant.
Due to the crossover between the other ideal reactor types, the semibatch uses all of the
terms in the general energy and material balances. This results in more complex
mathematical expressions. Since the single continuous stream may be either an input or
an output, the form of the equations depends upon the particular mode of operation.
Physically, the semibatch reactor looks similar to a batch reactor or a CSTR. Reaction
occurs in a stirred tank, with the following assumptions: (1) the contents of the tank are
well mixed, and (2) there are no inlet or outlet effects caused by the continuous stream.

CLASSIFICATION. The semibatch reactor is one of the primary ideal reactor types
since it can not be accurately described as either a continuous or a batch reactor. A
semibatch reactor is usually classified as a type of transient reactor.

DESIGN PARAMETERS. The major design parameters for a semibatch reactor are
similar to a batch reactor with the addition of flow into or out of the tank.

APPLICATIONS. The advantage of this reactor, with feed only, is for the control of
heat of extremely exothermic reactions. By inputting the feed gradually during the
course of the reaction, the concentration of feed in the reactor can be kept lower than in
normal batch operation. Also, the temperature of the feed stream, when cooler than the
reaction mixture, has a quenching effect. Some of the heat released during the reaction is
used to heat the feed material, thereby reducing the required capacity of the heating coils.
The semibatch can also be used to control the kinetics in multiple reaction sequences.
The selectivity may be shifted to one reaction by adding a reactant slowly. This keeps
one reactant concentration high with respect to the other.
 The semibatch can also be used for continuous product removal, such as vaporization of
the primary product. This can increase yield in equilibrium limited reactions.

ADVANTAGES-DISADVANTAGES. The temperature-controlling features of this

reaction scheme dominate selection and use of the reactor. However, the semibatch
reactor does have some of the advantages of batch reactors: temperature programming
with time and variable reaction time control.
The temperature conditions and the batch nature of this reactor are the primary
operational difficulties and make the reactor impractical for most reactions, even for
computer-controlled systems. The majority of reactions considered for semibatch are
highly exothermic and, as such, are dangerous and require special attention.

C. CONTINUOUS-STIRRED TANK

DESCRIPTION. The continuous-stirred tank reactor (CSTR) has continuous input and
output of material. The CSTR is well mixed with no dead zones or bypasses in ideal
operation. It may or may not include baffling. The assumptions made for the ideal CSTR
are (1) composition and temperature are uniform everywhere in the tank, (2) the effluent
composition is the same as that in the tank, and (3) the tank operates at steady state. [See
FLUID MIXING.]
We traditionally think of the CSTR as having the appearance of a mixing tank. This
need not be the case. The above assumptions can be met even in a long tube if the
mixing characteristics indicate high dispersion levels in the reactor. This is particularly
true of gassed liquids where the bubbling in the column mixes the liquid.

CLASSIFICATION. The continuous-stirred tank reactor is one of the two primary

types of ideal flow reactors. It is also referred to as a mixed-flow reactor, back-mix
reactor, or constant-flow stirred-tank reactor.

DESIGN PARAMETERS. The CSTR is not an integral reactor. Since the same
concentration exists everywhere, and the reactor is operating at steady state, there is only
one reaction rate at the average concentration in the tank. Since this concentration is low
because of the conversion in the tank, the value for the reaction rate is also low. This is
particularly significant for higherorder reactions compared with integral reactor systems.
Time is still an important variable for continuous systems, but it is modified to relate to
the steady-state conditions that exist in the reactor. This time variable is referred to as
space time. Space time is the reactor volume divided by the inlet volumetric flow rate. In
other words, it is the time required to process one reactor volume of feed material. Since
concentration versus real time remains constant during the course of a CSTR reaction,
rate-data acquisition requires dividing the difference in concentration from the inlet to the
outlet by the space time for the particular reactor operating conditions.

APPLICATIONS. The CSTR is particularly useful for reaction schemes that require
low concentration, such as selectivity between multiple reactions or substrate inhibition
in a chemostat (see Section IV). The reactor also has applications for heterogeneous
systems where high mixing gives high contact time between phases. Liquid-liquid
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