Chemical Product and Process Design

Dr. Aprilina Purbasari, ST, MT

Choice of Reactor
TYPES OF REACTION SYSTEMS
1. Single reactions.
Most reaction systems involve multiple reactions. In practice, the
secondary reactions can sometimes be neglected, leaving a single
primary reaction to consider. Single reactions are of the type:
• FEED → PRODUCT
or
• FEED → PRODUCT + BYPRODUCT
or
• FEED1 + FEED2 → PRODUCT
and so on.
2. Multiple reactions in parallel producing byproducts.
Rather than a single reaction, a system may involve secondary reactions producing
(additional) byproducts in parallel with the primary reaction. Multiple reactions in
parallel are of the type:
• FEED ---→ PRODUCT
• FEED ---→ BYPRODUCT
or
• FEED ---→ PRODUCT + BYPRODUCT1
• FEED ---→ BYPRODUCT2 + BYPRODUCT3
or
• FEED1 + FEED2 ---→ PRODUCT
• FEED1 + FEED2 ---→ BYPRODUCT
and so on.
3. Multiple reactions in series producing byproducts.
Rather than the primary and secondary reactions being in parallel, they can be
in series. Multiple reactions in series are of the type:
• FEED ---→ PRODUCT
• PRODUCT ---→ BYPRODUCT
or
• FEED ---→ PRODUCT + BYPRODUCT1
• PRODUCT ---→ BYPRODUCT2 + BYPRODUCT3
or
• FEED1 + FEED2 ---→ PRODUCT
• PRODUCT ---→ BYPRODUCT1 + BYPRODUCT2
and so on.

CH3OH + 1/2O2 ---→ HCHO + H2O

Methanol oxygen formaldehyde water
HCHO ---→ CO + H2
Formaldehyde carbon monoxide hydrogen
4. Mixed parallel and series reactions producing byproducts.
In more complex reaction systems, both parallel and series
reactions can occur together. Mixed parallel and series
reactions are of the type:
• FEED ---→ PRODUCT
• FEED ---→ BYPRODUCT
• PRODUCT ---→ BYPRODUCT
or
• FEED ---→ PRODUCT
• FEED ---→ BYPRODUCT1
• PRODUCT ---→ BYPRODUCT2
or
• FEED1 + FEED2 ---→ PRODUCT
• FEED1 + FEED2 ---→ BYPRODUCT1
• PRODUCT ---→ BYPRODUCT2 + BYPRODUCT3
5. Polymerization reactions.
• In polymerization reactions, monomer molecules are
reacted together to produce a high molar mass
polymer.
• Depending on the mechanical properties required of
the polymer, a mixture of monomers might be
reacted together to produce a high molar mass
copolymer.
• There are two broad types of polymerization
reactions, those that involve a termination step and
those that do not.
• An example that involves a termination step is free-radical polymerization
of an alkene molecule, known as addition polymerization.
• An initiation step first occurs:

• A propagation step involving growth around an active center follows:

and so on, leading to molecules of the structure:

• Eventually, the chain is terminated by steps such as the union of two

radicals that consume but do not generate radicals:
• An example of a polymerization without a
termination step is polycondensation.
6. Biochemical reactions.
Biochemical reactions, often referred to as fermentations, can be
divided into two broad types.
• In the first type, the reaction exploits the metabolic pathways in
selected microorganisms (especially bacteria, yeasts, moulds and
algae) to convert feed material (often called substrate in
biochemical reactor design) to the required product. The general
form of such reactions is:
• In the second group, the reaction is promoted by enzymes.
• Enzymes are the catalyst proteins produced by
microorganisms that accelerate chemical reactions in
microorganisms. The biochemical reactions employing
enzymes are of the general form:
REACTION PERFORMANCE
• Three important parameters are used to describe
their performance:
RATE OF REACTION
• To define the rate of a reaction, one of the components must
be selected and the rate defined in terms of that component.
• The rate of reaction is the number of moles formed with
respect to time, per unit volume of reaction mixture:
IDEALIZED REACTOR MODEL
CHOICE OF IDEALIZED REACTOR MODEL
REACTION EQUILIBRIUM
REACTOR TEMPERATURE
REACTOR PRESSURE
• The selection of reactor pressure for vapor-phase reversible
reactions depends on whether there is a decrease or an increase in
the number of moles.
• Increasing the pressure of vapor-phase reactions increases the rate
of reaction and hence decreases reactor volume both by decreasing
the residence time required for a given reactor conversion and
increasing the vapor density.
• For liquid-phase reactions, the effect of pressure on the selectivity
and reactor volume is less pronounced, and the pressure is likely to
be chosen to:
- prevent vaporization of the products;
- allow vaporization of liquid in the reactor so that it can be
condensed and refluxed back to the reactor as a means of removing
the heat of reaction;
- allow vaporization of one of the components in a reversible
reaction in order that removal increases maximum conversion;
- allow vaporization to feed the vapor directly into a distillation
operation to combine reactions with separation.
Catalysts

1. Homogeneous catalysts.
• With a homogeneous catalyst, the reaction
proceeds entirely in either the vapor or liquid
phase.
• The catalyst may modify the reaction mechanism by
participation in the reaction but is regenerated in a
subsequent step. The catalyst is then free to promote
further reaction.
2. Heterogeneous catalysts.
• In heterogeneous catalysis, the catalyst is in a
different phase from the reacting species.
• Most often, the heterogeneous catalyst is a solid,
acting on species in the liquid or gas phase. The solid
catalyst can be either of the following:
- Bulk catalytic materials, in which the gross
composition does not change significantly through
the material, such as platinum wire mesh.
- Supported catalysts, in which the active catalytic
material is dispersed over the surface of a porous
solid.
REACTOR CONFIGURATION
1. Tubular reactors.
• Although tubular reactors often take the actual form of
a tube, they can be any reactor in which there is steady
movement only in one direction.
• If heat needs to be added or removed as the reaction
proceeds, the tubes may be arranged in parallel, in a
construction similar to a shell-and-tube heat exchanger.
Here, the reactants are fed inside the tubes and a
cooling or heating medium is circulated around the
outside of the tubes.
• If a high temperature or high heat flux into the reactor
is required, then the tubes are constructed in the
radiant zone of a furnace.
2. Stirred-tank reactors.
• Stirred-tank reactors consist simply of an agitated tank and are used
for reactions involving a liquid. Applications include: homogeneous
liquid-phase / heterogeneous gas–liquid / heterogeneous liquid–
liquid / heterogeneous solid–liquid / heterogeneous gas–solid–
liquid reactions.
• Stirred-tank reactors can be operated in batch, semi-batch, or
continuous mode.
• In batch or semi-batch mode:
- operation is more flexible for variable production rates or for
manufacture of a variety of similar products in the same
equipment;
- labor costs tend to be higher (although this can be overcome to
some extent by use of computer control).
• In continuous operation, automatic control tends to be more
straightforward (leading to lower labor costs and greater
consistency of operation).
• Heat can be added to or removed from stirred-tank reactors via external
jackets (Figure 7.5a), internal coils (Figure 7.5b) or separate heat
exchangers by means of a flow loop (Figure 7.5c). Figure 7.5d shows
vaporization of the contents being condensed and refluxed to remove
heat. A variation on Figure 7.5d would not reflux the evaporated material
back to the reactor, but would remove it as a product. Removing
evaporated material in this way if it is a product or byproduct of a
reversible reaction can be used to increase equilibrium conversion.
3. Fixed-bed catalytic reactors.
• Here, the reactor is packed with particles of solid catalyst. Most
designs approximate to plug-flow behavior.
• The simplest form of fixed-bed catalytic reactor uses an adiabatic
arrangement, as shown in Figure 7.6a. If adiabatic operation is not
acceptable because of a large temperature rise for an exothermic
reaction or a large decrease for an endothermic reaction, then cold
shot or hot shot can be used, as shown in Figure 7.6b.
• Alternatively, a series of adiabatic beds with intermediate cooling
or heating can be used to maintain temperature control, as shown
in Figure 7.6c. The heating or cooling can be achieved by internal or
external heat exchangers.
• Tubular reactors similar to a shell-and-tube heat exchanger can be
used, in which the tubes are packed with catalyst, as shown in
Figure 7.6d. The heating or cooling medium circulates around the
outside of the tubes.
4. Fixed-bed noncatalytic reactors.
• Fixed-bed noncatalytic reactors can be used to react
a gas and a solid.

5. Moving-bed catalytic reactors.

• If a solid catalyst degrades in performance, the rate
of degradation in a fixed bed might be unacceptable.
In this case, a moving-bed reactor can be used.
• Here, the catalyst is kept in motion by the feed to the
reactor and the product. This makes it possible to
remove the catalyst continuously for regeneration.
An example of a refinery hydrocracker reactor is
illustrated in Figure 7.7a.
6. Fluidized-bed catalytic reactors.
• In fluidized-bed reactors, solid material in the form of
fine particles is held in suspension by the upward flow
of the reacting fluid. The effect of the rapid motion of
the particles is good heat transfer and temperature
uniformity. This prevents the formation of the hot
spots that can occur with fixed-bed reactors.
• The performance of fluidized-bed reactors is not
approximated by either the mixed-flow or plug-flow
idealized models. The solid phase tends to be in mixed-
flow, but the bubbles lead to the gas phase behaving
more like plug-flow. Overall, the performance of a
fluidized-bed reactor often lies somewhere between
the mixed-flow and plug-flow models.
7. Fluidized-bed noncatalytic reactors.
• Fluidized beds are also suited to gas–solid noncatalytic
reactions. All the advantages described earlier for gas–solid
catalytic reactions apply here.

8. Kilns.
• Reactions involving free-flowing solid, paste and slurry
materials can be carried out in kilns. In a rotary kiln, a
cylindrical shell is mounted with its axis making a small
angle to the horizontal and rotated slowly.
• The solid material to be reacted is fed to the elevated end
of the kiln and it tumbles down the kiln as a result of the
rotation. The behavior of the reactor usually approximates
plug-flow. High-temperature reactions demand refractory
lined steel shells and are usually heated by direct firing.