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CHAPTER 1

1.1 Background of Study


A remarkable invention for converting unsaturated hydrocarbons (alkene) to
giant molecules, today known as polymers, was discovered in the 1950s.
The combination of thousands of individual monomer molecules such as
propylene into a long, straight chain of polypropylene with commercial and
industrial applications was first made possible by the use of Ziegler or
Ziegler-Natta catalysts. In brief, the polymerization of propylene had been
carried out in a catalyst solution composed of titanium tetrachloride and
triethylaluminium in the presence of the monomer. Since then, the process
has been studied continuously and catalytic activities have been developed
to satisfy commercial needs. Polypropylene has been widely and
successfully used for industry because several of its characteristics can
serve in most possible applications.
Polyolefin are today the major plastics material in terms of production
capacity thanks to its versatility, low costs and excellent processability. The
global polypropylene market has become one of the fastest growing and
the production exceeds 30 million tons in 2000.
Polypropylene was discovered in 1954 and gains a strong popularity very
quickly due to the fact that polypropylene has the lowest density among
commodity plastics. Polypropylene has an excellent chemical resistance
and can be processed through many converting methods such as injection
molding and extrusion. Polypropylene is a polymer prepared catalytically
from propylene an important concept in understanding the link between the
structure of polypropylene and its properties is tacticity. The relative
orientation of each methyl group CH 3 relative to the methyl group in
neighboring monomer units has a strong effect on the polymers ability to
form crystals. A Ziegler-Natta catalyst is able to restrict linking of monomer
molecules to a specific regular orientation, either isotactic , when all methyl
groups are positioned at the same side with respect to to the backbone of
the polymer chain, or syndiotactic, when the positions of the methyl groups
alternate. Commercially available isotactic polypropylene is made with two
types of Ziegler-Natta catalysts. The first group of the catalyst
encompaases solid(mostly supported) catalysts and certain types of
soluble metallocene catalysts. Such isotactic macromolecules coil into a
helical shape; these helices then line up next to one another to form
crystals that give commercial isotactic polypropylene many of its desirable
properties.

Hydrocarbon slurry or suspension: uses liquid inert hydrocarbon


diluents in the reactor to facilitate transfer of propylene to the catalyst, the
removal of heat from the system, the deactivation/removal of the catalyst
as well as dissolving the atactic polymer. The ranger of grades that could
be produced was very limited. (The technology has fallen into disuse)
Bulk (or bulk slurry): uses liquid propylene of liquid inert hydrocarbon
diluents. The polymer does not dissolve into diluents, but rather rides on
the liquid propylene. The formed polymer is withdrawn any unreacted
monomer is flushed off.
Gas phase: uses gaseous polypropylene in contact with the solid catalyst
resulting in a fluidized-bed medium.
The large numbers of end-use applications for polypropylene are often
possible because of the ability to tailor grades with specific molecular
properties and additives during it manufacture. For example, antistatic
additives can be added to help polypropylene surfaces resist dust and dirt.
Many physical finishing techniques can also be used on polypropylene,
such as machining. Surface treatments can be applied to polypropylene
parts in order to promote adhesion of printing ink and paints.
Polypropylene is attractive to petrochemical companies because of its
great properties. For instance, polypropylene is semi-rigid, translucent, a
good chemical resistance, tough, a good fatigue resistance and a good
heat resistance. Moreover, polypropylene has high softening or glass-
transition point, high resistance to flexing stress, low water absorption,
good electrical resistance, a light weight, dimensional stability, high impact
strength and a non-toxicity property.

1.2 Aim of Study


To optimize production cost for the production of polypropylene
1.3 Objective of Study
1. To compare the result obtained from the various model processes
2. To check which of the model is most suitable for high production
Profitability.
3. To compare which is the most efficient process for the production of
polypropylene when compared to the best model with that from Indorama
(Eleme Petrochemical Company).

1.4 Problem Statement


It is a well know fact that continuous stirred tank reactors and plug flow
tubular reactors arranged in series behaved similar to a fluidized bed
reactor. This is gaining wider ground in chemical industries compared with
other processes. Using Aspen polymer software to simulate polymer
manufacturing processes and characterize polymer properties such as
molecular weight, melt flow index (MFI) and production rate. Also using the
process to model multisite Ziegler-Natta catalysts to predict their
characteristically broad molecular-weight distribution.

CHAPTER 2

2.0 LITERATURE REVIEW


CHAPTER 3

3.0 METHOD AND MODELLING

3.1 METHOD
Developing an accurate simulation of propylene polymerization in fluidized-
bed reactors using Aspen Polymers requires special expertise. Predicting
reliable physical and thermodynamic properties of a chemical system is
important in process simulation for simulating chemical unit operations
such as reactors and separators. Unfortunately, creating thermophysical
properties for polymers, as well as polymerization reaction models, is
especially challenging and requires attention to detail. Thermodynamic
phase equilibrium models are categorized as either activity-coefficient or
equation-of-state (EOS) based models. In the present work, EOS models
were selected for the polypropylene process due to the nature of the
species and high operating pressure involved. EOS models are suitable for
systems at moderate to high pressures and reactor pressure for this gas-
phase polypropylene process ranges from 20 to 30 bar [5]. According to
Gross and Sadowski [20], a model based on the perturbed-chain statistical
associating fluid theory (PC- SAFT EOS), is the best for describing physical
and thermodynamic properties of a polymeric systems. Therefore, PC-
SAFT EOS was used to model the physical and thermodynamic properties
for the polypropylene process. The PC-SAFT model is an extension of the
prestigious SAFT EOS model. The main difference between these
models is that the PC-SAFT model considers hard sphere chains while
SAFT model accounts for hard spheres. This allows PC-SAFT EOS to
include the connectivity of segments that comprise the chains when
considering the attractions between species. This improvement shows a
more realistic description of the thermodynamic behavior of chainlike
molecules [5, 21, 22]. The PC-SAFT EOS also shows superior prediction
for vapor-liquid equilibrium and binary mixtures of small molecules
compared to SAFT and Peng-Robinson models, respectively [5, 6].

Table 5 lists the components included in the model. The applied pure-
component parameters for the PC-SAFT equation of state model (EOS) are
listed in Table 6 [6]. The data listed in these tables were integrated into the
Aspen Polymers simulator associated with the built-in PC-SAFT EOS
model.

Table 5: component used for polypropylene gas phase


polymerization

Species Function
1. Propylene C 3 H 6 Monomer
2. Polypropylene(PP) Polymer
3. Propylene segment C 3 H 6 R Polymer segment
4. Hydrogen H 2 Chain transfer agent
5. Titanium Tetrachloride (CAT) Catalyst
6. Triethyl-Aluminium (COCAT) Co-catalyst
7. Nitrogen N 2 Inert
8. Water H 2 O Cooling water

Table 6: Pure component parameter for the PC-SAFT EOS [6]

No Component A U K K
B r mol g

1. Hydrogen H 2 0.8285 2.973 12.53 -
2. Propylene C 3 H 6 1.960 3.3536 207.2 -
3. Polypropylene(PP) - 4.147 298.6 0.0253
4. Catalyst 25 2.668 198.8 -
5. Co-catalyst 25 2.668 198.8 -
Based on the thermodynamic model and the component parameters that
are suitable for the reaction conditions involved in the present process [5,
6], a RCSTR module within Aspen Polymers was selected to model the
gas-phase fluidized polymerization reactor. Furthermore, the
characterization of the ZieglerNatta catalyst and a set of two-site kinetic
schemes with reaction rate constants were incorporated into the model.
The emulsion phase can be simply presented by a single RCSTR model
which takes gaseous feed that includes the propylene gas, hydrogen gas
and the nitrogen gas as an inert and 88% of the solid feed which is Ziegler-
Natta catalyst [14]. For modeling the bubble phase, which accounts for the
gaseous feed and 12% of the solid feed, there are two options in Aspen
Polymers: a single RPlug or a series of RCSTR. Since the behaviour of a
plug-flow reactor can be approximated by that of a multistage CSTR [23], a
series of four equal- volume RCSTR modules was chosen to represent the
bubble phase due to an impractical low polypropylene production using an
equivalent RPlug module.
A major problem faced during the process simulation was the convergence
of the recycle stream which was not solved in a previous work [6]. In the
present study, according to the calculation procedure of the process flow
sheet, the problem was addressed and solved with some difficulty. From
this angle, this work can be regarded as the first of its kind to be able to
estimate the real gas-phase fluidized bed polymerization system which
considers both the emulsion phase and bubble phase for predicting the
polymer production rate, weight average molecular weight, number
average molecular weight, PDI and MFI with Aspen Polymers. The flow
sheet for the complete gas phase catalytic propylene polymerization
fluidized-bed reactor is shown in Figure2.

Reaction mechanism with nominal kinetic parameters

Several other models have been proposed in the literature to describe the
kinetic reaction for a heterogeneous Ziegler-Natta catalyst [1, 12-15]. The
Ziegler-Natta catalyst, considering multiple active sites of two (2) or four (4)
and as well as heat- and mass-transfer resistance, tends to produce a
polymer with a broad molecular weight distribution. The effect of multiple
site types is more
significant than the effect of heat- and mass-transfer resistances. The
single-site kinetic model is incapable of describing the kinetic behavior,
production rate and molecular weight distribution of propylene
homopolymerization. The added complexity of using more sites may limit
the models use for simulation purposes, and the estimation of the large
number of kinetic parameters may be restrictive [12]. Therefore, a two-type
active site was considered in the present study to describe polymer
properties for both models. Using similar methodology to McAuley et al. [1],
Carvalho de et al. [12] and Kissin [13], the kinetic model was developed for
ZieglerNatta catalysts containing multiple active sites to describe the
homopolymer production rate, molecular weight and its distribution.
The reaction rate constants used in this work were taken from different
published works on similar reactive systems [1, 6, 15]. This is mainly due to
the lack of a unique source that covers all the kinetic parameters for
propylene polymerization. Characterization of polymer properties was
modeled using population balances and method of moments. The kinetic
scheme comprising of a series of elementary reactions and the rate
parameters, used for the two phase model and Aspen Polymers simulator,
are listed in Tables 1 and 2, respectively. Aspen Polymers and the two-
phase model were standardized to use the same components in the input
flow and kinetic parameters

Table 1 and Table 2

PROCESS MODELING METHODOLOGY USING TWO-PHASE MODEL

The kinetics of propylene homo-polymerization over a ZieglerNatta


catalyst based on the model developed by Shamiri et al. [14] and the
dynamic two-phase flow approach proposed by Cui et al. [16, 17] were
combined to provide a more realistic understanding of the phenomena
faced in the bed hydrodynamics. The kinetic model consists of mass
balances on the species present in the reactor written as a series of
algebraic and differential equations. Characterization of polymer properties
was modeled using population balances and method of moments which
were used to predict the polymer production rate, weight average molecular
weight and MFI. The set of moment equations are given in Table3.
. Table 3
The parameters used for the two-phase model are those reported by Cui et
al. [16]. Jafari et al. [18] showed that using the parameters reported by Cui
et al. [16], for either Geldart A or B particles, provide results that are in good
agreement with the experimental data involving fluidized bed reactors for
both the bubbling and turbulent fluidization regimes.
The assumptions considered in developing the model are summarized
below:
The fluidized bed comprises of two phases: bubble and emulsion.

The emulsion phase is not at the minimum fluidization condition and the
bubble phase contains solid particles.

Reactions occur in both bubble and emulsion phases.

There is negligible resistance to heat and mass transfer between the gas
and polymer particles due to small catalyst particles, low to moderate
catalyst activity or polymerization rates [19].

Constant mean particle size is assumed throughout the bed.

A two-site kinetic scheme is assumed.

Side reactions with poisons are neglected.

In a fluidized bed reactor, upward motion of the gas bubbles causes


enough mixing of solid
particles in the emulsion phase. Therefore, concentrations of various
species and temperature are nearly uniform in the emulsion phase.
Consequently, a pseudo-homogeneous CSTR is a valid assumption and
can be applied to the modelling process [1]. The bubbles travel up through
the bed at constant velocity and the particles within the bubbles present a
downward flow, growing in size and weight as they flow downwards which
makes the assumption of plug flow valid for such a regime in the bubble
phase.This two-phase model is based on the principles of fluidization and
the experimental findings on the significance of solid particles present in
the bubble phase and the excess gas in the emulsion phase [16, 17]. The
correlations needed for estimating the void fractions of the bubble and
emulsion phases from the dynamic two-phase model are summarized in
Table 4.
Table 4
Assuming that the only significant consumption of monomer is by the
propagation reaction and that consumption of hydrogen is by the transfer to
hydrogen reaction, the following expression for the consumption rate of
component (monomer and hydrogen) can be obtained:
For monomer:
(1) 1 ( ) [ ] (0, ) 1 NS i i j p k j R M Y j i
For hydrogen:
(2) 1 [ ] (0, ) ( ) 2 NS i i fh j R M Y j k j i
The total polymer production rate for each phase can be calculated from:
(3) 2 1 p i i i R Mw R
in which Ri is the instantaneous rate of reaction for monomer and
hydrogen.
The volumetric outflow rate of the polymer, Rv, can be determined from the
consumption rates of the monomers and the rate of change of the weight of
polymer in the reactor:
(4) / MwR dBdt w Rv s s
Control of MFI is an important issue for producing the needed
polypropylene grade. The MFI of a polymer is a function of its molecular
weight () which is related to the operating conditions of the reactor and the
feed composition. The relation between MFI and the weight average
molecular weights of polypropylene is given by [20]: M w
(5) 1 0.288 111525 M w MFI

3.2 MODELLING

We are going to use the Kunii-Levespiel bubbling model to describe


reactions in the fluidized bed reactor. In the model, the reactant gas enters
the bottom of the bed and flow up the reactor in the form of bubbles. As the
bubbles rise, mass transfer of the reactant gases takes place as they flow
(diffuse) in and out of the bubble to contact the solid particles where the
reaction product is formed. The product then flows back into the bubble
and finally exits the bed when the bubble reaches the top of the bed. The
rate at which the reactant and product transfer in and out of the bubble
affects the conversion, as does the time it takes for the bubble to pass
through the bed.
Consequently, we need to describe the velocity at which the bubbles move
through the column and the rate of transport of gases in and out of the
bubbles. To calculate these parameters, we need to determine a number of
fluid mechanics parameters associated with the fluidization process. These
are:

3.2.1 Minimium Fluidization Velocity( U ) mf

In the fluidized bed reactor calculations, the first step taking in resolving
problem is to calculate Minimium Fluidization Velocity which is the velocity
at which the fluidized bed reactor starts to fluidized. The Minimium
Fluidization Velocity can be calculated from an equation below which is a
form of Ergun equation for Geldart particles of type B (Lucas et al, 1986)
Re mf { 29.5 0.0357 Ar} 2 29.5 (3.1)
2 1

d 3p g polymer g g
Remf (3.2)
g2
Re mf g
U mf (3.3)
d pg
polymer Bulk
polymer density, g
g gravitational acceleration, g gas density

3.2.2 Minimium Fluidization Porosity( ) mf

The bed voidage at minimium fludization can be estimated by the


correlation of Broadhurst and Becker (1975):
0.029 0.021

0.72
g2 g
mf 0.586 (3.4)
g d 3
g polymer g p polymer
Where geometric constant 0.7 in this study

3.2.3 Bubble size:


The equations for the velocity of bubble rise are functions of the bubble
diameter, an elusive value to obtain. Velocity of bubble rise Ub single
velocity as might be expected, it has been found to depend on such factors
as bed diameter, height above the distributor plate, gas velocity, and the
components that affect the fluidization characteristics of the particles.
Unfortunately, for predictability, the bubble diameter also depends
significantly upon the type and number of baffles, heat exchangers tubes,
and so forth, within the fluidized bed (sometimes called internals). The
design of the distributor plate, which disperses the inlet gas over the bottom
of the bed, can also have a pronounced effect upon the bubble diameter.
Studies of bubble diameter carried out thus far have concentrated on
fluidized bed with no internals and have involved rather small beds. The
best relationship between bubble diameter and height in the column at this
writing seems to be that of Mori and Wen, 10 who correlated the data of
studies covering bed diameters of 7 to 130 cm, minimum fluidization
velocities of 0.5 to 20cm/s, and solid particle sizes of 0.006 to 0.045cm.
their principal equation was:
0.3 h
d bm d b
exp Dt
(3.5)
d bm d bo

In this equation, db is the bubble diameter in a bed of diameter Dt ,

observed at a height h above the distributor plate; d bo is the

diameter of the bubble formed initially just above the distributor plate, and
d bm is the maximum bubble diameter attained if all the bubbles in any
horizontal plane coalesce to form a single bubble (as they will do if the bed
is high enough). The maximum bubble diameter, d bm has been observed to
follow relationship
d bm 0.652[ Ac U 0 U mf ]0.4 (3.6)
For all beds, while the initial bubble diameter depends upon the type of
distributor plate. For porous plates, the relationship
d bo 0.00376U 0 U mf 2
(3.7)
d min imium Is observed, and for perforated plates, the relationship
0.4
d bo 0.347 Ac U 0 U mf 1 (3.8)
nd
this equation appears to be valid, in which nd is the number of perforations.
For beds with diameters between 30 and 130cm, these relations appear to
predict bubble diameters with an accuracy of about 50%; for beds with
diameters between 7 and 30cm, the accuracy of prediction appears to be
approximately +100%, -60% of the observed values.
Werther developed the following correlation based on a statistical
coalescence model: 11
d b =0.8531+0.272
U O U mf 3.1 0.0684
The bubble size predicted by this model is close to that predicted by Mori
and Wen for large diameter bed(2m) and smaller than that suggested by
Mori and Wen for small diameter beds (0.1m)

3.2.4 Bubble Velocity U br

From experiments with single bubbles, Davidson and Harrison found that
the velocity of rise of a single bubble could be related to the bubble size by
U br 0.71 gd b 2 (3.9)
1

When many bubbles are present, this velocity would be affected by other
factors. The more bubbles that are present, the less drag there would be on
an individual bubble; the bubble would carry each other up through the bed.
The greater number of bubbles would result from large amounts of gas
passing through the bed (i.e., a large value of U 0 ). Therefore, the larger the
value of U 0 )., the faster should be the velocity of a gas bubble as it rises
through the bed.
Other factors that should affect this term are viscosity of the gas and the
size and density of the solid particle that make up the bed. Both of these
terms also affect the Minimium Fluidization Velocity and so this term might
well appear in any relationship for the velocity of bubble rise; the higher the
Minimium Fluidization Velocity, the lower the velocity of the rising bubble.
Adopting an expression used in gas-liquid systems, Davidson and Harrison
proposed that the rate of bubble rise in a fluidized bed could be
represented by simply adding and substracting these terms: for situation
where many bubbles occur as in the case of a fluidized bed reactor. In a
fluidized state the bubble velocity U b
U b U br U 0 U mf (3.10)
U 0 Superficialvelocity
U mf velocityat the minimium fluidization
Substituting the velocity of single bubble
U b U 0 U mf 0.71 gd b 2 (3.11)
1

3.2.5 Bubble Fraction


Fraction of beds in the bubble phase using the Kunii-Levenspiel model, the
fraction of the bed occupied by the bubbles and wakes can be estimated by
material balances on the solid particles and the gas flows. The parameter is
the fraction of the total bed occupied by the part of the bubbles that does
not include the wake, and is the volume of wake per volume of bubble. The
bed fraction in the wakes is therefore . Wake angle and wake
fraction of three-dimensional bubbles at ambient conditions; evaluated from
x-ray photographs by Rowe and Partridge

3.2.6 Velocity of solid U S

The bed fraction in the emulsion phase (which includes the cloud) is
1 . Letting Ac and c representing the cross sectional area of the
bed and the density of the solid particles, respectively, a material balance
on the solids give:
Solid flowing downward in emulsion=Solid flowing upward in wakes
Ac c 1 U s U b c Ac (3.12)
U b
Us (3.13)
1
A material balance on the gas flows gives
AcU 0 Ac U b Ac mf U b Ac mf 1 U c (3.14)
(Total gas flow rate)=(gas flow in bubbles)+(gas flow in wakes)+(gas flow in
emulsion)
AcU 0 Ac U b Ac mf U b Ac mf 1 U c (3.15)
AcU c Total gas flow
Ac U b Gas flow in bubble
Ac mf U b Gas flow in wakes
Ac mf 1 U e Gas flow in the emulsion
U mf
The velocity of the emulsion phase Ue Us
mf

3.2.7 Volume fraction bubble


(in the fluidization literature, U s , is almost always taken as positive in the
downward direction). Factoring the cross-sectional area, we obtain an
expression for the fraction of the bed occupied by bubbles:
U 0 U mf
(3.16)
U b U mf 1
The wake parameter, is a function of the particle size. The value of has
been observed experimentally to vary between 0.25 and 1.0, with typical
value close to 0.4. Kunii and Levenspiel assume that the last equation can
be simplified to
U 0 U mf
(3.17)
Ub
5U mf
Which is valid for U b U mf ,(e.g. Ub )-------(3.18)
mf
The actual flow pattern in the fluidized bed reactor show a highly
complicated behavior due to gas-solid interactions. This phenomenon
corresponds to dynamic gas-solid distribution as reported by (Cui et al..,
2000). Based on the dynamic two-phase structure, the fraction of bed
containing the bubbles is expressed as:

3.2.8 Emulsion Velocity( U ) e

Many recent studies show that the emulsion phase does not stay at
minimum fluidization but it may contain more gas at higher gas velocity
( Abramhamson et al., 1980, Chaouki et al., 2000). It is expressed as :
U mf
The velocity of the emulsion phase Ue U s -------------(3.19)
mf

3.2.9 Bubble phase and Emulsion phase Voidage


The mean voidage of bubble and emulsion phase for Geldart B particle
were defined by Cui et al., (2000)
U 0 U mf
b 1 0.146 exp (3.20)
4.439
U 0 U mf
e mf 0.2 0.059 exp (3.21)
0.429
3.2.10 Mass Transfer Coefficient ( Mass Transport in
Fluidized Bed Reactor)
In the bubbling fluidized bed reactor, bubble exchanges mass with
emulsion phase, Kunii and Levenspiel(1969) considered that the mass is
transferred from the phase to the surrounding clouds and then to the
emulsion phase.
There are two types of mass transport between gas and solid. In some
situations this can affect the analysis of fluidized bed behavior significantly,
and in others it might not enter the calculations at all. In the treatment of
this type of transfer, it will be seen that this types of operations . the second
type of mass transfer is unique to fluidized bed operations. It concerns the
transfer of material between the bubbles and the clouds, and between the
cloud and the emulsion. In almost every type fluidized bed operations,
there are significant gas-phase concentration differences between the
various elements of the fluidized bed. Consequently, calculations involving
this type of mass transfer occur in almost every fluidized bed analysis.

Transfer between bubble, cloud and emulsion.

3.2.11 Gas Solid Mass Transfer


In the bubble phase of a fluidized bed, the solid particles are sufficiently
separated so that in effect there is mass transfer between a gas and single
particles.
The most widely used correlation for this purpose is the 1938 equation of
Froessling (1938) for mass transfer to single spheres given as:

The relative velocity between the solid particle and the gas used in
calculating the Reynolds number will be taken as
In the emulsion phase, the equation would be one that applied to fixed-bed
operation with a porosity in the bed equal to and a velocity of . the equation
recommended by Kunii and Levenspiel:

Mass transfer coefficients obtained from these relationships may then be


combined with mass transfer among the various phases in the fluidized bed
to yield the overall behavior with regard to the transport of mass. Owing to
the small particle sizes and high surface area per volume of solid used in
fluidized beds, the mass transfer from the gas to the surface is usually quite
rapid and consequently it seldom limits the reaction.
3.2.12 Mass Transfer between the Fluidized Bed
Phases
For the gas interchange between the bubble and the cloud, Kunii and
Levenspiel defined the mass transfer coefficient in the following manner:

Where and are the concentration of A in the bubble and cloud phase
respectively, and represents the number of moles of A transferred from
the bubble to the cloud per unit time unit volume of bubble (). The concept
of basing all mass transfer (and later, all reaction) on the bubble volume
proves to simplify the calculations markedly. For the products, (e.g., B in A-
B) the rate of transfer into the bubble from the cloud is given by a similar
equation

The mass transfer coefficient can also be thought of as an exchange


volume q between the bubble and the cloud.

Where

Using Davidsons expression for gas transfer between the bubble and the
cloud, and then basing it on the volume of the bubble, Kunii and Levenspiel
obtained this equation for evaluating

Where Umf is in cm/s, db is in cm, Dab is the diffusivity(cm2/s) and g is the


gravitational constant (980 cm/s2).
We note
And the order of magnitude of this coefficient is equal to 2s-1. Similarly,
these authors defind a mass transfer coefficient for gas interchange
between the cloud and the emulsion:

Where is the moles of A transferred from the cloud to the emulsion per unit
time per unit volume of bubble. Note thet even though this mass transfer
does not involve the bubble directly, it is still based on the bubble volume.
Using Higbies penetration theory and his analogy for mass transfer from a
bubble to a liquid, Kunii and Levenspiel developed an equation for
evaluating
Where U is the velocity of bubble rise in cm/s and the other symbols. And
the order of magnitude of this coefficient is equal to 1s-1. K can also be
thought of as the exchange volume between the cloud and the emulsion.
With the knowledge of mass transfer coefficients, the amount of gas
interchange between the phases of a fluidized bed can be calculated and
combined to predict the overall mass transfer behavior or reaction
behavior of fluidized bed process.

3.2.13 Heat Transfer Coefficient


The heat interchange coefficient between the bubble and emulsion phase
in the fluidized bed reactor can be written as:
=Heat interchange between bubble and cloud phase
= Heat interchange between cloud and emulsion phase
= Heat interchange between bubble and emulsion phase

3.2.14 REACTION KINETICS


3.2.14.1 Reaction in the Fluidized Bed Reactor
There are three (3) factors controlling the reaction in the fluidized bed
reactor
1. Mass transport of the reactant species from the bubble
phase to the cloud phase and into the emulsion phase so
that they dont get in-contact with the solid particle.
2. The type of reaction that occur inside the reactor to form the
product.
3. Ones the product are formed, they are transported backed to
the bubble phase

Reactor Behavoir in a Fluidized Bed


To use the Kunii-Levenspiel model to predict reaction rates in a fluidized
bed reactor, the reaction rate law for the heterogeneous reaction per
gram(or other fixed unit) of solid must be known. Then the reaction rate in
the bubble phase, the cloud, and the emulsion phase, all per unit of bubble
volume, can be calculated. Assuming that the reaction rates are known, the
overall reaction rate can be evaluated using the mass transfer relationship
represented in the preceding section. All this is accomplished in the
following fashion. We consider the an nth order, constant-volume catalytic
reaction.
In the bubble phase

In which the reaction rate is defind per unit volume of bubble. In the cloud
phase,
Similarly in the emulsion,

Where are the specific reaction rates in the emulsion, cloud and bubble
respectively. In the latter two equations, the reaction rate is also defined per
unit volume of bubble.
3.2.14.2
3.2.15

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