Polymerization reactors contain one or more phases.

There are examples

using solvents in which the reactants and products are in the liquid phase, the
reactants are fed as a liquid (gas) but the products are solid, or the reactants
are slurry and the products are soluble. Phase transformations can occur, and
polymers that form from the liquid phase may remain dissolved in the remaining
monomer or solvent, or they may precipitate. Sometimes beads are formed and
remain in suspension; sometimes emulsions form. In some processes, solid
polymers precipitate from a gas phase into a fluidized bed containing product
solids. Polymers are thought of as organic materials; however, inorganic
polymers may be also synthesized (e.g., using crystallization and precipitation).
Examples of inorganic polymers are zeolites.
The structure of the polymer determines its physical properties, e.g.,
crystallinity, refractive index, tensile strength, glass transition temperature (at
which the specific volume changes slope), and processability. The average
molecular weight can cover a wide range between 104 to 107. Given the
change in molecular weight, the viscosity can change dramatically as
conversion increases. For example, in styrene polymerization, the viscosity
increases by a factor of 106 as conversion increases from 0 to 60 percent.
Initiators of chain polymerization reactions have concentration as low as 108
gmol/L so they are highly sensitive to small concentrations of poisons and
impurities.
The reaction time can also vary. Reaction times for butadienestyrene
rubbers are 8 to 12 h; polyethylene molecules continue to grow for 30 min,
whereas ethyl acrylate in 20 percent emulsion reacts in less than 1 min, so
monomer must be added gradually to keep the temperature within limits. In
some cases, the adiabatic temperature rise may be very high.
Since it is impractical to fractionate the products and reformulate them
into desirable ranges of molecular weights, immediate attainment of desired
properties must be achieved through the correct choice of reactor type and
operating conditions, notably of distributions of residence time and
temperature. Reactor selection may be made on rational grounds, for historical
reasons, or to obtain a proprietary position.
Each reactor is designed based on the need for mass transfer, heat
transfer, and reaction. Stirred batch (autoclave) and continuous tubular
reactors are widely used because of their flexibility. In stirred tanks, ideal mixing is
typically not achieved, wide variations in temperatures may result, and stagnant
zones and bypassing may exist. Devices that counteract these unfavorable
characteristics include inserts that cause radial mixing, scraping impellers, screw
feeders, hollow-shaft impellers (with coolant flow through them), recirculation
using internal and external draft tubes, and so on. The high viscosity of bulk and
melt polymerization


2 Introduction to Polymer Technology | Types of Reactors for Polymer Processing

NONCATALYTIC GAS-PHASE REACTIONS.


Steam cracking of light
hydrocarbons in a tubular fired heater.
Steam cracking is a petrochemical
process in which saturated
hydrocarbons are broken down into
smaller, often unsaturated,
hydrocarbons. It is the principal
industrial method to produce the
lighter alkenes (commonly named
olefins), including ethene (ethylene)
and propene (propylene).







Pebble heater for the fixation of
nitrogen from air. Nitrogen fixation is a
process in which nitrogen (N2) in the
atmosphere is converted into
ammonium (NH4
+
). A Pebble Heater is
a heat exchanger utilizing refractory
pellets to store and give off heat.









3 Introduction to Polymer Technology | Types of Reactors for Polymer Processing



Flame reactor for the production of acetylene from
hydrocarbon gases or naphthas. These processes
use high temperature to convert the raw materials
into a wide variety of gases, including hydrogen,
carbon monoxide, carbon dioxide, acetylene, and
others. Acetylene may be generated by raising
the temperature of various hydrocarbons to the
point where their atomic bonds break, or crack, in
what is known as a thermal cracking process. After
the hydrocarbon atoms break apart, they can be
made to rebond to form different materials than
the original raw materials. This process is widely
used to convert oil or natural gas to a variety of
chemicals.






Flame reactor for acetylene from light
hydrocarbons. Acetylene may also be generated
by raising the temperature of various hydrocarbons
to the point where their atomic bonds break, or
crack, in what is known as a thermal cracking
process. After the hydrocarbon atoms break apart,
they can be made to rebond to form different
materials than the original raw materials. This
process is widely used to convert oil or natural gas
to a variety of chemicals.







4 Introduction to Polymer Technology | Types of Reactors for Polymer Processing

BATCH AND CONTINUOUS POLYMERIZATIONS.





Polyethylene in a tubular flow
reactor. this type of reactors
consist of long pipes (1-3 km)
with small inner diameters (5-10
cm) and thick reactor walls (2-5
cm) which are divided into
several reaction and cooling
zones. Each zone is equipped
with a jacket cooling system
used to remove the large
amounts of heat produced by
polymerization




Batch process for polystyrene. Batch
processes generally have a high
conversion efficiency, leaving only
small amounts of unreacted styrene
to be emitted should the reactor be
purged or opened between batches.










5 Introduction to Polymer Technology | Types of Reactors for Polymer Processing





Batch-continuous process for polystyrene. In
continuous processes, the chemical reaction
does not approach completion as efficiently as
in batch processes. As a result, a lower
percentage of styrene is converted to
polystyrene, and larger amounts of unreacted
styrene may be emitted from continuous process
sources.












Suspension (bead) process for polyvinylchloride. Suspension polymerization is a
heterogeneous radical polymerization process that uses mechanical agitation
to mix a monomer or mixture of monomers in a liquid phase, such as water,
while the monomers polymerize, forming spheres of polymer. In bead
polymerization, the polymer is soluble in its monomer and the result is a smooth,
translucent bead.

6 Introduction to Polymer Technology | Types of Reactors for Polymer Processing


Emulsion process for polyvinylchloride. Emulsion polymerisation produces finer
resin grades having much smaller particles, which are required by certain
applications. This type of resin is sometimes called paste PVC and referred to
within the industry using the abbreviation P-PVC to distinguish it from S-PVC.

Reference:

Robert Perry, D. G. (2008). Perry's Chemical Engineers' Handbook.