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VINYL
CHLORIDE
DROP BEHAVIOUR
POLYMERISATION
IN SUSPENSION
REACTORS
by
Mohamed ZERFA
A Doctoral Thesis
August 1994
by Mohamed Zerfa
DEDICATION
CIOM}rMOTHEQAND
FATHER
TO MySISUYER,SAND BROTHERS
TO ALL '}LOSE ` J-[OHELPED ME DURING THE HARD
TI v( 5
I DEDICATE
THIS MO1
iii
STWORK
Acknowledgements
Iv
SUMMARY
The suspension polymerisation of vinyl chloride is the main industrial process used
for the production of PVC. One of the key operations in this process is liquid-liquid
formed
by
depends
dispersion
The
the
such
a
system
upon
stability of
agitation.
drop
have
be
The
to
that
present
study
clarifies
controlled.
a number of parameters
behaviour in dispersion of vinyl chloride monomer, using poly(vinyl
alcohol)
stabilisers, before and during polymerisation. In order to carry out our experiments,
a11. capacity pressurised reactor system connected to an external microscopic
Parameters
designed
system.
affecting the
along
with
a
reflux
optical cell was
initial
VCM
such as residence
time, agitation speed, volume fraction and type and concentration of suspending
Sauter
in
details
have
been
the
and
a
correlation
relating
mean
some
studied
agent
diameter (D32) to the vessel geometry, the volume fraction and the Weber number
has been proposed. Studies of drop coalescence using a tracer ( dye ) under different
experimental
conditions
non-polymerising
showed that
the rate
of coalescence
between
agglomeration
processes in
suspension polymerisation
were
also
investigated. It was found that the method of addition of initiator was very important
final
The
it
the
the
the
of
product.
as
well
as
conversion
as affects
morphology
influence of the condenser operation in the suspension polymerisation of vinyl
formation
droplet
its
the
of
were also studied
mechanism
effects on
chloride and
from
investigated.
droplets
fate
the
the
condenser
were
returning
of
monomer
and
The external morphology of the final PVC particles was studied using scanning
electron microscopy ( SEM ) technique.
TABLE OF CONTENTS
Page
LIST OF TABLES
xi
LIST OF FIGURES
xiii
LIST OF SYMBOLS
xix
CHAPTER 1- INTRODUCTION
1.2 - Objectives
CHAPTER 2- LITERATURE
REVIEW
11
CHAPTER 3- THEORETICAL
CONSIDERATIONS
12
20
20
20
23
31
24
25
30
33
34
36
41
43
47
48
vi
42
44
48
52
3.4.4.1
Advantages
51
54
and disadvantages of
the
suspension
polymerisation process
55
56
61
of vinyl
chloride
suspension
polymerisation
61
65
73
73
89
89
AND EXPERIMENTAL
83
89
METHODS
93
5.1 - Materials
5.1.1 - The dispersed phase
93
96
97
99
100
droplets
distribution
chloride
of
vinyl
size
101
93
97
97
vii
99
102
103
105
105
107
110
agitation speed
111
110
111
117
121
125
125
6.2.2 - Effect of residence time on the vinyl chloride droplet size and
size distribution
132
6.2.3 - Influence of the type of suspending agent on the drop size and
size distribution of vinyl chloride
6.2.4 - Influence of the baffles on the droplet size and size distribution
6.2.5 - Effect of the suspending agent concentration on the volume and
droplets
distribution
chloride
of
vinyl
size
viii
136
147
151
vinyl chloride
6.2.7 - Generalised correlation relating the steady state drop size to the
Weber
fraction
the
the
number
and
volume
vessel geometry,
6.3 - Effect of mixing conditions on the coalescence rate between the
(dye
droplets
experiments)
vinyl chloride
168
176
experiments)
6.4 - PVA ( Alcotex spec."A" ) adsorption on vinyl chloride monomer
183
droplets
6.4.1 - Effect of residence time on PVA (72.5% hydr. ) adsorption on
VCM droplets
185
187
191
193
195
195
199
205
209
217
FOR FURTHER
222
WORK
222
226
ix
227
CHAPTER 8- REFERENCES
APPENDIX
240
APPENDIX
244
APPENDIX
260
APPENDIX
262
APPENDIX
264
APPENDIX
267
LIST OF TABLES
Table - 3.1 - Droplet size correlation for liquid-liquid dispersion in stirred vessels
Table - 3.2 - Range of application of impellers with relation to viscosity
Table - 3.3 - Recipe for poly(vinyl chloride) batch emulsion polymerisation
Table - 3.4 - Primary protective colloids used in the suspension polymerisation of
vinyl chloride
Table - 3.5 - Initiators for PVC suspension or mass polymerisation
Table - 3.6 - Typical suspension polymerisation recipe
Table - 3.7 - List of PVC nomenclature
Table - 5.1 - Some physical properties of the polymerisation initiator
Bis(4-t. butylcyclohexyl)peroxydicarbonate
Table - 5.2 - Some physical properties of toluene
Table - 5.3 - Physical properties of vinyl chloride
Table - 5.4 - Some physical properties of distilled water
Table - 5.5 - Some physical properties of the suspending agent (PVA) used
Table - 5.6 - Quantities of vinyl chloride, distilled water and suspending agent used
for each volume fraction
Table - 5.7 - Concentration of PVA at different volume fractions
Table - 6.1 - Effect of baffles on the mean drop size Dm and Sauter mean diameter
D32
Table - 6.2 - Reynolds number and microscale of turbulence values for different
agitator speed
Table - 6.3 - Variation of the Sauter mean diameter with agitator speed for S3
suspending agent
Table - 6.4 - Critical surface coverage at different agitation speeds ((p = 0.1)
Table - 6.5 - Values obtained for the density of the mixture (p,, ), the PVA
different
interfacial
(CPVA)
tension
the
at
volume
and
concentration
fractions
xi
Table - 6.6 - The percentile particle sizes by cumulative volume for different
conversions
Table - 6.7 - Variation of vinyl chloride monomer conversion and final PVC particles
porosity with reflux rate
Table - 6.8 - Variation of PVC particles porosity with the timing of reflux
xii
LIST OF FIGURES
acetate) on PVC
grain properties
Figure - 3.18 - Build-up of structure within the vinyl chloride droplet during
polymerisation
Figure - 3.19 - Schematic representation of the mechanism of vinyl chloride
polymerisation
Figure - 3.20 - Growth of a PVC suspension resin grain
Figure - 3.21 - Initial vinyl chloride emulsion
xiii
xlv
Figure - 6.10 - Variation of toluene Sauter mean diameter with residence time
Figure - 6.11 - Effect of baffles on the toluene drop size distribution
Figure - 6.12 - Vinyl chloride droplets, dispersed in distilled water, stabilised by
PVA at different agitation speeds
Figure - 6.13 - Variation of vinyl chloride Sauter mean diameter and mean drop
diameter with agitation speed
Figure - 6.14 - Variation of vinyl chloride Sauter mean diameter and mean drop
diameter with agitation speed on a log-log scale
Figure - 6.15 - Variation of vinyl chloride drop size distribution with agitator speed
Figure - 6.16 - Vinyl chloride droplets dispersed in distilled water, stabilised by PVA
at different residence time
Figure - 6.17 - Variation of vinyl chloride Sauter mean diameter and mean drop
diameter with residence time
Figure - 6.18 - Variation of vinyl chloride droplet size distribution with residence
time
Figure - 6.19 - Variation of dimentionless drop size with dimentionless time
Figure - 6.20 - Surface tensions for some aqueous solutions for Alcotex grades PVA
in
PVC
typically
polymerisation
used
against concentrations
Figure - 6.21 - Variation of vinyl chloride droplet size distribution with agitator speed
for PVA (KH17) stabiliser
Figure - 6.22 - Variation of vinyl chloride droplet size distribution with agitator speed
for PVA (Alcotex spec."A") stabiliser
Figure - 6.23 - Variation of vinyl chloride droplet size distribution with agitator speed
for PVA (Alcotex "A55") stabiliser
Figure - 6.24 -Variation of vinyl chloride droplet size distribution with agitator speed
for PVA (Polyvic S202) stabiliser
Figure - 6.25 - Variation of vinyl chloride droplet size distribution with agitator speed
for PVA (S3) stabiliser
Figure - 6.26 - Effect of the degree of hydrolysis on the mean drop diameter of
droplets
chloride
vinyl
Figure - 6.27 - Effect of the degree of hydrolysis on the Sauter mean diameter of
droplets
chloride
vinyl
xv
Figure - 6.28 - Variation of vinyl chloride droplet size distribution with agitator speed
in an unbaffled reactor
Figure - 6.29 - Effect of baffles on the mean drop diameter of vinyl chloride droplets
Figure - 6.30 - Effect of baffles on the Sauter mean diameter of vinyl chloride droplets
Figure - 6.31 - Variation of vinyl chloride drop size distribution at different PVA
concentrations
Figure - 6.32 - Variation of vinyl chloride Sauter mean diameter with PVA
different
agitation speeds
at
concentration
Figure - 6.33 - to - 6.37 - Variation of vinyl chloride volume distribution with PVA
different
agitation speeds
at
concentration
Figure - 6.38 - Variation of vinyl chloride drop size distribution at different volume
fractions
Figure - 6.39 - Variation of Sauter mean diameter with volume fraction at different
agitation speeds
Figure - 6.40 - to - 6.44 - Variation of vinyl chloride volume distribution with volume
fraction at different agitation speeds
Figure - 6.45 - Specific interfacial tension of Gohsenol solution against
trichloroethylene
Figure - 6.46 - Correlation of specific interfacial tensions
Figure - 6.47 - to - 6.52 - Weber number variation with Sauter mean diameter for
different volume fractions
Figure - 6.53 - Variation of the Weber number vs Sauter mean diameter slope with
fraction
volume
Figure - 6.54 - Correlation of VCM drop size with volume fraction and Weber number
Figure - 6.55 - Variation of Vc / (Vc + Vi) with residence time at different premixing
time of the non-dyed VCM droplets
Figure - 6.56 - Variation of Vc / (Vc + Vi) with residence time at different PVA
concentrations
Figure - 6.57 - Variation of Vc / (Vc + Vi) with residence time at different agitation
speeds
Figure - 6.58 - Dyed vinyl chloride droplets added to preformed suspensions at
different residence time of dyed VCM
xv'
xvii
Figure - 6.75 - SEM photographs of latex PVC particles during suspension PVC
reaction using reflux condenser
Figure - 6.76 - Changes occurring in vinyl chloride droplets during early stages of
suspension polymerisation
with reflux
xviii
LIST OF SYMBOLS
A=
A(ho)
constant
C=
cc
Concentration of PVA
CPVA
d=
D=
Impeller diameter
D32
Adhesion energy
Correlation factor
DA*
d;
d;
Dm
dma
dmin
Ea
Et
fl(p)
F=
Adhesion force
AGtotai =
AGelectrasttic
AG
vanderwalls
AGster =
=
Energy due to steric effects (repulsion force)
ho
I=
lo
K'
KL
I=
xix
L=
Macroscale of turbulence
N=
Impeller speed
Ti
Nt
viscosity group
P=
P*
R=
Gas constant
RA
Reynolds number
Re
Sc
Temperature
T=
TT
critical temperature
t=
t;
tmin
u2
u2(r)
distance r apart
Vu
VC
V;
Vs
W=
Blade width
We
Weber number
(We)crjt =
Greek
r
d
r
v=
E=
xx
7=
PC
force
(surface
per unit area)
shear stress
pd
pm
tid
6
6C
6d
cp
xxi
CHAPTER 1
I- INTRODUCTION
chloride),
at the
present day. It is characterised by its low cost and versatility of applications. Its popularity
is also due to its ability to incorporate different
high degree of chemical resistance. PVC polymer has found markets in a large number
of industries such as packaging, paints, surface coating, building
Because of the insolubility
polymerisation
Vinyl chloride
chloride) is commercially
The
by the suspension process. The latter process is presently used for the commercial
production
of approximately
80 % of the world's
PVC.
interface,
droplets
/
Vinyl
formed
film,
to
the
the
give
water
chloride
the thin colloidal
at
better elastic properties. The effect of the elastic properties is enhanced by increasing
droplets
the
the
coverage
of
the concentration of
suspending agent until, a certain surface
is reached. At that point, a "critical surface coverage" is established and, further increase
in the suspending agent concentration will have a very little effect on the drop stability.
In the suspension polymerisation process, the monomer phase is dispersed in the
dispersion
dispersion.
The
form
the
to
of
characteristics
a
continuous aqueous phase
are mainly governed by the physical and chemical properties of the components as well
feature
important
Another
features
this
two-phase
the
of
the
equipment.
of
mechanical
as
droplets.
It
is,
between
heat
the
transfer
is
the
to
the
and
mass
control
ability
system
liquid
droplets,
distribution
by
the
known
the
of
that,
and
size
size
controlling
also, well
it is possible to predict the size and size distribution of the final polymer particles. In the
between
the
transfer
the
mass
vinyl
chloride,
of
polymerisation
case of suspension
droplets is believed to be mainly due to coalescence. During collision, if two droplets
film
drain
down
for
liquid
long
to
to
the
in
a certain
together
enough
contact
remain
droplets
film
the
the
the
will coalesce.
thickness,
occur
and
will
rupture of
minimum
During the suspension polymerisation of vinyl chloride monomer, insoluble PVC
formation
different
The
droplets.
inside
is
formed
the
stages
of
particle
monomer
polymer
( i. e nucleation, growth and aggregation ), as well as the properties of the continuous
distribution
(i.
final
determine
the
and
the
e
grain
size,
size
particles
properties of
phase
in
One
the manufacture of
).
type
the
of surface active agents used
main
of
porosity
Suspension PVC polymers are partially hydrolysed poly( vinyl acetate ). Their function
is to adsorb at the monomer / water interface and, thus, prevent the coalescence of the
droplets. When adsorbed, the PVA forms a thin "skin" at the monomer surface at the
"skin"
formation
The
the
prolongs the contact time
the
of
polymerisation.
early stages of
for drop coalescence and thus reduces the probability of coalescence. Another feature
initially
is
that
the
of
reflux
condensers,
use
of vinyl chloride suspension polymerisation
having
different
PVC
does
heat
increase
transfer,
the
properties
to
particles
produce
used
from those produced without the occurrence of reflux. Consequently, there is a growing
in
detailed
the
for
taking
the
suspension
place
phenomena
of
understanding
a
more
need
droplets.
behaviour
the
to
the
those
of
monomer
related
polymerisation reactor especially
1.2 - Objectives :
The objectives of the present research project were to investigate the possibility of
influence
have
believed
the
to
on
the
a
great
are
which
parameters
of
controlling some
during
the
suspension
vinyl chloride polymer
particle size and particle morphology of
following
intended
it
For
the
to
aspects of vinyl
this
study
was
purpose,
polymerisation.
chloride suspension polymerisation:
A- Drop studies :
A. 1 - The study of the variation of the drop size and drop size distribution, which results
from changing parameters that can have an influence on the drop size, such as residence
time, turbulence intensity, baffles, volume fraction of the dispersed phase and suspending
These
type
experiments were performed using a simulated
concentration.
and
agent
monomer.
A. 2 - After having characterised the effect of the latter parameters using a simulated
monomer, some experiments were performed using vinyl chloride monomer.
A. 3 - The study of the mass transfer between the different phases ( from drop to drop,
from water to drop and vice versa ). This was performed by carrying out some dye
experiments.
A. 4 - The study of the extent of suspending agent adsorption on the monomer droplets.
B- Polymerisation experiments :
B. 1 - The study of the mechanism of droplets formation and subsequent droplets
different
during
the
stages of the vinyl chloride suspension
agglomeration
polymerisation.
B. 2 - The study of the influence of reflux condenser operation on the grain size and
morphology. This was performed using a series of model experiments.
CHAPTER 2
2- LITERATURE REVIEW
details
More
about the general principles and theories
polymerisation.
suspension
in
to
these
chapter -3-.
are
presented
subjects
related
dispersions :
2.1 - Liquid-liquid
Liquid-liquid
in
increase
in
There
to
order
are, general, used as multiphase process
engineering.
the interfacial area between the different phases to improve the interphase transport
dispersed
liquid
liquids
immiscible
When
two
a
system
containing
are
mixed,
rates.
droplets in a continuous phase is formed. In such a system, continuous break-up and
because
droplets
formed
the
of the turbulent
occur
simultaneously
coalescence of
for
is
it.
in
If
the
the
that
maintained
a sufficiently
of
system
agitation
exist
conditions
is established between break-up and
L.
C.
A.
Tavlarides,
L.
Coulaloglou,
H.
1966;
Valentas,
K.
(
and
al.
et
coalescence
1977; Narsimham, G. et al. 1979 ). At equilibrium, the breakage and coalescence
distribution
formed
droplets
the
the
the
of
size
and
size
average
rate
and
same
occur at
depend on the type and extend of agitation as well as on the physical properties of
the liquid mixture. The use of protective colloids such as PVA (partially hydrolysed
acetate)) or cellulose ethers may prevent coalescence and enhance the
drop stability by decreasing the interfacial tension. One of the main unit processes
poly(vinyl
involving
stabilised liquid-liquid
liquid-liquid
is
to
mainly
restricted
review
polymerisation.
The knowledge
Numerous
investigators
Tavlarides
(1969);
Gal-or
(
et
al.
vessels
flow,
dispersion
in
heat
the
transfer
as
as well
of
and mass
in the liquid-liquid
of Kolmogorov
about fifty
dispersions
years ago
hypothesis put forward was that, if the Reynolds number of the flow was high, the
from
be
liquid
in
estimated
the
of
could
a very small volume
system
properties of
( see chapter -3- for details on this theory ). Later,
Bachelor, G. K. (1947,1953)
and other workers extensively
J. O. (1959);
breakage
it
the
to
this
theory
of
and coalescence.
study
processes
and used
reviewed
This theory was investigated experimentally by many workers using different types
(
Calderbank,
P.
H.,
different
dispersed
techniques
experimental
and
phase systems
of
(1958); Shinnar, R. and Church, J.M., (1960); Shinnar, R., (1961); Chen, H. T. and
Middleman, S., (1967) and Sprow, F.B., (1967a)). Shinnar, R. (1960) tried to describe
both
breakage
influence
turbulence
the
and coalescence of
on
of
quantitatively
individual droplets by deriving relations and comparing them with experimental
dissipation
dependence
droplet
He,
the
on
energy
per
of
size
also, studied
evidence.
it
local
isotropy
by
the
theory
compared
and
with
of
unit mass, as predicted
different
He
data
of
sizes.
similar
reactor
vessels
geometrically
using
experimental
in
be
turbulence
theories
the
that
can
of
practical
value
of
statistical
concluded
F.
B.,
(1967a)
Sprow,
in
dispersions.
droplet
used an
agitated
size
estimating
determine
Coulter
(the
to
the
technique
counter)
electronic particle counting
distribution of drop sizes produced in turbulent liquid-liquid dispersion. He derived
dependence
isotropy,
local
based
the
that
the
theory
correct
predicts
of
on
an equation,
diameter.
impeller
drop
diameter
turbine
the
the
the
speed and
on
of
maximum
A variety of experimental approaches have been used to investigate the features of
dispersion behaviour. The most widely studied system is the impeller agitated,
baffled, batch, liquid-liquid dispersion. This system was used by many investigators
to study the variation of interfacial area, drop size distribution and breakage and
Coulaloglou,
R.,
(1961);
(
Shinnar,
function
of agitated speed
coalescence rates as a
C. A. and Taviarides, L. L., (1977); Brooks, B. W., (1979)), agitator type ( Skelland,
A. H. P. and Kanel, J.S., (1990)), residence time ( Chung, S.I., (1985); Hong, P.O.
C.
Lee,
J.
R.,
(1961);
(
Shinnar,
dimensions
M.,
(1983)),
Lee,
J.
and
vessels
and
Tasakorn, P., (1979)) and other physical parameters of the system. Brooks, B. W.,
(1979) developed a new technique to study the drop size distribution which consisted
in
He
decrease
dispersed
temperature.
the
of
a
small
as
a
result
phase
of solidifying
found that, for unbaffled vessels, mean drop diameters depended on impeller type
and were proportional to the stirrer speed raised to the power -1.2, while with a
turbine agitator the insertion of baffles appeared to lower the dependency of drop
O.
Lee,
J.
M.,
Hong,
P.
distribution.
the
and
size
size on stirrer speed and narrow
(1983) studied the changes of the average drop size and the minimum transition time
during
initial
liquid-liquid
dispersion.
the
to
steady
reach
state
period
of
required
The minimum transition time was found to depend on impeller speed and on the
impeller/tank diameter ratio as well as the system's physical properties. They also,
,
found that the average drop size changed exponentially from large to small while
the distribution changed less drastically from wide to narrow when speed increased.
Lee, J.C. and Tasakorn, P., (1979) reviewed the theory of drop break-up and described
in
liquid-liquid
for
drop
dispersions
the
size
stabilised
use
of
measurements
a method
to estimate the turbulence intensity factor. Results for the Sauter mean diameter in
dispersions of o-xylene stabilised with poly (vinyl alcohol) in baffled and unbaffled
tanks of different dimensions for phase volume fractions of 0.05 to 0.30 were also
for
baffled
The
obtained
vessels were correlated relating the Sauter
results
reported.
mean diameter to the volume fraction, the tank diameter and the impeller Weber
number. They, also, found that the intensity factor in baffled vessels was independent
of the tank size and the impeller speedwhile in unbaffled vessels it tended to increase
with increasing speed and tank size.
The effects of continuous phase viscosity on the drop size of liquid-liquid dispersions
in agitated vessels operated batchwise was experimentally examined by Stamatoudis,
M. and Tavlarides, L. L. (1985). They found that the effect of continuous phase
is
for
drop
distribution
high
the
size
most
pronounced
systems
of
on
viscosity
dispersed phase viscosities and that a logarithmic plot of the Sauter mean diameter
as a function of the impeller speed is a straight line, the slope of which varies with
the continuous phase viscosity. A year later, Calabrese, R.V. et al. (1986a, 1986b)
determined the extent to which dispersed phase viscosity and the interfacial tension
influence the equilibrium mean drop size and drop size distribution at constant
interfacial tension for dilute suspensionsby dispersing silicone oils of various grades
in water. They developed a mechanistic model for mean drop size which predicts
the moderate viscosity data and whose parameters correlate the high viscosity results.
They also, developed correlations for Sauter mean diameter using the latter
data
H.
Chen,
T.
to
their
the
of
and
compared
results
and
model
mechanistic
Middleman, S. (1967) and Arai, K. et al. (1977). A review of the work published in
the area of liquid-liquid dispersions was given more than a decade ago by Tavlarides,
L. L. and Stamatoudis, M. (1981). They discussed the dispersion phenomena such
distribution
drop
droplets,
breakage
the
and
presented
size
of
and
as coalescence
G.
E.
Recently,
Chatzi,
them.
that
predict
most widely used models and correlations
in
distributions
drop
the
(1991)
agitated
size
published a series of papers on
et al.
drop
impeller
the
They
temperature
size
the
on
speed
and
effect of
studied
vessels.
distributions. The use of laser diffraction technique to measure the drop size
in
increased
the
time
measuring small
the
sensitivity
and
sampling
shortened
diameter drops. They found that the system assumed characteristic bimodal
distributions within a very short time and that further stirring only reduced the drop
found
They
distribution.
their
the
also,
of
shape
sizes without substantially affecting
that an increase in temperature resulted in a size reduction and narrowing of the large
for
to
Furthermore,
the
distribution.
time
the
system
required
the
minimum
peak of
Weber
depend
found
different
the
to
number
on
conditions was
reach steady state at
of the main flow.
2.1.1 - Effect of surfactants :
Because of the complexity of the mixing process and its dependency upon a large
"clean"
systems
non-coalescing
with
number of parameters, many scientists work
(i. e. low dispersed to continuous phase ratio). Thus, most of the correlations and
(i.
liquid-liquid
"clean"
based
e. without
systems
on
models currently available are
industrial
in
trace
In
amounts of surface active
processes
most
reality,
surfactant).
impurities are frequently present. Some surface active agents are added intentionally
to obtain stable suspensions asis the casefor emulsion and suspensionpolymerisation
is
the
function
to
to
The
the
monomer/water
adsorb
agent
surface
active
of
processes.
interface and prevent other drops from approaching because of the steric repulsion
forces. Several investigations have been reported in the literature on the use of surface
active agents in liquid-liquid
R.
P.
Borwankar,
type
et al.
and
stabiliser
concentration.
variables such as monomer
(1986) tried to simulate the drop dispersion for suspension polymerisation of vinyl
dichloroethane
1,2
and ethylbenzene and using several
of
chloride using a mixture
HPMC (hydroxypropyl-methylcellulose)
products as suspending agents. They
determined the critical surface coverage of stabiliser necessaryto inhibit coalescence
diameter
Sauter
to the extent of agitation under turbulent
the
mean
and correlated
conditions. An in-situ photomicrographic technique was used to monitor the size
distribution of the suspended oil drops. They concluded that, polymeric suspension
in
dispersions
the
used
sufficient
against
coalescence,
when
stabilisers can stabilise
drop
distribution
H.
(1985)
Nilson,
the
of vinyl chloride
size
studied
et al.
quantities.
in water emulsions using a similar technique. They observed a large difference in
More
Chatzi,
depending
type
the
recently,
of
stabiliser
used.
on
coalescence stability,
E. G. et al. (1991) studied the effect of stabiliser concentration on the evolution of
drop size distribution. They determined the minimum time required for a system to
function
drop
diameters
the
of
as
a
average
reach a steady state and measured
developed
They,
temperature
also,
speed.
and
agitation
stabiliser concentration,
Sauter
diameter
(
(tr
time
transition
the
and
mean
minimum
correlations relating
in)
D32) with the Weber number of the main flow. Konno, M. et al. (1993) studied the
drop break-up process in a stabilised liquid-liquid
found
in
in
drop
that,
their
the
system
and
coalescence
absence
of
experimentally
break-up processes, at each impeller speed, drop size distributions had a similar
distribution form. They, also, proposed a new correlation equation, which expresses
the evolution of Sauter mean drop size over a wide range of drop sizes.
10
order
to describe
the phenomena
accurately
occurring
with
liquid-liquid
a turbulent dispersion
reaction,
investigators
are
involving
the
treatment
of
problems
permit
coalescence would
chemical
an agitated
Many
population
M. A. and Tavlarides,
L. L.
The former method was introduced by Hulburt, H. M. and Katz, S. (1964) and, later,
K. J. and Admundson,
developed
by Valentas,
description
of the integro-differential
Coulaloglou,
C. A. and Tavlarides.
population
N. R. (1976).
Later,
a detailed
functions
rates and used them to solve the general population
coalescence
describing
equation
drop interactions
by
determined
the
comparing with experimental
were
of
models
distributions
overcome
simplified
and mixing
difficulties
frequencies
combined
of solving numerically
model which
balance
the population
conditions.
To
balance equations, a
balance
by
Laso,
M.
Monte
the
presented
method
was
carlo
of
drop
based
discretisation
is
The
(1987).
the
of
spectrum
on
new model proposed
et al.
using a geometrical
optimising
simplified
by
breakage
The
evaluated
rates
were
and
coalescence
grid.
solution of the
have
been
(1987a)).
Although
M.
(Laso,
made
attempts
many
al.
et
model
A.
K.
J.
Chester,
Howarth,
W.
(1964);
J.
O.
(1955);
(Hinze,
not very well understood
11
(1991); and Palermo, T. (1991)). The most comprehensive models describing these
phenemena were presented by Chatzi, E. G. et al. (1989). They incorporated them in
a numerical algorithm to calculate the steady-state drop size distributions in a batch
stirred vessel. They, also, introduced a new breakage distribution function that
considers droplet broken into two daughters and several satellite droplets. As a result,
bimodal diameter density distributions were obtained using the homogeneous
interaction model developed by Valentas, J.G. and Admundson, N. R. (1966). Very
few measurements of bimodal drop size distributions in agitated dispersions have
been reported in the literature before (Ward, J.P. and Knudsen, J.G. (1967); Brown,
D. E. and Pitt, K. (1972); and Laso, M. et al. (1987a). Recent work by Chatzi, E. G.
And Kiparissides, C. (1992) established a breakage mechanism in order to predict
the bimodal size distributions by using the population balance formalism. The
proposed model, which is an attempt to incorporate the bimodality into the equations
describing the droplet interactions in agitated vessels, considers the volume
ratio
between the generated drops and the satellite drops to be proportional to the
parent
drop volume. This is a modified model to the one considered earlier (Chatzi, E. G.
et al. (1989)) as it considers the breakage of the parent drops into one daughter and
several satellite drops. The results obtained were in good agreement with those
observed experimentally.
2.2 - Vinyl chloride suspension polymerisation
Poly(vinyl
light initiated
polymerisation
of various vinyl
compounds. He reported that the white material produced had the elemental formula
C2H3C1and a density of 1.406 g/cm3. Despite these early discoveries the industrial
development of poly(vinyl chloride) did not get underway until the start
of the 20th
century. This was due to its poor thermal stability which was making processing
difficult.
However, in 1912 Fritz Matte, of the German company
12
polymerisation
solution
industry
develop
has
it
Since
to
the
to
then
and
expand
continued
polymerisation.
due
industry
is,
large
PVC
This
to
to
the
a
extent,
today.
of
expansion
enormous
of
its high versatility as a plastic raw material as it finds widespread application in
fittings,
films,
bottles
insulation,
etc..
pipes,
cable
emulsion paints, surface coatings,
At present approximately 80 % of the demand of poly(vinyl chloride) is produced
by suspension process, while
devoted
be
This
to the polymerisation
mainly
present review will
polymerisation.
of vinyl chloride using the suspension process.
Many scientists have studied the polymerisation
process of vinyl
chloride,
(1974);
F.
H.
(1951);
Ravey
Winslow,
J.
A.
(1980);
(Davidson,
et
al.
experimentally
Smallwood, P.V. (1986)) or theoretically by proposing a series of models to describe
the process (Ray, W. H. and Jain, S.K. (1975); Pinto, J.C. (1990); Sidiropoulou, ..
Because
(1991)).
T.
Y.
Xie,
(1990);
of the complexity of the
al.
et
and
et al.
hetero-phase polymerisation of the vinyl chloride (due to the insolubility
of the
have
been
large
in
its
concerned
of
papers
a
number
monomer),
poly(vinyl chloride)
discussion
kinetics.
A
its
on the work performed
comprehensive
mechanism and
with
bulk
to
the
and suspension polymerisation of vinyl chloride,
seventies
on
early
up
has been published by Kushanov, S.I. and Bort, D. N. (1973). They defined the main
bulk
hetero-phase
kinetics
(suspension)
the
of
and
mechanism
characteristics of
literature
data.
the
analysis
of
and
made
a
critical
chloride
of
vinyl
polymerisation
The bulk and suspension polymerisation processes are believed to have great
due
identical
(1968))
A.
(Crosato-Arnaldi,
to
the
et
al.
mechanistic similarities
microstructure
formation
it
is
Thus,
behaves
droplet
the
as
a
mini-"bulk"
reactor.
polymerisation process
intended that the extensive literature dealing with bulk polymerisation will, also, be
discussed here.
13
Bankoff, S.G. and Norris Shreves, R. (1953) were among the pioneers in trying to
in
the vinyl chloride polymerisation process such
the
of
variables
effects
understand
They
temperature
and
other
additives.
of
surfactant,
as nature of catalyst, nature
for
in
develop
latter
to
the
vinyl
a polymerisation procedure
parameters order
studied
feasible
in
high
a commercially
quality polymer
chloride which would yield a
bulk
between
They
the
and the suspension
close
similarity
a
observed
process.
direct
in
designed
(1972),
T.
Ueda,
that
equipment
such
a
way
some
et al.
processes.
formation
in
suspension
chloride
polymer
particle
of
vinyl
observation
microscopic
became possible. They studied the mode of transformation of monomer droplets into
in
factors
discussed
that
the
the
affect
change
particle
of
some
polymer particles and
size. An
extensive mechanistic
chloride
suspension
by
(1974).
Using
Ravey,
M.
later
al.
previous work
et
presented
polymerisation was
and their own experimental results, they resolved the suspension polymerisation
process into five discrete stagesand related them to the physical changes which occur
in the system. Due to the increasing importance of the finished product (PVC)
investigating
(especially
scientists
started
many
more
plasticised),
when
properties
the morphological aspect of the vinyl chloride suspension polymerisation process.
Parma, G. et al. (1977) investigated the particle morphology of poly(vinyl chloride)
bulk
during
polymerisation
conditions
radiation-induced
quiescent
produced under
70C.
They
transmission
to
temperature
electron microscopy
of
used
range
over a
-30
(TEM) to determine the particle morphology of the polymer. Their observations
For
to
the
polymerisation
early
stages
of
polymerisation.
confined
were mainly
temperature below 20C, the system remained predominantly homogeneous during
the entire polymerisation and the polymer particles increased in size linearly with
found
higher,
When
they
that the polymer
temperature
the
was
reaction
conversion.
finding,
Using
became
they
together.
their
cemented
particles rapidly settled and
formulated a process for particle formation and growth which resembles the one
in
Zichy,
E.
L.
(1977),
for
M.
(1971)
by
Fitch,
R.
studying
emulsion systems.
proposed
the morphology of polymerising vinyl chloride droplets, built a spinning drop
inertially.
Using
droplets
in
a
suspended
chloride
were
vinyl
which
apparatus
he
technique
observed the morphogenesis of the
scanning electron microscopy
from
the polymerisation of the suspended
granules
resulting
precipitating polymer
14
vinyl chloride droplet. He concluded that the colloidal stability of the precipitating
formation.
Zichy,
E.
L.,
internal
dominant
influence
the
on
aggregate
polymer was
be
internal
from
that
there
the
the
must
a repulsive
of
grains
size
also, concluded
force between the precipitated
polymer
particles. An investigation
of the
features
kinetic
of the vinyl chloride suspension polymerisation
and
morphological
into
by
injecting
chloride
monomer
a
additional
vinyl
out
carried
process was
He
different
two
conversions.
at
process
suspension
polymerisation
conventional
injection
in
both
for
long
the
time
the
cases,
with
periods
of
polymerisation
sustained
before pressure drop producing a more rapid decreasein properties such as porosity
drop,
injected
When
the
additional
after
pressure
monomer was
and surface area.
inferior
plasticiser absorption,
polymer growth produced a structure with noticeably
detrimental
loss
higher.
The
though
of
porosity and surface area values were
even
drop
in
polymerisation, was
occurs
post-pressure
overall porosity, which always
in
increased
level
the smaller pores, cementing the
to
of
polymerisation
an
assigned
initiator
be
by
believed
This
to
the
together.
precipitating
caused
was
particle
drop
in
the
the
as
pressure
was
surface
small
pores,
polymer
predominantly onto
in
liquid
last
the
these
monomer persists.
which
are
regions
passed, since
Davidson, J.A. and Witenhafer, B. F. (1980), in trying to understand the origin and
inside
forces
between
the vinyl chloride
the
the
particles
polymer
repulsive
nature of
droplets, examined the skin formation process in some detail. They found that at
in
in
low
the covering of
the
water phase resulted
conversion, polymerisation
very
the vinyl chloride droplet with a ca. 0.2 pm layer of water phase initiated polymer
particles. When this layer is complete, it prevented the escapeof the charging species,
formation
%
ions.
1-2
be
After
the
to
conversion
chloride
about
which are suspected
formed
became
is
the
the
electrically
earlier
and
agglomerates
skin
completed
of
fate
They
by
that
the
the
the
also
observed
adsorption of
charging species.
stabilised
of these stable agglomerates depended upon the agitation conditions employed.
A review of the state of knowledge on suspension PVC morphology was presented
by Allsopp, M. W (1981). He used Geil's terminology (Geil, P.H. (1977)) in order
to describe the changes taking place during vinyl chloride suspensionpolymerisation
formation.
for
He
three
also
and
mechanisms
grain
main routes
and proposed
VCM
detailed
the
suspension
schematic representation of
mechanism of
proposed a
15
investigated
V.
(1986)
Smallwood,
P.
More
experimentally
recently,
polymerisation.
the development of structure within grains of suspension PVC. He found that,
(i.
different
conditions
at
polymerisation
e. temperature,
although polymers produced
initiators)
had
different
type
and
of
colloid
protective
and
concentration
speed,
stirrer
final porosities the final size and number of primary particles reached approximately
3,
He
2.0x1011
1.4
limiting
m
also showed
the same
cm
respectively.
and
of
values
that the product's final porosity was strongly related to the conversion at which the
for
he
is
formed.
Furthermore,
the
suggested
a
model
primary particle network
mechanism by which agitation, the presence of surfactants and temperature control
the formation of the latter network. In a study of the formation of primary particles
in agitated bulk polymerisation of vinyl chloride Tornell, B. and Uustalu, J. (1988)
found that the mechanism of formation of primary particles was a two stage process.
According to the authors, the first stage occurred at the very beginning of the
initial
began
the
the
nucleated
particles
started
as
second
stage
while
polymerisation
to agglomerate and continued up to at least 7% conversion. Moreover, they found
that the primary particles were stable and did not agglomerate until reaching a limiting
They
lower
higher
found
be
to
also reported that
agitation
speeds.
at
size, which was
the rate of formation during the second stage was equal to the rate of particle
agglomeration. A study of the effect of using sorbitan esters as a means of controlling
the number of primary particles was also performed.
The product quality of suspension PVC is to a large extent controlled by the particular
is
the
the
process
conducted.
way
polymerisation
suspension stabiliser used as well as
Although a great deal of work has been devoted to the stabilised droplets, there is
few
PVC
The
literature
little
the
the
to
of
stabiliser
on
particle.
effect
related
very
literature
have
in
the
to
this
shown
subject
and
reported
are
related
studies which
that the porosity of a PVC resin is strongly affected by the surface activity of the
stabiliser ( Zichy, E. L. (1977); Clark, M. (1982); Nilson, H. et al. (1985a) and
Ormondroyd, S. (1988)), but, the mechanism by which the suspension stabilisers
Nilson,
H.
B.
(1988)).
is
(Tornell,
influence
their
et al.
mainly
unknown
still
exert
(1985a) prepared suspension PVC resins using different types and quantities of
stabilisers. They discussed the effect of the stabiliser systems on the pore structure
of the resins by referring to the interfacial behaviour of the stabiliser and the empirical
16
knowledge and confirmed that the porosity of the resin depended on the type of
is
hydrolysis
found
degree
When
PVA
that
the
they
also
of
was used,
stabiliser.
important. However, their data clearly showed that the porosity control in suspension
PVC was not solely due to the ability of the adsorbed stabiliser to lower the interfacial
tension at the VCM/water interface but, also, to other possible mechanisms by which
the stabiliser interferes with the primary particles. An in-depth study of the influence
alcohol) suspending agents on suspension poly(vinyl chloride)
brief
After
S.
(1988).
Ormondroyd,
by
a
presenting
morphology was published
he
PVC
the
related the properties
suspension polymerisation,
mechanism of
review of
of poly(vinyl
of vinyl
in
formation.
He
the
of
variations
poly(vinyl
effect
also studied
mechanism of particle
in
hydrolysis
degree
the
surface tension and
change
and viscosity on
of
acetate)
described method of achieving higher porosity by using low degree of hydrolysis
found
he
Furthermore,
(i.
that change
stabilisers).
co-suspending agents e. secondary
in the degree of hydrolysis of the poly(vinyl acetate) at a fixed molecular weight had
fixed
degree
in
than
at
a
weight
changes molecular
more effect on product properties
of hydrolysis.
Although the grain size distribution is an important property of a suspension PVC
I.
E.
And
Kummert,
(Hoffmann,
been
has
little
this
on
matter
published
resin, very
(1976); Barkley, L. M. (1976) and Nilsson, H. et al. (1983)). It is usually assumed
intensity
by
is
the
the
and
that the grain size controlled
suspension stabilising system
L.
M.
(1976)
Barkley,
I.
(1976)
E.
Kummert,
Hoffmann,
studied
and
and
of agitation.
the influence of agitation on the grain size. They showed that at low agitation an
increase in the agitation is followed by a decrease in the grain size. They also found
that there exists a critical agitation speed corresponding to a minimum grain size
The
in
larger
in
further
increase
the
surface
grains.
will
result
agitation
after which a
irregular
have
to
the
shown
an
the
conditions
was
critical
of
grains obtained at above
from
built
indicating
the
that
a number of coagulated
were
up
grains
appearance,
had
a smoother surface,
conditions
subgrains, while, grains polymerised at subcritical
drop
in
H.
(1983),
Nilsson,
the
studying
et al.
absence of coagulation.
suggesting
found
during
distribution
chloride
suspension polymerisation of vinyl
and grain size
that the average PVC grain volume at 5% conversion was five times larger than the
17
found
in
He
droplet
that
there
also
was
no
change
grain
volume.
average monomer
5%
full
between
conversion.
and
size
Because of the exothermicity of the vinyl chloride polymerisation reaction, it is very
important for the heat produced by the reaction to be removed (368 Kcal/Kg) to
is
In
heat
the
temperature.
polymerisation
of
suspension
removal
constant
maintain
helped by the presence of a continuous water phase which transfers the heat to the
becomes
larger
(i.
But,
jacket.
the
polymerisation
reactor
e.
as
cooled reactor
industrial
decreases
becomes
its
thus
to
and
surface
volume
ratio
reactors),
increasingly difficult to transfer the heat through the reactor jacket. The heat transfer
baffles,
but
increased
by
be
the
cooled
a more efficient way
use
of
water
slightly
can
is the use of reflux condensers. The latter technique has its inconvenient because it
disturbs the particle size and properties. This is due to the fact that during
large
(VCM)
the
the
amount of
chloride
monomer
vapours,
vinyl
of
condensation
behaviour
liquid
The
VCM
liquid
this
to
the
of
slurry.
polymerising
returns
cool
VCM when returned into the reaction medium is not understood. Although many
by
hard
facts.
have
time
the
they
theories,
of
non
confirmed
are
most
scientists
Despite the fact that many PVC producers use reflux condensers, the design and
few
details
kept
Thus,
is
time
the
very
are available
confidential.
process used most of
in the literature on condensers operation in suspension PVC production (Mironov,
A. A. et al. (1989) and Kobayashi et al. (1989)). Mironov, A. A. et al. (1989) studied
the relation between heat removal and polymer particle formation during suspension
polymerisation of vinyl chloride using a reactor with a reflux condenser. They
developed a mathematical expression describing the dependenceof polymer particle
diameter on the thermal load in the reflux condenser for various hydrodynamic
in
be
They
that
their
could
claimed
results
used
conditions and emulsion stabilisers.
the selection of condenser configuration as well as working conditions. Kobayashi
for
high
designed
(1989)
the
manufacture
of
porosity vinyl chloride
an apparatus
at al.
resins. The apparatus consisted of a reactor, a reflux condenser and a temporary
it
from
before
for
the
to the
the
tank
reflux
returning
monomer returning
storage
reactor. Thus, a suspension polymerised PVC having a porosity of 22.4 cm3/100g
was prepared when 30% of the monomer was temporarily stored after 45%
conversion and returned to the reactor after 55 % conversion. They found that without
18
PVC
had
17.6
the
the
temporary
of
monomer
prepared
a
porosity
of
storage
using
cm3/100g.
During the past 20 years several kinetic model have been proposed for the suspension
based
bulk
of
vinyl
chloride,
on the two-phase reaction scheme.
and
polymerisation
These models have been described in two review papers (Ugelstad, J. et al. (1981)
and Sidiropoulou, E. and Kiparissides, C. (1990)). Sidiropoulou, E. and Kiparissides,
C. (1990) presented a brief review of the mathematical models describing the
two-phase polymerisation of vinyl chloride in bulk and suspension reactors. After
investigating the development of a unifying frame-work for modelling the latter
had
fairly
described
the ability to predict
that
they
comprehensive
a
model
system,
the rate of polymerisation as well as the molecular properties of polymer as a function
be
in
The
to
the
model
presented
was
shown
good agreement
conditions.
process
of
before.
The
is
known
PVC
those
present
aim
models
published
not to
with
well
describe the vinyl chloride polymerisation kinetics or its various models but to
describe the models which are related to the mechanism of PVC formation. There
is very little work done on the development of models relating the particle
inside
the polymerising monomer
to
the
chemical
changes
physical
and
morphology
droplets (Kiparissides, C. (1990); Diamadopoulous, E. et al. (1990) and Kiparissides,
C. Et al. (1993)). Kiparissides, C. (1990) developed a microscopic particle
morphology model that can predict the dynamic behaviour of primary particle size
distribution in terms of the controlling process variables by formulating a population
balance equation to follow the time variation of the primary particle density function
from the nucleation of basic particles to the formation of particle aggregates. Also,
the model proposed was shown to have the ability to analyse the effects of secondary
dispersants on the primary particles. More recently, Kiparissides, C. et al. (1993)
formation
in
to
the
the
and
stability
of
primary
particles
problems related
analysed
VCM suspension and bulk polymerisation using theories of stability of colloidal
systems. They quantitatively investigated the dependence of the stability of primary
particles on the ionic strength of the medium, temperature and the total particle charge
in terms of the stability ratio and the particles coalescence rate constant. The
theoretical predictions obtained were in good agreement with the experimental data
in
literature.
the
published
19
CHAPTER 3
3- THEORETICAL
CONSIDERATIONS
dispersions :
When two immiscible liquids are brought into contact using mechanical agitation
importance
in
is
formed.
This
is
dispersion
a number of chemical
of
major
process
a
involving
heat
those
and mass transfer.
engineering operations, especially
3.1.1 - Hydrodynamic
20
deformation).
droplets
(cigar-shaped
small
off
Type 3- As the surface of the globule is deformed locally in various places by the
become
the
thus
forces,
bulges
of
parts
globule
and protuberances occur and
external
bodily separated (bulgy deformation).
/=__
'
TYPE-3-
TYPE-2-
TYPE -1"Lenticular"
"Cigar-shaped"
"Bulgy"
order of magnitude of :
:r
d
ti
Pr
21
[3.1]
Were d, Pdand d are the viscosity, density and diameter of the globule respectively
force
the
ti
per unit area.
surface
and
2- An interfacial tension force acting inwards at the interface of the globule trying
to maintain the sphericity against any deformation. This surface tension force is equal
to aid per unit area. Were is the interfacial tension between the two immiscible
phases and d is the diameter of the globule.
3- The fluid dynamic forces due to the combined effects of gravity, fluid flow and
inertia forces denoted by a shear stress ti (force per unit surface area). This force
is
function
the
of time.
and
surface
varies along
These three forces per unit area, if combined between each other as ratios, form three
dimentionless groups, two of which are independent.
The "generalised" drop Weber number :
We =
Td
[3.2]
We =
pu'
6
Re =d
[3.3]
tipj
Nv`_!
tr_
P16d
We
Re
[3.4]
It is shown from equation [3.2] that the greater the value of We the greater is the
force
interfacial
force
the
tension
old and, thus, the greater
T counteracting
external
the deformation. Hinze, C. O. (1955), also, has shown experimentally that there is a
22
break-up
(We)c,;,.
When
Weber
Weber
the
above
value
which
occurs.
critical
number
number is equal or slightly higher than (We)cr;t_the mechanism of breakage is quite
simple while for We (We)cri, this mechanism is very complex.
3.1.2 - Kolmogoroff's
[3.5]
"4
(v)
tc .
[3.6]
23
Re =
Were :N
ND
[3.7]
Rushton, J.H. et al (1950) proposed that for the local isotropy theory to be valid the
be
104.
If
latter
is
Reynolds
the
the
must
above
condition
satisfied,
number
value of
the droplet diameters d are much smaller than the macroscale of turbulence L (d<<L),
(d
larger
the
turbulence
than
11
microscale
of
and much
r). Thus :
Ld11
For droplets of diameter dTl, the viscous forces may be neglected in comparison
forces
fluctuations),
for
d
inertial
(turbulent
the
pressure
while
with
rj viscous
forces will dominate. If the conditions mentioned above for the existance of local
isotropy are met, then the mean square of relative velocity u2(r) between any two
points separated by a distance r is given by :
tt
2(r)
=
CIE2/3r2/3
C2Er2l
u2(r) =
for
for
>> r >> 11
L 11r
[3.8]
[3.9]
liquid-liquid
dispersions :
The physical and chemical phenomena taking place in an agitated vessel largely
depend upon the size of the dispersed droplets. The latter is determined by the relative
contribution of breakage and coalescence mechanisms. As mentioned earlier, the
droplets are subject to shear stressesand to turbulent velocity and pressure variations
at their interface. These processes deform the drops and may break them into smaller
droplets if the dynamic forces exceed the interfacial tension forces. At the same time,
theses droplets are also colliding with each other and these collisions may produce
coalescence if the colliding droplets remain together for a time long enough to enable
24
the rupture of the interfacial film (between the two colliding droplets). The drops
will be constantly breaking up and coalescing simultaneously and after a certain time
is
dynamic
a
equilibrium
reached. As the drops in the liquid-liquid
dispersion are
not uniform, investigators usually assume that there is a maximum drop diameter
(dra) above which stable drops do not exist (drop breakage control) and a minimum
drop diameter (dn,; below which there is no stable drops (coalescence control).
n)
3.1.3.1 - Maximum
Kolmogoroff, A. N. (1949) and Hinze, J.O. (1955) were the first to derive a relation
for the maximum drop diameter (d,,, ). Their basic assumption was that in order for
a drop to become unstable, the kinetic energy of the drop oscillations must be
sufficient to provide a gain in surface energy necessaryfor break-up. Since the kinetic
energy of the drop oscillations was proportional to p, u2(d)d3and the minimum gain
in surface energy proportional to ade, then the Weber number We (which is defined
has
kinetic
to
the
the
the
energy
surface
energy)
a critical value Wec,i,. of:
as
ratio of
Wecrit.= CI PC12(d)d 3/ad 2
Since turbulent flow is assumed locally isotropic and d
[3.10]
il, using equation [3.8]
we have :
3
d
Wecrjt_= (C'
E21
1p
)l6 = Constant
[3.11]
71)as :
dmax C,
(6/r1c)
l
h'
3/5s215
[3.12]
Rushton, J.H. et al. (1950) have shown experimentally that for high Reynolds
numbers, the energy input of mixing by the impeller per unit mass of the liquid in
the vessel is independent of the properties of the liquid and is a function only, of the
geometrical design of the agitator and its speed. Thus, the energy dissipation E is
F-= C3N3D2
25
[3.13]
Where C3 is a constant depending on the geometry of the vessel and the agitator.
Using equations [3.12] and [3.13] Shinnar, R. J. (1961) derived the following equation
for dmaxin turbulent agitated vessel :
dmax= C4((YIp)3/5N4/5D-4/5
[3.14]
dmax= C4D
Thus :d
P`N2D
-3/5
C4D
(We)-0.6
=
max C4(We)-0.6
=
D
[3.15]
By assuming a linear relationship between dm and the Sauter mean diameter d32
(Sprow, F.B. (1967) and Coulaloglou, C.A. and Tavlarides, L. L. (1976)) we have :
d32= C5dmax
[3.16]
[3.17]
dispersions
for non-coalescing systems (Yuang, H. G. et al. (1991)). Table - 3.1 - gives the most
important reported correlations for mean droplets size. The most frequently reported
correlation is of the form :
d3'
F
C7f(O)
(We)-o.
=
D
26
[3.18]
Q)
:
>~
E
N
E
N
s,
.c
c
c1
G
r
G
a)
col
a
"
z
"D
s
3
E
U_
Op
C
,=
_
^
F
'O
'7)
"L
"
y
N
U
'D
'cC'3
vl
C
N
C
M
C
N
C
M
1)
c'3
>
CC
ai
ate)
CC
ccl
C
O
C
pp
C
N
M
M
c
a
ro
F,
'C
-d
bA
O
"O
L
"
co
s
a
E
N
jam,
i.
c3
O
.
v'i
O
O
C
O
O
p
C
0
CD
vI
C
0
c
y
-14
U
8)
U
S
v
9"
4
CA
cz
0
Vy
O
C
C
'0
C
O
II
Q
II
!,
II
Q
'
(
b
M
ul
C
C
II
II
C
II
C
Cl
Vl
C
C
-+
V
C
O
II
C
II
Q
00
N
ri
C
C
II
\
V'1
C
C
.. i
00
O
II
O
p
II
'
"V
Zi
0
U
N
10
CID
o
,'
`n
c)
a
C
Q
W-) 2
_e
v:
Cr;
C
a
c
H
C)
>
27
C
C
_T
00
V]
_
-A
C
_
C
O
C
O
r
-
I--
L
n
N
O
cG3
E
+
d)
O
2
5
V
1
V
E.
.
L
V
C
L
'v,
a.
N
C
N
C
L
O
C
-E
"V
72
C
"
"_
3
.C
c
bq
U_
V
C
C1.
8
'V
C
N
p
G
'
rq
cn Q,
"3
"
L
=
Q)
E
N
E
CJ
OE
N
rI
-E
y
C
L
N
C_
S
Q)
4)
C
J
C_
L`
L
.D
'V
7J
.y
c--
s
6
i"
Cl
Z
y.,+
U
-C
.r_i
'C
'D
.n
C)
CD
rC
-C
16
16
16
IL
16 16 16
16
c
v^,
N
C
r
C
r
rC\
C
C
C
M
'ch
".-.
00
Vl
V)
CO
N
'O
M
M
M
M
O
cC^,
Cl
N
C
C)
61
Q
m^
to
'4D
n
II
I I
II
II
II
C
II
II
C
c
1
1
C
C
II
II
II
n
DC
x
oc
ON
CC
1
....
7:
7-
cri
Ci
--"
ti
p
-
Gq
'C.
oc
L
:z
28
nc
Where cp is the volume fraction of the dispersed phase. As the presence of the
dispersed phase may cause a damping of the turbulent fluctuations depending on the
volume fraction cp, a correlation factor f((p) expressed empirically by the linear
relation : f(cp) =1+
was found negligible for cp< 0.015 and linear for cp> 0.15 (Sprow, F.B. (1967);
Mlynek, Y. and Resnick, W. (1972) and Coulaloglou, C.A. and Tavlarides, L. L.
(1977)).
When the drop diameter is smaller than v (d < 11),drop breakage is due to viscous
shear forces. According to Taylor, G. I. (1934), the breakup of the drops under these
conditions is primarily a function of the Weber number. At critical conditions we
have :
Wecrit.
= , (au/ar) (d/6) =f(dIc)
[3.19]
Where d and , are the viscosities of the dispersed and the continuous phase
respectively. Using the relation of local isotropy :
2E/15v
=
(aular)2
Shinnar, R. (1961) derived the following equation :
dmax
C9(CFVc/24
c)ll2f(dI
c)
[3.20
Thus :
dmax
CIo6(v1c/2!
c)N-3/2D-lf(d'O
=
Where v is the kinematic viscosity and the viscosity.
29
[3.21]
3.1.3.2 - Minimum
Ea =A (h0)d
Where A(ho) is a constant (ho being the smallest distance between the two droplets).
Thus, the minimum droplet size (dm; will depend on the ratio of the turbulent
n)
fluctuation energy (Et) to the adhesion energy (Ea).The turbulent fluctuation energy
is proportional to pu2(d)d3. When Ea > Et coalescence of the droplets occur and d,,,;,,
is determined by :
C11pcu2(d)dmin
E,
C11Pcu2(d)dmin
A (h(,)d
A (h0)
= constant
[3.23]
11we have :
C(Ed)213
u2(d) =
2/3 dmin
8/3
=
C'13c2
3dmin
8/3
-
A (h0)
constant
30
[3.241
CIAN2D4/3'81
Hence :
3=
constant
m
r1c-318N-3/4D-"2
dmm-- C151-'
[3.25]
[3.26]
When dm; < 11(the force preventing coalescence is the viscous shear force), Sprow,
n
F.B. (1967b) presented the critical ratio which determines if the two drops will
coalesce as follow :
(Jua2)IF
= contant
[3.27]
Where Vu is the local gradient and F the adhesion force. Sprow, F.B. (1967b) found,
from dimensional analysis that :
1/2
VU = C1661/2vc
[3.28]
dmin
C17F
1/2'I-1/2
1/4t-1/4
Vc
F"c
[3.29]
31
dispersion the droplets must be larger than dm; (coalescence) and smaller than both
n
dma,(break-up) and dm (suspension). dm (suspension) was determined from the
relation
PC
f($)
C192
dmY
=
3
Pd- Pc g
[3.30]
Where f(cp) is an empirical function and cpthe volume fraction of the dispersed phase.
Equation
t<
suspensio
droplets
(dmax
-N
v
v
E
0
o
L
o
E
C
0)
O
J
Log
N(
Stirrer
speed)
32
dispersion. Experimental
latter
have
been
describe
the
to
techniques
parameters
summarised
used
methods and
by Tavlarides, L. L. and Stamatoudis, M. (1981). In this subsection, summaries of
the main techniques and experimental methods are presented. There are two main
group of methods, used to determine the interfacial area and the drop size. The
indirect methods can determine the interfacial area (A) and the Sauter mean diameter
(d32), while the direct methods determine the drop size and size distribution.
Depending on the end-use of the liquid-liquid dispersion process, the drop size may
be determined either by using the arithmetic mean drop diameter (dm)obtained from
the equation :
JNjd;
d,,,
Y,N;
[3.31]
Or from the Sauter mean diameter (volume to surface) obtained from the equation:
I N`d`
32
[3.32]
Ni`
Where Ni is the frequency of drops in the size range d, and dt+,, and di is the average
diameter in the interval i to i+1 and is calculated as :
d _ (d; +d; )/2
+,
The interfacial area per unit volume A is related to the Sauter mean diameter (d32)
dispersed
fraction
the
the
of
phase cpthrough the equation :
and
volume
A=
6
d3,
33
This method is based on the fact that when a parallel beam of light is passed
through a liquid-liquid
has
been
developed
by
Calderbank,
An
P.H. (1958) relating
scattering.
expression
the amount of light transmittance to the total interfacial area. He assumed that the
drops were uniform and found that :
RIO = exp[-1/4(A. l)/4]
[3.33]
Where Io is the amount of incident light, I the amount of light transmitted, I is the
length of the optical path and A the interfacial area per unit volume. This method
does not affect the system being measured.
b) - Chemical method :
This method involves the diffusion of a reactant A* from the dispersed phase into
the continuous phase, where the reaction occurs. The concentration of the reactant
A* in the dispersed phase is relatively unchanged. The reaction is assumed fast
enough to keep the concentration of A* in the continuous phase negligible, but not
fast enough for any amount ofA * to react at the interface. Using the latter assumptions
P.
V.
derived
for
first
Dankwerts,
(1951)
a
relation
a
or pseudo-first
and conditions,
order reaction
RA =ACA.
(DA*K'
+KL)1/2
[3.34]
where RA is the rate of extraction per unit area, A is the interfacial area per unit
volume of dispersion, DA* is the diffusion coefficient of A* in the continuous phase,
K' the reaction rate constant and KL the continuous phase mass transfer coefficient.
This method affects the interfacial area, as the mass transfer through the interface
changes the physico-chemical properties of the dispersion.
34
This method is relatively easy to perform but the coalescence during sampling
has to be inhibited. To avoid coalescence two types of measuring techniques are
interfacial
in
first
is
The
to
polymerisation
order to
usually used.
use an
one
W.
(1972)).
The
drop
Resnick,
(Mlynek,
Y.
drops
the
size and size
encapsulate
and
This
by
then
method has the
photomicrography.
are
obtained
disadvantage that a reactant has to be added to the dispersed phase before making
distribution
the dispersion. This can affect the interfacial tension and the coalescence frequency.
The second method is based upon stabilisation of a sample or of the entire mixture
by adding a surface active agent (i. e. partially hydrolysed poly(vinyl acetate),
hydroxypropyl methyl cellulose, ). Samples are then analysed by photography or
..
designed
S.
L.
(1977,1978)
Ross,
a photometer assembly
photomicrography.
et al.
to measure both the drop size and the dye concentration of the drops by forcing a
stabilised dispersion through a capillary tube (see Fig- 3.3 -). This method is suitable
for stabilised dispersions, as is the casefor suspension and emulsion polymerisation.
TO
WASTE STORAGE
TANK
PINHOLE
IN
BLACK PAPER
BEAM
SPLITTER
4
MCROSCOPE
/ETER
1
HEAD
REFLECTING
MIRROR
CAPILLARY
IRIS
455 CLASS
OPTICAL FILTER
PLASTIC
6T
D.C. LIGHT
SAMPLE
FRS
HANDLING SECTION
Fig - 3.3 - Microscope assembly for drop size and concentration measurements [after
Verhoff, F. H (1969)].
b) - In situ measurements :
This method gives measurements of the dispersion without disturbing its dynamic
designed
in
The
are
a manner to minimise the effect
conditions.
photo-probes used
on the dispersion. They use mainly the high speed cinephotography or photography
with a short duration flash (1 - 100 sec.) in order to be able to "freeze" the drop
motion. A photomicrographic. probe assembly was used by Coulaloglou, C. A. and
Tavlarides, L. L. (1976) to measure the drop size and size distributions at various
depths in the mixing vessel (see Fig - 3.4 -). They analysed dispersions with a volume
fraction of the dispersed phase of up to 0.15. Park, J.Y. and Blair, L. M. (1975)
designed a fibre optic probe assembly (shown in Fig - 3.5 -). The probe was
constructed of two 1/8 inch diameter fibre optic conduits which transfer a coherent
image from one face to the other. One conduit served to transmit light to the 4 mm
drop
faces
between
the
the
transmitted
the
the
other
and
of
conduits,
submerged
gap
dispersion image to its external face, upon which the camera was focussed. Through
this probe they measured the drop size by using high-speed cinephotography. Some
other workers have taken photographs through a window of the vessel (Chen, H. T.
G.
Calabrese,
Knudsen,
J.
(1970)
S.
Collins,
S.
B.
(1967);
Middleman,
and
and
and
R. V. et al. (1986)). This technique cannot be used for high phase fraction because
of the interference of the drops with the optical path.
3.1.5 - Analysis of drop breakage and coalescence in liquid-liquid
using mathematical
dispersion
models :
36
EYE PIECE
ADAPTOR AND
C JVERA
VESSEL PLATE
MICROSCO? t TL
(O. D= 25-0 mm)
OBJECTIVE
Li
PROTECTIVE CUP
'O. D =165rruni
GLASS PLATE
37
LIGHT CONDUIT
IMAGE
CONDUIT
STIRRED TANK
' inch
551"-:
Fig - 3.5 - Fibre optic probe assembly [after Park, J. Y. and Blair, L. M. (1975)].
A
balance
initially
the
population
equation
to
model.
made simplify
assumptions are
behaviour
droplet
the
describe
of
size
state
temporal
the
and steady
employed to
distribution is given by Stamatoudis, M. and Tavlarides, L. L. (1985) as :
Vm
r bl
(v'
la /v'
)N(
v' i) v dv' +
F(v
b
l
- v', v')dv =rv+
JOv`
d [N(t)A (v)]
rvmax
F(v, v')dv' +
dt
Jo
38
[3.35]
Where rb(v) is the number of drops of size v breaking per unit volume of dispersion
drops
dv'
is
F(v,
the
time.
of size v and v' coalescing
of
of
number
pairs
v')
per unit
X(v')
daughter
is
dispersion
time.
the
of
number
particles
unit
per
per unit volume of
(v',
dv
is
fraction
droplets
drop
V.
from
breakage
the
of
of volume
of a
v)
a
resulting
dv
is
drop
V.
A(v)
breakage
formed
by
the volume
the
of
a
of
volume
with volume v
of the drops of size v. N(t) is the number of drops of all sizes per unit volume at time
t and v,,, is the maximum drop size present in the dispersion.
The terms on the left hand side represent the contribution of drop volume v by
breakage of larger drops and by coalescence of smaller drops, respectively. The first
two terms on the right hand side represent the loss of drops of size v due to breakage
hand
is
last
drops.
The
the
term
the
on
side
to
right
other
coalescence with
and
depends
function
drop
breakage
The
term.
on the surface
rate
rb(v)
accumulation
tension and on the hydrodynamic field outside the drops. The drop coalescence rate
F(v, v'), also, depends on the turbulence conditions as well as the coalescence
balance
has
drops.
The
between
a
approach
population
colliding
efficiency
in
details
include
is
it
to
the
model
relative to
possible
significant advantage as
breakage and coalescence processes in terms of physical parameters and operating
between
favorable
3.6
Fig
the
experimental
agreement
shows
conditions.
C.
Coulaloglou,
A.
by
balance
the
and
used
model
population
observation and
Tavlarides, L. L. (1977) which resulted in a unimodal distribution. On the other hand
Chatzi, E. G. et al. (1989) used the population balance equation but introduced a new
breakage distribution function which considers droplet broken into two daughter and
density
bimodal
diameter
droplets.
they
obtained
as a result,
several satellite
distributions. Fig - 3.7 - shows that the proposed model has the ability to fit reasonably
(volume
for
low
data
coalescence
system
obtained
of
experimental
well a series
fraction = 0.02). Fig - 3.6 - and - 3.7 - confirm what was said above about the
has
been
balance
Despite
the
said earlier
all
what
equation.
population
versatility of
there is still no complete model which can be valid for all liquid-liquid dispersion
systems, and scientists are still at the stage of modeling one system at a time.
39
10
9
8
7
0
<6
`Z
THEORETICAL
~5
U)
z
C] 4
LJ
J
02
--J
1
n
v0
01
02
03
0.5
0,1
0.6
0.7
0.6
0.9
C, mm
Fig - 3.6 - Theoretical size distribution and experimental histograms : impeller region
(solid line), circulation region (dashed line), N* = 310 rpm, tp = 0.10, d32= 255 m
(experiment) versus 250 m (calculation). [from Coulaloglou. C. A. and Tavlarides,
L. L. (1977)].
40
300
250
200
150
100
50
20
40
60
100 120
Diameter, d ()
80
140 160
250
200
a
150
cu
1
v
00
a,
50
40
120
80
Diameter,
160
200
d ()
properties of a liquid-liquid
dispersion :
An interface is generally defined as the boundary zone between any two phases.
In macroscopic terms it is usually assumed that the two phases are immiscible
or
mutually saturated. The interface is characterised by an interfacial free energy, which
is the minimum amount of work required to create that interface. The interfacial free
energy per unit area represents the interfacial tension between two phases. When
one liquid phase is dispersed in a second immiscible phase a dispersion is formed
and the interfacial area is significantly increased. This increase in the interfacial area
41
results in a correspondingly large increase in the interfacial free energy of the system.
Thus, the dispersion becomes highly unstable thermodynamically, compared to the
state of minimum interfacial area (i. e flat interface). It is therefore important to
reduce the interfacial free energy if a stable dispersion is required. This can be
achieved by adding a surface active agent that adsorbs at the liquid-liquid interface
and, thus, reduces both the interfacial free energy and the interfacial tension. The
surface active agent , which adsorbs as an oriented interfacial film, forms a
mechanical, steric or electrical barrier around the dispersed droplets and prevents
their coalescence (Rosen, M. J. (1989)). The mechanical barrier prevents the drops
from coalescing during collision, while the steric and electrical barriers inhibit the
close approach of one drop to another. Thus, the total interaction energy between
the droplets can be written as (Ottewill, R. H. (1967)) :
w
w
total
wvan
electrostatic
AGsteric
der waals
[3.36]
Where OGerectrostatjc
is due to electrostatic forces of repulsion; AGvu
is
derwalls an
is a repulsion force due to the
attraction due to the van der waals forces, and AGS1eric
steric effects. Usually, when a nonionic stabiliser is present in the continuous phase
the repulsion forces due to steric effects AGsterconsiderably outweigh the other two
forces.
3.1.6.1 - Interfacial
tension :
The interfacial tension of immiscible liquids is less than the larger of the surface
tensions of the component
liquids.
are mutually
saturated, a
between the
vapor or gas :
6c/d= 16c- dl
42
[3.37]
Where :
One of the main characteristics of a surface active agent is its ability to adsorb at
the interface in an oriented manner. The efficiency of the adsorbed surface active
agent is determined by it s interfacial concentration, orientation and the energy
ionic
in
Surface
type
the
are
active
agents
usually
either
of
an
system.
changes
(sodium dodecyl sulfate(anionic), ethylhexadecyldimethyl
ammonium bromide
hydrolysed
poly(vinyl
acetate)) or finely
(HPMC),
divided inorganic
solids
RTd(lnC)
[3.38]
Where F is the amount of surface active agent per unit area of interface in excess of
that present in the bulk solution; C is the concentration of the surface active agent
in the solution; R is the gas constant ;T is the absolute temperature (K) and 6 the
interfacial tension.
When macromolecules are used as surface active agents, the homopolymers or
43
copolymers partition themselves between the two liquid phases as shown in Fig
-3.8-.
The interfacial layer is the region of thickness b. In the case of macromolecules, the
adsorption
does not concern the whole molecule but just segments of it. Also, the
adsorption of macromolecules
is usually irreversible.
00
0
00 0 00c
-000
00
5 0o
000
"0"
Y..
000.
00 00
000
0
000
0
co
. 00
0
See
e"
0000000**
;""1
"
a1P
There are various types of equipment for drop generation; among them are spray
nozzles, atomizers and mixers. The latter is the most used in liquid-liquid dispersion
systems. Mechanical agitation in the chemical industry is performed in a mixing
tank. The mixing performance is highly affected by the vessel geometry and
dimensions, type and dimensions of the mixing impeller as well as the baffles. The
details related to the main mechanical features of each type of equipment and the
44
range of their operating duties were discussed by Nagata, S. (1975), Oldshue, J.Y.
(1983) and Harnby, N. et al. (1992). A typical arrangement for a mechanically
agitated vessel is shown in Fig - 3.9 -
motor/gearbox
sh
jacket for
heat transr(
baffles
impeller
Fig - 3.9 - Typical arrangement for a mechanically agitated vessel [after Harnby, N.
et al. (1992)].
The "standard" geometry vessel presented in the latter figure is widely used for
liquid-liquid dispersions especially for research purposes. The vessel is a vertically
mounted cylindrical tank which typically will be filled to a depth equal to about one
tank diameter when running full. Its diameter ranges from 0.1 m (laboratory unit)
up to 10 m in large industrial instalations. The base of the tank may be flat, dished
or conical depending on its end use. The tank may, also, be fitted with a water jacket
or an internal coil as a heating or cooling system. Four equally spaced baffles, which
45
are usually
1/10 the tank diameter, may also be used to prevent gross vortexing
behaviour. They are usually flush mounted with the wall, although sometimes a small
clearance is left between the baffle and the wall. They are not generally required for
liquids. Fig - 3.10 - shows the typical geometry for some of the basic
types of impellers. There are usually mounted on a central vertical shaft inside the
high viscosity
of the liquid
plan view
A) Three-bladed propeller
C) Simple paddle
D) Anchor impeller
Fig - 3.10 - Typical geometry of some of the basic types of impellers [after Harnby,
N. (1992)].
46
Viscosity kg/msec.
Propeller
<2
Turbine
Paddle
<50
< 1000
Anchor
Higher viscosity
dispersion :
Among the factors governing the characteristics of a liquid-liquid dispersion are the
density,
These
the
the viscosity and
the
are
system.
mainly
physical properties of
the interfacial tension as they are used in the determination of the dimensionless
parameters characterising the dispersion such asthe Reynolds number and the Weber
is
formation
immiscible
liquids
When
there
two
a
of a continuous
are
mixed,
number.
density
is
determined
dispersed
The
the
of
system
using
average
phase.
phase and a
the arithmetic density average, which is defined as :
' O)Pc
1-
Pm=(ON
Where
[3.39]
a)
1+1.5+
(t
[3.40]
[3.1.6.1].
47
processes :
The production of polymer products, in addition to being the largest, is the most
complex industrial activity involving chemicals. This industry uses a wide variety
of monomer and additive combinations in order to provide a wider range of polymer
products. Thus, changes in the polymerisation process and production technology
continue to occur and depend on the end use of the final product.
Heterogeneous polymerisation may be carried out with the monomer alone (bulk),
in a solvent (solution), in an emulsion in water (emulsion), or in droplets suspended
in water (suspension), each one behaving as an individual bulk polymerisation
reactor. All four methods are commercially applied to radical initiated chain
polymers such as polystyrene and poly(vinyl chloride). Polymerisations are also
classified as homogeneous or heterogeneous depending on the solubility of the
reactants and products. This sub-section represents a brief survey of the main
polymerisation processes and their application to vinyl chloride polymerisation.
More attention is focussed on the suspension polymerisation process.
3.4.1 - Bulk (mass) polymerisation
In bulk polymerisation
monomer, initiator
of additives.
Although
the polymerisation
monomer,
initiator
is soluble
in the
and
is a particular problem.
the polymerisation
rapid increase in viscosity as the polymer content rises. Thus, in a number of bulk
polymerisations
conversion
chloride
insoluble
=8-
48
chloride)
is
a slurry of
The
in
formed
is
the
mixture.
commercial
reaction
polymer and monomer
C
70
40
between
is
and
using the Pechiney-st.
polymerisation process carried out
in
(8
25
first
The
the
takes
two
prepolymeriser
place
m3
step
gobain
step process.
The
%
712
second step takes place
to
takes
the
conversion.
capacity) and
product
in the polymeriser (12 - 50 m3 capacity) and takes the product to 70 -90 % conversion.
Fig - 3.11 - shows the equipment for two-step bulk polymerisation of vinyl chloride.
The prepolymeriser is a vertical stainless steel autoclave with a water cooled jacket,
first
baffles.
The
flat
four
bladed
turbine
step usually
and
agitator
a condenser, a
takes about 30 minutes and is terminated by initiator exhaustion, thus, short half life
Pre
Fig - 3.11 - Equipment for two-step bulk polymerisation of vinyl chloride [after
Schildknecht, C. E. (1977)]
49
Fig - 3.12 - General layout of ATO 50 m3 vertical reactor : 1, reactor shell and jacket;
2, upper screw agitator; 3, lower anchor agitator; 4, reflux condenser; 5, degassing
filter; 6, maximum PVC resin level; 7, discharge valve; 8, manhole; 9, packing seal
[after Burgess, R. H. (1982)].
50
In the solution polymerisation process a solvent for the monomer and (usually)
heat
is
to
take
the
The
is
of
the polymer
main advantage of a solvent
used.
This
the
process
the
system.
polymerisation
viscosity of
polymerisation and reduce
is often avoided unless there are outstanding advantages compared to the other three
The
the
because
solution
solvent.
the
costs of removing and recovering
of
processes
be
final
is
the
used without
can
solution
polymerisation process advantageous when
in
the
in
the
coatings
and
of
protective
the
manufacture
as
such
polymer
separating
fibres).
for
dope
into
(by
industry
spinning
the
a
polymer solution
textile
converting
When the solvent is not totally inert, it can influence the polymerisation reaction
In
degree
the
some
the
of polymerisation.
polymer and
rate, the molecular weight of
in
the monomer-solvent
initiator
miscible
or polymer product are not
cases the
F.
(Rodrigez,
following
have
In
the
combinations
this case we might
solution.
(1989)):
Combination
Soluble
Soluble
Soluble
Soluble
initiator
Soluble
Insoluble
Insoluble
Soluble
polymer
Soluble
Soluble
Insoluble
Insoluble
51
chloride
emulsion
polymerisation,
heat
jackets
fitted
the
to
of polymerisation.
remove
cooling
with
autoclaves
The
it
because
is
kept
temperature of the reaction mixture
constant with great accuracy
determines the quality of the PVC product. The polymerisation
6 and 9 hours. During
stirred. The
been
have
90
%
is
the
terminated
monomer
of
vinyl chloride
when about
reaction
batch
for
A
emulsion polymerisation
a
simple
recipe
converted.
is shown in table -
3.3 -. Ammonium
initiator
free
is
the
and sodium stearate acts as
radical
persulfate
micelle-generating
lattices
The
PVC
(surfactant).
produced are spherical
substance
52
micelle
JqR
"
".
t-tonomer
molec
Spa
Monomer
droplet
"""
""
""
-initi
:-
l
radaictaor
-'
".
ules
9 1*
"""
Water
Qbb
bbbbb --
-`
0-4
t, .
.
..
olymer
phmb
Demineralised water
140
Vinyl chloride
100
Stearic acid
0.8
Sodium hydroxide
0.12
Ammonium
0.12
persulfate
apolymerisation temperature 52 C
b part per hundred of monomer
Although using an emulsion allows faster rates of reaction at lower temperature than
it
the
more
and
makes
polymer
other processes, the residual surfactant contaminates
sensitive to heat and shear stress.
53
In this case the monomer dissolves its polymer. The monomer droplets pass through
An
little
to
transformed
example
spheres.
solid
clear
a viscous syrupy state and are
is
this
type
polystyrene.
of
polymer
of
54
process
Suspension polymerisation has a number of advantages over other polymerisation
processes (bulk, solution, and emulsion) :
low,
is
thus,
The
the
agitation
efficient
suspension
relatively
of
viscosity
overall
is possible.
heat
Easy
temperature
control.
and
removal
(compared
in
impurities
levels
Low
the
emulsion).
with
product
polymer
of
is
is
the
then
If
suitable
process
suspension
the
as
a
powder
required
product
polymer
because the energy required to disperse the monomer droplets is less than the energy
bulk).
finished
(compared
break
the
to
with
polymer
up
required
On the other hand, the disadvantages of the suspension polymerisation process are:
baffles, agitators and other surfaces.
build-up
Polymer
the
wall,
reactor
on
-
55
bulk
larger
than
Suspension
volumes
requires
reactor
polymerisation usually
50
%
because
the
about
water.
vessel contains
processes
bulk).
(compared
Waste
with
water problems
3.4.4.2 - Vinyl chloride suspension polymerisation
process :
56
Trade name
acetates)
Gohsenol KPO8
acetates)
Alcotex 72.5
Degree of hydrolysis
71 - 75
71.5-73.5
Alcotex 78
acetates)
Gohsenol KH-17
78.5-79.3
acetates)
Gohsenol GH-20
86.5 - 89
Hydroxypropylmethylcellulose
(HPMC)
Methocel
Cellulose ether
Cellosize
Cellulose ether
Methocel A
Cellulose ether
Hydroxyethylcellulose
Methylcellulose
(HEC)
(MC)
76 - 79
Supplied form
t112 C'
,
10 hours 1 hour 6 minutes
solution
37
51
66
Dilauroyl peroxide
solid
62
80
99
solid
43
60
78
solid
59
79
101
azobisisobutyronitrile
(AIBN)
VCMa, wt %
water
100 - 130
VCM
100
protective colloid(s)
0.05-0.15
initiator
0.03-0.07
57
polymerisation process. The final PVC grains are about 100 - 180 um in diameter
but the exact diameter depends on the suspending agent type(s) and concentration
(s) as well as the turbulence intensity. Agitation is of fundamental importance in the
suspension PVC process. Together with the suspending agent system it governs the
stability of the suspension during polymerisation as well as the particle size and
particle porosity (the morphological aspect is described in the next section). Thus,
it is important to control the agitation to produce the type of particles desired. It is
well known that high agitation speeds as well as (relatively) low agitation speeds
usually favor agglomeration of the formed particles. Thus, there is an optimum speed
which depends mainly on the reactor (this includes agitator and baffles) type, size,
and geometry. This is illustrated in Fig - 3.16 - which shows that, as the stirrer speed
increases, the grain size of the PVC particles first decreaseto a minimum size before
starting to increase. It also shows that by increasing the suspending agent
concentration the PVC grain size decreases.
90
1100
80
Pressure
----------------
70
U
a)
End of
batch
900
Batch temperature
60
1000
800
50
v
s
ai
i
700
Jacket temperature
a
E 40
N
N
Q)
600
L
1
30
500
20
400
10
300
0
0
100
300
200
400
Time, min
Fig - 3.14 - Reaction profile for a typical vinyl chloride suspension polymerisation
[After Clark, M. (1982)].
58
Aqueous charge
fictive
protective ccolloid
VCM
VCM
VCM gas
recovery
plant
Reactor
Cooling
water
Stripping
PVC slurry
column
Biowdown
vessel
Steam
Heat exchanger
PVC slurry
Driers
Bagging
bulk storage
dispatch
Centrifuge
[After
PVC
Fig - 3.15 production plant using the suspensionpolymerisation process.
Stephenson, R. C. and Smallwood, P.V. (1989)]
59
B
A
800
700
600
E
500
rye
,
YW
d
ii
300
:E
200
100
0i
250
iiti11
350
450
550
650
750
850
Fig - 3.16 - PVC resin median particle size vs agitator speed. Suspending agent per
100 grams of vinyl chloride : A, 0.06 gram; B, 0.09 gram; C, 0.12 gram. [After
Langsam, M. (1986)].
In the vinyl chloride suspension polymerisation process, two types of suspending
agents are usually used. They are called the primary and the secondary stabilisers.
Because of the demand for PVC particles with reduced residual VCM (vinyl chloride
it
in
is
that
the
controls the particle size
chosen a way
monomer)
primary stabiliser
"primaries"
in
Table
increases
Examples
type
this
of
are
the
shown
of
and
porosity.
increase
further
PVC
Secondary
3.4
the
to
the
porosity
of
stabilisers are used
-.
grains. One example of this type of stabiliser is the use of poly(vinyl acetate) with
S202
(50
%
degree
Polyvic
hydrolysis)
low
hydrolysis
degree
of
as
relatively
such
of
and Alcotex 55 (55% degree of hydrolysis). The effect of the degree of hydrolysis
of partially hydrolysed poly(vinyl
-3.17-.
60
E
)
E
200
40
U
cc
n 150
c
c7 30
80
70
60
120 L
60
80
70
Degree of hydrolysis, %
Degree of hydrolysis,
(b)
(a)
Fig - 3.17 - The effect of the degree of hydrolysis of poly(vinyl acetate) on PVC
[After
Stephenson,
C.
(b)
R.
(a)
size.
grain
porosity;
mean
grain
grain properties.
and Smallwood, P.V. (1989)].
3.5 - Particle formation and properties in the suspension polymerisation of vinyl
chloride
chloride
reaction
of VCM
follows
:
of
molecule, p,. - --, na, a double bond, is activated so that the double bond
opens and joins up with other similar molecules as seen below
chloride
CH., =CH
CIi., -C3I=
Cl
Vinyl chloride
CI
Poly(vinvl chloride)
61
21.
[3.41]
[3.42]
initiator
initiator
[I]
[I]
the
the
and
radicals
are
concentrations of
and
where
respectively and kd is the rate constant of initiator decomposition.
With [I] = [Io] exp (-kdt).
where f is the initiator efficiency factor, [Io] the initial concentration of initiator and
t the reaction time. The constant kd is related to the half life of the initiator t12 by :
k,
j1=
( fast)
loge 2
t2
I' +M -> R,
[3.44]
62
[3.45]
Where [M] is the concentration of VCM monomer and [R', ] is the concentration of
the growing radicals of chain lenght 1.
Propagation : It is a step process involving the addition of a polymer radical R',, to
a molecule of monomer M.
kp
R,, +M
R,
[3.461
[3.47]
Where kp is the rate constant for chain propagation and [R'] is the concentration of
the growing radicals of chain length n.
Chain transfer to monomer : It involves the transfer of the radicals from a growing
chain ( eg, R') to the VCM monomer molecules.
Rn +M
ktr
pn + R*
[3.48]
Where P, is the "dead" polymer and klr is the rate constant for chain transfer to
monomer.
The rate of transfer to monomer is given by :
[M]
Rt. = k,
r[R*1
[3.49]
RCH2CHC1.
RRCH=CHC1 + R,,,CH2CH2CI
+ R,,,CH2CHC1R;
R,
,
P,,.
[3.50]
Where kt is the rate constant for termination by disproportionation. Thus, the rate of
termination is given by :
63
Rt = k, [Rn] [R,,,]
B)-
[3.51]
[3.52]
k',,
(Rn)+M --- (Rn+,)
[3.53]
[3.54]
Where k'n is the rate constant for chain propagation and [(R'n)] is the concentration
length
the
trapped
of
chain
n.
growing radicals
of
Chain transfer to monomer:
k'tr
(Rn)+M->Pn+(R)
[3.55]
[3.56]
(R;) - R;
[3.57]
k',
(R,) + (R,; -> P,, + P,,,
t)
[3.581
Termination
(disproportionation)
64
Rt = kt [Rn] [R, ]
3.5.2 - Mechanism
morphological
of poly(vinyl
chloride)
particle
formation
and
its
65
Conversion
VCM
VCM
-20%
YCM
- 90l
Water
Water
- 90%
Fig - 3.18 - Build-up of structure within the vinyl chloride droplet during
(1989)].
P.
V.
Smallwood,
[After
polymerisation
66
SIZE
CONVERSION
Coiled
Macro
<1" o
Radicals
Micro
Domains
100A
i-2 ,'a
Domains
01-02 um
Primary
0.2-0-L.um
Particles
000
r
,
,.
/^
. ..
1-2
4-10 nor
Lm
1o
I
17
67
so
io
chloride
in
both
The
occurs
phases simultaneously and the
polymerisation
monomer phase.
form
domains
first
during
formed
to
the
which then grow
stage
aggregate
particles
in size to become primary particles of 0.2 - 0.8 m in size. These primary particles
by
This
be
believed
to
charges.
charge was
stabilised
negative
electrostatically
are
/
interface
ions
VCM
due
be
the
to
the
to
at
water
of
chloride
adsorption
postulated
(Davidson, J.A. and Witenhafer, D. E. (1980)). During the early stages the water
forms
/
interphase
the
at
water
monomer
soluble protective colloid, which adsorbs
is
believed
be
The
"skin"
droplets
"skin"
to
the
thin
to
against coalescence.
protect
a
Fig
3.21
Fig
3.20
PVC
the
and
suspending
agent.
and
of
a graft copolymer
droplets
the
chloride
and the
show
morphological changes of polymerising vinyl
initial emulsification of a VCM droplet respectively. As the polymerisation proceeds
further in the second stage, the primary particles grow in size by capture of newly
formed micro-domains. When they reach a critical size the electrostatic forces
become weak and the micro-domains agglomerate into closely packed clusters. As
the polymerisation continues in both phases, the quantity of polymer increases at the
is
This
liquid
two
the
stage
completed when the
phase
monomer phase.
expense of
70
is
This
of
approximately
occurs at a conversion
monomer-rich phase exhausted.
%, when the pressure, which has been constant up to this point, drops. During stage
three the polymerisation occurs in the monomer swollen polymer phase. Fig - 3.22
different
between
Fig
3.23
the
the
transfer
the
phases
and
show
monomer
and
Y.
(Xie,
T.
PVC
between
the
the
et al.
and
morphology
pressure
reactor
relationship
(1991)).
68
0
COO
0
U
CS
U
"*
"
O
v
sio
sy
e
S*
somas
seas
C
U
0
)
-
4
o
""
"sp,
+oU
cz
u
N
M
io"
ot
C3.. N
69
H7 0
"
CH7 = CHCI
Hydrophobic
end
Hydrophilic
Emulsification
end
Fig, - 3.21
Initial
[After
Davidson,
J.
A and Gardner,
vinyl
chloride
emulsification
K. L. (1983)].
VAPOR
VAPOR
PHASE
VCH
VCM
INTERFACE
VAPOR-WATER
WATER
PHASE
WATER
PHASE
VCH
PHASE
VCM
INTERFACE
PVC-WATER
POLYMER
PHASE
MONOMER
PHASE
Xf
Fig- 3.22 Monomer transfer before and after pressure drop (Xf being the
conversion
at which the pressure drop occurs) [After Xie, T. Y. et al. (1991)].
70
10
/
9
constant
pressure
the first
stage
the second
stage
pressure
drop
pressure
drop
6
a5
W4
a
3
formation
formation
of primary
particles
continuous
network
of
formation
of dense
skin and
rigid
porous
powder
of PVC
network
10
20
30
50
40
CONVERSION,
60
7.
70
80
x
90
100
Fig - 3.23 - Relationship between the reactor pressure and PVC morphology
development [After Xie, T. Y. et al. (1991)].
A summary on the terminology that is used to describe the morphology of PVC was
by
Geil,
P.
H.
is
based
It
M.
W.
(1981).
by
Allsopp,
a
on
paper
published
proposed
(1977) ( see Table - 3.7 - and Fig - 3.19 -).
71
Approximate size
Term
Range
Average
(um)
(um)
Origin or description
Visible
Grain
50 - 250
130
of free flowing
constituent
Sub-grain
10 - 150
40
Polymerised
Formed
Agglomerate
1-10
during
polymerisation
droplet.
monomer
early
by
stage
of
coalescence
of
0.6-0.8
0.8
(less
conversion
than
2%)
coalescence of micro-domain.
particles
by
Grows
about
0.2
particle
1000
nucleus. Contains
micro-domains
Only
Micro-domain
0.01-0.02
0.02
identified.
72
CHAPTER 4
73
r
OO
L
c
s
U .=
U
oc
CJ
U_
C
C
c3
;,
r/--J
vV
A\
i
f'
UU
Ic
CD
74
75
76
Fig - 4.2 - Details of the recess in the vessel wall for circulating water and the gas
bleed port ( dimensions in mm ).
77
depth x 68 mm width, running the entire circumference of the vessel was machined
in the outer surface of the wall (see Fig -4.2-). It was then covered over by welding
a stainless steel strip of 70 mm width x 1.4 mm thickness. Baffles were welded into
the recess in order to increase turbulence and heat transfer inside the water jacket.
2) - The temperature probe port :A high pressure temperature probe (stainless steel
probe, 3.5 mm diameter, 22 mm length, with a male nut 1/8" BSF) was fitted in the
base of the reactor tank. The temperature in the vessel was controlled using a digital
temperature indicator (with programmable alarm/external sensing probe) with a
temperature measuring range of -10 C to 110 C (resolution 0.1 C) and with a
selectable sensing (1 sec. or 10 sec.).
3)- The charge/discharge port :A Swagelok male connector (1/8" O. D tube - 1/8"
thread) was fitted in the base of the vessel for loading and unloading of the suspending
medium.
4) - The sampling system port :A male connector fitting (Swagelok male connector,
1/8" O.D tube -1/8" NPT thread) in the vessel's wall connected to an outside ON/OFF
ball valve allowed samples to be withdrawn from the reactor into the pressurised
optical cell (to be described in the next sub-chapter).
5)- The gas-bleed port : An overhead port in the wall of the vessel, directly opposite
to the sampling system port, was designed for purging the pressurised vessel and for
bursting
disc
device
indicator
to
the
and
a
a
pressure
medium
reaction
connecting
(see Fig -4.2- and Fig -4.3-). The fitting used was a Swagelok male connector (1/16"
O.D tubing - 1/8" NPT thread). The latter fitting allowed a stainless steel pipe (O. D
1/16") to be inserted into the vessel (see Fig -4.2-). The length of the stainless steel
tubing inside the reactor was adjusted so that it is slightly above the liquid level. It
O.
D
NPT
(1/8"
1/8"
tubing
to
tee
thread)
the
reactor
a
union
outside
was connected
from which one arm provided the connection to the venting line while the other arm
bursting
disc.
indicator
linked
the
to
the
and
pressure
was
6) - The seal mechanism : Because the reactor was designed for VCM dispersion
and polymerisation, special seals were required to prevent leakage of VCM from
following
had
be
For
this
the
to
the
shaft.
reason
requirements
met
around
agitator's
by the sealing mechanism :
15
bars.
Working
to
of
up
a) pressure
78
r-)
U
c3
C.'
O
cs
a)
1.11.1
O
r-.
E
CIL
x
w
M
'
79
b) - working temperature of up to 80 C.
c) - Chemically resistant to VCM.
d) - Sealing system to be used for a shaft diameter of 8 mm and a rotational speed
of up to 800 rpm.
e) - No lubrication so as to avoid contamination of the reaction mixture.
f) - Small volume (not too bulky for our system).
One of the best sealing systems that met our requirements was the use of lip seals.
They are Gylon (trade name of Garlock Ltd. ) lip-seals, made from a mixture of PTFE
following
have
the
advantages :
and graphite and
Good
(elastic).
memory
Low
thermal
expansion.
High
pressure capability.
for
liquids
PTFE
(suitable
Chemical
corrosive
and
of
pure
and
graphite
resistance
gases).
installation
dimensions.
Require
small
very
In order to avoid leakage, a multi-lip arrangement could be installed on very short
double-lip
for
lengths.
For
the
of
a
arrangement
use
our equipment, we opted
axial
with an atmosphere of nitrogen in between the two lips. The various components of
the seal mechanism are shown in Fig -4.4-. The leakage of VCM was eliminated by
internal
the
the
slightly
above
pressure of the reactor.
nitrogen
pressure
adjusting
The nitrogen was introduced between the two lips by machining a 12 mm diameter
hole, at 25 mm off the centre of the lid, down to a depth of 22 mm and connect it to
the agitator's shaft hole by machining a2 mm horizontal hole. This opening into the
centre hole occurs at the level of the stainless steel spacer ring (shown in Fig -4.5-)
between the two lip seals. When the nitrogen was admitted into the latter hole, it
entered the seal housing and filled the space between the spacer-ring and the wall of
the housing, it then passed through the 2 mm diameter hole in the spacer-ring and
VCM
from
inside
The
leakage
the
the
the
the vessel
the
of
of
entered
space of
ring.
by
because
the
the agitator's shaft and
the
confinement
of
of
nitrogen
was prevented
the two lip-seals. The lip-seal locking bush (male nut shown in Fig -4.5-) provided
the required compression to make good seals while the Viton o-ring protected the
seals against the metal of the stainless steel bush.
80
b
O
Ut
OU
coo
ct
C/]
U-
O
cS N
a)
Q
O
I
81
-z
un
0
9L
/-~\
cz
u
1
c3
U
U
_'/
hJ
CJ
"V
"ti
U
O
4-.
O
r-N
b0
U
cd
V)
d-
82
7)- The agitator : The agitator was made from stainless steel 316 rod. It is a six flat
blade turbine type mounted on a 12 mm diameter x 81 mm length shaft (portion
exposed to the liquid mixture and was responsible for creating the flow field). Fig
diagram
different
in
the
the
the
schematic
shows
of
stirrer
with
step
changes
-4.6diameter. The end sections (above and below the shaft portion exposed to the reactor
mixture) act as supports and are fitted inside special bearings. These bearings are
made from stainless steel and are dry running open ball type, measuring 16 mm O.D,
8 mm, I. D x4 mm. This type of design is necessary to keep the agitator in a vertical
position at all time and to avoid vibration. The bottom section, which is 8 mm
diameter x4 mm, allows the shaft to sit tightly in a bearing. The latter is plugged in
a hole machined in a stainless steel 316 disc measuring 60 mm diameter x 4.5 mm
(see Fig -4.7-). The disc is fitted in a matching recess machined at the centre of the
base of the reactor vessel. The diameter of the portion of shaft passing through the
top bearing is reduced to 8 mm and then reduced further to 7.9 mm diameter to be
accommodated inside the sealing system. The upper part of the shaft emerging from
the sealing system and the top of the lid (7 mm diameter x 75 mm) is coupled to the
drive shaft.
4.2 - Design and operation of the pressurised optical cell :
One of the main tasks of the research project was to design and operate an optical
microscope system that allows monitoring of the behaviour of the dispersed phase
before and during suspension polymerisation. For this purpose, several types of
optical systems were considered (including those described in chapter -3- ). Finally
the choice was to use an external microscopic optical cell. This choice was made
because the dispersion was stabilised using a suspending agent; thus, the sampling
would not disturb the droplets or change their properties. The primary target was to
design a system which meets the following requirements ( Davidson, J.A. (1975)
1)- It should safely withstand the pressure being used (about 12 bar).
2)- It should be capable of being used with commercially available microscope optics.
3)- The liquid layer inside the cell should be quite thin (because we are dealing with
liquid-liquid
83
Fig - 4.6 - Schematic diagram of the six flat blade turbine type agitator and it's shaft
(dimensions
in mm).
84
85
to be changed just by changing the thickness of the spacers. Sapphire windows were
inert,
hardness,
because
(extreme
their
chemically
easy
of
properties
surface
chosen
to clean without leaving scratches, and can withstand very high pressures). The
breaking strength of transparent vitreous silica windows of various diameters (D, )
may be calculated using the following formula (from leaflet supplied by Viteosil
and Spectrosil pressure windows) :
86
Sapphire
windows
ciam.
12.6
mm
1.6 mm
thick
Oz
mi
r- -
'
,
\
\,
.,,
7
24
Z0
Fig - 4.8 - Schematic diagram of the stainless steel pressurised optical cell
(dimensions in mm).
87
t=-
DP
[4.1]
168
t=-
P
D
[4.2]
840
Joint
Area
D
D,
above 368 bars. The latter window was tested successfully for pressures of up to 400
bars (well above our working pressure which is about 10 bars).
The top window was cemented inside the hole of the main body, while the bottom
bush.
locking
The sealantused was a silicone
to
the
top
the
of
window was cemented
rubber material (Silastic 738 RTV adhesive / sealant) which was applied to the
in
0.5
thickness
of
approximately
stainless
steel
surfaces
a
uniform
mm
pre-cleaned
and pressed slightly using the sapphire windows, then, left to dry at room temperature
for 48 hours. The internal PTFE spacing pieces were then inserted between the two
88
bush.
Despite
by
locking
tightening
the
the
then
assembled
cell was
windows and
all the precautions taken in designing the cell, eye protection was always worn when
handling pressure equipments.
4.3 - Design and operation of the reflux system :
One of the main aims of the research project was to develop a system that allowed
droplets
details
the
the
on
morphology
of
condenser
operation
effect
of
study of some
and uniformity
have been considered in the design of the reflux system, taking into account the need
for a continuous monitoring of the reflux rate. For this purpose, the system shown
in Fig -4.10- was designed. It consists mainly of a 80 cm long stainless steel pipe
The
jacket
diameter,
internal
8
window.
and a viewing
a cooling water
of about mm
latter system was connected to the top of the reactor's lid by an ON/OFF valve (8
This
internal
diameter)
gave the choice of using or not using the
at
each
end.
mm
in
be
it
Also,
the
to
the
stored
reflux
returning
permitted
reflux condenser system.
viewing chamber when needed.
4.3.1 - The cooling system :
The condenser's water jacket was made from 40 mm diameter brass pipe and was
inlet/outlet
The
long.
15
pipes
a
using
water
operated
condenser was
cm
about
(thus,
bath
the
the
temperature
to
to
cooling
water
of
control
a water
connected
controlling the reflux rate).
4.3.2 - The viewing window :
In order to measure the reflux rate, a conical stainless steel device was fixed under
the condenser inside the viewing window (see Fig -4.10- and -4.11-). It was machined
from a stainless steel 316 rod ( 30 mm diameter x 32.5 mm ). A hole of 1.3 mm in
diameter was drilled at the bottom of the cone to allow uniform droplets of VCM
to return to the mixing system. Another hole was drilled on the side wall of the cone
(4 mm internal diameter) with an angle of about 60 (see Fig -4.11-) in order to
body
(due
below
differences
between
the
and
above
conical
eliminate any pressure
to a difference of temperature). The latter was fixed to the lower pipe of the condenser
89
-D
L.
O
a
0
C
U
O
a)
Cl
a)
>
0
>
C
1C
L
O
3
0
cn
Z
0
4
DC_
a)
UU
C)
L
C)
Q)
-o
O
0
0
0
v
C
0
0
a)
a
0
C
C
3:
0
t
c
U)
90
b4
"Z
Fig - 4.11 - Schematic diagram of the conical body used in the reflux system
(dimensions in mm).
91
by
The
locking
counting the number of
screw.
reflux
rate
was
measured
using a
drops coming from the condenser per unit time. The volume of the drops was
determined using a calibration method (45 drops VCM / ml. ). On the top-left side
) of the viewing window, an ON / OFF venting valve ( 2.4 mm internal diameter)
build-up
heated
in
the
top
the
to
of
any
of
nitrogen
at
order
prevent
mounted
was
decrease
The
inhibit
(which
the
or
reflux
rate).
viewing window was
may
pipe
provided by E. V. C . It is a stainless steel double windowed pressure cell having a
capacity of 0.5 1.and a viewing area of 75 mm diameter. It can withstand a working
pressure of up to 25 bars. Each window was mounted onto the stainless steel body
diameter
The
bottom
bolts
the
of
pipe
and
a
side
cover.
using six stainless steel
PTFE
4
(8
to
to
the
a
mm,
mm
using
pipe
window
was
reduced
viewing
connected
O.D; 4 mm, I. D) in order to avoid having VCM vapours coming into the window
from the condensation side of the reflux system. The reflux rate was controlled by
few
into
A
(added
the
reactor).
experiments were
of
nitrogen
a
certain
amount
using
be
The
best
determine
to
to
the
used.
experimental
conditions
reactor's
performed
lid, as well as the stainless steel pipe leading to the condenser, were covered with
a heating tape in order to keep them at a temperature above the reaction temperature
lid.
did
the
that
occur
on
not
so
condensation
92
CHAPTER 5
5.1 - Materials :
This sub-chapter describes the physical properties of the materials used in the
experiments. The two phase system consisted of an aqueous continuous phase and
an organic dispersed phase.
5.1.1 - The dispersed phase :
Depending on the objectives of each set of experiments, the dispersed phase
following
the
systems:
of
one
of
consisted
for
Toluene
the
simulation experiments.
dispersion
for
(VCM)
Vinyl
the
experiments.
chloride
monomer
B
B
for
dye
(Sudan
Sudan
Vinyl
the
experiments
red
and
red
chloride monomer
dye is predissolved in VCM).
initiator
for
(the
X50
(initiator)
Vinyl
the
polymerisation experiments
chloride and
is highly soluble in VCM and is either predispersed in the continuous phase or
predissolved
in the VCM).
93
B)-
Initiator
Bis(4-t.
butylcyclohexyl)peroxydicarbonate
(trade
experiments
was
polymerisation
Chemie)
AKZO
1;
16-W25-GB
Perkadox
:
supplied by E. V. C
manufacturer
name :
(U. K Ltd). It's characteristics are shown in table - 5.1 -.
5.1
Some
physical properties
Bis(4-t. butylcyclohexyl)peroxydicarbonate.
Table
of
the polymerisation
initiator
Value
Property
Molecular weight
Theoretical active oxygen content (% pure peroxide)
Emergency temperature
Density
398.5
4.01 %
+35 C
1.0
25 %
Peroxide content
Active oxygen content
0.99-1.02%
25
'
13x10-"
t,,, =
x e14902
where t (sec.) and T (K)
Appearance
white suspension
suspension in water
Formulation
The same type of initiator ( X50 ) was also used in some experiments but as a solid
in
instead
of a suspension water.
white powder
C) - Toluene : The main physical properties of toluene are shown in table - 5.2 Table - 5.2 - Some physical properties of toluene.
Property
Value
weight
92.14
Boiling point
Refractive index (at 20 C)
111 C
1.4960
Density
0.867
Molecular
Viscosity ( at 20 C)
Surface tension (at 30 C)
0.590 (cp)
27.4 (dyn/cm)
94
D)-
Vinyl chloride :
Vinyl chloride monomer was supplied by E. V. C (U. K Ltd), in a large stainless steel
storage cylinder initially containing about 30 Kg of VCM. The physical properties
of vinyl chloride are shown in table - 5.3 Table - 5.3 - Physical properties vinyl chloride.
Property
value
Colorless, dense gas at room
temperature
and
ambient
pressure.
molecular weight
62.5
Vapor density
C)
(
melting point
-153.8
C)
(
boiling
point
normal
C)
15
index
(
at
refractive
-13.4
1.398
4.0
22.0
C,
in
VCM
(at
mg/kg)
solubility of water
-15
Liquid properties :
300
1100
Value at
-40C
374
liquid density
1014.4 983.4
viscosity (cp)
0.35
0.29
0.23
26
23
20
Temperature (C)
Vapor pressure (psi)
density
-20C
362
0C
349
947.1
10
20
30
40
50
60
70
22.2
35.1
52.9
70.0
91.7
119.4
150.4
95
Value
Density ( at 55 C)
0.9857
Viscosity ( at 55 C)
0.5040 (cp)
1.3289
67.91 (dyn/cm)
b) - suspending agents :
The suspending agents used in our experiments are partially hydrolysed poly(vinyl
acetate) with different properties (i. e degree of hydrolysis, molecular weight etc.).
They were supplied to us by E. V. C (U. K Ltd). Table - 5.5 - shows some of the
properties of PVA used.
Table - 5.5 - Some properties of the suspending agents (PVA) used.
Manufacturer
Trade name
Degree of hydr.
Molecular
(%)
weight
Polyvic S202
47
22300a
Alcotex "A55"
HARLOW Chemical Co
54 - 57
20400a
71.5-73.5
75000a
Gohsenol KH-17
NIPPON Gohsei
78.5-81.5
259000a
Gohsenol S3
NIPPON Gohsei
84
240000a
PVA 88%Hydr.
BDH
88
78000b
96
PVA (88% Hydr. ), Alcotex Spec."A", Gohsenol KH17 and Gohsenol S3 are used
"A55"
S202
Alcotex
Polyvic
are used as secondary
and
as primary stabilisers while
stabilisers.
5.2 - Experimental
methods :
97
98
the
between the drop size and the other parameters of the system. These
drop
drop
influence
have
believed
to
the
on
size
and
stability.
a
great
are
parameters
In these experiments,
the one litre autoclave was first charged with 900 ml. of
(free
degassed
(i.
later
of oxygen) several times
of
air)
using
nitrogen
e
removal
was
to remove the oxygen. About 100 gr. of vinyl chloride was then weighed and forced
into the autoclave using nitrogen pressure. The reactor was then sealed and the
C.
55
The
to
sampling method was the same as the
up
mixture stirred and warmed
heating
dispersion.
At
for
the
the
the
toluene
experiment,
was stopped
end
of
one used
and the reactor cooled down using cold water ( from the tap ). When the temperature
C,
below
20
fluid
dropped
the reactor was vented very slowly via the venting
the
of
hours
lasted
2
3
(the
4.3
This
Fig
).
(see
to
about
slow
release
of
pressure
valve
-
99
venting was done overnight). Once the venting was completed, the reactor was
heated up to 80 C and vented again for about 30 minutes, using a low pressure of
0.5
bar
(
), to remove the remaining vinyl chloride monomer, which was
nitrogen
dissolved in the continuous phase ( 1000 ppm ).
5.2.3.1 - Air monitoring
In view of the carcinogenic hazard of the vinyl chloride monomer, the VCM
during
VCM
in
both
the
the
the
of
autoclave
and
venting
air
around
concentration
is
in
This
discussed
had
be
to
the
monitoring
experiment
monitored.
of
each
at
end
this subsection.
A) - Air monitoring for VCM concentration :
Air monitoring for vinyl chloride concentration was performed using a Drager pump
together with a suitable drager tube (Drager tube Vinyl chloride 1/a ). The latter gas
detector pump is a hand-operated bellows pump (specifications given by
is
It
has
(1986)).
DRAGER,
closed when the
only
one
valve,
which
manufacturer;
head
belows.
The
in
is
the
pump
gas sample sucked and opens again on squeezing
has an aperture into which the Drager tube to be used is inserted. The drager tube
Its
is
"Vinyl
1/a".
for
tests
standard range of measurement
chloride
our
recommended
(at 20 C, 760 mm Hg) is :1 to 10 ppm ( with 5 strokes ) and 5 to 50 ppm ( with 20
is
follow
VCM
determination
).
The
as
:
of
concentration
strokes
(5
Suck
the
tube
the
through
the
number
of
strokes
with
corresponding
air sample
or 20).
layer
indicating
(initial
In
the
the
the
color
of
chloride
white
of
vinyl
presence
Drager tube Vinyl chloride 1/a) turns pale-yellow-orange over a varying length. The
total length of discoloration is a measure of the vinyl chloride concentration (in ppm;
1 ppm = 2.60 mg/m3 at the conditions indicated above).
The exposure level at the workplace must not exceed 5 ppm (Weiss, G. (1985);
Irving, N. (1986)). The maximum exposure level was set at 3 ppm.
From the tests conducted, the concentration of VCM was less than 1 ppm (no VCM
was detected).
B)-
At the end of each experiment the excess vinyl chloride was vented slowly via the
100
had
be
by
determining
The
to
of
vinyl
chloride
monitored
slow
release
venting valve.
the concentration
of VCM near the extractor area (in our case the fume cupboard).
From the beginning, it was anticipated that the maximum quantity of vinyl chloride
to be vented was 100 grams. Thus,
62.5 = 1.6 mol of VCM. By assuming that the vented vinyl chloride will immediately
/
be
V
1.6
22.4
1.
STP,
to
to
the
x
vented
was
mol
volume
standard
equilibrate
vcM=
mot = 35.84 1.= 35.84 x 10-3m3. of VCM gas. In order to maintain the concentration
less
CvcM
in
VCM
than
through
the
the
system
air
venting
extracted
gas
=5 ppm
of
(5 x 10-6) the following
relationship
must hold :
Vvc,
M
CvcmfxE
[5.1]
Where E is the extractor's gas flow rate (in m3/ min),. Thus for a gas (air and VCM)
flow rate of 44.4 m3 / min ( determined experimentally for our fume cupboard ;
0.74
/
),
flow
for
the necessary venting time will
sec.
area
was
in
a1
m2
air
average
be t= 162 min Thus the venting valve is adjusted so that the VCM evaporates
.
within a time of about t=3 hours.
5.2.3.2 - Effect of suspending agent concentration
distribution of vinyl chloride droplets :
The suspending agent solution was prepared by dissolving 4 grams PVA (Alcotex
hydrolysed
"A"
spec.
partly
agitation. When the solution became transparent, it was filtered and stored in a 200
ml flask.
During
concentration
this
series of experiments
the effect
of suspending
agent
has
droplets
the
of
vinyl chloride
[WtPVA/WtH,
0.1
for
in
5
into
the
the
about
minutes
mixture
was
stirred
reactor,
suspending agent
order to homogenize
the solution. The reactor was then sealed and purged with
hundred
One
the
to
times
grams of vinyl chloride
oxygen.
remove
several
nitrogen
101
forced
into
At
that time, the temperature of the
the
then
reactor.
weighed
and
was
mixture was about 15C. The system was then heated-up to the required temperature
( 55C) and, at the same time the stirrer was run for 30 minutes (30 minutes is the
following
the
to
time
state)
at
each
of
speeds : 250,350,
obtain a steady
necessary
500,650 and 800 rpm respectively. At the end of each stirring period a sample was
forced into the pressurised optical cell and photographs were taken and analysed.
The pressure inside the reactor during these experiments was about 9 bars (N2 ).
The volume % of monomer droplets for eachinterval i (of diameter D; ) was calculated
using the following expression :
(V%)1=
3
D,
x 100
n, x
n; x V; x 100
-3
Vt
[5.2]
n; x D;
Where D; is the average diameter in the interval i, n1is the number of droplets of
diameter D, and, V, and V; the total volume of the monomer droplets counted and the
diameter
D;
droplet
the
respectively.
of
volume of
5.2.3.3 - Effect of phase hold-up on the volume and size distribution
chloride droplets :
of vinyl
In order to simulate the vinyl chloride drop dispersion on an industrial scale, the
dispersed
investigated
hold-up
to continuous phaseratio of
a
using
effect was
phase
and 0.4 (by weight) respectively. These experiments were
PVA
hydr.
The
%
)
PVA
(
72.5
agent.
amount
of
as a suspending
performed using
The
for
(
0.3
).
the
gram
procedure was similar to
same
all experiments
used was
0.01,0.05,0.1,0.2,0.3
the one used in sub-section - 5.2.3 -. Because of the limitations due to the internal
volume of our reactor, the volume of the continuous phase was not constant (see
table - 5.6 -).
102
TABLE
distilled
Quantities
5.6
of
vinyl
chloride,
-
Vinyl chloride
Continuous phase
PVA weight
(cp)
weight (grams)
weight (grams)
(grams)
0.01
15
1000
0.3
0.05
50
1000
0.3
0.1
100
1000
0.3
0.2
200
900
0.3
0.3
300
800
0.3
0.4
400
700
0.3
Volume fraction
5.2.4 - Effect of mixing conditions on the coalescence rate between the vinyl
chloride droplets (dye experiments):
The aim of this series of experiments was to study the effect of experimental
For
this purpose, three parameters which are
the
rate.
coalescence
conditions on
investigated.
believed to have a great influence on the coalescencerate were
The latter are, the residence time, the suspending agent concentration and the
turbulence intensity ( agitation speed ). To perform this set of experiments, an
dye
0.1
SUDAN
"B"
developed.
red
was put
gram
of
was
experimental procedure
into a small stainless steel cylinder (150 ml. capacity). The latter was then purged
filled
The
25
the
to
of
chloride.
air
and
with
grams
vinyl
remove
with nitrogen
dissolution
dye.
The
in
to
the
the
then
of
order
accelerate
shaken
mixture was
small cylinder was fixed onto the top of the reactor's lid ( see FIG- 4.3 -) and
then connected to a nitrogen cylinder. The continuous phase (distilled water
containing the suspending agent) was charged into the reactor tank, which was then
forced
into
fresh
75
de-oxygenated.
then
chloride
was
grams
of
vinyl
sealed and
the reactor tank and stirred at the required agitation speed.The tank was then heated
dyed
into
later
VCM
55C.
At
the reactor's
the
to
added
stage,
monomer
was
a
up
103
for
intervals
and
analysed
at
regular
were
photographed
mixture and samples
dyed
droplets
differentiate
between
In
to
a
and
non-dyed
order
coalescence rate.
filter ( filter type tri-color green) was used for the microscope light which gives a
darker color for the dyed VCM droplets. The latter procedure was used throughout
this series of experiments.
5.2.5 - Effect of polymerisation
conditions
droplets. For
performed in order to
for
be
The
the
to
as
vinyl
same
used.
procedure used was
experimental conditions
5.2.3
).
The
(
dispersion
suspending agent used was
section
see
chloride
ALCOTEX spec. "A" ( 72.5 % degree of hydrolysis ) while the best agitator speed
less
found
(it
350
found
be
to
to
or
spherical particles).
give more
was
rpm
was
The initiator ( X50 ) was either predissolved in the monomer or suspended as a
dispersion in the continuous phase. The reaction temperature was 55C Because
.
the vinyl chloride polymerisation reaction is exothermic, the reaction temperature
bath
ice
into
by
the
water
used to cool the
some
regularly
adding
was controlled
forced
into
For
the pressurised optical cell
samples
were
each experiment,
reactor.
At
different
the end of
the
taken
of
polymerisation.
at
stages
and photographs were
each polymerisation experiment the heating was ceasedand the excessvinyl chloride
Once
the venting was
the
the
through
valve.
venting
extractor via
slowly vented
C
heated
80
to remove the residual
to
the
were
up
completed,
reactor's contents
VCM (about 1000 ppm) using the same method as for vinyl dispersion. The reactor
flask.
into
The
PVC
down
the
then
glass
product
a
and
content removed
cooled
was
filtration
by
Buchner
from
the
and was subsequently
continuous
phase
was separated
dried in a vacuum oven at about 50 C for 3 hours ( necessary drying time ).
104
adsorption :
The aim of this series of polymerisation experiments was to investigate the effect
PVA
initiator
the
the
as
well
as
adsorption
on conversion
method of addition of
of
following
For
function
this
the
experimental
purpose,
of conversion.
rate as a
"A")
Spec.
PVA
(Alcotex
A
was predissolved
procedure was used. certain amount of
in 1 litre of distilled water ( about 0.06 % (WtPVA/WtWATER))
and then poured into
the reactor. The continuous phase was maintained at about 15 C using cooling water
( through the reactor jacket ). Then 0.7 gram of initiator X50 in suspension ( 0.175
% Wxso/WVCM) was added into the continuous phase and stirred. The reactor was
then sealed and deaerated using Nitrogen. 100 grams of VCM was then forced into
the reactor and the agitator run at 350 rpm. The reaction mixture was then heated up
to 55 T. The reactions were run for 15,30,45,60,90,120,150,200,250,
and 300
).
At
(
the end of each reaction, the stirrer
reactions
separate
minutes respectively
for
4
about
minutes and a sample of the continuous phase was taken
was stopped
filtered,
dried
The
PVC
for
PVA
and
was
product
concentration.
and analysed
for
The
the second set of experiments except
was
used
same procedure
weighed.
that the initiator X50 ( solid powder ) was predissolved in the VCM prior to
polymerisation reaction.
5.2.6 - PVA (ALCOTEX
dispersion :
spec. "A")
adsorption
This series of experiments was performed in order to investigate the amount of PVA
adsorbed on the vinyl chloride-water
The first set of experiments
PVA
determine
the
to
of
concentration
effect
was aimed
interface.
C
55
350
T=
0.1,
N=
cp
rpm,
: =
The
120
time
the
concentrations of suspending agent
was
minutes.
and
residence
At the end of each
and 0.2 % (Wt. PVA/Wt"WATER).
run, the agitator was stopped and the mixture was allowed to separate (2 phases,
0.002,0.01,0.02,0.10
were
:
used
the VCM droplets phase and the water phase) for about 4 minutes. A sample of the
105
continuous phase was then taken slowly from the bottom valve of the reactor. It was
then degassed using nitrogen (to remove the VCM dissolved in the water) and
final
UV/VIS
for
PVA
the
concentration
of
using
a
adsorption method
analysed
(Tadros, Th. F. (1974)). The second set of experiments was concerned with
studying the effect of agitator speed ( drop size) on the amount of PVA adsorbed
at the interface. The same experimental conditions were used in this case except
that the initial PVA concentration was constant at 0.02%. Four experiments were
performed using an agitator speed of 250,350,500
650
and
rpm. The third series
cp
CPVA
(%)
0.1
0.2
0.3
0.4
0.051
0.057
0.064
0.073
The aim of the fourth experiment was to study the effect of residence time on PVA
350
initial
For
this
the
the
agitator
speed
was
set
at
rpm
and
purpose,
adsorption.
PVA concentration in the continuous phase was 0.02 %. During this experiment
samples were taken at different residence times (5,15,30,45,60,90
respectively ) using the same method described before. Another experiment was
performed to simulate the fate of refluxing VCM droplets, returning from the
condenser. The aim was to determine how the returning monomer droplets acquire
the stabiliser (is
the last stage of the fourth experiment ( after 120 minutes ), 50 grams of fresh VCM
for
to
the
and
agitation
an other 120 minutes. The agitator
were added
mixture
run
for
PVA
taken
then
the
and
analysed
stopped
and
a
sample
of
continuous
phase
was
concentration.
106
of PVA :
The general principle of this method is that in the presence of boric acid, PVAs
will form green complexes with iodine which absorb in the range 650 - 690 nm ( see
Fig - 5.1 - ). By measuring absorbance against an iodine / boric acid background, it
is possible to measure concentrations of PVA as low as 0.002 %.
The stock solutions required were prepared as follow :
A)-
distilled water (it is essential to ensure that all the solid is dissolved ).
B)- Iodine solution : 12.7 grams of iodine were dissolved in a concentrated solution
of 25 grams of potassium iodine in distilled water, then diluted to 1000 ml with
distilled water ( some iodine may remain undissolved ).
The preparation of the samples for UV / VIS was performed as follow :
1- The blank to be used as a background : To 2 ml of distilled water was added 10
ml of the stock boric acid solution followed by 0.1 ml of the stock iodine solution (
using a micropipette ), giving rise to a yellow solution. The UV / VIS cells should
be watched using this solution.
2- the PVA solution samples : To 2 ml of the PVA solution to be measured, 10 ml
of boric acid stock solution was added followed by 0.1 ml of the iodine stock solution.
This gave rise to a green complex. The intensity of the latter complex depends on
the concentration of the PVA in the solution. For the more concentrated PVA
solutions, the complex may appear towards the blue end of the spectrum.
By measuring the absorbance ( ordinate ) of the sample, the concentration of PVA
in the sample can be determined from the standard calibration
versus concentration
of PVA)
107
curve (absorbance
Enm]
ABSORBANCE
1
0.
(')
icic; c), c
C7
5
" r..
G i)c),
C)C
1
cj
i.
108
C) C)
ii
STANDARD
Cconc7
CURVE
_
.
:. _
1
i
109
CHAPTER 6
In this chapter, the experimental results aswell as a detailed discussion are presented.
Each sub-chapter deals with a certain type of parameters affecting the liquid-liquid
dispersion. Within each sub-chapter, the results obtained are discussed while the
data
The
in
the
of this chapter are
raw
next chapter.
conclusions are presented
presented in appendices -1- to -5-.
6.1 - Simulation experiments :
Because of its similar density with vinyl chloride, toluene was used in this series
dispersion
liquid-liquid
the
to
and to prevent
chloride
vinyl
of experiments simulate
during
difficulties
the use of vinyl chloride as the
that
may
arise
any experimental
dispersed phase. The object of this sub-section is not to present a detailed discussion
have
but
to
to
the
to
try
as
remarks
as
well
some
observations
and
make
of
results
for
different
dispersion
liquid-liquid
idea
behaviour
the
medium
of a stabilised
an
on
for
following
The
all
conditions
were
used
experimental
experimental conditions.
the experiments performed in this series, except for the last experiment
fraction)
0.03.
(volume
/
Dispersed
=
phase continuous phase ratio
C) = 55
(
Temperature
)=
10
(
bars
Pressure
-
110
Volume
the
of
continuous phase =11.
88
%
hydrolysed,
Suspending
average
molecular
alcohol),
agent
poly(vinyl
=
weight 77000 - 79000.
6.1.1 - Variation
with agitation
speed:
The stirrer was started and run for 30 minutes at each of the following agitator
speeds consecutively : 200,350,500,650
film.
The
drop
black
taken
size
graphic
and
white
using
a
period, photographs were
distribution and the mean drop size, were determined by projecting the images on a
6.1
droplets
(
Fig
).
The
diameter
the
the
see
of
screen and measuring manually
in
Fig
different
distribution
drop
are
shown
the
agitator
speed
at
size
variation of
6.2 -. As expected ( with reference to the literature ), an increase in agitation speed
has resulted in a narrowing of the size distribution. This effect appears to be more
influence
The
lower
of agitation speed,on the mean
speeds.
agitation
at
pronounced
drop diameter and the Sauter mean diameter is shown in Fig - 6.3 - and Fig - 6.4 -.
It can be seen, from the latter figures, that the mean drop size decreaseswhen the
be
decrease
Furthermore,
is
increased.
to
this
seems
more pronounced
agitation speed
is
This
high
low
than
not surprising, since the
at
agitation speed.
agitation speed
at
break-up effect occurs more often at higher agitation speed ( higher turbulence
intensity), while the coalescence has a relatively low influence, because of the
be
drop
The
that
could
measured
size
minimum
presence of suspending agent.
into
)
(
less
10
Drops
10
taken
than
m
were
not
im.
.
size
of
smaller
accurately was
account because their volume ratio was not significant.
6.1.2 - Variation
of toluene droplet
agent concentration
with suspending
111
100 m
Fig - 6.1 - Toluene droplets dispersed in water. Stabilised by PVA ( 88 % hydr. ) at
0.02 % concentration, after being stirred for 30 min at A) - 200 rpm, B) 350 rpm.
-
112
140
20
200 rpm
650 ipm
120
16
100
pF 12
90
60
40
20
LS
t43
224J
Drop
diamrtor
(1IIn
200
70
1350
co
800 rpm
rpm
150
50
40
100
zg
30
20
50
10
0
III II
i
I1
--F+--I
285
245
45
Drop diuneter
(um
45
85
125
165
Drop di-t.
(r
205
2,45
285
100
500 rpm
00
60
z
40
20
Fig - 6.2 - Variation of toluene droplet size distribution with agitator speed. (q =
0.03; PVA ( 88 % hydr. ) concentration = 0.02 % and stirring time = 30 min ).
113
00
ct
E
O
0
O
CA
a,
-Z
3
UM
tr
0pc;,
GG
O
O
O
7t
1)
11
U
p
C
>'
.
Cp
00
OC
i
QM
ri
OO
CD
OOOOOO
C)
114
CIA
C)
00
Ep
N
a)
OO
03
'bA
1110
kr)
Cn
.03
o
C5
tE
OO
OO
a II
NU
=C
QO
U
^p
O
0
Z.
00
00
iQ
P.
C)
O
N
CD
O
0000000000
d'
00
C
NO
o0
lO
le
115
_
Li.
m
O
, 00
120
0.0
100
002%
-%.
71
so
80
60
60
0
40
20
20
45
85
125
165
205
Drop di mci<r (um )
245
285
120
0.1 wu
0.002
, 00
40
80
s
60
r 0
,0
20
245
45
85
165
125
(um
Drop di-ter
205
245
285
Drop diunctcr
'RS
(-)
1.10
30
i
25
100
20
so
0,2
Do
z15
ao
10
20
0
Drop diometcr
(um )
45
85
125
165
205
Drop di mctcr (om )
245
285
Fig - 6.5 - Variation of toluene droplet size distribution with PVA ( 88 % hydr. )
30
)
0.03;
N=
350
((p
time
min
rpm;
stirring
concentration.
=
=
116
it
When
PVA
added,
no
was
was quite surprising to observe a very
concentrations.
high number of small droplets (< 20 gm) and a few relatively big drops. It appears
here that the very small droplets are relatively stable towards coalescence, even in
the absence of suspending agent, while the big drops are unstable. The latter
fact
by
big
drops
the
that
the
the
shape
was
confirmed
of
observation
was deformed.
The number of small drops was found to be decreasing, when the PVA concentration
fact
be
due
drops
bigger
increased.
This
diameter
to
the
that
may
of
relatively
was
are becoming more stable towards coalescence, because of the presence of
suspending agent. Fig - 6.5 - also shows that by increasing the PVA concentration,
the drop size distribution change from a bimodal to a monomodal system. This
bimodal distribution disappears when the concentration of PVA is above 0.01 %.
Fig - 6.6 - and Fig - 6.7 - show the variation of the mean drop diameter and the Sauter
increase
The
drop
low
diameter
PVA
the
concentration.
of
mean
size
at
with
mean
PVA concentrations can be explained by the fact that drops of relatively big diameter
interfacial
decrease
in
by
PVA
because
In
the
tension.
of
a
contrast,
are stabilised
above a certain critical amount of PVA, the mean diameter starts decreasing to
stabilise at a certain diameter.
6.1.3 - Variation
time:
with residence
These experiments were carried out, using the same experimental conditions as in
section 6.1.2 while the variable was the residence time of the toluene droplets. The
dispersed
is
defined
by
the
time
the
time
as
spent
phase inside the reactor.
residence
After starting the experiment, samples were forced into the optical cell and
following
the
each
of
residence times : 10,20,30,60 and 90 minutes
photographed at
respectively. The concentration of the suspending agent was 0.02 %, while the
agitation speed was 350 rpm. The results obtained for the drop size distribution are
shown in Fig - 6.8 -. The main observation from this figure is that the drop size
distribution
additionally, showed that, even after 90 minutes the system was not completely
117
N
O
Ov
ao
C
Oa
C3E
oc
OQr
Oa
II
OC
O
cn
II
EZ
O cr,
r
CCOOOCO
C
oo
118
7t
II
ct
Oy
LL
N
O
O
00
OC
U
171
00
00
c
03
".-
L-
o
Urp
00
OM
II
c;,
C, i
C14
C5
uM
o
oc
N&
z
0M
o
71
O'w
G
pO
000
00
o0
119
C
Ic
30
Ll0 mi.
25
150min
20
40
15
30
20
10
5
Drop di-tcr
(um )
45
85
125
165
(=)
Drop di-ctu
201
245
285
60
I20 min
50
1 90 min
40
40
30
30
20
20
L
5
a1
121
Rs
Drop divneter
(um
60
F3 0
50
-nin
40
z
30
20
45
95
125
165
Dropdimtr(m)
Fig - 6.8 - Variation of toluene droplet size distribution with residence time. ((p =
0.03; N= 350 rpm; PVA ( 88 % hydr. ) Concentration = 0.02 %)
120
stable. This is confirmed in Fig - 6.9 - and Fig - 6.10 - which show the mean drop
diameter and the Sauter mean diameter as a function of residence time. In these
figures, the diameter was found to be decreasing with time. Furthermore, it did not
seem to stabilise even after 90 minutes. The latter observation doesn't seem to be in
agreement with the literature where the drop size is supposedto decreasetill reaching
an equilibrium size below which no further decreaseis possible. This matter was not
pursued further (i. e confirmed by repeating the experiment) as it's not the object
of these simulation experiments.
6.1.4 Effect of baffles on toluene droplet size and size distribution
Two experiments were performed in this case, using a baffled and an unbaffled
reactor. In both experiments, PVA with a degree of hydrolysis of 72.5 %(0.02 %
concentration in the continuous phase) was used as a suspending agent while the
other parameters remain the same as in sub-section 6.1.3 The stirrer was run for
60 minutes at 350 rpm and 500 rpm respectively. Table - 6.1 - shows the effect of
baffles on the mean drop diameter and the Sauter mean diameter. It indicates that
by using baffles, the drop size decreases sharply at low agitation speed, while
,
at high speed the effect seems to have less influence. The drop size distribution,
displayed in Fig - 6.11 -, shows a very narrow size distribution while using baffles.
This experiment has confirmed the importance of using baffles, especially in
industrial processes, where
size distribution
is of great
importance.
Table - 6.1 - Effect of baffles on the mean drop size (Dm) and Sauter mean diameter
(D32)
"
Agitation
(rpm)
System
speed
Baffled
Unbaffled
Dm (m)
D32(m)
Dm (m)
D32(m)
350
34
43
76
111
500
25
29
34
58
121
ai
a
.. r
s..
UM
NN
C/I
C'C
01
v
Q
U
o
c
n
G
o
a
1-n
00
oo
00
NN
122
110
dj
O
oc
O
NU
O
'R
En
r.
MU
O
N
"
.-
CN
tn
cc
123
c4o
100
N=350rpm
baffled
so
N= 500 rpm
baffled
200
150
60
6
3
too
40
50
20
45
85
165
125
(um
Drop di-tcr
205
)
245
85
285
125
Drop diamc[cr (um )
120
50
N100
40
500 rpm
unbafiled
so
30
Z
60
20
40
20
10
Fig - 6.11 - Effect of baffles on the toluene drop size distribution. (cp = 0.03; PVA
( 72.5 % hydr. ) concentration = 0.02 %; residence time = 60 min )
124
and Rushton,
corresponding
J. H. et al (1950)).
Thus,
C. A. and Tavlarides,
impeller
Reynolds
L. L.
numbers
6.2
For the system used in these experiments, the Reynolds number has the form:
-.
Re= 4889.4 N.
125
Table - 6.2 - Reynolds number and microscale of turbulence values for different
agitator speed.
Re
(m)
N(rpm)
N(rps)
250
4.16
20340
12.23
350
5.83
28505
9.49
500
8.33
40729
7.26
650
10.83
52952
5.96
800
13.33
65175
5.11
Table - 6.2 - shows that the Reynolds number values in our experiments are well
be
In
isotropy
for
local
to
to
theory
compare
the
order
valid.
the
value
minimum
above
diameters
Sauter
droplets
turbulence
to
the
mean
i
the values of the microscale of
( D32), the average energy dissipation rate per unit mass ( e) was determined ( see
input
it
J.
defined
W.
(1979)
Manamey,
Mc
the
[
3.5
]
).
per unit
as
power
equation
flat
bladed
In
impeller,
P.
by
turbines
in
the
the
or
of
case
mass the volume swept
impellers, the volume swept by the impeller while rotating is :
'
[6.1]
V, =7t 2W
Where D and W are the impeller diameter and blade width respectively. Thus, the
is
input
:
mass
unit
per
power
P*=P=
V,
4P
2W
D
Tcp,
[6.2]
Where P is the power input into the impeller and pc is the density of the continuous
P
G
(1991)
E.
Ghatzi,
using the equation :
calculated
et al
phase.
P= Pop N3D 5
126
[6.3]
Where P is the power number of the six flat blade turbine impeller. For the system
while P. is constant due to the large values of
Re.The latter power number was determined experimentally by many workers and
was found to be in the range 4-6 (Lee, J.C. and Tasakorn, P. (1979); Nienow, A. W.
is
If
Po
Rushton,
J.
H.
(1950)).
Miles,
D.
(1971)
taken equal to 5 (mean
and
et al
and
value), the average energy dissipation rate per unit mass E will be :
100
=
[6.4]
N3D2
71
Thus, an expression for il could be derived using equation [ 3.5 ] and [ 6.4 ]:
7rv
1/4
[6.5]
110ON3D'
The values of 1 where determined using the latter equation and are presented in table
d
L
Ld1.
Where
6.2
These
the
and
are
condition
satisfy
clearly
values
-.
the macroscale of turbulence (taken equal to the impeller diameter) and the droplets
diameters (in the range of 10 - 100 m).
Fig - 6.12 - shows the variation of droplet size with agitation speed. It shows that,
0.1,
it
is
have
dispersed
to
to
a clear
possible
continuous phase of
even at a ratio of
image of vinyl chloride droplets. The variation of the mean drop diameter ( DR,) and
the Sauter mean diameter ( D31 ) with agitation speed is shown in Fig - 6.13 -. The
droplet-size seems to decrease sharply when the agitation speed is increased. Also
decreases
drop
higher
the
the
that
size
and
effect of agitation
speeds
at
we observe
tends to stabilise. When the data of D32 and Dm versus agitator speed N were plotted
on a log-log scale ( see Fig - 6.14 - ), straight lines were obtained confirming earlier
theories ( see chapter 3 ). The slopes of the lines were -1.17 and -1.14 for D32 and
Dm respectively.
confirming
the predominance
of
the breakage
controlled
value of -1.2,
mechanism
over
L.
L.
Stamatoudis,
Tavlarides,
Shinnar,
R.
J.
(1961),
for
(
this
and
system
coalescence
M. (1981)). The drop size distribution
increase
in
figure
6.15
in
Fig
This
that,
an
agitation
speed
shows
speed, as shown
-.
gives a narrow size distribution and a better uniformity.
127
100 m
Fig 6.12 Vinyl chloride droplets, dispersed in distilled water. Stabilised with PVA
( 72.5 % hydr. at 0.02 % concentration. After being stirred for 60 minutes at :A)
B)-350
rpm
rpm
andC)-500
rpm.
-250
128
a)
C)
oc
c^i "1
'
L O
O O
II
0
0
N
r
C) e,
E
'G O
II
0
0
E
a
a
-
r
I'
c
C
r
'
O
O
o>
C)
0
M
o-
cs
O
O
00
OOOMN
CN
( uzn ) Ja1auz1Tp
u1aTU.zainLS
129
L3
v,
C
F
0
0
0
.C
ce
O
A
ICI
^d
N
O
vs
O
c
bA
CZ
U
riD
b!
O
V
o
4-
ct
i
CA
O
O
cat '.Q
0
N
0
c
riD
0
0
130
bA
70
rym '
N-250
60
14 =650
rym
50
t 7Sp
40
z
Sio
30
20
85
85
D-P d-t<,
125
()
165
Drop
h-ctc(tsn)
X25
165
205
300
100
N= 350 rym
250
so
200
e
I
60
5
150
40
100
50
It
Drop
125
85
dimmetec (am )
Drop 'E-
(: m)
200
N= 500 rpm
750
100
50
as
Dcop d me
125
125
r (um )
Fig - 6.15 - Variation of vinyl chloride drop size distribution with agitator speed. (cp
60
0.02
%;
hydr.
%
0.1;
CPVA
(
72.5
time
min)
residence
=
=
=
131
6.2.2 - Effect of residence time on the Vinyl chloride droplet size and size
distribution :
The transitional behaviour of Vinyl chloride droplets and the minimum time
The
during
this
to
experiment.
stability,
state
was
studied
a
steady
reach
required
the droplet size and droplet size distribution
The stirrer was run at 500 rpm, and samples were photographed after a residence
and 120 minutes respectively. Fig - 6.16 - shows some
of the photographs of Vinyl chloride droplets samples taken during this experiment.
time of : 5,10,20,30,60,90
From Fig - 6.17 - and Fig - 6.18 - we can see that the droplet size and size distribution
are significantly affected by the residence time at the beginning of the experiment.
The drops are large initially,
with time
during the first 30 minutes to stabilise thereafter. It is noted that, after a residence
time of 30 minutes, the droplet size distribution
results are in agreement with the general theory ( McCoy, B. J. and Madden, A. J.
(1969); and Hong, P. O. and Lee, J.M. (1983 and 1985)). The initial decrease in drop
during
initial
dominates
fact
breakage
is
due
the
the
to
the
that
coalescence
rate
size
period of liquid-liquid
equilibrium
longer than the values cited in the literature for other liquid-liquid
interfacial
by
Nilson,
H
(1985),
).
As
the
et
al
shown
minutes
relatively
systems ( few
tension decreases
PVA
This
in
time
the
as
suspending
agent.
slow
presence
of
slowly with
Hong, P.O. and Lee, J.M. (1983), in trying to relate analytically the residence time
of the droplets (t) to the Sauter mean diameter ( D32 ), proposed the following
relation:
ae -a`
-1+
D3?
132
[6.6]
100 m
Fig - 6.16 Vinyl chloride droplets dispersed in distilled water, stabilised by PVA
( 72.5 % hydr. ) at 0.02 % concentration, after being stirred at 500
rpm for : A) -5
min B) - 10 min C) - 20 min D) - 30 min E) - 60 min and F) 120 min.
-
lt-"
133
( tun ) moloLuuipdompu1aW
if)
N
C
N
3
a
a
c
-c
-CD
vs
00
C
. ,.
N
1110
ei
U
^p C
CL
` II
a Z
E
'
a
O
II
cz
.O
O-
U
""
>, C
II
N
Cr
OO
O
vi
OO
d'
MMNN
134
1 -Z
b_A v:
250
s60
e5mn
100
ma
200
90
150
z so
1S
r5 100
40
50
125
Drop
205
165
85
diameser (a o)
D,? d-t
125
(-
165
140
=10
[- 90 qcm
mit
120
100
100
80
zz 80
60
60
40
40
1- --
-I-i
250
140
= 120 mm
120
200
100
150
60
too
40
e5
RS
Drop
dunerer
L
45
175
( um )
SS
125
Drop Lacc:c (- )
165
205
200
mu
I_t=3O
150
I.G
".
.
100
50
85
125
Fig - 6.18 - Variation of Vinyl chloride droplet size distribution with residence time.
(cp=0.1; N= 500 rpm. CPVA( 72.5 % hydr. )=0.02 %)
135
Where D"32 is a steady-state drop size ( constant for a given system ). For the latter
in
/
D*32)
In
(D32-D*32
be
time
the
a
to
should
result
versus
plots of
valid,
equation
be
dimensionless
is
/D*32)
D*32
Since
(D32
t
line.
the
time
can
value,
a
straight
is
N
instead
Nt
(
dimentionless
the agitator
into
where
transformed
value using
a
is
D32
to
Since
time
).
the
transition
and
avoid
constant,
the
after
of
value
speed
D*32was taken as the average of the
having a negative value for ( D32-D*32/D*32),
found
This
diameters
to
time.
Sauter
transition
was
value
after
mean
values of the
be equal to: D*32= 29.19 m. Fig - 6.19 - shows the variation of In (D32-D*32/ D*32)
linear
This
tendency confirming the validity of equation
(Nt).
a
shows
plot
with
[6.6]. The coefficients a and i of the latter equation were found equal to 1 and 0.083
respectively.
6.2.3 Influence of the type of suspending agent on the drop size and size
distribution
of Vinyl chloride :
In this series experiments, five types of PVA suspending agents with different
degree of hydrolysis were used and their effects on the drop size and size distribution
0.02
%;
30
CPVA
The
t=
min and cp
=
experimental conditions were:
established.
C.
They
by
E.
V.
for
been
have
0.1.
These
consist
us
provided
agents
suspending
=
of :
hydrolysed ( 84 %) PVA.
S3
Gohsenol
partly
KH17 partly hydrolysed (78 %) PVA.
Gohsenol
%)
PVA.
(
72.5
hydrolysed
Alcotex
spec"A" partly
hydrolysed ( 55 %) PVA.
"A55"
Alcotex
partly
).
in
50
%
PVA
(
hydrolysed
S202
Polyvic
methanol
partly
PVAs are water soluble polymers mainly used as protective
Partially
hydrolysed
colloids
for emulsion
liquid-liquid
5.5
But,
(see
different
table
weights
molecular
as well as
-).
degree
in
S.
(1988),
Ormondroyd,
by
the
that
the
it
has
been
changes
suggested
as
degrees of hydrolysis
in
has
fixed
hydrolysis
than
changes
molecular
more
effect
molecular weight
at a
of
136
O
O
O
0
0
0
-,
C)
0
0
N
--y
z
1121
C
O
O
O
---,
oZ
a)
c
i
0
0
o
i
o
-o 0
II
O>
cr
c
O
C
O>
U
CZ
o
Vi
CN
V7
c*;
II
(zE*Q/zc*Q-Hu)ut
137
in
6.20
decrease
in
Fig
hydrolysis.
As
degree
the
fixed
shown
of
weight at a
-a
degree of hydrolysis gives a lower surface tension, thus, a lower droplet size. Fig 6.21 - shows the drop size distribution at different agitation speeds for KH17
increase
in
figure
latter
from
is
It
the agitation
that,
the
an
evident
suspending agent.
drop
it
be
distribution.
Also
the
does
that,
size
seen
can
provide a narrow size
speed
distribution is almost unaffected by the decrease of agitation speedfrom 650 to 350
6.22
"A",
Alcotex
Fig
be
The
spec
with
made
about
can
same observation
rpm.
-,
but in this casethe agitation speedseemsto have a stronger effect and the distribution
is narrower. In contrast, Fig - 6.23 - shows that the agitation speed does not have a
is
"A55"
Alcotex
distribution
influence
the
used as suspending
when
on
size
great
6.24
it
low.
From
Fig
is
Also,
towards
the
very
coalescence
stability
agent.
-, can
be seen that when S202 is used as a stabiliser, the drop size distribution is relatively
is
low
but,
low
towards
the
coalescence
also
stability
speed
agitation
narrow even at
in this case. Thus, from these observations we can conclude that, a decrease in the
degree of hydrolysis will lower the degree of stability of the droplets towards
in
distribution
drop
the agitator
The
the
with
changes
size
evolution of
coalescence.
6.25
for
As
is
in
Fig
as
the
S3
other
a suspending agent shown
speed using
-.
drop
diameter
decreases
in
increase
the
and
agitator speed
stabilisers used, an
from
650
350
in
Also,
distribution.
to
agitator
speed
the
a reduction
size
narrows
in
6.3
diameter
(
Sauter
the
table
is
nor
the
as
seen
mean
neither
rpm affecting
-)
S3
6.25
Thus,
).
Fig
to
distribution
(
provide a relatively
stabiliser
seems
see
size
bigger drop diameter with almost the same degree of stability as for other high
degree of hydrolysis PVA's (i. e Alcotex spec. "A" and KH17). Fig - 6.26 - and Fig
diameter
Sauter
diameter
drop
6.27
the
the
mean
the
and
mean
of
variation
show
650
350,500
(
different
hydrolysis
degree
three
and
the
speeds
agitation
at
of
with
degree
hydrolysis
increasing
by
from
the
is
the
).
It
that,
these
of
results
evident
rpm
drop size is increasing ( except for "A55" were we had some problems dissolving it
in the continuous phase ). This is mainly due to the decrease in surface tension as
low
degree
hydrolysis
high
degree
fact,
both
6.20
In
in
Fig
the
the
of
and
shown
-.
for
Vinyl
have
hydrolysis
their
chloride
stabilisers
advantages when used as
of
degree
hydrolysis
high
The
PVA
of
gives a more
a
with
suspension polymerisation.
finer
hydrolysis
low
degree
PVA
drops
the
gives
and more
of
with a
while
stable
138
Aicctex
Grate
70
65
40
60
Z
E
55
;8
c
0
N
50
0
-06
45
40
C.C2
0.04
0.08
0.05
Cbncentrction
0.10
0.12
C14
of PVCH (,'aw/w)
Fig - 6.20 Surface tensions for some aqueous solutions for Alcotex grades of
partially hydrolysed PVA against concentrations typically used in PVC
polymerisation. (The naming of the product follows the standard convention, i. e.
Alcotex 88-08 is an 88 % hydrolysed with an aqueous solution viscosity of 8 cp
measured at 20 C for a4% wt. p
/ Wt\vater
solution). [ after Ormodroyd, S. (1988)]
139
60
080
Co
N= 3S0 rym
N=
650 rpm
50
40
60
30
40
20
20
10
Drop
6mmecx
(um
-+ 205
140
ioo
N= 500 pm
Ns ?50 rs
120
so
100
60
I
80
5
60
40
40
20
20
45
85
125
165
205
125
12(
Drop dixrs: er ua
Fig - 6.21 - Variation of Vinyl chloride droplet size distribution with agitator speed
for PVA ( 80 % hydr. ) KH17. ( For conditions described in sub-section 6.2.3
-)
140
100
N=350
N-650'pm
200
so
v 150
60
Cl 100
40
50
20
45
35
..
125
pdiamesr (um)
165
200
205
i
N= 3io rpn
N= 500 rpm
150
150
ioo
goo
c5
50
50
35
. op -mr
125
('
165
45
35
rop
125
--,
165
205
(uci
Fig - 6.22 - Variation of Vinyl chloride droplet size distribution with agitator speed
for PVA (72.5 % hydr. ) Alcotex Spec. "A". (For conditions described in sub-section
-6.2.3-)
141
200
80
[{ - 55J m
N6 350 rpm
150
60
",
.
40
l00
50
20
205
D-p &-
(-)
Drop
( em
120
100
:I= 500 m
loo
80
80
b
60
2
60
40
40
20
20
0
0
Dreg'5. m -()
Snate:
Fig - 6.23 - Variation of Vinyl chloride droplet size distribution with agitator speed
for PVA ( 55 % hydr. ) Alcotex "A55". (For conditions described in sub-section 6.2.3 -)
142
200
N=
rr= 3s0:
650 rpm
400
150
b 300
z 100
6200
50
IOU
45
85
125
Drop &ameter (um )
165
205
J: op Scu:
126
a (um )
300
I
FF-73
N= 500 rpm
00rpm
250
300
200
IZ
? 00
150
100
I00
.o
RS
- -
Drop h=ctr(=)
-r
125
? cp .ia2c:
a (-
Fig - 6.24 - Variation of Vinyl chloride droplet size distribution with agitator speed
for PVA ( 47 % hydr. ) Polyvic S202. (For conditions described in sub-section 6.2.3 -)
143
100
100
90
N=
90
330 rym
80
80
70
70
0
60
50
40
60
50
40
20
20
10
10
Drop da-tcc (m )
100
N=500
fi-
(-
r-3 soT
fpm
90
70
70
Drop,
90
80
50
45
45
100
90
60
650 rpm
30
30
Nm
60
50
40
40
i
30
30
20
20
10
10
0
5
45
85
D.
-P
125
di--
165
255
C=)
i:
cp rc<:
er (
Fig - 6.25 - Variation of Vinyl chloride droplet size distribution with agitator speed
for PVA ( 84 % hydr. ) S3. (For conditions described in sub-section 6.2.3
-)
144
00
O
'
C.
O
0o
to
INC
z
E
Ln
11
kn
II
if)
O O
y C
II
CC
II
CC
C
1
Oc
r
r-
OOOO
tn
7t
145
CIA
O
CA
it)
00
N
'.a
. r,
O
O
00
U
C
O
INC
Ii
:.d
con
O
O
rM
C/1
i
II
CIO
6-4
Q
"o
Op
-C II
ct
II
tf -)
lf
o
U
a
a
' II
O
vIj
14
ve.
N
Oc
ct
WO
mot'
CD
N
1^
146
(
high
degree of hydr. ) and secondary ( low degree
The
primary
porous particles.
of hydr. ) are used in suspension polymerisation for this purpose. Therefore, the idea
have
better
droplet
them
the
the
two
may
a
on
size and stability.
of
effect
of using
Table - 6.3 - Variation of the Sauter mean diameter with the agitator speed for S3
suspending agent.
N (rpm)
350
500
650
350
D32(m)
96.09
64.99
56.73
56.45
6.2.4 - Influence of the baffles on the droplet size and size distribution
An experiment was run in the same way as for the latter one but using an unbaffled
6.28
Fig
Alcotex
as
suspending
agent.
spec"A"
reactor with
- shows a relatively
wide range in the drop size distribution ( compared to the experiment in baffled
increases.
6.22
Also,
Fig
in
the
speed
we
gets
narrow
as
agitation
which
reactor
-)
This
is
due
to the quality of the
towards
mainly
coalescence.
note a good stability
diameter
Sauter
drop
baffles
The
the
the
to
than
effect.
mean
and
stabiliser rather
in
6.29
6.30
Fig
Fig
function
diameter
are
and
of
speed
shown
as
stirring
a
mean
dispersion in a baffled reactor produces a
These
that,
the
show
clearly
graphs
-.
smaller drop size. They additionally, show the samebehaviour towards the variation
baffles
It
is
that,
the
use
of
gives the system a
well
confirmed
of agitation speed.
We
better
homogeneity
tank.
to
compared
an
unbaffled
can conclude that,
relatively
when baffles are used, the drop size distribution
low agitator speed, while for high agitator speedthe differences between baffled and
less
become
pronounced.
systems
unbaffled
147
?0
100
I: J 3S0
=
rpm
90
x=sso.
60
80
50
70
0
60
40
50
a0
40
30
20
20
10
10
0
5
45
25
125
165
205
.5
85
12`
: 6`
2U5
.. pop.i< (m )
100
80
N= 00 rrm
00
60
60
z
a0
40
20
20
165
20S
Dr-p
i-
-. (-,
Drop 3ameta (u m)
Fig - 6.28 - Variation of Vinyl chloride droplet size distribution with agitator speed
in an unbaffled reactor. (CPVA( 72.5 % hydr. )=0.02 %; t= 30 min and (p = 0.1 )
148
0
o
N
-Q
U
V
rID
ox
o
rF
-o
IIM
v2
)
C)
O
U
-
II
L,
cd
o
N
co
II
c3
C%
U
u
o
a) C)
i
G)
00
0
00
C)
N
0000
V)
G1
N
M
I-
149
(1-1
bQ
U'
O
O
O
U
bA
_C
O
U M
.
O
U
& .E'Q-"
cam,O
O
O
C
O
cr'
Con
r
0
i
00
OOM
CD oooo0
( uzn) ialawi
p u-coiu zalnus
150
LI,
v
"
6.2.5 - Effect of the suspending agent concentration on the volume and size
distribution of vinyl chloride droplets :
In liquid-liquid mixing the suspending agent is said to be playing an important role
in stabilising and controlling the droplet size. In the suspension polymerisation of
latter
be
importance,
to
the
are
of
chloride,
effects
seen
great
since they are
vinyl
believed to be determining the particle size aswell asthe porosity of the final polymer
intended
is
This
to clarify the effect of suspending
of
experiments
product.
series
agent concentration on the drop size and stability, and to determine the necessary
72.5
%
hydr.
be
in
have
PVA
(Alcotex
"A",
)
to
to
spec.
used
order
a stable
amount of
system. In total, eight experiments were performed using 0,0.002,0.005,0.01,0.015,
0.02,0.1 and 0.2 % concentration of PVA. The volume fraction of the dispersed
phase was 0.1. Fig - 6.31 - shows the variation of the drop size distribution with PVA
concentration. As expected, an increase in PVA concentration did narrow the size
distribution. This is due to the fact that at low PVA concentration, the droplets were
not protected well enough to prevent their coalescence. Fig - 6.32 - shows the
variation of the Sauter mean diameter ( D32) with PVA concentration at different
agitation speeds. The latter figure shows that at low PVA concentrations, a sharp
decrease in drop diameter ( D32) is observed when we increase the concentration of
PVA. It, also, shows that there is a critical PVA concentration above which the drops
are more or less stable and that this critical concentration does not appear to be greatly
affected by the agitation speed. In the paper published by Borwankar, R. P. et al.
(1986), they calculated the critical surface coverage using the expression :
(1
S-
4)D32Cc
60
[6.7]
Where Ccis the critical concentration which was found to be equal to 0.012 %. The
latter value was calculated from Fig - 6.32 -. It is the minimum PVA concentration
necessary to obtain a constant drop size. Knowing the value of the critical
concentration, we can calculate the critical surface coverage (Se) at different phase
151
120
Cp. s -0
CPv'
002 %
0.02 %
100
60
00
z40
60
00
20
Mai
8
es
tz5
Drop d-.
D,, ps-(um)
-(-
IOU
70
Cpva = 0.005'.
60
80
50
x0
140
z
30
40
20
20
i
165
125
Dr
6--(-)
aS
80
Cpva=0.01'"
120
60
too
4o
60
4o
20
20
43
85
125
UropQlamtYtflU,
165
203
245
0
D-di--
100
Cp+a=0015%
so
60
40
20
",
z65
: kop . Lanctct (um )
"I
2M
Fig - 6.31 - Variation of Vinyl chloride drop size distribution at different PVA ( 72.5
% hydr. ) concentrations. ((p = 0.10, N= 350 rpm and residence time t= 30 minutes)
152
N
jO
c
c
0
O
O
OC
r
c
U
c
C
U
E
O
IC
C
cC
tr;
-4
C
"C
OQ
O7
Ai
ZM
Gr
O
O
L`.
il
Cp
II
Lr)
-O
ry
'
CJ
N
C
O
NO
N
rJ-
dN
oO
153
hold-up and drop diameters. For a volume fraction of 0.1 and an agitation speed of
500 rpm ( see Fig - 6.32 - ), we have D32= 36.2 gm which gives a value of S, equal
to 0.65x10-6 gr./cm2. Table - 6.4 - presents the critical surface coverage at different
agitation speedsfor a volume fraction of 0.1 and a PVA (72.5 % hydr. ) concentration
in the continuous phase of 0.02 %.
Table - 6.4 - Critical PVA surface coverage at different agitation speeds ((p = 0.1 )
N(rpm)
D32(m)
S, (gr. /cm')
250
91.1
1.64x106
350
61.5
1.11x10-6
500
36.2
0.65x 10-6
650
28.5
0.51x106
800
21.8
0.39x 10-6
dispersions. When no stabiliser was used, it was not possible to take a stable sample
into the sampling device. For this reason, the case when no stabiliser was added is
not discussed here.
154
0
c
r-,
OC
N
cs
C
O
NC
~r
O
U
Ua
ao
"
C
O
o-
C'. E
rO
Mz
NOOv,
ownlOA off,
155
LL,
vom,
0
o
IM
O
cz
C)
N
O
C
C
N
cs
Z
O
-"
Q
,
.
O
a)
O
O
C
v^.
0
Ep.
?o
II
z
M
O
,It
,.-.
0000
aiunjOA o/
156
G_UN
cn
LL
bA
N
O
cs
O
N
O
U
-Fr
CO
II
CD
cMNCO
auznlOA
157
C)
0
M
r-
N
O
ao
C3
n
N
O
cz
O
C
0
N
ct
U
C
Z
O
a
E
cz
0
Q
0
0
r
E
O
4O
..-,
,
C)
i
0
OOOOOOO
INC
tt
MN
-aumjon
158
b_A
D
O
M
r0
Cl
cz
'C3
,--,7
C
^'
.
d.)
U
Q
Q3
Oo
C
C
I
con
O
O
II
II
NZ
c
C'
CD
oc
00oc
O
G_-0U
d'
ouznlOA Ll1o
159
of vinyl
chloride :
Among the parameters that affect the drop dispersion is the volume fraction of the
dispersed phase. In order to investigate its effects, a series of experiments were
fraction
in
leaving
the
the
the other operating
volume
which
was
variable,
performed
conditions unchanged ( see table - 5.6 - for details of quantities used and sub-section
for
As
in
Fig
6.38
).
the
conditions
shown
experimental
which
presents
-5.2.3.3-,
variation of the drop size distribution at different phase hold-up, an increase in the
volume fraction of the dispersed phase does give a wider size distribution. Because
of the increase in the volume fraction of the dispersedphase, the probability of having
two drops entering in collision increases. This increase in the number of collisions
important.
in
Fig
6.39
the
the
coalescence
making
rate
more
shows
results
variation
of the Sauter mean diameter ( D32) at different phase hold-up. This figure indicates
that the size of the droplets increases when we increase the volume fraction due to
an increase in the coalescence rate. Moreover, it shows that this increase is more
pronounced at low agitation speedthan at high agitation speed. Similar observations
have been made by several other scientists for stabilised and non-stabilised droplets
( Vermeulen, T. et al (1955); Coulaloglou, C.A. et al (1977) and Chaffey, C.E.
(1991)). These observations are confirmed in Fig - 6.40 - to - 6.44 -, which show the
volume distribution as a function of phase hold-up at different agitation speeds. For
low agitation speeds ( 250 and 350 rpm), the volume distribution changes from a
monomodal to a multimodal distribution while for high agitator speeds the volume
distribution is mainly monomodal distribution.
160
lee
120
Vol. Gsl.
- 0.01
100
80
Z' 60
X
10
40
20
20
8S
121
IRS
Droy dismner
65
( gym)
70
120
Vol.s. - 005
Vol. f
L-0.7
60
i00
30
140
x
30
40
z0
20
10
165
Drop di--
(un
n. op,fi-(
100
205
"0
voi. : c - o.i
Voi. fracl
- O.J
60
30
60
z
z
30
40
20
20
10
c^265
Drop diamemr(
prop di
wn)
o.
205
?JS
r(gym)
Fig - 6.38 - Variation of Vinyl chloride drop size distribution at different volume
fraction. (N = 350 rpm; t= 30 min ; quantity of PVA ( 72.5 % hydr. = 0.3 gram
( see table 5.6 for details )
-
161
t
C
Z
E
.
M
C
O
O
00
M
C
C.
O
to
CS
to NO
C
1
I
O
U
C
0
N
O
O
Cr
+
U
a.
I
3 ?
C
c3
VO
Z *m
e3 U
Q) .)
O
M
R
CL
eil
O
N
c3
c.
O-
CU
Iif
c3
'C7
"
c3
O
00oco00000
dNo
00
C
00
%C
It
162
a =
cr,
U
42
.e
LL .
,b
ct'i
-
kf)
O
N
-H,
vM
C)
aM
>c
rte.
11O
o
aLUnTOAOlo
163
Lz
0
0
M
'd
)
a.
C
M
O
0
if)
aq
s
N
cZ
II
b
C
O
0
0
N
cn
M
N
a
y.
a
^.
b
C1
O
Q
O
O
'O
rn
Q) 'C7
C_
4-
C)
if)
":
to
.
O M
0oc
OC
auznlOA I'lo
164
bA
, z
O
cz
O
N
cs
aM
C)
O
1-1
O
rU-+
Q)
O
O
ENM
OU
C "
t..
U
j
.0.
C ...
O p
OU
pO
NO
000000
au lTOA %
165
II
O
O
M
cn
a
a
a
O
M
O
CZ
C)
tr)
N
a4
C13
C
O
N
OM
0
to
110
N
O
"
r.
aU
r
Q)
E
=
O
r-
"3
Q
I
0
c
O
O
kA-
OO
iii
Lr)
--- -C
MN
ownlOA I'lo
166
0
._
.
"
- ^>
U
40
tJoz
w
C)
O
'C3
Ct
O
CZ
p
CN
M
V'1
yC
O
1
CO
Q-
Ct
a3
Q
"
-)
f
EO
'
v
OC
c7s
c3
fl.
000C00
00
II
w.
ownlOA
167
6.2.7 - Generalised correlation relating the steady state drop size to the vessel
Weber
fraction
the
the
number :
and
volume
geometry,
The evolution of the drop size (Sauter mean diameter ) and the size distribution
fraction
dispersed-phase
impeller
in
and the
volume
speed,
with changes
be
important.
Thus,
have
been
to
shown
relatively
colloid
concentration of protective
latter
diameter
Sauter
have
investigators
to
the
tried
to
the
mean
correlate
various
fully
baffled
for
The
turbulent vessel
a
correlation
used
most
common
parameters.
has the following form:
D3-
-`
(1
4)W,
+b
=a
D
[6.8]
Were D is the impeller diameter and a, b and c are constants. The term (l+b (p)
level
down
in
damping
dispersed
influence
the
the
overall
the
phase
of
reflects
In
liquid
We
is
Weber
in
the
the
the
system.
of
turbulence
number
system, while
of
in
Weber
determine
the
the
number
relation to these
to
of
values
numerical
order
liquid
density
it
the
the
to
of
was necessary calculate
experimental conditions,
former
interface.
The
VCM-water
interfacial
the
tension
the
at
mixture as well as
in
density
determined
the
shown
chapter equation
weighted average
using
was
3-( equation [ 3.39 ] ).
The interfacial tension was estimated by using a correlation relating the specific
interfacial tension of Trichlorethylene/Gohsenol aqueous solution to the Vinyl
6.46
The
latter
6.45
Fig
Fig
(
/
Gohsenol
and
solution
see
aqueous
chloride
-).
figure have been provided to us by E. V. C. These correlation results have been
obtained at an experimental
C
55
C.
55
Thus,
tension
the
at
were extrapolated using the
values of surface
was
following equation (Perry, R. H. and Chilton, C.H. (1973)):
`_'"
168
[6.9]
0.6
0.5
GH-20
0.4
KH-20
KM-.
0.2
_
KP-08
`t7-"
KP-06
0.1
0.1
0.2
Concentration (%)
FIG
6.45
Specific
interfacial
Gohsenol
tension
of
solution against
trichloroethylene at 20 C by titrimetry ( jis-K-3362 ). ( data provided by the
manufacturer ).
0.6
C
m 0.5
0
Z
U,
0.4
J
T
0.3
Vinyl
0.2
0'.3
0.4
cnlpride/GOHSENOL
0.5
so. sain.
169
calculation
approximations
of the interfacial
area,
Antonof's
some
[6.10]
Gab = Ga - Gb
where Qand b are the surface tensions of the two saturated liquids a and b,
liquids.
The
between
interfacial
is
tension
the
two
the
results obtained are
,,
and
6.5
in
table
presented
Table - 6.5 - Values obtained for the density of the mixture (pt), the PVA
fractions
different
interfacial
(CPVA)
tension
the
volume
:
at
and
concentration
cp
0.01
0.05
0.10
0.20
0.30
0.40
P.
984.24
978.41
971.13
956.56
941.99
927.42
CPVA
0.030
0.032
0.033
0.037
0.043
0.050
13.7
13.3
13.2
12.8
11.9
11
14.47
14.04
13.94
13.52
12.57
11.62
(mN/m)
at20C
6 (mN/m)
at 55 C
Fig - 6.47 - to Fig - 6.52 - show the variation of Sauter mean diameter with the
Weber number to the power -0.6 at various values of volume fraction. The latter
figures confirm the assumptions that a straight line should result from these data
in
Fig
lines
(l+b(p)
to
these
that
the
seen
as
straight
are proportional
slope of
and
6.53
6.54
Fig
the
the
of
correlation,
shows
graphical
presentation
which
-.
seem to be in good agreement with equation [ 6.8 ]. Thus, fitting our data to the
latter equation gave the following correlation :
170
70
60
50
m
40
c 30
m
20
10
0
05
10
15
30
25
20
WVe0.6X103)
35
40
45
50
Fie, - 6.47 Weber number variation with Sauter mean diameter for cp= 0.01.
80
70
60
50
E
40
30
20
10
0
05
10
15
20
25
30
35
40
45
WW-'6(x103)
Fig - 6.48 Weber number variation with Sauter mean diameter for cp= 0.05.
-
171
50
100
90
80
70
60
. -
50
40
30
20
10
0
05
10
15
25
20
30
35
40
45
50
WVe-0.6(
x103)
Fig
6.49
Weber
Sauter
diameter
for
0.1.
number
mean
variation
with
cp
=
-
120
100
80
ri
60
^r:
40
m
20
0
05
10
15
25
20
W, 46
30
35
40
45
X 103)
Fig - 6.50 Weber number variation with Sauter mean diameter for cp 0.2.
-
172
50
140
m
120
100
I80
ri
60
40
20
0 K05
Fig
6.51
160
10
15
30
25
20
We-0.6(X 103)
35
40
45
z0
Weber
Sauter
diameter
for
0.3.
mean
number
variation
with
cp
=
-
140
120
100
30
60
40
20
0
05
10
15
_0
25
40
6X 103)
We-.
35
40
45
Fig - 6.52 Weber number variation with Sauter mean diameter for cD= 0.4.
-
173
50
Wit'
C
to
No
Cr
'r.
Cr
v1'
--r
te,
I.)
CC
d-
c^
(thq+i)L,
174
D U
.v
Ln
N
a)
N
C
lIc
Z
CO
cr;
+
N
C
C
a)
lei
C
U
0
0
vl,
O
C
CC
cr,
NN
fryy
--
(, 01X)(1 /`'Q
175
D2
=0.027(1+3.064)W.
[6.11]
for
176
the agitator speed500 rpm. The procedure used consisted of mixing the non-coloured
droplets and the continuous phase ( using the agitator) for a certain time t; and then
adding the dyed Vinyl chloride monomer. Photographs were then taken at different
time intervals and the ratio of the volume of the dyed droplets ( V, ) to the total
Vinyl
in
V;
Vc)
determined.
(
The results
the
+
chloride
present
of
volume
reactor
obtained are plotted in Fig - 6.55 - which shows the variation the latter ratio with
the residence time of the mixture t( coloured + non-coloured) at different premixing
time t; ( residence time of the non-coloured droplets prior to the addition of the
figure
for
VCM
).
The
that
the
shows
of
rate
coalescence
small values of
colored
for
is
(5
15
)
high,
time
t;
minutes
values of t; equal
and
relatively
while
premixing
is
This
is
lower.
due to the fact that the
30
the
coalescence
rate
minutes,
or above
for
drops
become
is
30
the
time
to
stable
about
necessary
relatively
premixing
minutes ( see Vinyl dispersion section in this chapter ). The shape of the curves
drawn on the latter figure, also show that there are two different stages, a first stage
of relatively high coalescence rate for residence times of less than 30 minutes, and
then a second stage where the coalescence rate is less important. Also, the latter
effect is more pronounced when the premixing time was small. This phenomenon
is quiet understandable because, even when the non-coloured droplets are stable, the
added dyed droplets are not and need the same residence as the non-coloured drops
to become stable and, thus, become more protected against coalescence.
The second parameter to be studied was the effect of suspending agent concentration
( CPVA)on the coalescence rate. For this, the non-coloured droplets were premixed
( at 500 rpm) for 30 minutes before forcing the dyed VCM into the reactor. Four
0.002,0.01,0.02
PVA
concentrations
of
performed
using
and
experiments were
0.1 % respectively. Fig - 6.56 - shows the variation of Vc /( Vc + V; ) with residence
time t at different PVA ( 72.5 % hydr. ) concentrations. From the latter figure we
distinguish two different set of curves. For low PVA concentrations ( i. e CPVA=
0.002,0.01 % ), most droplets coalesce after 15 minutes. This is due to the fact
that the quantities of PVA available in the continuous phase is not enough to protect
the VCM droplets ( the critical concentration was found to be about 0.012 %, see
177
a)
0
N
o
't3
E.
q)
.E
_
o
'cn O
cr
U
cz
C1'0
^
r-
G'
cc
OOCOOOO
[TA+OA)
11p
rh
/ 3A
178
M,
wc
C)
N
0
0
C1.
O
L.
'C)
'b
O
"'O
O
V
J
O
cC
U
a)
U
U
C
U
U
.C
cN
C
--"
-+
CT
oc
OOCCCOC
[TA+:
Ic
)A
.
v
) /'A
lc
II
MN
C=. U
179
sub-section - 6.2.5 - ), adding to the instability of the dyed droplets at the initial
stages. At relatively high PVA concentrations (VPVA= 0.02,0.10 % ), the coalescence
rate seem to be much lower because of the availability
PVA
of a necessary amount of
molecules to cover the droplets and protect them against coalescence. These
The third parameter to be studied was the effect of turbulence intensity on the
coalescence rate. The experimental procedure used in these experiments was similar
to the latter one (i. e 30 minutes for premixing time ). The concentration of PVA
used was 0.02 %. Three experiments were performed using an agitator speed of 250,
350 and 500 rpm respectively. Fig 6.57 shows the variation of V; /( V': + V; ) with
time at different agitator speeds. From the latter figure, it was observed that for an
agitator speed of 500 rpm the coalescence rate is relatively high ( all the droplets
became coloured after 90 minutes ) while for lower agitator speeds (N= 250 and
350 rpm) the coalescence rate is quite low. These results show that an increase in
the turbulence intensity increases the breakage rate as well as the coalescence rate.
It is, also, interesting to note that for an agitator speed of 500 rpm, the coalescence
rate has decreased after a residence time of 30 minutes ( two different slopes on the
curve) while for lower agitator speeds the latter effect is not observed. Fig - 6.58 shows the mixing that happens when the dyed vinyl chloride droplets are added to
non-coloured suspension. In conclusion, from these series of
experiments it was found that the coalescence rate rises relatively slowly with
a preformed
residence time (t) and pre-mixing time ( t; ), is roughly proportional to the agitator
speed and decreasessharply when increasing the concentration of suspending agent.
6.3.1 - Coalescence rate study using KH17 as a suspending agent ( dye
experiment ):
This experiment was performed in order to study the coalescence rate when
KH17 is used as stabiliser. The experimental procedure was the same as described
in the last section. The non-coloured Vinyl chloride droplets ( 100 grams) were
180
100 m
Fig - 6.58 - Dyed Vinyl chloride droplets added to preformed suspensionsat different
250
CPVA
N=
dyed
With
VCM.
time
and
rpm
=0.02%.
of
residence
B)-15min
C)-45min
D)-60min
182
E)-90min
A)-5
F)-150min.
min
C)
oc
CD
b
c+
y
U
Qi
U
"c c
.C
-
>
om
d-
`\U
--
N
GO
CCCCCO
to+DA
\O
)/
t
OA
181
MN
premixed
at 350 rpm for 30 minutes in order to stabilise the droplets. Then about
30 grams of dyed droplets was forced into the reactor. Samples of the mixture were
taken into the optical
cell and photographed at different time intervals (see Fig 6.58A -) and the total volume of coloured and non-coloured drops determined. The
results obtained are shown in Fig - 6.59 - which shows the variation of V, /( Vc +
V; ) with residence time (t) of the dyed droplets. Also plotted on the same figure,
using Alcotex
spec. "A"
that KH 17 is much more efficient in stabilising the VCM droplets as the coalescence
rate is relatively
very
low compared
with
Alcotex
spec. "A"
stabiliser ( which
was supposed to be a very good stabiliser ). During the initial stages of the mixing
operation (i. e up to about 45 minutes ), The two curves show a more or less similar
coalescence rate but later (i. e for a mixing
coalescence rate for KH17
and Alcotex
become proportional
to the
residence time and decrease for KH17 while increasing for Alcotex spec. "A". Thus,
in order to
use KH17.
spec. "A")
the initial
of polymer
particles by
In suspension
using water
acetate).
The steric repulsion forces due to the adsorbed layer of PVA at the monomer-water
interface increase the interfacial strength, thus, reducing the coalescence rate between
the droplets.
liquid-liquid
Despite
its importance,
the adsorption
of macromolecules
at a
chloride-water
experimental
conditions. In all these experiments, the stabiliser used was PVA type Alcotex
Spec."A" 72.5 % hydrolysed and the temperature of the liquid-liquid mixture was
55 T.
183
100 m
Fig - 6.58A - Dyed VCM droplets added to preformed suspensions at different
KH
350
CPVA
17.
With
N=
dyed
droplets,
time
and
rpm
stabilised using
of
residence
%.
A)
0.02
=
-5 min
B) - 15 min
C)
F) - 210 min
184
45
min
-
D) - 90 min
E) - 150 min
0
N
N
N
Q.
I)
U
c..
421
r
O
O
N
U
73
oO
'O
I
" E
1
- o
3 M
rU
>
+U
IN
i
i
i-o
v,
Ii
"y
r
7
Q
rU
era
l
OO
COOO
(! A+OA) / 3A
185
MN
CO
CL.
an initial solution
of 2% to a solution of 0.02
respectively and analysed for PVA concentration using a UV / VIS method described
in chapter
-5-.
Knowing
it is possible to determine
the quantity of PVA at the VCM / water interface. The results obtained are presented
in Fig 6.60
The latter figure shows the variation of PVA adsorbed
-.
is
%
PVA
[
(%
PVA;
VCM
The
time.
as
of
adsorbed
calculated
on
with residence
n;t;a,
)-(% PVAf; ) ], where t represents the residence time. The figure shows a relatively
a,
high adsorption rate at the initial stage and then a plateau indicating either a
graphically
"saturation"
0.0035 %) and the amount remaining in the water ( about 0.0 165 %)(
the addition
of these two percentages gives the initial % of PVA in the continuous phase ). The
in
"saturation"
the
that
this
the
same
shape
except
case
surface coverage also shows
is reached more quickly
2.8
/m2.
The
time required
a
surface
coverage
of
mg.
with
to reach equilibrium
Vinyl
by
the
needed
difference
in equilibrium
( 30 minutes ). This
could be
themselves by unfolding.
conformation
into the
is
reached quickly, the rearrangement and spreading ( or
adsorption
186
(Zur
if)
MMNN
Ilf)
1r)
kr)
6O
O
N
p.,
b1J
Od
U
N
ii
I'I
UU
\\\
mot'
a.,
O
zn
c,i
QN
OO
NC
II
O
*Z "Z
"" rC
cri S
--
O
CIA
O
O
O
ON
COO
OOO
( 'Yo) PagiosPL'VAd
187
bA
ri. U
interface
does
PVA
the
take some time. consequently,
the
molecules
at
unfolding) of
the time necessary for unfolding and rearrangement of the PVA molecules at the
Vinyl chloride-water interface is likely to be equal to the minimum time necessary
for the dispersion to reach a steady state. Furthermore, as mentioned by Lankveld,
J.M. G. and Lyklema, J. ( 1972 ), the stability of a dispersion is affected by the rate
interface.
PVA
the
the
the
unfolding
of
molecules
rate of
at
of adsorption as well as
6.4.2- Effect of turbulence intensity and drop size on the interfacial adsorption
of PVA on the VCM/water
This set of experiments
interface:
is concerned
of agitator
VCM
droplets-water
PVA
drop
D32
the
the
at
on
amount
of
adsorbed
and
size
speed
was 0.02 %(
concentration
determined as described
in chapter -5-. The results obtained are shown in Fig - 6.61 - and Fig - 6.62 -. these
figures show the variation of PVA adsorbed on VCM droplets with agitation
speed and the drop size ( D32 ) respectively.
increasing the agitation speed the % PVA adsorbed increases sharply up to 500 rpm
and then slowly
increase
increase
in
%
PVA
is
due
This
to
an
adsorption
afterwards.
The
droplets
VCM
interfacial
the
the
smaller.
surface coverage curve
get
as
of
area
shows an increase up to 500 rpm and then a slow decrease. The latter curve shows
a maximum
is
4.4
/m'
500
It
of
at
rpm.
probable that the slow
surface coverage
mg.
error or
that in fact the curve is a plateau in that area. It is also possible that some of the PVA
got absorbed ( PVA with low degree of hydrolysis is slightly soluble in VCM ) inside
the VCM droplets. Fig - 6.62 - was plotted using the results obtained from Fig - 6.61
vs
6.13
N
It
by
increasing
drop
PVA
Fig
(D32
).
that
the
and
adsorbed)
shows
-(
-
188
d'
a
I.)
C1.
c
MMNN
cc
c
c
s
C
O
N
(ID
a
O
U
>
C)
0
c
O
a.)
O
(ID
z
0
cQ
0
171-
C
C
A.. p
+- N
O -
II
cam,
0
O
N
--O
O0OOOC
COOOO
ON
oc
OOOO
c>
r,A U
lo ) PagiosPL'VAd
189
( ZW/"i?W) 051J0AO3az)Ljms
In
N
+
ddMMN
C/D
C
..
00
0
N
C
C
C
l)
V
vv
'
Q
+II
C O
--C
'=
>
,
_.__ ,
N
N
OO
N
O
O
O
00
O
O
paq.zoSP13
VAd
190
. -.
1r
GL 'G
diameter, both the % PVA adsorbed and the surface coverage decrease. As for Fig
-
6.61
the
maximum
-,
6.4.3- Effect of initial PVA concentration in the continuous phase on the quantity
of PVA adsorbed at the VCM / water interface:
The aim of this set of experiments was to investigate the variation of the quantity
of PVA adsorbed at the VCM water interface with the initial concentration of PVA.
Six experiments were performed using an initial concentration of PVA of 0.002,
/ Wt.
). The agitator speed
0.01,0.02,0.05,0.1 and 0.188 % respectively (Wt.
pvA
Water
350
120
the
time
rpm
and
residence
was
minutes. At the end of each experiment
was
its
PVA
the
taken
was
and
concentration determined.
sample
of
continuous
phase
a
The results obtained are shown in Fig - 6.63 -. Both the variation of % PVA
adsorbed and the surface coverage are showing roughly the same shape. They show
an initial increase in adsorption up to 0.02 % PVA concentration then a first plateau
from 0.02 % to 0.05 %. This might be due to the saturation of the first interfacial
layer. A second increase in PVA adsorption is observed between 0.05 % and 0.1
% PVA concentration and then another plateau which probably represents the
saturation of a second PVA layer. This multilayer characteristic was observed before
by Lankveld, J.M. G. and Lyklema, J. (1972) for some types of PVA. Goodall, A. R.
M.
J.
(1990),
Greenhill-Hooper,
and
used a monodisperse polystyrene as a polymer
bed to measure the adsorption isotherms for two types of partially hydrolysed PVA.
They found that the system reaches a first plateau before increasing again, indicative
of a multilayer adsorption. These authors did not comment on the PVA adsorption
mechanism. The multilayer adsorption mechanism observed in our experiments
could be explained as follows :
i) - For low PVA concentrations, the PVA molecules diffuse and adsorb into the
VCM / water interface. As the number of molecules adsorbed is relatively low
compared to the size of the interface, the PVA molecules will rearrange themselves
by infolding as well as replacing the less surface-active groups by more hydrophobic
ones, thus, having a larger number of segments per PVA molecule in the interfacial
region ( Zwick, M. M. (1965) and Chatzi, E. G. et al. (1991)). This mechanism might
191
( ZuT/"uz) aa13JOA00
aoijins
N
C)
00
11C
Itt
N
C
^
po
OO
)
L1.
O
v
-Z O
CD ZV
il
Z
ai
c
cq
j
CD
c64 C.,
U
NOU
C
O
C=
Cl
n
OO
--
CpO
O
( %, ) DaQJOSUc
v-
\/ /\, 4
192
rQ)
bA
O
J-
Spec. "A" ). For each experiment, the agitator was run for 120 minutes
at 350 rpm
and then a sample was taken and analysed for PVA
concentration.
The results
obtained are presented in Fig - 6.64 - which shows the variation of PVA adsorbed
with volume fraction. The figure shows a practically linear increase of % PVA
adsorbed with volume fraction while the surface coverage curve shows an increase
in surface coverage with volume fraction up to 8.5 mg. /m2 and then a slow decrease
(7.9 mg. /m2 ). By increasing the volume fraction, the interfacial area decreases (due
to the increase in the drop size) ( see sub-section 6.2.6 ), thus, more PVA molecules
are available in the continuous phase per unit area. The slow decrease in the surface
coverage for the high volume fraction ((p = 0.4) might be due to experimental error
while in fact there is a saturation of the interface ( the saturation value of surface
coverage was found in the last section to be equal to about 10 mg / m2 for a multilayer
adsorption ).
193
(ZW/SUI )afPIOAO3aoujms
r,
N
CN
00
13
00
lt
11C 1.10 Lr,
C.
I)
o..
N
E'
8
"
C
c?
O
G
U
cs
M
O
cr
i
O
_r
NJ
O
Lam
I'
N
O
U
c
0
c
cs
a
"
Op
O-
II
CL
d'
OOOO
OOOC
cr,
194
II
6.5 - Polymerisation
experiments:
and subsequent
droplet
agglomeration
for
different
experimental
A number of polymerisation
Vinyl
as monomers
chloride
experiments
) were performed
in order to determine
the best
experimental conditions to be used. For all the experiments performed (unless stated
otherwise ) the reaction temperature was 55 C while the agitator speed was 350
rpm. The initiator concentration ( X50 ) was 0.175 % (Wt. x50/ Wt"VCM)" The volume
fraction of the dispersed phase was 0.1 and the PVA ( Alcotex spec. "A" )
concentration
droplets
The aim of this series of experiments is to show the different stages of VCM
suspension polymerisation as well as to study the effect of the method of addition
of initiator on the morphology and uniformity of the polymerising Vinyl chloride
droplets. In each experiment, samples were forced into the pressurised optical cell
and photographs were taken at different stages of the polymerisation. Fig - 6.65 shows vinyl chloride suspension polymerisation at the early stages of the reaction.
In the latter experiment the initiator was suspendedin the continuous phase ( this
195
,rI
z
ii
I
C
100 .tm
Fig - 6.65 - Changes occurring in Vinyl chloride droplets during early stages of
350
0.175
%;
PVA
0.1;
X50
N=
(
(p
conc.
conc.
rpm;
polymerisation
=
suspension
=
=0.06%andT=55C).
A)-5min
B)-l0min
196
C)-20min
D)-60min.
initiator
addition
method of
of
( the lid was not heated ). It can be seen from the four photographs, that the droplets
are not uniform as some polymerised
stable and uniform primary particles formed after a reaction time of 5 minutes. These
growing primary particles are thought to be stabilised by electrostatic forces
due
to the presence of chloride ions (Rance, D. G. and Zichy, E. L. (1979) and Davidson,
J.A. and Witenhafer,
when
the primary
due to electrostatic
the stability
agglomerates
forces is inhibited
most of the primary particles have coagulated and formed a more or less continuous
"cloud" inside the droplet. After 60 minutes (photograph
the droplets is formed. The shape of the final PVC particle is defined at this stage
( if enough stabiliser is used to protect the drops ). This mechanism is similar to the
P. V. (1989) ( see Fig 3.18 ). In order to study the
initiator
the
addition
of
on the polymerising VCM droplets two
effect of
method of
one proposed by Smallwood,
were performed
experiments
ones. In the first experiment, the initiator was predissolved in the monomer and then
poured into the continuous
experiment the initiator
and polymerisation.
In the second
monomer was added. For each experiment samples were forced into the optical cell
at different
The results obtained are shown in Fig - 6.66 -. The photographs presented in the
latter figure
represent samples of vinyl chloride droplets during suspension
polymerisation
at different
the polymerisation
These results show that the diffusion of initiator from the continuous phase into the
VCM droplets is not instantaneous. They, also, show that the coalescence rate
197
"
AL
0
"
i
-
A3
Alb
100 m
Fig - 6.66 - Effect of the method of addition of initiator on the uniformity of the
Vinyl chloride droplets during suspension polymerisation (cp = 0.1; N= 350 rpm;
X50 conc. = 0.175 %; PVA conc. = 0.06 % and T= 55 C ).
A) -Initiator
-5 min
A2) - 20 min
198
A3) - 60 min.
B2) - 20 min
B3)-
between the droplets is relatively low at the early stagesof the polymerisation as the
initiator is not spreading rapidly between the VCM droplets. The effect of the method
of addition of initiator on the PVC particle size distribution is shown in Fig - 6.67
in
figure
distributions
latter
for
PVC
The
the
taken
size
shown
particles which
were
-.
were polymerised for 60 minutes and then the reaction was stopped and the PVC
particles filtered and dryed. A sample of PVC particles was then ultrasonically
dispersed in distilled water ( wetting of the PVC particles was improved by adding
a proprietary surfactant type Brij - 35 ) and then analysed using a coulter LS 130 laser
sizer. When the initiator was dispersed in the continuous phase a certain amount of
latex particles ( particles of a size < 10 pm ) were observed in the final product ( see
Fig - 6.67 A-). This confirms that emulsion polymerisation is also taking place.
This might be due to the fact that when the VCM diffuses into the continuous phase
( though in very small quantities ) it polymerises using the free dispersed initiator
which did not move into the VCM droplets forming latex particles. When the initiator
was predissolved in the VCM prior to polymerisation the particle size distribution
does not show any latex formation ( see Fig - 6.67 B-). It also shows the existence
of few large PVC particles probably formed by the coalescenceof smaller ones when
the reaction was stopped. Thus, the method of addition of initiator plays an important
degree
final
in
PVC particles (i. e. size,
determining
the
the
of
uniformity
of
role
size distribution, porosity and degree of conversion ). These effects will be studied
further in the next sub-section to determine whether or not the conversion is also
affected by the method of addition of initiator.
6.5.2 - Effect of method of addition of initiator
on conversion:
The aim of this series of polymerisation experiments was to investigate the effect
of the method of addition of initiator on the degree of conversion of the VCM
monomer. For this purpose, two sets of experiments were performed. The first set
of experiments consisted of determining the conversion vs time using X50 initiator
predispersed in the continuous phase as well as the investigation of the kinetic of
/
Spec.
)
droplet
PVA
"A"
(Alcotex
the
adsorption of
at
water interface during the
suspension polymerisation reaction. The second set of experiments was aimed to
compare the conversion vs time values of the latter curve with those determined
199
Differential Volume
6
5
V4
0
u3
m
e
%
1
0.1
0.2
0.4
1246
10
20
40 60
100
200
400
I 000
40 60
100
200
400
1000
Differential Volume
7
6
V5
0
14
u
m3
e
02
0.1
0.2
0.4
1246
10
20
Fig - 6.67 - suspension PVC particle size distribution ( reaction time 60 minutes,
PVA conc. = 0.06 %, X50 conc. = 0.175 %, T= 55 C and N= 350 rpm) for :
A) - Initiator ( X50 ) predispersed in the continuous phase.
B)-
200
the experimental procedure used was as follows: A certain amount of PVA ( Alcotex
in 1 litre of distilled water [ about 0.06 % (Wt.
PVA
Wt"waw, ] and then poured into the reactor. The continuous phase was maintained
spec. "A"
) was predissolved
jacket
).
Then
0.7
C
(
15
through
the
cooling
water
reactor
grams of
using
at about
initiator
phase and stirred. The reactor was then sealed and deaerated
into
forced
100
VCM
Nitrogen.
the reactor and the agitator
then
were
grams of
using
T.
55
heated
The suspension
The
350
to
then
up
rpm.
reaction mixture was
run at
polymerisation
150,200,250
for
were
run
reactions
At
(
).
300
the end of each
respectively
separate
reactions
and
minutes
for
4
(to
droplets
the
to separate
the
allow
was
stopped
about
minutes
stirrer
reaction,
from the continuous phase) and a sample of the continuous phase was taken and
analysed for PVA concentration. The stirrer was then run at 350 rpm while the venting
was taking place. The
The
initiator
for
that
the
the
experiments
except
second
set
of
same procedure was used
X50 ( solid powder
prior to reaction.
Fig - 6.68
the initiator
is uniformly
distributed between the VCM droplets. This enables them to polymerise uniformly
from
the beginning of the reaction. This was not the case when the initiator was
did
initiator
drops
because
in
the
not
get
enough
phase
some
continuous
predispersed
to polymerise
uniformly
from
for
initiator,
long
to
the continuous phase
time
either
get some
wait
a relatively
( latex particles, diffusion
free
)
by
radicals
coalescing with other polymerising
of
or
reaction. Table - 6.6 - shows
% volume for each polymerisation
particle
sizes by cumulative
The
X50
dispersed
in
the
continuous
phase.
results presented
conversion when
was
in the latter table show that above 20 % conversion, the coalescence between the
polymerising
stabiliser
201
0
0
m
U
0
OM
Q
it
n
N
C
s
s
yL
C-
0
cN
o
G
. rr.
1D
CIL
CO
CU
=O
n
C.
r-
O
r-
U
c3
Q
r-
Op
r."
O
C
.--.
II
.=
O
Q
O>
.mC
rU
"i
II
iQ
cco0
0
oc
( 0/ UOTSJaAUOO
.0)
202
10 %
25 %
50 %
75 %
90 %
3.4
8.153
24.63
48.77
78.63
113.8
7.2
25.38
40.56
62.33
89.73
121.5
13
29.96
44.79
67.71
105.2
153.1
20.8
33.34
51.64
83.34
135.8
199.7
34.5
60.41
95.49
160.1
247.1
330.5
54
58.05
115.6
252.8
420.3
605.7
90
127.7
241.7
354.2
458.9
554.6
Conversion (%)
The kinetics of PVA adsorption on the VCM / water interface during suspension
polymerisation is shown in Fig - 6.69 -. It shows the variation of PVA concentration
in the continuous phase with the polymerisation reaction time. From the later figure
we observe a sharp decrease in PVA concentration in the continuous phase at the
early stages of the conversion ( during the first five minutes ) where about half the
initial PVA is adsorbed and then a slow steady decreaseafterwards. When the reaction
is completed (i. e. = 90 % conversion ), about 95 % of the initial PVA is adsorbed
at the interface. The initial sharp decreasein the PVA concentration in the continuous
phase is probably due to the formation of the thin "skin" at the droplets interface
at the very early stages of the polymerisation (= 2% conversion ). Allsopp, M. W.
(1981) suggested that the relatively high adsorption rate ( compared with the case
when reaction is not taking place, see section - 6.4 -) is due to the nature of the
203
.IO
cr',
"3
C
. r.
II
I
C
U
Con
OOOCCOO
OCCCCCC
( off) uoiIL'ziuaOuoOVAd
204
interfacially adsorbed polymer, which lowers the covering power of the PVA, thus,
more is adsorbed from the aqueous phase. The skin formation
is believed to be
Vinyl chloride monomer and polymerisation. Because some droplets get more
initiator than others, the final product is a mixture of non-uniform particles with
some perfectly
uniformly distributed ( X50 solid predissolved in VCM ), the final particles are more
uniform in shapeas seen in Fig - 6.72 -. In both cases,the outside surface is relatively
smooth and there are some latex particles adhering to the surface of the "normal"
particles. Also, we can observe a uniform distribution of the macropores at the surface
of the particles.
6.5.3 - Polymerisation
The influence of the type of initiator was studied using KH 17 suspending agent
instead of Alcotex spec."A". The experimental procedure was the same as above
except that the initiator ( X50 solid) was predissolved in VCM. The concentration
). The suspension
of stabiliser ( KH17 ) used was 0.06 %( Wt. KH / Wt-water
205
-o Gl
v-
II
I
-
O
r-
U
o
M
II
o
N
O
O
-0
"
.
O
II
i
i
i
0
C)
00
>r
CD
o)
( i 00111W ) Itsozod
,
206
OO
I)
L'-,
O
>
207
208
polymerisation reaction was run for 180 minutes and samples were withdrawn into
the optical cell and photographed at different time intervals. Fig - 6.73 shows
the drop behaviour at the different stages of the Vinyl chloride suspension
polymerisation. From the latter figure, we observe that the droplets are bigger and
more uniform in size than when using Alcotex spec."A". The internal morphology
seem to be similar to the droplets produced using Alcotex spec. "A" stabiliser up to
a reaction time of 90 minutes, then the PVC particles start loosing their smooth
spherical shape and begin adhering to each other. The analysis of the final PVC
particles using SEM technique is shown in Fig - 6.72 - which shows an
agglomeration of PVC particles (photograph A) and a view of the surface of one
of the particles ( photograph B ). The surface looks very rough which shows that
KH 17 might be a good stabiliser at the early stagesof the polymerisation but once
the PVC particles are formed, the thin "skin" at the surface of the particle is not rigid
enough to preserve its shape beyond a certain conversion stage. The porosity of the
final PVC particles was relatively low ( using the cold plasticiser technique the
porosity was found equal to 14.05 % for a polymerisation conversion of 80 %).
When the initiator was predispersed in the continuous phase the porosity of the final
PVC grains decreased to 8.45 % and the conversion was 65 %. Thus, an addition of
a secondary stabiliser such as Alcotex spec. "A" at some stage of the polymerisation
reaction might keep the droplets stable for a longer time ( until they become rigid
enough to overcome interfacial pressures ). Also, the use of a mixture of suspending
agents ( KH17 and Alcotex spec. "A" ) from the beginning of the polymerisation
reaction could produce PVC particles with a more uniform size and a smooth surface.
The KH17 stabiliser enhances the uniformity of the initial VCM droplets while
Alcotex spec. "A" provides the rigidity needed for the outside skin as well as
conserving the final shape of the PVC particles.
6.5.4 - Effect of condenser operation
particle
morphology
during
suspension polymerisation
on the
and properties:
The aim of this series of experiments was to study the effect of condenser operation
during Vinyl chloride suspension polymerisation on the VCM drop behaviour. The
209
11
wO-
dm
"
,
,ob
m
4p.
i
E
IN
100 m
Fig
in vinyl
different
during
droplets
chloride
of suspension polymerisation
X50
(
KH
17
predissolved
stabiliser
as
using
), a) 15 min.
e) 90 min.
b) 30 min.
c) 45 min.
stages
in the
d) 60 min.
f) 120 min.
210
,'
Fig - 6.74 - SEM photographs of suspension PVC particles stabilised using KH17
( X50 predissolved in VCM ). a) PVC particles b) scanning of a surface of a PVC
particle.
211
reflux
chapter -4-.
experiments
morphology
this purpose,
three
experiments were performed using a reflux rate of 1.5,3 and >3 drops / second
increasing
final
It
by
that
the
the
was
observed
reflux
rate,
respectively.
conversion
( the final conversion is the conversion obtained after 3 hours polymerisation time
) decreases ( the degree of conversion was 77,62 and 60 % for reflux rates of 1.5,
2 and >3 drops / second respectively ). The porosity of the PVC particles was
determined and found to be relatively high compared with particles obtained when
the reflux is not occurring. These results are presented in table - 6.7 -.
Table - 6.7 - Variation of Vinyl chloride monomer conversion and final PVC particles
porosity with reflux rate :
drops
/
(
second)
reflux rate
1.5
>3
conversion (%)
81
77
60
62
porosity ( %)
23.5
28.02
28.1
31.69
particles increased
considerably. For this reason, it was necessary to centrifuge the final reaction
mixture before filtration (in
shows the latex particles
order to avoid blockage of the filter ). Fig - 6.75 produced during PVC suspension polymerisation
using a reflux rate of 1.5 drop / sec. These latex particles look to be spread over a
relatively wide size range and have a more or less spherical
Fig
6.76
during
(
it
),
taken
that
see
observed
reaction
was
although
photographs
the rate of coalescence was very low at the early stages of the suspension
polymerisation,
polymerising.
some of
VCM
(excluding
coalescence)
initiator:
212
PVC
during
PVC
latex
suspension
particles
Fig - 6.75 - SEM photographs of
/
).
drop
1.5
(
sec.
rate
reflux
condenser
reflux
using
reaction
213
40
44
;_
.
S
..
C
100 m
Fig - 6.76 - Changes occurring
suspension polymerisation
30 min.
c) 45 min.
in vinyl
during
droplets
early stages of
chloride
15
drops
/
)
(
min.
>3
sec.
a)
reflux
rate
with reflux
d) 60 min.
214
b)
a)- By diffusion of the initiator through the continuous phase into the fresh VCM
droplets.
b)- By the interaction of the latex particles present in the continuous phase with the
fresh VCM droplets.
c)- By the diffusion of free radicals from an "old" drop into a "fresh" drop through
the continuous phase. At a later stage (i. e t= 45 minutes see Fig - 6.76 - ), when a
"fresh" drop starts developing its internal structure there will not be enough PVA
to stabilise it and it may coalesce with an old drop thereby accelerating its
by gaining more initiator ). The particle size distribution of
polymerisation (
suspension PVC produced during the operation of the condenser shows a bimodal
distribution as seen in Fig - 6.77 -. This is due to two main reasons :
i) - The peak on the left hand side of the diagram represents the particles produced
by the "old" VCM droplets. These particles are relatively small in size compared
with the ones produced when the condenser is not in operation. This is due to fact
that the "old" droplets lost some of their VCM (by evaporation) and continued to
final
thus,
particles.
producing
smaller
polymerise,
ii )-
The second peak represents the PVC particles produced either by the
droplets
from
"fresh"
the
the condenser (these
returning
monomer
polymerisation of
droplets are bigger in size compared with the "old" ones ) or by the coalescence of
fresh and old droplets.
We, also, observe a big number of PVC latex particles.
The second set of experiments was performed to study the effect of timing of reflux
on the morphology
The same experimental procedure was used except that the reflux was started after
a polymerisation
with a reflux rate of about 1.6 drops / sec. For the morphology,
made for the first set of experiments
particles ( especially
apply
the observations
65
68
(
between
% ). The porosity results are shown
less
the
and
same
was more or
in table 6.8 These results show that when the reflux is delayed to a later stage
-.
-
215
Differential Volume
7I
1,
6v
0
1 4-
iil
r! '
',
nll,
jb
e
2 -1
lilt
Ilia
il
",
jj, l
l'i;
iili
1-
I'il
I;
I!
ll
0
0.2
0.1
0.4
10
46
40 60
20
200
100
400
1000
Differential Volume
/
6
EI
II
it
rl
eil
jl
Iil!
i ! jj
iI
32-4
11
l i
lhl
I!
til
0.1
0.2
0.4
46
10
20
i, III
II'
ifl
I'i
II
40 60
11
'Il
III'
11
100
200
400
216
reflux rate =
1000
final
PVC
is
the
the
the
of
porosity
particles
considerably
polymerisation,
of
increased. This indicates that the VCM drops once they become rigid they do not
loose their shape even after losing some of their swollen VCM by evaporation
during reflux. This loss of VCM might be replaced by water from the continuous
phase, thus filling the empty space inside the PVC particle and reducing the rate of
conversion.
Table - 6.8 - Variation of PVC particles porosity with the timing of reflux.
Delay time for reflux ( min)
30
60
60
84
96
73
99
Degree of conversion ( %)
77
65
66
68
(
%)
porosity
28
25.61
50.52
40.41
means. A polymerisation
condenser. The same experimental procedure was used as in sub-section - 6.5.1 (X50 conc. = 0.175 %, PVA (Alcotex spec. "A") conc. = 0.06 %, N= 350 rpm, cp
C).
50
fresh
30
VCM
0.1,
55
After
T=
time
a
of
minutes,
grams
of
reaction
=
for
into
forced
the
the
continued
reactor
and
reaction
another 150
monomer was
minutes. Samples of the reaction mixture were photographed at different reaction
times as shown in Fig - 6.78 -. This shows that the fresh drops formed from the
simulated reflux monomer are relatively much bigger than the old ones. This is
probably due to the unavailability of enough PVA in the continuous phase, thus, a
higher interfacial
217
100 m
Fig - 6.78 - Reflux simulation during suspension polymerisation. a) 30 min.
(before adding fresh VCM) b) 45 min. (i. e 15 min after adding fresh VCM) c) 60
min.
d) 90 min.
218
show that
the polymerisation
initiator
drops
"new"
in
latter
through the
their
the
that
the
getting
are
section
stated
The
is
little
these
that
at
stages.
occurring
coalescence
very
continuous phase and
conversion at the end of the polymerisation
63
%(
conversion calculated
was
reaction
The
i.
150
).
inside
VCM
the
the
total
grams
porosity of
e.
reactor
amount of
using
the final particles was found equal to 36.62 %. The second experiment was performed
in order to investigate
liquid-vapour
interface ( evaporation)
lose only
in
dyed
VCM
150
).
For
its
the
this
mixed
of
was
grams
purpose,
monomer?
of
part
droplets.
Then
for
in
30
350
the
to
stabilise
order
minutes
rpm
continuous phase at
the valve allowing
refluxed
monomer
the VCM vapours to get into the condenser was opened. The
coming
in
(
chapter -4 -) and, thus, not allowed to return
system
chamber see condenser
60
/
drops
The
min.
at
about
tank.
to the reactor
reflux rate was maintained constant
Samples of the mixture were taken into the optical cell at different
time intervals
6.79
in
Fig
Fig
and
are
presented
and photographed.
distribution
drop
6.80
They
the
the
with
and
size
of
size
variation
represent
-.
The results obtained
6.80
in
Fig
is
This
the
shows
variation
which
confirmed
also
observation
mixture).
is
latter
The
distribution
drop
time.
observation
very
the
with residence
size
of
important as it shows that the latex particles
reflux are not due mainly to a major reduction
formed during
219
with
free
due
the
to
the
of
macroradicals
growth
probably
phase stabilised by micelles.
polymerisation
available
in the continuous
C)
N
a ^
vO
II
-O
-. -
CA
C
0
3
N
i.
)
"Z:
O
-1-- 00 .
U
cn
'rU
p
U
C
Ti
0
n
cn
a 0
C/1
z
O
0
M
i
V')
i
0
N
C)
Ln
C)
Ln
It
220
o
>E
200
200
F-30
180
min
180
160
160
140
140
-
j120
120
8100
100
80
80
60
60
40
20
20
0
1ts
D -p
Aw ervm ()
d meter (,m)
roo
200
80 min
130
160
! SC
`40
: 20
! CO
100
90
60
;a
40
20
0
85
a5
Rop
ttt
25
(gym)
200
200
180
160
750
140
120
100
100
00
60
;o
40
20
D,. p d--
200
2ao t
60 min
ISO 160 +
120
140 tll
Q
100
100 }
IF_'
5J
'i
I
055
45
95
Drop 3voer
l`in)
Fig - 6.80 - Variation of VCM drop size distribution with residence time during
CPV.
drop
/
350
).
(N
(reflux
sec.;
reflux
rate
rpm;
=1
simulation
=
evaporation
A_
0.06%)
221
CHAPTER 7
222
223
6
0.027(1
+3.064)WL.
=
This correlation seem to be in good agreement with correlations found by other workers.
The third series of experiment was devoted to the study of the mass transfer ( by
for
VCM
droplets
different experimental conditions using a
)
between
the
coalescence
mixture of dyed and undyed droplets. It was found that the rate of coalescence rises
relatively slowly with residence time (t) and pre-mixing time (ti), is roughly proportional
to the agitator speed and decreasessharply when the concentration of suspending agent
is increased. Thus, the degree of coalescenceis mainly controlled by the residence time,
the agitator speed and the surface coverage of the suspending agent. It was also found
that the rate of coalescence was relatively low when KH17 was used as a stabiliser.
During the fourth series of experiments the kinetic mechanism of PVA ( Alcotex spec.
"A" ) adsorption on the Vinyl chloride / water interface was investigated for different
experimental conditions. It was found that :
B1- The saturation of the VCM / water interface with PVA is reached relatively quickly
(in less than 5 minutes ) with a surface coverage of 2.8 mg / m2, while the stability of
the VCM droplets is reached after 30 minutes. This is due to the fact that, although the
PVA molecules diffuse relatively quickly into the interface, their rearrangement and
spreading does take some time.
B2 - The surface coverage decreaseswhen the drop diameter is increased.
B3 -A multilayer system is formed at the VCM / water interface when high concentrations
of PVA ( Alcotex spec."A" ) are used. The first layer is well rearranged and spread ( by
unfolding)
224
well as determination
under polymerisation
conditions
as
225
). Do they stay as
drops or do they coalesce with the fresh droplets returning from the condenser?.
For this purpose, a series of experiments could be performed by allowing the evaporation
of some of the VCM during polymerisation
it
it
(
to return
trapping
then
not
allowing
and
into the reaction mixture ). The reaction is then continued till completion
particles analysed for particle size and porosity.
226
CHAPTER 8
8-REFERENCES
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239
APPENDIX
200 rpm
350 rpm
500 rpm
650 rpm
800 rpm
10 - 20
29
36
94
169
20 - 30
30 - 40
34
59
100
159
31
65
105
113
40 - 50
50 - 60
10
24
81
135
104
31
91
99
72
60 - 70
70 - 80
53
84
55
20
58
63
15
80 - 90
90 - 100
62
32
65
16
100-110
10
40
10
110-120
29
120-130
10
130 - 140
12
140-150
15
150-160
15
160-170
15
170 - 180
12
180-190
13
190 - 200
200 - 210
210 - 220
10
11
220 - 230
230 - 240
240 - 250
250 - 260
260 - 270
270 - 280
280-290
290 - 300
D32 (um)
193.43
92.55
70.9
53.44
46.36
Di (um)
240
Table -A1.2 - Variation of drop frequency with drop size at different suspending
agent (PVA ) concentrations.
0.2%
0.1 %
0.02%
0.01 %
0.002%
10 - 20
23
24
40
14
39
100
20 - 30
43
43
45
15
41
100
30 - 40
43
36
41
17
64
40 - 50
65
44
45
24
53
50 - 60
96
55
54
13
46
60-70
104
102
73
18
32
70 - 80
80 - 90
77
76
77
16
15
22
33
31
82
12
23
20
90 - 100
13
16
57
10
31
12
100- 110
45
13
22
110- 120
33
26
38
120- 130
13
19
33
130- 140
27
15
140-150
150 - 160
16
1
0
160-170
170- 180
180-190
190 - 200
200-210
210 - 220
220 - 230
230 - 240
240 - 250
250 - 260
Di (um)
260 - 270
270 - 280
0%
280 - 290
290 - 300
300-310
67.4
71.85
91.07
124.75
116.82
108.51
D32 (um)
241
20 min
30 min
60 min
90 min
10 - 20
25
26
31
19
20 - 30
30 - 40
13
23
31
34
23
27
19
19
19
40 - 50
50 - 60
21
11
17
19
18
17
13
13
15
60 - 70
70 - 80
17
18
29
42
20
13
24
34
35
80 - 90
20
16
38
52
45
90 - 100
100-110
28
18
39
54
43
15
21
49
42
24
110-120
21
40
52
45
10
120 - 130
18
29
35
26
130 - 140
27
17
30
19
140-150
17
15
15
150-160
160-170
170- 180
180-190
190 - 200
200 - 210
D32 (um)
122.3
119.16
113.01
104.83
88.25
Di (um)
242
Table - A1.4 - Variation of drop frequency with drop size at different agitator
speeds for an unbaffled system.
Unbaffled system
Baffled system
Di (um)
350 rpm
500 rpm
350 rpm
500 rpm
10 - 20
82
77
34
101
20 - 30
30 - 40
94
91
228
82
31
40
69
49
40 - 50
50 - 60
89
34
36
42
21
21
60-70
18
16
70-80
18
15
80 - 90
26
90 - 100
25
100-110
25
110- 120
47
120- 130
27
130-140
21
140-150
10
150- 160
160- 170
170 - 180
180- 190
190 - 200
D32 (um)
43
29
111
58
243
APPENDIX
2: Vinyl
dispersion
chloride
data
experimental
250 rpm 350 rpm 500 rpm 650 rpm 800 rpm
48
215
262
78
19
20-30
25
56
172
138
118
30 - 40
40 - 50
30
56
158
61
11
30
70
61
19
50 - 60
60-70
31
89
11
41
69
70 - 80
80 - 90
49
64
30
6
2
0
0
0
0
0
90 - 100
100-110
50
27
110-120
19
120 - 130
130- 140
D32 (um)
0
87.46
58.23
37.38
29.17
22.2
5 min
10 min
20 min
30 min
60 min
90 min
120 min
10-20
47
84
83
103
145
120
123
20-30
66
107
121
172
224
149
248
30-40
82
133
115
127
94
91
83
40 - 50
50 - 60
102
109
57
20
13
95
23
60 - 70
70-80
35
80-90
D32 (um)
50.51
40.24
35.73
31.53
29.3
29.84
28.43
244
350 rpm
38
500 rpm
650 rpm
350 rpm
56
66
50
54
64
67
72
21
49
71
79
40 - 50
50 - 60
14
82
94
121
27
82
51
76
60-70
32
59
13
31
70 - 80
80 - 90
39
14
53
90 - 100
100-110
53
44
110-120
24
120-130
12
130-140
140- 150
150- 160
160- 170
94.52
54.93
46.49
49.82
D32 (um)
245
350 rpm
500 rpm
650 rpm
350 rpm
10 - 20
63
107
209
183
20 - 30
30 - 40
82
181
152
134
58
127
51
66
40 - 50
56
81
17
16
50-60
61
15
60 - 70
84
70 - 80
52
80 - 90
23
90- 100
10
100-110
110-120
120- 130
12
130- 140
140-150
150-160
160- 170
66.24
38.81
28.86
28.86
D32 (um)
246
500 rpm
650 rpm
350 rpm
94
180
103
53
55
124
76
35
45
28
43
40 - 50
50 - 60
24
68
16
29
36
65
11
19
60-70
38
31
27
70 - 80
80-90
33
19
24
16
12
90- 100
100- 110
110- 120
120- 130
12
130 - 140
140-150
150-160
160 - 170
68.42
56.22
34.43
70.28
Di (um)
10 - 20
20 - 30
30 - 40
D32 (um)
500 rpm
650 rpm
350 rpm
270
439
367
175
75
18
196
85
10
41
40-50
50-60
60-70
D32 (um)
27.58
23.17
17.61
24.58
Di (um)
10-20
20 - 30
30 - 40
247
Di (um)
10 - 20
350 rpm
30
500 rpm
650 rpm
350 rpm
35
55
55
20 - 30
30 - 40
55
53
67
68
42
40
59
62
40 - 50
24
38
61
70
50 - 60
20
48
68
89
60 - 70
70 - 80
22
77
69
77
22
59
20
20
80 - 90
49
16
90 - 100
100- 110
50
30
110- 120
31
120- 130
15
130- 140
140- 150
150-160
160- 170
96.09
64.99
56.73
56.45
D32 (um)
248
350 rpm
27.58
500 rpm
650 rpm
23.17
17.61
56
68.42
56.22
34.43
72.5
66.24
38.81
28.86
80
94.52
54.93
46.49
84
96.09
64.99
56.73
500 rpm
111
650 rpm
129
350 rpm
180
20 - 30
30 - 40
55
91
120
147
39
72
74
84
40 - 50
80 - 90
50
40
38
34
40
42
24
14
90- 100
38
36
15
100-110
30
28
110- 120
28
22
120- 130
40
13
130 - 140
26
11
140 - 150
29
150- 160
29
160-170
19
170- 180
16
180 - 190
190 - 200
200-210
210 - 220
220-230
230-240
Di (um)
10 - 20
249
0.005 %
0.01 %
0.015 %
0.02 %
0.1%
0.2%
87
47
31
53
59
29
73
20-30
115
67
77
61
68
40
89
30-40
94
52
44
48
40
46
102
40-50
57
51
44
81
43
65
129
50 - 60
60 - 70
33
48
35
66
75
94
69
32
41
68
76
65
64
12
70 - 80
80 - 90
20
32
55
36
50
29
21
30
31
16
13
Di (um)
10-20
90 - 100
100-110
18
20
10
10
110-120
11
120- 130
130-140
140 - 150
150- 160
160- 170
170- 180
180 - 190
190 - 200
200-210
210-220
D32 (um)
99.53
69.73
67.05
59.92
60.85
62.03
52.69
250
Table - A2.11 - Variation of volume distribution (%) with drop size at different
PVA ( Alcotex spec. "A" 72.5 % hydr. ) concentrations (N = 250 rpm).
Di (um)
0.002%
0.02%
0.1 %
0.2%
10-20
0.133
0.1
0.06
0.06
20 - 30
30 - 40
0.66
0.57
0.41
0.48
0.98
0.9
0.97
0.53
1.71
2.16
1.53
1.32
2.25
1.43
1.36
1.39
3.06
3.11
3.67
3.07
4.28
5.66
10.37
80 - 90
90- 100
4.33
12.57
14.72
18.18
3.52
11.54
18.08
22.51
100-110
4.76
16.21
10.54
11.64
110- 120
11.61
21.29
16.77
18.69
120- 130
12.61
11.57
14.98
7.64
130- 140
2.89
6.62
5.9
4.12
140 - 150
1.79
4.92
150- 160
4.37
2.01
0.18
160- 170
2.64
170- 180
12.58
180- 190
3.72
190 - 200
4.35
3.55
200 - 210
210 - 220
5.06
5.83
220 - 230
230 - 240
6.67
40 - 50
50 - 60
60 - 70
70 - 80
251
Table - A2.12 - Variation of volume distribution (%) with drop size at different
PVA ( Alcotex spec. "A" 72.5 % hydr. ) concentrations (N = 350 rpm).
0.002%
0.02%
0.1%
0.2%
10-20
0.16
0.29
0.15
0.88
20 - 30
30 - 40
0.99
1.54
0.94
4.35
2.21
2.49
2.98
13.67
40 - 50
50 - 60
2.85
5.68
8.94
36.74
3.01
18.08
23.61
32.76
60 - 70
70 - 80
4.82
25.87
26.54
10.3
4.63
30.57
18.47
1.32
80 - 90
7.08
14.24
12.06
90 - 100
100-110
8.47
1.24
2.59
6.35
110-120
9.18
120- 130
3.22
130 - 140
10.8
3.72
140 - 150
5.02
150 - 160
10.22
160- 170
9.86
170- 180
2.94
180- 190
3.47
190 - 200
200 - 210
210 - 220
4.73
Di (um)
252
Table - A2.13 - Variation of volume distribution (%) with drop size at different
PVA ( Alcotex spec. "A" 72.5 % hydr. ) concentrations (N = 500 rpm).
Di (um)
0.002%
0.02%
0.1%
0.2%
10-20
0.51
1.7
1.83
1.58
20 - 30
30 - 40
3.86
13.49
11.92
19.91
5.06
23.58
37.57
54.96
40 - 50
50 - 60
4.64
35.55
40.4
18.75
6.47
15.96
6.86
2.63
60 - 70
70 - 80
5.52
7.02
1.42
2.17
6.22
2.7
80 - 90
7.41
90 - 100
100-110
14.95
9.31
110- 120
4.08
120 - 130
2.62
130 - 140
9.9
140 - 150
12.26
150- 160
160-170
7.19
170 - 180
180-190
253
Table - A2.14 - Variation of volume distribution (%) with drop size at different
PVA ( Alcotex spec. "A" 72.5 % hydr. ) concentrations (N = 650 rpm).
Di (um)
0.002%
0.02%
0.1 %
0.2%
10-20
0.81
16.11
3.57
5.08
20 - 30
30 - 40
5.73
51.71
24.47
62.58
6.71
26.38
48.48
31.17
40 - 50
50 - 60
9.57
5.8
12.67
1.16
5.83
1.54
60-70
7.92
70 - 80
80-90
6.95
13.91
90- 100
7.06
100-110
7.15
110-120
8.05
130-140
140-150
150-160
160 - 170
9.25
170 - 180
11.04
120- 130
180-190
Table - A2.15 - Variation of volume distribution (%) with drop size at different
PVA ( Alcotex spec. "A" 72.5 % hydr. ) concentrations (N = 800 rpm).
Di (um)
0.002%
0.02%
0.1%
02%
10-20
1.09
24.28
25.37
26.29
20 - 30
30 - 40
7.83
48.77
47.54
73.71
10.48
15.49
24.84
11
5.99
2.29
12.56
5.47
60 - 70
70 - 80
13.26
11.46
80 - 90
90- 100
7.41
100-110
6.99
110-120
4.59
120-130
5.9
130- 140
7.43
40 - 50
50 - 60
140-150
254
0.1 (ratio)
0.2 (ratio)
0.3 (ratio)
0.4 (ratio)
10-20
60
56
48
95
64
48
20 - 30
30 - 40
67
68
55
85
68
65
81
55
35
40
38
39
40-50
111
103
61
34
38
39
50 - 60
60 - 70
48
85
86
26
31
23
19
80
37
38
29
70 - 80
80 - 90
33
36
30
27
18
22
36
90 - 100
100-110
10
28
26
20
19
110-120
10
10
120-130
130-140
140- 150
150- 160
160- 170
170- 180
ISO- 190
190 - 200
44.01
48.63
60.85
71.08
85.96
91.73
D32 (um)
255
Table - A2.17 - Variation of volume distribution (%) with drop size at different
hydr.
)
250
"A"
%
(N
fractions
(PVA
Alcotex
72.5
spec.
rpm).
volume
=
0.1 (ratio)
0.2 (ratio)
0.3 (ratio)
0.4 (ratio)
10-20
0.15
0.24
0.02
0.03
20 - 30
30 - 40
0.75
1.1
0.14
0.18
1.14
1.17
0.41
0.18
40 - 50
1.98
1.14
0.63
0.17
50 - 60
60 - 70
2.67
1.63
1.06
0.45
7.5
2.09
1.83
0.52
70 - 80
80 - 90
9.83
4.13
2.11
0.96
16.89
5.35
3.07
1.57
Di (um)
90 - 100
100-110
17.23
3.73
5.48
1.84
19.54
14.49
4.18
2.18
110- 120
14.67
13.24
6.34
3.68
120- 130
6.28
9.57
10.86
3.15
130- 140
1.98
17.41
10.26
3.97
140 - 150
13.27
12.72
8.2
150- 160
6.08
13.46
6.01
160- 170
2.44
12.49
9.66
170- 180
2.92
4.47
11.53
180- 190
5.28
7.66
190 - 200
15.95
200 - 210
210 - 220
4.63
6.68
220 - 230
230 - 240
3.06
5.23
240 - 250
250 - 260
2.5
260 - 270
270 - 280
256
Table - A2.18 - Variation of volume distribution (%) with drop size at different
volume fractions (PVA Alcotex spec. "A" 72.5 % hydr. ) (N = 350 rpm).
Di ( um)
10-20
0.1 (ratio)
0.2 (ratio)
0.3 (ratio)
0.4 (ratio)
0.27
0.47
0.17
0.11
20 - 30
30 - 40
1.44
1.96
0.82
0.71
2.52
2.53
1.26
1.17
40 - 50
50 - 60
9.34
4.57
2.68
2.49
24.04
6.38
2.68
60 - 70
36.92
14.98
8.09
5.58
70 - 80
80 - 90
23.39
22.38
9.81
7.97
2.06
16.29
10.47
15.48
90- 100
12.64
18.6
15.61
100-110
6.82
17.94
15.4
110-120
4.48
11.78
10.65
120 - 130
2.88
3.03
9.57
130- 140
3.63
1.91
5.17
140- 150
9.45
4.27
150-160
160-170
3.15
170- 180
180- 190
4.43
190 - 200
257
Table - A2.19 - Variation of volume distribution (%) with drop size at different
%
hydr.
)
(N
500
"A"
72.5
fractions
(PVA
Alcotex
rpm).
spec.
volume
=
0.1 (ratio)
0.2 (ratio)
0.3 (ratio)
0.4 (ratio)
10-20
1.94
4.3
0.64
20 - 30
23.7
21.36
12.69
4.02
30 - 40
47.46
29.13
17.74
5.7
40 - 50
50 - 60
26.9
19.35
16.29
9.86
21.19
12.75
18.38
60 - 70
70 - 80
4.66
22.45
19.81
12.93
15.22
80 - 90
3.14
16.61
90 - 100
100-110
1.93
7.83
110-120
Di (um)
Table - A2.20 - Variation of volume distribution (%) with drop size at different
650
%
hydr.
)
(N
"A"
72.5
fractions
(PVA
Alcotex
rpm).
spec.
=
volume
Di ( um)
10-20
0.1 (ratio)
0.2 (ratio)
0.3 (ratio)
0.4 (ratio)
19.88
6.63
2.53
1.74
20 - 30
30 - 40
37.09
35.12
17.79
11.85
33.41
39.04
23.6
18.36
6.6
16.85
34.77
18.81
3.01
2.37
13.53
21.46
60-70
5.15
21.25
70 - 80
80-90
2.64
6.53
40 - 50
50 - 60
Table - A2.21 - Variation of volume distribution (%) with drop size at different
800
hydr.
)
(N
%
"A"
72.5
Alcotex
fractions
(PVA
rpm).
spec.
=
volume
Di ( um)
10-20
0.1 (ratio)
0.2 (ratio)
0.3 (ratio)
0.4 (ratio)
48.66
10.23
6.23
6.57
20 - 30
30 - 40
45.05
38.85
34.43
37.09
6.29
37.42
25.93
26.93
40 - 50
50 - 60
13.5
17.75
19.4
8.53
7.08
60 - 70
2.81
2.92
70 - 80
4.32
80 - 90
258
PVA conc. ( %)
0.002
250 rpm
116.6
350 rpm
500 rpm
650 rpm
800 rpm
99.53
76.32
67.75
55.22
0.005
109.9
69.73
46.31
37.47
34.98
0.01
96.67
67.05
47.1
37.36
28.02
0.015
82.89
59.92
39.08
28.52
26.47
0.02
91.02
60.85
36.1
27.51
21.35
0.1
96
62.03
36.81
30.47
22.98
0.2
91.36
52.69
33.67
26.61
21.27
250 rpm
48.83
350 rpm
500 rpm
650 rpm
800 rpm
44.01
28.47
25.66
22.53
0.05
76.02
48.63
32.79
24.57
21.03
0.1
91.02
60.85
36.1
27.51
21.35
0.2
104.35
71.08
34.96
29.59
27.74
0.3
126.7
85.96
43.54
37.21
31.41
0.4
157.65
91.73
58.22
42.79
30.34
259
APPENDIX
ti = 15 min
0.25
ti = 30 min
0.25
ti = 60 min
0.25
0.47
0.32
0.29
0.29
10 min
0.6
0.49
0.39
0.35
15 min
0.71
0.64
0.44
0.41
30 min
0.78
0.76
0.68
0.62
60 min
90 min
1
1
0.93
1
0.81
1
0.79
1
Residence time
0 min
5 min
0.002 %
0.01 %
0.02 %
0.1 %
0 min
5 min
0.25
0.25
0.25
0.25
0.68
0.6
0.29
0.26
15 min
0.91
0.83
0.41
0.28
30 min
0.86
0.62
0.3
60 min
0.97
0.79
0.65
90 min
120 min
1
1
1
1
1
1
0.84
1
260
500 rpm
350 rpm
250 rpm
0 min
5 min
0.25
0.25
0.25
0.29
0.25
0.25
10 min
0.35
0.29
0.27
15 min
0.41
0.34
0.29
30 min
45 min
0.62
0.36
0.3
0.705
0.38
0.36
60 min
0.79
0.47
0.38
90 min
120 min
150 min
180 min
1
1
1
1
0.63
0.91
1
1
0.51
0.7
0.8
1
Vc
Vc + Vi)
0.25
0.27
10
0.28
15
0.27
30
0.32
45
0.35
60
0.36
90
0.38
120
0.4
150
0.37
180
0.43
210
0.46
240
0.48
(ratio)
261
Table - A4.1 - Variation of PVA adsorbed on VCM droplets with residence time.
Residence time ( min)
0
Initial PVA ( %)
0.02046
0.00238
2.67036
15
0.02046
0.00281
2.76926
30
0.02046
0.00332
2.84358
45
0.02046
0.00367
3.03325
60
0.02046
0.00346
2.7507
90
0.02046
0.00361
2.82272
120
0.02046
0.00365
2.78678
0.02046
Table - A4.2 - Variation of PVA adsorbed on VCM droplets with agitation speed
N(
m)
250
Initial PVA ( %)
0.02
350
0.02
0.00338
2.9507
500
0.02
0.00748
4.3982
650
0.02
0.00864
3.8621
800
0.02
0.01021
3.599
/ m2 )
Table - A4.3 - Variation of PVA adsorbed on VCM droplets with Sauter mean
diameter.
% PVA adsorbed
86
0.02
0.00176
2.2704
58.2
0.02
0.00338
2.9507
39.2
0.02
0.00748
4.3982
29.8
23.5
0.02
0.02
0.00864
0.01021
3.8621
3.599
262
Table - A4.4 - Variation of PVA adsorbed on VCM droplets with the initial
PVA concentration in the continuous phase.
Initial PVA ( %)
0.00199
% PVA adsorbed
0.0014
0.01098
0.00354
3.5577
0.02046
0.00484
3.6953
0.049
0.10378
0.18519
0.005
0.01323
0.01319
3.8175
10.101
10.071
Volume fraction
0.0511
% PVA adsorbed
0.00627
0.057
0.01594
7.5449
0.2
0.064
0.02548
8.5216
0.3
0.073
0.03437
7.9051
0.4
263
0.1
APPENDIX
26.9
20.6
90
34.5
120
61
54
78
82
84
90
60
150
200
250
300
0
5
0.064
0.038
15
0.032
30
0.031
45
0.027
60
90
120
0.02
150
0.023
200
0.016
250
300
0.007
0.003
264
3.4
66.49
7.2
63.41
13
62.95
20.6
60.06
21
59.39
54
40.61
78
23.08
82
24.27
84
23.19
90
19.86
D32 (um)
30
49.12
40
49.33
50
44.21
60
43.28
70
34.87
80
37.14
90
36.57
100
38.1
110
33.55
265
00
a)
00
r1
0
"t
00
r-,
bA
CD
O
n
N
o
cli
N
O
oc
00
.c
N
00
Lr)
C) 0
U
N
"
Q)
E
C
00
r-
In
r-
C
C
C
iii
O
N
O
M
O
t
C
if)
C
C
\1O [l-
C
00
O
C
O
N
O
M
C
't
O
to
o
[-
C
00
O
\,C
266
APPENDIX
Differential Volume
5
4
V
o3
1
u
m
e2
0
0.1
0.2
0.4
1246
10
20
40 60
100
200
400
1000
400
1000
Differential Volume
76
V
0
14
U
m3
C
C-)
21U
,
0.1
0.2
0.4
1246
10
20
40 60
100
200
267
Differential Volume
5-
4-
0
1
u
in
e
3-
2-
1-
0.1
0.2
0.4
10
1246
20
40 60
100
200
40U
1000
Differential Volume
S
V4
0
u3
m
c
/U
1
.10.2
0.4
10
1246
20
40 60
100
200
268
400
1000
Differential Volume
6
5
V4
0
l
u3
m
e
0 -1-------r-0.1
0.2
I0.4
10
1246
2u
4u bu
I uu
Zuu
'+vu
1000
Differential Volume
v
t6
u
m
e4
1)
0.1
ir
0.2
0.4
1246
10
20
40 60
100
200
269
400
1000
Differential Volume
5
v
3
u
m
e2
0
0.1
0.2
0.4
1246
10
20
40 60
100
200
270
400
1000