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TRANSPORT CHARACTERISTICS OF POROUSCELLULOSE ACETATE MEMBRANES FORTHE REVERSE OSMOSIS SEPARATIONOF SUCROSE IN AQUEOUS SOLUTIONS
SHOJl KIMURA’ AND
S.
SOURIRAJAN
Division
of
Applied Chemistry, National Research Council, Ot:awa, Canada
Analysis of the reverse osmosis separation data for the system sucrose-water using a number of Loeb-Sourirajan type porous cellulose acetate membranes shows that the solute transport parameter,
DAM/K8,
forsucrose decreases with increase in its boundary concentration,
XA2.
The plot of log
DA,/K6
vs.
XA2
is
astraight line, and this relationship is independent of the combination of feed concentration and flow rateused, The slope of the above straight line is a function of the operating pressure, and at a given operatingpressure
is
essentially the same for all the membranes tested. For every film, a unique relationship existsbetween
DAM/K6
for sodium chloride and the extrapolated value of
DAM/K6
for sucrose at
XAz
=
0,
givingrise to a new method of expressing membrane selectivity on a relative scale. The predictability of membraneperformance for the reverse osmosis separation of sucrose in aqueous solution and the effect of membranecompaction on solute separation, from the initial specifications of the film given in terms
of
the pure waterpermeability constant and
DAM/K6
for sodium chloride, are illustrated and discussed.
HE
analysis of the reverse osmosis separation data for theTsystems glycerol-water, sodium chloride-water, and severalothers involving inorganic salts
in
aqueous solution using theLoeb-Sourirajan type of porous cellulose acetate membraneshas been reported (Kimura and Sourirajan, 1967
;
Sourirajanand Kimura, 1967). These systems are characterized by thefact that the solute transport parameter,
DA,w/K8,
is indepen-dent of the concentration of the boundary solution at any givenoperating pressure for a wide range of feed molalities and feedflow rates. The system sucrose-water is an example of one forwhich
DAM/K6
is dependent
on
the boundary concentration.This paper discussses the results of the analysis of the reverse
os-
mosis separation data for the system sucrose-water, using theabove type of porous cellulose acetate membranes.
Experimental Details
Reagent grade sucrose and porous cellulose acetate mem-branes (designated here as
CA-NRC-18
type films), made inthe laboratory, were used.These films were cast at -10’
C.
in accordance with the general method described earlier(Loeb and Sourirajan, 1963,
1964;
Sourirajan and Govindan,1967), using the following composition (weight per cent) for thefilm casting solution:acetone
68.0,
cellulose acetate (acetylcontent 39.870)
17.0,
water 13.5, and magnesium perchlorate1.5. The film details, apparatus, and experimental procedurehave been reported (Sourirajan,
1964,
1967;Sourirajan andGovindan, 1965). Membranes shrunk at different tempera-tures were used to give different levels of solute separation at agiven set of operating conditions.The aqueous sucrose solu-tion (feed) was pumped under pressure past the surface of themembrane held in a stainless steel pressure chamber providedwith two separate outlet openings, one for the flow of the mem-brane-permeated solution, and the other for the concentratedeffluent. A porous stainless steel plate, specified to have pores
of
average size equal to 5 microns, was mounted between the
1
Present address, Department
of
Chemical Engineering, Uni-versity
of
Tokyo,
Tokyo,
Japan.pump and the cell to act as
a
filter
for
dust particles whichmight otherwise clog the pores
on
the membrane surface.Unless otherwise stated, the experiments were of the short-run type, each lasting for about 2 hours, and were carried outat the laboratory temperature. A few experiments werecarried out for periods extending continuously up to 7 days.The reported product rates are those corrected to 25’
C.,
using the relative viscosity and density data for pure water.The feed rates used ranged from 120 to 560 cc. per minute,and the feed concentrations ranged from 0.1 to 2.OM. Ineach experiment, the solute separation,
j,
defined asmolality of feed
(ml)
-
molality of product
(ma)
f=
molality
of
feed
(ml)
the product rate,
[PR],
and the pure water permeability,
[PWP],
in grams per hour per 7.6 sq. cm. of effective filmarea were determined at the preset operating conditions.Inall cases, the terms “product” and “product rate” refer to themembrane-permeated solutions. The concentrations of thesolute in the feed and product solutions were determined byrefractive index measurements, using a precision Bausch andLomb refractometer. The accuracy of the separation data
is
within
ly0,
and that of
[PR]
and
[PWP]
data
is
within 3% inall cases. Aqueous sodium chloride (0.5M) feed solutionswere used to obtain transport data for membrane specifica-tions.
Results and Discussion
Osmotic Pressure, Molar Density, Kinematic Viscosity,and Diffusivity Date.
These data, given in Table
I
for thesystem sucrose-water at 25’
C.,
were computed from the wateractivity, density, viscosity, and diffusivity data given in theliterature (Hook and Russell, 1945; Robinson and Stokes,1959; Timmermans, 1960). Similar data for the systemsodium chloride-water have been reported (Kimura andSourirajan,
1968a).
Basic Transport Equations and Correlations.
TheKimura-Sourirajan analysis gives rise to the following basic
548
I&EC PROCESS DESIGN AND DEVELOPMENT
 
Table
1.
Osmotic Pressure, Molar Density, Kinematic Viscosity, and Diffusivity
for
System Sucrose-Water at
25'
C.
Molality
0
0.10.20.30.40.50.60.70.80.9
1
.o
1.21.41.61.82.02.53
.O
3.54.0
Concentration
of
SucroseMole fraction
X
703
0
1.7983.5905.3757.1548.92710.69312.45314.20715.95517.69621.16024.60028.01631.40834.77743.09651.27359.31267.216
Weight,
%
0
3.316.419.3112.0414.6117.0419.3321.5023.5525.5029.1232.4035.3938.1240.6446.1150.6654.5157.79
OsmoticPressure,P.S.I.
0
36731101481862252653053453874705576457348261069132415921866
MolarDensity,Moles/Cc
.
x
102
5.5355.4315.3305.2335.1405.0504.9654.8814.8024.7234.6494,5064.3734.2484.1314.0213.7713.5533.3623.193
KinematicViscosity,Cm
.
/Sec
.
x
102
0.89630.96151 ,03521.11511 ,20531 ,30331.41241.53301.66391.80831.96582.32702.75803.27013.87724,60237.058410.817116.506725,0529
Dz@usivity,Cm
.
/See.
X
706
0.5230.5090.4990.4900.4830.4770.4720.4670.4630.4590.4550.4480.4410.4340.4280.4210.4040.3870.370equations relating the pure water permeability constant,
A,
the transport of the solvent water,
NB,
the solute transportparameter,
DA,/K6,
and the mass transfer coefficient,
k:
[PWPI
A=
M,
X
7.6
X
3600
X
P
(3)
(4)From the
[PWP],
[PR],
and
f
data, the values of
A,
DAM/K8,
and
k
can be calculated for every experiment. Both
A
and
D,,/Kg
are dependent on the porous structure of the mem-brane surface, and hence they are different for different mem-branes; both are functions of operating pressure, and, in addi-tion,
DA,/K8
is dependent on the chemical nature of the solute.While Equations
1
to 4 are general for the reverse osmosisprocess, the correlations of the transport parameters can be dif-ferent for different type of membranes for a given solution sys-tem.
For
the type of membranes used in this work, at a givenoperating pressure, the values of
DA,/'K6
remain essentiallyconstant for a wide range of feed concentrations and feed flowrates for systems such as sodium chloride-water
or
glycerol-water (Kimura and Sourirajan, 1967; Sourirajan and Kimura,1967). Further, the mass transfer coefficient,
k,
is essentially afunction of feed flow rate and feed concentration, and the valuesof
k
for the above systems have been well correlated by a gen-eralized log-log plot of
NR~
us.
N8h/Ns2.3a.
On the basis of theabove correlations, a single set of experimental
[PWP],
[PR],
and
f
data obtained with a system such as sodium chloride-water at any given operating pressure specifies a film in termsof
A
and
DAM/K8
at that pressure.Table
I1
gives the specifica-tions of all the membranes used in this work in terms of
A
and
DAM/K8
for sodium chloride at the specified operating pressure.These specifications are based on the data obtained from short-run experiments and represent the initial characteristics of thefilm.
For
information, the table also includes the temperaturesat which the membranes were shrunk prior to use in the experi-
Membrane Specifications.
Toble
It.
Specifications
of
Porous Cellulose AcetateMembranes Used
Film
No.
292929303030343434111111111113113113114114114115116116116
A
X
706
Film Operating MoleH2OShrinkage Pressure,
Sq.
Cm.Temp.,
'
C. P.S.I.G. Sec. Atm.
86868684848480808086868679.579.579.57878787876.576.576.5500100015005001000150050010001500500
1000
150050010001500500
1000
1500500500100015002.3652.0661.8383.0112.6792.3773.7003.3112.8411.5741.4751.3934.2163.7503.3853.4863.1502.8785.6857.0456.1005.28652.042.940.0109.091.180.7720.1483.1350.02.142.132.12148.6110.094.247.739.535.4524.11183.0770.0604.5men ts
;
these temperatures have no precise significance from thepoint of view of membrane specification.
Experiments with Aqueous Sucrose Solutions.
Theseexperiments were carried out with the membranes specifiedin Table
I1
and using feed solutions in the concentration range
0.1
to
2.OM,
and feed flow rates in the range 120 to 560 cc.per minute at the operating pressures of 500,
1000,
and 1500p.s.i.g. Generally, for a given feed solution and feed molality,increase of operating pressure increases both
f
and
[PR];
for a given operating pressure and feed molality, both
f
and
[PR]
increase with increase in feed rate; and, for a givenoperating pressure and feed rate,
[PR]
decreases and
f
increasesat first and then passes through a slight maximum, with increasein feed molality. Some of these results have been reported(Sourirajan, 1967).
Variation of Solute Transport Parameter
DA,/K6
forSucrose with Boundary Concentration
XA2.
The values of
DA,/K6
and
X,,
calculated from the experimental
[PWP],[PR],
and
f
data for the system sucrose-water using Equations
1,
VOL.
7
NO.
4
OCTOBER
1968 549
 
2,
and
3
are plotted in Figure
1
for operating pressures of
500,
1000,
and
1500
p.s.i.g. for four different films involving soluteseparations in the range
54
to
99%.
These data show that
DAM/K6
for sucrose decreases with increase in
XAz;
the plot oflog
(DAM/K6)
us.
XAz
is
a
straight line and this relationship isindependent of the particular combination of the feed concen-tration and feed
flow
rate used. The slope of the above straightline is a function of the operating press= the higher the oper-ating pressure, the higher is the slope, and at
a
given operatingpressure the slope
is
essentially the same for all the films tested.Consequently, the relationship between the solute transportparameter and the boundary concentration for the systemsucrose-water can be expressed as
150
ALA
-
FILM TYPE
:
CA
-
NRC-
I8
SYSTEM: SUCROSE-WATERFEED MOLALITY:
0.1
to
2.0
M
00
'0
FILM
TYPE
:
CA-NRC-I8SYSTEM
:
SUCROSE-WATER
FEED
MOLALITY
:
0.1
to
2.OM
100
8060
50
0.33
40
30
NS
h
-
NSC
20
FEED RATE
:
120
to
560
OPERATING PRESSURE
cc/minute
0
500
p.r.i.g.
A
1000
p
3,i.g.
0
I500
p.3.i.g.
-
-
-
-
-
-
-
,114
I
II
I
II
IO
20
30
40
50
60
xA2
x
io3
Figure
1.
Variation
of
solute transport parameter forsucrose with its boundary concentration
40
r
I
where
(DAM/K6)
is the extrapolated value of
(DAM/K6)suorose
at
XA2
=
0,
XA2
is the mole fraction
of
sucroseat the concentrated boundary layer calculated from Equations
1
and
2,
and
E
is
a constant which is
a
function of the oper-ating pressure.Figure
2
gives the plot of the average value
of
E
us.
operatingpressure for the data presented in Figure
1.
The
E
values givenin Figure
2
are applicable for the type of membranes used inthis
work
for
XAz
x
lo3
values at least up to
30,
50,
and
70,
respectively, at the operating pressures of
500, 1000,
and
1500
p.s.i.g.Figure
3
relatesthe values
of
(DA,w/K6)NaC1
with those of
(DA,w/K6)*suorose
as afunction of operating pressure for several membranes of differ-ent surface porosities.Such a relationship illustrates
a
newmethod of expressing membrane selectivity on a relative scale,and is a useful way of characterizing different types of mem-branes.
For
the type of membranes used in this work, Figure
3
shows that the log-log plot of
(DA.~/KS)N~CI
US.
(DA,w/K6)
*suorose
is essentially a straight line whose slope depends on the operat-ing pressure.Figures
2
and
3
are useful; they define Equation
5
for any particular membrane whose
(DA.M/K6)NaCl
is
known.
Relative Scale
of
Membrane Selectivity.
1
I
'
II'II
FILM TYPE: CA-NRC-18OPERATING PRESSURE
30
A
34
rn
I13
0
114
0
3
x
t-
(DAM/K~)~,,,-~
cm./sec.
Figure
3.
tems sodium chloride-water and sucrose-waterRelative scale of membrane selectivity for sys-
I5t
IO
I I I
Ill11
I
Ill
I11
20 30 40506080
100
150
200
300
400
600
NR,
Figure
4.
system sucrose-waterExperimental mass transfer coefficient data for
550
I&EC PROCESS DESIGN
AND
DEVELOPMENT
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