CHAPTER 2

2.0 LITERATURE REVIEW

2.1 FLUIDIZATION

Fluidization is the process by which solid particles are transformed into fluid like state through
suspension in gas or liuid. The fluidized bed is mainly used for heterogeneous catalytic reaction catalyst
often looses it activity with operating time. If this decrease is rapid and senere, it is desirable to generate
catalyst continuously without shutting down the reactor. The fluidized bed provides an effective way to
achieve this objective.

THE VARIOUS STAGES DURING FLUIDIZATION PROCESS

FIXED BED
MINIMIUM FLUIDIZATION
AGGRESSIVE BUBBLING FLUIDIZATION
SLUGGING
LEAN PHASE FLUIDIZATION

FIXED BED

If the fluid is passed upward through bed of fine particles as shown in fig (a) at a low flow rate, the fluid
merely percolates through voids spaces between stationary particles. Such a bed is called fixed bed.

MINIMIUM FLUIDIZATION

At still higher velocity, a point is reached where all the particles are just suspended by the upward flowing
gas or fluid. At this point the frictional force between particle and fluid just counter balances the weight
of the particles, the vertical component of the compressive force between adjacent particles disappears,
and particles in that section. Th e bed is considered to be just fluidized and is referred as an incipiently
fluidized bed or a bed at minimium fluidization.

AGGRESSIVE BUBBLING FLUIDIZATION

Generally gas-solid systems behave uite differently, with an increase in flow rate beyond minimium
fluidization, large instabilities with bubbling and channeling of gas are observed. At higher flow rates,
agitation becomes more violent and movement of solid becomes more vigorous. In addition the bed does
not expand much beyond its volume at minimium fluidization. Such a bed, heterogeneously fluidized bed
or bubbling fluidized bed

SLUGGING

In gas-solid systems, gas bubbles coalesce and grow as they rise, and deep enough to spread across the
vessel. In the case of fine particles, they flow smoothly down by wall around the rising voids of gas. This
is termed as slugging with axial sluges.

For coarser particles, the portion of the bed above the bubble is pushed upward, as by a piston. Particles
rain down from the slug, which finally disintegrates. At about this time another slug forms, and this
unstable oscillatory motion is repeated. This is called a flat slug.

LEAN PHASE FLUIDIZATION WITH PNEUMATIC TRANSPORT

With further increase in velocity above turbulent fluidization, solids are carried out of the bed with the
gas. In this we have a disperse, dilute, or lean phase fluidized bed with pneumatic transport of solids.

In both turbulent and lean phase fluidization, large amounts of particles are entrained, precluding steady
state operations. For steady state operation in the contacting modes, entrained particles have to be
collected by cyclones and returned to the beds. In turbulent fluidized beds, inner cyclones can deal with
the moderate rate of entrainment is far larger in lean phase fluidized bed, which usually necessitates the
use of big cyclone collector outside the bed as shown in fig. this system is called as fast fluidized bed.

In fluid beds and fast fluidized beds, smooth and steady recirculation of solids through the dipleg or other
solid trapping device is crucial to good operations.these beds are called circulating fluidized beds.

In the spout bed, a high velocity spout of gas punches through the bed of solids, there by transporting
particles to the top of the bed. The rest of the solids move downward slowly around the spout and through
gently upward percolating gas, behaves somewhere between bubbling and spouting is also seen and this
may be called spouted fluidized bed behavior.

MECHANISM OF CATALYTIC POLYMERIZATION

Typical catalyst for catalytic polymerizations include, in order of importance, a protonic acids(Lewis
acids & Friedel halides), protonic acids and stable carbonium –ion salts. All these are strong electron
acceptors. Many of them particularly the lewis acids, require a cocatalyst, usually a Lewis base and other
proton donor, to initiate polymerization.

A polymerization of isobutylene by ALCL3 or BF3 takes place within a few seconds at -100 C. producing
polymer of molecular weight up to several millions.
MECHANISM:

In the polymerization of isobutylene with boron trifluoride catalyst, the first step is the reaction of the
catalyst and cocatalyst for ex. Water to form catalyst-cocatalyst complex that donates the proton to
isobutylene molecule, to give carbonium ion, (CH3)3C. this ion then reacts with monomer with the
reformation of a carbonium ion at the end of each step. The head to tail addition of monomer to ion is the
only one possible for energetic reasons. Since the reaction is generally carried out in a hydrocarbon
medium of low dielectric constant, the anion and the growing cationic end form an ion pair.

The termination of reaction can take place by the arrangement of the ion pair to yield a polymer molecule
with terminal unsaturation plus the original complex.

INITIATION

BF3  H 2O  BF3OH  H 


H  BF3OH   H 3C


PROPAGATION

TERMINATION

KINETICS:

Although many cationic polymerizations proceed so rapidly that it is difficult to establish the steady state,
the following kinetic scheme appears to be valid. Let the catalyst be A and the cocatalyst by RH.
Initiation, propagation, termination and transfer may be represented as follows:

A  RH  H  AR 

H  AR  M  HM  AR 

H  AR  M  HM X 1 AR 

HM X AR   M X  H  AR 

HM X  M  M X  HM  AR 

Here the rate of inbaton is

ri  KK i ARH M 

WHERE A is catalyst concentration

M  is monomer concentration
Rate of propagation


rp  k p HM  AR M  
And Rate of Termination


rt  k t HM  AR  
Applying steady state and rearranging overall rate of polymerization

Kki k p
r0  rp  ARH M 2
kt

Polyolefins polymerization process can be divided into two main types

 CATALYTIC
 HIGH PRESSURE FREE RADICAL

CATALYTIC POLYMERIZATION:

In catalytic polymerization the polymerization , takes place on the surface of catalyst. The heat removal
problem exists not only between the reaction fluid and coolant , but also between the catalyst and polymer
particle, and the fluid,insufficient heat transfer between the particles and the fluid may lead to an increase
in the particles temperature, called overheating or the hot spot formation. This may lead to heterogeneous
product properties and more likely, unstable reactor operation.

Sufficient agitation is needed to prevent the polymer particles from fusing. The surface of the polymer
particles may be soft and stickly due to overheating, swelling or low crystallinity of polymer. The
agglomeration of polymer particles often leads to unstable process operation.

The particles may also be attracted by the electrostatic forces. This can cause the particles to stick to the
walls of reactor. Again problems in process operation may follow with insufficient care.

TYPES OF CATALYTIC POLYMERIZATION

Catalytic polymerization processes can be divided into:

Liquid Phase- Slurry processes

Liquid Phase-Solution processes
Gas Phase
LIQUID PHASE –SLURRY PROCESSES

In slurry polymerization the catalyst and the growing polymer particles are suspended in liquid diluents.
The diluents may not contain compounds that irreversibly react with the active sites of the catalyst(i.e the
catalyst poisons) and it should not dissolve the polymer. It should however dissolve the reactive
compounds needed in the polymerization that are monomers. Co-monomers, hydrogen and isobutene or
propane is commonly used. The special feature of the Borstar process which use propane in a supercritical
state as a diluents.

The traditionally slurry polymerization reactors are continuously operating stirred tank reactors(CSTR).
They are equipped with an agitator to ensure sufficient stirring. They also have cooling jackets to remove
the heat of reaction. Since this alone does not provide sufficient cooling, they also have external heat
exchangers through which slurry is circulated.

A loop reactor is also used in a slurry polymerization. The reactor is a long circular pipe. Agitation is
achieved by pumping the slurry at high velocity through the reactor. The reactor has a cooling jacket to
remove the heat of reaction. Since a LOOP REACTOR HAS A HIGH ratio of surface area to volume,
the jacket can provide sufficient cooling.

The heat removal from the liquid is effective for this reason the slurry reactor has a high capacity per
volume. This means that the average residence time in a slurry reactor is relatively small about an hour. In
this respect loop reactors out performs CSTRs. Also the heat transfer between the fluid and particles is
effective enough in a slurry processes to prevent overheating of the particles. Solubility of polymer into
diluents retricts the product range in slurry processes.

The solubility depends on the density and MFR: the lower the density higher the solubility. The opposite
is true for the MFR. Thus LDPE products with density lower than 930Kg’m3 are not usually made by
slurry processes. The MFR range that can be produced in a slurry process is limited by the solubility of
hydrogen in the solvent selecting a catalyst with high hydrogen sensitivity can compensate this. Another
way to overcome the problem is to operate the reactor under supercritical conditions.

After the product is taken out of the reactor, the polymer needs to be separated from the fluid. If high
boiling diluents(such as hexane) are used, separation is achieved by centrifuging. The polymer is
pelletised and the fluid recovered and recycled. The recovery consists of separating the dissolved
polymer, separating the different fractions (propylene, co-monomer, diluents) and purifying them, the
purified material is then fed back into- the reactor. If a low boiling diluents(such as isobutene or propane)
is used. The polymer is usually separated from fluid by flashing. The polymer is then dried and pelletised.
The flash gases are separated and purified. After this, they are recycled back into the process. To
summarises, the slurry process has a short residence time resulting in short transitions. The reaction
medium is homogeneous(no hot spot).

On the other hand, the solubility of the polymer into the diluents limits the product range. Also, the
solubility may cause fauling of the reactor. The recovery of the unreacted material is sometimes
complicated, especially in case of high boiling diluents.

LIQUID PHASE SOLUTION POLYMERIZATION:

IN THIS KIND OF POLYMERIZATION, THE monomer is dissolved in a suitable inert solvent along
with the chain transfer agent, whenever used. The free radical initiator is also dissolved in the solvent
medium, while the ionic and co-ordination catalysts can either be dissolved or suspended. The presence of
the inert solvent medium helps to control the viscosity increase and promote heat transfer.

The major disadvantage of the solution polymerization technique is that however inert the selected
solvent may be, chain transfer to the solvent, cannot be completely ruled out and hence it is difficult to get
very high molecular weight products. The polymer formed will also have to be isolated from the solution
either by evaporation of the solvent or by precipitation of non-solvent and removal of their final traces is
always extremely difficult. Solution polymerization technique nevertheless, can advantageously be used
where the polymer is used in its solution form, as in case of certain adhesive and coating compositions, or
in system where the polymer formed is insoluble in its monomer or solvent and precipitates out as slurry
and is amenable for easy isolation.

Practically, industrial production of polyacrylonitrile is manufactured by free radical polymerization and

polyisobutylene by catalytic polymerization. Use solution technique.

GAS PHASE REACTOR:

In the gas phase reactor, catalyst and growing polymer particles are suspended in an upward gas flow.
The gas velocity is high enough to fluidized the particles but not high enough to entrain the polymer
reactor.

The particles then form a compact bed; so called fluidized bed. The gas enters the reactor at the bottom
through a metallic perforated plate, a gas distribution plate that evenly distributes the gas through the bed.
The unreacted gas leaves the reactor at the top. The pressure of the exit gas is then raised in a recycle gas
compressor and the gas is fed back into the bottom of the reactor.

The catalyst(or polymer containing active catalyst) is fed directly into the bed from where the polymer is
also collected. The gas flow carries the particles and provides an effective mixing of bed. As a rule, the
bed may assume to be perfectly mixed. The heat of polymerization is removed by cooling the recycle gas
on a heat exchanger, after the compressor cooling a gas is not as effective as cooling a liquid. This leads
to a lower capacity per volume than what can be obtained in slurry reactors.

This in turn means, a longer average residence time of about three hours. Adding a condensing
component into the recycled gas stream can increase the cooling capacity. The component is condensed,
either in a recycle gas cooler or in a separate cooling unit. When a liquid component is injected into the
bed together with the gas, it evaporates. The evaporation cools the bed effectively. This type of operation
is called condensing mode. Cooling may also cause other problems. If the catalyst is very active, it is
possible that the heat of polymerization is not transferred sufficiently from the particles to the surrounding
gas. Then the temperature of the particles increases and reaches the softening temperature of the polymer.
Tills may lead to the agglomeration of particles and chunk formation. This kind of behavior is called hot
spot formation. After the polymer is taken out of the reactor the gases are removed by reducing the
pressure. The unreacted gases are fed back into the recycle gas stream. No further separation or
purification steps are needed. The polymer is purged with nitrogen dried and palletized. As the polymer
Does not dissolved in the gas a very wide product range can be produced in a gas phase process.
Densities down to 910Kg/m3 may be produced. Even lower densities are possible but then the reactor
temperature must be selected so that it is lower than the softening reactor is unlimited. However, problem
may arise because of the high hydrogen concentration is needed to produce very high MFR’s. selecting a
catalyst with high hydrogen sensitivity may compensate this.

To summarise, gas phase processes are able to produce a very wide product range the process is simple
and economical; the average residence time is long which means long transition.

POLYMERIZATION OF OLEFINS: [UNIPOL PROCESS]

POLYPROPYLENE, on of the world largest volume plastic today, achieves position largely due to a
remarkable catalyst in concert with a remarkable fluidized bed process. On coming up with this catalyst,
which operates at relatively low pressure and temperature. Union carbide developed a unique and
versatile fluidized bed process called unipol, for producing linear low density polypropylene which is
rapidly replacing conventional process from the world.

In this process, (see fig) reactant gas (propylene with its co-monomers, butane and higher) is fed at a rate
of three to six times the minimum fluidization velocity into a bed of polypropylene particles kept at 75-
100 C and at 20atm. Extremely small silica supported catalyst particles are also fed into the bed
continuously. Polymerization occurs on the surface of catalyst, causing the particles to grow into large
granules of 100-250 um. The height of reactor size is reported to be 2.6-4.7 times the bed diameter. One
pass conversion of propylene is rather low, about 2%, so large recycle flows are needed. Since the
reaction is highly exothermic(3300Kj/Kg of propylene converted), it is important to avoid the hot spot
formation and local accumulation of catalyst at the walls of reactor, from the engineering point of view;
this process is gas-solid reaction with growing solids.

In the unipol process, two types of catalyst are used: chromium titanium compounds on silica carrier and
Ziegler. These catalysts are so active that more than 105 volumes of polymer can be produced by unit
mass of active ingredient in the catalyst. Because of the great dilution of catalyst in the granules formed
and their large, the raw product is ready for use without palletizing it or removing the catalyst. In addition
no solvent is used in the process and one marks the whole range of product from low to high-density
polymers. All these factors contribute to make this a remarkably efficient attractive and economical
process. Following the debut of unipol process fluidized bed catalytic polymerization has been
extensively investigated by many companies. For ex. Copolymerization of propylene with hexane-I and
octane-I have been developed by Exxon and by union carbide. Mitsui petrochemical and Motedison have
developed an ultra high performance MgCL2/TICL4 catalyst for the gas polymerization of propylene.
Union carbide already developed their own fluidized bed polypropylene process.
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