(ACS Symposium Volume 154) Albin F. Turbak (Eds.) - Synthetic Membranes - Volume II. Hyper - and Ultrafiltration Uses-American Chemical Society (1981)

Synthetic Membranes:
Volume II
Hyper- and Ultrafiltration Uses
In Synthetic Membranes: Volume II; Turbak, A.;

ACS Symposium Series; American Chemical Society: Washington, DC, 1981.
Synthetic Membranes:
Volume II
Hyper- and Ultrafiltration Uses
Albin F. Turbak, EDITOR

ITT Rayonier Inc.
Based on the 20th Anniversary
Symposium honoring Drs. Loeb and
Sourirajan sponsored by the
Cellulose, Paper, and Textile
Division at the Second
Chemical Congress of the
North American Continent,
Las Vegas, Nevada,
August 25-29, 1980.
ACS SYMPOSIUM SERIES 154
AMERICAN CHEMICAL SOCIETY
WASHINGTON, D. C . 1 9 81

L i b r a r y o f Congress CIP D a t a
Synthetic membranes.
( A C S symposium series, I S S N 0 0 9 7 - 6 1 5 6 ; 153-154)
Includes bibliographies and index.
Contents: v. 1. Desalination—v. 2. Hyper- and ultra-
filtration uses.
1. Membranes (Technology)—Congresses. I. Loeb,
Sidney. II. Sourirajan, S. III. Turbak, A l b i n F . ,
1929- I V . American Chemical Society. Cellulose,
Paper, and Textile D i v i s i o n . V . Series.
TP159.M4S95 660.2'8424 81-1259
I S B N 0 - 8 4 1 2 - 0 6 2 3 - 6 (v. 2 ) AACR2
I S B N 0 - 8 4 1 2 - 0 6 2 5 - 2 (set) A C S M C 8 154 1-474 1981
Copyright © 1981
American Chemical Society

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FOREWORD
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a medium for publishin
format of the Series parallels that of the continuing ADVANCES
I N CHEMISTRY SERIES except that in order to save time the
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PREFACE
T his volume is the result of a symposium honoring Drs. Sidney Loeb

and S. Sourirajan on the 20th anniversary of their discovery of the
first functionally useful reverse osmosis membrane. During this four-day
symposium membrane experts from 13 countries participated in paying
tribute to Drs. Loeb and Sourirajan's pioneering efforts and 55 papers
were presented covering most areas of membrane uses. These included
the salt-rejecting dense membranes for reverse osmosis, which, as Dr. Souri-
rajan noted in his plenary lecture, is really a misnomer and might be
described more accurately as hyperfiltration, and the more porous mem-
branes for ultrafiltration.
The large number o
in two volumes. Volum salt-rejecting
hyperfiltration membranes. Volume II covers hyper- and ultrafiltration
membrane utilization in the following areas: food, medicine, pulp, paper,
and textile industries, oily waste stream purification, and in the separation
of gases, polymers, organic solutes, and biopolymers.
Many of these uses are very significant since they are described from
the point of extensive commercial experience. This is particularly true of
the food, medical, and waste treatment fields. For example, cheese whey
solids that previously were pollution problems are recovered now at the
rate of several hundred tons/day and sold as valuable food. Similarly the
recent advances of hemofiltration over hemodialysis are improving the
quality of life for thousands of patients who suffer from renal failure.
Also pollution abatement by ultra- and hyperfiltration in the pulp, textile,
and steel-processing industries is now a commercial reality for certain
types of waste streams.
As the membrane field continues to expand, specific membranes will
be available to perform an ever-widening series of important functions and
much of the impetus for such expansion will be based on the original
efforts of Drs. Loeb and Sourirajan.
The overwhelming number of papers originally submitted for con-
sideration for this symposium coupled with the outstanding attendance at
the symposium attest to the high esteem in which these two gentlemen are
held by their peers. It was a distinct honor to take part in this 20th anni-
versary tribute. I would like to thank all of the participants for their
wonderful cooperation in making this occasion such a great success.
I.T.T. Rayonier, Inc. ALBIN F . TURBAK
Eastern Research Division

Whippany, NJ 07981 December 24, 1980.
ix

S. Sourirajan, Albin Turbak, and Sidney Loeb

DEDICATION
T wenty years ago two researchers laboring diligently at the University

of California at Los Angeles developed the first modified asymmetric
membranes which seemed to have commercial potential for what was to
become the exciting field that today is known as hyperfiltration or reverse
osmosis. Since that time, these dedicated scientists have given freely of
themselves and their talents not only to further contribute technically, but
also to help guide, teach d trai other t i thi frontie
It is little wonder the
countries throughout the world responded so enthusiastically to the initial
announcement regarding the organization of a symposium to recognize,
honor, and pay tribute to Drs. Sidney Loeb and S. Sourirajan on the 20th
anniversary of their initial contribution.
From the beginning it was apparent that this four-day symposium
covering a seeming myriad of membrane information and uses would be
one of the major events of the Fall 1980 Las Vegas A.C.S. National
Meeting. This symposium, highlighted by plenary lectures from Drs. Loeb
and Sourirajan, had an outstanding attendance. Even on the fourth day
there were still more people attending this symposium than normally are
present for the initial phases of most other sessions. This in itself says
more than anyone could say regarding the universal interest in membranes
and the high esteem in which Sid Loeb and S. Sourirajan are held by their
peers throughout the world.
Today their initial work on the preparation of suitable asymmetric
membranes has touched nearly every aspect of life including uses in water
purification, food technology, biological separations, waste treatment,
medical applications, and bioengineering, and this appears to be just the
beginning.
I know that I speak for all of their many friends when I take this
opportunity to wish Drs. Loeb and Sourirajan continued good health and, if
possible, even more success in their future research and development efforts.
ALBIN F. TURBAK
xi

1
Development of a Tomato Juice Concentration
System by Reverse Osmosis
K. ISHII, S. KONOMI, K. KOJIMA, and M. KAI
Daicel Chemical Industries, Ltd., 1 Teppo-cho, Sakai-shi, 590, Japan
N. UKAI and N. UNO
Kagome Co., Ltd., 3-14-15, Nishiki, Naka-ku, Nagoya-shi, 460, Japan
There have been man

technology to food i n d u s t r i e s
m e r c i a l success except those of d a i r y processes ( 1 ) . DAICEL has
been studying s i n c e 1971 the a p p l i c a t i o n of its cellulose a c e t a t e
RO membranes and polyacrylonitrile UF membranes to food, pharma-
ceutical, m e d i c a l , paper and other i n d u s t r i e s . As t o the use o f
membranes in food i n d u s t r i e s other than d a i r y processes, o n l y two
cases were developed to a semicommercial s c a l e , that is, grape
juice c o n c e n t r a t i o n f o r wine must and tomato juice c o n c e n t r a t i o n
f o r p r o c e s s i n g and storage of the j u i c e till next h a r v e s t .
The RO c o n c e n t r a t i o n of f r e s h fruit j u i c e has two diffcul-
ties. The one is that the h i g h osmotic pressure of fruit juice
prevents c o n c e n t r a t i n g the j u i c e to the r e q u i r e d c o n c e n t r a t i o n ,
and the other is the l o s s of light f l a v o r .
In case o f tomato j u i c e c o n c e n t r a t i o n , the r e q u i r e d product
sugar content is ca. 20%, which i s e x c e p t i o n a l l y low enough to be
a t t a i n e d by RO process. In a d d i t i o n , the l o s s of l i g h t f l a v o r
does not s i g n i f i c a n t l y s p o i l the commercial v a l u e . The expected
advantages of membrane process over c o n v e n t i o n a l evaporation proc-
ess was the improvement of the product q u a l i t y e s p e c i a l l y i n t a s t e
and c o l o r . The major problem was to develop a system which pro-
duces h i g h q u a l i t y condensed j u i c e without adding t o the cost over
that of the c o n v e n t i o n a l process. A j o i n t study s t a r t e d i n 1971
1
at DAICEL s l a b o r a t o r y , and a f t e r three seasons' f i e l d t e s t s a t
Kozakai, F u j i m i and I b a r a g i p l a n t s of Kagome Co., L t d . , a semi-
commercial equipment was b u i l t a t I b a r a g i p l a n t i n 1975. Since
3
then i t has been producing ca. 1 m /hr of concentrated f r e s h t o -
mato j u i c e .
Experimental
Tomato j u i c e . D i l u t e d canned tomato paste was used f o r l a b -

2
o r a t o r y experiments w i t h 28 cm f l a t membrane c e l l s . For f i e l d
t e s t s w i t h t u b u l a r membranes, s t e r i l i z e d f r e s h j u i c e was used.
0097-6156/81/0154-0001$05.00/0
© 1981 American Chemical Society

2 SYNTHETIC MEMBRANES: HF AND UF USES
.Membranes. Three d i f f e r e n t grades of.DAICEL's c e l l u l o s e

acetate RO membranes, DRS-97, DRS-95 and DRS-90 were used both i n
f l a t sheets and tubes. T h e i r NaCl r e j e c t i o n v a l u e s were 97%, 95%
and 90%, r e s p e c t i v e l y .
Apparatus and equipment. For l a b o r a t o r y experiments, two to

2
s i x f l a t membrane c e l l s of 28 cm e f f e c t i v e area and 0.3 mm chan-
n e l t h i c k n e s s were used i n s e r i e s w i t h a plunger pump of v a r i a b l e
2
output up to 50 1/hr under the pressure of up to 100 Kg/cm . For
f i e l d t e s t s , 12 to 192 membrane tubes (1.4 cm i n n e r diameter and
4.5 m by l e n g t h each) were used both i n s e r i e s and p a r a l l e l w i t h
3
one or two plunger pumps of v a r i a b l e output up to 2 m /hr under
2
the pressure of up to 70 Kg/cm . Both a s i n g l e - and a two-stage
system were examined.
Measurement and a n a l y s i s
measured using Tokyokeik
Sodium c h l o r i d e c o n c e n t r a t i o n was measured u s i n g TOA HA5a
e l e c t r i c c o n d u c t i v i t y meter.
Sugar c o n c e n t r a t i o n was determined by reversed phase l i q u i d
chromatograph w i t h a 4.6 mm<j) x 250 mm l e n g t h column of Nagel Nu-
c l e o s i l 5NH2 and a 70% a c e t o n i t r i l e aqueous b u f f e r s o l u t i o n fed
at the r a t e of 1.5 ml/min at 25°C. Shodex RI-SE11 refractometer
was used as the d e t e c t o r .
Amino a c i d s were q u a n t i t a t i v e l y determined u s i n g H i t a c h i KLA5
amino a c i d autoanalyzer w i t h a H i t a c h i Custom 2613 column and
c i t r a t e b u f f e r s o l u t i o n s , pH v a l u e s of which were 3.25 f o r phase
1, then 4.25 and 6.10 f o r phases 2 and 3, r e s p e c t i v e l y . The flow
r a t e of the b u f f e r s o l u t i o n was 1.0 ml/min and t h a t of the r e a -
gent, n i n h y d r i n , was 0.5 ml/min. The measurement was c a r r i e d out
at 55°C.
The sour t a s t i n g organic a c i d s were s e p a r a t e l y measured by
u s i n g Shimadzu t o t a l organic carbon meter.
In f i e l d t e s t s , sugar content was determined by r e f r a c t o m e t r y
and the t o t a l amount of amino a c i d n i t r o g e n was measured by K j e l -
dahl method and the q u a n t i t y of organic a c i d s was determined by
titration.
The c o l o r was measured u s i n g a c o l o r reference meter manufac-
tured by Nippon Denshoku Kogyo, L t d . The t a s t e was examined by a
panel composed of ten s k i l l e d persons.
R e s u l t s and d i s c u s s i o n s
Solute r e t e n t i o n . F i r s t l y , the r e j e c t i o n c h a r a c t e r i s t i c s of
p r i n c i p a l s o l u t e s of tomato j u i c e were measured w i t h three c e l l u -
l o s e acetate membranes of d i f f e r e n t sodium c h l o r i d e r e j e c t i o n s i n
order to determine which grade of the membranes should be em-
ployed f o r the most e f f i c i e n t c o n c e n t r a t i o n . Solute r e j e c t i o n
c h a r a c t e r i s t i c s of three grades of the membranes t e s t e d are l i s t -
ed i n Tables 1, 2 and 3.

1. ISHII E T A L . Tomato Juice Concentration System 3
Table I MEMBRANE PERFORMANCE ON SUGAR AQUEOUS SOLUTION
DRS-•97 DRS--95 DRS--90

SOLUTE FLUX REJ FLUX REJ FLUX REJ.
m/d % m/d % m/d %
NaCl .47 98 .6 1.31 95 .4 1 .71 90.0

GLUCOSE .37 >99 .9 1.31 99 .3 1 .67 97.3
FRUCTOSE .38 >99 .9 1.24 99 .2 1 .64 96.7
D-RIBOSE .36 99 .8 1.13 96 .8 1 .43 91.8
SUCROSE .40 >99 .9 1.33 >99 .9 1 .64 99.3
RAFFINOSE .49 >99 .9 1.34 >99 .9 1 .73 99.6
CONDITIONS:
2
MEMBRANE AREA: 28 cm
CONCENTRATIONS: 0.35%
PRESSURE: 40 Kg/cm
TEMPERATURE: 25°C
The sugar content of raw tomato j u i c e i s about 4.5% R e f r a c -

t i v e Index ( R I ) . The sugar l o s s d u r i n g the c o n c e n t r a t i o n up t o
20% RI must not exceed 5% of the t o t a l sugar contained i n raw
j u i c e . From the r e l a t i o n s h i p between c o n c e n t r a t i o n r a t i o and
s o l u t e r e t e n t i o n shown i n F i g u r e 1, the sugar r e j e c t i o n o f the
membrane to be employed must be over 97%. As l i s t e d i n Table 1,
a l l the membranes t e s t e d has r e j e c t i o n v a l u e s higher than ca. 97%
f o r glucose, f r u c t o s e and sucrose. The curves i l l u s t r a t e d i n
F i g u r e 1 were c a l c u l a t e d from the equation 3 d e r i v e d from mass
balance equation 1 and the r e l a t i o n s h i p between v o l u m e t r i c and
c o c e n t r a t i o n a l condensation r a t i o s 2 assuming that the membrane
r e j e c t i o n i s uniform throughout the whole membrane a r e a .
C 0 V x R e t e n t i o n (%)/100 = CV
0 (1)
R
(C/C ) = ( V / V )
0 0 (2)
R_1 1 1 / R
R e t e n t i o n (%) = 1 0 0 ( V o / V ) = 100(C/C ) "0 (3)
Loss (%) = 100-Retention (%) (4)
where V 0 = i n i t i a l volume
V = f i n a l volume
Co = i n i t i a l concentration
C = f i n a l concentration
R = r e j e c t i o n of the membrane
Table I I demonstrates a l l the membranes t e s t e d have amino

a c i d r e j e c t i o n v a l u e s over ca. 97%.

4 SYNTHETIC MEMBRANES: H F AND U F USES
Table I I MEMBRANE PERFORMANCE ON AMINOACID AQ. SOLN.

SOLUTE CONTENT /PRETENTION
(mg%) DRS-97 DRS-95 DRS-90
SERINE 10.1 99.6 99.1 97.6

VALINE 9.2 99.4 99.0 97.7
ARGININE 6.8 99.7 99.2 97.6
ASPARAGINE 6.6
GLUT AMINE 6.6 99.9 99.6 98.8
GLYCINE 4.8 99.7 98.6 96.5
GLUTAMIC ACID 4.0
PHENYLALANINE 2.4 99.8 98.9 96.7
LEUCINE 2.1 99.8 99.3 97.7
LYSINE 1.9 99.6 99.2 98.1
MEMBRANE AREA: 2
CONCENTRATION: 10-2 mg
pH: 4.2 (ADJUSTED BY ADDING CITRIC ACID)
2
PRESSURE: 40 Kg/cm
TEMPERATURE: 25°C
As f o r sour t a s t i n g o r g a n i c a c i d s , p e r m i s s i b l e l o s s up t o 10%
corresponds t o the membrane r e j e c t i o n of no l e s s than 93% which
w i l l be a l s o f u l f i l l e d by a l l the membranes t e s t e d as shown i n
Table I I I , as more than 90% of the organic a c i d i n tomato j u i c e i s
c i t r i c acid.
Table I I I MEMBRANE PERFORMANCE ON ACID AQ. SOLUTION
DRS--97 DRS--95 DRS--90

SOLUTE FLUX REJ. FLUX REJ. FLUX REJ.
(m/d) (%) (m/d) (%) ' (m/d) (%)
CITRIC ACID .54 98.0 1.50 97.1 1.93 94.5
LACTIC ACID .52 84.3 1.46 70.0 1.89 64.0
2
MEMBRANE AREA: 28 cm
CONCENTRATION: 0.1 wt%
2
PRESSURE: 40 Kg/cm
TEMPERATURE: 25°C
CIRCULATION RATE: 8 ml/min
CHANNEL THICKNESS: 0.3 mm
As t o water f l u x , DRS-90 membrane showed the h i g h e s t value

i n a l l cases; we concluded that DRS-90 i s best s u i t e d f o r m i n i -
mizing the membrane a r e a .
By the way, r e l a t i v e l y low f l u x and r e j e c t i o n v a l u e s
f o r D-ribose represented i n Table I suggest that D-ribose might
have a s p e c i f i c a l l y strong i n t e r a c t i o n w i t h c e l l u l o s e a c e t a t e RO
membranes.

ISHII E T A L . Tomato Juice Concentration System 5
Figure 2. Osmotic pressure of tomato juice

Water f l u x . Secondly, the e f f e c t s of f a c t o r s which were an-

t i c i p a t e d to i n f l u e n c e the membrane performance and the system
e f f i c i e n c y were evaluated. They were the osmotic pressure and
the v i s c o s i t y of tomato j u i c e as the f u n c t i o n of j u i c e concentra-
t i o n and feed v e l o c i t y , and o p e r a t i n g pressure. I t was observed
that the r i s e i n temperature i n c r e a s e s water f l u x .
F i g u r e 2 shows that the osmotic pressure of tomato j u i c e i n -
creases w i t h c o n c e n t r a t i o n . The osmotic pressure of 20%RI tomato
2
j u i c e was about 20 Kg/cm .
F i g u r e 3 i l l u s t r a t e s t h a t water f l u x decreases i n p r o p o r t i o n
to the l o g a r i t h m of j u i c e c o n c e n t r a t i o n . This r e l a t i o n s h i p sug-
gests that tomato j u i c e forms a g e l l a y e r which c o n t r o l s the wa-
t e r f l u x . In order to e l i m i n a t e the i n f l u e n c e of osmotic p r e s -
sure which e x p o n e n t i a l l y r i s e s w i t h j u i c e c o n c e n t r a t i o n , a s e r i e s
of experiments was c a r r i e d out, u s i n g a f l a t UF membrane which
permeates sugars and s a l t completely A i l l u s t r a t e d i Figur
4, water f l u x i s not s i g n i f i c a n t l
s i d e r i n g that t h i s UF membran permeate proportio
2
pressure up to 3 Kg/cm when pure water i s f e d , i t can be sup-
posed that water f l u x of tomato j u i c e i s governed by a g e l l a y e r .
The e f f e c t of j u i c e v e l o c i t y on water f l u x i s demonstrated
i n F i g u r e 5. This e f f e c t i s smaller than a n t i c i p a t e d from the
data shown i n F i g u r e 4. One reason of t h i s discrepancy might be
the d i f f e r e n c e of the tomato j u i c e used. Fresh j u i c e was used to
o b t a i n the r e l a t i o n s h i p summarized i n F i g u r e 5, w h i l e canned t o -
mato paste was used i n d i l u t e d form f o r the experiments shown i n
Figure 4. Another reason might be the d i f f e r e n c e i n flow chan-
n e l s , 1.4 cm i n n e r diameter tube and t h i n f l a t channel of 0.04-
0.06 cm t h i c k n e s s . Although the exact reason i s not c l e a r , the
r e s u l t s i l l u s t r a t e d i n F i g u r e 5 suggest that i t i s not necessary
to feed f r e s h tomato j u i c e at high v e l o c i t y to get h i g h water
flux.
F i g u r e 6 represents the r e l a t i o n s h i p between tomato j u i c e
v i s c o s i t y and f l o w v e l o c i t y . The measurement was done w i t h the
j u i c e prepared from canned paste, u s i n g a d i s c r o t a t i n g v i s c o s i -
meter. The v a l u e , v i s c o s i t y m u l t i p l i e d by v e l o c i t y was n e a r l y
independent of the v e l o c i t y . This suggests that the e f f e c t of
f l o w v e l o c i t y on the pressure drop would be s m a l l . This a l l o w s
the v a r i a t i o n of j u i c e feed v e l o c i t y i n a wide range without s i g -
n i f i c a n t change i n pressure drop.
In F i g u r e 7, the v i s c o s i t y of tomato j u i c e i n c r e a s e s n e a r l y
e x p o n e n t i a l l y w i t h j u i c e c o n c e n t r a t i o n . As a n t i c i p a t e d from the
r e s u l t s shown i n Figure 7, pressure drop r i s e s almost exponen-
t i a l l y w i t h i n c r e a s e i n c o n c e n t r a t i o n when f r e s h tomato j u i c e
was fed i n a t h i n tube of 0.4 cm inner diameter (Figure 8 ) .
System design
I f there were not a pressure drop along w i t h feed f l o w ! I f

so, i t would be easy to concentrate any s o l u t i o n up to the con-

ISHII E T A L . Tomato Juice Concentration System 7
JUICE CONCENTRATION (REFRACTIVE INDEX)
Figure 3. Water flux as a function of tomato juice concentration observed by using

12 membrane tubes. Circulating the juice and discarding the permeate.
KEY VELOCITY(cm/s) THICKNESS(cm)
•
•
37.8
13.9
0.04
0.04
A 2U.U 0.062
• 8.97 0.062
Figure 4. Water flux as a function of

pressure. A UF membrane (DUY-L)
i 2 3 w a
d- s use T n e
cut-off molecular weight
PRESSURE(Kg/cm ) 2
was 5 X 10 daltons.

R1--9.0
5 -3
L
.2
20 30 AO 50 60 80 100 120
JUICE FLOW VELOCITY ( cm/sec )
Figure 5. Effect of tomato juiceflowvelocity on waterfluxobserved by using 12

membrane tubes
KEY RI
24.8
£ •
A 13.5
o • 4.5
6
8
S 4
2 3 4
VELOCITY(cm/sec)
Figure 6. The viscosity of tomato juice decreases in proportion to the reciprocal

of juice velocity. Measured at 20°C by using a disc-rotating viscosimeter.

ISHII E T A L . Tomato Juice Concentration System
Figure 7. The effect of tomato juice concentration on the viscosity observed at

20°C by using a disc-rotating viscosimeter
Figure 8. The effect of tomato juice concentration on the pressure drop of the
juiceflowingthrough 4 mm X 4 mL tube at a velocity of 110 cm/s. Temperature:
24°-30°C.

c e n t r a t i o n l i m i t e d by the osmotic pressure of the feed s o l u t i o n ,

u s i n g a one-through s i n g l e - s t a g e system by simply extending the
feed f l o w l e n g t h . P r a c t i c a l l y , however, e f f e c t i v e pressure goes
down so much that the membrane performance and/or system e f f i -
c i e n c y a r e g r e a t l y decreased, and i t i s necessary to i n s e r t a
second pump i n the long f l o w l i n e and add pressure and v e l o c i t y
to the flow. Some devices t o match the d i v i d e d flows i s necessa-
ry. The l o s s of s o l u t e s can be decreased by r e p l a c i n g the second
stage membrane w i t h that of higher r e j e c t i o n . I n a s o p h i s t i c a t e d
scheme shown i n F i g u r e 9 ( 2 ) , the water f l u x or the o u t l e t con-
c e n t r a t i o n can be r a i s e d by employing a c o n s i d e r a b l y low r e j e c -
t i o n membrane a t the o u t l e t stage, w h i l e the use of a high r e j e c -
t i o n membrane i s r e q u i r e d a t the permeate d i s c a r d i n g stage i n o r -
der t o minimize the s o l u t e l o s s to the permeate.
From the s a n i t a r y p o i n t of view, i t i s necessary to minimize
the number of a r t i c l e s , such as r e s e r v o i r s , pumps, v a l v e s , gages
e t c . , which may cause contaminatio
i f these a r t i c l e s are s a n i t a r
a l s o u n d e s i r a b l e f o r s a n i t a r y reason s i n c e i t y i e l d s the ever-
staying-in-the-system p o r t i o n of the feed j u i c e . A c i r c u l a t i n g
system g e n e r a l l y r e q u i r e s more frequent c l e a n i n g and s t e r i l i z a -
t i o n than a one-through system.
As a l r e a d y been discussed i n the preceeding p a r t of t h i s pa-
per, the water f l u x and the pressure drop are both s t r o n g l y a f -
f e c t e d by the j u i c e c o n c e n t r a t i o n , w h i l e they a r e i n s e n s i t i v e to
the feed f l o w r a t e . The l a t t e r c h a r a c t e r i s t i c a l l o w s to i n c r e a s e
or decrease the feed f l o w v e l o c i t y a t w i l l w i t h s l i g h t change of
water f l u x and pressure drop. This makes i t p o s s i b l e to a t t a i n
the r e q u i r e d o u t l e t c o n c e n t r a t i o n w i t h one-through s i n g l e - s t a g e
system by simply decreasing the feed r a t e . The decrease i n feed
r a t e enhances the r a t i o , water f l u x to feed r a t e , hence r a i s e s
the v o l u m e t r i c c o n c e n t r a t i o n r a t i o as e l u c i d a t e d by equation 5:
(V /V) = V / ( V
0 0 0 - F) = 1/[1-(F/V )] 0 (5)
3
where Vo = feed r a t e (m /hr) = feed v e l o c i t y (m/hr) x cross
2
s e c t i o n (m )
3
V = o u t l e t r a t e (m ) = o u t l e t v e l o c i t y x cross s e c t i o n
3 2 3 2
F = water removal r a t e (m /m hr) = water f l u x (m /m hr)
2
x membrane area (m )
The o n l y p o s s i b l e problem of decreasing the feed r a t e was

whether the t h i c k e n i n g of g e l l a y e r and c o n c e n t r a t i o n p o l a r i z a -
t i o n due to the slow j u i c e speed would r a i s e the osmotic pressure
on the membrane surface as h i g h as the o p e r a t i n g pressure before
the bulk c o n c e n t r a t i o n reaches the r e q u i r e d v a l u e .
A f t e r the o p e r a t i n g c o n d i t i o n s f o r producing 20% RI concen-
t r a t e d j u i c e had been mastered by u s i n g a 12 to 96 tube s i n g l e
pass equipment ( 3 ) , i t was decided to b u i l d a semicommercial sys-
tem c o n s i s t e d of 1440 tubes. The flow diagram of the semicommer-

1. ISHII E T A L . Tomato Juice Concentration System
SINGLE-STAGE
-KE>-
ONE-THROUGH CIRCULATING
TWO-STAGE if
Journal of Applied Polymer Symposia
Figure 9. Four types of concentration systems (2)
STERILIZED FRESH JUICE

i
1 -1.2 m-
A A A A A A A
HEAT
EX. UP TO 92(Ucm0xA.5mL)TUBES/LINE
RESERVOIR 2
72 TUBES(K.Am2) 20 LINES = 288m
x
3
5m/h
3
~T~3£~4 m /h
Figure 10. Flow diagram of the semicommercial equipment built at Ibaragi Plant,
Kagome Co., Ltd

3
c i a l system i s shown i n F i g u r e 10. Approximately 5 m /hr s t e r i -
l i z e d f r e s h j u i c e i s f i r s t cooled to 30°C. R e s e r v o i r i s s e t i n
order to absorb the temporary unbalance of f l o w r a t e s . The j u i c e
i s then d i s t r i b u t e d to 20 l i n e s , each equipped w i t h 72 tubes.
2 3
T o t a l membrane area i s 288 m . About 4 m /hr o f permeate and c a ,
3
1 m /hr of product were expected. I t i s necessary to r i n s e the
outer surface of membrane tubes i n order t o prevent m i c r o b i a l
growth on i t .
Performance of the semicommercial equipment
In order to see how the j u i c e c o n c e n t r a t i o n goes up and how

the pressure and the f l o w v e l o c i t y go down as the j u i c e courses
the 72 tubes, gages and sampling p o r t s were b u i l t i n 2 l i n e s .
T y p i c a l observations are shown i n F i g u r e 11 and 12. Figure 11
demonstrates that the product c o n c e n t r a t i o n r i s e s t o 20% RI b
decreasing the feed v e l o c i t
under the i n l e t pressur Kg/cm
j u i c e was f e d a t 45 cm/sec, the l a s t s e v e r a l tubes h a r d l y con-
t r i b u t e d t o c o n c e n t r a t i o n , perhaps due to both low pressure
caused by pressure drop and h i g h osmotic pressure on the membrane
surface as the r e s u l t of the higher c o n c e n t r a t i o n and lower v e -
locity.
As i l l u s t r a t e d i n F i g u r e 12, the slower the feed v e l o c i t y ,
the more r a p i d l y diminishes the o p e r a t i n g pressure along w i t h the
j u i c e f l o w . This behavior corresponds to the experimental obser-
v a t i o n that the v i s c o s i t y of the j u i c e goes up n e a r l y exponen-
t i a l l y w i t h i n c r e a s e i n c o n c e n t r a t i o n and i t goes down almost i n
p r o p o r t i o n to the r e c i p r o c a l of feed v e l o c i t y . Considering t h a t
the c o n c e n t r a t i o n of the j u i c e s u p p l i e d a t 45 cm/sec h a r d l y r i s e s
i n the l a s t s e v e r a l tubes, the osmotic pressure on the membrane
2
surface can be estimated to be 30 t o 35. Kg/cm . While the osmo-
m e t r i c r e s u l t s shown i n F i g u r e 2 suggests that the osmotic p r e s -
sure of the bulk f l o w j u i c e must be about 20 Kg/cm.
The r e l a t i o n s h i p between water f l u x and j u i c e c o n c e n t r a t i o n
(Figure 13) observed by the semicommercial equipment i s n e a r l y
the same to that observed i n f i e l d t e s t s summarized i n F i g u r e 3.
F i g u r e 14 shows that the j u i c e v e l o c i t y dependance of water
f l u x i s s i m i l a r to that observed by the f i e l d t e s t s .
As i s seen i n Figure 15, the pressure drop rose e x p o n e n t i a l -
l y w i t h i n c r e a s e i n j u i c e c o n c e n t r a t i o n as had been observed i n
the model experiments i l l u s t r a t e d i n F i g u r e 8.
The q u a l i t y of the product i s s u p e r i o r to that of the con-
v e n t i o n a l i n c o l o r and t a s t e as shown i n Table IV.
The r e t e n t i o n of s o l u t e s i s more than r e q u i r e d as l i s t e d i n
Table V.

ISHII E T A L . Tomato Juice Concentration System
JUICE VELOCITY
20 - 20
• • 4 5 - 1 0 cm/sec
O 52-* 1 2
• 59-15
15 O 89*26 15
10
- 5
10 20 30 AO 50 60 70
NUMBER OF MEMBRANE TUBES
Figure 11. Tomato juice concentration observed along the juice flow through 72
membrane tubes at various feed velocities
70 70
60
50
AO
UJ 30 JUICE VELOCITY 30
• • A5*10 cm/sec
O 52*12
£ 20 • 59*15 20
O 89*26
10 - - 10
10 20 30 AO 50 60 70
NUMBER OF MEMBRANE TUBES
Figure 12. Tomato juice pressure observed along the juice flow through 72 mem-
brane tubes at various feed velocities

Figure 13. Water flux as the junction of tomato juice concentration. Semicom-
mercial plant (72 membrane tubes X 20 lines).
Figure 14. Effect of tomato juice flow velocity on water flux. Semicommercial
plant (72 membrane tubes X 20 lines).

1. ISHII E T A L . Tomato Juice Concentration System 15
VELOCITY (cm/sec)
® 300<
Figure 15. The influence of tomato juice

5 10 15 20 concentration on pressure drop (semi-
REFRACTIVE INDEX commercial system)

16 SYNTHETIC M E M B R A N E S : H F A N D U F USES
Table IV THE QUALITY OF RO-CONCENTRATED TOMATO JUICE
COLOR: LIGHTNESS 26 (BETTER)

REDNESS 29
YELLOWNESS 13
RED/YELLOW 2.2 (BETTER)
TASTE: PANEL BETTER
Table V THE SOLUTE RETENTION VALUES OF RO-CONCENTRATED

TOMATO JUICE
SUGARS 97%
ACIDS 92%
AMINO ACIDS 94%
VITAMIN C
Conclusion
Since the semicommercial equipment w i t h 20 l i n e s of 72 tubes

each was b u i l t i n 1975 a t I b a r a g i p l a n t o f Kagome Co., L t d . , i t
3
has been producing 1 m /hr o f 20% RI condensed f r e s h tomato j u i c e
of the q u a l i t y s u p e r i o r to that of the conventional product, w i t h
l i g h t e r and more r e d d i s h c o l o r and b e t t e r t a s t e .
The employment of the one-through s i n g l e - s t a g e system and
some devices f o r s a n i t a r y maintenance prolonged the s t e r i l i z a t i o n
i n t e r v a l and reduced the running c o s t .
Further lowering of the t o t a l cost would be expected by the
off-season use of the equipment.
References
1. S. S o u r i r a j a n (ed.), Reverse Osmosis and S y n t h e t i c Membranes,

p. 417-458, 515, 518, N a t i o n a l Research C o u n c i l Canada, O t t a -
wa, 1977.
H. Ohya (ed.), Maku Riyo G i j u t s u (Membrane A p p l i c a t i o n Tech-
nology) Handbook, p. 221-470, Saiwai Shobo, Tokyo, 1978.
2. R. L. Merson & L. F. Ginnette, J . A p p l . Polym. Symposia, 13,
309-322, 1970.
3. Unexamined Japan Patent No. 52-136942.
RECEIVED December 30, 1980.

2
Membrane Processes in Must and Wine Treatment
1 2
E. DRIOLI, G. ORLANDO, S. D'AMBRA , and A. A M A T I
Istituto di Principi di Ingegneria Chimica, University of Naples, Italy
Membrane processes are one o f the most important s e p a r a t i o n

technologies in food i n d u s t r y . The operate, a t room temperature,
r e q u i r e no a d d i t i o n of chemicals and are gentle and non-destruct
Their potentiality is confirmed by an annual growth r a t e
of 37% (1). However the major area f o r ultrafiltration and reverse
osmosis in food a p p l i c a t i o n s is mainly whey purification, and the
d a i r y i n d u s t r y in g e n e r a l . This market has been estimated of 2
million US d o l l a r s in 1976 and 5 million US d o l l a r s in 1981.
Pressure d r i v e n membrane processes will p l a y an important r o l e in

other areas typical o f the food i n d u s t r y and in the treatment o f
must and wine.
Great progress has been made d u r i n g the last few years in:
a) the development of new membranes w i t h h i g h r e s i s t a n c e t o
s o l v e n t s , pH, temperature, Cl2 e t c .
b) the development of membrane p l a n t e n g i n e e r i n g ;
c) in the b e t t e r understanding of f o u l i n g and membrane deterior
ation.
1
Current address: D'Ambra Vini d'Ischia, Ischia, Italy.
2 Current address: Istituto di tecniche agrarie, University of Bologna, Italy.
0097-6156/81/0154-0017$05.00/0

Wine technology now r e q u i r e s v a r i o u s s e p a r a t i o n techniques which

could p r o f i t a b l y be replaced by membrane processes ( 2 ) .
C e r t a i n enzymes present i n grapes are r e s p o n s i b l e f o r wine

problems such as c l o u d i n g , darkening or an o x i d i z e d t a s t e . To
prevent t h i s , w i n e r i e s r o u t i n e l y t r e a t must and wines w i t h s u l f u r
d i o x i d e . In a d d i t i o n to i t s a n t i m i c r o b i a l a c t i v i t y , SO2 has an
a n t i o x i d a t i v e p r o p e r t y which prevents browning and t a s t e d e f e c t s .
Polyphenoloxidase has d e t r i m e n t a l e f f e c t s on wine q u a l i t y . However
enzymes are a l s o responsable f o r the formation of c e r t a i n d e s r r
able e s t e r s which are e s s e n t i a l to the aroma or bouquet of the
wine.
Methods which reduce the u n d e s i r a b l e e f f e c t s of polyphenoloxid

ases i n c l u d e p r e s s i n g , c e n t r i f u g i n
f i n i n g and thermal treatment (70°C f o r 3 min).
Depending of the type of grapes, the length of fermentation and

the type of wine produced, the f r e s h wine a f t e r r a c k i n g and rough
f i l t r a t i o n may s t i l l be cloudy because of suspended c o l l o i d a l
p a r t i c l e s of grape or yeast components. This cloudiness may remain
f o r a long time. I t i s unusual when a good wine becomes b r i l l i a n _ t
l y c l e a r by n a t u r a l s e t t l i n g . With present technology, such cloudî
ness caused by grape of yeast p r o t e i n s , p e p t i d e s , p e c t i n s , gums,
dextrans unstable grape pigments, tannins e t c . may be removed
from wine by the j u d i c i o u s use of small amounts of f i n i n g agents.
These adsorb or c h e m i c a l l y and p h y s i c a l l y combine w i t h the
c o l l o i d a l p a r t i c l e s or n e u t r a l i z e t h e i r e l e c t r i c charges causing
them to agglomerate and g r a v i t a t e to the bottom. Such treatment
combined w i t h subsequent f i l t r a t i o n c l a r i f i e s the wine. B e n t o n i t e ,
one of the most popular f i n i n g agents i n winemaking, e f f e c t i v e l y
removes p r o t e i n m a t e r i a l s . A c t i v a t e d carbon, g e l a t i n , c a s e i n and
p o l y ( v i n y l p i r r o l i d o n e ) may a l s o be used and a i d i n the removal
of u n s t a b l e tannins and other pigments. U.S. r e g u l a t i o n s however
l i m i t the use of f i n i n g agents. The c l a r i f y i n g agents must not
remain i n the wine.
A f t e r fermentation, wine becomes supersaturated w i t h potassium

b i t a r t r a t e . The removal of t h i s excess i s necessary to avoid
sedimentation a f t e r the wine i s b o t t l e d . A c o l d s t a b i l i z a t i o n
technique where the wine i s c h i l l e d j u s t above i t s f r e e z i n g p o i n t
i s g e n e r a l l y used. P r o t e c t i v e c o l l o i d s , which prevent the c r y s t a l _ l
i z a t i o n of the excess potassium b i t a r t r a t e make a wine r e s i s t e n t
to c o l d s t a b i l i z a t i o n even during prolonged r e f r i g e r a t i o n . In those

2. DRIOLI E T A L . Must and Wine Treatment 19
cases i o n exchange treatment of the wine as been suggested t o

render the e n t i r e l o t of wine potassium b i t a r t r a t e s t a b l e when
blended back (2 ). E l e c t r o d i a l y s i s has a l s o been e x p l o r e d .
The i n h i b i t i o n of m a l o - l a c t i c fermentation can be obtained by SO2

(^30 m g / l i t e r ) , maintainance of storage temperature at l e s s than
18°C and adjustment of pH to at l e a s t below 3.3. K i l l i n g or
removing the b a c t e r i a from wine i s a more d e f i n i t e step t o
s t a b i l i z e wine a g a i n s t m a l o - l a c t i c f e r m e n t a t i o n . P a s t e u r i z a t i o n
and p a r t i c u l a r l y HTST treatment (high temperature, s h o r t time -
98°C f o r one second - w i t h r a p i d c o o l i n g ) i s o f t e n used. S t e r i l e
f i l t r a t i o n has a l s o been used w i t h 0.45ytun membrane f i l t e r s .
In t h i s paper p r e l i m i n a r y experimental r e s u l t s obtained i n a

University-Industry j o i n
t e s t s have been c a r r i e d
w e l l known winery. The aim was to analyze the p o t e n t i a l of u l t r a ,
f i l t r a t i o n and reverse osmosis i n s o l v i n g some of the problems
or i n improving the e x i s t i n g technology i n wine making. A
diagram of the p o t e n t i a l of pressure d r i v e n membranes i n must
treatment i s presented i n f i g . l .
In t h i s paper we w i l l d i s c u s s the experiments on must s t a b i l i z

a t i o n a v o i d i n g SO2 a d d i t i o n , and on the c o n t r o l of polyphenols
and c a t i o n s i n the must. Various polymeric membranes i n d i f f e r e n t
c o n f i g u r a t i o n s have been t e s t e d . The m a j o r i t y of them have alreacfy
been commercially used i n other food or biomedical a p p l i c a t i o n s .
EXPERIMENTAL
A l l the experiments d e s c r i b e d i n t h i s paper have been c a r r i e d out

on white must.
The m a j o r i t y of the u l t r a f i l t r a t i o n (UF) experiments have been

performed u s i n g the l a b o r a t o r y u n i t shown i n f i g . 2 . The apparatus
was constructed to use c a p i l l a r y membranes manufactured by the
Berghof I n s t i t u t e (Tubingen, Germany). The p h y s i c a l p r o p e r t i e s
of the membranes are given i n Table I .
Table I I shows the r e j e c t i o n f o r p r o t e i n s , p o l y p h e n o l s and sugars

measured u s i n g three d i f f e r e n t modulis. The must was f i l t e r e d
through a BMR 500515 modulus ( c u t - o f f 50.000 mw). The permeate
was then u l t r a f i l t e r e d through a BMR 10515 ( c u t - o f f 10.000 mw)
and the permeate from t h i s step was u l t r a f i l t e r e d through a BMR
021.006 ( c u t - o f f 2.000 mw) modulus.

ULTRAFILTRATION
STABILIZED MUST; IDEAL SUB

STRATE FOR SELECTED YEASTS
REVERSE OSMOSIS
NATURAL
DYES
Figure 1. Potentialities for UF and RO in must treatment
rs
M X V
Permeate
n
Figure 2. Schematic of UF equipment: M
B, capillary membrane modulus; S, must
reservoir; M, manometers.

TABLE I
C h a r a c t e r i s t i c s of the f i l t r a t i o n u n i t s .
cut-off tubes membrane max filtration

(MW) diameter area pressure capacity
(mm) (m ) 2
(bar) 2
(l/m h)
1 50.000 1.5 0.5 1.2 300
2 10.000 1.5 0.5 1.2 120
3 2.000
4 18.000 25.4 4.0 150
type : (1) BMR 500515

(2) BMR 100515
(3) BMR 021006
(4) HFM 180
TABLE I I
1 2 3 MUST
c
C
P R%
C
P R%
C
P R% i
(g/lt) (g/lt) (g/lt) (g/lt)
Total
0.129 8 0.118 16 0.118 16 0.140
nitrogen
Total
0.241 9 0.213 19 0.114 57 0.264
polyphen.
Sugar 162 0 162 0 162 0 162

Sugar r e j e c t i o n was always zero. Polyphenol r e j e c t i o n increased

from 9% to 57% w i t h decreasing membrane c u t - o f f . D i f f e r e n c e i n
polyphenol r e j e c t i o n have been observed when the must i s u l t r a
f i l t e r e d i n the f i r s t UF step w i t h the BMR 100515 and a f t e r w i t h
the BMR 021006, as reported i n t a b l e I I I . Fig.3 shows the t y p i c a l
behaviour of the u l t r a f i l t r a t e f l u x observed i n these experiments.
A constant f l u x was g e n e r a l l y obtained a f t e r two hours. Table IV
shows the f i n a l must u l t r a f i l t r a t e f l u x v a l u e s . A l l the
experiments were c a r r i e d out at the same a x i a l v e l o c i t y and at
the same a p p l i e d pressure. Table V shows r e s u l t s obtained w i t h
t u b u l a r membranes (Abcor-USA).
P a r t i c u l a r a t t e n t i o n was devoted to the c o n t r o l of membrane fouling

and membrane c l e a n i n g . A c i d - a l k a l i n
concentration chlorine
i n i t i a l f l u x e s was g e n e r a l l y 50% w i t h the new modulus, and higher
then 95% w i t h a used modulus. These r e s u l t s i n d i c a t e the e x i s t e n c e
of a c e r t a i n i r r e v e r s i b l e f o u l i n g of the new membranes, which come
to steady s t a t e v a l u e s , and does not increase w i t h membrane reuse.
The must u l t r a f i l t e r e d w i t h h i g h f l u x membranes has a l s o been

t r e a t e d w i t h membranes having intermediate or very h i g h r e j e c t i o n
f o r e l e c t r o l y t e s . C e l l u l o s e acetate and polyamide membranes were
used. The Reverse Osmosis apparatus shown i n f i g . 4 was used.
The t e s t s were c a r r i e d out w i t h high a x i a l flow r a t e , s u f f i c i e n t
to promote a t u r b u l e n t regime upstream from the semipermeable
membrane, f o r m i n i m i z i n g c o n c e n t r a t i o n p o l a r i z a t i o n phenomena ( 4 ) .
Table VI shows the r e j e c t i o n measured f o r t o t a l polyphenols

and sugars w i t h DDS 800 and PA 300 membranes. Sugar r e j e c t i o n s
increased from about 20% w i t h DDS 800 to 100% w i t h PA 300. Table
V I I shows the r e j e c t i o n s of v a r i o u s c a t i o n s u s i n g the PA 300
membrane. The r e j e c t i o n f o r the m a j o r i t y of c a t i o n s i s higher
+ + + +
than 97%. Only C u and Z n permeate e a s i l y through the membrane.
The r e j e c t i o n s f o r these two c a t i o n s i s e s s e n t i a l l y zero. The
reason i s a t t r i b u t e d to a h i g h s p e c i f i c i n t e r a c t i o n of Cu and Zn
w i t h the polymeric m a t e r i a l s forming the membranes and to Donnan
equilibrium.
F l u x decay i n the reverse osmosis t e s t has been determined and

minimized u s i n g appropriate f l u i d dynamic regimes. T y p i c a l f l u x
decay w i t h DDS 800 and PA 300 are shown i n F i g u r e 5 and 6. The
feed was must u l t r a f i l t e r e d through BMR c a p i l l a r y membranes.

TABLE I I I
BMR 100515 BMR 021006 MUST

c (g/lt) R% c (g/lt) R% c.(g/lt)
P
Total
0.218 20 0.151 45 0.274
nitrogen
Total
0.674 8 0.618 15 0.731
polyphenol
TABLE IV
Must u l t r a f i l t r a t e fluxes
P = 0.5 atm
T = 20°C
flux
MEMBRANE 2
1/m h
1 30
2 18
3 2,5
TABLE V
Membrane HFM 180

P = 2 atm
T = 25°C
2
J = 20,2 l/m h
c. c R%
I P
Total
741 mg/1 190 mg/1 74
nitrogen
Sugars 18% 18% 0

24 SYNTHETIC MEMBRANES: H F A N D U F USES
TABLE VI
DD S 800 PA 300 FEED
c (g/l)
p R% c (g/D
p
R% c.(g/l)
Total
0.130 52 0.016 94 0.26
Nitrogen
Total
0.243 45 0.012 98 0.51
Polyphenol
Sugars 134
TABLE V I I
Membrane PA 300
P = 34 atm
T = 10°C
c (mg/l)
i c (mg/l)
p R°(%)
N (total)
2 256 16 0.94
Polyphenols 576 12 0.98
Sugars 163 • 1 0 3
// 1.00
+
K 1255 18 0.98
+
Na 77 4 0.95
+ +
Ca 123 4 0.97
+ +
Mg 74 1 0.97
+ + +
Fe 11.5 1.6 0.86
+ +
Cu 0.9 0.9 0
+ +
Zn 2.3 1.9 0.17
Mn + +
0.9 // 1.00

BRM 50 05 15
T = 23 °C
2 0 0 Figure 3. UFfluxas a function of time:

t , min Feed, white must.
PC
V Figure 4. Scheme of RO laboratory ap-

Permeate
paratus: C, membrane cell; S, reservoir;
BT" P, volumetric pump.
80
E 40
Figure 5. Typical flux decay with CA

DDS-800 membranes. Feed: white must
previously ultraflltered through BMR-
200 400 600
100515 modulus; T = 10°C, P = 35
t , h atm.
PA 300
P= 32 atm
Figure 6. Typical flux behavior with

PA -300 polyamide composite membranes.
Feed: white must previously ultraflltered
20 through BMR-021006 modulus; T =
t .h 10°C.

I n t e r e s t i n g e f f e c t s have been observed on the u l t r a f i l t e r e d must

f o r what concerns c o l o r changes and wine s t a b i l i t y . The a n a l y s i s
of these e f f e c t s are s t i l l i n progress i n cooperation w i t h
s p e c i a l i s t i n winemaking.
DISCUSSION AND CONCLUSION.
The r e s u l t s described i n t h i s r e p o r t show some of the uses that

pressure d r i v e n membrane processes o f f e r i n the t r e a t i n g v i r g i n
must.
Polyphenol and p r o t e i n concentrations can be c o n t r o l l e d without
a f f e c t i n g the sugar content. The u l t r a f i l t e r e d must can be
concentrated by reverse osmosis w i t h membranes up to 100% r e j e c t i o n
+ +
f o r sugars. C u and Z n
concentrated must.
F l u x decays and r e j e c t i o n changes i n the UF s t e p s , depending upon

the feed c o n c e n t r a t i o n and experiment h i s t o r y , must be mainly
a t t r i b u t e d to c o n c e n t r a t i o n p o l a r i z a t i o n phenomena w i t h consequent
gel l a y e r formation of the p r e s s u r i z e d membrane s u r f a c e , f o r the
presence of p r o t e i n s , c o l l o i d s and i n general h i g h molecular
species i n the feed ( 3 ) .
LITERATURE CITED
1. Crull A.W., "The e v o l v i n g membrane market" P.041 Business

Communications CO., I n c . , Conn.USA
2. Dinsmoor Webb A., Chemistry of Winemaking", A.C.S. Advances i n
Chem.Series 137, Washington DC (1974)
3. Drioli, E., Dynamically formed and t r a n s i e n t membranes" i n

"Recent Advances in Separation Science", Ed.N.N.Li, v o l . 3 ,
CRC Press I n c . , (1977), p.343
4. Drioli, E., " P o l a r i z z a z i o n e per concentrazione" in "Ricerche

s u l processo ad osmosi i n v e r s a " , Quaderni IRSA, C.N.R.,
vol.22 (1977), p.177.
RECEIVED February 18, 1981.

3
Industrial Application of Ultrafiltration and
Hyperfiltration in the Food and Dairy Industries
OLE JENTOFT OLSEN

D D S - N A K S K O V , Division of the Danish Sugar Corporation, 4900 Nakskov, Denmark
The development s t a r t e
r e s u l t e d in something q u i t
b r a c k i s h water. I am q u i t e c e r t a i n that in those days they d i d not
t h i n k of Feta cheese and low-alcohol beer. I have s e l e c t e d these
products in order to show that membrane filtration is an accepted
process in the food i n d u s t r y and not j u s t a pipe dream of the f u -
t u r e , on which we all based our hopes during the first years of
the process.
Feta Cheese
Feta cheese o r i g i n a t e s from Greece, where it was originally

produced from yew s m i l k . Today it is an important i n g r e d i e n t of
'
the d a i l y d i e t in Southeast Europe and the A r a b i c c o u n t r i e s . I n

these countries the m i l k production i s too low to s u s t a i n a l e v e l
of s e l f - s u f f i c i e n c y w i t h t h i s type of cheese. Consequently s e v e r a l
North European c o u n t r i e s , among them Denmark, have s t a r t e d a com-
prehensive production of Feta cheese f o r export purposes.
The p r i n c i p l e of any cheese production i s that the m i l k p r o t e -
i n s are brought to an i n s o l u b l e form by means of enzymes, the so-
c a l l e d coagulation. Then the coagulated p r o t e i n i s s i f t e d from the
components of the remaining m i l k . These components being water,
s a l t s , l a c t o s e , and the whey p r o t e i n s lactalbumin and l a c t o g l o b u -
l i n . The whey p r o t e i n s c o n s t i t u t e up to 20% of the t o t a l p r o t e i n
content i n m i l k . So these p r o t e i n s are wasted during the process.
The p r i n c i p l e of cheese production by u l t r a f i l t r a t i o n i s that
the p r o t e i n s are concentrated by UF i n the s o l u b l e form, i . e . be-
f o r e the enzyme treatment. The concentration i s c o n t r o l l e d i n such
a way that the composition of the concentrate as regards f a t , pro-
t e i n , s a l t s and water, i s equivalent to the composition of the f i n -
ished cheese. I t i s at t h i s point the enzyme i s added, causing the
cheese to set i n the form, i n t o which i t has been poured. The whey
p r o t e i n s , which were p r e v i o u s l y wasted during the t r a d i t i o n a l pro-
cess, remain i n the f i n i s h e d cheese, r e s u l t i n g i n increased pro-
d u c t i o n and t h e r e f o r e higher p r o f i t s . I s h a l l r e v e r t to t h i s l a t e r .
0097-6156/81/0154-0027$05.00/0

Standardized Ultrafiltration Concentrate Pasteurization

Pasteurized 39.5 % T S Homogenisation
Milk 16.4 % Protein C u r d l i n g «- Rennet
17.8 % Fat
12.5 % T S
3.4 % Protein Permeate S o u r i n g -• 2-3 % whey
3.5 % fat 5.
+ salt
43.0 % T S
22.0 % Proteins
17.5 % Fat
3 % Salt
Figure 1. The UF process for feta cheese
Milk Fat Cheese Sales price

tons/day tons/day tons/day $/day
Traditional
300 41 73,800
method
Ultrafiltration
300 1.8 57 102,600
method
Extra Yield 16 28,800
Fat addition -=-6,700
Operation Costs -f 3,900
Profit by
the UF process 18,200
Figure 2. Economy in feta cheese production by UF

3. OLSEN Food and Dairy Industries 29
Figure 3. 0rum Plant
. . . . . . ~ . Unsoluble
Precipitation Drying—.....
Milkprotem
in. »• %
r • Soluble
Ultrafiltration Drying— ....
Milkprotem
-Ultrafiltration + Diaf iltration Drying—Whey-Protein
Sweet Whey-
Ultraf iltration Concentrate—Drying—Whey-Protein
Permeate
-Crystallization—Drying—Lactose
Acid W h e y
Acid Whey Ultrafiltration Drying—
Protein
Figure 4. UF of whey

SYNTHETIC MEMBRANES: H F AND U F USES
Figure 5. Denmark proteins (outside)
Figure 6. Denmark proteins (inside)

Figure 1 shows, how u l t r a f i l t r a t i o n i s incorporated i n the

process.
Today a l l Danish d a i r i e s producing Feta cheese, w i t h one ex-
c e p t i o n , base t h e i r production on u l t r a f i l t r a t i o n . The l a r g e s t of
these i n s t a l l a t i o n s , b u i l t i n 1977, i s today t r e a t i n g 300,000
m e t r i c tons m i l k d a i l y . Investment i n UF p l a n t s amounts t o approx.
1 m i l l . $. The economical s i d e of the matter i s as f o l l o w s (see
Figure 2 ) . Indeed, a notable increase i n p r o f i t s as a r e s u l t of
the work c a r r i e d out at UCLA i n 1960 and followed-up by DDS i n
1965.
Figure 3 shows the DDS UF-plant at the above mentioned Feta
cheese f a c t o r y . I t comprises a t o t a l of 20 DDS UF modules, type
35, each w i t h 27 m^ (approx. 297 f t ^ ) membrane area. The membrane
a p p l i e d i s o f s y n t h e t i c m a t e r i a l w i t h a nominal c u t - o f f value o f
2Q,000. The p l a n t can operate round the c l o c k , and the c l e a n i n g
time i s approx. 2 hour 24 hours Th c l e a n i n i c a r r i e d
out w i t h a s o l u t i o n of
s o l u t i o n of hot 0.3% n i t r i y
w i t h C l ^ . The membrane l i f e time i s approx. 1 year.
Proteins
The i n t r o d u c t i o n of membrane f i l t r a t i o n i n connection w i t h

d a i r y production has r e s u l t e d i n a wide range of new p r o t e i n en-
r i c h e d products of which the whey p r o t e i n s have a t t r a c t e d the
l a r g e s t amount of a t t e n t i o n .
F i g u r e 4 shows a few of the d i f f e r e n t products which are pro-
duced today.
The l a r g e s t d a i r y company i n Denmark, c a l l e d "Dairy Denmark"
i s , as f a r as I know, the most p r o g r e s s i v e one i n the world today
w i t h regards t o the production of whey p r o t e i n s by means of u l t r a -
f i l t r a t i o n . Figure 5 i s a photo of a q u i t e new p r o t e i n f a c t o r y ,
c a l l e d "Denmark P r o t e i n s " , whose s o l e purpose i s t o u l t r a f i l t r a t e
1,000 m e t r i c tons of whey per day f o r the p r o d u c t i o n of approx.
10 m e t r i c tons pure whey p r o t e i n i n powder form, and as a by-pro-
duct approx. 50 m e t r i c tons of l a c t o s e . The p l a n t was put i n t o
o p e r a t i o n i n May, 1980.
Up t i l l now nothing has been r e l e a s e d concerning the t o t a l
economy of the p l a n t , but I am convinced that "Dairy Denmark"
have made sure that the economy i s sound.
The essence of t h i s p l a n t i s of course the UF p l a n t i t s e l f ,
which i s shown i n Figure 6. I t i s a DDS plant of the same type as
at the Fe£a cheese d a i r y , c o n s i s t i n g of 45 modules, type 35, each
w i t h 42 m (452 f t ^ ) membrane area. The p l a n t i s f u l l y automatic,
c o n t r o l l e d by micro processors and i n t e g r a t e d i n a s u p e r i o r t o t a l
c o n t r o l of the whole f a c t o r y .
The p r i n c i p l e of the p l a n t c o n s t r u c t i o n i s shown i n F i g u r e 7.
I f a higher p u r i t y i s d e s i r e d than achieved by normal u l t r a f i l t r a -
t i o n , water may be added during the process ( d i a f i l t r a t i o n ) . I n
t h i s way more i m p u r i t i e s w i l l pass through the membranes.

-
f-Preconcentration—j Diafiltration—j— com!. 1
Feed
_tank
module
£ nil f If
Booster
pump
Feedpump
seo^p
Figure 7. Continuous UF Plant (principle)
Figure 8. Br<f>rup, HF of whey in Denmark

tons vapour kg fuel kWh

per ton water removed
Evaporation of whey
0.18 13.8 53.2
5 % TS - 20 % TS
Hyperfiltration of whey 6.8
5 % TS — 20 % TS
Saving in % 88
Figure 10. HF plant for removal of alcohol

Figure 11. Development center in the dairy industry (outside)
Figure 12. Development center in the dairy industry (inside)

OLSEN Food and Dairy Industries
Figure 13. DDS-NAKSKOV

The product composition, i . e . the p r o p o r t i o n between p r o t e i n

and l a c t o s e i n the f i n a l product, may be c o n t r o l l e d from the cen-
t r a l c o n t r o l room. Thus the f a c t o r y i s able to produce p r o t e i n
powder w i t h compositions v a r y i n g from approx. 35% p r o t e i n of t o -
t a l s o l i d s to approx. 85% p r o t e i n of t o t a l s o l i d s . The f i r s t men-
t i o n e d i s a product w i t h a composition l i k e cheap skim-milk pow-
der, whereas the l a t t e r i s an expensive product used f o r baby-
food and d i e t e t i c food.
Concentration of Whey
Today d i r e c t c o n c e n t r a t i o n of whey i s known and accepted as

an exceedingly a t t r a c t i v e supplement o r a l t e r n a t i v e to evapora-
tion.
2
F i g u r e 8 shows a t y p i c a l DDS RO plant c o n s i s t i n g of 14 19 m
2
(205 f t ) modules equipped w i t h membranes of c e l l u l o s e a c e t a t e
not v e r y d i f f e r e n t fro
tons are t r e a t e d d a i l y
F i g . 9 shows a comparison of the energy consumption by eva-
p o r a t i o n and h y p e r f i l t r a t i o n (also c a l l e d reverse osmosis).
Removal o f the A l c o h o l i n Beer
A new f i e l d i s the removal of a l c o h o l i n beer by means of

h y p e r f i l t r a t i o n . "De forenede B r y g g e r i e r " - perhaps b e t t e r known
under the names Tuborg and C a r l s b e r g - have developed a process
f o r removal of the a l c o h o l i n beer by means of the DDS h y p e r f i l -
t r a t i o n system. The advantages w i t h t h i s are that the a l c o h o l per-
centage may be adjusted according to the d i f f e r e n t marketing areas
- without having to change the brewing process.
Figure 10 shows a DDS p l a n t f o r the h y p e r f i l t r a t i o n of Beer.
DDS Development
I n order to emphasize how much we expect of the f u t u r e DDS

has b u i l t a new d a i r y f o r development purposes. The main o b j e c t s
being product and process development based on membrane f i l t r a -
t i o n i n the food i n d u s t r y . The d a i r y i s shown i n Figures 11 and
12.
DDS-Nakskov
F i g u r e 13 shows the DDS p r o d u c t i o n plant i n Denmark f o r mem-

brane f i l t r a t i o n equipment. Around 250 people are working i n t h i s
ever expanding company.

4
Fouling in Whey Reverse Osmosis
B. R. SMITH
CSIRO Division of Chemical Technology, P.O. Box 310,
South Melbourne, Australia 3205
Reverse osmosis, although originally developed f o r water des-

alination ( 1 ) , has bee
c o n c e n t r a t i o n problems
wastewaters, pulp and paper waste streams ( 4 ) , food processing
liquids ( 5 ) , and d a i r y wastes ( 6 ) .
Whey is a highly polluting waste stream (BOD5 about 40,000
ppm) from cheese and casein manufacture. Historically, whey has
been disposed of by feeding it to p i g s , by u s i n g it as a fertili-
ser, or by dumping it in sewers and watercourses. With i n c r e a s i n g
environmental c o n t r o l s , there is now more i n t e r e s t in whey utiliz-
ation. For whey c o n c e n t r a t i o n , reverse osmosis is attractive i n
that the process operates a t ambient temperatures, so that the
f u n c t i o n a l p r o p e r t i e s of the whey p r o t e i n s are l e s s a f f e c t e d and,
of course, the energy consumption is lower than f o r alternative
processes.
One of the important f a c t o r s determining the process econom-
ics is the f l u x d e c l i n e that is caused by a b u i l d - u p of whey com-
ponents a t the membrane s u r f a c e . It is the aim of t h i s paper t o
review the a p p l i c a t i o n of reverse osmosis to whey p r o c e s s i n g , and
in particular, to d i s c u s s the problem of membrane f o u l i n g .
Whey P r o p e r t i e s
There a r e two types of whey, c l a s s i f i e d (7) according t o

source: ( i ) "sweet" whey, which i s d e r i v e d from the manufacture of
products i n which rennet-type enzymes a r e used t o coagulate m i l k
(e.g. Gouda and Cheddar cheeses), and which has a minimum pH of
5.6, and ( i i ) " a c i d " whey, which i s d e r i v e d from acid-induced co-
a g u l a t i o n (e.g. cottage cheese and c a s e i n ) , and which has a maxi-
mum pH o f 5.1.
T y p i c a l concentrations of the major c o n s t i t u e n t s i n each type
of whey a r e l i s t e d i n Table I (8) :
0097-6156/81/0154-0037$05.00/0

Table I
HC1 c a s e i n whey Cheddar cheese whey
l a c t o s e , g/1 51.4 48.7

p r o t e i n , g/1 7.3 6.5
non-protein N, g/1 0.18 0.23
c i t r i c a c i d , g/1 1.93 1.56
calcium, g/1 1.11 0.47
phosphorus, g/1 0.78 0.54
pH 4.47 6.25
The osmotic pressure o
Whey P r o d u c t i o n
The s c a l e of whey production i s i l l u s t r a t e d i n Table I I

(summarized from reference 9 ) , which l i s t s the q u a n t i t i e s of whey
produced i n v a r i o u s c o u n t r i e s i n 1977 :
Table I I ( U n i t s : k i l o t o n n e s )
Country Sweet whey A c i d whey Total
U.S.A. 13,720 1,920 15,640

Canada 1,210 158 1,368
Australia 788 420 1,208
New Zealand 785 1,282 2,067
E.E.C. 22,800* 2,200* 25,000*
*1978 f i g u r e s , approximate only
In A u s t r a l i a , New Zealand and I r e l a n d , where d a i r y c a t t l e a r e

pasture-fed, whey production i s h i g h l y seasonal; the peak monthly
production may be up to twice the average monthly p r o d u c t i o n .
This r e s u l t s i n a lower p l a n t u t i l i z a t i o n i n whey processing i n
these c o u n t r i e s , and consequently greater emphasis on process
efficiency.
Membrane Processing of Whey
The development of commercial u l t r a f i l t r a t i o n equipment has

made recovery of the whey p r o t e i n s economically f e a s i b l e , and a
number of uses f o r the remaining l a c t o s e (the p r i n c i p a l BOD source)

4. SMITH Fouling 39
have been suggested i n an attempt to achieve complete u t i l i z a t i o n

of the whey s o l u t e s . Concentration of the whey (or whey u l t r a -
f i l t r a t e ) i s g e n e r a l l y necessary at some stage, perhaps p r i o r to
t r a n s p o r t to a c e n t r a l processing f a c i l i t y , or p r i o r to evaporat-
i o n , or to produce a concentrate which can be used d i r e c t l y .
S e v e r a l commercial whey reverse osmosis i n s t a l l a t i o n s are i n op-
e r a t i o n (10), notably i n Northern Europe where e s c a l a t i o n i n f u e l
costs has been a major f a c t o r , de Boer et a l . (11) have shown
that reverse osmosis i s more economic than evaporation up to a
volume r e d u c t i o n of 75%.
Reverse osmosis was f i r s t proposed as a method f o r the con-
c e n t r a t i o n of l i q u i d foods some f i f t e e n years ago (12), and s i n c e
that time, numerous s t u d i e s have been reported on aspects of the
u l t r a f i l t r a t i o n and reverse osmosis of whey. A common observat-
i o n has been the d e c l i n e i n f l u x r a t e through the membrane that
occurs during operation due to the accumulation of f o u l i n g l a y e r s
on the membrane surface
Membrane F o u l i n g Studies on Whey
Lim et a l . (13) s t u d i e d the reverse osmosis of cottage cheese

whey and showed that only part of the f o u l i n g l a y e r could be remo-
ved w i t h f l u i d shear, and that c a s e i n was the major component of
that which remained. The l a t t e r f i n d i n g was a s c r i b e d to the lower
d i f f u s i o n c o e f f i c i e n t of c a s e i n r e l a t i v e to the other s o l u t e s .
The f l u x r a t e s under v a r i o u s c o n d i t i o n s were used to c a l c u l a t e the
h y d r a u l i c r e s i s t a n c e s of the v a r i o u s l a y e r s , f o l l o w i n g the appr-
oach of Markley et a l . ( 1 4 ) ; these c a l c u l a t i o n s showed that the
r e s i s t a n c e of the f o u l i n g l a y e r was f i v e times the r e s i s t a n c e of
!
the membrane at low feed v e l o c i t i e s (Reynold s Number = 1500),
whereas i t was l e s s than the r e s i s t a n c e of the membrane at higher
feed v e l o c i t i e s (Reynold's Number = 5,900). The authors pointed
out that f o u l i n g of the membrane surface would r e t a r d d i f f u s i o n of
the m i c r o s o l u t e s , and so increase the m i c r o s o l u t e c o n c e n t r a t i o n
p o l a r i z a t i o n . F o u l i n g thus reduced f l u x r a t e s by c o n t r i b u t i n g an
added h y d r a u l i c r e s i s t a n c e , and by reducing the e f f e c t i v e d r i v i n g
f o r c e f o r water permeation through the membrane.
In an attempt to d i r e c t l y measure the amount of m a t e r i a l i n
the f o u l i n g l a y e r , Dejmek et a l . (15) studied the u l t r a f i l t r a t i o n
of 1^1 i - l a b e l l e d c a s e i n . A very slow accumulation a t the mem-
brane surface was observed, superimposed on the expected changes
due to feed flow r a t e , a p p l i e d pressure, e t c .
Lee and Merson (16) s t u d i e d the e f f e c t s of chemical t r e a t -
ments of cottage cheese whey on membrane f o u l i n g i n u l t r a f i l t r a t -
i o n . By examining the deposits obtained w i t h scanning e l e c t r o n
microscopy, they were able to c o r r e l a t e f l u x r a t e s w i t h the nature
of the deposits on the membrane. Calcium s e q u e s t r a t i o n gave
increased f l u x r a t e s , as d i d r a i s i n g the i o n i c s t r e n g t h of the
whey; these r e s u l t s i n d i c a t e d that f o u l i n g could be minimised by
d i s p e r s i n g the whey p r o t e i n s , and so preventing t h e i r d e p o s i t i o n
on the membrane.

More r e c e n t l y , Hiddink et a l . ( 6 ) , s t u d i e d the reverse

osmosis of Gouda cheese whey, and concluded that the f l u x - l i m i t -
ing f a c t o r s were the osmotic pressure of the feed, and membrane
f o u l i n g . F o u l i n g by p r o t e i n was observed w i t h d e i o n i z e d whey, 'and
w i t h whey that had been adjusted to pH 4.6; i n both cases, the
f o u l i n g was seen as a consequence of the lower s t a b i l i t y of the
whey p r o t e i n s r e s u l t i n g i n aggregation a t the membrane s u r f a c e .
Calcium phosphate d e p o s i t i o n was a l s o noted i f Gouda whey (pH 6.6)
was concentrated at 30 C over a concentration r a t i o of 1.6 : 1.
This source of f o u l i n g could be removed e i t h e r by exchanging the
calcium i n the whey f o r sodium, or by s l i g h t l y lowering the pH of
the whey.
As noted by Matthews (17), the s t u d i e s on membrane f o u l i n g
published so f a r would suggest that some of the p r o t e i n components
causing f o u l i n g are a f f e c t e d by such f a c t o r s as pH, i o n i c s t r e n g t h
and i o n i c composition ( p a r t i c u l a r l y calcium c o n c e n t r a t i o n )
I n t e r a c t i o n s between th
shown by P e r i and Dunkle
osmosis of s o l u t i o n s of whey components showed l i t t l e i n d i c a t i o n
of f o u l i n g ; only whole whey gave a steady d e c l i n e i n f l u x r a t e
w i t h time.
Whey Pretreatments t o Reduce F o u l i n g
The p o s s i b i l i t y of p r e t r e a t i n g the whey before membrane

processing to reduce f o u l i n g may be commercially a t t r a c t i v e ,
provided that the product p r o p e r t i e s , such as the f u n c t i o n a l i t y of
the p r o t e i n s , a r e not d e t r i m e n t a l l y a f f e c t e d . For whey u l t r a f i l -
t r a t i o n , pretreatment methods have been developed t o remove the
l i p i d f r a c t i o n (19, 20) which i n v o l v e f l o c c u l a t i o n and g r a v i t y
settling.
Hayes et a l . (21) s t u d i e d the e f f e c t s of pH v a r i a t i o n on the
u l t r a f i l t r a t i o n of Cheddar cheese and HC1 c a s e i n wheys. Their
e a r l i e r work had shown that both wheys gave low f l u x r a t e s a t pH
4.1 - 4.4, and high f l u x r a t e s below pH 3. F l u x r a t e s improved
f o r Cheddar cheese whey above pH 5, but there was l i t t l e improve-
ment w i t h HC1 c a s e i n whey. Heat treatment (80 C f o r 15 seconds)
of the c a s e i n whey followed by pH adjustment to an optimum between
5.2 and 5.9 r e s u l t e d i n marked decrease i n f o u l i n g . Demineraliz-
a t i o n o f , or EDTA a d d i t i o n t o , HC1 c a s e i n whey a l s o gave higher
f l u x r a t e s . These r e s u l t s were explained i n terms of a balance
between ( i ) a heat-induced i n t e r a c t i o n of c a s e i n w i t h $ - l a c t o g l o b -
u l i n and calcium, which formed aggregates which d i d not f o u l the
membrane, and ( i i ) i n c r e a s i n g calcium phosphate p r e c i p i t a t i o n as
the pH was r a i s e d , which would lead to lower f l u x r a t e s .
Smith and MacBean (22) a p p l i e d the pretreatments developed by
Hayes e t a l . (21) t o the reverse osmosis of HC1 c a s e i n and Cheddar
cheese wheys, but found that an i n c r e a s e i n f o u l i n g occurred com-

4. SMITH Fouling 41
pared to untreated whey. I t was a l s o found that the r a t e of f l u x

d e c l i n e decreased i f the whey was demineralized and increased i f
sodium c h l o r i d e was added. The r a t e of f l u x d e c l i n e was much
higher f o r HC1 c a s e i n whey than f o r Cheddar whey. These r e s u l t s
have been supported by those of Matthews et a l . (23) f o r the rev-
erse osmosis of u l t r a f i l t r a t e s from p r e t r e a t e d whey.
Hickey ( 8 ) , f o l l o w i n g on from the e a r l i e r A u s t r a l i a n work
(21, 22), c a r r i e d out d e t a i l e d l a b o r a t o r y s t u d i e s on the reverse
osmosis and u l t r a f i l t r a t i o n of HC1 c a s e i n and Cheddar cheese wheys
i n order t o c h a r a c t e r i z e the membrane f o u l i n g i n these systems.
Again, pretreatments i n v o l v i n g combinations of heat, pH a d j u s t -
ments, and calcium or c i t r a t e a d d i t i o n s l e d t o e s s e n t i a l l y oppo-
s i t e e f f e c t s i n reverse osmosis compared to u l t r a f i l t r a t i o n . This
was p a r t i c u l a r l y evident w i t h HC1 c a s e i n whey. For untreated HC1
c a s e i n whey, a minimum occurs i n the curve of permeation r a t e
versus pH. This l i k e l t r e f l e c t th i s o e l e c t r i p o i n t f th
f o u l i n g p r o t e i n s , as unde
s o l u b l e , and hence l i k e l y layer highe hyd
r a u l i c r e s i s t a n c e . A s i m i l a r f l u x minimum at the i s o e l e c t r i c
p o i n t has been reported f o r the u l t r a f i l t r a t i o n of g e l a t i n s o l u t -
ions by Akred et a l . (24). I n the reverse osmosis experiments,
the f l u x minimum occurred a t a higher pH than i n the u l t r a f i l t r a t -
i o n experiments; t h i s can be explained i n terms of the higher
i o n i c s t r e n g t h and/or l o c a l calcium concentration i n the reverse
osmosis boundary l a y e r causing a s h i f t i n the i s o e l e c t r i c p o i n t of
the f o u l i n g p r o t e i n s to a more a l k a l i n e pH value.
Membrane F o u l i n g Models
Merten et a l . (25) found that the simple r e l a t i o n s h i p
A ( l o g f l u x r a t e ) = constant x A ( l o g time ) (1)
described the f l u x d e c l i n e due to membrane compaction. The same

r e l a t i o n s h i p has been used s a t i s f a c t o r i l y to express f l u x d e c l i n e
r a t e s due to membrane f o u l i n g i n the reverse osmosis of such feed
streams as r i v e r water (26, 27) , decondary sewage e f f l u e n t (_3, 28)
and whey (22). I n s e v e r a l t h e o r e t i c a l s t u d i e s of membrane f o u l i n g
k i n e t i c s , equations c o n t a i n i n g exponential forms have been der-
i v e d ; i t i s l i k e l y that equation (1) i s simply an e m p i r i c a l appr-
oximation to these more complex r e l a t i o n s h i p s .
B l a t t et al.(29) developed what has become known as the " g e l
p o l a r i z a t i o n " theory f o r u l t r a f i l t r a t i o n , i n which the amount of
macromolecular m a t e r i a l i n the f o u l i n g l a y e r i s c o n t r o l l e d by i t s
b a c k - d i f f u s i o n r a t e i n t o the feed stream. The gradual d e c l i n e i n
f l u x observed i n some p r a c t i c a l systems was explained i n terms of
an i r r e v e r s i b l e c o n s o l i d a t i o n of the g e l l a y e r w i t h time, l e a d i n g
to a r e d u c t i o n i n the l a y e r ' s p e r m e a b i l i t y . Kimura and Nakao (2)
used B l a t t ' s approach to model the f o u l i n g of reverse osmosis

membranes by the suspended s o l i d s i n i n d u s t r i a l wastewater, and

were a b l e to -correlate t h e i r experimental r e s u l t s w i t h the d e r i v e d
equations. More r e c e n t l y , Gutman (30) extended the "turbulence
b u r s t " model f o r p a r t i c l e re-entrainment from a smooth impermeable
w a l l to f o u l i n g of reverse osmosis membranes. Both of these a n a l -
yses showed that the f l u x d e c l i n e depended on the f l u x of the un-
f o u l e d membrane, the mass t r a n s f e r c o e f f i c i e n t of the f o u l a n t and
i t s c o n c e n t r a t i o n , the feed v e l o c i t y , and the d e n s i t y and s p e c i f i c
h y d r a u l i c r e s i s t a n c e of the f o u l i n g l a y e r .
An e f f e c t not considered i n the above models i s the added
r e s i s t a n c e , caused by f o u l i n g , to s o l u t e b a c k - d i f f u s i o n from the
boundary l a y e r . F o u l i n g thus increases c o n c e n t r a t i o n p o l a r i z a t i o n
e f f e c t s and r a i s e s the osmotic pressure of the feed adjacent to
the membrane s u r f a c e , so reducing the d r i v i n g f o r c e f o r permeat-
i o n . T h i s f a c t o r was explored e x p e r i m e n t a l l y by Sheppard and
Thomas (31) by covering reverse osmosis membranes w i t h uniform
permeable p l a s t i c f i l m s
i v e model to c o r r e l a t e
s t u d i e d the c o n c e n t r a t i o n p o l a r i z a t i o n caused by the build-up of
r u s t f o u l i n g l a y e r s on reverse osmosis membranes but assumed (and
confirmed by experiment) that the r u s t l a y e r had n e g l i g i b l e hyd-
raulic resistance.
A f u r t h e r c o m p l i c a t i o n a r i s e s when the f o u l a n t c a r r i e s a
f i x e d charge, such as whey p r o t e i n i n s o l u t i o n s w i t h pH s i g n i f i c -
a n t l y d i f f e r e n t from the i s o e l e c t r i c p o i n t . Under these c o n d i t -
i o n s , the f o u l i n g l a y e r a c t s as a p o l y e l e c t r o l y t e membrane i n
s e r i e s w i t h the reverse osmosis membrane, and changes i n the s a l t
c o n c e n t r a t i o n at the surface of the reverse osmosis membrane would
be expected.
Conclusions
Membrane f o u l i n g i n the reverse osmosis of whey i s c l e a r l y a

complex phenomenon, because of the range of s o l u t e s present -
p r o t e i n s , l a c t o s e and s a l t s - and t h e i r i n t e r a c t i o n s w i t h each
other. Few d e t a i l e d s t u d i e s have been reported, and although some
i n s i g h t s can be gained from work on f o u l i n g i n u l t r a f i l t r a t i o n ,
a d d i t i o n a l f a c t o r s must be considered. The c o n d i t i o n s i n the fou-
l i n g l a y e r are, of course, somewhat d i f f e r e n t i n reverse osmosis
than i n u l t r a f i l t r a t i o n . The a p p l i e d pressure i s an order of
magnitude g r e a t e r , and t h i s may a f f e c t p r o t e i n i n t e r a c t i o n s ( 3 3 ) .
Probably more s i g n i f i c a n t l y , the i o n i c s t r e n g t h i n the f o u l i n g
l a y e r w i l l be considerably higher because of the r e j e c t i o n of low
molecular weight s o l u t e s by the membrane and the r e d u c t i o n i n the
d i f f u s i o n r a t e away from the membrane surface caused by the pres-
ence of the f o u l i n g l a y e r . I n p a r t i c u l a r , more h i g h l y r e j e c t e d
s o l u t e s such as calcium, phosphate, and l a c t o s e w i l l have higher
concentrations i n the f o u l i n g l a y e r r e l a t i v e to l e s s w e l l r e j e c t e d
s o l u t e s such as monovalent i o n s . P r e c i p i t a t i o n of calcium phos-
phate i n the f o u l i n g l a y e r i s t h e r e f o r e a p o s s i b l e e x p l a n a t i o n f o r

4. SMITH Fouling 43
the observed f o u l i n g (22), p a r t i c u l a r l y w i t h HC1 c a s e i n whey be-

cause o f i t s higher calcium content.
A l t e r i n g the s t a t e of aggregation of the f o u l i n g m a t e r i a l by
pretreatment of the whey caused l i t t l e change i n the reverse osmo-
s i s f l u x r a t e s . This r e s u l t , together w i t h the e f f e c t s of demin-
e r a l i z a t i o n or s a l t a d d i t i o n mentioned above, would suggest that
the f l u x - d e t e r m i n i n g process i n the reverse osmosis of whey i s the
c o n c e n t r a t i o n p o l a r i z a t i o n which i s increased by the presence of
the f o u l i n g l a y e r . The aggregates formed by the pretreatment
procedure, w h i l s t forming a more water-permeable f o u l i n g l a y e r as
shown by the u l t r a f i l t r a t i o n r e s u l t s , do not lead to a s i g n i f i c -
a n t l y greater b a c k - d i f f u s i o n r a t e of s o l u t e from the membrane
surface.
I t seems t h e r e f o r e , that the e s t a b l i s h e d procedures i n v o l v i n g
h i g h feed v e l o c i t y across the membrane s u r f a c e , a d d i t i o n a l t u r b u l -
ence promotion, e t c . , need to be a p p l i e d and optimized There i s
a need f o r a model f o
ates such f a c t o r s as th
by the f o u l i n g l a y e r , and Donnan e x c l u s i o n e f f e c t s due to charged
f o u l a n t s . C l e a r l y there i s scope f o r more d e t a i l e d experimental
work i n t h i s area.
Literature Cited
1. Loeb, S.; and S o u r i r a j a n , S; Sea water d e s a l i n a t i o n by means

of a semi-permeable membrane U.C.L.A. Dept. of Eng. Report
No. 60-60, 1960.
2. Kimura, S.; and Nakao, S-I.; D e s a l i n a t i o n , 1975, 17, 267.
3. W i n f i e l d , B.A.; Water Research, 1979, 13, 561.
4. Jonsson, G.; and K r i s t e n s e n , S.; D e s a l i n a t i o n , 1980, 32, 327.
5. Kennedy, T.J.; Monge, L.E.; McCoy, B.J.; and Merson, R.L.;
A.I.Ch.E. Symposium S e r i e s , 1973, 69, (132), 81.
6. Hiddink, J . ; de Boer, R.; and Nooy, P.F.C.; J. D a i r y Science
1980, 63, 204.
7. I n t e r n a t i o n a l Dairy Federation; Standards of identity f o r
whey powders, Report D-Doc. 1978, 49.
8. Hickey, M.W.; Hill, R.D.; and Smith, B.R.; N.Z.J. D a i r y . Sci.
Tech., 1980, 15, 109.
9. Z a l l , R.R.; Kuipers, A.; M u l l e r , L.L.; and M a r s h a l l , K.R.;
N.Z.J. D a i r y Science and Technology, 1979, 14 ( 2 ) , 79.
10. E r i k s s o n , P.; Nordeuropaesk Mejertidsskrift, 1977, 43, 238.
11. de Boer, R.; de Wit, J.N.; and Hiddink, J . ; J. Soc. D a i r y
Technol., 1977, 30, 112.
12. Morgan, A.J.; Lowe, E.; Merson, R.L.; Durkee, E.L.;
Food Technol., 1965, 19, 52.
13. Lim, T.H.,; Dunkley, W.L.; and Merson, R.L.; J . Dairy Sci.,
1971, 54(3), 306.
14. Markley, L.L.; Cross, R.A.; Bixler, H.J.; Hunter, J.A.;
G i l l m a n , W.S.; and Johnson, S.; U.S. Dept. of the Interior,
O f f i c e of S a l i n e Water, Res. Dev. Report No. 281, 1967.

15. Dejmek, P.; H a l l s t r o n , B.; K l i m a , A.; and Winge, L;

Lebensm.-Wiss. u. Technol., 1973, 6 (1), 26.
16. Lee, D.N.; and Merson, R.L.; J . Food Science, 1976, 41, 778.
17. Matthews, M.E.; N.Z.J. D a i r y Sci. and Technol., 1979, 14(2),
86.
18. P e r i , C.; and Dunkley, W.L.; J . Food Science, 1971, 36, 25.
19. de Wit, J.N.; Klarenbeck, G.; de Boer, R.; Proc. 20th I n t .
D a i r y Congress 1978, E, 919.
20. A t t e b e r y , J.M.; U.S. Patent 3 560 219, (2/2/71).
21. Hayes, J.F.; Dunkerley, J.A.; M u l l e r , L.L.; and Griffin,
A.T.; Aust. J . D a i r y Technol., 1974, 29, 132.
22. Smith, B.R.; and MacBean, R.D.; Aust. J . D a i r y Technol., 1978
33(2), 57.
23. Matthews, M.E.; Doughty, R.K.; and Short, J.L.; N.Z.J. D a i r y
S c i . Tech., 1978, 13, 216.
24. Akred, A.R.; Fane A.F.; and F r i e n d J.P.; Proc A.C.S
Symposium on Ultrafiltration
Washington, 1979.
25. Merten, U.; Lonsdale, H.K.; R i l e y , R.L.; and Voss, K.O.; U.S.
Dept. of the Interior, O f f i c e of S a l i n e Water, Res. Dev.
Report No. 265, 1967.
26. Sheppard, J.D.; Thomas, D.G.; and Channabasappa, K.C.;
D e s a l i n a t i o n , 1972, 11, 385.
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1977, 15(2), 193.
28. Wechsler, R.; Water Research, 1977, 11, 379.
29. B l a t t , W.F.; D r a v i d , A.; M i c h a e l s , A.S.; and Nelson, L.; i n
Membrane Science and Technology, ed. J.E. Flinn, Plenum Press
p.47, 1970.
30. Gutman, R.G.; The Chemical Engineer, 1977 No. 322, 510.
31. Sheppard, J.D.; and Thomas, D.G.; A.I.Ch.E. J o u r n a l , 1971,
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5
Development of a Cellulose Acetate Membrane and
a Module for Hemofiltration
M . K A I , K . ISHII, Z. H O N D A , and H . T S U G A Y A
Daicel Chemical Industries, Ltd., 1 Teppo-cho, Sakai-shi 590, Japan
M . M A E K A W A , T. K I S H I M O T O , and S. Y A M A G A M I
Osaka City University Medical School, 1-5-7 Asahi-machi, Abeno-ku,
Osaka-shi 545 Japan
Since Henderson opene gat applicatio

of ultrafiltration t o r e n a l failure as an alternative to hemodi-
alysis and p e r i t o n e a l dialysis, the ultrafiltration o f blood, he-
mofiltration, has been i n c r e a s i n g l y attracting both clinical and
pathological interest. I n the course of h e m o f i l t r a t i o n s t u d i e s ,
it has been amply confirmed that t h i s new therapy is effective
f o r treatment o f hemodialysis-difficulties p a t i e n t s who a r e not
compatible w i t h hemodialysis due t o s e r i o u s syndrome. Various
s t u d i e s are being under way concerning the mechanistic differ-
ences between h e m o f i l t r a t i o n and hemodialysis.
In hemodialysis the t r a n s p o r t of plasma s o l u t e s through mem-
brane is c o n t r o l l e d by c o n c e n t r a t i o n gradient and diffusion co-
efficient. Since diffusion coefficient decreases w i t h molecular
weight, the whole blood clearance (the amount o f removed s o l u t e
in u n i t time d i v i d e d by the s o l u t e c o n c e n t r a t i o n in the blood)
sharply diminishes w i t h molecular weight as illustrated in Figure
1 (1). I n h e m o f i l t r a t i o n , on the other hand, removal of s o l u t e s
is almost independent o f molecular weight up t o the c u t o f f molec-
u l a r weight o f the membrane. This d i f f e r e n c e in the clearance
f o r s o l u t e s l a r g e r than uric a c i d is r e l a t e d t o the f a c t that he-
mofiltration i s effective f o r hemodialysis-difficulties patients.
For h e m o f i l t r a t i o n t o be effective, the total amount o f blood wa-
t e r t o be ultrafiltered i n one treatment is 20 t o 23 liters de-
pending on p a t i e n t s ' c o n d i t i o n s . To complete each treatment i n
f i v e hours, h e m o f i l t e r , UF module f o r h e m o f i l t r a t i o n , i s r e q u i r e d
to permeate 66 t o 77 ml/min of water. None of h e m o f i l t e r s so f a r
in use meet this requirement. D a i c e l and Osaka C i t y U n i v e r s i t y
Medical School s t a r t e d a joint study t o develop a practically
more f e a s i b l e h e m o f i l t e r . The r e q u i r e d p r o p e r t i e s f o r a new he-
m o f i l t e r are s p e c i f i e d i n Table 1. I t is t o be noted i n Table 1
that UFR, ultrafiltration r a t e , i s not l e s s than 70 ml/min.
0097-6156/81/0154-0045$05.00/0

Table 1 REQUIRED PROPERTIES FOR A NEW HEMOFILTER
UFR >70 ml/min
2
Transmembrane Pressure £300 mmHg/cm
Permeation, of which <lxlO if

100%
molecular weight i s : >5xlO k
<0.1%
Priming volume
£100 ml
(Blood h o l d i n g volume)
R e s i d u a l blood volume <1 g
Blood c o m p a t i b i l i t y
Chemical s t a b i l i t y
Reasonable cost
Membrane development
So f a r as membrane performance i s concerned, an UF membrane

s u i t a b l e f o r h e m o f i l t r a t i o n could have been r e a d i l y developed out
of a s e r i e s of a c r y l o n i t r i l e copolymer UF membranes being s o l d by
D a i c e l . The cyano group i n a c r y l o n i t r i l e , however, suggested
that i t would be more d e s i r a b l e t o develop new membrane of other
m a t e r i a l s . C o n s i d e r i n g the requirements l i s t e d i n Table 1, c e l -
l u l o s e acetate was s e l e c t e d as a membrane m a t e r i a l among other
candiate polymers such as, p o l y s u l f o n e , polycarbonate, and other
c e l l u l o s i c s . More s p e c i f i c a l l y , c e l l u l o s e d i a c e t a t e was the ma-
t e r i a l f o r our e x t e n s i v e s t u d i e s . C e l l u l o s e d i a c e t a t e i s i n n e r t
to human blood, r e s i s t a n t t o s t e r i l i z i n g agents, m e c h a n i c a l l y
strong and i n e x p e n s i v e . I n a d d i t i o n , c e l l u l o s e d i a c e t a t e w i t h
i t s moderately p o l a r nature, h y d r o p h i l i c and hydrophobic proper-
t i e s and i t s s o l u b i l i t y i n a wide v a r i e t y of s o l v e n t s makes i t an
a t t r a c t i v e m a t e r i a l f o r s u p e r i o r membranes of v a r i o u s k i n d s . Of
course, the advantage of having some experiences i n h a n d l i n g t h i s
m a t e r i a l would be h e l p f u l i n the course of the development.
In order t o o b t a i n i n a v e r y short time an optimum c a s t i n g
dope composition which produces a membrane of r e q u i r e d perform-
ance, a guide l i n e l i s t e d i n Table I I was e s t a b l i s h e d , based on
our p r e v i o u s experience of membrane r e s e a r c h . M i x t u r e s of h i g h
and low b o i l i n g , water m i s s i b l e s o l v e n t s f o r c e l l u l o s e acetate
were employed as s o l v e n t s f o r dope. As f o r a d d i t i v e s to the dope

5. KAI E T A L . Hemofiltration 47
were employed mixtures of water and organic s o l v e n t s of l i m i t e d

water s o l u b i l i t y .
Table I I GUIDELINE TO AN OPTIMUM CASTING DOPE COMPOSITION
1. Cellulose diacetate c a . 13%

2. Mixed s o l v e n t : c a . 57%
2.1 Low b o i l i n g , water m i s s i b l e solvent
f o r CDA (eg. Acetone)
2.2 High b o i l i n g , water m i s s i b l e solvent
f o r CDA (eg. DMF)
3. Mixed a d d i t i v e : c a . 30%
3.1 P a r t i a l l y water s o l u b l e solvent
f o r CDA (eg
S w e l l i n g agen
l o s o l v e acetate)
3.2 Nonsolvent f o r CDA
(eg. Water, a l c o h o l s , g l y c o l s )
Experimental
Membrane p r e p a r a t i o n . Membranes were formed on p o l y e s t e r

c l o t h under the c o n d i t i o n s shown i n Table I I I by c a s t i n g a dope,
evaporating a p o r t i o n of s o l v e n t s , then immersing i n t o c h i l l e d
water.
Table I I I CASTING CONDITIONS
Dope i s c a s t c o n t i n u o u s l y on p o l y e s t e r c l o t h by
c a s t i n g machine.
As cast t h i c k n e s s 150 microns

C a s t i n g speed 5 cm/sec
Evaporation p e r i o d 30 sec
Evaporation temperature 27°C
Precipitant Water
Bath temperature 2°C
E v a l u a t i o n of membranes and modules. Membranes were e v a l u -

2
ated i n t h i n channel f l a t c e l l s of 25 cm e f f e c t i v e membrane area
and 200 micron channel t h i c k n e s s at the mean flo w v e l o c i t y of 1.3
2
x 1 0 cm/sec. A 0.2% ovalbumine aqueous s o l u t i o n was used w i t h
marker s o l u t e s d i s s o l v e d i n i t . Modules were t e s t e d by using the
same s o l u t i o n , bovine blood i n v i t r o and subsequently w i t h l i v i n g
dog under v a r i o u s flo w r a t e s , pressures, temperatures and p r o t e i n
concentrations.

A n a l y s i s . Ovalbumine (4.8 x 10 D a l t o n ) , bovine albumine

1 lf
(6.8 x 10 *), canine albumine (>6xl0 ), urea (60), c r e a t i n i n e
(113) and v i t a m i n B (1355) were q u a n t i t a t i v e l y determined e i -
1 2
ther by high performance GPC u s i n g Shodex Ionpack S-803 column or

by h i g h performance l i q u i d chromatography using Nagel N u c l e o s i l
7C-18 column. I n u l i n was measured by r e s o r c i n o l - t h i o u r e a c o l o r -
imetry a f t e r other saccharides were removed by yeast fermenta-
t i o n . Solvents i n g e l a t i o n b a t h water were determined u s i n g FID
gas chromatography (JEOL, JGC-20K) w i t h ethylene g l y c o l s u c c i -
nate-chromosorb W-AW column a t 150°C
Abbreviations.
NB n i t r o benzene
AP - acetophenone
IP - isophorone
BL - butyl lactat
CHX - cyclohexanon
FF - furfural
MEK - methyl e t h y l ketone
CA - c e l l o s o l v e acetate
Y-BL - y-butyrolactone
EL - ethyl lactate
DA - diacetone a l c o h o l
NMP - N-methyl p y r r o l i d o n e
DMF - NN-dimethyl formamide
CS - cellosolve
R e s u l t s and d i s c u s s i o n s
In Figures and Tables, values of water f l u x and ovalbumine

permeation are normalized t o the standard values f o r the purpose
of compensating f l u c t u a t i o n of i n d i v i d u a l experiments.
E f f e c t s of a d d i t i v e s . The r e s u l t s are summarized i n F i g u r e

2 i n terms of water s o l u b i l i t y of a d d i t i v e solvent and membrane
performance evaluated w i t h 0.2% ovalbumine aqueous s o l u t i o n . The
2 2
water f l u x r i s e s very s t e e p l y from zero t o 8.8xl0 ml/min.m i n
correspondence w i t h i n c r e a s e i n the water s o l u b i l i t y of a d d i t i v e
solvent from 1 t o 4 g / d l . Contrary t o the f a c t that the water
f l u x curve has a p l a t e a u f o r the a d d i t i v e water s o l u b i l i t y l a r g e r
than 4 g / d l , the ovalbumine permeation values f o r some water mis-
s i b l e a d d i t i v e s o l v e n t s are u n d e s i r a b l y higher than those f o r ad-
d i t i v e s o l v e n t s , of which water s o l u b i l i t y i s i n the range from
4 to 20 g / d l .
F i g u r e 3 i l l u s t r a t e s that membrane t h i c k n e s s i n c r e a s e s con-
s i s t e n t l y w i t h water s o l u b i l i t y of a d d i t i v e s o l v e n t s .
F i g u r e 4 shows the r e l a t i o n s h i p between membrane performance

S O L U T E MOLECULA
Journal o
Clinical Medicine weight (I)
CASTING DOPE COMPOSITION(WT7.)

CDA 13
AT 28
DMF 29
CA„
ADDITIVE -5
X 15 ~MErV
. WATER 15 CHX
BL DMF
t z
o
DA
CS
-2
NMP 2
EL! ZD
CHX
NB AP IP TBL
0 LOHV-
0.2 0.5 5 10 50 100
SOLUBILITY (g/dl at 20 *c)
Figure 2. Relationship between membrane performance and water solubility of

additive solvents: (0,%) solubility of additive solvents in water; (A, A) solubility
of water in additive solvents. Water flux is normalized to the standard value of 8.8
2 2
X 10 mL/min • m and ovalubumine permeation is normalized to the standard
value of 0.66%.

SYNTHETIC MEMBRANES: H F AND U F USES
Figure 3. Membrane thickness vs. water solubility of additive solvents
12-
1.0
0.8
.0.6
- OA
^0.2
20 30 40 50 60 70 80
MEMBRANE THICKNESS ( P )
Figure 4. Relationship between membrane performance and membrane thickness

and membrane t h i c k n e s s . Membranes from 30 to 60 microns i n t h i c k -

ess give h i g h water f l u x as w e l l as s u f f i c i e n t l y low ovalbumine
permeation f o r m a i n t a i n i n g the albumine l o s s under the r e q u i r e d
l e v e l . The membrane t h i c k n e s s from 30 to 60 microns are g i v e n by
the a d d i t i v e s o l v e n t s , of which water s o l u b i l i t y ranges from 4 t o
20 g / d l .
E f f e c t s of component r a t i o i n c a s t i n g dope. Among p a r t i a l l y

water s o l u b l e o r g a n i c s o l v e n t s which gave membranes from 30 to 60
microns i n t h i c k n e s s , cyclohexanone was chosen as the standard
a d d i t i v e solvent f o r s t u d i e s v a r y i n g c a s t i n g dope component r a -
t i o s . In Figure 5, each curve r e p r e s e n t s each r e l a t i o n s h i p be-
tween membrane performance (water f l u x and ovalbumine permeation)
and cyclohexanone content i n a given amount of a d d i t i v e s o l u t i o n
(cyclohexanone aqueous s o l u t i o n ) . As seen i n Figure 5, water
f l u x decreases v e r y r a p i d l y w i t h i n c r e a s e i n cyclohexanone con
tent over ca. 60%. On
observed i n ovalbumine
low permeation v a l u e s are o b t a i n a b l e o n l y i n the range of 40 t o
60% cyclohexanone content when the t o t a l amount o f the a d d i t i v e
s o l u t i o n was from 20 to 30% of the c a s t i n g dope.
S i m i l a r behavior was observed i n the r e l a t i o n s h i p between
membrane t h i c k n e s s and cyclohexanone content as shown i n F i g u r e
6. The membrane t h i c k n e s s comes to a minimum where permeation
has the lowest v a l u e . Scanning e l e c t r o n microscope s t u d i e s on
membrane s u b s t r a t e s t r u c t u r e revealed that a change from a f i n e l y
pored sponge s t r u c t u r e to a c o a r s e l y pored f i n g e r s t r u c t u r e oc-
curs at the p o i n t where the membrane t h i c k n e s s turns to go up
w i t h i n c r e a s e i n cyclohexanone content as a l r e a d y shown i n Figure
6.
Role of p a r t i a l l y water s o l u b l e a d d i t i v e s o l v e n t s . There

have been p u b l i s h e d many s t u d i e s on the membrane f o r m a t i o n mech-
anism and the e f f e c t s of s o l v e n t s , a d d i t i v e s ( s w e l l i n g agents o r
poreformers) and p r e c i p i t a n t s . Membrane performance and morphol-
ogy are w e l l c o r r e l a t e d to polymer p r e c i p i t a t i o n r a t e i n nascent
membrane (_2) . Low p r e c i p i t a t i o n r a t e g e n e r a l l y produces mem-
branes of f i n e l y pored sponge s u b s t r a t e s t r u c t u r e w i t h low s o l u t e
permeation. Remarks on s o l v e n t - p r e c i p i t a n t i n t e r a c t i o n by
Frommer et a l . (3) i s h e l p f u l to s p e c u l a t i o n on membrane forma-
t i o n . In the f o l l o w i n g paragraphs i s d i s c u s s e d the r o l e of p a r -
t i a l l y water s o l u b l e solvent as a p l a s t i c i z e r of nascent membrane
matrix.
As shown i n Figure 5, the v e r y steep drop of water f l u x c o r -
responding to the r i s e of cyclohexanone content higher than 0.6
was caused e i t h e r by decrease i n water or by i n c r e a s e i n c y c l o -
hexanone. In order to see which of these two components governs
t h i s sharp drop of water f l u x , numerical data on these descending
l i n e s are summarized i n Table IV.

52 SYNTHETIC M E M B R A N E S : H F AND U F USES
Figure 5. Membrane performance

cyclohexanone content in the
solution. Numbers attached
indicate the amount of additive solutions 0 0.2 0.4 0.6 0.8 1.0
in weight percent of dope. CHX/CHX*H 0
2
1 30 -
110
100
90
_L_
0,2 0.4 0.6 O.S
CHX/(CHX+WATER)
Figure 6. Membrane thickness vs. cyclohexanone content in the additive solution

of 25 wt % of dope

5. KAI E T A L . Hemofiltration
Table IV NUMERICAL DATA ON CYCLOHEXANONE AND WATER
FOR CYCLOHEXANONE/WATER >2
Additive Cyclo- Cyclo- Water Permea-

Solution hexanone Water hexanone/ flux tion
(%) (%) (%) water (-) (-) (-)
10 7 3 2.3 1.06 2.2
20 15 5 3.0 0.80 6.5
30 20 10 2.0 0.34 3.3
I t i s remarkable i n Table IV, that water f l u x decreases w i t h i n -

crease i n water. T h i s means the water f l u x promoting e f f e c t o f
water as the o n l y nonsolvent f o r c e l l u l o s e a c e t a t e contained i n
the c a s t i n g dope was suppressed by the c o e x i s t e n c e of p a r t i a l l y
water s o l u b l e s o l v e n t , cyclohexanone.
Increase of water i n the c a s t i n g dope a c c e l e r a t e s phase sep
a r a t i o n i n the e a r l y stage of g e l a t i o n and i n c r e a s e s the number
of and decreases the s i z e of p r e c i p i t a t i n g polymer cores. A cer
t a i n amount of water, t h e r e f o r e , i s necessary to o b t a i n a f i n e l y
pored membrane w i t h low s o l u t e p e r m e a b i l i t y ( 4 ) . T h i s e x p l a i n s
why the minimum permeation v a l u e f o r 10% a d d i t i v e i s more than
twice those f o r 20 to 30% a d d i t i v e s . A t the same time, however,
the nascent polymer cores seem to r a p i d l y l o s e f l e x i b i l i t y r e -
s u l t i n g i n the f i x a t i o n of the membrane m a t r i x at a r e l a t i v e l y
e a r l y stage of g e l a t i o n and thus g i v i n g a broad pore s i z e d i s t r i
b u t i o n . The nascent membrane m a t r i x , however, i s l i k e l y to keep
f l e x i b i l i t y to the r e l a t i v e l y l a t e stage of g e l a t i o n by the ex-
i s t e n c e o f cyclohexanone, a p o r t i o n of which may be l e f t p a r t i -
t i o n e d to the p r e c i p i t a t e d polymer phase due to i t s l i m i t e d s o l u
b i l i t y i n water. Thus, enhanced polymer f l e x i b i l i t y a c c e l e r a t e s
the polymer network to c o n t r a c t so as to make i n t e r s t i c e s o r
pores narrow enough to r e j e c t the passage of ovalbumine. I n -
crease i n water content, t h e r e f o r e , r e q u i r e s the augmentation o f
cyclohexanone and the both i n g r e d i e n t s work s y n e r g i s t i c a l l y .
However, i f the cyclohexancne content exceeds a c e r t a i n l e v e l ,
i . e . , 1.5 times of water, e x c e s s i v e c o n t r a c t i o n of h i g h l y s o l v -
ated polymer networks occurs l e a d i n g to c o l l a p s e of the i n t e r -
s t i c e s . A t the same time, t h i s c o n t r a c t i o n of nascent membrane
m a t r i x would cause the f o r m a t i o n of some s p e c i f i c chasms or v o i d
and make them l a r g e enough to pass ovalbumine f r e e l y . In sub-
s t r a t e where polymer c o n c e n t r a t i o n i s c o n s i d e r a b l y lower than
that o f s k i n l a y e r , tendency to c o n t r a c t i o n of polymer network
n e c e s s a r i l y y i e l d s numbers of l a r g e s i z e d v o i d s , and hence, r e -

Figure 7. Membrane cross-section for cyclohexanone content of 32 wt % of addi-

tive solution

tive solution

KAI E T A L . Hemofiltration

tive solution
Figure 10. Membrane cross-section for cyclohexanone content of 60 wt % of

additive solution

SYNTHETIC M E M B R A N E S : H F AND U F USES
Figure 11. Membrane cross-section for cyclohexanone content of 68 wt % of

additive solution
3.5
3.0
x 2.5
5
j 2.0
1 5
5
X
o
£ 1.0
D
O.JT-
_J_L_ • • •i
0.5 1 3 5 7 10
IMMERSION TIME UPSE(<Kin)
Figure 12. Ratio of total extracted amount of DMF to that of cyclohexanone nor-
malized to the ratio of initial contents in the casting dope The casting dope is
composed of 13 wt % CDA, 28 wt % acetone, 29 wt % DMF, 15 wt % cyclo-
hexanone, and 15 wt % water.

Figure 14. Structure of the developed module for hemofiltration, Daicel Hemo-
Fresh: 1, unit compartment; 1.1, membrane; 1.2: substrate cloth; 1.3, heat-sealed
side edge; 1,4, smooth-surfaced and corrugate-shaped blood compartment spacer;
2, PET spacer between unit compartments; 3, poly methane end seal; 4, case; 5, cap.

SYNTHETIC M E M B R A N E S : H F A N D U F USES
0 100 ZOO 300

BLOOD FLOW R A T E , (rnl/min)
Figure 15. UFR and pressure drop of the developed hemofilter as a function of
blood feed rate, Q bovine blood in vitro. Testing conditions: hematocritt; 28%;
B
total protein, 3 g/dL; temperature, 30°C; transmembrane pressure, 150-300 mm

2
Hg/cm .

duces the degree of whole c o n t r a c t i o n . The whole membrane t h i c k -

ness, t h e r e f o r e , turns to i n c r e a s e a t the p o i n t where water f l u x
begins to decrease due to u n d e s i r a b l e c o n t r a c t i o n of polymer n e t -
work i n s k i n l a y e r .
In order to c o n f i r m that cyclohexanone i s e x t r a c t e d more r e -
l u c t a n t l y than other s o l v e n t s , the c o n c e n t r a t i o n s of e x t r a c t e d
s o l v e n t s i n the g e l a t i o n bath water were measured w i t h immersion
time lapse by using gas chromatography. As i l l u s t r a t e d i n F i g u r e
12, the e x t r a c t i o n r a t e of cyclohexanone i s l e s s than 1/3 of
DMS's. I n case of well-known acetone-formamide c a s t i n g dope f o r
c e l l u l o s e d i a c e t a t e RO membrane, formamide i s e x t r a c t e d f a s t e r
than acetone when as cast membrane i s immersed i n t o c h i l l e d water
C5). The r o l e o f formamide, t h e r e f o r e , seems to be l i m i t e d t o
evaporation stage and v e r y e a r l y p e r i o d of immersion.
As discussed above, the mechanism how the mixed a d d i t i v e ,
nonsolvent (water) and p a r t i a l l wate s o l u b l s o l v e n t (cyclohex
anone) works i s supposedl
d i t i v e s , such as formamide
Separation c h a r a c t e r i s t i c s of the membrane. F i g u r e 13 shows

the s e p a r a t i o n c h a r a c t e r i s t i c s of the membrane being used f o r
manufacturing h e m o f i l t r a t i o n module i n D a i c e l . T h i r t e e n thousand
molecular weighted cytochrome C i n aqueous s o l u t i o n i s a b l e t o
permeate through t h i s membrane as w e l l as small molecules, such
as urea. At the same time, blood albumine i s r e t a i n e d almost
completely. With bovine blood s o l u t i o n , permeation v a l u e s of i n -
termediate molecular weighted s o l u t e s are somewhat reduced perhaps
due to p a r t i a l c l o g g i n g of pores w i t h blood p r o t e i n s and some r e -
t e n t i o n i n the p r o t e i n g e l l a y e r formed on the membrane s u r f a c e .
However, the permeation v a l u e s are s t i l l higher than those o f
other membranes so f a r a v a i l a b l e .
Module development
F i g u r e 14 demonstrates a unique device to secure a uniform

blood f l o w throughout the whole membrane area i n order to ensure
f u l l performance. As i s well-known, uniform and unstagnant blood
flow i s i n d i s p e n s a b l e f o r m i n i m i z i n g c l o t t i n g and hemolysis as
w e l l as ensuring f u l l performance of the membrane used. I n our
module, D a i c e l HemoFresh(a r e g i s t e r e d trademark), t h i s i s r e a l -
i z e d by i n s e r t i n g smooth-surfaced corrugate-shaped spacer i n each
blood compartment. T h i s h e m o f i l t e r c l e a r s UFR of 100 ml/min when
bovine blood s o l u t i o n c o n t a i n i n g ca. 3.5-4.0 g / d l of p r o t e i n i s
fed a t the r a t e of 200 ml/min under the transmembrane pressure of
2
150-300 mmHg/cm as shown i n F i g u r e 15. I t i s confirmed by i n
v i t r o and i n v i v o t e s t s that UFR of 100 ml/min f o r s a i d bovine
s o l u t i o n corresponds to UFR of 70 to 80 ml/min f o r c l i n i c a l a p p l i -
cation.

Conclusion
A new cellulose acetate membrane for hemofiltration was de
veloped by employing the mixtures of liquids of opposite proper
ties for both solvent for cellulose diacetate and additive to the
polymer solution. The additive was composed of water and organic
solvents of limited water solubility. The role of the additive
is likely to have somewhat different aspect from that of other
additives known so far.
A new high performance module, Daicel HemoFresh (a regis
tered trademark) for hemofiltration, is characterized by both su
perior membrane performance and good blood compatibility. It is
now being confirmed clinically that this module is superior to
other hemofilters so far available with regard to UFR, permeation
of undesirable solutes clotting hemolysis and the amount of
blood left behind in th
References
1. L. W. Henderson et al., J . Lab. Clin. Med., 85, 372, 1975.
2. J . L. Halary et al., Desalination, 13, 251, 1973.
J . Vinit et al., ibid., 15, 267, 1974.
J . Vinit et al., European Polym. J., 11, 71, 1975.
H. Strathmann et al., Desalination, 16, 179, 1975.
H. Strathmann et al., J . Appl. Polymer S c i . , 15, 811, 1979.
3. R. Bloch and M. A. Frommer, Desalination, 7, 259, 1970.
M. A. Frommer et al., i b i d . , 7, 393, 1970.
4. R. E. Resting, Synthetic Polymeric Membranes, p. 120,
McGraw-Hill, New York, 1971.
5. Unpublished data, Daicel Chemical Industries, Ltd., 1969.

6
Pressure Control of the Ultrafiltration Rate During
Hemodialysis with High-Flux Dialyzers and the
Time Dependence of Membrane Transport
Parameters
A L L E N ZELMAN, DAVID GISSER, GARY STRAIT,
and VICTOR BASTIDAS
Center for Biomedical Engineering, Rensselaer Polytechnic Institute, Troy, NY 12181
ROBERT STEPHEN, C A R L KABLITZ, JEFFREY HARROW,
BARRY DEETER, and W. J. K O L F F
Division of Artificial Organs, Universit
Recent hemodialysis research has focused a t t e n t i o n on the

"middle molecule hypothesis" (1, 2) which suggests that s o l u t e s i n
the "middle molecular weight" spectrum of 500-3000 daltons i n c l u d e
important uremic t o x i n s . I t appears that a s i g n i f i c a n t f r a c t i o n
of the d i a l y s i s p o p u l a t i o n could b e n e f i t from hemodialysis using
a membrane w i t h a l a r g e r pore s i z e . However, if the diameter of
the pore is doubled, the water l o s s will increase s i x t e e n times.
Thus, accurate and r e l i a b l e ultrafiltration c o n t r o l i s necessary
when using so c a l l e d "high f l u x membranes". The three e x t r a
c o r p o r e a l techniques used to remove middle molecules while
controlling ultrafiltration are: 1) hemoperfusion (3, 4); 2)
h e m o f i l t r a t i o n (5, 6, 7); and 3) d i a l y s i s with a d i a l y z e r which
contains a h i g h l y porous membrane capable of removing middle mole
c u l e s , such as the Hospal RP-6 d i a l y z e r (8, 9). Nevertheless,
there are problems with all three techniques. P r e d i l u t i o n hemo
filtration o f f e r s small molecule clearance comparable to
hemodialysis and e x c e l l e n t (~ 100 ml/min) middle molecule c l e a r
ance. I t is, however, q u i t e expensive and t e c h n i c a l l y complicated.
P o s t d i l u t i o n a l h e m o f i l t r a t i o n o f f e r s good middle molecule c l e a r
ance, but the small molecule clearance of 60-70 ml/min i s margin
al. Hemoperfusion has no capability f o r fluid removal and little
c a p a c i t y f o r urea removal; t h e r e f o r e , it fulfills only a supple
mentary r o l e i n the treatment of End Stage Renal Disease.
Hemodialysis with a high f l u x membrane used i n the standard
counter-current mode r e q u i r e s e i t h e r an expensive (~ $4,500)
ultrafiltration c o n t r o l system ( i n a d d i t i o n to the u s u a l $6,000
d i a l y s a t e d e l i v e r y system) or a closed circuit 70 liter d i a l y s a t e
tank wherein the adequacy of urea removal i s debatable: p a t i e n t s
using the tank system average 22% higher BUNs than p a t i e n t s on
standard s i n g l e pass systems (10).
The mean transmembrane h y d r o s t a t i c pressure drop, ΔP ,
m pri
m a r i l y determines the r a t e of u l t r a f i l t r a t i o n and i s given by
0097-6156/81/0154-0061$05.00/0

P + P P + P
3p - Bl Bo _ DI Do m
m I 1
AP i s r e l a t e d t o the u l t r a f i l t r a t i o n r a t e , Q , by
Q = L (AP - TT ) (2)
v p m p
where L i s the u l t r a f i l t r a t i o n index, TT i s the osmotic pressure
P P
of the plasma p r o t e i n s , P ^ and P ^ are the h y d r o s t a t i c pressures
q
of the blood i n and the blood out l i n e r e s p e c t i v e l y , P and P D I D O
are the h y d r o s t a t i c pressures of the d i a l y s a t e i n and d i a l y s a t e

out l i n e r e s p e c t i v e l y . C o n t r o l of A P o b v i o u s l y allows c o n t r o l of
m
Q .
v
Consider F i g u r e 1
s i s system i n counter-curren
maximizes the c o n c e n t r a t i o n d i f f e r e n c e across the membrane and
thus ensures maximum s o l u t e t r a n s f e r . However t h i s c o n f i g u r a t i o n
a l s o maximizes the transmembrane h y d r o s t a t i c pressure d i f f e r e n c e
and thus, maximizes the water f l u x . During hemodialysis the
h y d r o s t a t i c pressure of the blood must always be higher than the
pressure of the d i a l y s a t e to ensure s t e r i l i t y i n the event of
a membrane rupture. One has the f o l l o w i n g c o n s t r a i n t s during
counter-current f l o w P _ . > P ^ , P ^ . > P ^ , P „ > P - , (everywhere).
Bl Bo Di Do B D
From these c o n s t r a i n t s i t i s easy to see from Figure 1 that by
s e t t i n g d i a l y s a t e and blood pressure a t a r b i t r a r y v a l u e s , a m i n i -
mum A P can o n l y be generated to equal to ( P , , . - P ) . N
m DI DO
In the counter-current mode the magnitude of t h i s d i f f e r e n c e
i s s e t by the c o n s t r u c t i o n of the d i a l y z e r and the d i a l y s a t e pres-
sure c o n t r o l and i s g e n e r a l l y on the order of 50 mm Hg or g r e a t e r .
This minimum pressure w i l l induce an absolute minimum u l t r a f i l t r a -
t i o n r a t e of 350 ml/hr f o r a t y p i c a l high f l u x membrane. Thus,
when the p a t i e n t has l o s t s u f f i c i e n t water or perhaps when he does
not need to l o s e any water during d i a l y s i s , the p a t i e n t must con-
t i n u o u s l y be given s t e r i l e s a l i n e to make up f o r the minimum
u l t r a f i l t r a t i o n loses.
The purpose of t h i s research was to develop a simple and i n -
expensive hemodialysis p r o t o c o l w i t h the f o l l o w i n g o b j e c t i v e s :
(a) to ensure maximum removal of the "middle molecules" by u t i l i z -
i n g a h i g h l y porous membrane i n c o r p o r a t e d i n t o so c a l l e d "high
f l u x d i a l y z e r s " ; (b) to ensure normal removal of low molecular
weight s o l u t e s by u t i l i z i n g a s i n g l e pass d i a l y s i s d e l i v e r y system
(11); (c) to ensure accurate c o n t r o l of u l t r a f i l t r a t i o n by main-
t a i n i n g the transmembrane h y d r o s t a t i c pressure, A P ^ , a t
a p p r o p r i a t e s m a l l values e a s i l y read on standard d i a l y s i s equip-
ment; and (d) to accomplish the above o b j e c t i v e s without the use
of expensive v o l u m e t r i c or other s p e c i a l i z e d equipment.

6. ZELMAN ET AL. Hemodialysis 63
D e s c r i p t i o n of a Simple Means of C o n t r o l l i n g U l t r a f i l t r a t i o n .
Consider F i g u r e 2 w i t h co-current flows. When the h y d r o s t a t -

i c pressures have reached a steady s t a t e , the net f o r c e s a c t i n g on
the membrane are balanced, i . e . , mechanical e q u i l i b r i u m e x i s t s .
In a very s i m p l i f i e d view, the mechanical f o r c e balance can be
w r i t t e n a t any d i s t a n c e z along the l e n g t h of the membrane as
P ( z ) = P ( z ) + V(z)
B D (3)
where v(z) i s the r e s t o r i n g f o r c e s u p p l i e d by the membrane. I f

P (z)
fi i n c r e a s e s as a r e s u l t of increased blood f l o w , then the mem-
brane r e s i s t s bending i n t o the d i a l y s a t e path by an amount v ( z ) .
Thus, the transmembrane pressure a t z can be expressed by
AP (z) = P (z) - P
m B
Now consider t h a t i f . i n c r e a s e s , then P^Cz) i n c r e a s e s and

the membrane w i l l be f o r c e d i n t o the path of the d i a l y s a t e . The
r e s t r i c t i o n of d i a l y s a t e cross s e c t i o n w i l l cause the d i a l y s a t e
pressure t o i n c r e a s e when i s h e l d constant, so equation 4 w i l l
h o l d f o r new values of P _ ( z ) , P^Cz) and v ( z ) . I t i s apparent that
when the membrane becomes very d i s t e n s i b l e or f l e x i b l e , i . e . , v ( z )
tends toward z e r o , then P^Cz) - P^Cz) tends toward zero a l s o ,
i . e . , the membrane cannot support a h y d r o s t a t i c pressure drop.
Thus i f the membrane i s f r e e to move, the transmembrane pressure
drop w i l l tend toward a minimum value.
In the co-current mode (P^ - P_ ) can be made a r b i t r a r i l y
v
Bo Do
p
c l o s e t o zero by a d j u s t i n g 5 t h i s i s a standard adjustment on
D o
n e a r l y a l l d i a l y s a t e d e l i v e r y systems. However, the d e l i v e r y sys-

tem must have the c a p a b i l i t y of p r o v i d i n g a p o s i t i v e d i a l y s a t e
pressure equal to the blood venous pressure (~ 80 mm Hg). The
pressure drop ~ D p ™m a u t o m a t i c a l l y be adjusted to near
P
zero by the i n t e r a c t i o n of the co-current flows and d i s t e n s i b l e

membrane. Therefore by a d j u s t i n g P^ u n t i l AP = if , no matter
J
Do m p
how porous the membrane, the u l t r a f i l t r a t i o n r a t e can be brought
to zero when the d i a l y z e r i s operated i n the co-current mode.
Because our system i s a pressure c o n t r o l of u l t r a f i l t r a t i o n
r a t e , i t i s obvious that an accurate i n v i v o value of the u l t r a -
f i l t r a t i o n index, L^, i s r e q u i r e d . Our f i r s t attempts a t manual
determination of (12) produced only a very s m a l l amount of data
compared to the enormous e f f o r t necessary to c o l l e c t i t . Thus, an
automated system was designed and constructed f o r c o l l e c t i n g and
e v a l u a t i n g u l t r a f i l t r a t i o n data.

Counter-Current Flows
Figure 1. Countercurrent dialyzer set-up
r r
BOJ Bi,
BLOOD Q
Q
BO«- Bi
Q
DO«- DIALYSATE
Co-Current Flows
Figure 2. Cocurrent dialyzer set-up

Equipment and Methods.
The experimental set-up f o r f i n d i n g the i n v i v o v a l u e of L^

i s shown s c h e m a t i c a l l y i n F i g u r e 3. Blood i s withdrawn from the
p a t i e n t a t 225 ml/min. The d i a l y s a t e input i s 500 ml/min. The
d i a l y z e r i s operated i n the co-current mode. Two d i f f e r e n t i a l
pressure transducers (Model CD 7, Celesco Transducer Products,
Canoga Park, CA) monitor ( P -P ) =AP
f i ± D ± and ( P
B D ±-P ) =
B q D o
AP B D q t o ± 1 mm Hg. The pressures a r e time v a r y i n g due to p a t i e n t

unrest and the p u l s a t i l e nature of blood r o l l e r pumps. The analog
s i g n a l s of each pressure transducer demodulator i s sent to the
" u l t r a f i l t r a t i o n monitor" c o n t i n u o u s l y .
The d i a l y s a t e i s d e l i v e r e d i n the s i n g l e pass mode, but the
d i a l y s a t e tanks a r e arranged to mimic a c l o s e d system Dialysate
r e s e r v o i r s r e s t on a p l a t f o r m
monitored to ± 2 g by a
Corp., Boston, MA). Fresh d i a l y s a t e flows from one tank through
the d i a l y z e r and r e t u r n s to a d r a i n tank. The t o t a l weight of
these tanks may change- only as a r e s u l t of water l o s s by the
p a t i e n t or by compliance e f f e c t s of the d i a l y z e r . The Aimex
weighing system sends a continuous analog s i g n a l i n d i c a t i n g d i a l y -
sate weight as a f u n c t i o n of time t o the u l t r a f i l t r a t i o n monitor.
The u l t r a f i l t r a t i o n monitor i s a hard-wired, d i g i t a l s i g n a l pro-
cessor. I t s purpose is_ to average the input s i g n a l s of weight and
pressure and compute A P ( t ) , Q ( t ) and L ^ ( t ) . F i g u r e 4 i s a
m y
schematic of the o p e r a t i o n of the u l t r a f i l t r a t i o n monitor. The

time averaging systems operate i n the f o l l o w i n g way. About once a
sec a short data sample i s c o l l e c t e d from each i n p u t ; a f t e r about
2 min, 128 data p o i n t s a r e averaged and d i s p l a y e d on LED readouts.
The average i s updated f o r each sample. Since a l l v a r i a b l e s dur-
ing d i a l y s i s a r e s l o w l y v a r y i n g compared to 2 min and a l l n o i s e i s
f a s t compared t o 2 min, a 2 min time averaging system seemed to be
a reasonable f i r s t t r y . The u l t r a f i l t r a t i o n monitor had the f o l -
lowing ranges and i n v i t r o a c c u r a c i e s as a f u n c t i o n of time:
d i a l y s a t e weight changes ± 4 kg to ± 2 g; u l t r a f i l t r a t i o n r a t e ±
4000 ml/hr t o ± 2 ml/hr; mean transmembrane h y d r o s t a t i c pressure
± 250 mm Hg to ± 1 mm Hg; and the membrane h y d r a u l i c p e r m e a b i l i t y
( u l t r a f i l t r a t i o n index) 60 ml hr ^ mm Hg ^ to ± 0.8 ml hr ^
mm Hg .
Q and A P ^ were c o n t i n u o u s l y recorded on a 2 pen c h a r t r e -
V
corder t o an accuracy of 10 ml/hr and 2 mm Hg per d i v i s i o n (0.2

cm) a t a c h a r t speed o f 30 cm/hr. Data was read from the chart a t
2 min i n t e r v a l s . Data i s excluded from a n a l y s i s whenever changes
i n v a r i a b l e s i n v a l i d a t e the averaging of the u l t r a f i l t r a t i o n
monitor; approximately 50% of a l l data was excluded.
The mass t r a n s f e r of each s o l u t e was computed from the s t a n -
dard c l e a r a n c e , C, formula

SYNTHETIC MEMBRANES: H F AND UF USES
I20.P 120 $
LED OUTPUT
dialysate dialysate and
drain
recorder
<W(t)>
>r
î<Q (t)> v
-<AP (t)> m
*L (t) p
AP Ct)
BD1
Figure 3. Patient monitoring system. This apparatus was assembled only to deter-
mine the dialyzer UF index, L . Knowing L then allows safe high-flux dialysis
p p
without specialized equipment
j_J Differential AP +AP AP (t) Time <APjt)>

AP
BDo<^ BDo BDi m
Dialyzer Pressure Averaging -<AP (t)>

\
m
Transducers A P 2 System
BDi^
-H-p(t)
<AP (t)>
m
Electronic W(t) Time <W(t)> <Q»(t)>

Dialysate |-*| Weighing Averaging * Differentiator •<Q (t)>
v
System System
-<W(t)>
Figure 4. Schematic of the UF monitoring system

c _ ( ^ i S o ) Q f i o + ( 5
Bi
A l l c h e m i s t r i e s were determined by the c l i n i c a l l a b o r a t o r y at the
U n i v e r s i t y of Utah Medical Center. A d e t a i l e d e r r o r a n a l y s i s
shows the range of e r r o r s f o r clearance value to be between ± 10%
at the s t a r t of d i a l y s i s and 15% at the end of d i a l y s i s . Oncotic
pressures were measured w i t h a c o l l o i d osmometer (Model 186,
Instrumentation L a b o r a t o r i e s , Boston MA) to ± 0.2 mm Hg.
Curve f i t t i n g was performed by standard s t a t i s t i c a l means.
The l i n e a r r e g r e s s i o n used s t a t i s t i c a l package BMDPLR-Multiple
L i n e a r Regression, Health Science Computing F a c i l i t y , U n i v e r s i t y
of C a l i f o r n i a , Los Angeles, r e v i s e d A p r i l 1977. The n o n l i n e a r
r e g r e s s i o n used s t a t i s t i c a l package BMDP3R-Nonlinear r e g r e s s i o n ,
H e a l t h Sciences Computing F a c i l i t y , U n i v e r s i t y of C a l i f o r n i a , Los
Angeles, Revised A p r i l 1977 A l l data r e d u c t i o n was c a r r i e d out
at RPI u s i n g an IBM 303
c a r r i e d out at the U n i v e r s i t
Results
The equation assumed to p r o p e r l y p r e d i c t volume f l u x i s
Q ( t ) = L ( t ) (AP ( t ) - TT ( t ) ) (6)
v p m p
where
L ( t ) = L (1 - a t ) (7)
P P
and L^ i s the h y d r a u l i c p e r m e a b i l i t y ( u l t r a f i l t r a t i o n index) p r i o r
to blood e n t e r i n g the d i a l y z e r , a i s a constant and t i s time.
There are two means f o r e v a l u a t i n g equation 6: 1) one may assume
that TT ( t ) = TT i s a constant s i n c e TT ( t ) u s u a l l y v a r i e s by no
v v J J
p ' o p '
more than 4 mm Hg. One may then use n o n - l i n e a r r e g r e s s i o n and the
measurement of AP and Q to evaluate L , a and TT , o r ; 2) one may
m ^v p o
measure TT^(t) d i r e c t l y u s i n g a c o l l o i d osmometer and use a l i n e a r
r e g r e s s i o n to evaluate L^ and a from the measurements of Q^, AP^
andTTp(t). These methods are compared i n Tables I and I I f o r the
2
1.36 M , Gambro h i g h f l u x d i a l y z e r .
The values i n Table I are obtained by assuming that the
o n c o t i c pressure v a r i e s l i n e a r l y between i t s i n i t i a l value of
21.1 mm Hg and i t s f i n a l value of 24.8 mm Hg; the c o r r e l a t i o n co-
e f f i c i e n t f o r the l i n e a r r e g r e s s i o n was 0.99 f o r 7 values of
c o l l o i d osmotic pressure. F i f t y - o n e values of (Q , AP and TT )
r J
v m p
spaced every 2 minutes or longer gave the curve f i t i n d i c a t e d i n
Table I . The accuracy w i t h which the equation represented the
2
data i s ± 37 ml/hr and the c o r r e l a t i o n c o e f f i c i e n t , r , was 0.996.

TABLE I
U l t r a f i l t r a t i o n R e s u l t s - Gambro High F l u x D i a l y z e r
L i n e a r Regression, ^ ( t ) Measured by C o l l o i d Oncometer.
(^(t) = L (1 - a t ) ( A P ( t ) - IT ( t ) )
m
1 1 1
L =15.2 ml h r " mm Hg" ± 1.3%, a = 0.0591 h r " ± 6.7%
6
P
<TT> = 22.4 ± 1.11 mm Hg (21.1 -> 24.8)
2 1
r = 0.96, Q v ± 37 ml h r " , N = 51 (1 D i a l y s i s )
Of course, one cannot c l i n i c a l l y measure the o n c o t i c pressure

of the plasma p r o t e i n s
age v a l u e , 7T which i s
o
I I shows the r e s u l t s of determing TT ^ by n o n - l i n e a r r e g r e s s i o n from

the same (Q , AP ) data used i n Table I . The standard e r r o r i n
v m
the t r a n s p o r t c o e f f i c i e n t s i s somewhat g r e a t e r than when measuring
TT ( t ) d i r e c t l y , but the e r r o r i n u l t r a f i l t r a t i o n e v a l u a t i o n i s
only s l i g h t l y higher (2.7%).
TABLE I I
U l t r a f i l t r a t i o n R e s u l t s - Gambro High F l u x D i a l y z e r
Non-Linear Regression, TT Determined by Regression
Q = L (1 - a t ) (AP ( t )
p m
— TT o )
1 1 1
L =15.3 ml h r " mm Hg" ± 4.1%, a = - 0.0668 h r " ± 9.4%
5
P
1
Tr Q = 22.0 mm Hg ± 7.2%, Q v ± 38 ml h r " , N = 51 (1 D i a l y s i s )
2
The 1 m RP610 d i a l y z e r was c h a r a c t e r i z e d from data from 3
p a t i e n t s having one d i a l y s i s each, TT^ i n these experiments
represents an average p a t i e n t o n c o t i c pressure. Good data p o i n t s
were taken every 2 minutes f o r nine out of 12 p a t i e n t hours of
d i a l y s i s w i t h roughly equal numbers of data p o i n t s from each
p a t i e n t . The r e s u l t s are given i n Table I I I . The accuracy of
curve f i t i s ± 84 ml/hr.

TABLE I I I
U l t r a f i l t r a t i o n R e s u l t s - RP610 High F l u x D i a l y z e r
Three D i f f e r e n t P a t i e n t s , 1 D i a l y s i s Each,
Non-Linear Regression, I T Determined by Regression
q
L (1 - at)(AP ( t ) - I T )
p m o
1 1 1
17.3 ml h r " mm Hg" ± 1.8%, a = 0.0806 h r " ± 5.2%
1
24.2 mm Hg ± 4.5%, ± 84 ml h r " , N = 269
Data from two d i a l y s e

and three d i a l y s e s u s i n
ure 5, 6 and 7. The decrease i n L^ ( c a l l e d water p e r m e a b i l i t y ,
h y d r a u l i c p e r m e a b i l i t y , o r u l t r a f i l t r a t i o n index) w i t h time i s
d e p i c t e d i n F i g u r e 5. Figures 6 and 7 show the e f f e c t of
membrane-blood i n t e r a c t i o n . By i n i t i a t i n g the p l o t s at the same
u l t r a f i l t r a t i o n r a t e , h o l d i n g the pressure constant and comparing
the decrease w i t h and without normalized area, one can determine
which membrane more r e a d i l y changes i t s t r a n s p o r t p r o p e r t i e s i n
the presence of blood.
Clearance values were taken a t hourly i n t e r v a l s during d i a l y -
s i s . One group i s r e p o r t e d , Table IV, where the u l t r a f i l t r a t i o n
r a t e i s brought to e s s e n t i a l l y zero by adjustment of mean t r a n s -
membrane pressure to 21 mm Hg. A second group were taken at
random u l t r a f i l t r a t i o n values and these are reported i n Tables V
and VI.
TABLE IV
2
In Vivo Data f o r 1.36 m Gambro High F l u x D i a l y z e r at
Zero U l t r a f i l t r a t i o n Rate and Blood Flow a t 225 ml/min
Inorganic Uric
Urea Creatinine Phosphorus Acid
ml/min 136±7 121±8 119±6 110±8
N = 25 (3 D i a l y s e s , 1 P a t i e n t )

0 1 2 3 4 5
Co-current flows, ir - 7r p r o t e i n
Figure 5. In vivo UF index as a function of time
0 1 2 3 4 5
t(hours)
Figure 6. Decay of UF rate with time at various fixed transmembrane hydrostatic

pressures

ZELMAN ET AL. Hemodialysis
I I l I l I
0 1 2 3 4 5
t(hour)
Figure 7. Decay of UF rate with time at various fixed transmembrane hydrostatic

pressures and per meters squared of membrane

TABLE V
2
In Vivo Data f o r 1.36 m Gambro High F l u x D i a l y z e r a t Random
U l t r a f i l t r a t i o n Rates and Blood Flow a t 225 ml/min
Inorganic Uric
ml/min 125±6 112±6 103±10 104±9
<Q > = 570 ± 321 ml/hr

v
<t> = 1.6 ± .6 Hours i n t o D i a l y s i s
N = 11 (2 D i a l y s e s , 1 P a t i e n t )
2
In Vivo Data f o r 1.0 m RP610 High F l u x D i a l y z e r a t Random
U l t r a f i l t r a t i o n Rates and Blood Flow a t 225 ml/min
Inorganic Uric
ml/min 126±4 110±4 96±5 88±6
<Q > = 1354 ± 418 ml/hr

v
<t> =2.2 ± 1.4 Hours i n t o D i a l y s i s
N = 11 (2 D i a l y s e s , 2 D i f f e r e n t P a t i e n t s )
Discussion
The r e s u l t s o f t h i s i n v e s t i g a t i o n which are c l i n i c a l l y s i g -

n i f i c a n t are; 1) an accurate and simple means f o r c o n t r o l l i n g
u l t r a f i l t r a t i o n during hemodialysis w i t h "high f l u x " d i a l y z e r s has
been developed, and 2) a formula which can a c c u r a t e l y p r e d i c t the
u l t r a f i l t r a t i o n r a t e from measurement of h y d r o s t a t i c pressures
alone has been determined. I t i s now p o s s i b l e f o r any hemodialy-
s i s c l i n i c to b e n e f i t from the use of high f l u x d i a l y z e r s by
implementing the pressure c o n t r o l of u l t r a f i l t r a t i o n as described
here.
The p h y s i c a l i n t e r p r e t a t i o n of these r e s u l t s i s r a t h e r
s t r a i g h t f o r w a r d . We have shown equation 6 as an accurate
r e p r e s e n t a t i o n of u l t r a f i l t r a t i o n during hemodialysis. The e f f e c -
t i v e s o l u t e transmembrane osmotic pressure d i f f e r e n c e s given by
E C A T T . , where a. i s the Staverman r e f l e c t i o n c o e f f i c i e n t have been
experimentally determined to be n e g l i b l e i n these systems;

measurement of TT d i r e c t l y and numerical determination of TT from

p °
the AP and data gives e s s e n t i a l l y the same r e s u l t s . This i s
not s u r p r i s i n g s i n c e one i s d e a l i n g w i t h h i g h l y porous and h i g h l y
hydrated membranes. These data t h e r e f o r e i n d i c a t e that the de-
crease i n u l t r a f i l t r a t i o n r a t e i s s o l e l y due to a decrease i n the
u l t r a f i l t r a t i o n index, L , not a change i n osmotic pressure across
the d i a l y z e r . There a r e a t l e a s t 2 models to e x p l a i n t h i s : 1) a
g e l of p r o t e i n i s b u i l d i n g up on the surface of the membrane; 2)
the p r o t e i n i s b i n d i n g t o the membrane and plugging pores. I f one
considers the pore b l o c k i n g model using P o i s e u i l l e flow and the
F i c k d i f f u s i o n equation as rough approximations f o r volume and
s o l u t e flow r e s p e c t i v e l y , i t i s e a s i l y seen that the s o l u t e flow
i s p r o p o r t i o n a l to the pore r a d i u s squared, but that the volume
flow i s p r o p o r t i o n a l to the f o u r t h power of the r a d i u s . A 40%
decrease i n water flow woul
flow. The g e l model woul
because the d i f f u s i o n pathway through the membrane-gel l a y e r would
i n c r e a s e . The clearance data i n d i c a t e s that there was no s t a t i s -
t i c a l l y s i g n i f i c a n t change i n clearance r e l a t i v e to e i t h e r
u l t r a f i l t r a t i o n r a t e or time. That i s to say the magnitude of the
clearance was s u f f i c i e n t to ensure proper d i a l y s i s f o r p a t i e n t s ,
but the random e r r o r i n determining the clearance value was
s u f f i c i e n t l y l a r g e to v o i d f u r t h e r a n a l y s i s .
F i g u r e 6 i n d i c a t e s that the u l t r a f i l t r a t i o n index of the RP-
2
610 d i a l y z e r decreased more r a p i d l y than that of the 1.36 m
Gambro high f l u x d i a l y z e r . When the u l t r a f i l t r a t i o n r a t e s are
normalized f o r u n i t area of membrane, the e f f e c t i s more pro-
nounced as seen i n Figure 7. Apparently the membrane of the RP-
610 d i a l y z e r accumulates more " g e l l a y e r " than the Gambro high
f l u x d i a l y z e r when both are run a t the same u l t r a f i l t r a t i o n r a t e .
This may i n d i c a t e l e s s protein-membrane i n t e r a c t i o n or a b e t t e r
i n t e r n a l design g i v i n g high sheer r a t e s f o r the Gambro. However,
both d i a l y z e r s w i l l remove s i g n i f i c a n t l y greater amounts of s o l -
utes i n the 1000 MW range than conventional d i a l y z e r s .
I t i s hoped that t h i s i n v e s t i g a t i o n w i l l lead to a b e t t e r
understanding of d i a l y z e r performance and a b e t t e r therapy f o r
hemodialysis p a t i e n t s .

Acknowledgement
This research was supported i n p a r t by the g e n e r o s i t y of Mr.

Peter Thompson, P r e s i d e n t of Aimex Corp., Boston, MA 02109; the
D i v i s i o n o f A r t i f i c i a l Organs, U n i v e r s i t y of Utah Medical Center;
and PHS-NIH grant #1 R01 HL24466.
Literature Cited
1. Babb, A.L., Popovich, R.P., Christopher, T.G., and Scribner,

B.H. American Society for A r t i f i c i a l Internal Organs,
17:81, 1971.
2. Scribner, B.H., Farrell, P., Milulinovic, J., and Babb, A.L.
Proc 5th Int Cong Nephrol, 3:190, 1972.
3. Chang, T.M.S., Gonda
Am Soc Artif Int Organs, ,
4. Chang, T.M.S., Chinito, E., Barre, B., Cole, C., and Hewish,
M. Trans Am Soc Artif Int Organs, 21:502, 1975.
5. Bosch, J.P., Geronemus, R., Glabman, S., Lysaght, M., Khan,
T., and Albertini, B.V. A r t i f i c i a l Organs, 2:339, 1978.
6. Quellhorst, E., Schuenemann, B., and Borghardt, J.
A r t i f i c i a l Organs, 2:334, 1978.
7. Henderson,L.W.,Ford, C.A., and Lysaght, M.J. Contractors
Conference, A r t i f i c i a l Kidney Chronic Uremia Program,
NIAMDD, pp. 132, 1976.
8. Brunner, H., Mann, H., Essers, V., Schulthesis,R.,Byrne,
T., and Heintz, R. A r t i f i c i a l Organs, 2:375, 1978.
9. Man, N.K., Granger, A., Jungers, P., Rondon-Nucette, M.,
Zingraff, J., Sausse, A., and Funch-Grentana, J.L.
E.D.T.A., 1973.
10. Ventelon, J., Perrone, B., Jcannot, F., Laurial, F., and
Schrameck, E. Communication Presented to the Swedish
Nephrology Society Fund, April 25, 1975.
11. Zelman, A., and Gisser, D. Journal of Dialysis, 3(2&3):237,
1979.
12. Zelman, A., Bulloch, E., Stephen, R. , Kablitz, C., Duffy,
D., and Kolff, W.J. To be published in J. A r t i f i c i a l
Organs, 1980.

7
Ultrafiltration Rates and Rejection of Solutes by
Cellulosic Hollow Fibers
E. KLEIN, F. F. HOLLAND, and K. EBERLE
Gulf South Research Institute, P.O. Box 26518, New Orleans, L A 70186
R. P. WENDT
Gulf South Research Institute and Loyola University, New Orleans, L A 70118
A major o b j e c t i v e
h e m o f i l t e r s is t o c o r r e l a t e ultrafiltration r a t e s and s o l u t e
clearances w i t h the operating v a r i a b l e s of the h e m o f i l t e r such as
pressure, blood flow r a t e , and s o l u t e concentration i n the blood.
The mathematical model f o r the process should be kept relatively
simple t o facilitate day-to-day computations and a l l o w conceptual
i n s i g h t s . The model developed f o r Cuprophan hollow f i b e r s in
this study has two p a r t s : (1) intrinsic transport p r o p e r t i e s of
the f i b e r s and (2) a fluid dynamic and thermodynamic d e s c r i p t i o n
of the t e s t fluid (blood) w i t h i n the fibers.
Transport P r o p e r t i e s . Important transmembrane t r a n s p o r t

parameters of the fibers a r e Lp, the h y d r a u l i c c o n d u c t i v i t y ; Pm,
the diffusive p e r m e a b i l i t y f o r a given s o l u t e ; a, the s o l u t e
reflection coefficient; and R, the s o l u t e r e j e c t i o n . These
coefficients appear in the f o l l o w i n g equations, which are assumed
to be valid a t the steady s t a t e a t each p o s i t i o n Z along the
fiber w a l l :
J = L (AP - a Air) (1)

V P
J d-a)(C-C )
W P
j = j (l-a)C _ (2)
s v w $ _^ e
6
<S = J ( l - a ) / P
v m (3)
R = 1 - (C /C ) p w (4)
Here J and J a r e the transmembrane f l u i d and s o l u t e f l u x d e n s i -

t i e s ; XP and §TT are the h y d r o s t a t i c and osmotic pressure d i f f e r -
ences ( i n s i d e minus outside) across the f i b e r w a l l ; C i s the
" w a l l " concentration; i . e . , s o l u t e concentration immediately
adjacent to the solution-membrane i n t e r f a c e w i t h i n the f i b e r
annulus; C i s l o c a l f i l t r a t e or product concentration a t the
outer surfRce of the f i b e r ; and $ i s the transmembrane P£cl£t
0097-6156/81/0154-0075$08.50/0

number. For a s o l u t e such as albumin, to which Cuprophan i s

v i r t u a l l y impermeable, a = 1 and volume f l u x i s given by
J = L (AP-TT) (5)
v p
Lower-molecular-weight s o l u t e s such as myoglobin and i n u l i n ,
have 0<a<l, and e x h i b i t a f i n i t e s o l u t e f l u x during u l t r a f i l -
t r a t i o n . L o c a l f i l t r a t e c o n c e n t r a t i o n , Cp, i s then given by
6
Cp = J / J
v ()
s v
S u b s t i t u t i o n of Equation 6 i n Equations 2 and 4 y i e l d s the
Spiegler-Kedem r e j e c t i o n equation (1_)
3 3
R = (e -l)/(e -a)
a (7)
The response of R to 3
values of a. For 3<<1, R
brane d i f f u s i o n d i s s i p a t e s the c o n c e n t r a t i o n d i f f e r e n c e created
by the convective s i e v i n g term, J ( l - o ) C i n Equation 2. For
W
3>3, R->a because d i f f u s i o n i s dominated b y c o n v e c t i o n .
Three f a c t o r s can complicate t h i s t h e o r e t i c a l behavior of R
when a p p l i e d to hollow f i b e r s . F i r s t , the volume flow J , and
hence 3 and R, may decrease w i t h d i s t a n c e along the f i b e r , because
of e i t h e r an a p p r e c i a b l e a x i a l pressure drop or an i n c r e a s i n g
back osmotic pressure exerted by accumulated s o l u t e w i t h i n the
f i b e r . Hence, an o v e r a l l observed value f o r R w i l l be an i n t e -
grated average along the f i b e r l e n g t h .
A second c o m p l i c a t i n g f a c t o r i n h o l l o w - f i b e r experiments i s
that i t i s v i r t u a l l y impossible to measure e i t h e r the l o c a l w a l l
c o n c e n t r a t i o n , C , i n s i t u w i t h i n a hollow f i b e r of s m a l l diameter
(e.g., 0.02 cm) or C , the l o c a l f i l t r a t e c o n c e n t r a t i o n at the
e x t e r i o r surface of f i b e r . Instead, the a c c e s s i b l e q u a n t i t i e s
are the e n t e r i n g feed stream c o n c e n t r a t i o n , C , and an average
c o n c e n t r a t i o n , C of f i l t r a t e c o l l e c t e d from the e n t i r e f i b e r .
In terms of t h e s l measurable c o n c e n t r a t i o n s , the observed r e j e c -
t i o n , R , , i s defined as
obs
R obs
, = 1 - (C p /C o') v (8)
J
A c o n c e n t r a t i o n boundary l a y e r theory c l e a r l y i s needed to r e l a t e

to C , so that membrane p r o p e r t i e s such as L , a, and P can
q
be c o r r e l a t e d w i t h R at v a r i o u s o p e r a t i n g c o n d i t i o n s . 2 l s o ,
s i n c e TT i n Equations I and 5 i s an independently determined
f u n c t i o n of C, a boundary l a y e r theory could c o r r e l a t e the ob-
served f i l t r a t e v e l o c i t y , J (averaged -along the f i b e r l e n g t h ) ,
w i t h average a p p l i e d pressure A P . For s u f f i c i e n t l y high a x i a l
flow v e l o c i t i e s , C - C , and a major t h e o r e t i c a l b a r r i e r to data
7
a n a l y s i s i s removed . Some e a r l y work i n reverse osmosis (2) was
done w i t h f l a t - s h e e t membranes and l a r g e feed stream v e l o c i t i e s ,
on the order of 100 cm/sec, so that R , - R. But f o r hollow
obs

7. KLEIN ET AL. Cellulosic Hollow Fibers 77
f i b e r s used i n t h i s work, a x i a l flow v e l o c i t i e s were l e s s than

about 4 cm/sec to avoid l a r g e a x i a l pressure drops which might
rupture the f i b e r s or r e s u l t i n a s i g n i f i c a n t decrease of u l t r a -
f i l t r a t i o n w i t h l e n g t h . Thus, the search f o r an a p p r o p r i a t e and
r e l a t i v e l y simple boundary l a y e r theory f o r hollow f i b e r s became
a necessary p a r t of t h i s study.
A t h i r d p o s s i b l e c o m p l i c a t i n g f a c t o r i n r e j e c t i o n measure-
ments, e s p e c i a l l y w i t h p r o t e i n s o l u t i o n , i s p h y s i c a l i n t e r a c t i o n
of the s o l u t e w i t h the membrane s u r f a c e . Solute a d s o r p t i o n , f o r
example, could a l t e r the parameters L , a or P and cause anamo-
l o u s r e j e c t i o n . An e a r l i e r search (3^ f o r a d s o r p t i o n e f f e c t s by
a c e l l u l o s i c membrane was negative. Although other i n v e s t i g a t o r s
have reported such e f f e c t s w i t h n o n - c e l l u l o s i c membranes, t h e
e f f e c t s w i t h Cuprophan f i b e r s were not observed, and a d s o r p t i o n
parameters were not i n c l u d e d i n t h i s t r a n s p o r t model.
Another solute-membran i n t e r a c t i o n formatio f
c i p i t a t e d g e l at the solution-membran
considered i n our model. Ge formatio during p r o t e i u l t r a
f i l t r a t i o n i s a major premise of many t h e o r e t i c a l and experimen-
t a l s t u d i e s , but as i s discussed l a t e r , there was no evidence f o r
g e l formation during the experiments w i t h p r o t e i n c o n t a i n i n g
systems. A l l of our mathematical modeling and data a n a l y s i s i s
for the p r e g e l r e g i o n of h e m o f i l t r a t i o n .
Boundary Layer Theory. The Reynolds number f o r flow-through

hollow f i b e r s during our experiments was at^most about 0.02 cm
(diameter) x 4 cm/sec ( v e l o c i t y ) x 1.0 g/cm ( d e n s i t y ) / 0.007
p o i s e ( v i s c o s i t y ) - 11; t h e r e f o r e , a boundary l a y e r theory i s
needed f o r laminar flow i n tubes. Because of i t s s i m p l i c i t y , t h e
most a t t r a c t i v e a v a i l a b l e theory i s an approximate r e s u l t of
t h i n - f i l m theory. This theory i s r e s t r i c t e d to a d e s c r i p t i o n of
boundary l a y e r s that are t h i n i n comparison to the tube r a d i u s .
Furthermore, the u l t r a f i l t r a t e v e l o c i t y , J , must not vary along
the tube l e n g t h ( u n i f o r m - w a l l - f l u x t h e o r y ) . At the c e n t e r l i n e or
a x i s of the f i b e r , the impermeable s o l u t e c o n c e n t r a t i o n C = C
(the e n t e r i n g feed stream c o n c e n t r a t i o n ) , but w i t h i n the t h i n
boundary l a y e r C f o r a t o t a l l y impermeable s o l u t e i s given by
the f o l l o w i n g approximate r e s u l t s (_4, 5^, _6,)
1.219(Pe 2^1/3
E)
C C e (9)
w o
Pe J r/(2D) (10)
E 2J Z/(U r ) (11)
v o
i-u /u
7 (12)
Z o
Q (Z)/Q.B
V (.13)

Here Pe i s the w a l l P e c l e t number, a dimensionless v a r i a b l e f o r

the r a d i a l c o n v e c t i v e - d i f f u s i v e process i n s o l u t i o n w i t h i n the
f i b e r annulus, which should be d i s t i n g u i s h e d from $, the t r a n s -
membrane P e c l e t number given p r e v i o u s l y f o r t r a n s p o r t across the
f i b e r w a l l ; r i s the f i b e r r a d i u s ; D i s the s o l u t e d i f f u s i v i t y
i n b u l k s o l u t i o n ; and E i s the e x t r a c t i o n r a t i o a t a d i s t a n c e Z
along the f i b e r from the feed stream entrance of the f i b e r . As
given by Equation 12, E i s the f r a c t i o n a l change i n average a x i a l
flow (averaged over the f i b e r c r o s s - s e c t i o n a l area normal to the
a x i s ) , where and U are a x i a l flow v e l o c i t i e s at Z and the
q
entrance, r e s p e c t i v e l y . E i s a l s o the r a t i o of t o t a l u l t r a f i l -
t r a t e f l u x up to Z, Q ( Z ) , t o flow r a t e of feed stream e n t e r i n g
the f i b e r , Q_. For processes considered i n t h i s study, Pe
can be thought of as a reduced u l t r a f i l t r a t e v e l o c i t y . For the
general cases o f s o l u t e s w i t h R <^ 1, i t can be shown (5_, 6)
that
C /C C /C 1 C /C ( 1 4 )
< w o>R<l = < w o W ^ " ^ < w oW
where (C /C ) T i s the boundary l a y e r modulus when R<1, and
w r <
( C ^ / C ) ^ i s the modulus given by t h i n f i l m theory f o r imperme-

o R =
able s o l u t e s (Equation 9).

The above equations, a f t e r t r a n s f o r m a t i o n to r e c t a n g u l a r
channel geometry and a p p r o p r i a t e i n t e g r a t i o n along the channel
l e n g t h , have been used s u c c e s s f u l l y t o c o r r e l a t e R ^ w i t h R ( a , 3)
Q S
f o r r e j e c t i o n experiments i n a f l a t - p l a t e c e l l f o r c o n d i t i o n s
where E<0.1 ( 7 ) . Equation 14 has a l s o been t e s t e d against exact
t h i n - f i l m f i l m theory f o r the f l a t - p l a t e geometry and found to be
i n good agreement (within 10%) f o r R = 1 when Pe E<0.33 and f o r
2
R = 0.75 where Pe E<2.7 ( 5 ) . A s i m i l a r t h e o r e t i c a l t e s t has not

been performed f o r the t u b u l a r geometry, although an exact theory
f o r imperfect r e j e c t i o n i s a v a i l a b l e ( 8 ) . This theory r e q u i r e s
e x t e n s i v e computation and i s not s u i t a b l e f o r general data
analysis.
A l l of the t h i n - f i l m t h e o r i e s , approximate and exact, a r e
r e s t r i c t e d t o the d e s c r i p t i o n of developing boundary l a y e r s t h a t
have not penetrated t o the channel center l i n e . For our e x p e r i -
ments a t l a r g e e x t r a c t i o n r a t i o s (E>0.3), the boundary l a y e r i s
b e l i e v e d to be f u l l y - d e v e l o p e d , i . e . , the center l i n e concentra-
t i o n i s greater than C . F o r t u n a t e l y , there are a v a i l a b l e simple
a n a l y t i c forms f o r the boundary l a y e r modulus t h a t d e s c r i b e both
the developing and f u l l y developed regions (9, 10). They were
derived f o r the case o f uniform w a l l - f l u x u l t r a f i l t r a t i o n out of
p e r f e c t l y impermeable (R = 1) t u b u l a r membranes. These equations
were examined to see how they could be adapted t o the case of
i m p e r f e c t l y r e j e c t i n g membranes.
For r e j e c t i o n of t r a c e r s o l u t e s out o f s a l i n e s o l u t i o n s , t h e
u n i f o r m - w a l l - f l u x r e s t r i c t i o n i s not a problem, because the a x i a l
pressure drop i s g e n e r a l l y l e s s than 10% of the average transmem-
brane pressure. Constant J w i t h l e n g t h along the tube i s not
expected f o r experiments wi?h p r o t e i n s o l u t i o n s because p r o t e i n

7. KLEIN E T A L . Cellulosic Hollow Fibers 79
b u i l d s up the back osmotic pressure at the w a l l ; TT should i n c r e a s e

w i t h Z, and J should decrease, s i n c e AP - constant (Equation 5 ) .
Nonetheless, over the range of pressure and a x i a l flows used i n
our experiments w i t h c a l f serum and bovine serum albumin, the
average J at a given AP was independent of f i b e r l e n g t h , suggest-
ing that ?he c o n d i t i o n of uniform w a l l f l u x holds even f o r p r o t e i n
s o l u t i o n s . Thus, the uniform w a l l f l u x equations f o r developing
and f u l l y developed boundary l a y e r s were a p p l i c a b l e f o r a l l
experiments.
The a n a l y t i c a l forms d e r i v e d by Dresner (11) f o r r e c t a n g u l a r
channels were converted f o r t u b u l a r geometry (9, 10). By compari-
son w i t h exact r e s u l t s obtained by i n f i n i t e s e r i e s methods, a
s e m i - e m p i r i c a l form was d e r i v e d (12) to extend Dresner's a n a l y t i c a l
r e s u l t beyond the entrance r e g i o n . For our experiments the
f o l l o w i n g r e s u l t s are important:
C /C = 1 + 1.219 (Pe
w b '
2
when Pe E <0.04 (15)
2 2 1/2
C /C w b = 1+0.5 Pe E + 5[l-exp (-Pe E/6) ]
2
when Pe E >0.04 (16)
1 2 3
( c
w / bJ A Ab
c
O = + 0-916 Pe + 0.348 P e + 0.592 P e
where Pe <3.3 (17)
The boundary l a y e r modulus i s now C /C^, w i t h reduced by

i n s t e a d of C . Here i s the locaY b u l k or mixing-cup concentra-
t i o n , the a x i a l flow-weighted average across the f i b e r c r o s s -
section:
= /CudA
b (UA) (18)
where U i s the c r o s s - s e c t i o n a l average of the a x i a l v e l o c i t y a t

Z. For a p e r f e c t l y r e j e c t i n g membrane,
C b = CU /U o (19)
Equation 17 gives the asymptotic l i m i t of the boundary l a y e r

modulus i n the far-downstream r e g i o n of the f u l l y developed
r e g i o n ; i . e . , f o r a given v a l u e f o r the w a l l P£cl£t number, the
modulus C^/C^ e v e n t u a l l y becomes independent of E and hence Z and
U , and dependent only on Pe and hence J . To r e p l a c e Equations 15
q
and 16 an e x p o n e n t i a l form was found to Se accurate w i t h i n 10%

f o r c / c
w b'
1 2 1 9 ( P e V / 3 20
v s , =- ' < >
2
where Pe E<1.3.

Graphs f o r Equations 15, 16, and 20 a r e shown i n F i g u r e 2, and

f o r Equation 17 i n F i g u r e 3. H o r i z o n t a l l i n e s i n F i g u r e 2 r e p r e -
sent the asymptotic l i m i t f o r C /C, f o r an experiment w i t h a
given P e c l e t number. For exampYe, f o r a r e j e c t i o n experiment of
myoglobin from s a l i n e s o l u t i o n , D = 0.172 x 10 cm/sec, r =
0.011 cm, and J = 1.88 x 10 cm/sec (constant w i t h a x i a l
d i s t a n c e ) ; thusY Pe = 0.6. I f C /C were computed w i t h i n c r e a s i n g
w b
d i s t a n c e , Z, along the f i b e r l e n g t h , or e q u i v a l e n t l y , wittj iijiGrêas-

ing E, then Equation 20 would be used up to the v a l u e (Pe E)
0.43, or E = 0.22 f o r the given P£cl£t number. I f E>0.22, then
C /C, would begin l o s i n g i t s dependence on E a t E>>0.22, to reach
=
e v e n t u a l l y a v a l u e (C /C^Kg 1-688 as given by Equation 17. I t
i s not c l e a r y e t e x a c t l y wnln the s w i t c h should be made from
Equation 20 to Equation 17 as i n t e g r a t i o n occurs along the
f i b e r . Rather r a p i d " p e e l i n g away" (9) occurs from Equations 15
and 16 f o r Pe<2, but w hav t tried t t th tw equation
by a smooth curve f o r ever
tions described l a t e r , w
e x t r a c t i o n r a t i o , E , beyond which the asymptotic form (C /CtÂs
must be used. The c r i t e r i o n f o r s w i t c h i n g f o r t o t a l l y r e j e c t e d
s o l u t e s a t a f i x e d Pe'cle't number i s ,
C /C w b (Eq. 20) = ( C / C ) w b A s (Eq. 17) (21)
or
0.552 (22)
2 3
E c = (l/Pe )(Log(C /C ) ) w b A s
A l l of the above equations were o r i g i n a l l y d e r i v e d f o r

p e r f e c t l y r e j e c t i n g membranes, R = 1 . For the general case, R < 1 ,
the o b s e r v a t i o n ( 1 0 ) was used t h a t to a good approximation any
boundary l a y e r modulus f o r imperfect membranes, (C / C j is
r e l a t e d to t h a t f o r p e r f e c t membranes, (C /C,)„ ., by W
w b R=l
(C /C C /C ) / R+ 1 R C /C ] (23
w b>R<l - ( „ b R=l [ ( - )( w b>R=l >
This general and u s e f u l equation i s i d e n t i c a l i n form to Equation 1 4
given e a r l i e r f o r the s p e c i a l case of t h i n f i l m theory. The
modulus ( ^ / C J J T ^ - I i s given by any of the Equations 1 5 through 1 7
or 2 0 . I t was shown to be accurate w i t h i n 1 0 % f o r R = 0 . 8 w i t h
Pe as l a r g e as 7 4 ( 1 0 ) as compared w i t h exact t h e o r i e s f o r the
developing r e g i o n . Now, f o r imperfect membranes, the c r i t i c a l
e x t r a c t i o n r a t i o can be d e f i n e d as t h a t v a l u e f o r E which causes
( C / C (C /C 24
W b > R < l * w b > A s , R<1 < >
This c r i t e r i o n when i n s e r t e d i n t o Equation 2 3 a l g e b r a i c a l l y im-
p l i e s the c r i t e r i o n given before f o r p e r f e c t membranes,

KLEIN ET AL. Cellulosic Hollow Fibers 81

C /C ) ( E q 2 0 ) (C /C ( E q 1 ? ) ( 2 5 )
< w b R=l - - w b > A s , R=l -
To summarize, the proposed boundary l a y e r theory f o r r e -
j e c t i o n experiments across imperfect membranes i n v o l v e s a n a l y t i c
expressions f o r two regions of boundary l a y e r development, c o r r e c -
ted f o r R<1 by Equation 23, and c o r r e c t e d by the c o n d i t i o n f o r
s w i t c h i n g , Equation 22. How i n t e g r a t i o n s a r e performed to o b t a i n
an i m p l i c i t r e l a t i o n between R ^ and R i s shown l a t e r . Values
g
c a l c u l a t e d f o r R a t v a r i o u s vaSuls f o r J a r e then used to c a l c u -

l a t e a and P f o r the f i b e r membrane, according to Equation 7.
For experiments w i t h p r o t e i n s , t h i s theory, together w i t h
data f o r osmotic p r e s s u r e , a l s o a i d s i n e x p l a i n i n g the r a t h e r
unusual response of u l t r a f i l t r a t i o n r a t e to pressure and the
v i r t u a l independence of t h i s response from f i b e r l e n g t h and a x i a l
flow v e l o c i t y . Osmotic pressure data a r e a v a i l a b l e i n the l i t e r a -
t u r e f o r bovine serum albumin a t pH 7.4 ( 3 ) and osmotic pressure
measurements of moderat
bovine c a l f serum.
Data Reduction
Working Equations f o r R e j e c t i o n Experiments i n S a l i n e . Raw

daâ from the r e j e c t i o n experiments are (total f i l t r a t e rate,
cm / s e c ) , Q ( t o t a l i n l e t feed stream ^low r a t e , cm / s e c ) , C
B
(feed stream i n l e t c o n c e n t r a t i o n , g/cm ) , and C (average f i l t r a t e

c o n c e n t r a t i o n , g/cm ). R i s c a l c u l a t e d acco?ding to Equation 8,
and E^ ( t o t a l e x t r a c t i o n r a t i o f o r e n t i r e f i b e r length) i s given
by Equation 13 w i t h Q (L) = Q . I f J i s constant along the
V
f i b e r , then i t i s c a l c u l a t e d ¥rom
J v = Q /(2TrrLN)
v (26)
where N i s the number of f i b e r s per bundle. The average a x i a l

v e l o c i t y i s given by
U q = Q /(Trr N)
B
2
(27)
A r e l a t i o n i s needed between these measurable q u a n t i t i e s and

R, the i n t r i n s i c r e j e c t i o n c o e f f i c i e n t d e f i n e d by Equation 4.
F i r s t , J i s d e f i n e d as the l o c a l a x i a l s o l u t e f l u x averaged over
g
the f i b e r c r o s s - s e c t i o n w i t h a x i a l d i f f u s i o n n e g l i g i b l e ,
J U C 28
s - b < >
At the steady s t a t e f o r s o l u t e w i t h i n the f i b e r ,

where the l a s t term represents s o l u t e l o s s across the w a l l . By

using Equation 4 and 6 we f i n d
J = C (l-R)J (30)
S W V
J - (C /C, )C, ( l - R ) J (31)

s w b b v
A l s o , s i n c e t o t a l f l u i d volume w i t h i n the f i b e r i s conserved,
|^ = - 2 J , (32)
9z v/r
A f t e r the d e r i v a t i v e i n Equation 29 i s taken by u s i n g Equations 31
and 32, the mass balance equation f o r s o l u t e can be w r i t t e n
dC /C b b = (2J /r)[l
v
I n t e g r a t i o n along the f i b e r l e n g t h y i e l d s
L L
Log ( C / C ) = ( 2 J / r ) / d Z / U - ( l - R ) / ( C / C ) d Z / U
b b v o o w b (34)
R i s introduced by u s i n g another form of the mass balance

Q b g
equation f o r the f i b e r ,
2 2
C U irr = C, ULirr + 2-rrrJ C L (35)
o o b vp
where
L
C = (1/L) / C dz (36)
p o p
A l s o , from Equation 8,
C = C (1-R , ) (37)
p o obs
Thus Equation 35 can be rearranged t o read
c I
X = [ i - V i - W ^ - V ( 3 8 )
where we have used (compare Equation 32)
U = U - 2J Z/r (39)
o v
and Equation 12 f o r E a t U = g . Therefore, Equation 34 i s an q
i m p l i c i t f u n c t i o n of R, w i t h ^ / C ^ r e l a t e d to R by Equation 38, Q b s
ang C /C given by Equation 23. For convenience we i n t e g r a t e

b
i r e c t l y using Equation 39, and change v a r i a b l e s so that

Equation 34 becomes a f u n c t i o n of Pe and E :
Li
log [1-E ( l - R ) ] = - ( l - R ) / E ( C / C ) d E / ( l - E )
L o b s o L (40)
w b R < 1

84 SYNTHETIC MEMBRANES: H F AND UF USES
I f f o r a given experiment a c r i t i c a l l e n g t h or e x t r a c t i o n r a t i o
e x i s t s , i . e . , E ( c a l c u l a t e d from Equation 22) <E , then the
above i n t e g r a t i o n along the f i b e r l e n g t h must be done s e q u e n t i a l l y ,
f i r s t over the r e g i o n 0<E<E where C /C, i s given by Equation 23
and 20, then over the asymptotic r e g i o n E <E<E^ where the boundary
l a y e r modulus i s given by Equations 23 anS 17. The l a t t e r i n t e -
g r a t i o n can be performed a n a l y t i c a l l y , and Equation 40, w i t h a l l
terms brought on one s i d e , becomes
( C / C ) d E
EC w b
f(R) = 0 = log[l-E (l-R L o b s )] + (l-R) / o [ R + ( 1 _ R ) ( C /0](1-E)
W D
(1-R)(C /C, )
+ [R (1-R)(C / C )
+ ] log [(1-E )/(1-E )] c L (41)
W D A
Here C^/C^ a n d
^S/SÂ e x p l i c i t l y y Equation
17, r e s p e c t i v e l y , and E i s c a l c u l a t e d according to Equation 22
f o r the given Pe'cle't number. The computational problem i s t o
E
f i n d the root R of f ( R ) a t the data p o i n t R > J > « Since no
Qbs v L
a n a l y t i c a l form was discovered f o r the i n t e g r a l i n Equation 41,

i t must be evaluated e i t h e r n u m e r i c a l l y or by u s i n g an accurate
approximation.
An i t e r a t i v e scheme would i n v o l v e guessing a v a l u e f o r R,
e v a l u a t i n g the i n t e g r a l and other terms i n Equation 41, t e s t i n g
the c a l c u l a t e d v a l u e f o r f ( R ) , and s y s t e m a t i c a l l y a d j u s t i n g R
u n t i l f ( R ) i s s u f f i c i e n t l y c l o s e to zero. To f i n d the most
e f f i c i e n t way to evaluate the i n t e g r a l so that an i t e r a t i v e
scheme based on the method of i n t e r v a l h a l v i n g could be used w i t h
a desk-top computer to c a l c u l a t e R, Simpson's 1/3- r u l e and the
Gaussian quadrature were t r i e d . About 20 i n t e r v a l s f o r the 1/3
r u l e and 5 i n t e r v a l s f o r the quadrature were s u f f i c i e n t to achieve
b e t t e r than 0.5% accuracy over the e n t i r e range of u s e f u l values
f o r E (0-K).99) and Pe (0->3). A t h i r d procedure was t r i e d , c a l l e d
the "mid-point" approximation. This method leads to an a n a l y t i c
form f o r the i n t e g r a l and a consequent q u a d r a t i c form f o r f ( R )
which can be solved a l g e b r a i c a l l y _ f o r R. According to the mid-
p o i n t method, the average v a l u e , I , of the i n t e g r a l from 0 to E
i s approximated by the i n t e g r a l evaluated a t E /2, ° c
E 2 1 3
I = /C ex [1.219(Pe E) / ]dE
P = £ j ^
Z 1/J C
[R+(1-R)exp(l.219(Pe E) )](1-E)
2 1 / 3
_ E exp(1.219(Pe E / 2 ) )
- E I = — (43)
m p 2 1/3
° [R+(l-R)exp(1.219(Pe E /2) c )](l-E /2) c
Percentage e r r o r s i n t h i s approximation as a f u n c t i o n of E are

i l l u s t r a t e d i n F i g u r e 4 f o r Pe = 1.0 and f o r R = 0.1 and 0.9.

Figure 4. Errors in I ("see Equation 42) incurred by using midpoint approximation

at Pe = 1.0

For E l e s s than 0.4 the e r r o r s a r e l e s s than about 2%, a t o l e r -

a b l e e r r o r f o r a n a l y s i s of most of our data. The r o o t R of the
q u a d r a t i c f u n c t i o n f ( R ) , which i s obtained when E I i s sub- c
s t i t u t e d f o r the i n t e g r a l i n Equation 41, i s given by Equation 1A

(Appendix A). We used t h i s equation f o r a l l of our c a l c u l a t i o n s
i n c l u d i n g those w i t h E >0.4, s i n c e sample c a l c u l a t i o n s performed
c
i t e r a t i v e l y and w i t h I evaluated by Simpson's r u l e , gave f i n a l

values of R d i f f e r i n g by l e s s than 1% from those found by u s i n g
the mid-point approximation f o r I .
F i n d i n g R w i t h e i t h e r method r e q u i r e s a v a l u e f o r E - c
F i g u r e 5 i s a graph of E versus Pe c a l c u l a t e d according to

Equation 22. There was some concern about the s e n s i t i v i t y of the
c a l c u l a t e d v a l u e f o r R to the choice of E . The asymptotic form
f o r the boundary-layer modulus, Equation 57, was used f o r E>E
even though that form i s t r u l y exact a t E>>E f o r a given w a l l
a t E > E
P e c l e t number. L o c a l l y , the e x p o n e n t i a l form f o r C /C^ C
can be much l a r g e r tha

the choice of E would
sum of the i n t e g r a l s along the e n t i r e f i b e r l e n g t h that helps
determine R, not the l o c a l v a l u e s . To t e s t the s e n s i t i v i t y of R
to the choice of E , the sum of i n t e g r a l s i n Equation 41 which
help determine R was c a l c u l a t e d ,
J
s o A
[R+(l-R)(C /C )](l-E)
w b
+
[R+d-R)^/^)^] (44)
c c a r e
Here (C /C, ) and ( / ) w b given by Equations 20 and 17,
A s
W
r e s p e c t i v e l y ; E i s a n asiumed v a l u e f o r E>_E , and E^ i s E f o r a
given experiment. I n F i g u r e 6 i s a graph of the percentage e r r o r
i n I i n c u r r e d by u s i n g E >E , [ I (E ) - I (E ) ] x 100/1 (E ) ,
versus E^, f o r R = 0.5, P =°0.5 I n d ^ = 8.3$0. Three values of
E^ were used. A remarkabfe i n s e n s i t i v i t y t o the choice of EAÊ
C
i s shown f o r these c o n d i t i o n s , which a r e i n the midrange of
values f o r most of the s a l i n e experiments. Thus, although a l l of
the data was reduced by u s i n g Equation 41 w i t h E given by
Equation 22, f o r most experiments the choice of 6 was not c r i t i -
c a l . Only f o r values of E >0.5 can the choice cause a p p r e c i a b l e
L
e r r o r i n c a l c u l a t i o n s of R from R . I n f a c t , f o r experiments
o b g
w i t h E <0.5, the concept of an asymptotic l i m i t could be dispensed

L
w i t h without a f f e c t i n g c a l c u l a t i o n s of R by much more than the

experimental e r r o r i n measuring R .
Values c a l c u l a t e d f o r the i n t r i n s i c r e j e c t i o n c o e f f i c i e n t a t
each v a l u e f o r were used to f i n d a and P i n Equation 7,
according to a Newton-Rhaphson i t e r a t i v e l e a s t - s q u a r e s procedure
p r e v i o u s l y described (7).
U l t r a f i l t r a t i o n Experiments. There i s no boundary l a y e r

theory f o r u l t r a f i l t r a t i o n of p r o t e i n s i n tubes f o r the general
case of a p p l i e d pressures comparable t o reverse osmotic pressures.
The process i n v o l v e s complete r e j e c t i o n of p r o t e i n , and most

KLEIN ET AL. Cellulosic Hollow Fibers
Figure 6. Errors incurred by choice of E for R = 0.5 and Pe == 0.5

c

88 SYNTHETIC M E M B R A N E S : HF AND UF USES
l i k e l y , non-uniform w a l l f l u x e s . The theory f o r the p r e g e l

r e g i o n d e r i v e d (13) u s i n g an i n t e g r a l method comes c l o s e s t to our-
needs, but i t a p p l i e s to u l t r a f i l t r a t i o n c e l l s w i t h t h i n rectangu-
l a r channels; furthermore, i t i s l i m i t e d to the developing boundary
l a y e r r e g i o n where s o l u t e c o n c e n t r a t i o n at the center l i n e r e t a i n s
i t s o r i g i n a l i n l e t v a l u e . A s i m i l a r theory i s needed f o r tubes,
to extend through the f u l l y developed r e g i o n . _However, as the
presented data shows, the graphs of J versus P f o r c a l f serum
and BSA are remarkably independent of the f i b e r l e n g t h and the
a x i a l f l o w v e l o c i t y . This independence from l e n g t h f o r the
average J suggest the p o s s i b i l i t y t h a t the l o c a l i s approxi-
mately independent of d i s t a n c e Z; consequently the simple equations
from uniform w a l l f l u x theory given e a r l i e r may be v a l i d f o r
p r o t e i n u l t r a f i l t r a t i o n . The independence from a x i a l v e l o c i t y
f u r t h e r suggests that the process may be i n the asymptotic r e g i o n
of the f u l l y developed boundary l a y e r because there i s a weak
f u n c t i o n of a x i a l v e l o c i t
form f o r C /C^ from u n i f o r m - w a l l - f l u
f T
not be appYicable because according to D a r c y s Law (Equation 5)
a constant J w i t h Z would imply a constant TT w i t h Z when AP -
constant witK Z. I f IT i s independent of Z, then so must be the
average w a l l c o n c e n t r a t i o n C . But t h i s average would be given
approximately by I , the micf-point approximation ( c f . Equation
43 w i t h R = 1 f o r pFoteins and E E ). A constant I
2 implies
P
that Pe EL/2 = J^rZ/(4U D ) " i s independent of Z f o r a g i v e n J 2 v
and U ; tfeis requirement* i s i m p o s s i b l e unless D i s allowed to

v a r y c l i r e c t l y w i t h Z. I t appears then, that the asymptotic
r e s u l t i s the only equation from u n i f o r m - w a l l - f l u x theory that
can p o s s i b l y c o r r e l a t e our u l t r a f i l t r a t i o n data.
The range of Pe f o r p r o t e i n as a s o l u t e i s about 0.5 to 2
f o r our experiments, i m p l y i n g E = 0.2 to 0.5. Extraction ratios,
E > f o r most experiments were below t h i s range, and asymptotic
L
behavior would not normally be expected on the b a s i s of uniform-

w a l l - f l u x theory. However, the strong dependence of TT on C f o r
p r o t e i n s o l u t i o n s may r e s u l t i n a r a p i d buildup of s o l u t e and
back osmotic pressure immediately downstream from the f i b e r
entrance; t h i s buildup opposes the constant a p p l i e d pressure to
o b t a i n a n e a r l y uniform w a l l f l u x and asymptotic boundary l a y e r
f o r most of the f i b e r l e n g t h .
A n a l y t i c expressions f o r the p r o t e i n osmotic pressure were
needed to t e s t the a p p l i c a b i l i t y of uniform w a l l f l u x theory.
V i l k e r ' s data (3) a t pH 7.4 were used f o r BSA, i n t e r p o l a t e d over
our range of i n t e r e s t and converted to our c o n c e n t r a t i o n u n i t s
(g/1 of s o l u t i o n ) by u s i n g a p r o t e i n p a r t i a l s p e c i f i c volume of
0.746 cm /g. The data were f i t by the method of l e a s t squares to
a polynomial; the r e s u l t a n t e x p r e s s i o n f o r BSA at 37°C i s
Tr(atm) = 3.464 x 10~" C (1 + 1.284

4
x 10~ C2
+ 1.135 x 10" C5 2
+
7 3
2.078 x 10 C ) (45)

Our own osmotic pressure data f o r c a l f serum at 37°C can be ex-

pressed by a 2-parameter power s e r i e s (14).
Tr(atm) = (25.451/M)C (1+rc + 0.625r C + 0.2869r C + 2 2 3 3
4 4 5 5 6 6
0.1103r C + 0.03806r C + 0.0138r C ) (46)
where
C<340 g/1
3
(M = 53438, r = 3.574 x 10" 1/g)
Graphs of TT versus C f o r c a l f serum and BSA are shown i n F i g u r e 7.

No exact theory f o r p r o t e i n u l t r a f i l t r a t i o n i s a v a i l a b l e t o
t e s t the asymptotic theor a g a i n s t i t validit
only be i n f e r r e d by how
data used only one a d j u s t a b l parameter, protei d i f f u s i v i t y
The value c a l c u l a t e d f o r D f o r BSA systems was compared w i t h that
i n the l i t e r a t u r e . For c a l f serum there are no p u b l i s h e d d i f f u s i o n
data, and i n t e r n a l consistancy of r e s u l t s was the primary c r i t e r i o n
f o r success. A patterned search program was used to f i n d the
r
l e a s t value_of the_sum £ [ (P - ) /?] ^ f ° s e v e r a l s e t s of
values f o r J and P measured a t a given a x i a l v e l o c i t y f l o w
p
through a p a r t i c u l a r h o l l o w - f i b e r bundle. ^ defined by a
c a c
rearrangement of Equation 5,
AP = P = J /L +
1 TT (47)
calc v p
where L i s the h y d r a u l i c c o n d u c t i v i t y measured s e p a r a t e l y i n
s a l i n e i o l u t i o n . To s t a r t the search, values f o r Pe were c a l c u l a -
ted at each data p o i n t by u s i n g an i n i t i a l guess f o r p r o t e i n d i f -
f u s i v i t y , D. Equation 17 was then used to f i n d C , w i t h the
a r i t h m e t i c mean f o r the bulk c o n c e n t r a t i o n (between i n l e t and
e x i t ) r e l a t e d to the known i n l e t c o n c e n t r a t i o n by
C b = C (l-0.5 E )/(1-E )
Q L L (48)
Resultant values f o r C were used to c a l c u l a t e TT according t o

Equations 46 or 47, which l e d to values f o r P c a l (Equation 47)
to be used i n the l e a s t - s q u a r e s sum. According So i t s i n t e r n a l
c r i t e r i o n , the patterned-search program then s y s t e m a t i c a l l y
changed D u n t i l i t s optimum value was found f o r the given set of
s e v e r a l measured values f o r J and P.
v
R e j e c t i o n C o e f f i c i e n t s f o r P r o t e i n U l t r a f i l t r a t i o n Experiments.
Since the data f o r u l t r a f i l t r a t i o n r a t e s seem to imply the c o n d i -
t i o n of uniform w a l l f l u x , the c a l c u l a t i o n procedure f o r f i n d i n g
R f o r these experiments was i d e n t i c a l w i t h t h a t used f o r s a l i n e
s o l u t i o n s . No doubt the d i f f u s i v i t y of the s m a l l s o l u t e s w i t h i n

the concentrated p r o t e i n boundary l a y e r w i l l d i f f e r from that

used f o r s a l i n e systems, but i n the absence of f a c t u a l knowledge
of that d i f f e r e n c e the s a l i n e values f o r D f o r each s o l u t e were
used.
Experimental
Samples. Cuproammonium c e l l u l o s e f i b e r s made by Enka

G l a n z s t o f f AG were used i n the study. The f i b e r s designated
Cuprophan HDF, (Table I) are intended f o r a p p l i c a t i o n i n hemo-
f i l t r a t i o n and g e n e r a l l y are c h a r a c t e r i z e d by having 5 to 10
times the h y d r a u l i c p e r m e a b i l i t y of s i m i l a r f i b e r s made f o r
hemodialysis. F i b e r samples were t e s t e d i n dog-bone shaped
experimental d i a l y z e r s having f i b e r lengths of 20.5 cm and f i l a m e n t
numbers of 2940, 5870, and 8800. With a nominal i n s i d e f i b e r
diameter of 0^0215 cm, surface areas of these devices were
0.4 m , 0.8 m , and 1.2
t e s t bundles c o n t a i n i n
to 40 cm.
TABLE I . PROPERTIES OF CUPROPHAN FIBER BUNDLES
Number of
Bundle fibers I.D. O.D. Length Arâ LpxlO 5
number N cm cm cm cm cm/atra-5
I 160 0.0263 0.0326 11.5 152 23.1
II 160 0.0263 0.0326 18.5 245 23.1
III 160 0.0263 0.0326 41.5 549 23.1
IV 8800 0.0263 0.0326 20.5 1.49x10* 22.5
V 160 0.0259 0.0336 20 260 44
Measurement of J and R , .
v . To t e s t s o l u t e r e j e c t i o n and
v o l u m e t r i c f l u x by the w a l l s of hollow f i b e r potted i n small t e s t
bundles, the device shown i n Figure 8 was used. The s o l u t e was
c i r c u l a t e d from a n i t r o g e n p r e s s u r i z e d r e s e r v o i r through the
f i b e r bundle and returned. C i r c u l a t i o n was e f f e c t e d by a c a l i -
brated p e r i s t a l t i c pump. A bubble trap was provided at the i n l e t
header, and the i n l e t pressure and r e t u r n pressure were measured
w i t h c a l i b r a t e d t e s t gauges. The e x t e r i o r of the f i b e r s was set
at atmospheric pressure, and transmembrane pressure was c a l c u l a t e d
from the mean of the i n l e t and o u t l e t pressure. By using the
p r e s s u r i z e d r e s e r v o i r , transmembrane pressure and a x i a l flow r a t e
were v a r i e d independently. U l t r a f i l t r a t e was c o l l e c t e d i n a
tared weighing d i s h so that f l u x could be c a l c u l a t e d from the
c o l l e c t i o n time and f i n a l mass of the d i s h . This g r a v i m e t r i c
f l u x determination gave higher p r e c i s i o n ( f o r the s m a l l sample
c o l l e c t e d i n these s t u d i e s ) than a v o l u m e t r i c method. The s o l u t e
r e s e r v o i r and u l t r a f i l t r a t e c o l l e c t i o n v e s s e l were immersed i n a
37°C water bath.

KLEIN E T A L . Cellulosic Hollow Fibers
C(g/L)
Figure 7. Osmotic pressure for calf serum and BSA
Peristaltic
Ni
Stirrer Weighing Dish
Figure 8. Schematic of apparatus used to test bundles

Test s o l u t e s were d i s s o l v e d i n 0.85% NaCl s t a b i l i z e d w i t h

200 ppm NaN^. The r e j e c t i o n of four t e s t s o l u t e s was measured:
n
5
MW Concentration D x 10 (cm7u)
Vitamin B-12 1355 0.005% 0.379
Myoglobin 17000 0.01% 0.172
Inulin 5200 0.01% 0.215
Cytochrome C 13500 0.01% 0.198
Vitamin B-12 and myoglobin and i n u l i n and cytochrome C were

p a i r e d i n s o l u t i o n so that only two separate s o l u t i o n s had to be
f i l t e r e d . Vitamin B-12, myoglobin, and cytochrome C (Sigma
Chemical Co.) concentrations were followed s p e c t r o p h o t o m e t r i c a l l y ,
and i n u l i n was followed by l i q u i d s c i n t i l l a t i o n counting of the
C-14 l a b e l e d t r a c e r (New England N u c l e a r ) . Vitamin B-12 absorbance
was read a t 361 nm maximu
separate the s m a l l absorbanc
t h e i r r e s p e c t i v e peak maximums, simultaneous equations d e s c r i b i n g
the t o t a l absorbance were solved by u s i n g independently measured
a b s o r p t i v i t y c o e f f i c i e n t s f o r each pure s o l u t e . Cytochrome C
absorbance a t 410 nm was used f o r a n a l y s i s . R e j e c t i o n data were
c o l l e c t e d as a f u n c t i o n of transmembrane v o l u m e t r i c f l u x ( J ).
The v o l u m e t r i c f l u x was c a l c u l a t e d from the t e s t bundle surface
area and r a t e of u l t r a f i l t r a t i o n .
The observed r e j e c t i o n (R , ) was c a l c u l a t e d from the s o l u t e
c o n c e n t r a t i o n i n the r e c i r c u l a t i n g r e s e r v o i r C and u l t r a f i l t r a t e
0^ using Equation 2:
R , = 1 - (C /C ) (49)
obs p o
The UFR and s o l u t e r e j e c t i o n f o r t e s t d i a l y z e r s were measured
by u s i n g the experimental apparatus shown Jin F i g u r e 9. The t e s t
s o l u t i o n c o n t a i n i n g e i t h e r v i t a m i n B-12 and myoglobin or i n u l i n
and cytochrome C i n s a l i n e s o l u t i o n was c i r c u l a t e d by a v a r i a b l e
speed p e r i s t a l t i c pump. A c a l i b r a t e d Rotometer was used to
measure feed s o l u t i o n flow r a t e . Pressures on the i n l e t and
o u t l e t flow streams were measured by t e s t gauges. Care was taken
to maintain the s o l u t i o n l e v e l i n bubble traps even w i t h the
d i a l y z e r midpoint and s o l u t i o n i n the r e s e r v o i r to avoid syphoning
e f f e c t s . The u l t r a f i l t r a t e flow was continuously measured by
another c a l i b r a t e d flow meter placed i n the c o l l e c t i o n tube.
Transmembrane pressure was v a r i e d by a metering v a l v e r e s t r i c t i n g
the feed s o l u t i o n r e t u r n l i n e flow. The t e s t s o l u t i o n r e s e r v o i r
contained 2 l i t e r s of s o l u t i o n ; i t was immersed i n a waterbath
and continuously s t i r r e d by means of a magnetic s t i r r e r . Solute
c o n c e n t r a t i o n i n the feed s o l u t i o n and u l t r a f i l t r a t e was analyzed
a f t e r the system had come to e q u i l i b r i u m . U l t r a f i l t r a t e flow
r a t e , and -feed i n l e t and o u t l e t pressures were read j u s t before
the samples were withdrawn f o r a n a l y s i s . A sample volume of only
0.5 ml was r e q u i r e d f o r a n a l y s i s .
Each t e s t d i a l y z e r was evaluated a t i n l e t feed flow r a t e s of
200, 300, and 400 ml/min and transmembrane pressures up to 22 p s i

(1.5 atm). From t h i s data s e t , the f o l l o w i n g parameters can be

c a l c u l a t e d : u l t r a f i l t r a t i o n r a t e Q (ml/sec), v o l u m e t r i c f l u x J
= Q /A (cm/sec), observed r e j e c t i o n R Q b g = 1 - (C / C ) , and feed
Q
f l o w r a t e Q (ml/sec).
In both the t e s t d i a l y z e r s and t e s t bundles, the s o l v e n t
used was 0.85% s a l i n e b u f f e r e d w i t h sodium phosphate (0.05M) o r
membrane f i l t e r e d (0.45 urn) f e t a l c a l f serum ( B i o l o g i c a l s , Kansas
C i t y ) (6-7% p r o t e i n ) . P r o t e i n a n a l y s i s was performed by the
method of Lowry.
Measurement of Osmotic Pressure. Osmotic pressure as a

f u n c t i o n of serum p r o t e i n c o n c e n t r a t i o n was measured by a membrane
technique. Bovine c a l f serum s o l u t i o n s c o n t a i n i n g v a r y i n g p r o t e i n
concentrations from 3.85 g/100 ml of s o l u t i o n to 41.7 g/100 ml of
s o l u t i o n were prepared by d i l u t i o n or c o n c e n t r a t i o n from normal
bovine c a l f serum. Th d solution d b
u l t r a f i l t r a t i o n using a
w i t h a high f l u x Cupropha (molecula weigh
<20,000 D a l t o n s ) . The s o l u t i o n s were assayed f o r t o t a l p r o t e i n
by the method of Lowery and were then loaded i n t o smaller s t i r r e d
c e l l (Amicon Model 12), and the u l t r a f i l t r a t i o n r a t e was measured
at v a r y i n g a p p l i e d pressures. During t h i s measurement, changes
i n p r o t e i n c o n c e n t r a t i o n due to f l u i d l o s s were minimzed by use
of a micropipet to c o l l e c t u l t r a f i l t r a t e . The low u l t r a f i l t r a t i o n
r a t e used i n these experiments and h i g h shear achieved i n the
s m a l l r a d i u s r a p i d l y s t i r r e d (1200 rpm) c e l l e f f e c t i v e l y minimized
boundary l a y e r concentrations of p r o t e i n at the membrane w a l l as
shown by l i n e a r p l o t s of u l t r a f i l t r a t i o n r a t e (ml/sec) as a
f u n c t i o n of a p p l i e d pressure. From these p l o t s the osmotic
pressure at each p r o t e i n c o n c e n t r a t i o n was obtained as the a b s c i s s a
i n t e r c e p t ("Q^ = 0). A l l data were taken at 37°C.
Results
R e j e c t i o n Experiments. In Figures 10 through 15 and i n

Table I I , t y p i c a l data of r e j e c t i o n versus J are given f o r four
s o l u t e s i n s a l i n e and serum systems. For myoglobin and c y t o -
chrome C the observed values f o r R (open c i r c l e s and t r i a n g l e s )
r i s e to a maximum and then f a l l o f f w i t h f u r t h e r i n c r e a s e i n J .
Experiments w i t h i n u l i n and B-12 (open squares and x's) were not
performed at s u f f i c i e n t l y h i g h volume f l u x e s to produce maxima i n
^"obs" Corrected values f o r R, c a l c u l a t e d from observed values by
using Equation 41, are entered on the graphs as shaded o r c l o s e d
c i r c l e s , t r i a n g l e s , e t c . I f the boundary l a y e r theory i s v a l i d ,
then according to F i g u r e 1 f o r the Spiegler-Kedem equation, each
graph of R (corrected) versus J should a s y m p t o t i c a l l y approach a
h o r i z o n t a l l i n e , R -> a, a t l a r g e J , and vary l i n e a r l y w i t h J as
J •> 0. This behavior i s f o l l o w e d by myoglobin and cytochrome C
v
i n serum, and f o r i n u l i n and B-12 i n s a l i n e . Anomalous behavior

i s shown by i n u l i n and B-12 i n serum: The graphs i n t e r s e c t the
J - a x i s f a r short of the o r i g i n at J = 0 . In s a l i n e the c o r r e c t e d
v
values f o r R f o r myoglobin and cytochrome C tend to e v e n t u a l l y

SYNTHETIC MEMBRANES: HF AND UF USES
Peristaltic Pump
Stirrer
Figure 9. Schematic of apparatus used for test dialyzers
i.o
Figure 10. R vs. J in serum: L = 41.5; U = 0.92 cm/s; L = 23.1 X 10'

v 0 p

KLEIN ET AL. Cellulosic Hollow Fibers 95

Figure 14. R vs. J for myoglobin in saline: L = 20.5; U = 0.70 cm/'s; L

v 0 p =
22.5 X 10 5

KLEIN E T A L . Cellulosic Hollow Fibers
TABLE II. DATA FROM REJECTION EXPERIMENTS
P(O) P(L) P 1 0 P E
V " "obs <" 3
c h ST
atmospheres cm /s
System 3, Bundle I I I : M y o g l o b i n i n Serum

3
Q « 0.082 cm /s
0.,197 0.,163 0.180 10.1 0. 808 0.0703 0.029 0..123 0..827 0.820
0.,279 0.,245 0.,262 14 .3 0. 828 0.0996 0..041 0..174 0.,853 0.844
0. 361 0.,340 0.,351 17 .5 0. 826 0.,122 0..050 0.,213 0..856 0.845
0. 497 0.470 0. 484 21 .8 0. 840 0.,152 0..062 0.,266 0.,874 0.862
0. 592 0. 579 0. 586 24 .5 0. 829 0.171 0..069 0.,299 0.,870 0.855
0. 722 0. 708 0. 715
0. 824 0. 824 0. 824
0. 960 0. 960 0. 960 32 .2 0. 837 0.224 0.,090 0. 393 0. 889 0.870
System 14, Bundle i V: Cytochrome --C i n S a l i n e

= 0.263 cm Is
0. 116 0. 054 0. 085 5 .3 0. 546 0. 067 0. 028 0. 020 0. 560 0.557

0. 225 0. 157 0. 191 9.2 0. 580 0. 116 0. 048 0. 035 0. 603 0.598
0. 334 0. 265 0. 300 12,.8 0. 617 0.161 0. 066 0. 049 0. 647 0.641
0.449 0. 388 0. 419 15,.8 0.640 0. 199 0. 080 0. 060 0. 677 0.669
0. 572 0. 511 0. 542 18..9 0. 652 0. 238 0. 095 0. 072 0. 695 0.686
0. 694 0. 647 0. 671 21..8 0. 656 0. 274 0. 109 0. 083 0. 705 0.695
0. 810 0. 762 0. 786 23..6 0. 655 0. 297 0. 117 0. 090 0. 708 0.697
0. 967 0. 939 0. 953 26._ 9 0. 652 0. 338 0. 132 0. 102 0. 713 0.700
System 10, Bundle IV: I n u l i n i n Sa 1 i n e

3,
Q B - 6.67cm / s
0.113 0 .077 0.095 333 0..087 0.068 0.029 0 .050 0..093 0.092
0.192 0.159 0.178 525 0,.103 0.108 0.045 0.079 0 .121 0.112
0.263 0.236 0.250 775 0,.139 0.159 0.065 0.116 0.163 0.156
0.344 0 .317 0.331 1000 0,.139 0.205 0.083 0.150 0,.171 0.162
0.401 0.377 0.389 1208 0,.146 0.248 0.099 0 .181 0.187 0.175
0.472 0.447 0.460 1442 0,.153 0.296 0.117 0 .216 0.206 0.182
0.540 0.514 0.527 1642 0,.180 0.337 0.132 0 .246 0..251 0.227
0.603 0.579 0.605 1883 0,.165 0.386 0.149 0 .282 0.242 0.217
0.675 0.653 0.664 2133 0 .158 0.438 0.167 0 .320 0.245 0.216
0.739 0.710 0.725 2383 o..134 0.489 0.184 0.357 0.223 0.192

decrease at higher values f o r J . Whether these are t h e o r e t i c a l

or experimental anomalies cannot be a s c e r t a i n e d , e s p e c i a l l y f o r
the complex serum systems where the assumption of u n i f o r m - w a l l -
f l u x i s not l i k e l y to be e n t i r e l y v a l i d . However, i n s a l i n e __
systems t h i s assumption probably i s v a l i d , s i n c e P(0) - P(L) << P
(Table I I ) . F a i l u r e of the boundary l a y e r theory at l a r g e values
f o r J i s probably because (C /C, ) - cannot be simply and accu-
c c
r a t e l y r e l a t e d to ( / )w b R = 1 Equation 23.
In c a l c u l a t i o n s of a and P from values f o r R and J anoma- v
m
l o u s data p o i n t s , such as R f o r m y o g l o b i n , F i g u r e 11, f o r
J >0.4 x 10 cm/sec were not used. Data subject to t h i s e x c l u -
s i o n procedure such as those shown i n Table I I were used to c a l -
c u l a t e values f o r a and P given i n Table I I I . Since f i b e r
bundles I through IV are composed of f i b e r s w i t h e s s e n t i a l l y the
same L , they are expected to have s i m i l a r t r a n s p o r t p r o p e r t i e s .
er bundle V, w i t h an L almost twice that of the other
bundles, has values f o
only s l i g h t l y l e s s tha
a l l bundles, the r e l a t i v e l y l a r g e u n c e r t a i n t i e s i n a and P f o r
i n u l i n and B-12 r e s u l t from the low transmembrane Pe'cle't numbers,
$, f o r those s o l u t e s , which makes i t d i f f i c u l t to reach the
p l a t e a u r e g i o n of the R versus J graph where a can be determined
w i t h greater accuracy. Conversely, i t i s d i f f i c u l t to get good
accuracy i n P f o r l a r g e s o l u t e s , because $ w i l l be l a r g e even at
s m a l l J and graph of R versus J w i l l have few p o i n t s i n the
r a p i d l y r i s i n g r e g i o n near the o r i g i n .
For h i g h - f l u x membranes, i t i s d i f f i c u l t to get independent
measurements of P from a "pure" d i f f u s i o n experiment where
s o l u t i o n c i r c u l a t e s through the f i b e r lumen, s i n c e a p p r e c i a b l e
convective f l u x w i l l always accompany d i f f u s i o n . For the low-
f l u x d i a l y s i s membranes of an e a r l i e r study (7) a comparison was
p o s s i b l e between v a l u e s f o r P measured independently i n d i f f u s i o n
and r e j e c t i o n experiments; the agreement was good, i m p l y i n g
probable accuracy to the present r e s u l t s which were a l s o obtained
by c u r v e - f i t t i n g to the Spiegler-Kedem equation.
The e f f e c t of serum on r e j e c t i o n of s o l u t e s , as compared
w i t h r e j e c t i o n measured out of s a l i n e , can be addressed i n l i g h t
of data f o r c e l l u l o s i c membranes. F i g u r e s 10 and 11 demonstrate
an e f f e c t c o n s i s t e n t l y observed f o r the s o l u t e s myoglobin and
cytochrome C, The observed and c o r r e c t e d r e j e c t i o n values f e l l
o f f at approximately >0.6 x 10~ cm/sec from a p l a t e a u when
s a l i n e was the s o l v e n t , whereas i n serum the R versus J graphs
were as p r e d i c t e d from the Spiegler-Kedem equation. The r e l a t i v e
e f f e c t s of serum or BSA on R , and on r e s u l t a n t values f o r a
and P^ f o r the two l a r g e s o l u t l s , are s m a l l . For cytochrome C i n
serum and s a l i n e the d i f f e r e n c e between values i s at most 11%,
and f o r myoglobin the d i f f e r e n c e i s about 4% (Table I I I ) . In
summary, p r o t e i n i n the s o l v e n t r e s u l t s i n n e g l i g i b l y s m a l l
i n c r e a s e s i n s o l u t e r e j e c t i o n by the c e l l u l o s i c membranes s t u d i e d
i n t h i s work.
F i n a l l y , we note the r a t h e r s m a l l d i f f e r e n c e s given i n
Table I I between R c a l c u l a t e d according to u n i f o r m - w a l l - f l u x

TABLE I I I . VALUES FOR o AND Pin MEASURED IN REJECTION EXPERIMENTS
System Bundle Uo B- 12 A Tnulin Cytochrotne- A Myoglobin

A
a Pm X 10* 0 Pm X 10 a Pm 4
No. No. So Lvent cm/s a Pm X 10 K 10
1 I Serum 0 .92 0 10 + 0.39 1.10 + 6.4 - - 0.79 + 0.02 0 04 + 0 01 0.84 + 0.05 0.05 + 0.01
2 I Serum 3 .06 - - - - 0.82 + 0.01 0 04 + 0 01 0.89 + 0.03 0.03 + 0.03
3 II Serum 0 92 - - - - 0.85 + 0.02 0 06 0 03 0.88 + 0.02 0.04 + 0.01
4 II Serum 3 06 - - - - 0.83 + 0.03 0 05 + 0 01 0.87 + 0.01 0.02 + 0.01
5 II Saline 3 .06 0 14 + 0.02 0 90 + 0.60 0. 24 + 0. 03 0 28 + 0.10 0.72 + 0.01 0 01 + 0 02 0.84 + 0.01 0.01 + 0.01
6 III Serum 0 92 - - - - 0.83 + 0.04 0 04 + 0 02 0.89 + 0.05 0.04 + 0.02
7 III Serum 3 06 - - - - 0.82 + 0.03 0 04 + 0 02 0.91 + 0.03 0.04 + 0.01
8 IV BAS (0.5%) 1 40 0 24 + 0.16 1 30 + 1,26 - - - - 0.81 + 0.02 0.03 + 0.02
9 IV BAS (10%) 0 70 - - - - - - 0.86 0.03 0.02 + 0.02
10 IV Saline 1 .40 0 18 + 0.11 1 70 + 1.79 0. 31 + 0. 17 0 70 + 0.66 0.63 + 0.07 0 09 + 0 09 0.77 + 0.03 0.02 + 0.02
11 IV Saline 0 70 0 10 + 0.03 0 86 + 0.69 0. 62 + 1. 27 1 73 + 4.28 0.66 + 0.06 0 07 + 0 04 0.76 + 0.04 0.04 + 0.02

12 V Serum 0 92 - - - - 0.75 + 0.05 0 09 + 0 03 0.85 + 0.05 0.07 + 0.03
13 V Serum 3 06 - - - - 0.73 + 0.03 0 10 + 0 03 0.84 ± 0.03 0.09 + 0.03
14 V Saline 3 06 0 11 + 0.04 0 81 + 0.60 0. 25 + 0. 05 0 55 + 0.30 0.71 + 0.10 0 06 + 0 08 0.82 + 0.02 0.03 + 0.02

theory, and c a l c u l a t e d from the R , according to Equations 8,

9 (with E = ET/2), and 14. Appreciable d i f f e r e n c e s occurr only
for E >0.2.
P r o t e i n U l t r a f i l t r a t i o n Experiments. In Table IV and i n
Figures 16 through 19, t y p i c a l data obtained i n u l t r a f i l t r a t i o n
experiments w i t h serum and BSA are shown. Values f o r TT i n
Table IV were c a l c u l a t e d by using a rearrangement of Equation 5,
7 = P - J /L (50)
v p
w i t h P = AP, the average transmembrane pressure and J the average
f i l t r a t e v e l o c i t y . Graphs of TT versus C f o r serum and BSA
(Figure 7) were used to c a l c u l a t e the average w a l l c o n c e n t r a t i o n ,
C , which produced the reverse-osmotic pressure and the consequent
r e d u c t i o n of f i l t r a t e v e l o c i t y of p r o t e i n systems below that
obtained i n s a l i n e at comparable pressures (cf dashed l i n e s i n
Figures 16 through 18)
C never was l a r g e r tha
trie s o l u b i l i t y has been independently measured to be about 580
g/% (17), w e l l above the estimated w a l l concentrations i n our
experiments. A l s o , the graphs of J versus P never reach a^
h o r i z o n t a l p l a t e a u r e g i o n where J becomes independent of P.
Therefore, there can be no j u s t i f i c a t i o n f o r i n v o k i n g a _ g e l - l a y e r
hypothesis to e x p l a i n the observed graphs of J versus P. Instead,
as explained p r e v i o u s l y , a boundary l a y e r theory must be used to
p r e d i c t C , TT, and hence J at the given o p e r a t i n g _ c o n d i t i o n s .
The remarkable independence of the J versus P graphs from
a x i a l v e l o c i t y and f i b e r l e n g t h , i l l u s t r a t e d i n Figures 14 through
17, suggests the e x i s t a n c e of an asymptotic boundary l a y e r r e g i o n
of f u l l y developed flow. C a l c u l a t e d values f o r D, obtained by
u s i n g the u n i f o r m - w a l l - f l u x are shown i n Tables V and VI. For
serum, data p o i n t s f o r P >0.5 atm were excluded; f o r BSA, data
p o i n t s at a l l pressures were included to c a l c u l a t e D. For serum
(Table V) there i s a s m a l l trend to i n c r e a s e D w h i l e i n ^ r e a ^ i n g L
and decreasing U , but an average v a l u e , D"= 1.41 x 10~ cm /sec,
c o r r e l a t e s a l l o? the serum data f o r bundles I - I I I w e l l f o r
P <0.5 atm (cf s o l i d l i n e s i n Figures 14 and 15). R e s u l t s f o r D
c a l c u l a t e d from data f o r BSA at four concentrations are shown i n
Table VI. There i s a d e f i n i t e and strong i n c r e a s e of D w i t h C ,
but again, as w i t h c a l f serum, only a s m a l l dependence on U . °
Except f o r D at C = 195_^/£, the c a l c u l a t e d d i f f u s i v i t i e s are
q
below the range 6-8 x 10" p r e v i o u s l y measured f o r BSA by a

l i g h t - s c a t t e r i n g technique (15).
L i n e s drawn i n F i g u r e 18 were c a l c u l a t e d by using the respec-
t i v e values f o r D at each c o n c e n t r a t i o n . The t a n g e n t i a l approach
of the curve f o r C = 5 g/£ to the curve obtained w i t h s a l i n e
Q
supports the view that these c e l l u l o s i c membranes do not s t r o n g l y

absorb p r o t e i n s on t h e i r s u r f a c e .

0.28 | 1 1 1 1 1—• r
Figure 15. R vs. J for insulin in saline: L = 20.5; U = 0.70 cm/s; L = 22.5 X
v G
5
10'

i.o ~i 1 1 r
0.9
Figure 17. J vs. P for calf serum

v
0.2 0.3 0 4 0.5 0.6 0.7 0.8 0.9
through fibers of three lengths at U 0 =
3.06 cm/s P (atm)
Figure 18. J vs. P for BSA in large

v 0.2 0.3 0.4 0.5 0.6 0 . 7 0.8 0.9
ENKA bundle P (atm)

'I A R L E . I V , TYI'JCAL DA'I A J'r'OM U L T R A F I L T R A T I O N KXl'I.K I MLNTS
Bund]!<• I l l : 55.7 g/1 Calf Serum at U° - 0.92 cm/5

P(0) P(L) P ;10
0 y. 3
"n C
atmospheres V w
0.184 0. 143
0.285 0. 252 0.,269 14. 8 0.152 166
0.381 0. 347 0.,364 19. 0 0.214 202
0.470 0.442 0.,456 21. 4 0.287 237
0.579 0. 545 0.,562 23. 3 0.378 269
0.722 0. 708 0.,715 28. 6 0.489 301
0.824 0. 810 0.,817 31. 1 0.572 320
0.967 0. 967 0..967 33. 8 0.700 348
Bund]e I V : 74.4 g/1 BSA(pH 7.4) at U° = 0.70 cm/s
0.108 0. 068 0.,088 40 0.076 92

0.140 0. 099 0,.119 145 0.076 92
0.174 0. 135 0..155 213 0.091 100
0.255 0. 223 0..240 355 0.133 121
0.321 0. 287 0..304 433 0.174 137
0.379 0. 349 0,.364 512 0.211 151
0.426 0. 391 0..408 542 0.246 162
0.546 0. 516 0..531 625 0.344 189
0.647 0. 615 0,.631 722 0.416 203
0.715 0. 684 0..700 767 0.471 215
0.813 0. 785 0,.800 817 0.555 228

TABLE V. PROTEIN DIFFUSIVITIES CALCULATED FROM

ULTRAFILTRATION DATA FOR CALF SERUM
Uo (cm/s)
Bundle L (cm) 0.92 3. 06
I 11.5 1.39 1.,20
II 18.5 1.47 1..36
III 41.5 1.57 1,.48
TABLE V I . BSA DIFFUSIVITIES CALCULATED FROM

ULTRAFILTRATIO
CI (g/1) .70 1.40
2
74.4 3.02 2.97 (cm /s)
102 4.26 4.03

195 8.46 7.02
Conclusions
The boundary-layer theory used here to c o r r e c t observed

r e j e c t i o n c o e f f i c i e n t s i s an improvement over t h i n - f i l m theory,
but i t appears l i m i t e d to f i l t r a t e v e l o c i t i e s , J , below about
0.5 x 10 cm/sec f o r h i g h l y r e j e c t e d s o l u t e s . Xn exact theory
f o r incomplete r e j e c t i o n by h o l l o w f i b e r s i s needed to d e f i n e the
v a l i d i t y of Equation 23, over the range of c o n d i t i o n s of the
experiments.
As a one-parameter c o r r e l a t i o n of u l t r a f i l t r a t i o n data at a
given C , the osmotic/asymptotic method does an e x c e l l e n t j o b .
q
The parameter, D , c a l c u l a t e d i s probably s t r o n g l y r e l a t e d to a

true p r o t e i n d i f f u s i v i t y , but an exact boundary l a y e r theory f o r
p r o t e i n s o l u t i o n s i s needed to a c c u r a t e l y e s t a b l i s h t h a t r e l a t i o n -
s h i p . However, i r r e s p e c t i v e of a t h e o r e t i c a l _ e x p l a n a t i o n , the
observed independence of graphs of J versus P from a x i a l v e l o c i t y
and f i b e r l e n g t h i s a new r e g i o n of ?he p r o t e i n u l t r a f i l t r a t i o n
process that should be i n v e s t i g a t e d f u r t h e r .
I t seems c l e a r from the r e j e c t i o n and u l t r a f i l t r a t i o n data
that there i s no a p p r e c i a b l e p r o t e i n a d s o r p t i o n on the c e l l u l o s i c
f i b e r s . The t r a n s p o r t p r o p e r t i e s measured i n s a l i n e are of good
p r e d i c t i v e value f o r both serum and BSA experiments.

LIST OF SYMBOLS
J Transmembrane f i l t r a t e v e l o c i t y (cm/s)
v
Lp Membrane h y d r a u l i c c o n d u c t i v i t y (cm/atm-s)
P H y d r o s t a t i c pressure (atm)
JJ S o l u t i o n osmotic pressure (atm)
Cp Solute c o n c e n t r a t i o n i n f i l t r a t e (g/cm^, g/1)
C Solute c o n c e n t r a t i o n at feedstream-membrane i n t e r f a c e
w
(g/cm.3, g/1) 2
J Transmembrane s o l u t e f l u x (g/cm-s)
s
a R e f l e c t i o n o r Staverman c o e f f i c i e n t
R R e j e c t i o n c o e f f i c i e n t (Equation 4)
P D i f f u s i v e p e r m e a b i l i t y c o e f f i c i e n t (cm/s)
m
3 Transmembrane P e c l e t number (Equation 3)

RobgObserved r e j e c t i o n c o e f f i c i e n t (Equation 8)
C Solute c o n c e n t r a t i o
Q
C Bulk or mixing-pot c o n c e n t r a t i o
D
P Wall P e c l e t number (Equation 10)

e
r F i b e r r a d i u s (cm)
D Solute d i f f u s i v i t y i n s o l u t i o n (cm /s)
Z Distance along f i b e r a x i s (cm)
U Average a x i a l v e l o c i t y of e n t e r i n g feedstream (cm/s)
0
U Average a x i a l v e l o c i t y of feedstream at a x i a l p o s i t i o n Z
z
(cm/s)
E E x t r a c t i o n r a t i o up to a x i a l p o s i t i o n Z (Equations 11 - 13)
Q F i l t r a t e flow r a t e (crn^/s)
v
Qg E n t e r i n g feedstream flow r a t e (cm^/s)

E C r i t i c a l e x t r a c t i o n r a t i o (Equation 22)
c
L Length of f i b e r (cm)
N Number of f i b e r s per bundle ^
a
J Average a x i a l s o l u t e f l u x (g/cm-s)
s
E L E x t r a c t i o n r a t i o over e n t i r e l e n g t h of f i b e r
I I n t e g r a l , defined by (Equation 42)
Appendix
Equation 43 f o r the i n t e g r a l I i s i n s e r t e d i n t o Equation 41,

the s u b s t i t u t i o n :
R = 67(1 + 6) (1A)
i s introduced, and the p o s i t i v e root o f F (6) i s found:

2
<S = (-b+(b -4c)^)/2 (2A)
b =0(1+E /(1-E /2)G)+(C /C ) (l-B/G)

c c W b as (3A)
c =e(C /C ) [L-B/G+E /(l-E /2)G]

w b as c c (4A)

G = log [l-E (l-R L o b s )] (5A)
B = log [(1-E )/(1-E )J L C (6A)

2 l / 3
e = e 1.29(Pe E /2) c (7A)
Abstract
Solute r e j e c t i o n f o r four s o l u t e s and ultrafiltration rates

f o r two p r o t e i n s o l u t i o n s have been measured f o r h i g h - f l u x cellu-
losic h o l l o w - f i b e r bundles of three lengths.
Myoglobin, cytochrome-C, inulin, and v i t a m i n B-12 were the
s o l u t e s studied in s a l i n e , c a l f serum, and BSA systems a t 37°C
and pH 7.4. Observed s o l u t e r e j e c t i o n s were c o r r e c t e d to in-
trinsic values by using
f o r the developing and f u l l y - d e v e l o p e
Spiegler-Kedem equation (1) f o r r e j e c t i o n versus volume flow was
used to c a l c u l a t e reflection coefficients and diffusive perme-
abilities f o r each s o l u t e . There was no significant d i f f e r e n c e
between rejection parameters measured in saline and p r o t e i n
solutions.
Ultrafiltration velocities of the p r o t e i n s o l u t i o n s a t each
transmembrane pressure showed a remarkable independence from
fiber l e n g t h (L) and axial flo w velocity (Uo). This new r e g i o n
of the h e m o f i l t r a t i o n process is d i s t i n g u i s h e d from the familiar
p r e g e l and g e l regions where ultrafiltration velocities depend
s t r o n g l y on L and Uo. Data f o r this new r e g i o n were s u c c e s s f u l l y
c o r r e l a t e d a t a given p r o t e i n c o n c e n t r a t i o n by using osmotic
pressure data and the equation from u n i f o r m - w a l l - f l u x theory for
boundary l a y e r concentrations in the asymptotic r e g i o n of fully
developed flow. The one floating parameter, D ( p r o t e i n diffu-
sivity), in this c o r r e l a t i o n had a smaller value than expected
f o r BSA and depended s t r o n g l y on the c o n c e n t r a t i o n of BSA.
Ac kno wl ed gmen t
This work was supported by Contract N01-AM-2-2221 from the

A r t i f i c i a l Kidney-Chronic Uremia Program of the N a t i o n a l I n s t i t u t e
of A r t h r i t i s , Metabolism and D i g e s t i v e Diseases, N a t i o n a l I n s t i t u t e
of Health.
The authors a r e g r a t e f u l to W.N. G i l l of The State U n i v e r s i t y

of New York a t B u f f a l o f o r h i s suggestion to use u n i f o r m - w a l l -
flux-boundary-layer theory i n the developing and asymptotic
C ANC
r e g i o n s , together w i t h the r e l a t i o n between (C / ^)R<1 *
(C^/C^) 1 ? to analyze r e j e c t i o n data. The authors a l s o appre-
c i a t e tne h e l p f u l i n t e r e s t of M.R. Doshi of the I n s t i t u t e of
Paper Chemistry i n the p r o t e i n u l t r a f i l t r a t i o n work and g r a t e -
f u l l y acknowledge the help of P. B e d u e r f t i g , T. S u l l i , J . Hamaker,
and J . H a r r e l l f o r t h e i r help i n the p r e p a r a t i o n of t h i s manuscript.

Literature Cited
1. Spiegler, K.S., and Kedem, O., Desalination, 1966, 1, 327.
2. Johnson, J.S.,Jr., Dresner, J., and Kraus, K.A., "Hyperfiltra-
tion (Reverse Osmosis)," in "Principles of Desalination,"
K.S. Spiegler (Ed.), Academic Press: New York, 1966.
3. Vilker, V.L., "The Ultrafiltration of Biological Macromole-
cules," Ph.D. Thesis, MIT, Cambridge, Mass., 1976.
4. Bird, R.B., Stewart, W.E., and Lightfoot, E.N., "Transport
Phenomena," John Wiley: New York, 1970.
5. Dorzansky, L.J., "An Experimental Study of Reverse Osmosis
in a Horizontal Tube Combined d d Convection,"
Ph.D. Thesis, Clarkso
York, 1973.
6. Derzansky, L.J., and G i l l , W.N., A I Ch E J, 1974, 20, 751.
7. Wendt, R.P., E. Klein, Bresler, E.H., Holland, F.F., Serino,
R.M., and V i l l a , H., J. Membrane Sci 1979, 5, 23.
8. Mastrominico, C., "Reverse Osmosis in Laminar Flow in Annuli,"
M.S. Thesis, Clarkson College of Technology, Potsdam, New
York, 1968.
9. Sherwood, T.K., Brian, P.L.T., Fisher, R.E., and Dresner,
L., Ind. Eng. Chem. Fund., 1965, 4, 113.
10. G i l l , W.N., Derzansky, L.J., and Dishi, M.R., "Convective
Diffusion in Laminar and Turbulent Flow Hyperfiltration
(Reverse Osmosis) Systems," in "Surface and Colloid Science,"
Vol. 4, E. Matijeric (Ed.), Wiley-Interscience: New York,
1971.
11. Dresner, L., "Boundary Layer Buildup in the Demineralization
of Salt Water by Reverse Osmosis," Oak Ridge National Labora-
tory Report 3621, 1964.
12. Fisher, R.E., Sherwood, T.K., and Brian, P.L.T., "Salt
Concentration at the Surface of Tubular Reverse Osmosis
Membranes," Office of Saline Water, U.S. Department of the
Interior, Research and Development Progress Report No. 141,
1965.
13. Leung, W., and Probstein, R.F. Ind. Eng. Chem. Fundam.,
1971, 18, 274.
14. Ross, P.D., and Minton, A.P., J. Mol. Biol., 1977, 112, 437.

15. Phillies, G.D.J., Benedek, G.B., and Mayer, N.A., J . Chem.

Phys., 1976, 65, 1883.
16. K l e i n , E., Holland, F.F., and E b e r l e , K., J . Membrane Sci.,

1979, 5, 173.
17. K o z i n s k i , A.A., and L i g h t f o o t , E.N., A. I. Ch. E. J., 1972,

18, 1030.

8
Dialysis Processing of Cryopreserved Red Blood
Cells
ALLEN ZELMAN, DAVID GISSER, and DEXTER SMITH

Center for Biomedical Engineering, Rennsselaer Polytechnic Institute, Troy, NY 12181
ROBERT STEPHEN
Division of Artificial Organs, University of Utah, Salt Lake City, UT 74112
Red c e l l s , frozen i presenc glycerol,

º
for years at -80 C with excellent post-thaw recovery and i n vivo
survival.
Today, three approaches to red cell freezing and deglycerol-
i z a t i o n are i n clinical use: the agglomeration method (1), the
low glycerol method developed i n the United States (2, 3) and i n
Europe (4) and the high glycerol procedure (5) modified and
adopted by the American Red Cross (6). Estimates of the extent
to which these three procedures are used i n North America, based
on sales of glycerol solutions during 1976 by United States manu
facturers, t o t a l 25,000 units processed by agglomeration, 30,000
by the low glycerol method and 165,000 by the high glycerol pro
cedure. A l l procedures y i e l d a product of essentially equivalent
quality (7, 8). Differences i n the rate of use to some extent
reflect differences i n processing costs as well as the very large
impact of the Red Cross Blood Program which processes an e s t i
mated 50% of all units frozen i n North America.
Of a l l the uses for frozen red c e l l s probably the most im
portant and far reaching would be their use for inventory control.
F i r s t , i n regional blood centers, c e l l s collected during peak
collection times of the year could be maintained i n storage for
use i n times of d e f i c i t . Second, small isolated hospitals, be
cause of irregular needs, now must either tolerate an excessive
rate of outdating or engage i n an extensive exchange program with
a distant regional center. Frozen red c e l l s would be a solution
for both of these inventory control problems but only provided
that the glycerolization procedure was rapid, simple and econom
ical.
Some of the problems surrounding the removal of glycerol
from the high glycerol preparation have been overcome through the
use of c e l l washing devices. One of these, developed by the
Haemonetics Company (Braintree, MA) and based on the Cohn Frac-
tionator, performs a continuous flow wash i n a disposable bowl.
The other apparatus developed by the IBM Corporation, conducts an
automated batch wash i n a disposable bag. Although effective,
0097-6156/81/0154-0109$05.00/0
these devices add c o n s i d e r a b l e cost to the use of f r o z e n c e l l s .

The c a p i t a l equipment ranges from over $5,000 to over $17,000
w i t h the d i s p o s a b l e p l a s t i c components ranging from about $8.00
to over $20.00. The washing p r o t o c o l s r e q u i r e roughly 30 minutes
per u n i t and these devices w i l l wash only a s i n g l e u n i t at a
time.
Advantages of Frozen Red C e l l s Using Current Processing Methods.
Long term p r e s e r v a t i o n i s the most obvious asset of f r o z e n

red c e l l s and one which i n e a r l i e r days was assumed to be the only
novel v i r t u e . This extended s h e l f l i f e has proven i n v a l u a b l e f o r
the p r e s e r v a t i o n of r a r e types and c e l l s f o r a u t o t r a n s f u s i o n . I n -
ventory c o n t r o l i s an important a p p l i c a t i o n as w e l l , but one whose
f u l l p o t e n t i a l has been l i m i t e d by the high cost of f r o z e n c e l l s .
Reduced i n c i d e n c e i non-hemolyti t r a n s f u s i o r e a c t i o n s
T u l l i s , Haynes et a l . (9
b e n e f i t s of d e g l y c e r o l i z i n g g deglyceroliza
t i o n removes v i r t u a l l y a l l the plasma, the p l a t e l e t s , and most of
the leukocytes. White c e l l s are l e s s permeable to g l y c e r o l than
red c e l l s and the g l y c e r o l i z i n g procedure used f o r red c e l l s i s
damaging to leukocytes. Most of these c e l l s are destroyed by
g l y c e r o l i z a t i o n alone w i t h a d d i t i o n a l d e s t r u c t i o n o c c u r r i n g during
f r e e z i n g and thawing. V a l e r i (10) has shown that the p r o p o r t i o n
of i n t a c t white c e l l s remaining f o l l o w i n g d e g l y c e r o l i z a t i o n de-
creases w i t h 4 storage of the blood p r i o r to f r e e z i n g . A f t e r
10 days, 1% or l e s s of the leukocytes w i l l remain f o l l o w i n g
deglycerolization.
S e n s i t i z a t i o n to h i s t o c o m p a t i b i l i t y antigens i s presumed to
be reduced i n frequency i n p a t i e n t s r e c e i v i n g leukocyte-poor de-
g l y c e r o l i z e d c e l l suspensions. To a considerable extent, i t i s
the presumption that reducing s e n s i t i z a t i o n should be b e n e f i c i a l
to t r a n s p l a n t r e c i p i e n t s that has l e d to widespread use of f r o z e n
red c e l l s i n d i a l y s i s c e n t e r s . Reports have both supported and
c o n t r a d i c t e d these conjectures and the immunological v i r t u e s of
f r o z e n red c e l l s f o r d i a l y s i s p a t i e n t s remains u n c e r t a i n .
Reduction i n the i n c i d e n c e of p o s t - t r a n s f u s i o n h e p a t i t i s has
been reported as a r e s u l t of conversion to f r o z e n red c e l l s . With
exception of the study by T u l l i s (11), the observations are r e t r o -
s p e c t i v e , u n c o n t r o l l e d and f a i l to provide unequivocal evidence
that red c e l l f r e e z i n g i s a defense against t h i s disease. The
study by T u l l i s , although w e l l - d e s i g n e d , i s g e n e r a l l y considered
to comprise too few cases of h e p a t i t i s to be c o n c l u s i v e .
Mandatory t e s t i n g has r e s u l t e d i n a s u b s t a n t i a l r e d u c t i o n of
type B h e p a t i t i s as a t r a n s f u s i o n problem (12). The dominant
c l i n i c a l disease now i n v o l v e s a v i r u s which i s n e i t h e r type A nor
type B so that i t cannot be p r e d i c t e d w i t h confidence that the
v i r u s or v i r u s e s i n v o l v e d i n present day p o s t - t r a n s f u s i o n h e p a t i -
t i s w i l l respond l i k e the type B v i r u s to f r e e z i n g and
deglycerolization.

8. ZELMAN ET AL. Cryopreserved Red Blood Cells 111
Low temperature storage accounts f o r the s i m p l i c i t y of the

c u r r e n t procedure. Storage at -80 C i n mechanical f r e e z e r s i s
e a s i l y o b t a i n a b l e even though the equipment i s expensive and main-
tenance and r e p a i r r e q u i r e s p e c i a l i z e d experience. The imminent
a v a i l a b i l i t y of a procedure p e r m i t t i n g storage at -20 C (13)
e s s e n t i a l l y e l i m i n a t e s storage f a c i l i t y o b s t a c l e s to the use of
frozen c e l l s .
Disadvantages of Frozen Red C e l l s Using Current Processing

Methods.
P r o c e s s i n g time, from the removal of a u n i t from the f r e e z e r

to the removal of d e g l y c e r o l i z e d c e l l s from the washing apparatus,
r e q u i r e s an absolute minimum of 30 minutes (14). Time of pro-
c e s s i n g i s an e f f e c t i v e o b s t a c l e to the use of f r o z e n red c e l l s
f o r emergency a p p l i c a t i o n unde t circumstances O th othe
hand, when f r o z e n c e l l
scale within a hospital, deglycerolize
f o r emergency use appears to be e n t i r e l y f e a s i b l e , and at l e a s t
two l a r g e general h o s p i t a l s have reported outdating r a t e s of 5%
(15) and 1% or l e s s (16), r e s p e c t i v e l y .
The 24 hour outdating p e r i o d c o n s t i t u t e s one of the major
problems w i t h f r o z e n red c e l l s today. This i s p a r t i c u l a r l y t r u e
when c e l l s are d e g l y c e r o l i z e d at a blood center and d e l i v e r e d t o
a h o s p i t a l at some d i s t a n c e . A u n i t of c e l l s s p e c i f i c a l l y d i r e c t -
ed to a p a r t i c u l a r p a t i e n t , and then not used, f r e q u e n t l y cannot
be crossmatched f o r some other r e c i p i e n t w i t h i n the 24 hour l i m i t .
The 24 hour outdating i s imposed because of the hazard of b a c t e r -
i a l contamination during p r o c e s s i n g .
P r o c e s s i n g of m u l t i p l e u n i t s imposes a s p e c i a l hardship where
more than one u n i t has been d e g l y c e r o l i z e d i n the Haemonetics d i s -
posable bowl. Blood centers preparing f r o z e n red c e l l s under
Federal l i c e n s e are r e q u i r e d to use a v a r i e t y of safeguards t o
assure t h a t a l l u n i t s washed through the same bowl are d e l i v e r e d
to a s i n g l e r e c i p i e n t . Changes i n the design of the Haemonetics
apparatus could o b v i a t e the need to prepare m u l t i p l e u n i t s w i t h
the same bowl. But acceptable economics and more r a p i d and s i m u l -
taneous d e g l y c e r o l i z a t i o n are a necessary goal of blood t a n k i n g .
Cost continues to be the predominant disadvantage of f r o z e n
red c e l l s , although one l a r g e general h o s p i t a l r e p o r t s t h a t , s i n c e
c o n v e r t i n g almost e n t i r e l y to f r o z e n or washed red c e l l s , the cost
per thousand u n i t s of matched, f r o z e n c e l l s i s only 44% more than
matched whole blood. At the present time, disposable s u p p l i e s f o r
g l y c e r o l i z a t i o n and d e g l y c e r o l i z a t i o n t o t a l at l e a s t $35.00 per
u n i t . The present s c a l e of red c e l l f r e e z i n g i s already
s u f f i c i e n t to o b t a i n cost r e d u c t i o n s from volume production and i t
seems u n l i k e l y t h a t s u b s t a n t i a l f u r t h e r reductions i n the costs of
d i s p o s a b l e s can be a n t i c i p a t e d .
Hemolysis during d e g l y c e r o l i z a t i o n accounts f o r up to 12%
l o s s of the red blood c e l l s . The v a r i o u s s t e r i l e s o l u t i o n s used

112 synthetic membranes: hf and uf uses
i n RBC washing lowers the o s m o l a l i t y too f a s t f o r the c e l l s to

accomodate and the c e l l s rupture. These l o s s e s are o b v i o u s l y a
major cost f a c t o r .
A New Method f o r Adding and Removing C r y o p r o t e c t i v e Agents.
We propose a new method f o r both g l y c e r o l i z a t i o n and

d e g l y c e r o l i z a t i o n , based on the use of a blood bag composed en-
t i r e l y of semi-permeable membrane m a t e r i a l , as shown i n Figure 1.
Because the membrane i t s e l f would form an absolute b a r r i e r f o r
pyrogens, v i r u s e s and b a c t e r i a , c o s t l y s t e r i l e s o l u t i o n s are
t o t a l l y avoided. Since the blood could be c o l l e c t e d and m a i n t a i n -
ed i n a s t e r i l e environment, the 24 hour outdating p e r i o d could
probably be g r e a t l y increased. The process could be e a s i l y auto-
mated and c a r r i e d out without t e c h n i c i a n attendance. Processing
of m u l t i p l e u n i t s simultaneously could be accomplished without
f e a r of cross contaminatio
contained w i t h i n i t s ow
would undoubtedly be g r e a t l y decreased because membrane m a t e r i a l
i s not very expensive and none of the s t e r i l e s o l u t i o n s would be
needed. Objections to using membranes comparable to those used i n
hemodialysis f o r such a procedure would be that hemoglobin and
c e l l fragments formed during the freezing-thawing process could
not be washed out as i n present methods. I f hemolysis could be
e l i m i n a t e d by a more g e n t l e washing procedure, the only o b j e c t i o n
to t h i s membrane process would be the r e t e n t i o n of white c e l l
fragments: however, a d m i n i s t r a t i o n of whole blood has s i m i l a r
consequences.
Methods.
F i g u r e 2 i s a schematic of the t r a n s p o r t c e l l which holds the

blood bag. The bag i s placed i n a " w a f f l e i r o n " l i k e c e l l which
a l l o w s the c e l l to be e a s i l y opened and c l o s e d . D i a l y s a t e enters
the bottom, t r a v e l s through a p l a s t i c mesh which acts both as a
" d i a l y s a t e mixer" and as a membrane support. The d i a l y s a t e e x i t s
and then r e - e n t e r s a t the bottom. I n t h i s manner both s i d e s of
the blood bag a r e washed by the s i n g l e d i a l y s a t e stream. The bag
volume i s designed t o " f i l l " the compartment; t h i s prevents os-
mosis, due t o plasma p r o t e i n s , from s w e l l i n g the bag and d i l u t i n g
the red blood c e l l s . The bag i s formed by h e a t - s e a l i n g p o l y c a r -
bonate membrane (American Membrane, Covina, CA). For the i n v i t r o
experiments reported here, the bag i s f i l l e d w i t h 350 ml of out-
dated, human blood which has been g l y c e r o l i z e d according t o
standard procedures s e t by the American Red Cross. The bags have
2
960 cm area on each s i d e . The t r a n s p o r t c e l l i s mounted on a
shaker (Eberbach Corp, Ann Arbor, MI) and i s shaken a t 160 r e v o l u -
t i o n s per minute t o enhance mixing of the blood i n the blood bag
during d i a l y s i s .
The primary c o n s i d e r a t i o n s i n the design of the apparatus

ZELMAN ET AL. Cryopreserved Red Blood Cells 1
Membrane Blood B a g Maintains Sterility During

blood h a n d l i n g and storage
Figure 1. Schematic for a membrane blood bag for maintaining sterility during
glycerolization and deglycerolization
Membrane support and

dialysate dialysate mixingmesh
dialysate
Transport- CeH made like a "Waffle Iron"
Figure 2. Schematic of the transport cell that holds the blood bag

114 SYNTHETIC MEMBRANES: HF AND U F USES
are: 1) t o have the d i a l y s a t e f l o w i n g as f a s t as p r a c t i c a l , w i t h -

out wasting s a l t , t o f a c i l i t a t e mass t r a n s f e r , and 2) to lower the
d i a l y s a t e o s m o l a l i t y smoothly from - 4000 mosm to 265 mosm d u r i n g
a time span s u f f i c i e n t l y f a s t to be e f f i c i e n t , but not so f a s t as
to cause osmotic hemolysis.
F i g u r e 3 shows s c h e m a t i c a l l y the p r i n c i p l e components of the
system. Tap water i s drawn by a d i a l y s a t e d e l i v e r y system (B-D
Drake-Willock, P o r t l a n d , OR) commonly used f o r h e m o d i a l y s i s ^ This
system produces d i a l y s a t e a t r a t e s of up to 600 ml/min a t 38 C by
d i l u t i n g a concentrate w i t h tap water. The f r e s h l y made d i a l y s a t e
i s piped t o a mixing f l a s k c o n t a i n i n g - 2500 ml of 4500 mosm
d i a l y s a t e . As the d i a l y s a t e i s f o r c e d i n t o the f l a s k the d i a l y -
sate l e a v i n g the f l a s k and e n t e r i n g the t r a n s p o r t c e l l v a r i e s i n
o s m o l a l i t y w i t h time according t o Table I .
TABLE I
E x p o n e n t i a l Decay of D i a l y s a t e O s m o l a l i t y
C ( t ) = C (o) + ( C
D D C o n c - C (o))
D
Tank
C ( t )
V°> * Tank * % ™
Dialysate Concentrate D i a l y s a t e to
Delivery Tank Transport
System Cell
T i s time, i s the constant r a t e of volume flow to the

t r a n s p o r t c e l l , V_ . i s the volume of the concentrate tank, CL(o)
lank. u
and Crj (°) a r e the incoming d i a l y s a t e and i n i t i a l tank concen-
onc
t r a t e c o n c e n t r a t i o n s r e s p e c t i v e l y and are constant i n time. This

method o f d i a l y s a t e d e l i v e r y produces a very smooth e x p o n e n t i a l
decay from very high o s m o l a l i t y to that of standard d i a l y s a t e .
The s a l t c o n c e n t r a t i o n s of the blood bag a f t e r d e g l y c e r o l i z a t i o n
w i l l be e s s e n t i a l l y that of the d i a l y s a t e and are l i s t e d i n Table
I I f o r these experiments. Other c o n c e n t r a t i o n s can be e a s i l y sub-
s t i t u t e d f o r those chosen here.
TABLE I I
Composition of D i a l y s a t e a t 265 mosm
Na 130 meq/L C l " 102 meq/L

+
K 2 meq/L Ac 31 meq/L
+2
Glucose 200 mg%
Kg 1 meq/L
(11.1 m M)

ZELMAN ET AL. Cryopreserved Red Blood Cells 1
Sink f h- p water
a
Deglycerolizing System
»265mosm dialysate
|osm(t)
concentrat
d i a l y s a t e delivery 9IOOmosm/
system circulation
4500mosm [
initial v o l u m e
* 2500ml Transport Cell
Figure 3. Schematic of the laboratory set-up for deglycerolization
800r
• * 30 minutes
* « 4 5 minute*
600 ^ • « 60 minutes
acceptable level of
residual glycerol
in blood
T3
200 400 6O0 800 IOOO 1200
m { /
Q D ( min)
Figure 4. Residual glycerol left in 350 mL of red blood cells after deglyceroliza-
tion

Having passed through the t r a n s p o r t c e l l , the g l y c e r o l d i s s o l v e d

i n the d i a l y s a t e i s put i n the s i n k d r a i n . The c i r c u l a t i o n pump
on t h e f l a s k maintains a w e l l mixed s o l u t i o n .
These experiments were aimed to determine three v a r i a b l e s f o r
o p t i m i z a t i o n of t h i s process: 1) What should be the i n i t i a l
d i a l y s a t e o s m o l a l i t y i n order to prevent hemolysis? 2) What i s
the f a s t e s t r a t e a t which the o s m o l a l i t y may be lowered without
hemolysis? 3) How long should d i a l y s i s continue before the
g l y c e r o l i s a t acceptable l e v e l s (< 200 mosm)?
Since we knew that i n i t i a t i n g d i a l y s i s w i t h an o s m o l a l i t y
above that of the i n i t i a l g l y c e r o l would prevent hemolysis, we
simply i n i t i a t e d a research program to determine an optimum value
% T
of (— ) as given i n Table I .
Tank
R e s u l t s With D i s c u s s i o n .
F i g u r e 4 shows the r e s u l t s of d e g l y c e r o l i z a t i o n using our

2
f i r s t prototype t r a n s p o r t c e l l of 960 cm area f o r each s i d e of
2
the membrane bag, i . e . , 1920 cm t o t a l area. I t i s c l e a r that
about 50% of the samples were p r o p e r l y d e g l y c e r o l i z e d . Dye t e s t s
on the f l o w p a t t e r n s i n the t e s t c e l l i n d i c a t e d that the s c a t t e r
i n data was more l i k e l y due to i r r e g u l a r d i a l y s a t e flow paths
r a t h e r than to b i o l o g i c a l i r r e g u l a r i t y . But these r e s u l t s do i n -
d i c a t e v i a b i l i t y of the process and p o i n t d i r e c t l y toward con-
s t r u c t i o n of an improved d i a l y s i s system.
A f t e r each experiment the e x t r a c e l l u l a r f l u i d was checked f o r
plasma hemoglobin. I n our l a s t 29 experiments, 11 showed zero
hemolysis w i t h an average change i n plasma hemoglobin of 183 mg %
± 203 mg % w i t h a range of (0 - 500 mg % ) . The American Red Cross
s e t s the l i m i t of plasma hemoglobin f o r r e i n f u s i o n a t 500 mg %.
Thus even w i t h the outdated blood, which i s very f r a g i l e , our
method e x c e l s i n preventing r e d c e l l l o s s e s .
The long term goals of t h i s p r o j e c t a r e to d e g l y c e r o l i z e
400 ml of red blood c e l l s i n about 30 minutes. These p r e l i m i n a r y
data i n d i c a t e that t h i s g o a l can be met by proper design of the
t r a n s p o r t c e l l . At the time of t h i s w r i t i n g a new prototype c e l l
2
i s being assembled w i t h a membrane area of 1419 cm (each s i d e )
and w i t h d i a l y s a t e flow p a t t e r n s designed to ensure u n i f o r m i t y of
f l u i d d i s t r i b u t i o n across the surfaces of the blood bag. This new
t e s t c e l l w i l l c e r t a i n l y achieve our g o a l . Our primary need now
i s f o r a bag composed of a p i n h o l e f r e e membrane m a t e r i a l . The
bag must be p i n h o l e f r e e to ensure s t e r i l i t y ; perhaps a double
l a y e r membrane would meet t h i s g o a l . We can expect that i n the
near f u t u r e membrane technology w i l l p l a y a f a r greater r o l e i n
the blood banking and blood processing i n d u s t r y .

8. ZELMAN ET AL. Cryopreserved Red Blood Cells 117
Acknowledgement
This research could not have been conducted without the h e l p ,

encouragement and c r i t i c i s m of Dr. H. Meryman, ANRC, Washington,
D.C., Dr. A. B r i t t e n , ANRC, Albany, N.Y., and Dr. J . Eisenmann,
Baker Bros., Stroughton, MA. This research i s supported i n part
by P u b l i c H e a l t h S e r v i c e s grant #NIH 3 R01 HL24466.
Literature Cited
1. Huggins, C.E. Science, 139:504, 1963.
2. P e r t , J.H., Schork, P.K., Moore, R. C l i n . Res., 11 (1):197,

1963.
3. Rowe, A.W. I n : Red Cell F r e e z i n g AABB Workshop pp 55-71

1973.
4. K r i j n e n , H.W., Goudsmit, R., deWit, JJ Fr M. Bibl. Haemat.,

29 (3):807-813, 1968.
5. Tullis, J.L. (Proceedings 9th) Conference on the Plasma

P r o t e i n Cellular Elements o f the Blood, p. 17-18. Cambridge,
MA, P r o t e i n Foundation, 1954.
6. Meryman, H.T. and Hornblower, M. T r a n s f u s i o n , 16:159, 1976.
7. Meryman, H.T. and Hornblower, M. T r a n s f u s i o n ( i n p r e s s ) .
8. V a l e r i , C.R. I n : Red Cell F r e e z i n g : A T e c h n i c a l Workshop.

AABB. pp. 1-30, 1973.
9. Tullis, J.L., Haynes, L.L., P y l e , H.M. Arch. Surg. (Chicago)

81 (1):169-172, 1960.
10. Crowley, J.P. and Valeri, C.R. T r a n s f u s i o n , 14 (3):196, 1974.
11. Tullis, J.L., Hinman, J., S p r o u l , M.T. JAMA 214:719-723,

1970.
12. Conrad, M.E. Am. J. Hematol., 1:357-365, 1976.
13. Meryman, H.T. and Hornblower, M. (Presented a t the 15th

Annual Meeting) S o c i e t y f o r Cryobiology. Tokyo, August 6-10,
1978.
14. Meryman, H.T. I n : Red Cell F r e e z i n g : A T e c h n i c a l Workshop.

AABB. pp. 73-86, 1973.
15. Meryman, H.T. Am. J o u r n a l , of Med. Tech., 41:265-282, 1975.

16. Huggins, C.E. I n : Red Cell F r e e z i n g . AABB Workshop, pp.
31-53, 1973.
R E C E I V E D December 4, 1980.

9
Effect of Gel Layer on Rejection and Fractionation
of Different-Molecular-Weight Solutes by
Ultrafiltration
SHIN-ICHI N A K A O and SHOJI K I M U R A

Institute of Industrial Science, University of Tokyo, Tokyo 106, Japan
I t is well known tha gel layer hig

stances or suspended matters tend t o form on the membrane s u r f a c e ,
which sometimes c o n t r o l s the overall phenomena, that is, it limits
the permeate flux and a f f e c t s the rejection nature of membranes.
As a result it happens that d i f f e r e n t membranes behave almost same
a f t e r the g e l l a y e r formation, even though the manufacturers c l a i m
that t h e i r own membrane have b e t t e r q u a l i t y .
In the usual a p p l i c a t i o n s of membrane processes, such as
water d e s a l i n a t i o n , suspended matters are removed from feed so-
l u t i o n s by a p p l y i n g many types of pretreatments. But in the ap-
plication f o r food processing or medical use, the adoption of
pretreatment is u s u a l l y meaningless, and the d e p o s i t i o n of the g e l
l a y e r is unavoidable. Thus it becomes necessary t o understand the
nature of gel l a y e r and t o know how t o c o n t r o l it. But so f a r
t h i s k i n d of research is scarce and the analytical treatment is
inconclusive.
We have been studying t h i s problem as an extension of our re-
search on the f o u l i n g of membrane by the d e p o s i t i o n of suspended
matters (1). We first s t u d i e d on the r e s i s t a n c e of g e l l a y e r t o
permeation (2), next on the c h a r a c t e r i z a t i o n of ultrafiltration
membranes (3) regarding the s o l u t e r e j e c t i o n , and lastly on the
e f f e c t of gel l a y e r on the s o l u t e s r e j e c t i o n and f r a c t i o n a t i o n .
Though t h i s paper is mainly concerned w i t h t h i s last aspect, we
want to q u i c k l y review the previous results.
The c o n c e n t r a t i o n and the r e s i s t a n c e of g e l l a y e r
The concentration p r o f i l e i n the boundary l a y e r on the mem-

brane surface w i t h g e l l a y e r i s shown i n F i g . 1. At steady s t a t e
most o f the s o l u t e conveyed by flow t o the membrane d i f f u s e back
due t o the c o n c e n t r a t i o n gradient and the r e s t permeate through
the membrane. This mass balance i s given as
0097-6156/81/0154-0119$05.00/0

Boundary c o n d i t i o n s are
X=0; C=C b
X=6; C=C g (2)
Solutes f l u x through membrane J s i s given as
JQ
=
Jv •
Using Equations (2) and ( 3 ) , Equation (1) i s i n t e g r a t e d as
follows:
C —C
g
J = fc'ln(
v r
L
r
b~"H
where fe i s mass t r a n s f e r c o e f f i c i e n t d e f i n e d as
D (5)
6
In Equation ( 4 ) , i f the membrane has a very h i g h r e j e c t i o n o f so-

l u t e s , the term C can be neglected. Then
p
J = fe-£n( 7 ^ )
v
L
(6)
b
Eq. ( 6 ) i s u s u a l l y c a l l e d g e l p o l a r i z a t i o n equation and the value
of Cg, which can be obtained by e x t r a p o l a t i o n of J "H) i n the p l o t V
of J against l o g Cb> i s considered as constant; that dependent on

v
the s o l u t e m a t e r i a l but not dependent on the experimental con-

ditions.
A f t e r we s t a r t e d t o analyse the data of u l t r a f i l t r a t i o n ex-
periment, we came t o c o n c l u s i o n that t h i s assumption i s not
c o r r e c t . So we decided to measure d i r e c t l y Cg a t each experiment
by s c r a t c h i n g out the g e l l a y e r from membrane a f t e r measuring
steady s t a t e f l u x . Solutes used were p o l y v i n y l alcohol(PVA) and
ovalbumin. I t was found t h a t Cg i s not constant, but was depen-
dent on the experimental c o n d i t i o n as shown i n F i g . 2, where a
case of PVA i s p l o t t e d .
By the measurement of Cg value i t became a l s o p o s s i b l e to
o b t a i n k value using Eq. ( 6 ) . Using t h i s fe, Sherwood No. obtained
are p l o t t e d a g a i n s t Reynolds and Schmidt No. i n F i g . 3, where the
s o l i d l i n e gives the D e i s s l e r c o r r e l a t i o n , that i s v a l i d i n the
l a r g e Schmidt No. range and given as
875 0 25
Nsh=0.023N °' Re N Sc - (7)

NAKAO AND KIMURA Effect of Gel Layer cn Refection 121
Boundary Layer
I Gel Layer
1 ( /A
\ dx /
bulk ( product
\
Membrane
American Institute of
Chemical Engineers Journal Figure 1. Gel polarization schematic (2)
1 2 j 1 1 1 i r
0 t 1 1 1 1 1 1
0 0.4 0.8 1.2
Figure 2. Gel layer concentrations of
Cb ( wt % ) PVA 224 measured directly as a function
of bulk concentration and feed velocity
American Institute of using T4/A(black) and T2/A(white)
Chemical Engineers Journal membranes (2)

These f a c t s show that the a c t u a l Cg value can be c a l c u l a t e d by

Eq. (6) by knowing appropriate k value.
From the other p o i n t of view the u l t r a f i l t r a t i o n f l u x i s
given by the r e s i s t a n c e law as
= AP (8)
s p e c t i v e l y . Although Eq. (6) and (8) both give f l u x , t h e i r r e -

l a t i o n has not been i n v e s t i g a t e d . When Rg i s p l o t t e d against Cg,
the r e l a t i o n were found t o e x i s t as shown i n F i g . 4, where Rg i s
p r o p o r t i o n a l to C l - 7 . P r e c i s e meaning of t h i s r e l a t i o n i s not
g
yet known, but i t enables now to p r e d i c t J at given c o n d i t i o n s .

v
One example i s given i n the f o l l o w i n g . F i g . 5 shows the t y p i c a l

p l o t f o l l o w i n g the g e l p o l a r i z a t i o model suggested b Eq (6)
w i t h the assumption tha
data but s o l i d l i n e s ar y
!
using Eqs. ( 6 ) , ( 8 ) , D e i s s l e r s c o r r e l a t i o n and the r e l a t i o n shown
i n F i g . 4. These f i g u r e s c l e a r l y show the d i f f e r e n c e of the as-
sumption regarding the value of g e l l a y e r concentration.
C h a r a c t e r i z a t i o n of u l t r a f i l t r a t i o n membrane
Before d i s c u s s i n g the r e j e c t i o n c h a r a c t e r i s t i c s of membrane

w i t h g e l l a y e r , the property of membrane without g e l l a y e r should
be determined. Various t r a n s p o r t equations have been used, some
of which are based on the p a r t i c u l a r mechanism, the others are
based on the phenomenology. According to the l a t t e r the f o l l o w i n g
equations are presented ( 4 ) .
J v = Lp(AP-aAII) (9)
JS = P(Cm-Cp) + ( l - a ) j c
v (10)
In these equations, the membrane c h a r a c t e r i s t i c s are described by

three parameters, pure water p e r m e a b i l i t y Lp, s o l u t e p e r m e a b i l i t y
P and r e f l e c t i o n c o e f f i c i e n t a. The_determination of these para-
meters i s very important. The term C i n Eq. (10) shows the
average concentration on both sides of a membrane and the l o g a -
r i t h m i c mean i s u s u a l l y used.
In the case of high r e j e c t i o n membrane, the value of AC i s so
l a r g e that the l o g a r i t h m i c mean c o n c e n t r a t i o n does no longer cor-
respond to c o r r e c t average. To solve t h i s problem, S p i e g l e r and
Kedem (5) d i v i d e d the membrane i n t o d i f f e r e n t i a l elements i n the
d i r e c t i o n of i t s thickness and a p p l i e d Eq.(10) i n i t as the form
of d i f f e r e n t i a l equation. The r e s u l t of i n t e g r a t i o n i s expressed
as a(i-F)
=
R (ID
1-crF
where

NAKAO A N D KIMURA Effect of Gel Layer on Rejection 123
' 1 1
- • -
o • /
- _
103
n
a/5R> o
• IS
JO Ik
- ^ Figure 3. Comparisons of mass transfer
1 1 tion for PVA 224 (O), PVA 205 ([J),

and ovalbumin (A) under three condi-
104 105 2
tions: white, pressure = 10 kg/cm , mem-
Kj 0 . 8 7 5 M 0.25
"Re ^Sc
brane tube I.D. = 1.25 cm; black, 2 kg/
2 2
cm , 2.54 cm; half-black, 5 kg/cm , 1.25
American Institute of cm and a line indicating the Desissler
Chemical Engineers Journal correlation (2).
1
1 1 r
Figure 4. Relationships between the re-

—' 1 i i l_ sistance to a flow and the concentration
0.5 1 2 5 10 of gel layer for PVA 224 (white) and
Cg ( wt % )
ovalbumin (black) under various condi-
tions: pressure = 2 kg/cm, membrane
2
American Institute of diameter = 2.54 cm (O); 5 kg/cm , 1.25

1 0 2
Chemical Engineers Journal cm O ; kg/cm , 1.25 cm (A) (2).

12
• r
T4/A
PWP
10 K g / c m 2
o\ 95 cm/s
102 103 10"
bulk concentration ( ppm )
American Institute of Chemical Engineers Journal
Figure 5. Experimental fluxes for the T4/A membrane, with a 1.25-cm diameter,
treating PVA 224 aqueous solutions under three kinds of feed velocities (2)
> i 1
PWP
T4/A
^ ^ ^ 9 5 cm/s 10 Kg/cm2
"
-
• . 1
Figure 6. Comparisons between experi-
mental and calculated fluxes for PVA 224 102 103 104
aqueous solutions under three kinds of bulk concentration ( ppm )

feed velocities. Curves are calculated
from Equations 6, 7, and 8, and the rela- American Institute of
tion shown in Figure 4 (2). Chemical Engineers Journal

9. NAKAO A N D KIMURA Effect of Gel Layer on Rejection 125
F = exp(-i£ • J ) V (12)
Equation (9) does not change by the same treatment. The a p p l i -

c a b i l i t y of these equations t o u l t r a f i l t r a t i o n membrane i s not
f u l l y e s t a b l i s h e d and the determination method of parameters i n
these equations from the experimental data i s not f i x e d y e t . For
such purposes the f o l l o w i n g experiments were conducted.
Two kinds of c e l l u l o s e acetate u l t r a f i l t r a t i o n t u b u l a r mem-
branes (T2/A and T4/A) produced by Paterson Candy I n t e r n a t i o n a l ,
L i m i t e d , England, were employed i n t h i s study. S i x kinds of so-
l u t e s , polyethylene g l y c o l (PEG//4000) , v i t a m i n Bi2> r a f f i n o s e ,
sucrose, glucose, and g l y c e r i n , were used. Molecular weights,
d i f f u s i v i t i e s and molecular r a d i i of these s o l u t e s are shown i n
Table 1. The experimental apparatus i s shown s c h e m a t i c a l l y i n
F i g . 7.
Two kinds of experiment
periment, four feed v e l o c i t i e
employed and the pressure was kept constant a t 8 atm. In the
other, v a r i o u s pressures between 2 and 12 atm were employed and
the v e l o c i t y was kept constant at 58 cm/s. The temperature o f
feed s o l u t i o n was c o n t r o l l e d a t 25°C by a thermostat throughout
a l l the experimental runs. The c o n c e n t r a t i o n of the feed s o l u t i o n
ranged from 100 to 2000 ppm.
Three parameters, Lp, O and P, which describe the membrane
c h a r a c t e r i s t i c s were determined i n the f o l l o w i n g manner.
Pure water p e r m e a b i l i t y Lp was obtained from the experiment
of pure water permeation u s i n g Eq. ( 9 ) , i n which the osmotic
pressure d i f f e r e n c e All i s zero.
Two parameters O and P were f i r s t determined by using the
l o g a r i t h m i c mean c o n c e n t r a t i o n C£ . Equation (10) i s r e w r i t t e n as
m
-So" = P + ( l - a ) . - ^ - (14)
where AC=C -Cp i s the c o n c e n t r a t i o n d i f f e r e n c e . As i l l u s t r a t e d i n

m
F i g . 8, there i s good l i n e a r c o r r e l a t i o n between Js/AC and

Jv'Qgm/Ac, and the parameters a and P were obtained from the slope
and i n t e r c e p t . Then, to examine the accuracy of these parameters,
the r e a l r e j e c t i o n R was c a l c u l a t e d by means of Eqs. (11) and (12)
using these v a l u e s , and p l o t t e d R versus 1 / J as dotted l i n e s i n
V
F i g . 9. I n the region of low f l u x , the c a l c u l a t e d l i n e s agreed

w e l l w i t h the experimental data, but i n the high f l u x area, the
agreement between both values were not good. The use of l o g a -
r i t h m i c mean c o n c e n t r a t i o n , t h e r e f o r e , i s only v a l i d i n the low
f l u x region.
In Eqs. (11) and (12), F~K) a t high f l u x and hence the r e -
f l e c t i o n c o e f f i c i e n t O i s the l i m i t i n g value of R.
J v -*°°;R (13)

Modules
J Concentrate
Product
Feed
PCV
American Institute of Chemical Engineers Journal
Figure 7. Schematicflowsheet of the experimental apparatus (2)
Figure 8. Determination of a- and P of

A 6 8 10 12
T4/A membrane by using the logarith-
mic mean concentration C l m ' J v / A C x 10*

This f a c t has been used f o r the determination o f a by p l o t t i n g R

vs. J or R v s . 1 / J and by e x t r a p o l a t i n g J ^°° or 1/J -H). But i t
v V v V
was only i n the case of h i g h o r low r e j e c t e d s o l u t e s that t h i s

p l o t became a s t r a i g h t l i n e , as i l l u s t r a t e d i n F i g . 9., and the
values of a e x t r a p o l a t e d were not accurate.
The d i r e c t curve f i t t i n g of Eqs. (11) and (12) was a l s o a t -
tempted. When O i s assumed t o have a c e r t a i n v a l u e , the average
and standard d e v i a t i o n of P f o r a l l experimental data o f one so-
l u t e and membrane can be c a l c u l a t e d u s i n g Eqs. (11) and (12). By
c a l c u l a t i n g the standard d e v i a t i o n a t a d i f f e r e n t value o f a, i t s
most s u i t a b l e value i s determined when the standard d e v i a t i o n be-
comes minimum. P i s then given as the average of a l l data. The
best f i t t i n g curves are i l l u s t r a t e d i n F i g . 9 as s o l i d l i n e s and
the values of G, P and i t s standard d e v i a t i o n l i s t e d i n Table 2.
The c a l c u l a t e d l i n e s agreed very w e l l w i t h the experimental data
for a l l solutes.
I t i s apparent fro
Kedem equations, Eqs. (11) and (12), were s u i t a b l e as t r a n s p o r t
equations of u l t r a f i l t r a t i o n and the c u r v e - f i t t i n g method was the
best f o r the determination o f the membrane parameters, O and P.
The r e j e c t i o n of s o l u t e s by g e l
Our next step i s t o determine O and P values of g e l l a y e r .

To do that equations are needed, which d e a l w i t h the case t h a t the
two d i f f e r e n t membranes are i n s e r i e s , which were developed by
J a g u r - G r o d z i n s k i & Kedem ( 6 ) . F o l l o w i n g t h i s treatment r e j e c t i o n
of s e r i e s membranes i s given by
P _ (l-F )(l-a )+Fg(l-a )(l-Fma )-(l-cJ )(l-am)

g m g m g n s .
K ± D )
(1-Fg)(l-a )+F (l-a )(1-F a ) m g g m m
where
J 1 0
F g = exp{- ^ ~ S > } (16)
J 1 gm
F m = exp{- v< ~ >} (17)
*m
S u f f i x g corresponds t o g e l l a y e r and m corresponds t o membrane,

and a and P are a l r e a d y determined.
m m So the next step i s t o ob-
t a i n Og and Pg from the experimental data by the curve f i t t i n g
method e x p l a i n e d p r e v i o u s l y .
The experimental apparatus and membranes used are same as
before. As a g e l l a y e r forming s o l u t e ovalbumin, and as the other
s o l u t e v i t a m i n B 1 2 were used.
Since the g e l l a y e r thickness changes depending on the pres-
sure, feed v e l o c i t y and bulk c o n c e n t r a t i o n , i t i s necessary t o
s p e c i f y the t h i c k n e s s t o o b t a i n Og and Pg of the g e l l a y e r . Only

0 5 10 15 20 25 30
2 2 3
1/J V x 10' ( cm s/cm )
Figure 9. Plot of R vs. 7/J : ( v ) determined by the method of curve fitting;

( ) determined by using the logarithmic mean concentration; ( ) extrapo-
lation of 1/J -> 0 for the determination of o-. PEG#4000 (\>); Vitamin B (O);
V
raffinose (\7); sucrose (•); glucose (A); glycerin (0).
100
80
Ovalbumin and Vitamin Bl2
55 60
T 5 / A - 6 membrane
= 40
Vitamin B12
20
J I L_
Figure 10. Rejection of Vitamin B 0 2 4 6 8 10 12
12
vs. pressure Pressure ( Kg/cm ) J

Table 1 Molecular weights, d i f f u s i v i t i e s

and Stokes r a d i i of s o l u t e s
8
Molecular D x 10 r s x io
Solute weight 2
(cm /s) (cm)
PEG #4000 3000 1.5 16.3
Vitamin B l 2 1355 3.3 7.4
Raffinose 504 4.2 5.8
Sucrose 342 5.2 4.7
Glucose 180 6.9 3.6
Glycerin 92 9.5 2.6
Table 2 Parameters O and P, and i t s standard

d e v i a t i o n of the T4/A membrane determined
by the method of curve f i t t i n g
4
P x 10 Standard
Solute a (cm/s) deviation
PEG #4000 0.93 0.52 1,7 x 10" !
Vitamin B12 0.81 3.0 3.1 x 10 ;
Raffinose 0.66 7.8 3.9 x 10 :
1
Sucrose 0.63 17 1.8 x 10
Glucose 0.30 17 4.5 x 10 '
Glycerin 0.18 55 1.7 x 10
Table 3 Values of Q and P of ovalbumin g g
gel layer. Solute ; vitamin B ^ *
R P x 10
g O
g
(atm/cm. s ) (cm/s)
g
40000 0.99 1.4
20000 0.99 2.9
10000 0.99 5.6
8000 0.99 6.8
Values of 0* and P m m of a membrane a r e ;

3
a m = 0.89, P = 1.1 x l ( T
m (cm/s)

100
Rg=40000
oc 4 0
Figure 11. Plots of rejection of Vitamin Vitamin B12 one solute

B against i / J : (
v ) determined by a
method of curve fitting; black, Vitamin
B single solute; white, ovalbumin +
12
5 10 15 20
3
Vitamin B, two solutes.

2
1/J *10~
V (s/cm)
i 1 1 r
I i i 1 1 1—J
3 4 5
10 10 10
Figure 12. Relationship between P of K
Vitamin B and R
12 K
Rg ( Kg cm7cm s" ) 1

9. NAKAO AND KIMURA Effect of Gel Layer on Rejection 131
index to s p e c i f y the thickness i s the g e l l a y e r r e s i s t a n c e , Rg.

To determine 0~ and Pg values i t i s necessary to measure the r e -
j e c t i o n at d i f f e r e n t volume f l u x , Jv, that means i t i s necessary
to perform experiment at d i f f e r e n t pressures. And at d i f f e r e n t
pressures Rg changes, when the bulk c o n c e n t r a t i o n i s kept constant.
To keep Rg value constant at d i f f e r e n t pressure i t i s necessary t o
change bulk c o n c e n t r a t i o n or the feed v e l o c i t y . In our experiment
the l a t t e r was kept constant, w h i l e the bulk c o n c e n t r a t i o n was ad-
j u s t e d to keep Rg constant. Even so i t i s hard to keep Rg pre-
c i s e l y constant. Therefore f i n a l l y the experimental r e l a t i o n s
between Rg and r e j e c t i o n , R, were obtained by p l o t t i n g data on the
graph and R values were read at appropriate Rg by i n t e r p o l a t i o n .
A f t e r o b t a i n i n g the o r i g i n a l data i t i s necessary to c o r r e c t
the e f f e c t of the c o n c e n t r a t i o n p o l a r i z a t i o n . In the mixed so-
l u t i o n s i t i s not c e r t a i n whether i t i s p o s s i b l e to use the mass
t r a n s f e r c o e f f i c i e n t determine
value are used s i n c e n
r e j e c t i o n , R, thus obtained are shown i n F i g . 10 f o r v i t a m i n B 1 2
only and f o r the case w i t h ovalbumin g e l l a y e r . I n t h i s f i g u r e
i t i s shown the r e j e c t i o n of d i f f e r e n t membrane are same due t o
the g e l l a y e r formation of ovalbumin.
The p l o t of R against 1 / J i s shown i n F i g . 11. In the
V
f i g u r e s o l i d l i n e s are drawn by curve f i t t i n g using Eq. (15) a t

each Rg value. Values of Og and Pg are shown i n Table 3. (Jg i s
0.99 and not dependent on Rg, but P i s dependent on Rg. The r e -
g
l a t i o n between Pg and Rg i s shown i n F i g . 12, which shows Pg i s

i n v e r s e l y p r o p o r t i o n a l to Rg. That means P i s i n v e r s e l y pro-
g
p o r t i o n a l to the g e l l a y e r t h i c k n e s s , which i s considered to be

the reasonable c o n c l u s i o n . Further progress i s being attempted
to check these r e s u l t s w i t h other s o l u t e s - g e l l a y e r systems.
Conclusion
I t was found that the g e l l a y e r c o n c e n t r a t i o n i s not con-

s t a n t , but v a r i a b l e , which can be p r e d i c t e d by u s i n g the o r d i n a r y
c o n c e n t r a t i o n p o l a r i z a t i o n model w i t h appropriate mass t r a n s f e r
c o e f f i c i e n t . A l s o t h i s c o n c e n t r a t i o n has a p a r t i c u l a r r e l a t i o n
w i t h the g e l l a y e r r e s i s t a n c e . Using t h i s r e l a t i o n the f l u x
through the membrane can be c a l c u l a t e d f o r the case of g e l l a y e r
formation.
R e j e c t i o n c h a r a c t e r i s t i c s of u l t r a f i l t r a t i o n membrane were
analysed and method to determine the t r a n s p o r t c o e f f i c i e n t s i s
developed. A l s o the r e j e c t i o n c h a r a c t e r i s t i c s of membrane w i t h
g e l l a y e r were analysed and i t i s found that the t r a n s p o r t co-
e f f i c i e n t s of g e l l a y e r have a d e f i n i t e r e l a t i o n w i t h the g e l
l a y e r r e s i s t a n c e , and perhaps w i t h g e l l a y e r t h i c k n e s s .

Notation
C = c o n c e n t r a t i o n of s o l u t e , wt%
2
D = d i f f u s i v i t y , cm /s
J = permeation v e l o c i t y of s o l u t e through membrane, cm/s
s
3
J = volume f l u x through membrane, cm /cm *s
v
fe = mass t r a n s f e r c o e f f i c i e n t , cm/s
3 z
Lp = pure water p e r m e a b i l i t y , cm /cm «S-atm
NRe = Reynolds number
=
Nsc Schmidt number
N =
Sh Sherwood number
2
Ap = pressure d i f f e r e n c e , Kg/cm
P = s o l u t e p e r m e a b i l i t y , cm/s
2
R = r e s i s t a n c e to a flow, Kg.cm" /cm-s~
or
R = real rejection
X = d i s t a n c e , cm
6 = boundary l a y e r t h i c k n e s s , cm
All = osmotic pressure d i f f e r e n c e , atm
0 = reflection coefficient
Subscripts
b = bulk
g = g e l layer
m - membrane
p = product
Literature Cited
1. Kimura, S; Nakao, S. D e s a l i n a t i o n , 1975, 17, 267.

2. Nakao, S; Nomura, T; Kimura, S. AICHE J., 1979, 25, 615.
3. Nakao, S; Kimura, S. J . Chem. Eng. Japan, in press.
4. Kedem, O; Katchalsky, A. Biochim. Biophys. Acta, 1958,27,229.
5. S p i e g l e r , K.S; Kedem, O. D e s a l i n a t i o n , 1966, 1, 311.
6. J a g u r - G r o d z i n s k i , J ; Kedem, O. D e s a l i n a t i o n , 1966, 1, 327.

10
Application of Ultra- and Hyperfiltration During

Production of Enzymatically Modified Proteins
H. SEJR OLSEN and J. ADLER-NISSEN

Enzyme Applications Research and Development, Novo Industri A/S,
Novo Allé, DK-2880 Bagsvaerd, Denmark
A p p l i c a t i o n of membrane processes during production of puri-

fied food p r o t e i n s i s a
functional properties o
These p r o p e r t i e s are mostly found t o be s u p e r i o r t o those of de
natured p r o t e i n s . However, not all p o s s i b l e needs o f the modern
food i n d u s t r y are fulfilled by using n a t i v e p r o t e i n s i n s t e a d of
denatured ones. Therefore, enzymatic m o d i f i c a t i o n of p r o t e i n s has
been demonstrated as a p o s s i b l e means o f meeting the needs of the
food i n d u s t r y f o r h i g h - q u a l i t y p r o t e i n i n g r e d i e n t s ( 2 ) , (13),
(14).
Membrane processes have a potential a p p l i c a t i o n w i t h i n many
areas of industrial enzymatic h y d r o l y s i s of p r o t e i n s . Table I
shows how membrane processes can be a p p l i e d i n the d i f f e r e n t
types of enzymatic m o d i f i c a t i o n of p r o t e i n . Thus membrane pro-
cesses may be used f o r pre-treatment of p r o t e i n s , f o r the r e -
a c t i o n step and as an essential p a r t of the purification o r post
-treatment step.
In the f o l l o w i n g , r e s u l t s from our work w i t h these processes
i n Novo's pilot p l a n t f o r Enzyme A p p l i c a t i o n will be presented.
The r e s u l t s demonstrate t h a t the f u n c t i o n a l p r o p e r t i e s of some
of the p r o t e i n products obtained were improved to such an extent
that the membrane processes may become very important in the mo-
dern p r o t e i n technology. Owing to the i n t e r e s t i n g p r e l i m i n a r y r e -
s u l t s obtained regarding f u n c t i o n a l p r o p e r t i e s , l e s s a t t e n t i o n
has been paid to a thorough i n v e s t i g a t i o n of the u n i t operations
as such.
General C h a r a c t e r i s t i c s of Enzymatic H y d r o l y s i s . As e a r l i e r
reported (2_) , a l i m i t e d h y d r o l y s i s of a p r o t e i n product may im-
prove c e r t a i n f u n c t i o n a l p r o p e r t i e s such as whipping and emulsi-
fying capacity.
These improvements are dependent on the enzyme and on the
p r i n c i p l e by which the r e a c t i o n i s c o n t r o l l e d . The p r e f e r a b l e way
of c o n t r o l l i n g the m o d i f i c a t i o n i s by a p p l i c a t i o n of the pH-stat-
technique, by which the base consumption used f o r maintaining pH
0097-6156/81/0154-0133$09.25/0

during the p r o t e o l y t i c r e a c t i o n i s d i r e c t l y converted to degree

of h y d r o l y s i s 02). Degree of h y d r o l y s i s , DH, i s the p r o p o r t i o n
between the number of peptide bonds cleaved and the t o t a l number
of peptide bonds i n the i n t a c t p r o t e i n ( 3 ) .
P r o t e o l y t i c a l l y modified p r o t e i n s which have been thoroughly
enzyme digested are low molecular p r o t e i n h y d r o l y s a t e s . Such pro-
ducts have o f t e n l e s s pronounced foaming o r e m u l s i f y i n g proper-
t i e s than p r o t e i n s which have been only s l i g h t l y hydrolyzed (2) .
However, a need f o r t h i s k i n d of p r o t e i n products appears i n the
beverage i n d u s t r y f o r enrichment o f s o f t d r i n k s w i t h p r o t e i n and
i n the meat i n d u s t r y f o r pumping of whole meat cuts w i t h low cost
p r o t e i n s . Important p r o p e r t i e s of low molecular p r o t e i n h y d r o l y -
sates are a bland t a s t e and a complete s o l u b i l i t y over the wide
pH-range used i n foods.
The production method f o r low molecular p r o t e i n hydrolysates
has been described e a r l i e r (40 A c o n t r o l l e d batch h y d r o l y s i s
using the pH-stat i s performed
then recovered by e.g. s o l i d
used f o r c o n c e n t r a t i o n and/or d e s a l i n a t i o n . Instead of using the
c o n t r o l l e d batch h y d r o l y s i s and s o l i d s s e p a r a t i o n processes, the
s e p a r a t i o n of peptides may be performed from an enzyme-substrate
r e a c t i o n mixture under continuous u l t r a f i l t r a t i o n i n a s o - c a l l e d
membrane r e a c t o r .
H i g h l y F u n c t i o n a l Soy P r o t e i n s
Native soy p r o t e i n i s o l a t e may be produced by u l t r a f i l t r a -

t i o n of an aqueous e x t r a c t of d e f a t t e d soy bean meal, (1), ( 5 ) .
The process layout i s shown i n F i g . 1. A c a r e f u l s e l e c t i o n of
membrane parameters such as flow v e l o c i t y , pressure drop, tempe-
r a t u r e , and of the type of membrane and modules i s important i n
order to o b t a i n a bean p r o t e i n i s o l a t e by a d i r e c t u l t r a f i l t r a -
t i o n of the c l a r i f i e d e x t r a c t ( 5 ) . The p r o t e i n i s o l a t e has a pro-
t e i n - d r y matter r a t i o higher than 90% (N x 6.25), when using t h i s
process.
H i t h e r t o , enzymatic m o d i f i c a t i o n of u l t r a f i l t e r e d soy pro-
t e i n s has not been described. The present i n v e s t i g a t i o n shows
that p r o t e i n products w i t h b e t t e r p r o p e r t i e s than e n z y m a t i c a l l y
modified a c i d p r e c i p i t a t e d p r o t e i n s can be produced by a s u i t a b l e
combination of the i n v o l v e d u n i t o p e r a t i o n s .
M o d i f i c a t i o n of U l t r a f i l t e r e d versus A c i d P r e c i p i t a t e d
Soy P r o t e i n . When the r e t e n t a t e obtained from the u l t r a f i l -
t r a t i o n of soybean e x t r a c t i s subjected to an enzymatic h y d r o l y -
s i s as described e a r l i e r (2) f o r a c i d p r e c i p i t a t e d p r o t e i n , a
h y d r o l y s i s curve (DH versus time) may be drawn. A comparison of
such h y d r o l y s i s curves i s shown i n F i g . 2 f o r a c i d p r e c i p i t a t e d
soy p r o t e i n i s o l a t e and u l t r a f i l t e r e d soy p r o t e i n i s o l a t e . The
curves a r e drawn on the b a s i s of the same h y d r o l y s i s parameters.
The enzyme used i s the m i c r o b i a l a l k a l i n e protease s u b t i l i s i n
C a r l s b e r g (ALCALASE® ).

O L S E N A N D ADLER—NISSEN Enzymatically Modified Proteins 1
Table I. Application of Membrane Processes During

Enzymatic Modification of Proteins
TYPES OF ENZY-
ENZYMATIC
MATIC MODIFIED PRETREATMENTS POSTTREATMENTS
REACTION STEP
PROTEINS
HIGHLY PRODUCTION OF MOLECULAR
FUNCTIONAL NATIVE PROTEIN - SEPARATION
PROTEINS ISOLATE BY UF BY UF
CONCENTRATION
- - AND/OR DESA-
LOW MOLECULAR
PROTEIN HYDRO-
LYZATES
MEMBRANE CONCENTRATION
- REACTOR BY AND/OR DESA-
UF LINATION BY HF
UF ~ ULTRAFILTRATION
HF ~ HYPERFILTRATION
Soy meal Water
50% T\
(Nx6.25)
Extraction (Liq./solid-ratio: 10:1)
Extract 4% ( N x 6 . 2 5 ) _j C oonncceei n t r a t e 2 2 - 2 5 % (Nx6.25)
Centrifuge
Remanence
(sludge) filtration meate
8% ( N x 6 . 2 5 ) (batch) 0.15%
(Nx6.25)
Spray Protein isolate

drying Q Q % ( N x 6 > 2 5)
Figure 1. Production of soy protein isolate by UF in pilot plant

I t appears from F i g . 2 t h a t the u l t r a f i l t e r e d soy p r o t e i n

i s o l a t e i s hydrolyzed c o n s i d e r a b l y more slowly than the a c i d pre-
c i p i t a t e d p r o t e i n . This i s due to the compact molecular s t r u c t u r e
of the u l t r a f i l t e r e d p r o t e i n , which i s s t i l l i n the n a t i v e s t a t e .
That the degree of denaturation of a p r o t e i n s u b s t r a t e has a pro-
found i n f l u e n c e on the k i n e t i c s of the p r o t e o l y s i s has been known
f o r long, see Christensen ( 6 ) . I t should be noted that s u b t i l i s i n
C a r l s b e r g i s not i n h i b i t e d by the protease i n h i b i t o r s present i n
n a t i v e bean p r o t e i n ( 7 ) .
Using the u l t r a f i l t e r e d soy p r o t e i n i s o l a t e described pre-
v i o u s l y ( F i g . 1 ) , a s e r i e s of hydrolysates covering a range of
DH-values (DH = 0 to DH = 6%) was made i n the l a b o r a t o r y using
the method o u t l i n e d i n F i g . 3. In a l l cases the h y d r o l y s i s was
terminated by a d d i t i o n of HC1 to pH = 4.2 to i n a c t i v a t e the en-
zyme. A f t e r 30 minutes, pH was readjusted to pH = 7.0 by using
NaOH. NaCl was added u n t i l the f i n a l c o n c e n t r a t i o n i n a 10% pro-
t e i n (N x 6.25) s o l u t i o
The whipping expansio
a s o l u t i o n having 3% p r o t e i n ( 2 ) . F i g u r e 4 shows whipping expan-
s i o n versus DH f o r u l t r a f i l t e r e d and a c i d - p r e c i p i t a t e d soy pro-
t e i n s modified by A l c a l a s e . S i m i l a r r e s u l t s have a l s o been found
f o r u l t r a f i l t e r e d and a c i d - p r e c i p i t a t e d p r o t e i n s from faba beans
( V i c i a faba) ( S e j r Olsen, unpublished r e s u l t s ) .
I t appears from F i g . 4 that i n the case of the a c i d - p r e c i p i -
t a t e d p r o t e i n , higher DH-values cause a d i s t i n c t r e d u c t i o n of the
whipping expansion. The i n c r e a s i n g content of small peptides r e -
s u l t i n g from a more pronounced degradation of the p r o t e i n s at the
high DH values i s assumed to be r e s p o n s i b l e f o r t h i s r e d u c t i o n of
foaming a b i l i t y . Removal of the small peptides during the pro-
c e s s i n g of the u n r e f i n e d soy meal to the f i n a l whipping agent
might t h e r e f o r e have a p o s i t i v e e f f e c t on the foaming a b i l i t y .
Experimental D e t a i l s . In order to examine the above hypo-

t h e s i s , the enzymatic h y d r o l y s i s was c a r r i e d out at d i f f e r e n t
stages during the soy i s o l a t e process. Four process combinations
examined i n our p i l o t p l a n t are o u t l i n e d s c h e m a t i c a l l y i n F i g . 5.
In a l l cases the f o l l o w i n g procedure was used:
D e f a t t e d , dehulled white soy meal from Aarhus O l i e f a b r i k A/S

was e x t r a c t e d w i t h water at pH = 8.0 using a l i q u i d : s o l i d
r a t i o of 10 : 1.
A l l c e n t r i f u g a t i o n s were c a r r i e d out i n a W e s t f a l i a SB-7
solids ejecting centrifuge.
A l l u l t r a f i l t r a t i o n s were made on a DDS-modul type 35 at
2
50°C using polysulphone membranes type GR6-P at 3 kp/cm .
The module had 2.25 m2 of membrane area.
Hydrolyses were made by use of ALCALASE 0.6 L at pH = 8.0
i n pH-stat.

OLSEN A N D ADLER—NISSEN Emymatically Modified Proteins 137
% DH'
Cone, of substrate: Soy protein isolate
_ S= 8% N x 6 . 2 5 Purin?. 500 E ^
16
pH 8.0
- 50°C Cone, o f enzyme:

12
E/S = 2 . 0 % A l c a l a s e 0.6L
(E = 0 . 1 6 % )
8 -
Soy p r o t e i n i s o l a t e _
4
ultrafi1tered
r i
3
min
Figure 2. Hydrolysis curves for soy protein isolates
> ^ ^ D i l u t e d
(Soy UF-retentate j
V^_8% Nx6.25 y
ALCALASE pH-STAT hydrolysis
4N NaOH at pH = 8 . 0 , 50°C
\
6N HC1 Enzyme i n a c t i v a t i o n
pH 4 . 2 , 50°C, 30 min.
•
4N NaOH »• Adjustment of
pH to 7.0
•
Sol i d NaCl Adjustment to
14.6g NaCl/lOOg Nx6.25
Freeze drying
Figure 3. Laboratory method for proteolytic modification of ultraflltered soy pro-

tein isolate

i i i i T r— i 1 •
% Whipping expansion
1600
Ultrafiltered
1200 -
800 - i /
/ /
/ /
400 / /
Acid precipitated
A* /
T i
1 2
% DH
Figure 4. Whipping expansions vs. DH for soy protein hydrolysates
EXTRACTION EXTRACTION EXTRACTION EXTRACTION
1 ! 1
HYDROLYSIS CENTRIFUGATION CENTRIFUGATION CENTRIFUGATION
1 1 1 1
INACTIVATION HYDROLYSIS ULTRAPILTRATIOR" •OLTRAPIETRATION"
1 1 1 1
CENTRIFUGATION INACTIVATION ' H Y D R O L Y S I S ' ' H ? G R 0 C ? 5 I 5 '
1 1 1 1
"OCTRAFILTRATIUR" CENTRIFUGATION INACTIVATION INACTIVATION
1 1 1 1
DRYING "OCrariCTRATTOR" DRYING CENTRIFUGATION
I 1
I III
DRYING 'OCTRAPICTRATIOflJ
l
II
DRYING
IY
Figure 5. Process combinations investigated for production of highly functional
enzymatically modified soy proteins

10. OLSEN A N D ADLER—NISSEN Enzymatically Modified Proteins 139
In a l l cases h y d r o l y s i s to DH = 3% and DH = 6% was made and

i n a c t i v a t i o n was c a r r i e d out a t pH = 4.0 (50°C) f o r 30 minu-
tes. The general h y d r o l y s i s parameters were:
Substrate c o n c e n t r a t i o n s : S = 3 to 8% (N x 6.25)
Enzyme/substrate r a t i o : E/S = 2% ALCALASE 0.6 L
Temperature: T = 50°C
pH: pH = 8.0
Some of the d i f f e r e n t u l t r a f i l t r a t i o n processes w i t h i n the
four process combinations i n c l u d e d i a f i l t r a t i o n as w e l l . When
d i a f i l t r a t i o n was included at a stage, the sequence, u l t r a f i l t r a -
t i o n - d i a f i l t r a t i o n - u l t r a f i l t r a t i o n , was used i n order to ob-
t a i n a high s e p a r a t i o n e f f i c i e n c y and membrane c a p a c i t y ( 8 ) .
The f i n a l p r o t e i n products were analysed and evaluated f o r
t h e i r whipping expansion, foam s t a b i l i t y and i n the case of the
DH-6%-products f o r bakin performanc i meringu b a t t e
w e l l . The a n a l y t i c a l procedure
Methods of A n a l y s i s
Whipping Expansion. C a r r i e d out as d e s c r i b e d p r e v i o u s l y

(2).
Foam S t a b i l i t y . A p l a s t i c c y l i n d e r (diameter 7 cm, h e i g h t
9 cm) having a w i r e net w i t h a mesh s i z e of 1 mm x 1 mm i s f i l -
led w i t h foam and the amount of foam i s found by weighing (A
gram) . The c y l i n d e r i s then placed on a funnel on top of a g l a s s
c y l i n d e r of 100 ml. A f t e r 30 minutes the weight (B) of drained
l i q u i d i n the g l a s s c y l i n d e r i s determined. The foam s t a b i l i t y
FS i s d e f i n e d by the equation:
A B
FS = ~ x 100%
A
Baking Performance of Meringue B a t t e r . To 100 ml of a 12%
w/w (N x 6.25) s o l u t i o n a t pH = 7.0 of the whipping agent, 150 g
of saccharose i s added. The saccharose i s completely d i s s o l v e d by
gentle s t i r r i n g at room temperature.
The s o l u t i o n i s then whipped a t speed I I I (260 rpm) f o r 10
minutes i n a Hobart Mixer (model N - 50) u s i n g a w i r e whisk. Im-
mediately a f t e r w a r d s , t e n samples of 10 ml are t r a n s f e r r e d to an
aluminium t r a y a t separate p o s i t i o n s by means of a s y r i n g e .
Baking i s then performed a t 130°C f o r 1 hour. A f t e r c o o l i n g t o
ambient temperature, the weight, the height (h) and the diameter
(d) are determined. The volume i s c a l c u l a t e d assuming that the
meringue i s a s p h e r i c a l segment having the volume:
1 2 ^ 2
Z z
V=-g-xTrx(h +|- x ) d
The apparent d e n s i t y i s then c a l c u l a t e d , and the s m a l l e r the den-

s i t y , the b e t t e r the baking performance, provided that the s u r -
face i s s t i l l smooth and the shape i s maintained.

Amino-acid Analyses. C a r r i e d out by B i o t e k n i s k I n s t i t u t ,

K o l d i n g , Denmark.
TCA-soluble N i t r o g e n . Measured i n 0.8 N t r i c h l o r o a c e t i c

a c i d (TCA) u s i n g the method of Becker et a l . ( 9 ) .
Nitrogen S o l u b i l i t y . C a r r i e d out as d e s c r i b e d p r e v i o u s l y
(2).
Free Alpha-amino Groups. Measured by the TNBS-method (10).
Crossed Immunoelectrophoresis. The method i s d e s c r i b e d by

Weeke (11) .
R e s u l t s and D i s c u s s i o n
Data from the membran

l i b . Average permeate f l u x e s of the same order of magnitude were
seen i n a l l combinations, whether the u l t r a f i l t r a t i o n s were per-
formed on enzyme t r e a t e d p r o t e i n s or on raw bean e x t r a c t . This
i n d i c a t e s that p r o t e i n molecules capable of forming a g e l on the
membrane surface are s t i l l present a f t e r the enzymatic m o d i f i c a -
t i o n . The s i z e of the permeate f l u x e s obtained i s i n the i n t e r v a l
of about 20-40 l/h/m2, which i s i n the economically a t t r a c t i v e
range of the process ( 5 ) . The p r o t e i n y i e l d s shown i n Table I l i a
and I l l b are based on 100% recovery of phases. The reason f o r the
r a t h e r low y i e l d s are low n i t r o g e n s o l u b i l i t y of the soy meal
used, v i z . about 60% at pH = 8. As about 90% of p r o t e i n may be
water e x t r a c t e d from a l e s s denatured soy meal (12), the o v e r a l l
y i e l d s would be about 50% higher i f such a raw m a t e r i a l i s used.
I f the combinations I , I I and IV are compared w i t h respect
to the y i e l d s and f u n c t i o n a l p r o p e r t i e s , i t appears that both
whipping expansion and foam s t a b i l i t y are h i g h e s t at the h i g h DH-
v a l u e . However, due to h i g h e r content of low molecular peptides
at the high DH-value, the o v e r a l l p r o t e i n (N x 6.25) y i e l d s are
lower. The processes have to be evaluated more thoroughly i n o r -
der to f i n d a compromise between the p r o t e i n y i e l d s and the func-
t i o n a l i t y wanted.
When comparing the f u n c t i o n a l i t y s t u d i e s w i t h the chemical
p r o p e r t i e s of the DH = 3%-products g i v e n i n Table I l i a , no s i g n i -
f i c a n t c o r r e l a t i o n i s found between T C A - s o l u b i l i t y , p s i ( p r o t e i n
s o l u b i l i t y index) at pH = 4.5 or the p s i at pH = 7.0. Omitting
the I I I combination which i s made by a method which r e t a i n s some
denatured p r o t e i n (see ( 2 ) ) , only the content of leu-NH^ equiva-
l e n t s s i g n i f i c a n t l y c o r r e l a t e s w i t h the whipping expansion and
the foam s t a b i l i t y . I n c l u d i n g the r e s u l t s from Table I l l b , the
curves shown i n F i g . 6 and F i g . 7 c l e a r l y show that the higher
the content of f r e e NTJ^-groups, the h i g h e r the whipping expansion
and foam s t a b i l i t y of the i s o l a t e d p r o t e i n s , although the process
combinations were d i f f e r e n t . This confirms the s i g n i f i c a n c e of

10. O L S E N A N D ADLER—NISSEN Enzymatically Modified Proteins 141
Table H a . Ultrafiltration/Diafiltration Processing Data ( D H = 3%)
Retentates
Average
Process UF Average permeate
Before Final
combi- or Prot.reflux 7
nation DF %(Nx6.25) %(Nx6.25) tention % 1/h/nT
UF 2.9 9.3 30.1

I DF 9.3 9.3 70.7 26.7
UF 9.3 18.0 20.0
UF 2.3 10.9 75.5 35.6

II DF 10.9 10.1 92.9 34.7
U
III UF 2.8 18.3 93.1 36.0
UF 3.2 9.8 92.2 41.9

IV 1 s t
DF 9.8 15.7 98.2 26.7
IV 2 n d UF 3.3 10.4 84.4 no data
Table l i b . Ultrafiltration/Diafiltration Processing Data ( D H = 6%)
Retentates
Average
Process UF Average permeate
Before Final
combi- or Prot.reflux 7
nation DF % ( N x 6 . 2 5 ) %(Nx6.25) tention % 1/h/ni
I UF 3.1 7.4 55.8 38.5

DF 7.4 6.7 83.2 no d a t a
II UF 1.8 12.4 69.1 31.1
III UF See table 2a See 6 - 1061a
IV 1 s t UF 2.8 9.9 95.4 43.4

DF 9.9 12.5 98.5 21.7
IV 2 n d UF 3.3 6.3 74.2 39.1

Table Ilia. Protein Yields and Some Properties of the D H 3 %

Products Made by Different Process Combinations
Process combination I II III IV
% Protein y i e l d 39.5 30.9 55.3 28.6

(based on soy meal)
Coniposi t i o n :
% PY/HY 96.0 93.1 77.9 95.5
Functionality:
% Whipping exp. ) 667 733 1566 1650
7o Foam s t a b i 1 i t y 9 12 no data 42
Chemical prop.:
% psi i n TCA 10.0 13.2 17.7 13.4
% psi at pH - 4.5 42.7 47.8 42.6 49.7
% psi a t pH = 7.
leu-NH^, mol/kg prot
DH= -0.2 DH = 0.8 DH = 3.1 DH = 1.8
Immuno precip. 6 archs 6 archs 6 archs 6 archs
l
) at pH 7.0
Table Illb. Protein Yields and Some Properties of the D H 6%

Products Made by Different Process Combinations
Process combination I II III IV
7o P r o t e i n y i e l d
(based on soy meal) 34.3 22.3 55.3 23.8
Composition:
% PY/HY 90.1 91.1 77.6 91.2
Methionin (g/16gN) 1.06 1.10 1 .36 0.95
C y s t i n (g/16gN) 1.76 1.93 1.44 1.75
Functionali ty:
% Whipping exp. * 833 1317 1570 2484
% Foam s t a b i 1 i t y 20 50 no data 69
Density o f mering. 0.11 ± 0.096 ± 0.21 ± 0.17 ±
g/m3 ** O.Ol 0.004 0.01 0.02
Chemical prop.:
% psi i n TCA 20.0 19.0 32.0 30.1
% psi at pH = 4.5 51.0 54.6 53.8 71.7
% psi a t pH = 7.0 92.0 100.0 68.9 99.5
leu-NH^,mol/kg 0.42 ~ 0.49 ~ 0.87 ~ 0.67 ~
protein DH = 0.9 DH = 1.7 DH = 6.4 DH = 4.0
Immuno p r e c i p . 3 archs 5 archs 4 archs 2 archs
3
* a t pH 7.0 ** w i t h eggwhites: 0.12 g/cm

10. OLSEN AND ADLER—NISSEN Enzymatically Modified Proteins 143
% WHIPPING EXPANSION
0.3 0.
Figure 6. Whipping expansion vs. the number of free NH groups for highly func-
2
tional soy protein ultraflltered after hydrolysis
Figure 7. Foam stability vs. the number of free NH groups for highly functional
2
soy protein ultraflltered after hydrolysis

using DH as the c o n t r o l l i n g parameter during p r o t e i n h y d r o l y s i s .

The values of p s i i n TCA and p s i a t pH = 4.5 give a rough measure
of the content of low molecular p r o t e i n s . The presence of arches
determined by crossed Immunoelectrophoresis demonstrates that
some high molecular p r o t e i n s are r e t a i n e d i n the modified pro-
ducts. For example IV-DH 6%, which has the best f u n c t i o n a l i t y ,
c o n s i s t s of only two s i n g l e high molecular p r o t e i n f r a c t i o n s com-
pared to the IV-DH 3% which has s i x f r a c t i o n s . Further studies
are r e q u i r e d to e l u c i d a t e the s t r u c t u r a l composition of these
high molecular p r o t e i n f r a c t i o n s i n r e l a t i o n to the f u n c t i o n a l i t y .
The presence of c y s t i n e i s important f o r i r r e v e r s i b l e g e l
formation, but as the content of c y s t i n e i s p r a c t i c a l l y the same
i n the hydrolysate made by I , I I and IV as shown i n Table I l l b ,
i t i s concluded that the c y s t i n e content i s not r e s p o n s i b l e f o r
the d i f f e r e n c e s seen i n whipping p r o p e r t i e s .
A preliminary organolepti evaluatio di
not show any b i t t e r n e s s
the b i t t e r n e s s of soy p r o t e i n hydrolyzed w i t h A l c a l a s e only be
comes pronounced a t DH-values of 7% and above ( 2 ) . Therefore, the
present products may be used as n u t r i t i o u s i n g r e d i e n t s and h i g h l y
f u n c t i o n a l p r o t e i n s as w e l l . I n many food formulations they may
serve as s u b s t i t u t e s f o r egg-white. This was f o r example demon-
s t r a t e d i n meringue b a t t e r s (see Table I l l b ) .
I s o e l e c t r i c Soluble P r o t e i n Hydrolysates
An i n d u s t r i a l process has been developed f o r production of

i s o e l e c t r i c s o l u b l e soy p r o t e i n hydrolysate w i t h no b i t t e r n e s s
and a bland t a s t e (13). The raw m a t e r i a l may be a c i d washed soy
white f l a k e s , soy p r o t e i n concentrate o r soy p r o t e i n i s o l a t e The v
raw m a t e r i a l i s hydrolyzed by the a l k a l i n e protease ALCALASE® to

a s p e c i f i e d degree o f h y d r o l y s i s using the pH-stat a t pH = 8.0
(4).
Extensive p r o t e o l y s i s of a p r o t e i n o f t e n r e s u l t s i n the f o r -
mation of b i t t e r peptides ( 2 ) . Therefore, a compromise between
high p r o t e i n y i e l d and low b i t t e r n e s s has to be found when
choosing the DH-value a t which the h y d r o l y s i s r e a c t i o n should be
terminated. For the present process a DH-value of about 10% seems
to be a reasonable value. The t e r m i n a t i o n i s performed by a c i d
i n a c t i v a t i o n of the enzyme and the a c i d used should be chosen i n
accordance w i t h the d e s i r e d o r g a n o l e p t i c c h a r a c t e r i s t i c s of the
f i n a l h y d r o l y s a t e . A t o t a l l y n o n - b i t t e r product can be produced
by use of an organic a c i d l i k e m a l i c or c i t r i c a c i d . Due to the
masking e f f e c t s o f such a c i d s , a b s o l u t e l y no b i t t e r n e s s can be
detected even when the t a s t e e v a l u a t i o n i s performed a t n e u t r a l
pH. Such products are found most s u i t a b l e f o r s o f t d r i n k s . How-
ever, when i n o r g a n i c a c i d s , e.g. h y d r o c h l o r i c or phosphoric acids
are used, a s l i g h t b i t t e r n e s s may be detected i n the pure h y d r o l y -
sate. However, when evaluated i n f o r instance a meat product, no
b i t t e r n e s s a t a l l can be t a s t e d even when the hydrolysate i s added
up to a p r o p o r t i o n of 1 : 3 of hydrolyzed p r o t e i n to meat p r o t e i n .

A flow sheet of ISSPH-production i s given i n F i g . 8. The

carbon treatment removes the l a s t t r a c e s of soy o f f - f l a v o u r s .
Using the recommended process parameters, the f i l t e r e d hy-
d r o l y s a t e c o n t a i n s about 3% p r o t e i n . H y p e r f i l t r a t i o n i s t h e r e f o r e
an a t t r a c t i v e process to use f o r c o n c e n t r a t i o n before d r y i n g .
In p i l o t p l a n t experiments we have used a 7 m^ DDS-module
type 40 w i t h t i g h t c e l l u l o s e acetate membranes type DDS-990. Con-
c e n t r a t i o n has been performed at pH = 4.0-4.5 i n a batch system
at ambient temperature using 30 kp/m^ d e l i v e r e d by a Rannie p i s -
ton pump.
In Table IV the composition of r e t e n t a t e s and average per-
meate f l u x e s are shown f o r d i f f e r e n t types of ISSPH. Volumesôf
700-900 l i t r e s of c l e a r h y d r o l y s a t e s were t r e a t e d on the 7 m DDS-
module, except f o r one experiment i n which o n l y 60 l i t r e s were
t r e a t e d on a 0.36 m DDS-LAB-module. The p r o t e i n l o s s i n the per-
meate was below 3% i n a l experiments F i g u r 9 typica
f l u x and dry matter curv
permeate. U n f o r t u n a t e l y the f l u x decreases r a t h e r much d u r i n g the
process. Both increase i n osmotic pressure and c o n c e n t r a t i o n po-
l a r i z a t i o n are r e s p o n s i b l e f o r t h i s dependence. L a t e r s t u d i e s
have shown that the f l u x r a t e can be improved by i n c r e a s i n g the
flow v e l o c i t y over the membrane s u r f a c e .
D e s a l i n a t i o n of ISSPH. S p e c i f i c a p p l i c a t i o n s of ISSPH may

r e q u i r e a reduced content of s a l t s , mainly NaCl. The membrane
DDS-865, a c e l l u l o s e membrane, has been used f o r both d i r e c t hy-
p e r f i l t r a t i o n and f o r d i a f i l t r a t i o n , and i t appears that i t has
a h i g h r e t e n t i o n of hydrolyzed p r o t e i n and a low r e t e n t i o n of
s a l t . In Table V r e s u l t s are shown from an experiment i n which a
h y d r o l y s a t e of soy p r o t e i n i s o l a t e c o n t a i n i n g NaCl-HCl i s d e s a l i -
nated.
From a mass balance on n i t r o g e n (N) as w e l l as on n o n - n i t r o -
gen m a t e r i a l (NNM) the f o l l o w i n g has been found:
direct hyperfiltration: 11% l o s s of N,

74%removing of NNM
hyperfiltration
and d i a f i l t r a t i o n : 23% l o s s of N,
93% removing of NNM.
For most a p p l i c a t i o n s the product which may be obtained by
the d i r e c t h y p e r f i l t r a t i o n i s s u f f i c i e n t l y d e s a l i n a t e d and the
p r o t e i n l o s s of about 11% may be accepted. P r e l i m i n a r y r e s u l t s
a l s o seem to i n d i c a t e a s l i g h t r e d u c t i o n i n b i t t e r n e s s and soy
o f f - f l a v o u r due to removal of very small b i t t e r peptides and
other f l a v o u r compounds i n the permeate when t h i s d e s a l i n a t i o n
membrane i s used.
Process f o r D e c o l o r a t i o n of Slaughterhouse Blood. A novel

p r o t e i n i n g r e d i e n t can be manufactured by a c o n t r o l l e d enzymatic

MIXING H20, S5°C

Protei n
(Soy concentrate or isolate)
HYDROLYSIS IN NaOH S = 8% protein

S T I R R E D TANK (pH-stat) E/S =
2.0% A l c a l a s e 0.6
50-55°C, pH 8.0
ENZYME
Acid DH = 10% - 3 h
INACTIVATION
organic acid,
pH 4.0-4.2
1. CENTRIFUGATION Soli ds-ejecting

c e n t r i fuge
H20
FURTHER CENTR. FILTRATION
~1
SIudge
(unconverted
protein and
0.1% w/v
other insol-
uble material)
FILTRATION
Further treatment
Figure 8. Flow sheet: production of a nonbitter, soluble soy protein hydrolysate

suitable for incorporation into soft drinks and other low pH foods.
__1 1 1 1 1
20 40 60 80
X%
2
Figure 9. Hyperfiltration of HCl-containing ISSPH: flux in 1/h/m ; X, per-
centage of water removed; DM, percentage of dry matter (rejractometer).

OLSEN A N D ADLER—NISSEN Enzymatically Modified Proteins
Table I V . Processing Data Regarding Hyperfiltration of ISSPH
Type o f ISSPH Retentate Av. Average

Vol. p r e s - permeate
Before Final
A c i d used cone. sure flux «
DH(%) for inact. %x6.25 %DM %Nx6.25 %DM ratio Bar l/h/nf
10 ma 1 i c 2.7 4.5 14.3 22.3 5.1 20 3.80
10 HC1 3.5 4.3 21.1 26.2 6.1 34 4.46
10 HC1 2.0 2.8 14.2 17.6 6.7 34 4.67
15 mal i c 1.8 3.2 13.0 23.3 7.3 29 4.80
10 ma 1 i c 3.9 5.6 12.4 19.8 3.4 32 4.03
15 mal i c 3.5 5.4 16.8 27.5 4.9 32 7.08
10 HC1 - 3.9* - 30.2* 7.1 30 7.48

10 mal i c
10 malic
* by r e f r a c t o m e t e r **60 l i t r e s t r e a t e d on a D D S - L A B - m o d u l e
Table V . Desalination of ISSPH by Hyperfiltration on

a DDS-865 C A Membrane
Permeate X Y Permeate Retentate

flux o /iwater %water
Nx6.25
removed added
0/
1/h/nT %Nx6.25 %Nx6.25 /o

DM
51.7 0 - - - 3.44 4.20 81.9
45.0 16.7 - - - - - -
38.3 41.7 - 0.25 0.80 6.00 6.89 87.1
25.3 66.6 - - - - - -
13.0 83.3 - 1.25 2.52 18.31 19.90 92.0
7.0 87.5 - (10.44) ( Z l . 0 8 ) - - -

8.7 87.5 0 - - - - -
7.8 33.0 33.0 1.38 2.23 20.38 21.27 95.8
8.3 133.0 133.0
8.0 233.3 233.3 0.69 0.77 18.50 18.23 101.5
8.7 300.0 300.0 (10.94) (11.28)
2
DDS-LAB-module, average pressure: 29 kp/cm , 20-30°C

h y d r o l y s i s and subsequent d e c o l o r a t i o n of the red blood c e l l

f r a c t i o n a r i s i n g as a by-product i n plasma recovery (14). A flow
sheet of t h i s process i s shown i n F i g . 10. The process i s much
s i m i l a r to t h a t of ISSPH-production.
H y p e r f i l t r a t i o n serves the purpose of c o n c e n t r a t i o n of both
plasma and h y d r o l y s a t e s e p a r a t e l y . F l u x data are very s i m i l a r to
those obtained on soy p r o t e i n h y d r o l y s a t e s , and a l s o the t o t a l
economy of such process seems a t t r a c t i v e . The main reason i s that
slaughterhouse blood i n most cases i s regarded as a waste product
having no v a l u e , or even a negative v a l u e .
D i s c u s s i o n . In the above-mentioned examples membrane pro-

cesses are found u s e f u l f o r both c o n c e n t r a t i o n and d e s a l i n a t i o n .
One reason f o r recommending h y p e r f i l t r a t i o n i n s t e a d of evapora-
t i o n i n t h i s area i s the economical f a c t o r s . M u l t i - s t e p - e v a p o r a -
t o r s are s t i l l more economi tha osmosi i bi
p l a n t s , but the productio
p r o b a b i l i t y be d i s t r i b u t e
p l a n t s r e q u i r i n g new investments. At a time w i t h i n c r e a s i n g costs
of energy, h y p e r f i l t r a t i o n i s recommendable i n such p l a n t s . A l s o ,
the freedom of choosing membranes which may improve the q u a l i t y
of the p r o t e i n s , f o r example by removing of o f f - f l a v o u r s and s a l t ,
speaks f o r h y p e r f i l t r a t i o n .
Continuous P r o t e i n H y d r o l y s i s i n a Membrane Reactor
The membrane r e a c t o r i s an u l t r a f i l t r a t i o n system, i n which

a high c o n c e n t r a t i o n of h y d r o l y t i c enzyme i s confined. High mo-
l e c u l a r weight s u b s t r a t e i s fed continuously to the r e a c t o r , and
the low molecular weight products are removed simultaneously as
permeate. I d e a l l y , a steady s t a t e i s reached, i n which the degra-
d a t i o n of the s u b s t r a t e i s c a r r i e d out i n d e f i n i t e l y w i t h high e f -
f i c i e n c y and n e g l i g i b l e l o s s of enzyme.
The membrane r e a c t o r concept was demonstrated i n l a b o r a t o r y
scale a decade ago by Butterworth et a l . (15) and by Ghose and
K o s t i c k (16) i n s t u d i e s on the h y d r o l y s i s of s t a r c h and c e l l u l o -
se, r e s p e c t i v e l y . L a t e r on s e v e r a l p u b l i c a t i o n s have appeared
d e s c r i b i n g the analogous, continuous conversion of v a r i o u s pro-
t e i n s i n t o peptides intended f o r human n u t r i t i o n (17-22). Among
these works only that of Iaccobucci et a l . (18) presents a quan-
t i t a t i v e model of the membrane r e a c t o r i n continuous p r o t e i n hy-
d r o l y s i s , and i t i s a l s o the only demonstration of the p r a c t i c a l
f e a s i b i l i t y of the concept i n p i l o t p l a n t s c a l e .
Iaccobucci et a l . (18) a p p l i e d an a c i d , thermostable fungal
protease from P e n i c i l l i u m duponti i n t h e i r work. The choice of
t h i s enzyme had two advantages: The h y d r o l y s i s c o n d i t i o n s ensured
v i r t u a l s t e r i l i t y (pH = 3.7, 60°C) and the peptides were q u i t e
p a l a t a b l e (23). A major disadvantage of working i n the a c i d range
i s that soy p r o t e i n i s o l a t e , which was used as s u b s t r a t e , i s i n -
s o l u b l e . In p r a c t i c e t h i s causes mechanical problems i f the sub-
s t r a t e c o n c e n t r a t i o n i s not kept s u f f i c i e n t l y low (18).

As described p r e v i o u s l y i n the present p u b l i c a t i o n , we have

developed a batch process f o r producing i s o e l e c t r i c s o l u b l e soy
p r o t e i n hydrolysate (ISSPH) w i t h a bland t a s t e . From s t u d i e s o f
the k i n e t i c s of the h y d r o l y s i s r e a c t i o n , which takes place i n
t h i s process, we have come to the c o n c l u s i o n that the r e a c t i o n i s
adequately c o n t r o l l e d by keeping pH constant and monitoring DH.
Termination of the r e a c t i o n at a preset value of DH ensures a r e -
p r o d u c i b l e , optimal o r g a n o l e p t i c q u a l i t y of the product.
In the f o l l o w i n g the p o s s i b i l i t i e s are discussed of produ-
c i n g ISSPH w i t h a f i x e d DH-value during a continuous h y d r o l y s i s
r e a c t i o n i n a membrane r e a c t o r using s i m i l a r h y d r o l y s i s c o n d i -
t i o n s as i n the batch process. The s l i g h t l y a l k a l i n e c o n d i t i o n s
are advantageous from a mechanical p o i n t of view, because the
substrate i s d i s p e r s i b l e / s o l u b l e , but may a l s o imply a greater
r i s k of i n f e c t i o n . The change from an i n s o l u b l e to a s o l u b l e sub-
s t r a t e , and i n p a r t i c u l a r the a p p l i c a t i o n of the DH concent im-
mediately l e d to the c o n c l u s i o
described by Iaccobucc
s u b s t i t u t e d by an independently derived and more complete model,
which only on c e r t a i n p o i n t s i s i n s p i r e d by the former. The f u l l
d e r i v a t i o n of the model i s described i n the Appendix of the pre-
sent p u b l i c a t i o n . Based on the k i n e t i c s of the batch h y d r o l y s i s
i t i s demonstrated i n t h i s model that i t i s p o s s i b l e to run the
membrane r e a c t o r i n steady s t a t e , i . e . DH can be kept constant i n
the r e a c t o r . The steady s t a t e i s i n t r i n s i c a l l y s t a b l e and can be
achieved immediately by c a r r y i n g out the h y d r o l y s i s as a batch
r e a c t i o n w i t h zero membrane f l u x u n t i l the d e s i r e d DH-value i s
reached, c f . F i g . 11. A t t h i s p o i n t , the f l u x i s increased to a
preset v a l u e , and i f the various parameters i n the system have
been chosen c o r r e c t l y , DH w i l l be maintained constant.
A few experiments have been c a r r i e d out i n the l a b o r a t o r y
s c a l e w i t h a one l i t r e h y d r o l y s i s v e s s e l , connected to a small
i m p e l l e r pump and a S a r t o r i u s l a b o r a t o r y module f i t t e d w i t h DDS
GR6-P membranes (0.2 m^). However, the flow r e s i s t a n c e i n t h i s
module was too l a r g e , and i t was soon concluded that a resonably
constant f l u x was u n a t t a i n a b l e . Despite these d i f f i c u l t i e s , the
q u a l i t a t i v e behaviour of the r e a c t o r v a r i a b l e s could be p r e d i c t e d
from the model and v e r i f i e d e x p e r i m e n t a l l y . For example, w i t h de-
c r e a s i n g f l u x DH i n c r e a s e d , but the r a t e of the base consumption
decreased, w h i l e the p r o t e i n c o n c e n t r a t i o n i n the permeate r e -
mained q u i t e s t a b l e as p r e d i c t e d . The hydrolysate was evaluated
and found comparable i n q u a l i t y t o ISSPH produced i n the batch
process. These r e s u l t s have encouraged us to continue the work
i n p i l o t p l a n t w i t h the DDS-35 module, where we can expect con-
s i d e r a b l y more favourable flow c o n d i t i o n s . The f i r s t experiments
c a r r i e d o^t so f a r i n d i c a t e ^ t h a t a reasonable f l u x i n the order
of 50 1/m /h (approx. 1 1/m /min.) can be a t t a i n e d but that foam-
ing problems n e c e s s i t a t e the c o n s t r u c t i o n of p r e s s u r i z e d a i r f r e e
r e a c t o r . Future s t u d i e s w i l l t h e r e f o r e be needed t o produce a
complete experimental v e r i f i c a t i o n of the derived model.

Bl ood
Plasma fraction
CENTRIFU6ATI0NL__^
Cell fraction 60 % v / v
40 % v/v
HEMOLYSIS
Acid
HYDROLYSIS IN STIRRED TANK ENZYME INACTIVATION
S = 8 % protein DH = 1 8 %
E/S = 4 % A l c a l a s e 0 . 6 L pH 4 . 0
T = 550C, pH = 8.5 HCL o r o r g a n i c
acid
SEPARATION
^Sludg
K FILTRATION
H20
SEPARATION II FILTRATION OR EVAPORATION
1
Sludge^ CARBON TREATMENT - 1
SPRAY DRYING
Dark coloured insolubles

Decoloured product
Figure 10. Enzymatic decoloration of blood
Figure 11. Base Consumption—ideal steady-state protein concentration at t = Po 0

An overview of the v a r i a b l e s i n the membrane r e a c t o r process

i s given i n F i g . 12, and those equations, which are most r e l e v a n t
from an engineering p o i n t of view, are summarized i n Box 1. The
s i g n i f i c a n c e of most of the v a r i a b l e s should appear from F i g . 13
and Box 1 immediately, - f o r a f u l l e x p l a n a t i o n , the reader i s
r e f e r r e d to the appendix.
The main r a t i o n a l e behind the membrane r e a c t o r g e n e r a l l y ap-
pears to be savings of enzyme and the high conversion y i e l d , com-
pared w i t h a batch h y d r o l y s i s process, I t should perhaps be men-
t i o n e d that the emphasis on enzyme c o s t s i s not p a r t i c u l a r l y r e -
levant i n the present case, as the major cost f a c t o r s f o r the ex-
i s t i n g batch process are the raw m a t e r i a l s and the c a p i t a l costs
(13). In any case the r a t i o n a l e i s based on the assumption that
the r e a c t i o n can be c a r r i e d on f o r many c y c l e s w i t h no or only a
s l i g h t purging. However, i f a s u b s t a n t i a l f r a c t i o n of the sub-
s t r a t e i s non-degradable i n e r t m a t e r i a l w i l l r a p i d l y b u i l d up
i n the r e a c t o r causing
i s necessary i f the c o n c e n t r a t i o
at a reasonably low l e v e l . This has a d r a s t i c , negative i n f l u e n c e
on the instantaneous y i e l d , as demonstrated i n F i g . 14 and Table
VI. A l s o the enzyme l o s s d u r i n g purging w i l l be c o n s i d e r a b l e un-
l e s s the f r a c t i o n (y) of degradable p r o t e i n i n the s u b s t r a t e i s
c l o s e to 100%. For soy p r o t e i n i s o l a t e Iaccobucci et a l . (18)
found t h a t 6.2% of the p r o t e i n i n the s u b s t r a t e accumulated as
i n e r t m a t e r i a l - i n other words, when comparing the membrane pro-
cess w i t h the batch process, i t seems most r e l e v a n t to use y =
94%.
I f a short c y c l e time i s chosen (e.g. 10 min.) Table V I
shows that the enzyme consumption w i l l be much higher than i n the
batch process, as soon as purging s t a r t s (1.8 hours from s t a r t ) .
The enzyme consumption can be decreased by e n l a r g i n g the r e a c t o r
s i z e , as enzyme c o n c e n t r a t i o n and r e a c t o r s i z e are i n v e r s e l y pro-
p o r t i o n a l (eq. I , Box 1 ) , but i t w i l l s t i l l be of the same order
of magnitude as i n the batch process. The i n c r e a s e i n r e a c t o r
s i z e has, however, the disadvantage that more p r o t e i n s u b s t r a t e
i s confined and l o s t i n the end (Table V I ) . The concomitant l o s s
of confined enzyme i s found to be the same i n both cases, which
i s obvious from eq. I .
I f we look at Table V I I , the f i g u r e s f o r a t o t a l run of
twelve hours are g i v e n , and i t appears that the short c y c l e time
w i l l give a 1% higher p r o t e i n y i e l d than the long c y c l e time, but
at the expense of a much higher enzyme consumption. A y i e l d above
80% appears at the f i r s t glance favourable compared w i t h the
batch process where the h y d r o l y s i s process y i e l d s a l i t t l e above
60% (13). However, the y i e l d s must be compared w i t h respect t o
the o r i g i n a l raw m a t e r i a l : soy white f l a k e s . I t i s , of course,
necessary to feed the r e a c t o r w i t h soy i s o l a t e and t h i s i s pro-
duced from white f l a k e s i n a y i e l d of 60-65%. Based on white
f l a k e s the p r o t e i n y i e l d of the membrane process as w e l l as the
batch process w i l l be approximately 50%.

INPUT:
SUBSTRATE FEED (COMPENSATED FOR NaOH AND ENZYME
FLOWS)
NaOH FROM pH-STAT PR = PROTEIN CONCENTRATION
SR = A C C E S S I B L E PROTEIN CONC.
(ENZYME)
FEED VELOCITY = & x(l+&)
REACTOR:
MEMBRANE
P = PROTEIN CONCENTRATION
REACTOR
S = A C C E S S I B L E PROTEIN =
SUBSTRATE CONC.
pH 8.0 50°C
OS = SOLUBILIZED, PERMEABLE
PROTEIN CONC.
i—r
PERMEATE PURG
E ENZYME CONC
FLUX = * =
OUTPUT:
PY = PROTEIN CONC. IN PERMEATE

(-OS)
3 = PURGE COEFFICIENT
Figure 12. Variables in reactor model
Figure 13. SHC for soy isolate & alcalase

O L S E N A N D ADLER—NISSEN Enzymatically Modified Proteins
Table V I . Some Key Figures for the Production of

ISSPH on the Membrane Reactor
M/ $ y 3 n a b Substrate
V processed
M/*
at n Q , kg
% % hours % AU/kg
98 2.7 6 94. 1 9.9 150 AU 15.0

10
96
mi n .
94
98 2.7 24 c
94.1 2.5 5 8 . 2 C
96 5.6 11.3 88.3 5.0 150 AU 27.8

40
94 8.7 7.3 82.7 7.5 & 18.2
mi n .
92 11.9 5.3 77.3 10.0 2.4 kg 13.4
90 15.4 4.0 72.0 12.5 10.2
a) Enzyme c o n s u m p t i o n per kg substrate

b) Enzyme a n d s u b s t r a t e present at start in reactor
c) Unrealistic in practice because of microbial deterioration
Table VII. Total-Yield Calculations on the Membrane Reactor
E prm2 membrane E n z . / Total

y n
t n
o
subst. yield
Subst. Enz.
ratio
used used
cycle
kg AU AU/kg %
time % AU/1
10 98 36 29.8 296 9.9 94.0

mi n . 96 72 17 15 30.6 612 20.0 88.0
94 11 31 . 5 946 30.0 82.3
40 98 36 31 . 2 150 4.8 89.7

min. 96 18 17 3.75 31 . 3 158 5.0 87.2
94 11 32.2 241 7.5 81.3

1
I: E ~ i x PR x (E/S) „ x
v cu
M ' 'SHC k(DH)
PR
III: e
[PR X (1-y)
p
IV: n = y x |\ - -2. x ( i - y ) ]
m
n = (t-t ) x ~
Q (number of c y c l e s )
Z P
m o
VI: n =
b PR x (1-y) PR
Substrate used: M x [p^ + PR x ( n + 3 x t (n -n ))]

t Q
Enzyme used: MxEx [ l + n t x C + $ x (n -n )]

t Q
n Q x y + ( n - n ) x T] - P /PR
t Q Q
Total y i e l d : ^
Box 1. Equations used i n engineering c a l c u l a t i o n s of the membra-

ne r e a c t o r
The d e r i v a t i o n of the equations i s given i n the appendix.
I i s used f o r c a l c u l a t i n g the enzyme c o n c e n t r a t i o n from the

k i n e t i c data of the batch h y d r o l y s i s .
II gives P q ( p r o t e i n cone, a t s t a r t i n r e a c t o r )
III gives 3, the purge c o e f f i c i e n t from acceptable l e v e l of
i n e r t matter = Z
m
IV gives n, the instantaneous yield
V gives the number of c y c l e s f o r a given p e r i o d
VI gives the number of c y c l e s before purging must be s t a r t e d .

I f we b r i e f l y consider the main investments i n the two pro-

cesses f o r a production o f 1000 tons of ISSPH per year and i n -
clude i n the membrane process equipment f o r producing soy i s o -
l a t e , the membrane process appears to r e q u i r e s l i g h t l y higher
t o t a l investments.
The r e s u l t s given above i n d i c a t e that there i s no obvious
advantage o f s u b s t i t u t i n g the e x i s t i n g batch process f o r produc-
t i o n of ISSPH by a membrane r e a c t o r process. However, t h i s does
not i n general mean that continuous p r o t e i n h y d r o l y s i s i n a mem-
brane r e a c t o r w i l l be uneconomical. For example i f the sub-
s t r a t e i s more completely degradable than soy p r o t e i n ( c a s e i n
might be such a s u b s t r a t e ) , i t i s expected that i n a small s c a l e
p l a n t (where the c a p i t a l costs would favour the membrane r e a c t o r )
the membrane r e a c t o r process could be very a t t r a c t i v e . The pro-
d u c t i o n of p r o t e i n hydrolysates f o r d i e t e t i c and medical use,
could w e l l be considered i n t h i s context
APPENDIX
Development of a K i n e t i c Model f o r P r o t e i n H y d r o l y s i s i n a
Membrane Reactor
General c o n s i d e r a t i o n s
Basis f o r the k i n e t i c model i s a standard batch h y d r o l y s i s expe-

riment (2,). F i g . 14 shows the standard h y d r o l y s i s curve f o r soy
p r o t e i n i s o l a t e - A l c a l a s e . The r e a c t i o n constant (pseudo f i r s t
order r a t e constant) i s c a l c u l a t e d from the standard curve by
f i t t i n g the inverse curve i n a small DH-range (ADH ^1.3%) to a se-
cond order Newton-Gregory polynomium (24), and f i n d i n g v(DH) by
d i f f e r e n t i a t i o n . This procedure has i n our experience proved t o
be the simplest and most r e l i a b l e way o f o b t a i n i n g values o f the
r e a c t i o n r a t e . k(DH) i s shown i n f i g . 15. - i t v a r i e s s t r o n g l y
w i t h DH.
As demonstrated p r e v i o u s l y (25) there i s substrate s a t u r a t -
ion throughout the r e a c t i o n which means that f o r a constant E/S
v(DH) and t h e r e f o r e k(DH) i s independent o f S. A l s o , E/S and
v(DH) are p r o p o r t i o n a l to each other as usual ( i b i d ) .
F i g . 12 gives an overview of the v a r i a b l e s i n the r e a c t o r
model. In accordance w i t h what was demonstrated by Iacobucci e t
a l . (18) i t i s assumed that the c o n c e n t r a t i o n of s o l u b i l i z e d ,
permeable p r o t e i n i s equal on both sides of the membrane. This
assumption i s s u b s t a n t i a t e d by the f a c t that the p r o t e i n h y d r o l y -
zate c o n s i s t s mainly o f s m a l l e r , s o l u b l e peptides and unconverted
p r o t e i n (2). The c o n c e n t r a t i o n of a c c e s s i b l e p r o t e i n i n the feed
stream, SR, w i l l be smaller than PR, as i t i s l i k e l y that a s m a l l ,
constant percentage of the p r o t e i n i s undegradable, i n accordance
w i t h what was found by Iacobucci e t a l . (18). This f r a c t i o n
counts as p r o t e i n i n a K j e l d a h l a n a l y s i s , but i s otherwise c o n s i -

p =6%, PR=4%, 1=3% (50% o f PJ

o m x
o'
100
80
\ Number o f c y c l e s
60 \ b e f o r e purging becomes
40
20
1 ,
Figure 14. Relationship between certain important variables in the membrane

reactor
Figure 15. The reaction constant, k(DH), from the standard hydrolysis curve

10. OLSEN A N D ADLER—NissEN Enzymatically Modified Proteins 157
dered i n e r t , i . e . i t i s assumed that i t s accumulation i n the r e -

tentate does not i n f l u e n c e the h y d r o l y s i s k i n e t i c s a p p r e c i a b l y .
This assumption w i l l be s u b s t a n t i a t e d l a t e r .
I t has been found i n batch h y d r o l y s i s experiments that the
p r o p o r t i o n of s o l u b l e n i t r o g e n to t o t a l n i t r o g e n i s g r a d u a l l y i n -
creasing w i t h DH (2). For a constant DH t h i s p r o p o r t i o n i s inde-
pendent of S (26) i n accordance w i t h the f a c t that v(DH) i s inde-
pendent of S. I t thus seems reasonable to assume that OS/S w i l l
be a monotonously i n c r e a s i n g f u n c t i o n of DH and independent of S.
The r e l a t i v e increase of OS/S w i l l always be equal to or smaller
than the corresponding r e l a t i v e increase i n DH - t h i s i s a mathe-
m a t i c a l consequence of the f a c t that the average peptide chain
l e n g t h i n the s o l u b l e f r a c t i o n of a hydrolyzate w i l l be constant
or decreasing w i t h DH (26).
In batch h y d r o l y s i s experiments we have g e n e r a l l y not d i -
s t i n g u i s h e d between S
dard h y d r o l y s i s curve.
i s c r u c i a l i n the present case where i n e r t p r o t e i n (N*6.25) ac-
cumulates. P denotes the p r o t e i n c o n c e n t r a t i o n i n the beginning
q
of the experiment.
F i g . 11 shows the p r i n c i p l e s i n an i d e a l , steady s t a t e expe-
riment. A t t=0 the h y d r o l y s i s i s s t a r t e d as a batch h y d r o l y s i s
(<S> = 0). When the d e s i r e d DH-value has been reached (DH=DH a t Q
t=t ) the membrane r e a c t o r i s s t a r t e d , i . e . peptides are permea-

t i n g through the membrane w i t h the volume f l u x , $, and f r e s h sub-
s t r a t e i s added continuously to r e p l a c e the degraded p r o t e i n .
In the f o l l o w i n g i t w i l l be proved that i f the values of the i n -
dependent v a r i a b l e s ( i . e . PR, P , E , M, $ and 3) have been chosen
c o r r e c t l y , the r e a c t o r w i l l immediately be i n steady s t a t e , most
g e n e r a l l y defined as DH remaining c o n s t a n t l y equal to D H . The q
equations which describe the r e l a t i o n s h i p between the v a r i a b l e s

w i l l be derived i n the f o l l o w i n g s e c t i o n s .
The above general c o n s i d e r a t i o n s are summarized i n Box 2.
The steady-state equations
The most general d e f i n i t i o n of steady s t a t e was given p r e v i o u s l y

namely that DH should remain constant. However, t h i s d e f i n i t i o n
i s too general to be of p r a c t i c a l use, and i t i s t h e r e f o r e neces-
sary i n the f o l l o w i n g to assume that the f o l l o w i n g parameters a l -
so remain constant throughout the experiment:
PR, M, E, $ (and 3) a l l constant (9)
Convenience d i c t a t e s that PR and M should remain constant.

E i s kept constant by r e p l a c i n g the l o s s of enzyme through i n -
a c t i v a t i o n , permeation and purging. $ can be regulated by the
pressure drop and can be maintained reasonable constant i n a
w e l l b u i l t system i n which high flow rates are obtained.
Q u a s i - s t a t i o n a r y c o n d i t i o n s , i . e . slow changes i n the above
parameters w i l l be d e a l t w i t h l a t e r .

Mass balance c o n s i d e r a t i o n s i n the time p e r i o d t Q to ( t +dt)

lead to the f o l l o w i n g : °
E/P
v(DH) = x v(DH) _, which can be w r i t t e n as
CIJ
(E/S) c
'SHC
d(DH) _E
=
x DH x k(DH) (1)
dt P (E/S)
c SHC
PY = OS (2)
SR S - , . ^ .
y =
P R P = (3
Accumulated inert material:
Z= (4)
P
" = " o <ft>
S P P X
OS
f(DH) (indep. of S) (5)
s
d(OS/S) < d (DH)
o < (6)
OS/S DH
which i n combination w i t h (3) leads t o :
d(OS/P )
d(OS/S) Q
d(DH)
0 <
OS/S OS/P DH (7)
Base consumption i n batch experiment:

DH
X X M X S (8)
B
- 01 X h
tot W
where: a i s the d i s s o c i a t i o n f a c t o r f o r the
amino group. I n the present case,
where pH = 8.0 and pK = 7.1,
a = 0.88
n
t o t i s the t o t a l content o f peptide bonds
i n the p r o t e i n . I n the present case,
h = 7.8 meqv./g (Nx6.25) (soy p r o t e i n )
Box 2. Summary of fundamental r e l a t i o n s h i p s which are g e n e r a l l y

valid

SR x $ x (1 + 3) x dt = PY x $ x dt + S x $ x M d t + M x dS
(input) (output) (accum.)
(10)
or:
| | = | x [SR x (1+3) - P Y - 3 x S] (11)
Note t h a t S denotes hydrolyzed as w e l l as unhydrolyzed p r o t e i n .

: T e a<
^ i d e d s u b s t r a t e from the feed i s the l e f t s i d e
of eq. ( 1 0 ) , t h i s substrate s h a l l be hydrolyzed to DH , c f r . eq.
(8): °
/DH \
dB = a x h x I—£) x SR x $ x (1+3) x dt (12)
tot \ 1 0 0 '
Base consumption thus take

tion:
D H
dB / \
-rr
dt = "
a x ht o tx V
[ — x SR x <D x (l+g)
1 0 0
(13)
Now, i f the h y d r o l y s i s were continued as a batch h y d r o l y s i s i n

the p e r i o d t to ( t +dt), DH would i n c r e a s e from D H to (DH + q Q
d ( D H ) ) . This i n c r e a s e i n DH would of course be accompanied by a

consumption of base. From eq. ( 8 ) we know t h a t dB and d ( D H ) are
p r o p o r t i o n a l i n the batch h y d r o l y s i s , where S i s constant (and
equal to P ) . Thus
q
d B
^ = a x hu t o t x M x P o x _ x1 - Ad(DH)
_ i (,1 4v)
1 7
I n s e r t i n g eq. ( 1 ) i n eq. ( 1 4 ) f o r DH = D H q gives:

JT> -j /DH \
^ = a x h t Q t xM x E xî- x ^ x k(DH )Q (15)
N e i t h e r eq. ( 1 3 ) nor eq. ( 1 5 ) depend on the a c t u a l s u b s t r a t e con-

c e n t r a t i o n i n the r e a c t o r . In both equations i t can be seen that
the steady s t a t e c r i t e r i a i n eq. ( 9 ) r e s u l t i n dB/.dt. being
constant w i t h time, c f r . f i g . 1 2 . Eq. ( 1 3 ) and eq. ( 1 5 ) can the-
r e f o r e be e q u a l i z e d , whereby a, h and ( D H / 1 0 0 ) cancel out:
t Q
SR x $ x (1+3) =M xE x I x k(DH ) (16)

( E / S )
SHC °
or; as
SR = y x P R (eq. ( 3 ) ) :

E = * x y x PR x ( u p ) x ( E / ) S S H C x (17)
o
Eq. (17) i s the d e s i r e d r e l a t i o n s h i p between the v a r i a b l e s i n

steady s t a t e .
d : F o r
^H^^Î§^»2I2^H£^_fe§I§n£2_i:D-^£2§ X_^^£2 DH=DH (con-
s t a n t ) eq. (7) leads to that (OS/P ) must be constant w i t S time.
As OS/S i s a f u n c t i o n of DH and independent of S, c f r . eq. (5) we
can see that S must be constant i n steady s t a t e . Eq. (11) t h e r e -
f o r e leads t o :
0 = | x [SR x(l+3) - PY - 3 * S] (18)

or:
PY = SR x (1+3) -
As PY=0S, eq. (19) can be rearranged to give
f?Sy f ( H ) = M
D o x (i + f 3 ) - 3 (20)
From (3) i t i s seen that SR/S = PR/P ; i n s e r t i n g t h i s i n (20) g i -

ves:
f ( D K ) = |5 x (1+B) - 6
Q (21)
o
(21) i s used to c a l c u l a t e P (assuming f(DH) i s known f o r DH =

DH ). o
(3) i n s e r t e d i n (19) g i v e s :
PY = y x [PR x (1+3) - 3 x P ] Q (22)
In case 3 = 0, PY = y x PR, y can thus be measured e a s i l y by K j e l -

dahl analyses on the permeate i n steady s t a t e w i t h no purge.
S t a b i l i t y of the steady s t a t e
In the f o l l o w i n g i t w i l l be proved that the steady s t a t e , as i t

i s defined by eq. (17) i s i n t r i n s i c a l l y s t a b l e . I n other words
when the independent v a r i a b l e s , E, $, M, SR and 3 are kept con-
s t a n t , the system should s t a b i l i z e i t s e l f around the p r e d i c t e d
values of DH = DH and S = S .
o o
Mass balance c o n s i d e r a t i o n s on the d e f i n i t i o n of DH, i . e .
the percentage of peptide bonds cleaved, immediately lead to the
r e s u l t t h a t an instantaneous change i n S leads to an i n v e r s e l y
p r o p o r t i o n a l change i n DH.

(f) t - - c — >
The addition of fresh, unhydrolysed substrate does not per se

change the reaction rate, expressed as dB/dt, because we have
substrate saturation in the system. This is also indirectly ex-
pressed in equations (13) and (15) which do not contain any term
in S. However, dB/dt does change because of the change in DH,
and i t is now postulated that this change is adequately described
by eq. (15):
dB __ x h ^ x M x E x7 ¥ - 7 -L x -(jffi) x
k(DH) (15a)
dt " " "tot ~ " ~ " ~ (E/S)
SHC
The v a l i d i t y of eq (15a) rest th assumptio that th

addition of fresh substrat
result in a new substrat compositio y
t i c a l to a hydrolyzate with a correspondingly lower DH-value as
given by eq. (23). This is only approximately true in r e a l i t y ,
but i t has been demonstrated that dB/dt does increase considerab-
ly when fresh substrate is added to a batch hydrolysis experi-
ment (26). This observation is in qualitative accordance with
eq. (15a) and this is sufficient for the following line of argu-
ments .
Differentiation of eq. (8) leads to
dB d (DH) DH 1
x dt = a x h M x sx 100
+ M x dS x
lOOJ
(24)
dt tot
The period t to (t+dt) is now considered. After the change

l i i i S from S to ( S +AS) (AS>0), we know from eq. (23) that DH
is lowered and that dB/dt in eq. (24) increases compared with
equations (13) and (15). The increase in fresh substrate which
shall be hydrolyzed to the new, lower value of DH, is as in eq.
(13) equal to the amount supplied by the feed. Thus the second
term in the bracket in eq. (24) i s equal to:
DH
SR x $ x (1+3) x J g L x dt < S R x <£> x (1+3) xY^xdt (25)
dB 1 1
The right side is equal to -r— x — x
dt a h _
tot
before the instantaneous change in S from S t i l S + A S (see q Q
13)). As dB/dt increases after this change, (25) proves that the
f i r s t term in the bracket in (24) must be positive;

M x (S +AS) x i i 2 | ) > 0
Q (26)
and consequently: d(DH) >0.
I f AS < 0 a s i m i l a r l i n e o f arguments w i l l lead to the con-

c l u s i o n that DH w i l l immediately assume a new higher value and
t h e r e a f t e r decrease. We have thus demonstrated that there i s ne-
g a t i v e feed-back i n the system w i t h respect to DH.
The instantaneous change i n S (AS>0) w i l l , of course, not

change OS as i t i s assumed t h a t the f r e s h s u b s t r a t e does not con-
t r i b u t e t o OS. However, i t can be shown that immediately a f t e r ,
OS w i l l begin to r i s e because the i n e q u a l i t y (6) w i l l always be
v a l i d . I n the present case where OS i s not changed immediately
the e q u a l i t y s i g n w i l l h o l
From eq. (5) we get:
OS = f(DH ) x S (5a)
o o' o
OS = f(DH) x ( S + A S ) Q (5b)
0 S S + A S
rn,-
Whichu
g i• v e s : ^ g - = f(DH)
jf—j- ^xo— - , _(27
9
o 'o o
S + A S
or: OS_>M_ * °
OS - DH S
o o o
The lowest p o s s i b l e value o f DH/DH i s according to eq. (23) e-

qual to S / S , i n the present case: S / ( S + A S ) . Thus the inequa-
Q Q
l i t y below must h o l d , as soon as DH r e i n c r e a s e s towards DH .

o
*L > J!°— (29)

v
DH S +AS '
o o
Combining eq. (29) and eq. (28) leads t o :
OS
> 1
0S~
o
The r i s e i n OS means that P Y w i l l r i s e , because OS = P Y , From
eq. (11):

| | = | x [SRx(l+3) - PY - B*S] (11)
we can then conclude t h a t because both PY and S are l a r g e r than

p r e v i o u s l y , dS/dt (which i s zero i n steady s t a t e ) must be n e g a t i -
ve .
A s i m i l a r l i n e of arguments leads to the c o n c l u s i o n t h a t i f

AS < 0, dS/dt w i l l be p o s i t i v e . There i s t h e r e f o r e negative
feed-back i n the system w i t h r e s p e c t to S.
The demonstration of negative feed-back f o r the two dependent

v a r i a b l e s , DH and S, i s proof of the i n t r i n s i c s t a b i l i t y of the
steady s t a t e .
Quasi-stationary condition
I f the changes i n the independent parameters are slow, we have

q u a s i - s t a t i o n a r y c o n d i t i o n s and the steady s t a t e equations w i l l
h o l d . By slow changes i s meant that the r a t e of change i n DH
caused thereby i s slow compared to the r e a c t i o n r a t e , d(DH)/dt,
as given by eq. (1).
ADH
« jT- x -^t|j x DH x k(DH) (30)
At
o SHC
The r e l e v a n t steady s t a t e equations are:
E =| x R x ( l
S + e ) x ( /S)
E S H C x- L ^ (17a)
PY - SR x (1 + 3) - 3 x s (19a)
f(DH) = x (1+3) - 3 (20a)
From f i g . 15 i s obtained t h a t :
DH = 8 =>k(DH) := 160 min

DH = 9 => do. = 230 min
DH = 10 => do. = 310 min
DH = 11 do. = 420 min
Consequently, even r a t h e r l a r g e changes i n the independent

v a r i a b l e s w i l l o n l y lead to comparatively small changes i n DH.
For example, a 20% r e l a t i v e change i n E, $, M, SR og (1+B) w i l l
only change DH approximately 0.6 u n i t s (e.g. from 10 to 10.6%).

The corresponding r e l a t i v e change i n f(DH) i s l e s s than 6% and

t h i s leads again to a change i n S of l e s s than 6%, eq.(20a), pro-
< < :
v i d e d 3 1 - This i s of c o n s i d e r a b l e importance i n p r a c t i c e , as
i t i s d i f f i c u l t to avoid some decrease i n the values of E and $
d u r i n g continuous o p e r a t i o n of the membrane r e a c t o r due to f o u l -
ing and enzyme l o s s e s . F o r t u n a t e l y , according to eq. (17a) E and
$ w i l l p a r t i a l l y counteract each other i n t h e i r e f f e c t on DH.
The above has the p r a c t i c a l consequence t h a t because

y x (1+3)c*l i n most cases, E i s adequately given by the s i m p l i -
f i e d equation:
E i x PR x (E/S) X
(17b)
SHC k(DH)
At any time the DH-value can be c a l c u l a t e d q u i t e simply from the

base consumption i n th
(31)
As the r e l a t i v e change i n DH i s l e s s than the r e l a t i v e de-

crease i n <£> i t appears from eq. (31) that AB/At w i l l decrease w i t h
decreasing $, although DH a c t u a l l y i n c r e a s e s !
The change i n PY as a r e s u l t of changes i n the independent

parameters i s n e g l i g i b l e . This i s evident from eq. (19a) because
S changes only s l i g h t l y and 3 << 1. I t w i l l t h e r e f o r e be obser-
ved i n p r a c t i c e t h a t PY remains very s t a b l e during the o p e r a t i o n
of the r e a c t o r .
The q u e s t i o n of accumulated, i n e r t matter. The data of I a -

cobucci et a l . (18) i n d i c a t e t h a t even c o n s i d e r a b l e amounts of
accumulated i n e r t matter ( h a l f of t o t a l s o l i d s content i n the r e -
a c t o r ) d i d not d i s t u r b the steady s t a t e . How the case w i l l be i n
the present system, where A l c a l a s e i s used i n s t e a d of P.duponti
protease has not yet been i n v e s t i g a t e d , but as i t w i l l be shown
i n the f o l l o w i n g i t seems p l a u s i b l e t h a t a s i m i l a r r e s u l t could
be obtained.
I t seams reasonable to assume that the most l i k e l y k i n e t i c
e f f e c t , i f any at a l l , of the i n e r t r e s i d u a l matter from the de-
g r a d a t i o n of soy p r o t e i n w i l l be that of a c o m p e t i t i v e enzyme i n -
h i b i t o r . As demonstrated p r e v i o u s l y (25), V decreases but K r e -
mains f a i r l y constant w i t h i n c r e a s i n g DH. No non-competative i n -
h i b i t i o n of A l c a l a s e takes place i n the system at l e a s t at DH =
0 ( f i g . 3, i b i d . ) . I f these observations are e x t r a p o l a t e d V
drops to zero, but K can be expected to remain constant (or at
l e a s t not decrease) f o r the undegradable r e s i d u e .
The standard Michaelis-Menten equation f o r competitive i n h i -
bition i s :

V ( 3 2 )
1 + K /S x (1+I/K.)
m I
From the above we can expect that K. ~ K ~ 0.7% (average of

K values i n f i g . 4, i b i d . ) . I f S = 6% and I changes from 0 to
1/?, the decrease i n v w i l l be 15%. This w i l l correspond to a de-
crease i n E of 15%. The p o s s i b l e i n h i b i t o r y e f f e c t of the accumu-
l a t e d i n e r t matter could thus be counteracted by g r a d u a l l y i n c r e a -
s i n g E.
Future experiments w i l l be needed to e l u c i d a t e the k i n e t i c
e f f e c t s of the i n e r t matter. However, the above c o n s i d e r a t i o n s
i n d i c a t e t h a t the problems encountered i n p r a c t i c e w i l l be s m a l l .
The c o n c e n t r a t i o n o f i n e r t m a t e r i a l , Z, i n the r e a c t o r can
be found from the p r o t e i n mass balance:
PR x $ x (1+3) x
(33)
By a p p l y i n g the e x p r e s s i o n f o r PY i n steady s t a t e as g i v e n by eq.

(22), eq. (33) i s reduced t o :
PR x (1+3) x (1-y) = 3 x (P-yxP ) + | x | | Q (34)
From eq. (4) we know: Z = P - y x P q and dZ = dP. Thus
| x | | + 3 x Z = PR x (1+3) x (1-y) (35)
Eq. (35) i s a l i n e a r , f i r s t order d i f f e r e n t i a l equation (3>0).

The boundary c o n d i t i o n i s t h a t Z = P x (1-y) f o r t = t , inde-
q Q
pendently of 3 . The s o l u t i o n to eq. (35) i s then:
-3 x ^x( -t ) t
x e M o
(36)
( 1 3 )
For t =» oc z = PR x + x (1-y) (37)
1 lm p
In case 3 = 0, (35) i s immediately s o l v e d :
Z = - x PR x ( t - t ) + P Q Q x (1-y) ( 3 8 )
As expected, Z increases l i n e a r l y w i t h time, when there i s no pur-

ge.

Compensation f o r Enzyme Losses
Enzyme i s l o s t through p u r g i n g , i n a c t i v a t i o n and permeation.

A l l three are p r o p o r t i o n a l t o E. The mass balance on the enzyme
gives:
M x d E = $ x 3 x E x d t + C x E x d t 1
(purge) (mactiv.)
+ C 2 x <£> x E x dt
(permeation) (39)
or:
=
¥ [I X ( 6 + C
2 ) + C
l x d t ( 4 o )
I f the i n a c t i v a t i o
p l i f i e d to
f- ~ | x (3 + C ) x dt (41)
or on f i n i t e form:
J« (S+C) x At (42)
Yield Calculations
The instantaneous y i e l d , r| i s d e f i n e d as the p r o p o r t i o n be-

tween the s u b s t r a t e f l u x and the permeate f l u x ( p r o t e i n b a s i s ) .
From the p r o t e i n mass balance (33), r| i s immediately obtained:
P 0
n
n = y x 1 ~ PR — X
(1+3)
(43)
The t o t a l y i e l d i s the y i e l d based on a complete run, i n -

c l u d i n g the s t a r t i n g up. The p r o t e i n present i n the r e a c t o r at
t = t cannot be recovered i n the end, because i f the s u b s t r a t e
o .
feed i s i n t e r r u p t e d (PR = 0 ) , DH cannot be maintained constant,
but w i l l increase r a p i d l y .
The most economical way of running the r e a c t o r i s to keep
3 = 0 u n t i l Z reaches a p r e s e t l i m i t , Z . The number of c y c l e s ,
m
i . e . : ri = ( t - t ) x ^, which corresponds to Z i s found by
solving (38):
Z P
n = 2 - _° (44)
K J
o PR x (1-y) PR ™
F o l l o w i n g the p e r i o d g i v e n by n , purging i s e s t a b l i s h e d
and i s found s o l v i n g ( 3 7 ) :

z
r
1 (45)
2 -y)
LPR x (l-y
Combining eq. ( 4 5 ) w i t h eq. ( 4 3 ) g i v e s :
n = y x [ l - _° x ( l - y ) l (46)
L
^m •*
In one c y c l e the mass of substrate f e d i s PR x M x ( 1 + 3 ) .

In n c y c l e s (n >n ) the t o t a l y i e l d ( i n c l u d i n g the l o s s of pro-
t e i n confined a t tfte end), can be c a l c u l a t e d from the instaneous
yields:
Product formed:
n Q x y x PR x M + (n - n ) x n x PR x M x (1+3)
Substrate used:
Mxp + n x PR x M + (n -n ) x PR x M x (1+3)
o o t o y
The l a s t can be s i m p l i f i e d slightly to:
M x [P + PR x (n + 3(n -n ))]
Q t t o
m s. i • u
Total y i e l d = o
n x + (n -n ) x
t o J y (1+3) x n
(47)
P
p| + n + 3(n -n ) t t Q
In most p r a c t i c a l cases, where 3 i s small and the number of cyc-

l e s i s 1 0 - 1 0 0 , eq. ( 4 7 ) can be s i m p l i f i e d t o :
n x y + (n -n ) x n - P /PR
Total y i e l d « — — (48)
n
t
The amount of enzyme consumed i s M x E x (3+G) per c y c l e .

T o t a l amount of enzyme i n n c y c l e s i s then ( i n c l u d i n g i n i t a l en-
fc
zyme) :
Enzyme used: M xE +n x C x M x E + (n^-n ) x (3+C) x M x E
o t o
or: (49)
Enzyme used: MxEx [ l + n t x C +3 X

(n ~n ) ]
t (50)

Acknowledgement
We wish to thank the s t a f f a t Enzyme A p p l i c a t i o n Technology P i l o t

P l a n t and at Enzyme A p p l i c a t i o n Technology I f o r t h e i r s k i l l f u l
a s s i s t a n c e i n a l l the p r a c t i c a l work c a r r i e d out i n connection
w i t h t h i s paper. A l s o we want to thank Mr. Peer N. J0rgensen a t
Pharmacological Laboratory - Novo I n d u s t r i A/S, Bagsvaerd f o r the
immunochemical examinations. F i n a l l y we thank our c o l l e a g u e ,
Mr. F i n n Jacobsen f o r drawing our a t t e n t i o n to the p o s s i b i l i t i e s
of u s i n g h y p e r f i l t r a t i o n f o r d e s a l i n a t i o n of ISSPH.
Literature cited
1. Manak, L . J . , Lawhon, J.T., and Lusas, E.W., J . Food Sci.

(1980) 45, 236-245
2. A d l e r - N i s s e n , J.,
(1979) 92, 125-146.
3. A d l e r - N i s s e n , J., J . A g r i c . Food Chem. (1976) 24, 1090-93
4. A d l e r - N i s s e n , J., Process Biochem. (1977) 12 ( 6 ) , 18-23,32.
5. Sejr Olsen, H., Lebensm.-Wiss. u.-Technol., (1978) 11,57-64.
6. C h r i s t e n s e n , L.K., Compt.-rend. Lab C a r l s b e r g , Sér. chim.,

(1952) 28 ( 1 ) , 39-169.
7. Novo I n d u s t r i A/S, " P r o t e o l y t i c Enzymes f o r the M o d i f i c a t i o n

of Food P r o t e i n s " , IB 163, Bagsvaerd 1978.
8. S e j r Olsen, H., Isolation of Bean P r o t e i n by Ultrafiltration

In: Proceedings of the I n t e r n a t i o n a l symp. on Sep. proc. by
Membranes, Ion-exchange and Freeze-concentration i n Food I n -
d u s t r y . IUF0ST and FEEC, P a r i s (1975), p. A 6-1, A6-21.
9. Becker, H.C., M i l n e r , R.T., and Nagel, R.H., Cereal Chem.

(1940) 17, 447-457.
10. A d l e r - N i s s e n , J . , J. A g r i c . Food Chem., (1979) 27, 1256-62.
11. Weeke, B., 3. Crossed Immunoelectrophoresis, p. 47-56. I n :

N.H. Axelsen, J . Krøll and B. Weeke: A Manual of Q u a n t i t a -
t i v e Immunoelectrophoresis - Methods and A p p l i c a t i o n s . Uni-
versitetsforlaget, Oslo, 1973.
12. Smith, A.K., and Circle, S.J., Ind. Eng. Chem. (1938) 30,
1414-1418.

10. OLSEN AND ADLER-NISSEN Enzymatically Modified Proteins 169
13. Sejr Olsen, H., A d l e r - N i s s e n , J . , Process Biochem. (1979)

14 (7) 6-8, 10-11.
14. Novo I n d u s t r i A/S, " D e c o l o r a t i o n o f Slaughter House Blood

by Enzymatic M o d i f i c a t i o n " . IB 225, Bagsvaerd 1980.
15. Butterworth, T.A., Wang, D.I.C., Sinskey, A . J . , B i o t e c h n o l .

Bioengin. (1970), 12, 615-631.
16. Ghose, T.K., K o s t i c k , J.A., B i o t e c h n o l . B i o e n g i n . (1970),

12, 921-946.
17. Roozen, J.P, Pilnik, W., Process Biochem. (1973), 8, 24-25
18. I a c o b u c c i , G.A., Myers M.J. Emi S. Myers D.V. Proc IV

I n t . Cong. Food S c i
19. Bhumiratana, S., Hill Jr., C.G., Amundson, C.H., J . Food Sci.
(1978), 42, 1016-1021.
20. Payne, R.E., Hill Jr., C.G., Amundson, C.H., J . Food Sci.
(1978), 43, 385-389.
21. Cunningham, S.D., Cater, CM., Mattil, K.F.,J.Food Sci.

(1978), 43, 1477-1480.
22. Roozen, J.P., Pilnik, W., Enzyme Microb. Technol. (1979), J.,
122-124.
23. Myers, D.V., R i c k s , E., Myers, M.J., W i l k i n s o n , M., Iacobuc-

ci, G.A., Proc. IV I n t . Congr. Food Sci. Technol., Madrid
1974, 5, 96-102.
24. Bennet, A.A., M i l n e , W.E., Bateman, H.,"Numerical I n t e -

g r a t i o n of Differential Equations", Dover P u b l . , I n c . ,
N.Y. 1956, p. 27.
25. A d l e r - N i s s e n , J., Ann. Nutr. A l i m . (1978), 32, 205-216
26. A d l e r - N i s s e n , J., Unpublished experiments.
R E C E I V E D December 4, 1980.

11
Separation of Biopolymer from Fermentation
Broths
W. L . G R I F F I T H , A . L . C O M P E R E , C. G . W E S T M O R E L A N D ,
and J. S. J O H N S O N , JR.
Chemistry Division, Oak Ridge National Laboratory, Oak Ridge, TN 37830
The separations f e a s i b l
mously over the last generation. The developments t h i s symposium
has commemorated, and the i n d i v i d u a l s it has honored, have been
l a r g e l y r e s p o n s i b l e . The removal o f d i s s o l v e d s o l u t e s o r other
low-molecular-weight substances from water by hyperfiltration or
reverse osmosis, which the L o e b - S o u r i r i j a n membrane made techni-
cally and economically feasible, has become an industrial-scale
operation. Ultrafiltration o f colloids and filtration of coarser
m a t e r i a l s from liquids have become much more efficient w i t h the
use o f cross flow o f liquid to slow the b u i l d u p o f filtercake;
a p p r e c i a t i o n o f the b e n e f i t s from shear a t the i n t e r f a c e has
become much more general from the n e c e s s i t y of controlling con-
centration polarization and f o u l i n g in salt filtration.
This paper is an account of our attempts t o apply these
developments t o a c l a s s which still poses formidable problems:
s e p a r a t i o n from each other of two substances, both dispersed in a
liquid as aggregates o f different but l a r g e size. Even though
filters are now likely to be a v a i l a b l e o f pore dimensions which
should d i s c r i m i n a t e , the filter cake o r dynamic membrane that
b u i l d s up soon dominates, and the pore s i z e of the filter becomes
i r r e l e v a n t . One more than likely ends up concentrating both sub-
stances, r a t h e r than passing one w i t h the liquid through the
filter.
In research aimed a t lower chemical costs f o r enhanced oil
recovery, we are attempting a s e p a r a t i o n of t h i s type, biopolymer
from fermentation b r o t h . The m o t i v a t i o n is to e l i m i n a t e the con-
ventional precipitation of polymer by a l c o h o l a d d i t i o n , a step
which c o n t r i b u t e s a s u b s t a n t i a l fraction of p r o d u c t i o n c o s t ,
perhaps as much as 40%, w i t h the n e c e s s i t y to recover a l c o h o l for
r e c y c l e (Figure l). P r e c i p i t a t i o n i s necessary to prepare a dry
product, economical to s h i p . (Concentrated b r o t h , prepared a t a
c e n t r a l facility, is a l s o proposed, a t a penalty in t r a n s p o r t a -
t i o n costs.)
Biopolymers are needed in petroleum p r o d u c t i o n to i n c r e a s e
viscosities of fluids i n j e c t e d i n t o f o r m a t i o n , to improve sweep
0097-6156/81/0154-0171$05.50/0
i n water f l o o d s , and to prevent viscous f i n g e r i n g i n s u r f a c t a n t ,

or m i c e l l a r , f l o o d s . I f one attempts to d r i v e s u r f a c t a n t o r
banked o i l w i t h water, which i s of lower v i s c o s i t y than the
d r i v e n banks, an unstable f r o n t develops, and e v e n t u a l l y water
breaks through prematurely to the production w e l l . A path of low
r e s i s t a n c e to flow between i n j e c t i o n and production w e l l s i s
e s t a b l i s h e d , and much of the o i l and expensive chemicals are thus
not f o r c e d toward the production w e l l . R a i s i n g v i s c o s i t y of the
d r i v e water, and perhaps of the s u r f a c t a n t bank, by polymer
a d d i t i o n tends to counteract t h i s d i f f i c u l t y .
A wet s e p a r a t i o n of biopolymer from broth would be p a r t i c u -
l a r l y advantageous i f biopolymer were produced near the s i t e of
use. Not only would the expense of a l c o h o l p r e c i p i t a t i o n be
bypassed, but a l s o the d i f f i c u l t r e d i s p e r s i o n of dry biopolymer
i n t o aqueous s o l u t i o n s and removal of c e l l d e b r i s and p o o r l y
dispersed polymer fragments e t c . which would plu th f
the formation.
Large q u a n t i t i e s woul program
In a recent f i e l d p i l o t , f o r example, i n v o l v i n g nine i n j e c t i o n
and 16 production w e l l s , about 770,000 pounds of polyacrylamide
were used CO . (Approximately the same amount of biopolymer
would have been required.) I n a f u l l - s c a l e p r o j e c t , much more
would be needed, a rough r u l e of thumb being one to two pounds
of polymer per b a r r e l of p r o j e c t e d enhanced o i l . An o n - s i t e
production f a c i l i t y i s t h e r e f o r e an o p t i o n . Biopolymers have
c e r t a i n advantages over p a r t i a l l y hydrolyzed polyacrylamides, the
other l e a d i n g candidate; they are l e s s s e n s i t i v e to s a l i n i t y and
hardness ions and are l e s s degraded by shear, among other aspects.
They are more expensive, however. Lowering cost through f i e l d
production would l e s s e n t h i s disadvantage.
The c r i t e r i o n of a good s e p a r a t i o n i s production of a s o l u -
t i o n of the d e s i r e d v i s c o s i t y which does not unacceptably plug
formations, without l o s s of s u b s t a n t i a l f r a c t i o n s of the polymer
i n the process. Diatomaceous earth f i l t r a t i o n s have c u s t o m a r i l y
been used to remove plugging c o n s t i t u e n t s . In f i l t r a t i o n of
fermentation b r o t h s , p a r t i c u l a r l y i n the f i e l d , i t i s d e s i r a b l e
to minimize use of these f i l t e r a i d s . I f the biomass i s h e a v i l y
contaminated w i t h them, p o s s i b l e b e n e f i c i a l use as a c a t t l e - f e e d
supplement may be i n h i b i t e d , and an expensive waste d i s p o s a l
problem may be i n c u r r e d : a cost adding 20£ to 40c/lb of polymer
i s conceivable.
In our e v a l u a t i o n of p o s s i b i l i t i e s of lowering biopolymer
costs i n o i l recovery, we concluded that s c l e r o g l u c a n s probably
were a b e t t e r choice f o r f i e l d production than the more u s u a l l y
considered xanthan gums ( 2 ) . V i s c o s i t y p r o p e r t i e s of s o l u t i o n s
of the two are s i m i l a r , but the organisms {Sotevotvum votfst'l^
et a l . ) producing s c l e r o g l u c a n s are more g e n e t i c a l l y s t a b l e than
those producing xanthan gums (Xanthanomas campestvis), are l e s s
pathogenic to p l a n t s , and because they produce a c i d during f e r -
mentation, t h e i r b r o t h s , which may reach pH values as low as 1.5,

11. GRIFFITH ET AL. Biopolymer from Fermentation Broths 173
are l e s s l i a b l e t o contamination by unwanted s p e c i e s . We have

p r e v i o u s l y reported r e s u l t s of fermentation w i t h t h i s c l a s s , both
w i t h c o n v e n t i o n a l glucose as carbon source (_3) and w i t h waste o r
low-value carbohydrates ( 4 ) . Other scleroglucan-producing organ-
isms (mushrooms) have a l s o been investigated (5) . Some p r e l i m i n -
ary s t u d i e s of s e p a r a t i o n of biopolymers from b r o t h have been
reported e a r l i e r 06, 7 ) , as w e l l as of treatment w i t h enzymes
which reduce plugging by degrading p o o r l y d i s p e r s e d polymeric
aggregates ( 8 ) . Here we summarize the present s t a t u s , from these
and other r e s u l t s . F u r t h e r d e t a i l s can be found i n p e r i o d i c
reports (9).
Experimental
Fermentation and b r o t h treatment. Only an o u t l i n e w i l l be

given here; d e t a i l s ma b found i reference 3 d4 Bench
s c a l e fermentations wer
batches i n a 1 4 - l i t e r Chemapec fermenter, type GF0014, sparged
by a i r a t a r a t e of one volume per volume of broth/minute.
Mechanical a g i t a t i o n was a t 300 rpm, and a t ambient temperature.
The organisms used were Sclerotium rolfsii 15206 o r a p r o d u c t i o n
c u l t u r e provided by Ceca, S.A. The medium contained per l i t e r ,
3 g NaN0 , 1 g K H P 0 , 0.5 g MgSO^, 0.7 H 0, 0.5 g KC1, 30 g
3 2 4 2
glucose, 0.05 g FeS0 , and 1 g Ambrex 1003 yeast e x t r a c t , plus

4
s m a l l amounts of anti-foam agents. Fermentations were allowed t o

proceed u n t i l polymer p r o d u c t i o n was maximal, a c o n d i t i o n u s u a l l y
reached when reducing sugar l e v e l was about 0.5%. Biopolymer
f o r microscreen t e s t s was produced i n the ORNL B i o l o g y D i v i s i o n
4 0 0 - l i t e r fermenter.
Assay of polymer was by p r e c i p i t a t i o n w i t h i s o p r o p y l a l c o h o l .
Procedures v a r i e d i n d e t a i l from time to time, but i n g e n e r a l ,
biomass was removed by c e n t r i f u g a t i o n before p r e c i p i t a t i o n . B i o -
mass was taken to be " v o l a t i l e suspended s o l i d s , " the weight l o s s
of the washed c e n t r i f u g a t e between 102°C and 550°C.
Broth i s u s u a l l y heated to stop fermentation, n e u t r a l i z e d ,
and subjected to shear to r e l e a s e polymer attached to c e l l w a l l s .
Figure 2 summarizes e f f e c t s of v a r i o u s orders of c a r r y i n g out
these treatments on v i s c o s i t y . I t i s c l e a r that the f i r s t b l e n d -
ing to which the sample i s subjected has the g r e a t e s t e f f e c t on
the v i s c o s i t y .
These treatments have some e f f e c t on m y c e l i a l m i c r o s t r u c t u r e ,
as the photomicrographs o f F i g u r e 3 i l l u s t r a t e . The n e u t r a l i z e d
and blended (NB) b r o t h had r e l a t i v e l y s m a l l amounts of p a r t i c l e s
other than mycellium. The f i b r i l s were h i g h l y branched and
aggregated i n loose t a n g l e s . A f t e r a u t o c l a v i n g (NBA), the
tangles were more c l o s e l y packed, and the f i b r i l s s h o r t e r . Fur-
ther b l e n d i n g (NBAB) broke up the t i g h t aggregates and produced
some s m a l l p a r t i c u l a t e s . A d d i t i o n a l a u t o c l a v i n g (NBABA) increased
breakdown of c e l l f i b r i l s and r e s u l t e d i n a r e l a t i v e l y l a r g e
number of f i n e p a r t i c l e s . Even the f i n e p a r t i c l e s , however, are

Conventional
Heat, Diatomaceous
-neutralIzation, • Earth ' Alcohol — Drying Ship t o f i e l d
blending, etc. Filtration Precipitation
Biomass t o
I
Alcohol recovery
waste and r e c y c l e
Diatomaceous E a r t h
Injection into - . F i l t r a t i o n , perhaps - • Redisperse
formation enzyme t r e a t m e n t
AttzAncuUvz in-i>Ajhx production
Heat, Polishing F i l t r a t i o n ,
Broth—* neutralization,- - Microscreening - » p e r h a p s enzyme Injection into
blending, etc. treatment formation
supplement?)
Figure 1. Separation of biopolymer from fermentation broth. (Application: mo-

bility control for enhanced oil recovery.)
554 476lBlendl
1
Neutral-
——*^>C
lyre
548
Blend
844
Figure 2. Viscosities of fermenter sample of laboratory-produced glucan after

various treatments: blend, 60 s at low speed of blender; heat, to 90°C for ~ 30
min; neutralize, to pH 6.5-7.0. Numbers refer to viscosities in centipoise, measured
at 60 rpm Brook field LVT, spindle No. 3, T = 25° ± 1°C.

GRIFFITH ET AL. Biopolymer from Fermentation Broths
Figure 3. Photomicrographs of culture broth after treatment: upper left,

upper right, NBA; lower left, NBAB; lower right, NBABA.

s e v e r a l orders of magnitude l a r g e r than the expected s i z e of

biopolymer s p e c i e s .
A x i a l f i l t r a t i o n . In most of our bench-scale f i l t r a t i o n s

cross flow was e f f e c t e d by use of a x i a l f i l t e r s (10). In t h i s
c o n f i g u r a t i o n (Figure 4 ) , a membrane i s wrapped around a r o t o r ,
which i s spun i n a chamber, i n t o which feed i s introduced under
pressure. The r o t o r i s p e r f o r a t e d , and passages are provided f o r
f i l t r a t e (e.g., by an i n t e r v e n i n g screen) from the membrane to
these h o l e s . F i l t r a t e e x i t s through the a x i s . R o t a t i o n speeds
p r o v i d i n g v e l o c i t i e s of up to about 15 f t / s e c at the membrane-
feed i n t e r f a c e can be a t t a i n e d i n a v a i l a b l e equipment.
P l e a t e d u l t r a f i l t r a t i o n module. The a x i a l f i l t e r i s conven-

i e n t f o r experiments, i n that volumes s m a l l r e l a t i v e to o r d i n a r y
u l t r a f i l t r a t i o n systems can be s t u d i e d and i n t h a t pumping of
viscous solutions i s l i m i t e
t r a t e or concentrate b l e
necessary to maintain d e s i r e d cross flow v e l o c i t i e s . There i s no
obvious reason i t could not be s c a l e d up to moderate s i z e s f o r
p r a c t i c a l s e p a r a t i o n s , but so f a r as we know, no large-volume
a x i a l f i l t e r s are a v a i l a b l e . For the operations of i n t e r e s t ,
any of the commercial u l t r a f i l t r a t i o n systems would be candidates.
We have t e s t e d one module, r e c e n t l y developed by Gelman, which
i n c o r p o r a t e s a pleated membrane (Figure 5 ) , w i t h somewhat more
open feed passages than those of spiral-wound membranes, and
which allows backwashing. Other a p p l i c a t i o n s of the module were
discussed at t h i s symposium by A. K o r i n i n a paper coauthored
by G. B. Tanny, and a w r i t t e n account i s presumably i n these
proceedings.
Microscreens. In the course of t h i s research, we came to

the o p i n i o n that a p r e l i m i n a r y screening to remove most of the
biomass was d e s i r a b l e . We s h a l l report e v a l u a t i o n s of micro-
screens, or m i c r o s t r a i n e r s , f o r t h i s purpose. These devices have
been a v a i l a b l e f o r s e v e r a l decades f o r waste water treatment (11).
They are low-hydraulic-head f i l t e r s , comprised of a screen
mounted on a r o t a t i n g drum. Apertures of a v a i l a b l e screens range
down to micron s i z e s . Feed i s introduced i n t o the drum. F i l t e r -
cake c o n t r o l i s by backwash w i t h a i r or a p o r t i o n of the f i l t r a t e ,
once each r o t a t i o n , the backwash being caught i n a t r a y . A
schematic i s shown i n F i g u r e 6.
In p i l o t - s c a l e t e s t s , we used a mobile u n i t provided by the
Envirex d i v i s i o n of the Rexnord Company. The drum was four f e e t
i n diameter by two f e e t long. To a i d i n planning p i l o t t e s t s , we
a l s o c a r r i e d out some p r e l i m i n a r y one-cycle short-time ( l e s s than
30 sec) t e s t s of screens i n bench-scale apparatuses, designed
by manufacturers to evaluate the p o t e n t i a l of microscreens.

i MOTOR
Figure 5. Gelman pleated crossflowfiltercartridge. Cartridge components: (A) a

porous pleated support screen to provide mechanical support under applied pres-
sure; (B) the pleated microporousfiltrationelement; (C) the pleated spacer which
creates the thinflowchannel and promotes turbulentflow;(D) the impermeable
film which creates theflowchannel; (E) a porous support tube to provide an exit
for permeate; (F) open-end cap which provides for exit of productflow;(G) closed-
end cap completely which seals one end of module; (H) outer seal ring which creates
the seal between the impermeable film in the module and the interior of the housing.
The back pressure support tube is not pictured. The ends of the cartridge are potted
and sealed. A space between the ends of Film D and the end seals is provided to
allow the entrance and exit of theflow-channelfluid.
Figure 6. Microscreenflowpattern

Results
Laboratory t e s t s . A p r e l i m i n a r y t e s t of a x i a l f i l t r a t i o n on
broth from a s c l e r o g l u c a n fermentation, d i l u t e d to give a s o l u -
t i o n w i t h i n the range of v i s c o s i t i e s used i n o i l recovery, was
encouraging. I n passage through 1.2 um Acropor (Gelman) membranes
there was no s i g n i f i c a n t l o s s of v i s c o s i t y , measured under the
same shear r a t e , e i t h e r of the broth or of resuspended dry glucan
or xanthan polymer (range from 20 to 25 c p ) . The f i l t r a t i o n was
c a r r i e d out at 20 p s i g and a t 2000 rpm, corresponding to about
11 f t / s e c a t the membrane s u r f a c e . A x i a l f i l t r a t i o n appeared to
lower g r e a t l y the l e v e l of plugging c o n s t i t u e n t s . Figure 7 com-
pares the f l u x d e c l i n e i n passage through 1.2 um f i l t e r s , without
c r o s s f l o w , of the three polymer s o l u t i o n s before and a f t e r a x i a l
f i l t r a t i o n ( a x i a l f i l t r a t i o n f l u x e s a t the time of c o l l e c t i o n of
the samples f o r the plugging t e s t s are l i s t e d i n the f i g u r e
legend.) I t can be see
the f i l t r a t e s . The fermente
was g r e a t e s t before a x i a l f i l t r a t i o n , had the lowest plugging
r a t e subsequently.
These r e s u l t s were obtained w i t h a d i l u t e d b r o t h , without
n e u t r a l i z a t i o n , a u t o c l a v i n g , and b l e n d i n g steps. Although they
i n d i c a t e a p o t e n t i a l of cross flow i n these s e p a r a t i o n s , i t i s
not s u r p r i s i n g that r e s u l t s o f subsequent t e s t s were not always
r e p r o d u c i b l e . Without going i n t o d e t a i l , l a t e r r e s u l t s i m p l i e d
that a two-step s e p a r a t i o n , i n v o l v i n g a coarse screening to
remove most of the biomass, f o l l o w e d by a p o l i s h i n g f i l t r a t i o n to
reduce plugging c o n s t i t u e n t s to a t o l e r a b l e l e v e l , would be
advantageous. The b u l k of the biomass would be uncontaminated
by diatomaceous earth and might t h e r e f o r e be s u i t a b l e as a
c a t t l e - f e e d a d d i t i v e . P o l i s h i n g the e f f l u e n t from screening w i t h
f i l t e r a i d would pose much l e s s of a waste d i s p o s a l problem than
t r e a t i n g the d i l u t e d b r o t h d i r e c t l y . However, the p o s s i b i l i t y of
e l i m i n a t i n g f i l t e r a i d use a l t o g e t h e r by u l t r a f i l t r a t i o n should be
improved w i t h lower biomass content.
Some bench-scale t e s t s i n d i c a t i n g the p o t e n t i a l of t h i s
scheme were d e s c r i b e d i n reference 6. Here we summarize some
l a t e r r e s u l t s of experiments designed i n the l i g h t of our e x p e r i -
ence i n the e a r l i e r runs. I n these, b r o t h was heated, n e u t r a l -
i z e d , and blended, and d i l u t e d to about one gram of biopolymer
per l i t e r . I t was then stored under r e f r i g e r a t i o n u n t i l use.
P a r t was subjected to screening w i t h a metal screen of about
125 um apertures, mounted on an a x i a l f i l t e r . Most of the b i o -
mass was removed i n t h i s s t e p , w i t h no s i g n i f i c a n t l o s s of v i s -
c o s i t y . Fluxes i n the coarse screening were s e v e r a l hundred
g a l l o n s per square f o o t per day.
The screened b r o t h was then compared w i t h unscreened b r o t h
i n p o l i s h i n g by the a x i a l f i l t e r wrapped w i t h 5 um Nuclepore
membranes. F i g u r e 8 compares the f l u x e s . Neither are as h i g h
as one might hope, though the screened feed values appear

GRIFFITH ET AL. Biopolymer from Fermentation Broths
AXIAL FILTRATION
at pH FLUX, g p d / f t 2 *
XAN FLOOD: 500 P P m •
FILTRATE A 6 350
GLUCAN :
PPT. BY B U T Y L ALCOHOL , 5 0 0 ppm •
FILTRATE • 4.5 215
FERMENTOR BROTH, DILUTED 10/1 •

FILTRATE O
* Average when filtrate collected

tor plugging test
Figure 7. Plugging of 1.2-}xm Millipore filter by polymer solutions under 15 psig

pressure; before and after axial filtration through 1.2-jxm Acropor filter (20 psig,
2000 rpm or ~ 11 ft/s). Viscosities of all solutions are 20 to 25 cps.

SCREENED UNSCREENED
O 3 PSI _
- • 12 PSI
1
M
I «
o
c
- E -
E
u
—o m -
X*
—1
O -
- • U.
X
0 o -
— O
• O
—
- i
-
O •
• i
1 I . I . I . . 1 . 1 I . I . 1 1
3 10 20 30 40 50 0 10 20 30 40 50 60
TIME (min)
Figure 8. Fluxes in axial filtration of diluted glucan fermenter broth through 5-^m
Nuclepore filters (2000 rpm ~ 11 ft/s)

somewhat h i g h e r . Figures 9 and 10 compare plugging by the f i l -

t r a t e s from the p o l i s h i n g a x i a l f i l t r a t i o n w i t h the r e s p e c t i v e
feeds, d i l u t e d broth and screened d i l u t e d b r o t h . I t can be seen
that the f l u x d e c l i n e w i t h both the f i l t r a t e s i s much l e s s than
for the feeds. The slopes o f the f l u x d e c l i n e s are not markedly
d i f f e r e n t f o r p o l i s h e d f i l t r a t e s from screened and unscreened
feeds. However, the f l u x e s i n plugging t e s t s w i t h the f i l t r a t e
from the screened feed appear s i g n i f i c a n t l y h i g h e r than w i t h the
f i l t r a t e from the unscreened feed.
Figures 11 and 12 compare the v i s c o s i t i e s of the a x i a l f i l -
t r a t i o n e f f l u e n t s and feeds f o r the screened and unscreened
b r o t h s . Here there i s a c l e a r advantage of the screening step.
There i s l i t t l e decrease of v i s c o s i t y between feed and f i l t r a t e
for the screened m a t e r i a l , but about a 25% decrease f o r the
unscreened. There are sometimes decreases i n v i s c o s i t y i n c u r r e d
from diatomaceous earth f i l t r a t i o n
The r e s u l t s i n Figure
r e s u l t s i n reference 6
use here of Nuclepore f i l t e r s , which have c y l i n d r i c a l pores nor-
mal to the surface i n a narrow s i z e range, r a t h e r than the
Acropor membranes i n reference 6, whose pores are more tortuous.
We do not have s u f f i c i e n t i n f o r m a t i o n f o r a d e f i n i t i v e c o n c l u s i o n
on t h i s p o i n t . However, a l a t e r comparison of f l u x e s i n a x i a l
f i l t r a t i o n by the two types (Figure 13) does not i n d i c a t e any
great d i f f e r e n c e . Comparisons of v i s c o s i t y of feeds and f i l t r a t e
and of plugging r a t e s of f i l t r a t e s a l s o d i d not support a s i g n i f -
i c a n t d i f f e r e n c e between Nuclepore and Acropor.
Removal of biomass by microscreens. Laboratory t e s t s :

P r e l i m i n a r y e v a l u a t i o n of microscreens, or m i c r o s t r a i n e r s , as a
commercially a v a i l a b l e device f o r the i n i t i a l removal of the
b u l k of the biomass from b r o t h was c a r r i e d out by means of bench
once-through t e s t s of f i l t r a t i o n w i t h s m a l l areas of screens of
p l a s t i c and of s t a i n l e s s s t e e l having d i f f e r e n t a p e r t u r e s , on
broths subjected to d i f f e r e n t p r e l i m i n a r y treatments. These
procedures have been designed by the manufacturers to simulate
the performance f o r times comparable to backwash i n t e r v a l s and to
give i n f o r m a t i o n a l l o w i n g p r o j e c t i o n of the s i z e of a treatment
system necessary f o r a given a p p l i c a t i o n . Although the r e s u l t s
were u s e f u l i n planning the subsequent t e s t s w i t h the mobile
p i l o t u n i t , they were not c l o s e l y p r e d i c t i v e of performance. The
reason i s not c l e a r , but i t i s p o s s i b l e that backwash i n the
p i l o t u n i t was not complete w i t h these feeds, and there was some
c o n t r i b u t i o n of cake to the f i l t r a t i o n .
The r e s u l t s d i d i n d i c a t e that under the proper c o n d i t i o n s
biomass could be separated from b r o t h without a p p r e c i a b l e f i l t r a -
t i o n of biopolymer and that performance v a r i e d w i d e l y w i t h the
h i s t o r y of the b r o t h . F i g u r e 14 i l l u s t r a t e s e f f e c t s of b r o t h
treatment. Large d i f f e r e n c e s i n the f r a c t i o n a l removals of b i o -
mass are apparent f o r d i f f e r e n t screen apertures and treatments

Figure 9. Unscreened feed for axial filtration: plugging of 1.2-/xm Nuclepore filters
by filtrate from Nuclepore filter mounted on axial filter (plugging test pressure
= 12 psi).

GRIFFITH ET AL. Biopolymer from Fermentation Broths 183
TIME (min)
Figure 10. Screened feed for axialfiltration:plugging of 1.2-pm Milliporefilterby

filtrate from 5-^m Nucleporefiltermounted on axialfilter(plugging test pressure,
12 psi).

"I 1—I | I I I 11 1 1—I | I I I 11 1 1—I | I I I LI
I I I I 11 _l I I I I II I
10 100
l
SHEAR RATE (••c~ )
Figure 11. Unscreened feed: comparison of viscosities of feed and filtrates from
axial filtration (25°C; axial filtration through 5-^m Nuclepore filter)

1000 r
• FEED
100 h
o
Tr-
J I L_ I I II I I II.I i mil
100 1000
SHEAR RATE (NC ')
Figure 12. Screened feed: comparison of viscosities of feed and filtrates from axial
filtration (25°C; axial filtration through 5-fim Nuclepore filter).

I i I
SCREENED THROUGH FILTERED THROUGH ~

o 200 MESH 5/xm ACROPOR
• 120 MESH 5/xm ACROPOR
A 200 MESH 5/xm NUCLEPORE
• 200 MESH 3/xm NUCLEPORE
E 10
E
D
0.5
O
•
A
u
T^
TIME (hr)
Figure 13. Axial filtration at a rotational speed of 2,000 rpm (~ 11 ft/s) of

screened fermenter broth at 7.5:1 dilution and 7 psi
Treatment
• NB
O NBA
A NBAB
+ NBABA
O NBABH
I I 1 _J_
Figure 14. Biomass removal. Effect of 0 10 20 30 40 50 60
media aperture and broth treatment at
11-in. hydraulic head. APERTURE, /um

(the treatment symbols were i d e n t i f i e d i n the d i s c u s s i o n of

Figure 3, except f o r H, which s i g n i f i e s f i l t e r e d w h i l e h o t ) . How-
ever, w i t h i n s c a t t e r , there appeared t o be no d i f f e r e n c e s i n the
v i s c o s i t i e s o f feeds and f i l t r a t e s .
P i l o t t e s t s : Even w i t h 3 5 0 - l i t e r fermentations, d i l u t e d t o
v i s c o s i t i e s i n the i n j e c t i o n range, the volume of feed was l e s s
than i d e a l f o r the Rexnord mobile p i l o t u n i t . To make runs over
the times and under the c o n d i t i o n s we wished, i t was necessary t o
r e c y c l e e f f l u e n t and m a t e r i a l c o l l e c t e d i n backwashing to the
feed tank. F o r these t e s t s , feed was n e u t r a l i z e d w i t h NaOH and
p a s t e u r i z e d i n the fermenter; i t i s b e l i e v e d that adequate b l e n d -
i n g was accomplished by shear from s t i r r i n g during d i l u t i o n and
from pumps, along w i t h passage through other elements o f the
system.
Figure 15 presents f r a c t i o n a l biomass removal i n runs w i t h
p o l y e s t e r screens of s e v e r a l d i f f e r e n sizes
f o r 21 um f i l t e r media
above 80%. For some reason, y second-stag
screen of 21 um e f f l u e n t gave l i t t l e improvement although s i n g l e -
stage removal by 1 um screens were good.
F i g u r e 16a compares biomass c o n c e n t r a t i o n a t v a r i o u s p o i n t s
i n the system f o r the run w i t h 21 um screen. Although biomass
removal i n t h i s run was the lowest of the t e s t s i n Figure 14, i t
can be seen that biomass i s over a f a c t o r of ten h i g h e r i n back-
wash than i n f i l t r a t e . Figure 16b i n d i c a t e s that polymer concen-
t r a t i o n i s s i m i l a r a t a l l p o i n t s and i s not being removed by the
f i l t e r . This behavior was general i n a l l s i n g l e - s t a g e micro-
screen runs and was confirmed by the f a c t that v i s c o s i t i e s o f
samples a t d i f f e r e n t p o i n t s were not s t a t i s t i c a l l y d i f f e r e n t .
The e f f l u e n t from the two-stage (21 um f o l l o w e d by 1 um) screen-
i n g had a lower v i s c o s i t y than the feed.
The p o s s i b i l i t y that microscreening alone might be adequate
without p o l i s h i n g f i l t r a t i o n was evaluated i n the plugging t e s t s
summarized i n F i g u r e 17a. I t appears that f u r t h e r treatment i s
necessary.
P o l i s h i n g of microscreen e f f l u e n t s : Diatomaceous earth
treatment should be much e a s i e r and l e s s c o s t l y a f t e r micro-
screening, b u t a l t e r n a t i v e s are s t i l l d e s i r a b l e . F i g u r e 17b com-
pares plugging of microscreen e f f l u e n t before and a f t e r f u r t h e r
f i l t r a t i o n through 1.2 um Gelman Acropor AN f i l t e r s i n an a x i a l
c o n f i g u r a t i o n and i n the p l e a t e d c a r t r i d g e of F i g u r e 5. Plugging
rates are g r e a t l y decreased, the Gelman c a r t r i d g e (loop) g i v i n g
s o l u t i o n of the h i g h e s t f l u x e s . However, the f i l t r a t e s from i t
were somewhat lower i n v i s c o s i t y than the feeds. The r e s u l t s
w i t h the a x i a l f i l t e r appear l e s s f a v o r a b l e than i n e a r l i e r
t e s t s w i t h prescreened feeds, and i t i s suspected that there may
have been leakage around s e a l s i n t h i s case.

Figure 15. Volatile suspended solids removal efficiencies for various media: +,
6 fxm; 0 , 1 / z r a ; A, 21 jxm; and m
1 n following 21 yjn.

- 1.5 -
\
1.4
1.3
CO
9 1.2
_i
o 1 1
CO
1.0
Q
UJ 0 . 9
Q
Z 0,8
UJ
Q.
CO 0 . 7
z> 0 . 6
C
UJO 0.5
_J
0.4
< 0.3
o_ l 0 . 2
>
0.1
0 10
TIME (h)
Figure 16. Concentrations at various

points in the microscreen system equipped
with 21-fim screens: a, volatile suspended
TIME (hr) solids; b, polymer. • , feed tank; O, in-
fluent; %, effluent; -\~, backwash.

! !
! ! I 1 11 "'"I I " T"T" 1 Mil"
• =91 6yLim-
10 1 _ o = 146 1/j.m
E A = 173 21/xm =
+ =145 Feed =
i i i n i i i i i i i 111
10 10 10
E L A P S E D TIME (mm)
(a)
1
IO
10"
10 E
Figure 17. Plugging test results: a, pilot

microscreen effluents; b, filtrates from
1 2
polishing by crossflow filtration through 10° io io
1.2-fxm Acropor filter in axial filter (1.5 E L A P S E D TIME (min)
psi, 1000 rpm) and in pleated cartridge
(loop). (b)

Discussion
Although there are a considerable number of questions yet

needing answers, the r e s u l t s so f a r are promising w i t h respect t o
f i l t r a t i o n without f i l t e r a i d , or w i t h much l e s s than i s customary,
for s e p a r a t i o n of biopolymer from fermentation b r o t h . Table 1
summarizes estimates o f c a p i t a l costs and power requirements f o r
a ton of biopolymer per day s e p a r a t i o n p l a n t by diatomaceous
earth f i l t r a t i o n , c e n t r i f u g a t i o n , and microscreening. The micro-
screening i s lowest, but a p o l i s h i n g step would have to be added.
With respect to microscreening of s c l e r o g l u c a n b r o t h s , t e s t s
should be c a r r i e d out on b r o t h n e u t r a l i z e d by l i m e . Because some
of the a c i d produced i n the fermentation i s o x a l i c , i t s removal
i s probably necessary before i n j e c t i o n , to avoid p r e c i p i t a t i o n
as calcium o x a l a t e i n the formation. Lime p r e c i p i t a t i o n should
e f f e c t t h i s . I t i s probabl tha f i l t r a t i o w i t h calciu o x a l a t
i n the feed w i l l procee
i t i s d i f f i c u l t to p r e d i c t whethe performance be b e t t e o
worse.
Further o p t i m i z a t i o n of the p o l i s h i n g step i s c l e a r l y nec-
essary. The mediocre f l u x e s i n c r o s s - f l o w and a x i a l f i l t r a t i o n
suggest that systems a l l o w i n g backwash at frequent i n t e r v a l s may
be necessary. Many commercial u l t r a f i l t r a t i o n systems, i n c l u d i n g
the one used here, have t h i s c a p a b i l i t y .
The biomass c o n c e n t r a t i o n i n the microscreen backwash i s low.
We have e s t a b l i s h e d however that c e n t r i f u g a t i o n at 2800 g appears
to a l l o w c o n c e n t r a t i o n up to 2 or 3% dry s o l i d s , or by about a
f a c t o r of ten. The pasty cake obtained could be used d i r e c t l y as
an animal-feed a d d i t i v e i f there were a market nearby, or could
be d r i e d f o r shipment. C e n t r i f u g a t i o n of microscreen backwash i s
a r e l a t i v e l y low cost o p e r a t i o n ; we estimate that i t would add
$10,000 to the c a p i t a l cost and 2 hp to the power requirement o f
the estimates i n Table 1.
Table 1
3
Cost and energy of processes f o r a 1 0 kg/day
6
(10 l i t e r s / d a y ) i n s t a l l a t i o n
Capital
Process Cost, 1 0 3
$ Power, hp
DE filter 155 180

Centrifuge-'- 107 40
Microscreen^ 80 8
Maxium power demands up to 60 hp.

P o l i s h i n g step r e q u i r e d .

Moderate decreases i n v i s c o s i t y i n p o l i s h i n g f i l t r a t i o n do
not n e c e s s a r i l y imply biopolymer l o s s . So long as polymer i s not
incorporated i n f i l t e r c a k e as i t would be i n diatomaceous earth
f i l t r a t i o n (or i f i t can be backwashed o f f , even i f i t i s ) , i t
should be p o s s i b l e to operate w i t h a feed of h i g h e r v i s c o s i t y than
necessary f o r i n j e c t i o n , and to r e c y c l e feed through the f i l t r a -
t i o n apparatus, perhaps a f t e r d i l u t i o n . Another p o s s i b i l i t y would
be to r e c y c l e p o l i s h i n g f i l t r a t i o n blowdown i n t o the microscreen-
ing system.
Acknowledgments
Research was sponsored by the D i v i s i o n of Chemical Sciences,

O f f i c e of B a s i c Energy Sciences, U. S. Department of Energy, under
c o n t r a c t W-7405-eng-26 w i t h Union Carbide Corporation.
We are indebted to J B Cravens of Rexnord f o r c o l l a b o r a t i o n
on bench-scale and p i l o
M. V. Long of the ORNL
fermentations f o r these t e s t s . S. V. Greene and J . M. Crenshaw
provided t e c h n i c a l a s s i s t a n c e i n many aspects of the research.
Literature Cited
1. K l e i n s c h m i d t , R. F. "North Burbank U n i t T e r t i a r y Recovery

Pilot Test," Final Report, Phillips Petroleum Co. to U. S.
Dept. of Energy DOE/ET/13067-60 (1980).
2. Baldwin, W. H., et al., "Chemicals f o r Enhanced Oil Recovery,"
Annual Report, April 1977-April 1978, U. S. Dept. of Energy
BETC/W-26-4.
3. Griffith, W. L.; Compere, A. L. Developments I n d u s t r i a l
M i c r o b i o l o g y , 1978, 19, 609.
4. Compere, A. L.; Griffith, W. L. Developments I n d u s t r i a l
M i c r o b i o l o g y , 1978, 19, 601.
5. Compere, A. L.; Griffith, W. L.; Greene, S. V. Developments
Industrial M i c r o b i o l o g y , 1980, 21, 461
6. Griffith, W. L.; Tanny, G. B.; Compere, A. L. Developments
Industrial M i c r o b i o l o g y , 1979, 20, 743.
7. Griffith, W. L.; Compere, A. L.; Cravens, J. B.; E r i c k s o n ,
P. R. Developments I n d u s t r i a l M i c r o b i o l o g y , submitted.
8. Griffith, W. L.; Compere, A. L.; Crenshaw, J. M. Developments
Industrial M i c r o b i o l o g y , 1980, 21, 451.
9. Compere, A. L., et al., "Chemicals f o r Enhanced Oil Recovery,"
Q u a r t e r l y r e p o r t s f o r Winter, Summer, and Fall 1979,
Department of Energy BETC/W26-5, BETC/W26-10, BETC/W26-15.
10. Kraus, K. A., Proceedings 29th I n d u s t r i a l Waste Conference,
Purdue Research Foundation, 1974, 1059.
11. Cravens, J. B.; Kormanik, R. A. J . Water Pollution C o n t r o l
F e d e r a t i o n , in p r e s s .

12
Externally Wound Tubular Membrane Elements in
Modular Assemblies: Production and Application
S. M A N J I K I A N
A R A M C O , Dhahran, Saudi Arabia
C. K . W O J C I K
University of Petroleum & Minerals, Dhahran, Saudi Arabia
Tubular R.O. system

when compared w i t h the g spiral
hollow f i n e f i b e r type R.O. systems. I n the water d e s a l i n a t i o n
field, the h i g h membrane packing d e n s i t y of spiral and hollow f i n e
fiber systems has given them an overwhelming economic advantage
over t u b u l a r systems. However, the advantageous design f e a t u r e of
spiral and hollow f i n e fiber u n i t s a l s o serves t o limit t h e i r
a p p l i c a t i o n t o relatively c l e a r fluids f r e e of colloidal and par-
ticulate matter. This effectively curtails their practical
a p p l i c a t i o n in areas such as the s e p a r a t i o n and c o n c e n t r a t i o n of
fluid foods, pharmaceutical mixtures and the treatment of indus-
trial wastes. Tubular system can and should effectively fill this
gap.
The e x t e r n a l l y wound t u b u l a r membrane system and c o n v e n t i o n a l
t u b u l a r designs have the necessary d e s i g n , p r o d u c t i o n and func-
tional f e a t u r e s t o meet more demanding task of p r o c e s s i n g fluids
of h i g h p a r t i c u l a t e content and, in r o t a r y assemblies, treatment
of d e l i c a t e and structurally s e n s i t i v e fluids and chemical
mixtures.
System D e s c r i p t i o n
The e x t e r n a l l y wound membranes were developed by U n i v e r s a l

Water Corp., San Diego, C a l i f o r n i a . I n t h i s d e s i g n , the membrane
element c o n s i s t s of a porous supporting tube on which are s i m u l -
taneously wound, i n h e l i c a l f a s h i o n , a s t r i p of permeable f a b r i c
o v e r l a i d w i t h a h e l i c a l wound s t r i p of semipermeable membrane f i l m .
Adjacent turns of the membrane overlap i n winding, and these over-
laps a r e sealed by a bonding solvent so t h a t , the membrane i t s e l f
0097-6156/81/0154-0193$05.00/0

forms a u n i t a r y tube e n c l o s i n g the f a b r i c and the porous support-

ing tube. A diagram of such h e l i c a l l y wound membrane element i s
shown i n F i g . 1.
Modular assemblies designed t o house a number of h e l i c a l e l e -
ments a r e constructed by arranging i n d i v i d u a l membrane elements,
i n spaced r e l a t i o n s h i p s , w i t h i n f l o w guide tubes i n s i d e a s u i t a b l e
pressure v e s s e l . V a r i o u s diameter flow tubes are used t o p r o v i d e
the d e s i r e d annular spacing between membrane surfaces and b r i n e
flow channel w a l l s . By t h i s means the cross s e c t i o n a l area of
b r i n e flow channels around each element can be s e l e c t e d t o p r o v i d e
best c o n d i t i o n s f o r s p e c i f i c processing a p p l i c a t i o n s . For example,
a r e l a t i v e l y wide spacing may be r e q u i r e d f o r f l u i d s that are v i s -
cous or have a h i g h content of p a r t i c u l a t e or c o l l o i d a l matter as
i n food p r o c e s s i n g a p p l i c a t i o n s . On the other hand, c l o s e spacing
may be r e q u i r e d i n water d e s a l i n a t i o n a p p l i c a t i o n s t o prevent con-
c e n t r a t i o n p o l a r i z a t i o n by producing a t u r b u l e n t f l o w and t o
reduce pumping r a t e s . Th
F i g . 2.
A module j u s t described i s a f i x e d module i n which the mem-
brane elements a r e s t a t i o n a r y . A r a d i c a l departure from the con-
v e n t i o n a l mode of R.O. systems o p e r a t i o n s i s the r o t a r y system
wherein e x t e r n a l l y wound membrane elements c l u s t e r e d around a
c e n t r a l s h a f t a r e r o t a t e d i n a s t a t i o n a r y pressure v e s s e l f i l l e d
w i t h p r e s s u r i z e d feed stock. Here the separated permeate i s
replaced by an equivalent volume of f r e s h feed stock under a con-
stant head. The b a s i c r o t a r y concept i s depicted i n F i g . 3.
The most important f e a t u r e s of the e x t e r n a l l y wound membranes
are:
• Low c o s t . No advanced technology o r s o p h i s t i c a t e d equip-
ment i s i n v o l v e d i n making of such membrane elements. They
can be manufactured on s i t e .
• S e r v i c e a b i l i t y and maintenance. Being on the outer surface
of t u b u l a r elements, the membranes a r e r e a d i l y a c c e s s i b l e
to i n s p e c t i o n and c l e a n i n g . Assembly and disassembly of
modules can be accomplished e a s i l y and q u i c k l y i n the f l u i d .
• Good mechanical r e l i a b i l i t y of the system. The membrane
elements a r e subjected t o compressive s t r e s s e s o n l y , t h e r e -
f o r e , n o n - c o r r o s i v e m a t e r i a l s of lower t e n s i l e s t r e n g t h
may be used.
Membranes
Membranes f o r e x t e r n a l l y wound elements were e i t h e r obtained

as f i n i s h e d product from commercial sources, or produced in-house
from raw m a t e r i a l s .
Purchased membranes were i n i t i a l l y t e s t e d f o r compliance w i t h
the s p e c i f i c a t i o n s designed t o assure t h e i r s u i t a b i l i t y f o r wind-
ing o p e r a t i o n s ( t h i c k n e s s , t e n s i l e s t r e n g t h and e l o n g a t i o n ) and
for t h e i r performance c h a r a c t e r i s t i c s ( f l u x and s a l t r e j e c t i o n )

12. MANJIKIAN A N D WOJCIK Tubular Membrane Elements 195
I
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12. MANJIKIAN AND wojciK Tubular Membrane Elements 197
κ.

w i t h i n the p r e s c r i b e d range of o p e r a t i o n . A f t e r meeting success-

f u l l y these s p e c i f i c a t i o n s , they were evaluated i n teridb of t h e i r
a p p l i c a b i l i t y to h e l i c a l winding and c o m p a t i b i l i t y w i t h overlap
s e a l a n t s . Most of the commercial membranes were found to be s u i t -
able f o r h e l i c a l winding a p p l i c a t i o n .
The in-house membranes were f a b r i c a t e d , w i t h minor m o d i f i c a -
t i o n s , along w e l l e s t a b l i s h e d procedures which i n c l u d e d : formula-
t i o n , c a s t i n g or forming, g e l l a t i o n and c u r i n g a t elevated temper-
a t u r e s . Various c a s t i n g s o l u t i o n s were t r i e d f i r s t f o r t h e i r per-
formance as f l a t t e s t membranes before t h e i r s u i t a b i l i t y f o r wind-
ing operations was considered. The p r e f e r r e d c a s t i n g f o r m u l a t i o n
f o r membranes used i n the h e l i c a l l y wound elements comprises:
24% C e l l u l o s e acetate E-398-6 or -10
29% Formamide
35% Acetone
12% P y r i d i n e
A d d i t i o n of p y r i d i n e t o
i n membranes having s u p e r i o propertie
t h e i r s t r e n g t h and d u c t i l i t y .
P r i o r t o c a s t i n g , the mixed formulations were f i l t e r e d f o r
removal of p a r t i c u l a t e and i n s o l u a b l e matter and t r a n s f e r r e d to
s p e c i a l c a n i s t e r s . Casting was done a t ambient temperatures and
water c u r i n g a t 1°C f o r a p e r i o d of 45 minutes. P r i o r t o use, the
membranes were f i r s t annealed and then s l i t i n t o s t r i p s , say
1.065 ± 0.005 i n c h wide f o r a 7/16 i n c h diameter element, and
r o l l e d on s p e c i a l capsules f o r i n s e r t i o n i n t o winding feeders. The
c u r i n g temperatures r e q u i r e d f o r given performance s p e c i f i c a t i o n s
f o r the e x t e r n a l l y would membranes were found t o be 2 t o 5 C
higher than those f o r f l a t membranes. For b r a c k i s h water a p p l i c a -
t i o n s , the membrane elements were cured a t 84 C ± 0.2 C f o r the
p e r i o d of 10 ± 0.5 minutes.
Support S t r u c t u r e s
In the c o n s t r u c t i o n and assembly of e x t e r n a l l y wound t u b u l a r

membrane systems, the support s t r u c t u r e i s g e n e r a l l y a r i g i d non-
compressible t u b u l a r body of s u f f i c i e n t mechanical s t r e n g t h t o
withstand r e q u i r e d operating pressures and of adequate p o r o s i t y t o
f r e e l y transmit the separated permeate. M a t e r i a l s having uniform
p o r o s i t y would be the most d e s i r a b l e , however, c e l l u l a r p o r o s i t y
i s o f t e n (at l e a s t i n the cases tested) a s s o c i a t e d w i t h low
mechanical s t r e n g t h , l a c k of u n i f j r m i t y and long term r e l i a b i l i t y
and a r e l a t i v e l y high cost of production. I n absence of such
m a t e r i a l s , p o r o s i t y i n supporting tubes was achieved by d r i l l i n g
holes a t spaced i n t e r v a l s u s i n g a s p e c i a l l y designed m u l t i - s p i n d l e
d r i l l i n g f i x t u r e . I t was e s t a b l i s h e d experimentally that the most
s a t i s f a c t o r y passage of water was achieved through 0.028 i n c h
diameter p e r f o r a t i o n s spaced at three i n c h i n t e r v a l s along two
s t r a i g h t l i n e s 180 degrees apart.

12. MANJIKIAN AND WOJCIK Tubular Membrane Elements 199
D e s i r a b l e p r o p e r t i e s f o r supporting tubes are: c o r r o s i o n

r e s i s t a n c e , thermal s t a b i l i t y , dimensional s t a b i l i t y under wet
c o n d i t i o n s , c o m p a t i b i l i t y w i t h other components of the module,
mechanical s t r e n g t h , and good m a c h i n e a b i l i t y .
A h i g h l y p r a c t i c a l m a t e r i a l i s ABS ( a c r y l o n i t r i t e - b u t a d i e n e -
s t y r e n e ) . Membrane elements, f a b r i c a t e d w i t h 7/16 nominal
diameters extruded ABS tubing as support s t r u c t u r e s , were success-
f u l l y operated a t pressure up t o 1500 p s i g .
Backing M a t e r i a l s
Backing m a t e r i a l s are used i n the c o n s t r u c t i o n and assembly

of e x t e r n a l l y wound t u b u l a r membrane elements t o provide f o r
l a t e r a l t r a n s f e r of permeate t o spaced p e r f o r a t i o n s i t e s i n the
support s t r u c t u r e . P r i n c i p a l c h a r a c t e r i s t i c s d e s i r a b l e i n membrane
backing m a t e r i a l s i n c l u d h i g h p o r o s i t f o adequat l i q u i d
meation a t minimum p r e s s u r e s
surface t e x t u r e t o minimiz g g
membrane s u r f a c e s and mechanical s t r e n g t h t o b r i d g e over p e r f o r a -
t i o n s i n the support tube.
Dacron pressed paper was found t o be h i g h l y adequate f o r per-
meate t r a n s p o r t w h i l e possessing the wet s t r e n g t h p l a s t i c proper-
t i e s needed i n winding o p e r a t i o n s . Dacron paper was a l s o used i n
c a s t i n g membranes d i r e c t l y on support s t r u c t u r e s .
Sealants
In the f a b r i c a t i o n of e x t e r n a l l y wound t u b u l a r membrane

elements and modular assemblies s o l v e n t bonding f l u i d s and 0-rings
are commonly used as s e a l a n t s . I n winding o p e r a t i o n s , s t r i p s o f
membranes a r e wound i n an overlapping manner t o form a u n i t a r y
tube where h e l i c a l winding overlaps a r e s o l v e n t bonded d u r i n g
winding w h i l e the ends of the windings are sealed t o the support
tube. Commercially a v a i l a b l e glues and bonding mixtures were
found t o be i m p r a c t i c a l i n the continuous and immediate s e a l i n g
requirements of the winding process. Most of the epoxy formula-
t i o n s were r e j e c t e d because of t h e i r s e t t i n g and c u r i n g time
requirements. Commonly known c e l l u l o s e acetate s o l v e n t s were
t e s t e d i n d i v i d u a l l y and i n combination. I n g e n e r a l , pure s o l v e n t s
were found t o be too strong f o r t h a t purpose, as they tended t o
penetrate membrane surfaces r a t h e r than spread over the overlap
i n t e r f a c e , thus, r e s u l t i n g i n an i m p e r f e c t l y bonded seams, w i t h
p h y s i c a l l y weak and b r i t t l e areas at the j o i n t . E x p e r i m e n t a l l y ,
weak s o l v e n t s i n combination w i t h d i l u e n t s and p l a s t i c i z e r s were
found t o be h i g h l y acceptable. A composition, found t o be the
most e f f e c t i v e , c o n s i s t e d of a mixture of t r i a c e t i n and a l c o h o l .
C e l l u l o s e a c e t a t e was added t o the mixture to i n c r e a s e i t s v i s -
c o s i t y and a dye t o c o l o r i t f o r the q u a l i t y c o n t r o l purposes. This
mixture, a weak s o l v e n t by i t s e l f , produced an extremely strong and
r e l i a b l e bond of the membrane o v e r l a p s . The composition of t h i s
sealant mixture was:

Triacetin 94 p a r t s by volume
1-Propanol 6* p a r t s by volume
C e l l u l o s e acetate
(E 398 - 10) 3 g per 100 ml of t r i a c e t i n
Red commercial dye 1 g per l i t e r of mix.
The bond obtained u s i n g t h i s sealant was found t o be e f f e c t i v e

w i t h both wet and d r y membranes. F u r t h e r , t e n s i l e t e s t s showed
that the bond was a t l e a s t as strong as the membrane i t s e l f . Most
important, the bonding took p l a c e i n s t a n t a n e o u s l y a t ambient tem-
peratures. No c u r i n g or s e t t i n g time i s r e q u i r e d . Hence, t h i s
bonding method was found t o be i d e a l l y s u i t e d f o r the automatic
and continuous winding of membrane elements. Pressure adhesive
tape was used f o r s e a l i n g membrane winding edges and a f f i x i n g same
to the supporting tube.
Structural Materials
As noted above, e x t e r n a l l y wound t u b u l a r membrane elements

are f a b r i c a t e d p r i m a r i l y of extruded ABS tubing ( n a t u r a l ) , c e l l u -
l o s i c or blend membranes and dacron paper. The c a r t r i d g e assembly
designed t o house the membrane elements and provide f o r the u n i -
form d i s t r i b u t i o n / f l o w of feed stock i s f a b r i c a t e d of extruded
t h i n w a l l e d p o l y s t y r e n e headers. Pressure v e s s e l s were f a b r i c a t e d
e i t h e r by u s i n g epoxy coated s t e e l pipe or f i b e r g l a s s v e s s e l s .
H e l i c a l Winding Process
Fabrication/assembly of e x t e r n a l l y wound t u b u l a r membrane

elements i s accomplished by s p e c i a l l y designed equipment that
simultaneously and c o n t i n u o u s l y winds, i n h e l i c a l f a s h i o n , i n f i n i t e
lengths of membrane and backing m a t e r i a l s t r i p s onto p r e f a b r i c a t e d
t u b u l a r support s t r u c t u r e s . Membrane s t r i p winding overlaps are
solvent bonded during the winding process.
A s u c c e s s f u l method f o r a c h i e v i n g t h i s motion i s based on the
use of three d r i v i n g r o l l e r s e q u a l l y spaced on the circumference
of the support tube. In o p e r a t i o n such r o l l e r s are i n compressive
contact w i t h the surface of the supporting tube and p o s i t i o n e d a t
an angle t o i t s a x i s . The r o l l e r s are d r i v e n by a s i n g l e motor
and thus r o t a t e a t i d e n t i c a l speeds. This arrangement imparts a
p r e c i s e h e l i c a l motion t o the element support tubing w i t h respect
to the s t a t i o n a r y feeding spools.
To maintain a constant h e l i x angle, s y n c h r o n i z a t i o n of r o t a r y
and l i n e a r motions i s e s s e n t i a l . A l s o , the determination and use
of backing m a t e r i a l s and membrane s t r i p s of proper width i s
important i n o p t i m i z i n g the e f f e c t i v e membrane surface area f o r a
given support tubing nominal diameter. The geometrical r e l a t i o n -
ships between these widths and the h e l i x angle are given i n F i g . 4.
Here, the h e l i x angle i s denoted by a, d i s the diameter of the

Figure 4. Winding geometry
Backing m a t e r i a l
(a)

supporting tube ( i t i s a l s o the nominal diameter of the element),

and c i s the amount of membrane overlap ( u s u a l l y 0.062 t o 0.125
in.). I n p r a c t i c e , the h e l i x angle was s e t i n the range of 35 -
45°.
Another important f a c t o r i n the winding o p e r a t i o n i s t e n s i o n
a p p l i e d t o the backing m a t e r i a l and t o the membrane s t r i p . Tension
i s needed t o i n s u r e smooth w r i n k l e - f r e e wound surfaces and t o pro-
v i d e the necessary pressure between membrane overlaps t o o b t a i n
proper ponding. A minimum t e n s i o n of about 3 l b / i n i s r e q u i r e d f o r
winding the backing m a t e r i a l , w h i l e the optimal t e n s i o n f o r mem-
brane s t r i p s amounted t o 1 l b / i n .
Winding machinery comprises: (1) a d r i v e mechanism t o provide
means f o r imparting simultaneous r o t a r y and l i n e a r motion t o sup-
port s t r u c t u r e s i n a continuous manner, (2) membrane and backing
m a t e r i a l feeder c a r t r i d g e s , (3) a sealant a p p l i c a t o r assembly, (4)
electromechanical c o n t r o l s (5) t off/separatio tooling d
(6) completed element handlin
Modular Assemblies
A modular assembly housing e x t e r n a l l y wound t u b u l a r membrane

elements may be d e f i n e d as a pressure v e s s e l w i t h i n which a r e
assembled a m u l t i p l i c i t y of i n d i v i d u a l elements, means f o r connec-
t i n g and s e a l i n g s a i d elements t o common headers and a feed stock
d i s t r i b u t i o n system that provides f o r adequate feed f l o w across
membrane s u r f a c e s .
In the development and design of modular assemblies^ housing
a m u l t i p l i c i t y of e x t e r n a l l y wound t u b u l a r membrane elements, the
f o l l o w i n g f a c t o r s were considered: e f f e c t i v e n e s s of element pack-
ing arrangements and d e n s i t y , feed stock d i s t r i b u t i o n p a t t e r n s f o r
c o n t r o l l e d and uniform feed f l o w across membrane s u r f a c e s , s e a l i n g
r e l i a b i l i t y of modular sub-assemblies, o v e r a l l system r e l i a b i l i t y ,
module s e r v i c e a b i l i t y and ease of maintenance, system p r o d u c t i b i l -
i t y , and economic v i a b i l i t y .
In u t i l i z a t i o n of e x t e r n a l l y wound t u b u l a r membrane elements
i n modular assemblies f o r conventional systems o p e r a t i o n s , that i s ,
s e l e c t i v e s e p a r a t i o n v i a the c i r c u l a t i o n of p r e s s u r i z e d feed across
membrane s u r f a c e s , flow guide tubes were found t o be e s s e n t i a l f o r
the proper d i s t r i b u t i o n and c o n t r o l of feed flow. This was
achieved s i n g u l a r l y by the use of i n d i v i d u a l element shrouds or
flow tubes c r e a t i n g an annular gap through which feed stock was
c i r c u l a t e d across membrane s u r f a c e s .
A r e p r e s e n t a t i v e multi-element modular assembly i s depicted
i n F i g . 2. I n t h i s design the module comprises three major com-
ponents:
• 36 membrane element assemblies
• flow guide tube c a r t r i d g e assembly
• 5 i n . diameter 12 f t . long pressure v e s s e l .

12. MANJIKIAN A N D WOJCIK Tubular Membrane Elements 203
Rotary Modules
Conventional reverse osmosis systems are g e n e r a l l y designed

to operate by p r e s s u r i z i n g raw feed f l u i d s to r e q u i r e d operating
pressures and c i r c u l a t i n g s a i d f l u i d s across membrane s u r f a c e s .
To meet the operating requirements of the reverse osmosis process,
a pumping system i s commonly used t o p r e s s u r i z e and c i r c u l a t e feed
f l u i d s a t s u f f i c i e n t v e l o c i t i e s to maintain the d e s i r e d turbulence
and t o provide p r e s s u r i z e d make-up f l u i d t o r e p l a c e withdrawn per-
meate and concentrate f l u i d s .
The above approach i s o f t e n uneconomical and energy consuming
s i n c e i n most cases s u b s t a n t i a l amounts of p r e s s u r i z e d f l u i d are
r e q u i r e d t o maintain the d e s i r e d t u r b u l e n t flow. A d d i t i o n a l l y , i n
treatment of c e r t a i n f l u i d s c o n t a i n i n g c o l l o i d a l and p a r t i c u l a t e
matter, t u r b u l e n t flow of the raw f l u i d does not always accomplish
the c l e a n i n g a c t i o n necessar
f r e e of f o u l i n g d e p o s i t s
A unique and improved method which s u b s t a n t i a l l y reduces the
r e q u i r e d amount of p r e s s u r i z e d f l u i d flow has been developed by
U n i v e r s a l Water Corporation. I n t h i s approach the pumping system
i s p r i m a r i l y employed t o p r e s s u r i z e the raw f l u i d and a r o t a b l e
assembly c a r r y i n g membrane elements i s used t o provide turbulence
over the membrane s u r f a c e s . This approach separates the f u n c t i o n s
of p r e s s u r i z a t i o n and feed f l u i d r e c i r c u l a t i o n . Thus, the pumping
system needs t o p r e s s u r i z e and pump only the volume of feed stock
necessary t o make up f o r the separated permeate w h i l e r o t a t i o n of
the membrane element assembly provides the d e s i r e d turbulence.
A d d i t i o n a l l y , and more s p e c i f i c a l l y i n batch processing systems,
p r e s s u r i z a t i o n can be achieved by means other than a pump.
In essence,a r o t a r y system comprises a pressure v e s s e l con-
t a i n i n g a r o t a b l e assembly c a r r y i n g membrane elements, means f o r
p r e s s u r i z i n g the f l u i d feed, and means f o r r o t a t i n g the membrane-
element assembly. A conceptual r e n d i t i o n of a r o t a r y module i s
shown i n F i g . 3, and a flow schematic of a r o t a r y system i s shown
i n F i g . 5.
Main advantages of the r o t a r y approach i n c l u d e :
• reduced energy consumption
• continuous by-batch operation convenient f o r food proces-
sing
• minimal exposure of t r e a t e d f l u i d s to pumping system,
pressure f l u c t u a t i o n s and contamination
• reduced c l e a n i n g and maintenance costs
• high s u i t a b i l i t y f o r maximum r e c o v e r i e s and e f f i c i e n t
c o n c e n t r a t i o n of t r e a t e d f l u i d
r e l a t i v e l y uniform c o n c e n t r a t i o n of feed f l u i d s w i t h i n
modules
• s u i t a b i l i t y f o r use w i t h f l u i d s c o n t a i n i n g p a r t i c u l a t e and
c o l l o i d a l matter.
• l i m i t e d exposure of t r e a t e d f l u i d s t o contamination.

to
o
4^
Control Electric
Box Motor
Module
P r e s s u r e Gage
7N
Shutoff
Valve
Dump
EH valve
Pressure
Regulator
H
w
Accumulator H
3
Pump V V w

w
>
Tank w

>
d
Figure 5. Flow diagram for rotary module
12. MANJIKIAN AND WOJCIK Tubular Membrane Elements 205
The r o t a r y concept makes p o s s i b l e the design of modular

assemblies which would t r u l y permit the i n s i t u c l e a n i n g of mem-
branes during operation by simply changing the d i r e c t i o n and r a t e
of r o t a t i o n s .
Areas of A p p l i c a t i o n
R.O. systems u t i l i z i n g e x t e r n a l l y wound t u b u l a r membrane e l e -

ment i n modular assemblies have been used i n the d e s a l i n a t i o n of
b r a c k i s h and sea waters, the treatment and/or concentration of
i n d u s t r i a l waste waters, the separation/concentration of f l u i d
food, pharmaceuticals and chemical s o l u t i o n s , and the manufacture
of water p u r i f i e r s f o r domestic use. G e n e r a l l y , e x t e r n a l l y wound
t u b u l a r membrane systems have been found t o be h i g h l y s u i t a b l e f o r
u l t r a f i l t r a t i o n a p p l i c a t i o n s i n the processing i n d u s t r y and i n
water p o l l u t i o n c o n t r o
More s p e c i f i c a l l y
conventional mode o r as r o t a r y u n i t s have been s u c c e s s f u l l y
u t i l i z e d i n a p p l i c a t i o n s such as the recovery of p r o t e i n and l a c -
tose from cheese whey^ separation of fermentation products, con-
c e n t r a t i o n of f l u i d s foods and j u i c e s , manually operable sea water
d e s a l i n a t o r s , recovery of s t a r c h from potato processing f l u i d s , and
processing/separation of pharmaceutical and chemical mixtures.

13
Membrane Development, Production, and Use in
Hyperfiltration Systems
W. KOFOD NIELSEN
A/S De Danske Sukkerfabrikker, Driftteknisk Laboratorium, 4900 Nakskov, Denmark
At an anniversary like this, it is usual to look back through

the p e r i o d i n q u e s t i o n
The great discover
to consider reverse osmosis as an industrial process.
The core of membrane filtration i s the membrane, but the core
in itself must be surrounded o r supported, and t h i s leads to the
system o r module in which the membrane is mounted.
During these 20 years, a l a r g e number of module systems has
been made. The first idea was t o use the conventional filter press,
the plate-and-frame system, as done by A e r o j e t General Corp. How-
ever, t h i s system never proved to be very s u c c e s s f u l in the U.S.A.,
and consequently new c o n f i g u r a t i o n s , such as tubes, hollow f i b e r s ,
and spiral-wound systems were invented.
The red thread through the whole p e r i o d was d e s a l i n a t i o n of
sea and b r a c k i s h water, and grants sponsored by the O f f i c e of
S a l i n e Water d i r e c t e d the development i n t o t h i s field.
In Europe, and e s p e c i a l l y by our company, The Danish Sugar
Corporation, DDS, in Denmark, we attacked the problem i n a differ-
ent way. P r i m a r i l y , we saw a great number of advantages in the
plate-and-frame system, and by s o l v i n g some of the problems, such
as s e a l i n g s , manufacturing of p l a t e s and frames by injection mould-
i n g , e t c . , in 1970 we came up w i t h a system which a t that time we
considered to be a competitive product.
At that time, we saw the most a c c e s s i b l e market i n the pharma-
c e u t i c a l and food and d a i r y i n d u s t r i e s , because w i t h i n these indu-
stries membrane filtration was so advantageous that the relatively
high investment and operating costs were no impediment.
L a t e r , our system proved to work s u c c e s s f u l l y a l s o f o r d e s a l -
i n a t i o n of water, but the development through the pharmaceutical
to the food and d a i r y i n d u s t r i e s and pulp and paper i n d u s t r y d i d
give a great deal of experience which has been extremely v a l u a b l e
f o r our design of water d e s a l i n a t i o n p l a n t s as constructed today.
0097-6156/81/0154-0207$05.00/ 0

The Plate-and-Frame Membrane-Filtration System
The DDS plate-and-frame system and the p r i n c i p l e of i t are

shown i n Figures 1, 2, and 3.
I s h a l l not go i n t o d e t a i l s on the p r i n c i p l e , as i t has been
published a t s e v e r a l occasions (1, 2 ) , but some c o n s i d e r a t i o n
ought t o be given to the reasons why t h i s system has proved to be
s u c c e s s f u l w i t h i n such a wide range of a p p l i c a t i o n s , and below we
s t a t e some f a c t o r s which i n our o p i n i o n p l a y an important r o l e i n
this respect.
The System
(1) I n j e c t i o n moulding of support and spacer p l a t e s makes a
low-cost, l a r g e - s c a l e p r o d u c t i o n method p o s s i b l e .
(2) The s p e c i a l l y developed s e a l i n g system i n our p l a s t i c
p l a t e s , where the very membran i d l betwee tw
p l a t e s , gives a system
no 0 - r i n g s e a l i n g s are necessary
(3) The flow-channel design can b« optimized, dead spots
avoided, and the dead volume minimized.
(4) Very high f l e x i b i l i t y i n s e r i e s and p a r a l l e l arrangements
w i t h i n one module.
(5) Flow v e l o c i t y and f l o w d i s t r i b u t i o n a r e e a s i l y c o n t r o l l e d .
(6) The permeate s i d e i s l i q u i d - f i l l e d and kept a t a low i n -
t e r n a l volume, and there i s flow i n a l l p a r t s of the permeate
system, s e c u r i n g safe b a c t e r i o l o g i c a l c o n d i t i o n s .
(7) Each membrane p a i r i s e a s i l y i n s p e c t e d , s e c u r i n g product-
q u a l i t y c o n t r o l , and i n case of membrane r u p t u r e , the membrane can
be detected and e a s i l y exchanged.
The Membrane
(1) Any membrane cast i n sheet form of s u f f i c i e n t dimensions
can be mounted i n t o the system.
(2) The d i s t a n c e between membrane development and membrane
p r o d u c t i o n , u t i l i z a t i o n , and a p p l i c a t i o n i s the s m a l l e s t p o s s i b l e .
(3) During p r o d u c t i o n , a very e f f e c t i v e q u a l i t y c o n t r o l i s
p o s s i b l e , s i n c e each piece of membrane i s i n s p e c t e d , and membranes
w i t h f a u l t s are discharged.
I t h i n k , these t e n f a c t o r s e x p l a i n some of the obvious advan-

tages obtained by a plate-and-frame system. However, I would l i k e
to add that without the great work c a r r i e d out by Dr. R.F. Madsen
i n our company who s t a r t e d a research programme w i t h i n t h i s f i e l d
some 15 years ago, there would be no DDS plate-and-frame system
today ( 3 ) .
Review of Membrane Development
The development of reverse-osmosis membranes began w i t h i n -

v e s t i g a t i o n s made by Reid and Breton (4) i n 1959 on dense f i l m s of

13. NIELSEN Membrane Development in HF 209
Internal Flow, UF
Concentrate
Internal Flow, HF
Concentrate 4 ^1^^!^$^^$^$^
Permeate <4— • • • • B I V/Vy\ wmmmmmmm
Pe r meate ^_ • M B H B H H H I y/y^\ mmmmmmmmm
Permeate 4— yVyvh MHM^^H
Feed + ^ ' " ^ ^^,^^',^^^$^1
Figure 1. The principal configuration of DDS plate-and-f rame systems

2
Figure 2. The 30-cm module containing 19-m membrane area
2
Figure 3. The 35-cm module containing 27-m membrane area

c e l l u l o s e a c e t a t e (CA). This l e d to the development by Loeb and

S o u r i r a j a n 05) of the manufacture of an asymmetric, skinned CA
membrane w i t h a f l u x of up to 500 times higher than seen b e f o r e .
CA was d i s s o l v e d i n acetone, and water and magnesium p e r c h l o r a t e
were added as s w e l l i n g agent. The c a s t i n g was performed at -11°C.
A l a t e r development was made by M a n j i k i a n et a l . ( 6 ) , i n which
formamide was s u b s t i t u t e d f o r magnesium perchlorate/water.
A c o n s i d e r a b l e step forward was the c e l l u l o s e t r i a c e t a t e
blend membrane (CA CTA) of S a l t o n s t a l l ( 7 ) . L a t e r , membranes pro-
duced from CTA alone have been manufactured w i t h p r o p e r t i e s
s u p e r i o r to those of CA and CA/CTA membranes.
A s p e c i a l development was the work c a r r i e d out by R e s t i n g (8)
who invented the "dry process" f o r producing dry/wet r e v e r s i b l e
asymmetric membranes by complete evaporation.
P a r a l l e l to the development of sheet membranes based on CA
and CTA, the developmen
made. With the developmen
ators based on aromatic polyamides, the hollow f i n e f i b e r s were a
r e a l i s t i c a l t e r n a t i v e to CA membranes.
L a t e r , hollow f i b e r s made from CTA were spun by Dow Chemical
(9, 10) .
The t h i n - f i l m composite membrane developed by R i l e y et a l .
(11) l e d to the PA-300 membrane produced by UOP. W i t h i n the t h i n -
f i l m composite membrane development, a remarkable work was done
at the North S t a r Research I n s t i t u t e by Cadotte et a l . (12, 13^, 14_)
l e a d i n g to the NS-100, NS-200, and NS-300 membranes.
L a t e r , a group of people from the North S t a r Research I n s t i -
t u t e founded the company FilmTec, and i n 1979 the FT-30 membrane
was introduced (15), and t h i s membrane seems to be the best of
t h i n - f i l m composite membranes t i l l now.
At the same time, a number of Japanese companies introduced
new membranes, of which the membrane from Toray (16) should be
mentioned.
Also membranes from other polymers, such as sulphonated p o l y -
sulphone and polyphenylene o x i d e , were r e p o r t e d , but apparently
they were not put i n t o p r o d u c t i o n . This a l s o counts f o r the p o l y -
benzimidazole (PBI) introduced by the Celanese Research Company
(17).
The company T e i j i n i n Japan introduced a polybenzimidazolone
membrane which was claimed to be on the market.
Besides t h i s development of reverse-osmosis membranes, there
was a simultaneous development of u l t r a f i l t r a t i o n membranes, which
began w i t h Michaels (18). For UF, membranes from c e l l u l o s e a c e t a t e ,
polyamides, polysulphone, p o l y v i n y l i d e n f l u o r i d e , p o l y t e t r a f l u o r i d e ,
and p o l y a c r y l i c a c i d are produced and commercialized by v a r i o u s
companies.
F i n a l l y , the development of i n o r g a n i c membranes ought to be
mentioned. To our knowledge, the only c o m m e r c i a l i z a t i o n i s the
carbon tubes developed by Union Carbide f o r u l t r a f i l t r a t i o n .
The membrane-development review i s i n d i c a t e d i n Figure 4.

Membrane Development
When l o o k i n g a t the membrane development c a r r i e d out through-

out the world, there i s a l a r g e number of l i t e r a t u r e d e s c r i b i n g
s e v e r a l new membranes. However, when l o o k i n g a t the p r a c t i c a l r e -
s u l t s of t h i s development, they are r a t h e r poor.
Since the f i r s t c e l l u l o s e - a c e t a t e membrane was made, and the
hollow f i n e f i b e r was introduced, very few new membranes f o r r e -
verse osmosis have been brought on the market.
Why i s that so? P r i m a r i l y , the way from c a s t i n g a membrane
i n the l a b o r a t o r y and to have i t running i n production i s long and
d i f f i c u l t and r e q u i r e s f a c i l i t i e s and machinery which are o f t e n
not a v a i l a b l e f o r people doing research a t f o r instance u n i v e r s i -
t i e s . I n our company, the membrane research and development i s not
f i n i s h e d u n t i l a f i n a l formula and procedure f o r c a s t i n g the mem-
brane i n i n d u s t r i a l s c a l
P r e v i o u s l y , our membrane
port paper, but today we u s u a l l y cast the membranes on the support
paper. This gives a reinforcement of the membrane, and g e n e r a l l y
i t prolonges the l i f e t i m e .
The v a r i o u s steps i n membrane development can be summarized
as f o l l o w s :
S e l e c t i o n of New Polymers. This i s a f i e l d where most e f f o r t s

have been made to produce b e t t e r membranes. However, when l o o k i n g
f o r polymers, one must r e a l i z e that even w i t h a considerable
growth of RO/UF, the q u a n t i t i e s of polymers necessary to cover the
demand are l i m i t e d .
Consequently, manufacturers of polymers show only a small
i n t e r e s t i n developing s p e c i a l polymers f o r membrane f i l t r a t i o n .
On the other hand, i t might s t i l l be worthwhile f o r the p o l y -
mer i n d u s t r y to take a c l o s e r look a t the subject s i n c e the p r i c e
f o r polymers f o r t h i s use i s l e s s important than u s u a l l y because
the raw-material cost of polymers i s only a small part of the
t o t a l production costs f o r membranes.
M o d i f i c a t i o n of Polymers. One way to solve the problem of

f i n d i n g good polymers f o r membranes i s t o make m o d i f i c a t i o n s of
the chemical s t r u c t u r e of the polymer. Sulphonation f o r i n s t a n c e
of polysulphone (19) i s a w e l l known example of how a hydrophobic
polymer can be modified to a h y d r o p h i l i c polymer w i t h charged
groups. Other attemps have been made, f o r instance to modify c e l l u -
lose acetate by p u t t i n g charged p o s i t i v e groups i n the form of
quaternary ammonium i n t o the polymer (20).
Production of New Polymers. The polybenzimidazole developed

as a raw m a t e r i a l f o r s p e c i a l l y thermal-stable t e x t i l e f i b e r s by
the Celanese Research Company proved to be a p o t e n t i a l membrane
polymer due to the e x c e p t i o n a l l y high water a b s o r p t i o n (17).

Formulation of Casting S o l u t i o n s . Once a polymer has been

s e l e c t e d , the next step i s f o r m u l a t i o n of the c a s t i n g dope. This
includes f i n d i n g s o l v e n t s , s w e l l i n g agents, and non s o l v e n t s , and
making a formula f o r the p r o p o r t i o n of the d i f f e r e n t substances.
The s o l u b i l i t y parameters are of a c e r t a i n h e l p , but s t i l l i t i s
mainly t r i a l and e r r o r through l o t s of experiments which leads to
the r e s u l t .
Casting on Glass P l a t e s . When the c a s t i n g dope i s ready f o r

t r i a l , the f i r s t step i s u s u a l l y to cast i t on a glass p l a t e under
controlled conditions.
Casting on Machine. When t e s t s of the membranes from the

glass p l a t e s prove to be s a t i s f a c t o r y , the next step w i l l be pre-
p a r a t i o n of l a r g e r q u a n t i t i e s of c a s t i n g dope f o r c a s t i n g e x p e r i -
ments on the membrane-casting machine This i s u s u a l l y the most
d i f f i c u l t step which i
spect, the r e p r o d u c i b i l i t
f o r going on w i t h the p r o j e c t .
Heat Treatment and Various Other M o d i f i c a t i o n s . Heat t r e a t -

ment and other m o d i f i c a t i o n s , such as chemical treatment of the
membrane, are w e l l known as a l a s t step to modify or " t a i l o r " the
membrane f o r i t s f i n a l use.
Support Paper. The s e l e c t i o n of support paper i s a very im-

portant part of the membrane development. This i s o f t e n done i n
cooperation w i t h the manufacturer of support paper. However, a l s o
here i t must be r e a l i z e d that despite an extremely high growth of
membrane f i l t r a t i o n , the amount of support paper i s very small
compared to the usual manufacturing of paper.
We have found that non-wowens of p o l y e s t e r or polypropylene
and p o s s i b l y polyethylene provide the best m a t e r i a l f o r RO and UF
membranes.
The membrane-development procedure i s shown i n Figure 5.

As to membrane development, i t should f i n a l l y be remarked
that u s u a l l y the requirements to new membranes w i l l be p r o p e r t i e s
corresponding to those f o r d e s a l i n a t i o n of sea or b r a c k i s h water.
We found that a membrane being able to r e j e c t sugar up t o
100 percent i s a very i n t e r e s t i n g membrane f o r c o n c e n t r a t i o n of
waste waters or i n d u s t r i a l process streams. For c e l l u l o s e acetate,
t h i s corresponds to 85-90% s a l t r e j e c t i o n which i s u s u a l l y con-
sidered being too low f o r d e s a l i n a t i o n . I t h i n k that s e v e r a l mem-
branes of polymers a l t e r n a t i v e to CA could f u l f i l these r e q u i r e -
ments and that such membranes have been l o s t i n the hunt f o r a
high degree of d e s a l i n a t i o n .
UF membranes are u s u a l l y c h a r a c t e r i z e d as asymmetric b a r r i e r s
where the support l a y e r gives an i n s i g n i f i c a n t c o n t r i b u t i o n to
flow r e s i s t a n c e , and where the s k i n l a y e r gives the membrane i t s

Reid dense films Michaels CA, PS, PVDF

Loeb-Sourirajan asymmetric others PTFE, PAA, PPO
Manjikian improvement
Saltonstall CA/CTA
\
Kesting dry process
\
/
CA
way
\
Membrane Development
/
others
I
hollow fiber
\
thin film
/
SulphonatedPS,PPO
I
Du Pont B5,9,10
\
Riley UOP-PA-300
Polybenzimidazole-PBI Dow CTA Cadotte NS, NS-100,200,300
Polybenzimidazolone-PBIO Film Tec FT-30
Figure 4. Membrane-development review
Selection ofi new

new^ ^Solvents
Modificationn JPolymers] Formulation of [Casting dope^Swelling agents
Production of n e w ^ ^ I I T ^ N o n solvents
•Casting on
Reproducibility Glass plates
Membrane
^Testing
••Testing" Membrane Membrane casting

-Casting on
sheet machine
Heat treatment/
other modifications
Membrane for
production
Figure 5. Membrane-development procedure

r e j e c t i o n / s e p a r a t i o n c h a r a c t e r i s t i c s . I n our system, we operate i n

a wide pressure range f o r UF from 1 to 10 b a r s . I n order to give
the membrane an optimum performance r a t e and to c r e a t e c o n d i t i o n s
f o r being able to c l e a n and s a n i t a r i z e l a r g e continuous p l a n t s a t
high temperatures, we found i t r e l e v a n t to l i m i t the r e s i s t a n c e to
flow i n the membrane, and t h i s i s done by i n c r e a s i n g the flow r e -
s i s t a n c e i n the support l a y e r .
Membrane P r o d u c t i o n
The membrane production steps are shown i n Figure 6. Since

many of the steps are s i m i l a r to those mentioned i n the previous
s e c t i o n , I s h a l l not go through a l l of them, but draw the a t t e n -
t i o n to some s p e c i a l issues connected to membrane p r o d u c t i o n .
The exchange of experience between membrane producers i s very
l i m i t e d , and t h i s f a c t i e a s i l explaine decis
i v e r o l e the membrane play
amount of know-how contained i n the a b i l i t y to produce membranes.
Some membrane producers consider membrane p r o d u c t i o n more as
an a r t , and i n some respects t h i s might w e l l be t r u e .
The machinery used f o r the p r o d u c t i o n i s not something you
can buy, but i t must be developed and produced by the manufacturer
himself.
The storage and h a n d l i n g of s o l v e n t s need s p e c i a l care, and
the s e c u r i t y r e g u l a t i o n s i n our country are very s t r i c t today.
This a l s o i n v o l v e s the c a s t i n g machine and a s s o c i a t e d machinery,
where high s e c u r i t y r e g u l a t i o n s a r e r e q u i r e d .
The v e n t i l a t i o n and a i r - c o n d i t i o n i n g system i s an important
part of the machinery and r e q u i r e s great care to operate s a t i s -
factorily.
In order to o b t a i n a good membrane q u a l i t y and a high degree
of u t i l i z a t i o n , a c a r e f u l o p e r a t i o n i s necessary. This r e q u i r e s
s k i l l e d people who know t h e i r j o b .
Q u a l i t y c o n t r o l i s i n v o l v e d i n s e v e r a l steps i n the manufac-
t u r i n g process, as shown i n Figure 6. The advantage i n our system
of c u t t i n g the r o l l i n t o the r e q u i r e d s i z e s of membranes f o r our
v a r i o u s s i z e s of modules i s that we can have a v i s u a l or s i m i l a r
i n s p e c t i o n i n the very l a s t step of manufacturing, and membranes
w i t h c a s t i n g f a u l t s can be taken out. This ensures the customer
the best p o s s i b l e q u a l i t y of membrane.
The environmental p r o t e c t i o n a l s o r e q u i r e s a t t e n t i o n to the
waste water which has to be c a r e f u l l y considered.
Membrane U t i l i z a t i o n
From a customer's p o i n t of view, membrane u t i l i z a t i o n i s ex-

tremely important. Having invested i n a membrane f i l t r a t i o n p l a n t ,
he must consider the f o l l o w i n g p o i n t s c a r e f u l l y :
Membrane l i f e t i m e
Membrane-exchange costs

Security i n delivery
Shut-down p e r i o d f o r exchange
P o s s i b i l i t y of membrane i n s p e c t i o n
Product c o n t r o l .
In order t o secure the customer, the membrane manufacturer
u s u a l l y gives some k i n d of guarantee. When comparing guarantee
data, i t must be done c a r e f u l l y , and as a common g u i d e l i n e , the
o v e r a l l cost per product u n i t f o r exchange where a l l the above
mentioned s u b j e c t s are converted i n t o cash should be used.
However, t h i s i s not very easy. Membrane guarantees of 2-3
years f o r water d e s a l i n a t i o n i s not unusual, even when the mem-
branes have to be exchanged each year. The membrane manufacturer
c o u l d , of course, compensate f o r t h i s by a d j u s t i n g the membrane-
exchange p r i c e .
When comparing d i f f e r e n t systems as the customer has to do,
i t i s worthwhile to look t th b a s i p r i n c i p l f th syste d
the way i n which the membrane
1. Hollow F i b e r s syste
exchanged, i n c l u d i n g membrane, support, f l o w channel, and h i g h -
pressure v e s s e l .
2. Spiral-Wound Systems. The package c o n s i s t i n g of membrane
support m a t e r i a l and f l o w channels are exchanged from the h i g h -
pressure tube.
3. Tubular Systems. The membrane i s g e n e r a l l y c a s t on the
i n s i d e of a porous g l a s s - f i b e r tube o r i n s e r t e d l o o s e l y i n t o a
s t a i n l e s s - s t e e l tube.
4. Plate-and-Frame Systems. The membrane c a s t on support
paper i s exchanged and r e p l a c e d by membranes cut out i n the proper
size.
In respect to manufacturing c o s t s , t r a n s p o r t c o s t s , and hand-

l i n g , the plate-and-frame system should have the most economical
exchange procedure. The drawback i s the necessary work i n making
the exchange which i s u s u a l l y made by the customer, but f o r des-
a l i n a t i o n p l a n t s t h i s i s l e s s important s i n c e they are o f t e n s i t u -
ated i n areas where labour c o s t s are low.
This does not mean that plate-and-frame systems do have the
lowest o p e r a t i n g costs i n respect to membrane exchange, but we
b e l i e v e that the b a s i c p r i n c i p l e of reducing the exchange c o s t s
counts i n favour of plate-and-frame systems. The c o n t r o l of pro-
duct q u a l i t y from m e m b r a n e - f i l t r a t i o n p l a n t s has a l s o been im-
proved i n the plate-and-frame systems, because very small membrane
areas can be i n s p e c t e d , and i n case of membrane leakage, the mem-
brane i n q u e s t i o n can be exchanged i n a short time. F i g u r e 7 shows
the membrane-exchange procedure.
In the food and d a i r y i n d u s t r i e s , the s a n i t a t i o n and c l e a n i n g
of the p l a n t are extremely important. Here, the easy access t o
each membrane i s very v a l u a b l e f o r the i n s p e c t i o n as w e l l as an
immediate exchange of broken membranes, s e c u r i n g optimum b a c t e r i o -
logical conditions.

Storage
I Solvents|lPolymersh Preparation of -Mixing—Filtration-
ition—|
casting dope
1 I Membrane casting Casting

QUALITY
CONTROL
l r machine dope
Membrane Membrane QUALITY

Heat treatment
sheet sheet CONTROL
Packing
Module i Membrane
•IINSPECTIONH
production storage
Figure 6. Membrane-production scheme
Figure 7. Membrane exchange in a 35-cm module

S e c u r i t y i n d e l i v e r y i s most l i k e l y best obtained by d e a l i n g

w i t h companies of a reasonable s i z e and w e l l introduced i n the
f i e l d of membrane f i l t r a t i o n . But a l s o here, the plate-and-frame
system has an a d d i t i o n a l advantage, because membranes from other
manufacturers who can c a s t membranes i n sheet form can be used
d i r e c t i n our modules, though t h i s i s not something DDS i s very
much i n favour o f .
T h i n - F i l m Composite Membranes
F i n a l l y , I s h a l l b r i e f l y mention the t h i n - f i l m composite mem-

brane. I n our d e s c r i p t i o n of membrane development and p r o d u c t i o n ,
t h i s was not i n c l u d e d because the c o n d i t i o n s i n v o l v e d are r a t h e r
d i f f e r e n t , both i n respect to development and to p r o d u c t i o n .
When the t h i n - f i l m composite membrane was i n t r o d u c e d , many
people considered i t to be too d i f f i c u l t to handle i n p r a c t i c a l
l i f e . However, recent p u b l i c a t i o n
problems have been overcom
f i l m composite membranes on the market. We are here t h i n k i n g of
the PA-300 from UOP and the recent p u b l i c a t i o n from FilmTec (15).
Membranes i n the Future
Twenty years have passed s i n c e the f i r s t membrane f o r d e s a l i -

n a t i o n was made. Today, membrane f i l t r a t i o n i s an e s t a b l i s h e d pro-
cess which has been i n t e g r a t e d i n a number of i n d u s t r i a l a p p l i c a -
tions .
What can be expected i n the next twenty years?
We b e l i e v e that f o r reverse osmosis new membranes w i t h h i g h
chemical s t a b i l i t y , h i g h temperature r e s i s t a n c e , and improved per-
formance r a t e s i n respect to r e j e c t i o n c h a r a c t e r i s t i c s and f l u x
r a t e s are coming on the market very soon i n the form of improved
t h i n - f i l m composite membranes.
Besides b o o s t i n g the market f o r d e s a l i n a t i o n by RO, t h i s
means new a p p l i c a t i o n s i n a l a r g e number of processes w i t h i n the
food, d a i r y , and pharmaceutical i n d u s t r i e s and f o r waste-water
treatment. E s p e c i a l l y the o i l shortage and i n c r e a s i n g energy
p r i c e s tend to r e i n f o r c e the search f o r energy-saving methods of
which RO i s a very good example.
The breakthrough f o r UF was made when we could r e p l a c e the
c e l l u l o s e - a c e t a t e membranes by more r e s i s t a n t m a t e r i a l s . We expect
the same breakthrough f o r RO i n the years to come.
The development of the membrane p r o d u c t i o n to r e a l l a r g e -
s c a l e p r o d u c t i o n w i l l i n c r e a s e the r e a l i a b i l i t y of membrane-filtra-
t i o n p l a n t s and i n c r e a s e the competitive power of the membrane-
f i l t r a t i o n process.
A l s o i n the f i e l d of UF, new s o l v e n t - r e s i s t a n t membranes w i l l
increase the a p p l i c a t i o n range, e.g. to the o i l i n d u s t r y .

Literature
1. N i e l s e n , W.K., Madsen, R.F., Olsen, O.J., D e s a l i n a t i o n , 1980,

32, 309-326.
2. Madsen, R.F., N i e l s e n , W.K., ACS, Washington D.C., Sept. 1979.
3. Madsen, R.F., Ed. "Hyperfiltration and Ultrafiltration in
Plate-and-Frame Systems", E l s e v i e r , Amsterdam, 1977.
4. Reid, C.E., Breton, E.J., J. A p p l . Polymer Sci., 1959,1,133.
5. Loeb, S., S o u r i r a j a n , S., Advan. Chem. Ser., 1962, 38, 117.
6. M a n j i k i a n , S., Loeb, S., McCutchan, J.W., Proc. First Int.
Symp., Paper SWD/12, Washington D.C., Oct. 3-9, 1965.
7. S a l t o n s t a l l , C.W., OSW R&D Progress Report No. 434, June 1969.
8. K e s t i n g , R., U.S. Patent 3,884,801, May 20, 1975.
9. Dow Chemical Company, U.S. Patent 3,423,491, 1966.
10. Anon. Membrane D i g e s t , U.S. Dept. of the Interior, OSW, 1972,
1, 23.
11. R i l e y , R.L., Lonsdale
Polymer Sci., 1967, 11, 2143.
12. R o z e l l e , L.T., Cadotte, J.E., Cobian, K.E., Kopp, C.V., in
S o u r i r a j a n , S., Ed. "Reverse Osmosis and S y n t h e t i c Membranes",
N a t i o n a l Research C o u n c i l Canada, Ottawa, 1977, Ch. 12, p. 249.
13. Cadotte, J.E., Kopp, C.V., Cobian, K.E., R o z e l l e , L.T., I n
Situ-Formed Condensation Polymers f o r Reverse Osmosis Mem-
branes: Second Phase, Report No. PB-234198, N a t i o n a l T e c h n i c a l
Information S e r v i c e , S p r i n g f i e l d , VA, June 1974.
14. Cadotte, J.E., Steuck, M.J., Petersen, R.J., Research on I n
Situ-Formed Condensation Polymer f o r Reverse Osmosis Membranes,
N a t i o n a l T e c h n i c a l Information S e r v i c e , S p r i n g f i e l d , VA,
March 1978.
15. Cadotte, J.E., P e t e r s e n , R.J., Larson, R.E., E r i c k s o n , E.E.,
D e s a l i n a t i o n , 1980, 32, 25-31.
16. K u r i h a r a , M., Kanamaru, N., Harumiya, N., Yoshimura, K.,
Hagiwara, S., D e s a l i n a t i o n , 1980, 32, 13-23.
17. Model, F.S., Davis, H.J., Poist, J.E., in S o u r i r a j a n , S. Ed.
"Reverse Osmosis and S y n t h e t i c Membranes", N a t i o n a l Research
C o u n c i l Canada, Ottawa, 1977, Ch. 11, p. 231.
18. M i c h a e l s , A.S., in Perry E.S., Ed. "Advances in Separations
and Purifications", I n t e r s c i e n c e P u b l . , New York, 1968.
19. Chapurlat, R., Proc. of the 4 t hInt.Symp. on Fresh Water
from the Sea,Vol.4, 1973, 83-93.
20. R e s t i n g , R.E., Jackson, K.F., Newman, J.M., Proc. of the 5th
I n t . Symp. on Fresh Water from the Sea, V o l . 4, 1976, 73-78.

14
Multiyear Experience with Oily and Organic
Chemical Waste Treatment Using Reverse Osmosis
D. D E A N SPATZ
Osmonics, Inc., 15404 Industrial Road, Hopkins, MN 55343
I appreciate this opportunity to speak at the same time on

the last day of this symposium just as my close friend and mentor
Dr. Sourirajan spoke o
concluding his talk, Dr Souriraja , potentia
of reverse osmosis processes and reverse osmosis membrane to
contribute s i g n i f i c a n t l y to the health and welfare of all being
and also to the progress of many f i e l d s of science, engineering,
biology and medicine is far more than what one can comprehend
at any time."
Whether we c a l l the process we have talked about during this
week reverse osmosis or hyperfiltration or u l t r a f i l t r a t i o n is of
little importance. The important thing is that the membrane
invented by Loeb and Sourirajan s l i g h t l y over 20 years ago is a
marketable product and has a fantastic future. Too often we
allow semantics to act as a barrier to our mutual understanding
of this technology.
After listening to these other fine papers, I guess I should
feel lucky to be able to attend this symposium and even luckier
to present a paper. My paper has no fancy equations. Yes, I
studied Mass Transport by Byrd, Stewart and Lightfoot, but it
has been a few years since I could understand the equations which
have been projected on the screen in the last three days. I do
not consider myself a scientist perhaps a technologist and
most definitely an entrepreneur of reasonable success.
Dr. Sourirajan has had much to do with my success and to the
success of our technology. I feel that a short history of one
of those successes would be a fitting tribute to this man who
has lived "reverse osmosis" for the last 24 years of his life.
In 1964, while studying at Dartmouth College and considering
what would be the best method of removing salt from brackish
water, I had the great opportunity to meet with Dr. Loeb and
later on with Dr. Sourirajan. This was in 1964, and at that time
my colleagues and I decided that reverse osmosis had to be the
0097-6156/81/0154-0221$05.00/0

most e c o n o m i c a l way t o remove t h e s a l t s from b r a c k i s h w a t e r .

C e r t a i n l y t h e commitment t o t h i s t e c h n o l o g y t h a t Dr. S o u r i r a j a n
had was i n s t r u m e n t a l i n making me d e c i d e t o w o r k i n t h i s f i e l d .
W i t h t h e h e l p o f Dr. S o u r i r a j a n and Dr. Myron T r i b u s , we o b t a i n e d
a c o n t r a c t from t h e O f f i c e o f S a l i n e Water w h i c h c a r r i e d t h r o u g h
1968.
In 1 9 6 9 , I founded Osmonics, Inc. t o c a r r y the technology o f
r e v e r s e o s m o s i s and u l t r a f i l t r a t i o n t o t h e m a r k e t p l a c e . We
o r i g i n a l l y p u r c h a s e d membrane from Eastman Kodak Company and
made o u r own s p i r a l e l e m e n t s . We c o n t i n u e d p u r c h a s i n g membrane
u n t i l Kodak d e c i d e d not t o remain i n t h e membrane b u s i n e s s and
we d e c i d e d t o b e g i n t h e m a n u f a c t u r e o f membrane. By 1 9 7 3 , we
were i n f u l l p r o d u c t i o n m a n u f a c t u r i n g c e l l u l o s e a c e t a t e membrane
using the L o e b - S o u r i r a j a n approach. One y e a r l a t e r , we w e r e
m a n u f a c t u r i n g p o l y s u l f o n e membrane f o r u l t r a f i l t r a t i o n . Last
y e a r , 1 9 7 9 , Osmonics m a n u f a c t u r e d o v e r one m i l l i o n s q u a r e f e e t
o f RO/UF membrane.
Osmonics became a
coming p u b l i c we have grown a t an a v e r a g e r a t e i n e x c e s s o f 33%
per year. T h i s i s e q u i v a l e n t t o i n c r e a s i n g i n s i z e twenty times
o v e r a t e n y e a r p e r i o d . Osmonics has been p r o f i t a b l e i n e v e r y
y e a r s i n c e 1 9 7 3 , t h e y e a r we f i r s t s t a r t e d t o p r o d u c e membrane.
S i n c e 1 9 7 3 , o u r s a l e s and p r o f i t s have i n c r e a s e d i n each s u c c e s -
s i v e y e a r . We now o c c u p y 4 6 , 0 0 0 s q u a r e f e e t o f m a n u f a c t u r i n g
s p a c e and we a r e i n t h e p r o c e s s o f b u i l d i n g a new 8 5 , 0 0 0 s q u a r e
foot manufacturing f a c i l i t y t o c o n s o l i d a t e our business.
ALL OF THIS SUCCESS I OFFER TO THIS MEETING AS A TRIBUTE TO
THE PIONEER OF OUR TECHNOLOGY, MY ESTEEMED MENTOR-—DR. S.
SOURIRAJAN.
Di s c u s s i on
Now t h a t t h e most i m p o r t a n t p a r t o f my t a l k i s f i n i s h e d , I
w o u l d l i k e t o t e l l you about two c a s e h i s t o r i e s where RO/UF was
used t o s a t i s f y a w a t e r p o l l u t i o n c o n t r o l p r o b l e m . But b e f o r e we
g e t i n t o t h e c a s e h i s t o r y , l e t us r e v i e w some o f t h e b a s i c
c r i t e r i a we use i n an RO/UF s y s t e m .
F i g u r e 1 w i l l g i v e you an i d e a o f RO/UF e q u i p m e n t . T h i s i s
a p h o t o g r a p h we c a l l t h e " l a r g e s t t o t h e s m a l l e s t " . It w i l l give
you an i d e a o f one o f t h e s m a l l e s t R 0 u n i t s on t h e m a r k e t b e i n g
h e l d i n t h e e n g i n e e r ' s hand and n e x t t o t h e e n g i n e e r one o f t h e
l a r g e s t R 0 u n i t s put o n t o a s i n g l e s k i d . There are l a r g e r R0
u n i t s t h a n t h e one shown but most o f t h e s e o c c u p y two s k i d s o r
a r e f a b r i c a t e d on t h e j o b s i t e . In a d d i t i o n t o t h e s m a l l e s t and
l a r g e s t m a c h i n e i s a medium s i z e d c a b i n e t R 0 u n i t f o r t h e
p r o d u c t i o n of medical pure w a t e r .
F i g u r e 2 shows a g e n e r a l i z e d v i e w o f r e v e r s e o s m o s i s / u 1 t r a -
filtration. You w i l l n o t e t h a t t h e a r t i s t has p u r p o s e l y shown
t h e membrane h a v i n g an i s o t r o p i c n a t u r e , i . e . , a dense t o p s k i n
w i t h s m a l l pores w i t h a very porous s u p p o r t l a y e r . The f e e d

14. SPATZ Waste Treatment Using RO 223
Figure 1. RO/UF equipment. This photograph contains one of the smallest RO

units on the market and one of the largest RO units. There are larger RO units
than the one shown but most of these occupy two skids or are fabricated on the fob
site. In addition to the smallest and largest machines, there is a medium-sized cabi-
net RO unit for the production of medical pure water.
Figure 2. A generalized view of RO/UF. Note that the artist purposely has shown
the membrane having an isotropic nature, i.e., a dense topskin with small pores with
a very porous support layer. The feed solution flows between the two membranes
and as the pressurized feed solution passes over the membranes, permeate passes
through the membranes and concentrate exits from between the membranes. The
artist has made an effort to show that the impurities in the water are being concen-
trated as the permeate is being removed.

s o l u t i o n flows between the two membranes and as the p r e s s u r i z e d

feed s o l u t i o n passes over the membranes, permeate passes through
the membranes and concentrate e x i t s from between the membranes.
You w i l l a l s o note that the a r t i s t has made an e f f o r t to show
that the i m p u r i t i e s i n the water are being concentrated as the
permeate i s being removed.
Stepping from the g e n e r a l i z e d concept of RO/UF to the more
s p e c i f i c mechanism we have Figure 3. Figure 3 shows the mech-
anism of u l t r a f i l t r a t i o n . This i s u l t r a f i l t r a t i o n as defined i n
the marketplace. Note that t h i s membrane has pores which are too
large to e f f e c t d e s a l t i n g but are small enough t o remove prac-
t i c a l l y a l l of the organic molecules l a r g e r than 1000 molecular
weight.
Figure h shows the mechanism of what i s g e n e r a l l y r e f e r r e d
to as reverse osmosis in the marketplace. As you can see, the
pore s i z e i s approximately equal to twice the thickness o f the
pure water layer over th
This membrane, when constructe
t y p i c a l l y remove over 33% o f the organics in excess of 200
molecular weight and removes over 3&% of monosaccharides such
as dextrose end glucose.
But look aren't these membranes r e a l l y the same w i t h the
exception o f the f a c t that the pores are s m a l l e r f o r the one we
consider an R0 membrane and l a r g e r f o r the one we consider a UF
membrane? Yes, they are b a s i c a l l y the same membrane and they
are made i n p r a c t i c a l l y the same manner. However, most users
f e e l uncomfortable in c a l l i n g both o f these membranes by one name
and those o f us in the marketplace have t h e r e f o r e , i n f o r m a l l y
agreed to c a l l a membrane which r e j e c t s s a l t s a reverse osmosis
membrane and a membrane which does not r e j e c t s a l t s but i s o f a
pore s i z e s m a l l e r than 0.05 microns an u l t r a f i l t r a t i o n membrane.
I purposely picked two a p p l i c a t i o n s t o discuss where an R0
membrane i s being used f o r what i s considered a UF a p p l i c a t i o n .
In other words, a membrane w i t h very small pores i s being used
to remove organic matter g e n e r a l l y l a r g e r than 500-1000 molecular
weight. Do we c a l l i t reverse osmosis o r do we c a l l i t u l t r a -
f i l t r a t i o n ? Let's compromise and c a l l i t RO/UF.
These two a p p l i c a t i o n s were a l s o purposely chosen because
too many researchers are o v e r l y concerned about the RO/UF mem-
brane used f o r water p u r i f i c a t i o n . At t h i s meeting others have
t a l k e d some about RO/UF used i n food processing and my d i s c u s s i o n
should help you see the d i v e r s i t y o f our technology.
The key to the s u c c e s s f u l use of the RO/UF membrane i s i n
the packaging o f the membrane. U n t i l economical, e a s i l y f a b r i -
cated and s t a b l e packages were developed, membranes were of
l i t t l e commercial value. We use the s p i r a l wound type of mem-
brane element f o r a l l of our equipment. Other packages such as
the tube, the hollow f i b e r w i t h bore flow and the hollow f i b e r
w i t h o u t s i d e flow are a l l v a l u a b l e and useful packages. However,
the s p i r a l package i s by f a r the most u n i v e r s a l in i t s a b i l i t y t o

Figure 3. Mechanism of UF as defined in the marketplace. This membrane has

pores that are too large to effect desalting but are small enough to remove practi-
cally all of the organic molecules larger than 1000 mol wt.
Figure 4. Mechanism of RO in the marketplace. The pore size is approximately

equal to twice the thickness of the pure water layer over the membrane which is
void of any ions. This membrane, when constructed of CA, typically will remove
over 99% of the organics in excess of 200 mol wt and removes over 98% of mono-
saccharides such as dextrose and glucose.

t r e a t a l l t y p e s o f w a t e r , w a s t e w a t e r , and i n d u s t r i a l s o l u t i o n s .
We have h a n d l e d many s o l u t i o n s w h i c h a r e n o r m a l l y n o t c o n s i d e r e d
a p p r o p r i a t e f o r s p i r a l wound membrane e l e m e n t s s i m p l y by a p p l y i n g
good c h e m i c a l e n g i n e e r i n g p r a c t i c e .
L e t ' s t a k e a q u i c k l o o k a t t h e s p i r a l membrane e l e m e n t s o
t h a t a l l o f us have t h e o p p o r t u n i t y t o u n d e r s t a n d i t s makeup.
T h i s i s a f i g u r e o f a p a r t i a l l y u n r o l l e d s p i r a l membrane e l e m e n t
w h i c h we c a l l a s e p r a l a t o r ( F i g u r e 5 ) . The s e p r a l a t o r has a
permeate t u b e f o r c o l l e c t i n g t h e p e r m e a t e , t h e membrane i s l a i d
o n t o a permeate c a r r i e r m a t e r i a l and t h e edges o f t h e membrane
and t h e permeate c a r r i e r a r e g l u e d t o g e t h e r . The membrane i s
i n t e g r a l l y c a s t o n t o a b a c k i n g m a t e r i a l as shown i n t h e f i g u r e .
F i g u r e 6 i s an e n l a r g e m e n t o f c r o s s s e c t i o n s o f t h e s e p r a l a t o r .
You c a n s e e t h e two l a y e r s o f membrane w h i c h a r e s i m i l a r t o t h e
i d e a l i z e d RO/UF d r a w i n g i n F i g u r e 1. In o r d e r t o c o n s t r u c t t h e
s e p r a l a t o r , a mesh s p a c e r i s used t o keep t h e membranes f r o m
t o u c h i n g each o t h e r . Thi
lence promoter. The mes
i n t h i c k n e s s b u t can be e i t h e r t h i n n e r o r t h i c k e r as r e q u i r e d .
I t i s n o t u n u s u a l t o go as t h i n as 2 0 m i l s ( 0 . 5 0 8 mm) n o r as
t h i c k as 6 0 m i l s ( 1 . 5 3 mm) o r even 120 m i l s ( 3 - 0 5 mm). We have
f o u n d t h a t a 30 mi 1 t h i c k n e s s a l l o w s us t o o p t i m i z e t u r b u l e n c e ,
m a i n t a i n r e l a t i v e l y low f l o w s and r e d u c e t h e pumping e n e r g y r e -
q u i r e d t o have m i n i m a l f o u l i n g o f t h e membrane. Once t h e
permeate goes t h r o u g h t h e membrane i t e n t e r s t h e permeate c a r r i e r
which i s a r e l a t i v e l y porous s y n t h e t i c m a t e r i a l . The permeate
c a r r i e r i s c o n n e c t e d t o t h e permeate t u b e and s m a l l h o l e s c a r r y
the permeate from t h e permeate c a r r i e r t o t h e permeate t u b e and
f i n a l l y t o t h e permeate c o l l e c t i o n m a n i f o l d . The end c r o s s
s e c t i o n shows how t h e permeate p r o c e e d s t h r o u g h t h e permeate
c a r r i e r s p i r a l l y t o t h e permeate t u b e .
S p i r a l wound e l e m e n t s have been used by a number o f compa-
nies i n the water p u r i f i c a t i o n area s i n c e 1968. Osmonics has
been u n i q u e i n t h a t we have used s p i r a l s on a v e r y l a r g e number
of n o n - w a t e r p u r i f i c a t i o n a p p l i c a t i o n s , i n c l u d i n g o i l c o n c e n t r a -
t i o n , l a t e x c o n c e n t r a t i o n and o f c o u r s e , t h e c o n c e n t r a t i o n and
f r a c t i o n a t i o n o f c h e e s e whey. In f a c t , o u r i n s t a l l e d c a p a c i t y on
c h e e s e whey i s a p p r o x i m a t e l y 3 2 4 , 0 0 0 s q . f t . ( 2 9 , 1 6 0 m ) o f mem-
2
b r a n e o r 2 0 m i l e s ( 3 2 km) o f membrane as i t comes o f f o f o u r

m a c h i n e r y 3 f t . (1 m e t e r ) w i d e . Or, i f you p r e f e r the i n s t a l l e d
c a p a c i t y i s c a p a b l e o f h a n d l i n g 8 0 0 , 0 0 0 l b s ( 3 6 0 , 0 0 0 kg) o f
c h e e s e whey p e r h o u r .
Case H i s t o r y - W h i t e s t o n e C h e m i c a l Co.
The f i r s t c a s e h i s t o r y we w i l l d i s c u s s i s a medium s i z e d
c h e m i c a l company, W h i t e s t o n e C h e m i c a l Co. w h i c h i s a d e p a r t m e n t
of BASF W y a n d o t t e C o r p o r a t i o n . They m a n u f a c t u r e s p e c i a l t y
o r g a n i c c h e m i c a l s and a r e l o c a t e d i n S p a r t a n b u r g , S o u t h C a r o l i n a .
W h i t e s t o n e manufactures p r i m a r i l y a l k o x y l a t e s ; s u r f a c t a n t s from

Figure 5. A partially unrolled spiral membrane element known as a sepralator.

The sepralator has a permeate tube for collecting the permeate; the membrane is
laid onto a permeate carrier material and the edges of the membrane and the per-
meate carrier are glued together. The membrane is integrally cast onto a backing
material as shown in the figure.
Figure 6. An enlargement of the cross-sections of the sepralator. Note the two

layers of membrane which are similar to the idealized RO/UF drawing in Figure 1.
In order to construct the sepralator, a mesh spacer is used to keep the membranes
from touching each other and is used also as a turbulence promoter.

p r o p y l e n e and e t h y l e n e o x i d e , and e s t e r s f o r t h e t e x t i l e i n d u s t r y .
The p l a n t has t h e c a p a c i t y t o m a n u f a c t u r e 35 m i l l i o n pounds
( 1 5 . 8 m i l l i o n kg) o f p r o d u c t p e r y e a r and g e n e r a t e s a p p r o x i m a t e l y
3 0 , 0 0 0 g a l l o n s (114 m3) o f w a s t e w a t e r p e r day. Because White-
stone i s a manufacturer o f s p e c i a l t y o r g a n i c chemicals the waste
w a t e r i s composed p r i m a r i l y o f o r g a n i c s . The p r i m a r y s o u r c e s o f
p o l l u t i o n a r e r e a c t o r and e q u i p m e n t w a s h o u t s and some s p i l l a g e .
These p o l l u t a n t s cause problems i n meeting the b i o c h e m i c a l oxygen
demand (BOD), t o t a l s u s p e n d e d s o l i d s ( T S S ) , ammonia, p h e n o l , and
petroleum hydrocarbon standards. From 1971 t h r o u g h 1 9 7 7 , White-
s t o n e C h e m i c a l had r e l i e d on b i o l o g i c a l d i g e s t i o n o f the o r g a n i c s
i n i t s w a s t e w a t e r i n o r d e r t o meet t h e EPA g u i d e l i n e s .
However, w i t h more s t r i n g e n t g u i d e l i n e s and s i n c e W h i t e s t o n e
was d i s c h a r g i n g i t s w a s t e a f t e r t r e a t m e n t d i r e c t l y t o a s t r e a m ,
i t was d e c i d e d t o i n s t a l l an RO s y s t e m on t h e f i n a l a e r a t i o n
pond. A p i l o t t e s t o f a p p r o x i m a t e l y 1000 h o u r s showed t h e use
f u l n e s s of r e v e r s e osmosi
membrane e l e m e n t s and s y s t e
g u a r a n t e e a r e a s o n a b l e l i f e and o p e r a t i n g c h a r a c t e r i s t i c s t o
Whi t e s t o n e .
W h i t e s t o n e d i d e v a l u a t e many a l t e r n a t i v e s p r i o r t o c h o o s i n g
RO. They d e c i d e d t o use RO b e c a u s e t h e i n i t i a l c o s t was low,
m a i n t e n a n c e r e q u i r e m e n t s were low and o p e r a t o r a t t e n t i o n was
m i n i m a l compared t o t h e a l t e r n a t i v e s . Whitestone a l s o c a l c u l a t e d
t h a t t h e o p e r a t i n g c o s t s , b o t h i n manpower needs and i n a c t u a l
c h e m i c a l s and membrane r e p l a c e m e n t , was l e s s t h a n o t h e r a l t e r n a -
tives. S i n c e t h e RO s y s t e m w o u l d be o p e r a t i n g on b i o l o g i c a l l y
a c t i v e m a t e r i a l s i t was d e c i d e d t h a t c l e a n i n g e v e r y 8 h o u r s w o u l d
be a p p r o p r i a t e . T h e r e f o r e , an a u t o m a t i c C l e a n - I n - P l a c e (CIP)
s y s t e m was d e v e l o p e d and i n s t a l l e d w i t h t h e RO u n i t . There i s
t y p i c a l l y a k0% r e d u c t i o n i n p e r m e a t e r a t e due t o f o u l i n g p r i o r
t o t h e t i m e t h a t W h i t e s t o n e c l e a n s t h e RO u n i t .
The b a s i c w a s t e t r e a t m e n t s y s t e m a t W h i t e s t o n e i n c l u d e s :
Feed pumps from t h e c o l l e c t i o n a r e a
Bag f i l t e r s
The RO u n i t
Permeate s t o r a g e tank
M i x i ng p i t
D i s c h a r g e pumps
CIP s y s t e m .
The s y s t e m i s housed i n a p r e - e n g i n e e r e d m e t a l b u i l d i n g o f
s u f f i c i e n t s i z e t o add a d d i t i o n a l t r e a t m e n t c a p a c i t y i f and when
t h e need a r i s e s . The e n t i r e s y s t e m was b u i l t and i n s t a l l e d f o r
l e s s t h a n $ 1 0 0 , 0 0 0 and has been i n o p e r a t i o n s i n c e J u n e o f 1977.
The R0 m a c h i n e c o n s i s t s o f 78 s e p r a l a t o r s u s i n g S E P A ® - 9 7
membrane. A 50 Hp m o t o r i s t h e o n l y e n e r g y r e q u i r e d and i t runs
a pump s u p p l y i n g p r e s s u r e t o t h e membranes a t 4 5 0 t o 480 p s i g
(3041-3243 kPa). The most common f e e d w a t e r t e m p e r a t u r e t o t h e
R0 i s 8 0 - 8 5 ° F ( 2 7 - 3 0 ° C ) but t h e t e m p e r a t u r e w i l l f l u c t u a t e de-
p e n d i n g on t h e s p e c i f i c t i m e o f t h e y e a r . The m a c h i n e i s r u n n i n g

at 35% r e c o v e r y o f t h e f e e d as p e r m e a t e . In o t h e r w o r d s , 35% o f
the w a t e r t h a t e n t e r s t h e m a c h i n e comes o u t as permeate and 5% i s
concentrate. The permeate i s m e e t i n g a l l o f t h e EPA r e q u i r e m e n t s
for d i s c h a r g e t o the stream.
The s y s t e m does g e t d i r t y and r e q u i r e s CIP c l e a n i n g about
e v e r y 8 h o u r s . A l g a e blooms have p e r i o d i c a l l y c a u s e d a p r o b l e m
but c h l o r i n e f e e d c o u p l e d w i t h a d d i t i o n a l c l e a n i n g u s i n g a p r o -
p r i e t a r y c l e a n e r has a l w a y s r e s t o r e d t h e permeate r a t e . Sepra-
l a t o r l i f e a p p e a r s t o be about 2k months and W h i t e s t o n e has
changed t h e i r s e p r a l a t o r s once i n t h e l a s t 3 y e a r s . Even though
c l e a n i n g e v e r y 8 h o u r s may a p p e a r t o be e x c e s s i v e t o some o f y o u
who have s p e n t most o f y o u r t i m e i n t h e b r a c k i s h o r s e a w a t e r
p u r i f i c a t i o n a r e a , i t i s economical f o r Whitestone t o clean that
o f t e n r a t h e r t h a n s p e n d i n g e x c e s s i v e t i m e t r y i n g t o d e v e l o p some
t y p e o f u n i q u e method f o r p r e t r e a t m e n t t h a t w o u l d r e d u c e t h e
c l e a n i n g f r e q u e n c y . A t t h i s time t h e system i s p e r f o r m i n g w e l l
membrane l i f e i s r e a s o n a b l
ments a r e b e i n g met.
Case H i s t o r y #2 - Cummins E n g i n e Company, C h a r l e s t o n , South

C a r o l i na
A n o t h e r i n s t a l l a t i o n i n S o u t h C a r o l i n a b u t o f much l a r g e r
p h y s i c a l s i z e i s t h e Cummins C h a r l e s t o n D i v i s i o n o f Cummins
E n g i n e Company. T h i s l o c a t i o n has o v e r 900,000 s q u a r e f e e t
(81,000 s q . m.) o f m a n u f a c t u r i n g f a c i l i t y . The m a n u f a c t u r i n g
o p e r a t i o n s a r e c e n t e r e d a r o u n d m a n u f a c t u r e , a s s e m b l y and t e s t i n g
of d i e s e l engines. V a r i o u s u n i t o p e r a t i o n s i n c l u d e g r i n d i n g ,
machining, parts washing, parts c l e a n i n g , assembly, p a i n t i n g ,
t e s t i n g and s t o r a g e . The n a t u r e o f t h e o p e r a t i o n s i s s u c h t h a t
c o n s i d e r a b l e volumes o f o i l o r o i l y compounds a r e u s e d . The
m a j o r c o n t r i b u t o r t o t h e w a s t e w a t e r a t Cummins i s t h e t e s t i n g
f a c i l i t y where t h e e n g i n e s a r e t e s t e d p r i o r t o s h i p m e n t . A l l of
the w a s t e w a t e r p r o d u c t i o n a t Cummins amounts t o a p p r o x i m a t e l y
180,000 g a l / d a y (681 m3/day).
The w a s t e w a t e r i s composed o f c o o l a n t s , c u t t i n g o i l s , d i e s e l
f u e l , l u b r i c a t i o n o i l s , h y d r a u l i c o i l s , wash t a n k s o l u t i o n s , de-
g r e a s e r s , and p h o s p h a t e r i n s e from t h e p a i n t i n g o p e r a t i o n . A
t y p i c a l a n a l y s i s o f t h e w a s t e w a t e r shows:
pH = 8
T o t a l d i s s o l v e d s o l i d s = 1106 mg/1
T o t a l suspended s o l i d s = 76 mg/1
BOD = 325 mg/1
T o t a l p h o s p h a t e = 15 mg/1
I r o n = 3.7 mg/1
Aluminum = k.O mg/1
Lead = L e s s t h a n 0.01 mg/1
O i l and G r e a s e = 700 mg/1

A f t e r a m i n i m a l amount o f t e s t i n g , an 0SM0® d u a l RO s y s t e m
was i n s t a l l e d and s t a r t e d up i n e a r l y 1 3 7 5 . Each o f t h e two RO
m a c h i n e s c o n t a i n s 120 s e p r a l a t o r s . Each m a c h i n e i s d e s i g n e d f o r
60 gpm ( 1 3 . 6 m 3 / h r ) p e r m e a t e r a t e a t 4 0 0 - 5 0 0 p s i g ( 2 7 0 2 - 3 0 4 1 kPa)
and 9 5 t o 97% r e c o v e r y o f t h e f e e d as p e r m e a t e . F i g u r e 7 shows
t h e s y s t e m a t Cummins. The w a s t e w a t e r i s c o l l e c t e d i n d i f f e r e n t
h o l d i n g c o n t a i n e r s , pumped t h r o u g h the bag f i l t e r s and c a r t r i d g e
f i l t e r s p r i o r t o t h e R0 m a c h i n e and t h e n t o t h e R0 m a c h i n e .
On s t a r t - u p i t was r e c o g n i z e d t h a t t h i s s y s t e m s h o u l d have
had more e x t e n s i v e p i l o t t e s t i n g . U n f o r t u n a t e l y , t h e e n g i n e manu-
f a c t u r i n g was not even i n p a r t i a l o p e r a t i o n when t h e p i l o t t e s t s
w e r e run and s y n t h e s i z e d w a s t e had t o be used. By t h e t i m e t h e
m a c h i n e was s t a r t e d up t h e l a g o o n s used by Cummins f o r w a s t e
w a t e r s t o r a g e had d e v e l o p e d a s u b s t a n t i a l a l g a e bloom t h a t was
never a n t i c i p a t e d . However, t h i s p r o b l e m d i d a l l o w us t o l e a r n
how t o remove a l g a e when i t has f o u l e d t h e R0 s y s t e m . We a l s o
l e a r n e d how t o remove o i
of c h l o r i n e i s about t h
of a l g a e f r o m t h e R0 m a c h i n e s . Once t h e f i r s t bloom o f a l g a e was
taken c a r e of the machines s t a b i l i z e d , r e q u i r i n g c l e a n i n g every
24-36 hours. As l o n g as t h e Cummins o p e r a t o r p r a c t i c e d good
c l e a n i n g t e c h n i q u e s and t o o k r e a s o n a b l e c a r e w i t h t h e R0 u n i t ,
the system performed very w e l l . I f c l e a n i n g was m i s s e d o r done
i n c o m p l e t e l y t h e r e s u l t a n t f o u l i n g t o o k two t o t h r e e days t o
ove rcome.
The e n g i n e e r s a t Cummins had h e a r d t h a t i t was u n u s u a l f o r R0
e q u i p m e n t t o be c l e a n e d as o f t e n as e v e r y 24 t o 36 h o u r s . They
d e c i d e d t o i n v e s t i g a t e the p o s s i b i l i t y of p r e t r e a t i n g the waste
w a t e r p r i o r t o t h e R0 o r p o s s i b l y r e p l a c i n g t h e R0 w i t h some
o t h e r d e v i c e which would r e q u i r e less o p e r a t o r a t t e n t i o n . It is
i n t e r e s t i n g a t t h i s p o i n t t o compare t h e a t t i t u d e o f t h e o p e r a -
t o r s a t W h i t e s t o n e C h e m i c a l , who w e r e p r e p a r e d t o c l e a n t h e R0
u n i t b a s e d on t h e p i l o t t e s t s , t o t h e o p e r a t o r s a t Cummins who
were u n p r e p a r e d t o c l e a n t h e R0 u n i t and t h e r e f o r e , were u p s e t by
a c l e a n i n g f r e q u e n c y w h i c h was 1/3 as o f t e n as t h e c l e a n i n g
frequency at Whitestone.
Cummins d i d e x t e n s i v e t e s t i n g w h i c h i s s u m m a r i z e d as f o l l o w s :
1. D i a t o m a c e o u s e a r t h f i l t r a t i o n was used w i t h many t y p e s o f
d i a t o m a c e o u s e a r t h (DE) o f b o t h t h e o i l a b s o r b i n g and
s t a n d a r d t y p e s . The DE f i l t r a t i o n p r o d u c e d good q u a l i t y
w a t e r removing as much as 35% o f t h e t o t a l s u s p e n d e d
s o l i d s and 50% o f t h e o i l . However, r a p i d b l i n d i n g o f
t h e DE r e q u i r e d f r e q u e n t changes on t h e p r e c o a t and
caused c o n c e r n a b o u t t h e d i s p o s a l o f the c o n t a m i n a t e d DE.
The DE d i d r e d u c e t h e f o u l i n g on t h e R0 u n i t and
w o u l d have e x t e n d e d t h e c l e a n i n g c y c l e f o r t h e R0. How-
e v e r , i n o r d e r t o o b t a i n an e c o n o m i c a l f i l t r a t i o n run
w i t h t h e DE, p r e f i 1 t r a t i o n p r i o r t o t h e DE w o u l d be r e -
quired. S i n c e t h e o b j e c t i v e was t o p r e t r e a t t h e R0 and
not t o have two p r e t r e a t m e n t s , Cummins d e c i d e d t o d r o p
c o n s i d e r a t i o n o f t h e DE f i l t e r s as p r e t r e a t m e n t .

Figure 7. System at Cummins. The waste water is collected in different holding containers, pumped

through bag and cartridge filters prior to the RO machine, and then put through to the RO machine.
K>
Figure 8. A typical RO system with a clean-in-place (CIP) unit adjacent to the

RO. The CIP unit is plumbed into the RO unit so that the operator can CIP the
RO system by simply changing three valves and making certain that the cleaning
chemicals are used.
Figure 9. A bag filter system used for pretreatment prior to an oily waste applica-
tion. We are using 5-fi-rated bags which we feel are approximately equal to 15-fx
cartridge filters. Bags are valuable because the waste that is collected can be thrown
away.

SPATZ Waste Treatment Using RO 233
Figure 10. The actual operating installation of a system that uses both spiral-
wound UF and spiral-wound RO to handle oily waste which also is contaminated
with phosphates
Figure 11. A beaker containing the concentrate from an RO unit on oily waste
and a second beaker showing the permeate from oily waste processing. Normally
the oily wastes can be concentrated until the oil "breaks" due to concentration and
separate phases are apparent to the naked eye.

2. The n e x t method o f p r e t r e a t m e n t w h i c h was t r i e d was

ultrafiltration. P i l o t s i z e UF u n i t s u s i n g t h e h o l l o w
f i b e r b o r e f l o w t y p e c a r t r i d g e and t h e 1" t u b e module
w e r e t e s t e d . As w o u l d be e x p e c t e d , t h e permeate from
the UF u n i t was q u i t e c l e a r and when used as f e e d f o r
the RO, a b s o l u t e l y no f o u l i n g was a p p a r e n t .
However, t h e UF f o u l e d a t about t h e same r a t e as
t h e RO had f o u l e d . The UF c o u l d be c l e a n e d j u s t as t h e
RO c o u l d be c l e a n e d .
The Cummins e n g i n e e r s d e c i d e d t h a t UF as a p r e -
t r e a t m e n t t o RO i n t h i s c a s e was n o t e c o n o m i c a l b e c a u s e
o f e x c e s s i v e c a p i t a l and o p e r a t i n g c o s t s and s h o u l d n o t
be p u r s u e d . As an a s i d e , Osmonics does have some i n s t a l -
l a t i o n s where UF p r i o r t o RO i s a v i a b l e p r e t r e a t m e n t
and can be e c o n o m i c a l l y j u s t i f i e d . I t j u s t d i d not f i t
this application
3. A new p r o c e s s c a l l e
uses a c o n v e n t i o n a g
and t h e n t h e a d d i t i o n o f e l e c t r i c i t y t o a i d i n f o r m i n g a
f l o e o f t h e suspended o r emulsed o i l s . On-site p i l o t
d a t a c o u l d n o t be c o l l e c t e d w i t h i n a r e a s o n a b l e t i m e and
Cummins d e c i d e d n o t t o p u r s u e t h e e c l e c t i c s y s t e m .
4. C h e m i c a l t r e a t m e n t and s e t t l i n g i s t h e most commonly
used method o f t r e a t i n g w a s t e w a t e r . Alum and p o l y m e r
f l o c c u l a t i n g a g e n t s were used and were f o u n d t o be
s u c c e s s f u l i n p r e t r e a t i n g the waste water p r i o r t o the
RO u n i t . One o f t h e b i g a d v a n t a g e s o f a c h e m i c a l s y s t e m
i s t h a t i t can be t a i l o r e d on a d a i l y b a s i s t o meet
changing requirements. The o p e r a t o r can c o n s i d e r t h e
d i f f e r i n g w a t e r coming t o t h e w a s t e t r e a t m e n t p l a n t .
However, t h e p r o c e s s i s o p e r a t o r i n t e n s i v e .
Cummins has n o t t o t a l l y d e c i d e d t o go w i t h c h e m i c a l
treatment s i n c e the cost o f d i s p o s i n g o f the sludge
c o u l d be e x c e s s i v e .
5. A f a i r l y new t e c h n o l o g y w h i c h many p e o p l e i n t h e w a s t e
treatment o f o i l s f i r m l y b e l i e v e i n i s d i s s o l v e d a i r
f l o t a t i o n (DAF). DAF was o r i g i n a l l y t r i e d a t Cummins
but e i t h e r t h e o i l a t Cummins was t o o s o l u b l e o r t h e
c o n c e n t r a t i o n was t o o low t o h o l d t o g e t h e r t h e f l o e f o r
a l o n g enough p e r i o d t o have r e a s o n a b l e f l o t a t i o n . After
the f i r s t r e v i e w , t h e a i r f l o t a t i o n p r o c e s s was c o n s i d -
ered not a p p r o p r i a t e .
S u b s e q u e n t t o t h e g e n e r a l t e s t i n g and c o n t i n u e d
o p e r a t i o n o f t h e s y s t e m as o r i g i n a l l y i n s t a l l e d , Cummins
d i d a d d i t i o n a l t e s t i n g w i t h DAF. They f o u n d t h a t t h e
DAF w o r k e d f i n e i f t h e o i l c o n c e n t r a t i o n i n t h e w a s t e
s o l u t i o n was s u f f i c i e n t l y h i g h . A f t e r a program o f
w a t e r c o n s e r v a t i o n gave a r e d u c e d t o t a l e f f l u e n t f l o w
and an i n c r e a s e d o i l c o n c e n t r a t i o n , a d d i t i o n a l t e s t s w e r e
run w i t h DAF. A g a i n , alum and p o l y m e r w e r e added. A t

t h i s s t a g e t h e DAF p r o v e d t o be a r e a s o n a b l e and a t t r a c -
t i n g method o f removing a good s h a r e o f t h e h e a v i e r o i l s
and o t h e r c o n t a m i n a n t s w h i c h w e r e p r o b a b l y f o u l i n g t h e
RO u n i t .
At t h e p r e s e n t t i m e , Cummins has d e c i d e d t o i n s t a l l a p r e -
t r e a t m e n t s y s t e m u s i n g d i s s o l v e d a i r f l o t a t i o n as t h e p r i m a r y
t r e a t m e n t f o l l o w e d by an a n t h r a c i t e / s a n d b a c k w a s h a b l e f i l t e r and
an a c t i v a t e d c a r b o n p o l i s h i n g f i l t e r . The e f f l u e n t from t h e
f i l t e r s t h e n goes t o t h e RO u n i t . The RO w i l l remove t h e l a s t
t r a c e s o f the most s o l u b l e o i l s and o r g a n i c s . I t i s Cummins'
i n t e n t i o n t o have t h e e f f l u e n t f r o m t h e f i l t e r s a t a t u r b i d i t y o f
l e s s t h a n kS JTU's. T h i s s h o u l d keep t h e RO u n i t s f r o m f o u l i n g
and w i l l a l l o w t h e RO t o be used w i t h m i n i m a l c l e a n i n g .
L i k e a l l u n i t c h e m i c a l p r o c e s s e s , t h e RO i s u s u a l l y n o t
c a p a b l e o f s t a n d i n g e n t i r e l y by i t s e l f . The i m p o r t a n t t h i n g t o
remember i s t h a t a s y s t e
product. In t h e c a s e o
dissolved a i r f l o t a t i o n , anthracite/sand f i l t r a t i o n , activated
c a r b o n f i l t r a t i o n and RO. In t h e c a s e o f W h i t e s t o n e C h e m i c a l , t h e
c o m p l e t e s y s t e m i n c l u d e s RO and a c l e a n i n g regimen t o m a i n t a i n
the RO a t t h e r e q u i r e d p e r m e a t e f l o w r a t e . Time w i l l t e l l w h i c h
of t h e s e a l t e r n a t i v e s has t h e b e s t e c o n o m i c s . The e c o n o m i c s and
the p r o p e r s y s t e m u s i n g RO a r e b o t h dependent on t h e p r o b l e m t h a t
requires a solution.
Cone 1 us i o n
In c o n c l u s i o n , I w o u l d l i k e t o l e a v e you w i t h two t h o u g h t s :
F i r s t , I am o f t e n a s k e d by i n v e s t m e n t b a n k e r s and t h o s e
who f o l l o w o u r t e c h n o l o g y , why t h i s t e c h n o l o g y has n o t grown
as f a s t as e v e r y o n e s a i d i t w o u l d . A t f i r s t my i n c l i n a t i o n
was somewhat d e f e n s i v e , but t h e n I d i d some r e s e a r c h i n t o t h e
g r o w t h o f o t h e r new t e c h n o l o g i e s . I looked a t :
- S e m i c o n d u c t o r s w h i c h were i n v e n t e d a t t h e t u r n o f t h e
c e n t u r y and have o n l y seen g r o w t h i n t h e l a s t decade.
- C o l o r e d t e l e v i s i o n w h i c h was a r o u n d i n 1925 but n e v e r
became a v i a b l e p r o d u c t u n t i l I 9 6 0 — 3 5 y e a r s l a t e r .
- N u c l e a r r e a c t i o n s , w o u l d we say 1933 f o r t h e i n v e n t i o n ?
Is t h e b u s i n e s s r e a l l y t h a t b i g even now?
My f e l l o w membrane t e c h n o l o g i s t s , d o n o t become d e f e n -
s i v e when someone a s k s t h e g r o w t h q u e s t i o n , i n s t e a d a s k them
t o t e l l y o u one o t h e r t e c h n o l o g y w h i c h 10 y e a r s a f t e r i t s
i n v e n t i o n had more t h a n 10 a c t i v e companies s e l l i n g p r o d u c t s
u s i n g t h i s t e c h n o l o g y and now o n l y 2 0 y e a r s l a t e r has p r o b -
a b l y 3 0 a c t i v e m a n u f a c t u r i n g companies and as many more who
are r e s e a r c h i n g t h e p o s s i b i l i t y o f e n t e r i n g t h e f i e l d .
S e c o n d l y , I want t o remind a l l o f y o u t h a t t h e o n l y t r u e
t e s t o f t h e w o r t h o f any r e s e a r c h i s t h e u l t i m a t e e f f e c t o f
t h a t r e s e a r c h on s o c i e t y i n g e n e r a l and i n t h e m a r k e t p l a c e i n
particular. Twenty y e a r s a f t e r t h e b e g i n n i n g o f r e v e r s e

o s m o s i s and u l t r a f i l t r a t i o n , t h e m a r k e t p l a c e has p r o c l a i m e d
t h a t t h i s membrane t e c h n o l o g y i s a s u c c e s s . We a l l l o o k
forward t o t h e next twenty y e a r s which w i l l see t h i s t e c h -
n o l o g y emerge as one o f t h e g r e a t e s t b a s i c i n v e n t i o n s o f
the 20th Century.
Acknow1edgemen t s
I w i s h t o e x t e n d my d e e p e s t a p p r e c i a t i o n t o Dr. S. S o u r i r a j a n
who f o r o v e r 16 y e a r s has h e l p e d me t o g a i n a b e t t e r u n d e r s t a n d i n g
o f t h i s u n i q u e f i e l d o f r e v e r s e o s m o s i s and u l t r a f i l t r a t i o n and t o
t h e f o l l o w i n g f o u r i n d i v i d u a l s whose p e r s o n a l a t t e n t i o n t o my r e -
q u e s t s f o r i n f o r m a t i o n on t h e c a s e s t u d i e s h e l p e d me i n p r e p a r i n g
this talk.
B e a l , Thomas W., O p e r a t i o n
BASF W y a n d o t t e C o r p . , S p a r t a n b u r g
F r a n k l i n , P a t r i c i a V., P.E., Cummins C h a r l e s t o n , I n c . ,

C h a r l e s t o n , SC
K a r a s i e w i c z , W. R i c h a r d , P.E., M c N a i r , G o r d o n , J o h n s o n and
K a r a s i e w i c z Company, C o l u m b i a , SC
Davis, W i l l i a m , Sepratech I n c . , Rock H i l l , SC

15
A Novel Membrane System for the Ultrafiltration
of Oil Emulsions
G. B. TANNY and A. KORIN

Gelman Sciences, Inc., 600 S. Wagner Rd., Ann Arbor, MI 48106
The c o n c e n t r a t i o n
importance, encompassin
c o o l i n g or c u t t i n g f l u i d s ( 1 ) , the p r o c e s s i n g o f foods, and
c e r t a i n pharmaceutical p r e p a r a t i o n s . When one takes i n t o con-
s i d e r a t i o n the increased use o f microemulsions(2), f u r t h e r
growth in this area may be a n t i c i p a t e d . Ultrafiltration has
q u i c k l y become the method o f choice f o r c a r r y i n g out t h i s pro
cess (1), and in the past a r e p o r t has been made on the use o f
a new c o n v e n t i o n a l thin-film composite UF membrane(3) t o ac-
complish t h i s g o a l .
The present c o n t r i b u t i o n d e s c r i b e s a novel low pressure,
high f l u x system which utilizes an "in situ" dynamically formed
silica membrane particularly s u i t e d f o r the ultrafiltration of
emulsions. The support f o r this s e l e c t i v e l a y e r o f silica was a
p l e a t e d , t h i n channel c r o s s f l o w module(4) (tradename "Acro-
flux", Gelman Sciences, Inc.) c o n t a i n i n g 0.1 m o f 0.2 um pore
2
size acrylonitrile copolymer membrane.

This design c o n f i g u r a t i o n f o r flat sheet microporous mem-
brane is relatively new and t h e r e f o r e bears d e s c r i p t i o n . Through
the p l e a t i n g process one creates a p l e a t pack o f flow channels
c o n s i s t i n g o f : (1) a cover channel m a t e r i a l ; ( 2 ) a t u r b u l e n t
flow promoting spacer; and ( 3 ) the microporous membrane support.
A cross s e c t i o n o f one o f these p l e a t e d channels is shown in
Figure 1 a . The p l e a t pack is then arranged about a c e n t r a l
d r a i n tube, glue seamed down the l o n g i t u d i n a l a x i s , and a s e a l
r i n g is added t o prevent fluid bypass. A schematic o f the c a r -
t r i d g e in i t s housing is shown i n F i g u r e 1 b . Since the cover
channel m a t e r i a l does not extend i n t o the glue s e a l s a t each end
of the c a r t r i d g e , and is somewhat f r e e t o move, i t facilitates
backwashing and is thus e s p e c i a l l y s u i t e d t o the membrane regen-
e r a t i o n aspect o f dynamically formed membrane a p p l i c a t i o n s .
In the s e c t i o n s which f o l l o w , we shall examine (a) the hy-
drodynamics o f this new module, (b) the formation and p r o p e r t i e s
0097-6156/81/0154-0237$05.50/0

Figure lb. Schematic of an Aeroflux cartridge in a housing

15. TANNY AND KORIN UF of Oil Emulsions 239
of the s i l i c a dynamic membrane, and (c) i t s performance i n the

module w i t h o i l / w a t e r emulsions under v a r i o u s c o n d i t i o n s .
A. Theory: Operation and Hydrodynamic A n a l y s i s o f the A e r o f l u x

Module. The schematic cross s e c t i o n o f a s i n g l e p l e a t e d
channel o f a u n i t mounted i n i t s housing i s shown i n F i g u r e
2. I n the case under c o n s i d e r a t i o n , the f l e x i b l e channel
cover w a l l m a t e r i a l i s impermeable to flow and a l l the space
between i t and the w a l l o f the housing becomes p r e s s u r i z e d
to Pp, the feed entrance pressure. Thus, at any p o i n t
w i t h i n the l e n g t h o f the channel, a pressure drop,
Pp-P(x), e x i s t s both along the channel and across the
channel cover w a l l . T h i s pressure drop helps to seat the
channel cover w a l l on the spacer and maintain channel dimen-
sions. (On the other hand, during the b a c k f l u s h o p e r a t i o n ,
the channel cover w a l l i s somewhat f r e e to move away from
the spacer to f a c i l i t a t
Let us conside
ment dx along the channel. Assuming u n i t a r y w i d t h , the
change i n the flow r a t e , dQ, i s given by:
P(x) - P
-dQ = ^ dx (1)
m
The change i n pressure down the channel over the same

element dx i s given by the equation (JL):
(2)
n
-dP = aQ dx
where "a" i s the constant r e f l e c t i n g the f r i c t i o n and height

of the spacer ( i d e n t i c a l to that o f the channel) and "n" i s
a constant, w i t h the values
n = 1, f o r laminar flow, and

n = 2 , f o r t u r b u l e n t flow.
Combining equations ( 1 ) and ( 2 ) y i e l d s :
dQ = _ J L_ ( 3 )
K D J
dP aR n
m n
Q
Rearranging and i n t e g r a t i n g t o the a p p r o p r i a t e boundary

c o n d i t i o n s , one o b t a i n s :
( n
Q d Q = _ L / ( _
P P p ) d P (4)

This equation can now be used to o b t a i n the f o l l o w i n g r e -

l a t i o n s h i p s between the e x p e r i m e n t a l l y r e l e v a n t f a c t o r s , A p^,
the t o t a l trans-channel pressure drop, A P , the average op-
Q R
e r a t i n g pressure ,Q, the permeation r a t e , and X = — : (see Ap-

pendix No. 1 ) . P
1. For the t u r b u l e n t flow c o n d i t i o n :
,1/2 3/2
A
-(f) Y Q
p ( 5 )
where
Z = 1/3 [ ( 1 + X ) 3
-X ]3
(6)
Y = 1- -= (8)
2AP
and APm = R 0 p (9)
m m P
These r e l a t i o n s can be used t o generate the d i a -
gram i n F i g u r e 3 , which d e f i n e s the a n t i c i p a t e d range
o f pressure drop and average pressure necessary t o
achieve any d e s i r e d permeation r a t e a t some d e s i r e d
r a t i o o f r e t e n t a t e to permeation flow r a t e .
2. For laminar flow c o n d i t i o n s
1 / 2
/ s \
A P
C =
(2k) Qp Y 1/2 < Y < 1 (10)
where 3 = [(1+X) 2
- X J/2
2
(11)
Dynamic Membrane Formation. Colloidal oxides filtered
through microporous supports t y p i c a l l y g i v e r i s e t o " C l a s s
I I " dynamically formed membranes, whose formation mechanism
c h a r a c t e r i s t i c s and p r o p e r t i e s have been r e v i e w e d . The
most important r e l a t i o n s a r e :
(12)
where
(13)

Figure 2. Schematic of a flow in a thin channel
Figure 3. Experimental results of hydrodynamic test of 10-in. Acroflux cartridges.

The shadowed area covers the ranges of the experimental points.

t i s time, A i s membrane area, n i s the l i q u i d v i s c o s i t y , C

i s the c o n c e n t r a t i o n o f the cake forming p a r t i c u l a t e and
RQ i s the hydrodynamic r e s i s t a n c e of the cake formed. Thus,
we also a n t i c i p a t e Qp m (k? )^2
# should be noted that the
above r e l a t i o n s are only r e a l l y v a l i d f o r the i n i t i a l stages
of dynamic membrane formation, i n which the convective
f o r c e s b r i n g i n g c o l l o i d a l m a t e r i a l up to the membrane sur-
face are f a r l a r g e r than any " l i f t " e f f e c t s which are pres-
ent due to the t u r b u l e n t flow r e g i m e .
Experimental
A. T e s t i n g o f A e r o f l u x C a r t r i d g e Hydrodynamics. The apparatus

used f o r flow experiments was otherwise i d e n t i c a l to t h a t
described i n Reference (4), except that the crossflow c a r -
t r i d g e housing used was polypropylene (model #12806) In
order to avoid f a l s
i n plumbing, the gauge
were attached d i r e c t l y to the housing. A l l experiments were
c a r r i e d out using 0.2 um f i l t e r e d w e l l water, maintained by
a heat exchanger at a constant temperature o f 20 + 0.5°C.
S i x p o i n t s ranging from 2-10 gpm f o r the product flow
rate were t e s t e d at r e j e c t / p r o d u c t flow r a t i o s between 0.1
and 1.0. At each s e t t i n g , the pressure drops were allowed
to reach e q u i l i b r i u m ( u s u a l l y w i t h i n 2 minutes) and then r e -
corded.
B. S i 0 Dynamically Formed Membranes. The procedures and equip-
2
ment used to create the dynamically formed membrane have a l -

ready been described i n an e a r l i e r work \Z', but w i l l be
discussed b r i e f l y .
A 500 ppm d i s p e r s i o n of s i l i c a (Cab-O-Sil, EH-5, Calbot
Corp.), 8 l i t e r s i n volume, was prepared by d i l u t i o n of a 2
g/1 d i s p e r s i o n which had been sonicated f o r 40 min. i n a
Bransonic u l t r a s o n i c bath. The t u r b i d i t y of the f i n a l s o l u -
t i o n was 24 NTU. With the permeate valve c l o s e d , the c r o s s -
flow v e l o c i t y and formation pressure were s e t . Timing f o r a
t o t a l o f 30 min. was begun when the permeate was opened, and
readings o f permeate flow rate and t u r b i d i t y were taken at
periodic intervals. A f t e r formation, and without a l l o w i n g
system shut-down, the s i l i c a s o l u t i o n was flushed out with
DI water and replaced with the Pazomus B o i l emulsion.
(Emulsion concentrations are % v o l / v o l , e.g., 3% represents
30 cc/1 o f the commercial mixture.)
C. Analytic Procedures
1. T o t a l Organic Carbon A n a l y s i s (TOC). TOC a n a l y s i s was

c a r r i e d out on a Beckman 915A T o t a l Organic Carbon an-
a l y z e r according to the standard procedures used with
t h i s instrument.

15. TANNY A N D KORIN UF of Oil Emulsions 243
2. Hydrocarbon E x t r a c t a b l e s with Freon Measured by IR.

Extractable o i l was measured by a modified Standard
a. To 200 cc o f sample, 20 cc o f 2N HC1 i s added plus

4 cc o f saturated NaCl.
b. The above s o l u t i o n i s placed i n a s e p a r a t i n g fun-
nel to which 30 cc o f Freon TF i s added and shaken
f o r 3-5 min. The mixture i s then allowed to sep-
arate and the lower f r a c t i o n (Freon) i s removed
and added to a 100 ml volumetric f l a s k by d r i p p i n g
through a f i l t e r funnel c o n t a i n i n g Na2S0i| on a
paper f i l t e r . T h i s procedure i s repeated five
times and the volume i s made up o f 100 cc (part o f
the Freon evaporates).
c. H a l f an hour to one hour p r i o r to IR a n a l y s i s , 1g
of Na2S0i| i s added to the volumetric f l a s k
d. IR a n a l y s i
c e l l s an
1
ated i n the range o f 3100-2700 cm" . The spec-
trum o f the sample v s . Freon blank i s then gener-
ated and the absorbance, A, a t 2960 cm" i s calcu-
T
l a t e d from A = -lnY~- Sample CH^ content i s ob-
o
t a i n e d from a c a l i b r a t i o n curve.
3. C o n d u c t i v i t y . Measurements were made with a Radiometer
Type CDM-2d c o n d u c t i v i t y meter.
Results and D i s c u s s i o n
A. Hydrodynamics o f the A e r o f l u x Module The experimentally ob-

tained r e l a t i o n s h i p s f o r a 10" long A e r o f l u x c a r t r i d g e , op-
erating on pure water at v a r i o u s r a t i o s o f X = QR/QP, i s
shown i n F i g u r e 3* As a n t i c i p a t e d , a s t r a i g h t l i n e r e l a t i o n
i s obtained between A P and Q . m p
For d i f f e r e n t values o f X, APrj shows a c l e a r l y non-

l i n e a r behaviour, which i s a n t i c i p a t e d f o r t u r b u l e n t flow
c o n d i t i o n s ( c f . , Equation 5 ) . In F i g u r e s 4 and 5, l o g - l o g
p l o t s o f t h e o r e t i c a l values o f APrj vs Qp a t a given v a l -
ue o f X are shown with experimental r e s u l t s . The slope o f
3/2, p r e d i c t e d by Equation 5, seems to f i t the r e s u l t s q u i t e
well.
S i m i l a r p l o t s are shown i n F i g u r e 6 f o r the 20" module.
In t h i s case, at lower values o f X, one a l s o f i n d s that a
p o r t i o n o f the r e s u l t s f i t the laminar flow model, and the
slope o f l o g A P Q vs l o g Qp i s u n i t y .
Aside from f a c i l i t a t i n g the design and i n i t i a l choice
of operating c o n d i t i o n s , the r e s u l t s i n F i g u r e s 4-6 make i t
p o s s i b l e to know the s t a t e o f hydrodynamic flow f o r any

Figure 4. Log-log plot of thin channel

pressure drop of 10-in. Acroflux vs. per-
meate rate at various X = Q / Q values:
R P

given u n i t and set of operating c o n d i t i o n s . Since u l t r a f i l -

t r a t i o n flow rates are very s e n s i t i v e to boundary l a y e r phe-
nomena, one s t r i v e s to achieve w e l l developed turbulence at
the lowest value of Q r p o s s i b l e , i n order to minimize the
pumping energy r e q u i r e d . F i g u r e 6 shows that the 20" Acro-
f l u x u n i t i s quite e f f i c i e n t . Examining the curve f o r X =
0.2, one f i n d s that a retentate flow of only 1.5-2 gpm i s
sufficient to create turbulent flow under c o n d i t i o n s i n
which one i s removing 7-10 gpm of product, i . e . , the recov-
ery r a t i o , R.R. i s :
R.R. = x 100? = 83.3?
Of course, these r e s u l t s are f o r pure water and when

the u n i t i s used with a dynamically formed membrane, the i n -
creased membrane r e s i s t a n c e does not allow us to draw such
high absolute value
i s that the r a t i o o
the channel w i l l not change s i g n i f i c a n t l y and thus the over-
a l l module e f f i c i e n c y can be expected to remain at a high
value.
B. Dynamically Formed Si02 Membranes
1. Membrane Formation. In e a r l i e r work^^ i t was found
that fumed s i l i c a p a r t i c l e s could be dispersed i n aque-
ous suspension with the a i d of u l t r a s o n i c sound. Ob-
s e r v a t i o n s under the e l e c t r o n microscope showed that
the d i s p e r s i o n contained d i s c - l i k e p a r t i c l e s , approxi-
mately 150-200 I i n diameter and 70-80 I i n height.
F i l t r a t i o n experiments c a r r i e d out i n the "dead-end"
mode ( i . e . , zero crossflow v e l o c i t y ) on 0.2 um membrane
support showed t y p i c a l Class II cake formation k i n e t -
i c s , i . e . , the permeation rate decreased according to
equation (12). However, as may be seen from Figure 7,
the decrease i n the permeation rate observed during
0 , 1
formation i n the crossflow module i s only t ~ , con-
s i d e r a b l y slower than the f ° * 5 dependence p r e d i c t e d
and observed e a r l i e r . T h i s d i f f e r e n c e may be expected
due to the presence of l i f t f o r c e s created by turbu-
lence i n the crossflow device, and models f o r the hy-
drodynamics i n such cases have been proposed.(J)
A f t e r formation, we u t i l i z e d pure water to measure
the hydraulic permeability, L p (cm/atm-min) of the
dynamic l a y e r . For a constant crossflow v e l o c i t y , L p
i s seen to decrease with an i n c r e a s e i n the pressure of

formation, as seen from T r i a l s 1-4 i n Table 1. This
could be i n t e r p r e t e d e i t h e r as due to an i n c r e a s e i n
the thickness of the dynamic l a y e r or a " t i g h t e n i n g " of

20.01 1 1 1—i—i i i i |
Figure 6. Channel pressure drop of

in. Acroflux vs. permeate rate at various
X = Q / Q p values: A , LO; O, 0.6; X ,
R
20.0
0.2. Qp (gpm)
9 -
S -
7 —
3 -
2 I I I I 1 I I 1 I I I 1
1 2 3 4 5 6 7 8 9 10 20 30 40
t (mm.)
Figure 7. Permeate rate vs. circulation time of 500-ppm dispersion of silica using
6-in. Acroflux capsule

TANNY A N D KORIN UF of Oil Emulsions 247
i t s s t r u c t u r e due to the a p p l i e d pressure on the c o l -

l o i d a l cake. Since the membranes show some s a l t r e j e c -
t i o n toward d i l u t e s o l u t i o n s (10~3M) o f sodium s u l -
fate (Na2S0ij), one would a l s o expect t h i s rejection
to i n c r e a s e i f the matrix undergoes compaction at h i g h -
er formation pressures, even at the low pressures i n -
volved. (This c o n c e n t r a t i o n o f Na2S0i| s o l u t i o n was
chosen because i t has roughly the same conductance as
the o i l emulsion.)
f
The true measure o f the dynamicJLayer s s e l e c t i v -
i t y , i s the i n t r i n s i c s a l t r e j e c t i o n , Ri t« However, due n
to c o n c e n t r a t i o n p o l a r i z a t i o n e f f e c t s caused by the
l a r g e volume flow through the membrane, one a c t u a l l y
measures R , the apparent s a l t r e j e c t i o n , given by
0 D S
the r e l a t i o n
where C p and Cf are the product and feed s a l t con-

centrations respectively. From s t u d i e s on concentra-
tion polarization and membrane performance, i t has
been found p o s s i b l e to account f o r these e f f e c t s by
the r e l a t i o n ( 1 2 )
1-R , kJ 1-R. .
n obs v , int ,*r\
l n + l n ( 1 6 )
- R — = J J 5 1
obs U R. .
int
where k i s a constant i n f l u e n c e d by the hydrodynamic

c o n d i t i o n s i n the system and U i s the crossflow v e l o c -
i t y which, f o r the module, i s taken as the pumping
rate. Thus, i f the s a l t r e j e c t i o n i s measured at a
number o f pressures and/or_crossflow v e l o c i t i e s , the
c a n b e
i n t r i n s i c salt rejection, R i t n obtained from
intercept of a plot of
1-R . J
, obs v
ln vs.
R . 0.75 TT
obs U
Examples o f such p l o t s can be found i n F i g u r e 8,

f o r three d i f f e r e n t dynamic membrane formation c o n d i -
tions. As p r e d i c t e d by equation (16), the data y i e l d s
good s t r a i g h t l i n e p l o t s , and the values o f R i t c a l - n
culated from the i n t e r c e p t s are given i n Table 1. One

sees that the s a l t r e j e c t i o n i n c r e a s e s from 28? to 33?
when the formation pressure i s i n c r e a s e d from 10 to 15
psi. Thus the corresponding decrease i n L ( c f . p

Table 1) i s due, at l e a s t i n p a r t , to a t i g h t e r c o l -
l o i d layer structure. Membranes formed at the same
pressure but d i f f e r e n t c r o s s f l o w v e l o c i t i e s show s i m i -
l a r values o f R^ ( T r i a l s 5-8 i n Table 1), although a t
nt
the higher v e l o c i t i e s there i s some decrease, which

may be due to i m p e r f e c t i o n s i n the t h i n n e r dynamically
formed l a y e r .
2. Performance with O i l Emulsions
a. Flow Rate. In F i g u r e 9, p l o t s are shown f o r the
flow rate versus a p p l i e d pressure f o r an o i l
emulsion c o n t a i n i n g 2.5-3-0? o i l ( v o l / v o l ) . The
dotted s t r a i g h t l i n e represents the pure water
flow r a t e , while the curves obtained f o r the o i l
emulsion at d i f f e r e n t c r o s s f l o w v e l o c i t i e s are
t y p i c a l o f s i t u a t i o n s i n which formation o f a
boundary l a y e r r e s t r i c t s the flow o f water In
t h i s case
the membran
water by t h e i r presence. At higher pressures, the
l a y e r t h i c k n e s s and the packing d e n s i t y i n c r e a s e s
so that the water flow remains constant. Such be-
haviour has been observed p r e v i o u s l y , with o i l
emulsions, blood and proteinaceous s o l u t i o n s and
has been c l a s s i f i e d as " C l a s s I " dynamic membrane
formation^). Since the phenomenon involves
boundary l a y e r hydrodynamics, the s t i r r i n g c o n d i -
t i o n s should c l e a r l y a f f e c t the performance. Thus
we see that at higher c r o s s f l o w v e l o c i t i e s , the
e a r l y data remain c l o s e r to the pure water per-
formance l i n e , and the plateau assumes a higher
constant flow r a t e .
The value o f the exponential dependence o f
the product flow rate on the c r o s s f l o w v e l o c i t y
is indicative o f the hydrodynamic conditions
which p r e v a i l . The plateau values, or near p l a -
teau values o f the product flow are shown i n F i g -
ure 10, p l o t t e d versus the c r o s s f l o w v e l o c i t y ,
and the slope i s found to have a value o f 0.86.
For a t u r b u l e n t flow s i t u a t i o n i n a tube, the
mass t r a n s f e r c o e f f i c i e n t i s given b y ^ H ) .
7 / 8 1 / 4
Sh = 0.023 R S (17)
e c
, \7/8, IH xl J/4
Sh* 0.023 ( J ? ) (2) dB)
i.e., Sh« U

TANNY AND KORIN UF of Oil Emulsions 249
Figure 9. UF of a 3% oil emulsion with a dynamically formed Si0 membrane in 2
a pleated crossflow module. Q (gpm): #, 0.67; 0,1.0;

R 1.33; A , 1.67.

SYNTHETIC MEMBRANES: H F A N D U F USES
where U i s the crossflow v e l o c i t y , d i s the tube

diameter, v i s the kinematic v i s c o s i t y and D i s
the d i f f u s i o n c o e f f i c i e n t . Thus the dependence
of product flow on the crossflow velocity i s
c l e a r l y c o n s i s t e n t with turbulent flow c o n d i t i o n s .
Q u a l i t y o f the Product. Results f o r the r e j e c -
t i o n o f TOC, e x t r a c t a b l e s and c o n d u c t i v i t y , are
q u i t e dependent on the type o f s u r f a c t a n t s i n the
c u t t i n g o i l emulsion t e s t e d . Tests on o i l used
i n the present study, "Pazomus B", showed that i t
contains an a n i o n i c s u r f a c t a n t , which i s probably
a sulphonic a c i d , since chemical a n a l y s i s showed
that i t contained sulfur. Other n e u t r a l p o l a r
molecules, such as a l c o h o l s , may a l s o be present.
For 3% "Paz" s o l u t i o n s , the average values o f the
product TOC a r e shown i n Table 2 They range
from 160-50
obtaine
b r a n e ^ ) , xhe r e s u l t s o f e x t r a c t i o n experiments
are lower than TOC because TOC a l s o measures the
presence o f small, p o l a r , water s o l u b l e s p e c i e s .
These are only p a r t i a l l y extracted by the Freon
i n the course o f these a n a l y s i s .
An examination o f the data f o r dynamic mem-
branes formed under various c o n d i t i o n s suggests
that a combination o f higher pressure and c r o s s -
flow rate y i e l d s both the highest product f l u x
and lowest o i l e x t r a c t i o n values. However, the
o v e r a l l impression i s that the TOC or e x t r a c t -
ables l e v e l o f the product i s f a r l e s s s e n s i t i v e
to formation c o n d i t i o n s than the h y d r a u l i c perme-
a b i l i t y or even the i n t r i n s i c s a l t r e j e c t i o n t o -
ward 10~3M Na2S0i| solutions. Further evi-
dence o f t h i s l a c k o f s e n s i t i v i t y can be seen i n
Table 2. At a l a t e r stage i n the work, i t was
realized that conductance measurements o f the
feed and product could be used to examine the
d i s t r i b u t i o n o f s u r f a c t a n t between the l a r g e r o i l
drops r e t a i n e d by the dynamic membrane, and small
conductive surfactant micelles (approximately
100-200A) which pass through. As the r e s u l t s i n
Table 2 demonstrate, about 50-60% o f the conduc-
t i v e species are r e t a i n e d by the membrane. Since
the membrane has some i n t r i n s i c rejection f o r
d i l u t e s a l t s , i t i s p o s s i b l e that part o f the
smaller charged species are a l s o r e j e c t e d .
E f f e c t s o f Concentration and Time. Since real
systems w i l l have to concentrate the o i l emulsion
to relatively large volume fractions of o i l
( i . e . , 25-40%), and work f o r extended periods o f

TABLE I
P r o p e r t i e s o f Dynamically Formed S i l i c a Membranes On

0.2 um Membrane A c r o f l u x Capsules (1000 cm2 area)
Membrane Formation Intrinsic

Conditions Hydraulic Rejection of
Crossflow
3
Capsule T r i a l Pressure Rate Permeability, L 10" M ]N a S 0 2 4
(atm) Upm) (cm/min-atm) p
10 1 0.5 2.5 0.40 27

10 2 0.67 2.5 0.34 28
10 3 1.0 2.5 0.20 33
4 4 2.3
11 5 0.67
11 6 0.67 3.75 0.23 28
11 7 0.67 4.5 0.37 21
11 8 0.67 5.5 0.34 21
TABLE I I
U l t r a f i l t r a t i o n T r i a l s o f Various S i l i c a Dynamic Membranes

with Pazomus BB O i l Emulsion
Membrane
Formation Concentration o f Permeate
Trial TOC Feed TOC Species Containing % R e j e c t i o n
Number* Concentration Average CHpFunctionality Conductivity
(ppm) (ppm) (ppm)
1 20,000 220 + 10 99 59+2
2 20,000 180 + 10 95 + 5 59 + 2
3 17,000 225 + 10 96 51
4 12,500 48
5 23,000
170 + 30
250 + 10 137
-50
6 22,000 280 + 30 108 46
7 22,000 235 + 5 46 51
8 19,000 230 36 42
c f Table I f o r c o n d i t i o n s o f membrane formation.

Figure 10. Dependence of the permea-

tion rate on the crossflow pumping rate
in the UF of a 3% oil emulsion by a dy-
namically formed Si0 membrane in a
2
pleated crossflow module: d, Trial 2; X,

Trial 3; A, Trial 4; Trial 6; O, Trial "0.5 10 2.0 3.0
7; A, Trial 8. Crossflow pumping rale (gpm)
2 5 10 20 50 100
Figure 11. Permeate flow rate vs. batch
oil emulsion concentration % Oil Emulsion
0 10 20 30 AO 50 60 70 80 90
Time(hrs)
Figure 12. Long-term UF performance of a dynamically formed SiO membrane z
in a pleated crossflow module: P = 1.5 atm; 1.67-gpm crossflow initial feed con-
a r
centration == 3.6%; T = 32°C.

time, these aspects were a l s o examined. In F i g -

ure 11, the r e s u l t s of two batch c o n c e n t r a t i o n
t r i a l s are shown, i n which the flow r a t e has been
p l o t t e d vs. l o g Cg, the o i l emulsion concentra-
tion. As observed e a r l i e r i n our study of UF
membranes(3) y a s t r a i g h t l i n e r e l a t i o n i s ob-
t a i n e d . For the c l e a n "Paz" emulsion, f l u x e s of
0.02 cm/min (approximately 7 gfd) can s t i l l be
a n t i c i p a t e d f o r emulsions c o n t a i n i n g 40-50? o i l .
A t e s t of over 80 h r s . operation on a s i n g l e
dynamically formed l a y e r was a l s o undertaken to
examine the continuous operation behaviour. Dur-
ing t h i s time, the membrane was subjected to sev-
e r a l shut-downs and r e s t a r t s , as w e l l as a con-
c e n t r a t i o n c y c l e . As may be seen from F i g u r e 12,
the membran showed almost chang eithe i
flux o
which occurre
operation. However, i n a d d i t i o n , the membrane
appears to have taken the shut-down and r e s t a r t
o p e r a t i o n with no i l l e f f e c t s . I t should be
pointed out that t h i s was not always the case.
The A c r o f l u x module used i n t h i s t r i a l was t i g h t -
l y packed and showed no v i s i b l e movement of the
p l e a t s when p r e s s u r i z e d , whereas e a r l i e r u n i t s
sometimes showed such e f f e c t s . Movement of the
p l e a t s upon r e - p r e s s u r i z a t i o n cracked the dynamic
l a y e r i n e a r l i e r t r i a l s and caused an o i l leak
i n t o the product compartment. In such cases, a
new dynamic membrane had to be formed, and feed
introduced without a l l o w i n g system shut-down.
Nomenclature
Symbols Q Volumetric Flow Rate

P Pressure
C Concentration
Subscripts c Flow Channel
m Membrane
P Permeate Stream
F Feed Stream
R Retentate Stream
Terms Volumetric flow rate of the retentate
QR stream (gal or l i t e r s per min.)
Volumetric flow rate of the permeate
Qp stream ( g a l or l i t e r s per min.)
^c Pressure drop across flow channel ( p s i or
2
kg/cm )
AP m Average pressure drop across membrane ( p s i
2
or kg/cm )

APp = Pressure drog across membrane a t i n l e t

2
(psi or kg/cm )
Pp = Pressure o f the feed stream ( p s i g or
2
kg/cm g)
Pp = Pressure o f the permeate stream ( p s i g or
2
kg/cm g)
Pp = Pressure o f the r e t e n t a t e stream ( p s i g or
2
kg/cm g)
AP C = Pp - Pp = Pressure drop across channel
APp = Pp - Pp = Pressure drop across mem-
brane a t i n l e t
2AP + AP
m c
APp = P
AP +AP P +P
_ F R _ F R p _ Avg. pressure drop
m " 2 ~ 2 ~ P ~ across membrane.
AP
m
= Resistance o f membrane to flow o f l i q u i d
*P
_5 = Cross-flow r a t i o
Q
P
Q.
R
RR = —
Q = Recovery Ratio
F
^P
R
1 - -pr~ = R e j e c t i o n
°F
R = Membrane Resistance
m
Appendix 1
Performing the i n t e g r a t i o n o f Eq. 4 y i e l d s :
p 2
P 2
g Q P P + P U ;
n+U F R J " aR I 2 F P 2 R V
m
Inserting i n t o the right-hand side o f the equation
P Pr r
P P r
F P F R

enables us to rearrange and r e s t a t e t h i s r i g h t side
1 (2)
aR
m L
1 (P _P ) ( _ P
aR F RM 2 F
Where from the i d e n t i t i e s i n equation 2, and assuming n above i s

2, we o b t a i n
Equation #3 can be w r i t t e n as f o l l o w s :
QdZ = K, AP AP (4)
P 1 m c
where
Z = \ ((1+X) - X ) 3 3
and X
K, = l/aR
1 m
Rearrangement o f equation 4 can be done using the f o l l o w i n g sub-

stitution:
/ A P
AP = 2AP m
(1-
\ x
A "
m
T h i s equation can be w r i t t e n as f o l l o w s :
/ A P \
A P = A P /2(1-T-^ (5)
m c \
x
AP /
m/
S u b s t i t u t i o n of the above i n equation #4 w i l l obtain:
1- Ap / A P
R m

Rearrangement w i l l o b t a i n
Knowing that
1 / 2 2
AP \ AP AP
1 r 1 r r
1 = +
" AP 2AP 8AP
m / m m
and assuming that only the f i r s t two terms o f the s e r i e s can be

used
AP
whenAP r ^ P
A m then y =1 - % -
AP
1
whenA P^ << AP ffl then y =1 - 2 A P** *
Therefore equation 6 can be w r i t t e n as f o l l o w s :
1/2
=
P
c f ¥) Q
P / 2 ( y ) w h e r e
2 < Y < 1 ( 7 )
In the case o f laminar flow through the channel, the value o f n

w i l l be 1 and then
dp = a Q L
where a£, i s a f r i c t i o n c o e f f i c i e n t r e s p e c t i v e to laminar flow

at the channel. In t h i s case equation 3 w i l l have the f o l l o w i n g
form:
2
3 Q = K AP AP T (8)
r L C m
2 2
where 3 = ( ( 1 + X ) - X ) 1/2 X = —
and K L = l/(a R ) L m
s u b s t i t u t i o n o f eq. 5 i n t o eq. 8 r e s u l t s i n

A P
2 2 / r
v
m
thus, when the square root term i s developed i n t o a s e r i e s , then
and therefore,
A P = |^ Q y where 1/2< y < 1 (9)

c K p L
One can assume that i n a case o f laminar flow through a short

channel A P £ AP
m and thus
r 3 ^ 1/2 and
1/2
A P = Q
c P v
ft)
^ L
REFERENCES
1. Brandon, C.H., 5 t h . Seminar on Memb. Sep. Tech., Clemson

U n i v e r s i t y , S.C., May 12, 13, 14, 1980.
2. F r i b e r g , S. Chem. Tech., 1976, p. 124.
3. Tanny, G. B.; H e i s l e r , M. A.C.S. Symp. Ultra Filtration

Membr., Washington, D.C., 1979.
4. Tanny, G.B.; Hauk, D. Separation Sci. and Tech., 1980, 15,

317.
5. Perry, R.H.; C h i l t o n , C.H. Chem. Eng. Handbook (5th. E d i -

t i o n ) , McGraw Hill.
6. Tanny, G.B.; Perry, R.H. Separation & Pur. Methods, 1978,

7(2), 183-220.

7. B e l f o r t , G.; Reed, R.H. 5th. Seminar on Memb. Sep. Tech.,

Clemson U n i v e r s i t y S.C., May 12, 13, 14, 1980.
8. "Standard Methods f o r the Examination o f Water and Waste-

water"; Am. Pub. Health Assoc., Inc., NY 1979.
9. F r e l i c h , D.; PhD T h e s i s , Feinberg Graduate School, Weizmann

I n s t i t u t e , Rehovot, I s r a e l .
10. Shor, A.J.; Kraus, K.H.; Johnson, J.S.; Smith, W.T. Ind.
Eng. Chem. Fund., 1968, 7, 44.
11. C h i l t o n , T.H.; Colburn, A. Ind. Eng. Chem., 1934, 26, 1183.
RECEIVED December 18, 1980

16
Engineering Aspects of the Continuous Membrane
Column
1
JOHN M. THORMAN and SUN-TAK HWANG
Chemical and Materials Engineering, The University of Iowa, Iowa City, IA 52242
The partial enrichment of gas mixtures via membranes has long

been recognized as a n o v e l separatio technique Prio t 1950
only a l i m i t e d amount o
E a r l y a p p l i c a t i o n s were uniqu hydroge purificatio
through s i l v e r - p a l l a d i u m a l l o y s , helium recovery through silica
g l a s s , and uranium isotope s e p a r a t i o n . However, in recent years
there has been an explosion of activity d i r e c t e d toward the immi-
nent and widespread commercialization of gas permeation technology,
Gas permeation separations are becoming l e s s novel and more
practical.
In p a r t i c u l a r , s u b s t a n t i a l progress has been made during the
past decade. Plug-flow separation models of c a p i l l a r y permeators
have been confirmed experimentally by s e v e r a l i n v e s t i g a t o r s (1,2,
3,4) . S p e c i f i c studies of c a p i l l a r y membranes and permeators have
a l s o been made concerning a x i a l pressure l o s s (2,5,6,7) , c a p i l l a r y
deformation (4,5,8), process v a r i a b l e s and broken f i b e r s ( 7 ) , flow
patterns and purge streams (9), the pressure dependency of perme-
ability c o e f f i c i e n t s (10,11,12,13), and two-membrance permeators
(15,16). Work with axisymmetric membranes has been i n i t i a t e d
(17). Cascade separations have been advanced by other researchers
(18,19,20,21,22). Commerical u n i t s , such as the Du Pont Permasep
(23) and Monsanto Prism Separator (24) , have been developed f o r
e n r i c h i n g hydrogen, carbon monoxide, ammonia, and other i n d u s t r i a l
gases. Extensive reviews of these and other recent advances i n
the area of gas permeation can be found i n books by Hwang and
Kammermeyer (25) and Meares (26).
In a d d i t i o n to the above c o n t r i b u t i o n s another i d e a , r e f e r r e d
to as "the continuous membrance column," was developed i n the l a t e
1970's (27,28,29). In essence t h i s concept s t a t e s that the gas
permeation cell, t r a d i t i o n a l l y regarded as a s i n g l e - s t a g e separa-
tion u n i t , i s a c t u a l l y a s e l f - c o n t a i n e d continuous cascade. The
1
Current address: Monsanto Chemical Intermediates Company, Texas City, T X 77590.
0097-6156/81/0154-0259$05.25/0

260 SYNTHETIC M E M B R A N E S : HF AND U F USES
more permeable gas i s s t r i p p e d from the high-pressure stream

along the membrane; however, when the c e l l i s operated i n the
countercurrent, plug-flow mode, and the amount of permeation i s
maximized r e l a t i v e t o product stream f l o w r a t e s , a strong i n t e r n a l
r e f l u x a c t i o n i s c r e a t e d . I n p r i n c i p l e , the components of a
b i n a r y mixture can be enriched i n d e f i n i t e l y , provided that the
membrane employed e x h i b i t s some f i n i t e s e l e c t i v i t y .
Although the s e p a r a t i o n mechanisms f o r membrane and e q u i l i -
brium processes d i f f e r , o p e r a t i o n of a membrance column i s analo-
gous to that of packed d i s t i l l a t i o n and e x t r a c t i o n columns. As
shown i n F i g u r e 1, a feed stream i s c e n t r a l l y introduced, and pro-
duct streams a r e withdrawn from the ends of the column. The
column can be d i v i d e d i n t o s t r i p p i n g and e n r i c h i n g s e c t i o n s . Note
that gas on the low-pressure s i d e of the membrane i s r e c y c l e d to
the high-pressure s i d e v i a a compressor. I n t h i s manner the more
permeable gas i s c o n t i n u a l l y c a r r i e d toward and c o l l e c t e d near the
compressor, w h i l e the l e s
toward and concentrate
absence of backmixing i s very important, s i n c e any a x i a l mixing
w i l l tend to e q u a l i z e compositions. The degree of s e p a r a t i o n
achieved depends on product f l o w r a t e s , membrane s e l e c t i v i t y ,
amount of l o c a l permeation, and column l e n g t h .
E a r l i e r papers on the continuous membrane column (28,29) have
discussed the s e p a r a t i o n of C O 2 - N 2 , C O 2 - O 2 and O 2 - N 2 ( a i r ) mix-
tures i n s t r i p p e r , e n r i c h e r and t o t a l column u n i t s composed of
35 s i l i c o n e rubber c a p i l l a r i e s . A c h a r a c t e r i z a t i o n of the mem-
brane column using a membrane u n i t concept (analogous to t r a n s f e r
u n i t concept — HTU, NTU) has a l s o been presented. The purpose of
t h i s paper i s to present some new data and d i s c u s s i o n s on the
extended study of continuous membrane column. S p e c i f i c a l l y , the
t o p i c s of multicomponent s e p a r a t i o n s , inherent s i m u l a t i o n d i f f i -
c u l t i e s , composition minima i n the e n r i c h i n g s e c t i o n , v a r i a t i o n of
experimental parameters, and l o c a l HMU v a r i a t i o n along the column
w i l l be covered.
Multicomponents Systems
Thus f a r , only b i n a r y mixtures have been separated i n the

t o t a l membrane column. R e s u l t s of t h i s work have been discussed
elsewhere (28,29). A sample s h e l l - s i d e composition p r o f i l e from
a t o t a l column experiment w i t h a C O 2 - O 2 mixture i s shown i n
F i g u r e 2. Table I summarizes the t o t a l column data obtained to
date.
One of the next steps i n developing the continuous membrane
column w i l l be to o b t a i n extensive data on multicomponent systems.
Some p r e l i m i n a r y experiments w i t h a C^-CH^-^ mixture using a
s t r i p p e r have a l r e a d y been conducted. The r e s u l t s of two such
experiments are presented i n F i g u r e s 3 and 4. The agreement
between experiment and model i s e x c e l l e n t .

16. THORMAN AND HWANG Continuous Membrane Column 261
MOST
PERMEABLE - COMPRESSOR
GAS
LOW PRESSURE
PRESSURIZED FEED
( GAS MIXTURE).
HIG
LEAST
PERMEABLE
GAS
Figure 1. Schematic of the total column
100
co -o 2 2
90 o EXPT
CALC'D
80
^ ^ ^ ^ ^
70 - FEED* 57.2 % C0 2
s 6 0
o
£ 50
40
ENRICHING STRIPPING
30 SECTION SECTION
20 I I I I I I I I I I
0.0 1.0 2.0 3.0 4.0 5.0

10 LENGTH,m
Figure 2. Shell-side composition profile of the total membrane column for the
C0 —0 mixture 2 2

TABLE I . PERFORMANCE OF THE CONTINUOUS MEMBRANE COLUMN
Gas System C0 -N
2 2 C 0 N C0 C0 N 0 -N
2 2
2 2 2°2 2°2 °2- 2
Feed Composition 54.8 52.6 57.2 57.0 21.0 20.9

(% 1st Gas)
Top Product Composition 94.5 94.6 87.3 88.3 36.8 41.7

(% 1st Gas) (94.4) (95.2) (86.3) (88.7) (36.8) (41.7)
Bottom Product Composition

17.8 8.2 20.5 22.6 15.1 19.6
(% 1st Gas)
Top Product Flow Rate

(ymbl/s) 4.83 2.37 7.90 7.46 1.79 0.993
Bottom Product Flow Rate

5.77 2.59 6.74 7.10 4.34 12.92
(ymol/s)

Feed Flow Rate
10.60 4.96 14.64 14.56 6.13 13.853
(ymol/s)
Compressor Load (ymol/s) (87.7) (91.7) (84.0) (88.69) (12.66) (13.13)

T o t a l Column Length (m) 5.12 5.12 5.12 5.12 4.24 4.24
TABLE I . (cont'd.)
o
>
Enriching Section 3.11 3.11 3.11 3.11 2.13 2.13 >

Length (m) o
a
Stripping Section 2.01 2.01 2.01 2.01 2.11 2.11
Length (m) o
Pressure a t Compressor 226.62 223.86 224.85 223.89 230.14 227.34

(kPa) (224.89) (222.73) (223.31) (222.56) (230.28) (227.11)
Enriching Section 7.62 8.06 7.35 7.81 0.83 1.03 S'

Pressure Loss (kPa) (5.98) (6.92) (6.03) (6.82) (0.88) (1.03) R
K
Pressure Loss (kPa) (1.16) (0.80) (1.80) (1.96) (0.80) (1.80) s
99.07 99.27 101.22 98.59 2
S h e l l - S i d e Pressure (kPa) 99.27 98.78
297.8 302.7 296.3 297.1

Enriching Section 298.3 298.5
Temperature (K)

Temperature (K)

to
ON
Figure 3. Shell-side composition profiles for the C0 -CH -N

2 fy 2 mixture in a strip-
per at total reflux
Figure 4. Shell-side composition profiles for the C0, -CH

-N mixture
- 2t
in a strip-
2 h
per with bottom product

In modeling multicomponent systems i t i s necessary to modify

the a x i a l pressure l o s s , gas permeation and c o n c e n t r a t i o n g r a d i -
ents p r e v i o u s l y d e s c r i b e d (28). The governing equations, r e q u i r e d
to execute the numerical s i m u l a t i o n over i n f i n i t e s i m a l segments
along the membrane column as shown i n F i g u r e 5 a r e :
>
K yqRT 4Re z
dP w _ 8yqRT
dz 4 Re r .
rrN(r_ ) P L Re /(3P) - rrN(r.) P/(2yqRT) 3
rrN(r.) P 4
Z 1; z x 1
(i)
27rN
dz n(r
, /, r . .) E [Q.(x.P
^ J j X - y.P ) ]
Jo
(2)
and
dx. 2TTNQ.(X.P - y.P )

(3)
dz £n(r / r . ) j dz
o 1
for j l,2,...,n-l
where
2 3
i ( l + 0.75Re - 0.0407Re + 0.0125Re (A)
w w w
K 0 -1 4- 0.056Re - 0.0153Re (5)

w w
The f o l l o w i n g o v e r a l l and component balances are a l s o r e q u i r e d :
q - q = G -G B B (6)
x.q y G
for j = 1,2,••»,n-l (7)
B. B
J
Of course,
E x =i (8)
J
j
A l l procedures f o r executing the numerical s i m u l a t i o n of a
multicomponent s e p a r a t i o n are s i m i l a r to those described f o r a
b i n a r y system, except f o r e v a l u a t i n g the i n i t i a l permeate composi-
t i o n at the r e s i d u e end of the s t r i p p e r . A g a i n , the i n i t i a l per-
meate composition w i l l be that of the mixture which permeates
through the endmost increment of the membrane. The a p p r o p r i a t e
relations are:

J
J o i \ j J V
for j = 1,2,.
and
E y B = i do)
A t r i a l - a n d - e r r o r s o l u t i o n i s necessary. By e s t i m a t i n g the v a l u e
of dq/dz each of the component equations (9) and (10) can be
solved f o r y . I f y B B > > 1, y B << 0 or ^ y f 1, then dq/dz
g #
must be r e v i s e d . Determination of dq/dz can be f a c i l i t a t e d by

employing an i t e r a t i v e
h a l v i n g or the secant metho
The multicomponent data obtained from o p e r a t i n g a s t r i p p e r a t
t o t a l r e f l u x and w i t h bottom product are p a r t i c u l a r l y i n t e r e s t i n g .
The feed mixtures were comparable i n each case, roughly 53% C O 2 -
25% CH^-22% N 2 , as were feed pressure (225 kPa), ambient pressure
(99 kPa) and temperature (300 K ) . The pure-gas p e r m e a b i l i t i e s of
carbon d i o x i d e and methane are approximately 12 and 3.3 times
greater than that of n i t r o g e n , r e s p e c t i v e l y . F i g u r e s 3 and 4
show t h a t at s t e a d y - s t a t e the composition of the most permeable
gas, carbon d i o x i d e , s t e a d i l y decreases, w h i l e t h a t of the l e a s t
permeable gas, n i t r o g e n , i n c r e a s e s along the column. The compo-
s i t i o n of methane, w i t h an intermediate p e r m e a b i l i t y , passes
through a maximum.
The curves shown i n F i g u r e s 3 and 4 are simulated composition
p r o f i l e s based on experimental data. The c a l c u l a t e d trends f i t
the experimental compositions q u i t e w e l l , and i n each case the
experimental methane peak i s w e l l d e s c r i b e d . This demonstrates
that the b a s i c model f o r the membrane column can be a p p l i e d to
multicomponent systems as w e l l as to b i n a r y m i x t u r e s .
The e x i s t e n c e of a methane peak i s not considered a phenom-
enon t h a t w i l l always occur w i t h i n t e r m e d i a t e l y permeable gases
i n multicomponent m i x t u r e s . Rather, the peak i s thought to be the
r e s u l t of a combination of f a c t o r s . These f a c t o r s i n c l u d e com-
p o s i t i o n of the feed m i x t u r e , pure-gas p e r m e a b i l i t i e s , and the
i n t e r n a l r e f l u x r a t i o . For i n s t a n c e , F i g u r e 3 i n d i c a t e s t h a t the
intermediate-gas composition p r o f i l e w i l l s t e a d i l y decrease i n a
s t r i p p e r 1.0 m l o n g , but otherwise i d e n t i c a l to the column used
i n t h i s study, fed w i t h a 63.6% N - 32.3% CH - 4.1% C 0 mixture
2 4 2
under s i m i l a r t o t a l r e f l u x c o n d i t i o n s . The presence of an i n t e r -

mediate peak, however, i s r e m i n i s c e n t of multicomponent d i s t i l l a -
t i o n p r o f i l e s and r a i s e s the p o s s i b i l i t y of withdrawing a s i d e
stream enriched w i t h an i n t e r m e d i a t e gas.

L o c a l HMU V a r i a t i o n
The performance o f the continuous membrane column was char-

a c t e r i z e d e a r l i e r (28) i n a manner analogous t o the t r a n s f e r u n i t
concept f o r packed columns. The expressions developed f o r NMU
( d i f f i c u l t y of separation) and HMU ( e f f i c i e n c y ) were
rT
dx
NMU = (11)
B x - y P - x{ ( 1 - Q ) (x - y P ) + Q
r r r r (1 -P) }
r
and
HMU = (12)
rT 2TTNQ.JP
d
q to r
B <
F i g u r e 6 i l l u s t r a t e s the change i n HMU and NMU over 1 0 0 mm sec-

t i o n s along the column. The curves are f o r the C O 2 - O 2 system,
but q u a l i t a t i v e l y represent both the e n r i c h i n g and s t r i p p i n g
s e c t i o n s f o r a l l of the C O 2 - N 2 , C O 2 - O 2 and O 2 - N 2 systems i n v e s t i -
gated.
The HMU trend shows t h a t e f f i c i e n c y goes up (HMU goes down)
s i g n i f i c a n t l y as the a x i a l flow r a t e decreases w i t h i n the column.
In some i n s t a n c e s , l o c a l HMU values change almost an order of
magnitude. Since HMU and NMU vary i n v e r s e l y over a given i n t e r -
v a l , the number of membrane u n i t s achieved i n each s e c t i o n i n -
creases d r a m a t i c a l l y w i t h decreasing flow r a t e s . Note that i t i s
the m o d i f i c a t i o n of column o p e r a t i n g v a r i a b l e s contained i n the
HMU expression that u l t i m a t e l y determine the v a l u e HMU when the
column l e n g t h i s f i x e d .
Composition Minima
U s u a l l y i n an e n r i c h e r o r the e n r i c h i n g s e c t i o n of the mem-

brane column, the more permeable component i s s t e a d i l y concen-
t r a t e d from the feed i n l e t to the compressor. However, some of
the r e s u l t s show that the s h e l l - s i d e and even the tube-side com-
p o s i t i o n p r o f i l e s can pass through a minimum. Note the e x p e r i -
mental data i n Figures 7 and 8. I n these cases the feed f l o w i s
r e l a t i v e l y slow and r e f l u x a c t i o n , r a t h e r than b u l k f l o w , i s pre-
dominant. F i g u r e 8 i l l u s t r a t e s t h a t a composition minimum can
a l s o occur during o p e r a t i o n of the t o t a l column when the r e s i d u e
flow r a t e from the e n r i c h i n g s e c t i o n i s too slow.
Figures 7 and 8 i n c o r p o r a t e c a l c u l a t e d tube- and s h e l l - s i d e
c o n c e n t r a t i o n p r o f i l e s f o r the unique C 0 - N 2 and O 2 - N 2 ( a i r ) data,
2
and a l s o i l l u s t r a t e l o c a l permeate composition v a r i a t i o n . Each

f i g u r e shows that the c o n c e n t r a t i o n of more permeable gas s t e a d i l y
decreases i n the d i r e c t i o n of flow along the high-pressure (tube)

PT PO
qT I • G T
x t y r
1 L
P+dP Po
q +dq 1 t G+dG
x + dx
dz
1 1 y+dy
P
q
1 t
• 1
Po
G
X y
Figure 5. Modeling of the membrane

column
Figure 6. Local variation of NMU and HMU within a section of the membrane
column

THORMAN AND HWANG Continuous Membrane Column 269
^. C0 -N
2 2 LOCAL PERMEATE
COMPOSITION
SHELL-SIDE
COMPOSITION
o \ — TUBE-SIDE
COMPOSITION
\ "
O EXPERIMENTAL
\
\
- \
•s
FEED = 44.1 % C 0
8.31
— TOP FEED- • —
i i
0.0 0.5 1.0 1.5 2.0
LENGTH, m
Figure 7. Composition minima for the C0 -N 2 2 system in an enricher with top

product
Figure 8. Composition minimum for the 0 -N 2 2 (air) system in an enricher with

top product

s i d e of the e n r i c h e r . This r e s u l t s i n a lower percentage of more

permeable gas passing through the membrane. E v e n t u a l l y , because
of strong r e f l u x a c t i o n , the l o c a l permeate composition matches
the s h e l l - s i d e (low-pressure s i d e ) composition. At that p o i n t
enrichment ceases. Continuing toward the bottom of the e n r i c h e r ,
the s h e l l - s i d e c o n c e n t r a t i o n of more permeable gas d e c l i n e s u n t i l
the r e l a t i v e amount of permeate i s i n s u f f i c i e n t to f u r t h e r lower
the c o n c e n t r a t i o n of the incoming low-pressure stream. The pro-
f i l e then increases toward the feed i n l e t . Hence a s h e l l - s i d e
c o n c e n t r a t i o n minimum i s formed.
F i g u r e 7 shows that a c o n c e n t r a t i o n minimum can a l s o occur
on the high-pressure s i d e proceeding again toward the bottom of
the e n r i c h e r , the c o n c e n t r a t i o n of more permeable gas passing
through the membrane g r a d u a l l y becomes l e s s than that on the tube
(high pressure) s i d e . Thus, the c o n c e n t r a t i o n of the more per-
meable gas increases toward th botto product o u t l e t Ther i
no tube-side compositio
meate composition does no compositio
profile.
I t should be pointed out that o p e r a t i o n of an e n r i c h e r and
t o t a l column (Figure 9) i s l e s s e f f i c i e n t when a c o n c e n t r a t i o n
minimum occurs. I n other words, the same enrichment can be
accomplished w i t h a s h o r t e r column. This c o n d i t i o n can be e a s i l y
remedied by i n c r e a s i n g the f l o w r a t e on the high-pressure s i d e of
the membrane.
Simulation D i f f i c u l t i e s
The numerical s i m u l a t i o n of the t o t a l membrane column works

w e l l , but does c o n t a i n some inherent problems. These problems
r e l a t e to r e s t r i c t i o n s i n the d i r e c t i o n that i n t e g r a t i o n s a r e
executed, and to the i n f l u e n c e of propagated e r r o r s i n the f i n a l
results.
A l l c a l c u l a t i o n s , except those i n v o l v i n g a t o t a l r e f l u x
s t r i p p e r , should be i n i t i a t e d a t the bottom of a column s e c t i o n
for two reasons. F i r s t , numerical i n s t a b i l i t y i s observed i n a
s t r i p p i n g s e c t i o n w i t h a bottom product when i n t e g r a t i o n i s
d i r e c t e d from the feed p o i n t toward the bottom o u t l e t . I n t e g r a -
t i o n i s s t a b l e , however, from the bottom o u t l e t to the feed p o i n t ,
except i n some instances of wide-open f l o w . Secondly, a t the top
of the column i t i s d i f f i c u l t to a c c u r a t e l y measure flow r a t e s of
streams e n t e r i n g and e x i t i n g the e n r i c h i n g s e c t i o n near the com-
p r e s s o r . Were values of these flow r a t e s provided, along w i t h
gas composition and pressure a t the compressor, i n t e g r a t i o n could
be executed from the top of the e n r i c h i n g s e c t i o n to the feed
point.
The propagation of measurement and c a l c u l a t i o n e r r o r s can
a l s o be a problem. I n g e n e r a l , experimental e r r o r s i n boundary
c o n d i t i o n s a t the bottom of the column and c a l c u l a t i o n e r r o r s i n
the model are propagated along the s t r i p p i n g s e c t i o n , introduced

to and f u r t h e r compounded i n the m a t e r i a l balance around the feed

p o i n t , and a m p l i f i e d again i n the e n r i c h i n g s e c t i o n . I f a t any
step i n the s i m u l a t i o n the absolute values of composition or flow
r a t e s become comparable w i t h t h e i r r e s p e c t i v e e r r o r s , there i s a
strong l i k e l i h o o d that the ensuing c a l c u l a t e d p r o f i l e s w i l l
d e v i a t e s i g n i f i c a n t l y from the experimental p r o f i l e s . The most
s u s c e p t i b l e q u a n t i t i e s i n the s i m u l a t i o n a r e the boundary condi-
t i o n s a t the residue o u t l e t s of the s t r i p p i n g and e n r i c h i n g sec-
tions .
The e f f e c t of p e r t u r b i n g a boundary c o n d i t i o n a t the b o t -
tom of a s t r i p p i n g s e c t i o n i s i l l u s t r a t e d i n Figure 10. The
experimental composition of the bottom product f o r the C O 2 - N 2
system i s only 1.7% C O 2 . The simulated s h e l l - s i d e composition
p r o f i l e based on t h i s v a l u e f o l l o w s the experimental t r e n d , but
i s c o n s i s t e n t l y higher. A f t e r s l i g h t l y a l t e r i n g the bottom com-
p o s i t i o n to 1.3% C O 2 , th c a l c u l a t e d p r o f i l d condition t
the opposite end of th
mental data. I n t h i s exampl y
v a r i e d . I t should be remembered that both the composition and
flow r a t e of the bottom product may c o n t a i n measurement e r r o r s
comparable to t h e i r absolute values. I n such cases i t i s recom-
mended that measurements be taken c a r e f u l l y and that i n i t i a l con-
d i t i o n s i n the s i m u l a t i o n be perturbed w i t h i n the range of e x p e r i -
mental e r r o r i n order to appreciate the p o s s i b l e range of c a l c u l a -
ted r e s u l t s .
The inherent s i m u l a t i o n d i f f i c u l t y accompanying a low
residue flow r a t e from the e n r i c h i n g s e c t i o n of a t o t a l column i s
shown i n F i g u r e 11. R e f e r r i n g to F i g u r e 1, the m a t e r i a l balance
around the feed p o i n t i n v o l v e s an e x t e r n a l feed and the residue
stream from the e n r i c h i n g s e c t i o n , which combine to form an i n t e r -
n a l feed to the s t r i p p i n g s e c t i o n . I n the column s i m u l a t i o n the
composition and flow r a t e of the residue stream are determined
using experimental values f o r the e x t e r n a l feed, and c a l c u l a t e d
values f o r the i n t e r n a l feed to the s t r i p p i n g s e c t i o n . I n some
cases the c a l c u l a t e d and experimental e r r o r s may negate one
another. However, when the actual residue flow r a t e i s s m a l l
r e l a t i v e to the e x t e r n a l feed, i t i s more l i k e l y that e r r o r s i n
the c a l c u l a t e d flow r a t e and composition of i n t e r n a l feed to the
s t r i p p i n g s e c t i o n w i l l be a m p l i f i e d i n determining the calculated
values of the residue stream from the e n r i c h i n g s e c t i o n . Depend-
ing on how s e n s i t i v e the e n r i c h i n g s e c t i o n s i m u l a t i o n i s to propa-
gated e r r o r s i n the boundary c o n d i t i o n s , the c a l c u l a t e d p r o f i l e s
for the e n r i c h i n g s e c t i o n can d i f f e r markedly from experimental
profiles.
Should the c a l c u l a t e d p r o f i l e s i n the e n r i c h i n g s e c t i o n be
erroneous due to u n c e r t a i n t i e s i n the boundary conditions the c o r -
r e c t p r o f i l e s can be found by employing a shooting technique. The
input data f o r the s i m u l a t i o n are again based on measurements sub-
j e c t to experimental e r r o r . By p e r t u r b i n g one or more values
w i t h i n the bounds of experimental e r r o r , the e n r i c h i n g s e c t i o n

C 0 2 - N 2
O 3
O
O
o
o
° 0
FEED = 54.2 % C0 2
ENRICHING
i i i i i i i i i i
0.0 1.0 2.0 3.0 4.0 5.0
LENGTH,m
Figure 9. Shell-side composition profile minimum for the C0 -N 2 2 mixture in the

total membrane column
90
LENGTH, m
Figure 10. Sensitivity of the stripper shell-side composition profile to the bottom
product composition

40 0 -N (AIR)
2 2
FEED
COMPOSITION
(% o ) 2
35 20.9
21.1
21.3
CM
21.9
o EXPT
X
° 30
25
ENRICHING STRIPPING
SECTION SECTION
20
I I I I I I 1 1 1 _ L
0.0 1.0 2.0 3.0 4.0 5.0

LENGTH, m
Figure 11. Sensitivity of the shell-side composition profile to the feed composition
in the total column simulation
0 -N (AIR)
2 2 FEED
0 1 2 3 4 5
LENGTH,m
Figure 12. Effect of column length on enrichment in a total reflux enricher

boundary c o n d i t i o n s can be r e c a l c u l a t e d . This procedure i s one

of t r i a l - a n d - e r r o r and can be e x e r c i s e d when an experimental pro-
f i l e , such as the s h e l l - s i d e composition i s a v a i l a b l e f o r f i t t i n g .
Figure 11 i l l u s t r a t e s the a p p l i c a t i o n of t h i s shooting technique
by p e r t u r b i n g only the e x t e r n a l feed composition.
Parameter V a r i a t i o n
The e f f e c t of column l e n g t h on the degree of enrichment i n a

t o t a l r e f l u x e n r i c h e r i s shown i n F i g u r e 12. Feed flow r a t e s were
p r a c t i c a l l y the same t o t o t a l r e f l u x e n r i c h e r s 3, 4 or 5m i n
l e n g t h . The output pressure of the compressor was comparable i n
each i n s t a n c e , ranging from 229-231 kPa. The data i n d i c a t e that
e x t r a membrane surface area r e s u l t s i n a f u r t h e r accumulation of the
more permeable gas i n the e n r i c h e r . The amount of permeation be-
comes g r e a t e r r e l a t i v e t o the feed flow r a t e ; hence g r e a t e r en-
richment of mixture occur
case, an 0 -N2 ( a i r ) m i x t u r e
2
sor increased approximately 4% w i t h each a d d i t i o n a l meter of tube

bundle.
F i g u r e 13 shows that e s s e n t i a l l y i d e n t i c a l p r o f i l e s a r e
obtained when s t r i p p e r s of 3, 4 and 5m are operated a t the same
11
"cut ( r a t i o of permeate t o f e e d ) . However, u n l i k e the e x p e r i -
mental work l e a d i n g t o F i g u r e 12, feed flow r a t e s were v a r i e d w i t h
column l e n g t h i n order to maintain the v a l u e of " c u t " constant.
Once a g a i n , the experimental and c a l c u l a t e d composition p r o f i l e s
are i n e x c e l l e n t agreement.
The e f f e c t of feed f l o w r a t e on the performance of a t o t a l
r e f l u x e n r i c h e r of f i x e d length was discussed i n an e a r l i e r paper
(29). I n g e n e r a l , the degree of enrichment increased as the
amount of permeation became greater r e l a t i v e t o the feed f l o w
rate.
Conclusions
1. According t o membrane u n i t a n a l y s i s , the e f f i c i e n c y of a

permeation c e l l increases s i g n i f i c a n t l y as a x i a l f l o w r a t e
decreases.
2. A composition minimum can occur i n an e n r i c h e r or i n the

e n r i c h i n g s e c t i o n o f a t o t a l column on the low- and h i g h -
pressure s i d e s of the membrane. Such o p e r a t i o n i s i n e f f i -
c i e n t , and can be remedied by i n c r e a s i n g the a x i a l f l o w r a t e
on the high-pressure s i d e of the column.
3. The s e p a r a t i o n model, which was p r e v i o u s l y a p p l i e d only t o

b i n a r y systems, has been s u c c e s s f u l l y extended to d e s c r i b e
the s e p a r a t i o n of a multicomponent gas mixture.

Figure 13. Shell-side composition profile variation with a comparable cut and a
variable column length

4. Inherent d i f f i c u l t i e s accompany some s i m u l a t i o n s of the

continuous membrane column. P e r t u r b a t i o n of boundary con-
d i t i o n s w i t h i n the range of experimental e r r o r may be
necessary i n c e r t a i n instances to achieve a proper f i t of
experimental data.
5. I n c r e a s i n g the amount of permeation r e l a t i v e to the feed

flow r a t e i n a t o t a l r e f l u x e n r i c h e r enhances the degree
of enrichment of the more permeable gas.
Acknowledgment
This m a t e r i a l i s based upon work supported by the N a t i o n a l

Science Foundation under Grant No. ENG78-10850.
Nomenclature
G = s h e l l - s i d e flo r a t e , umole/s
HMU = height of a membrane u n i t as d e f i n e d by Equation (12), n
K n = f u n c t i o n of Re as d e f i n e d by Equation (4)
JL W
K 0 = f u n c t i o n of Re as d e f i n e d by Equation (5)
z w
n = t o t a l number of components i n mixture
N = number of c a p i l l a r i e s
NMU = number of membrane u n i t s as d e f i n e d by Equation (11)
P = absolute l o c a l tube-side pressure, kPa
P Q = atmospheric pressure, kPa
P = P /P
r o
q = tube-side f l o w r a t e , ymol/s
2
Q = p e r m e a b i l i t y c o e f f i c i e n t mol-m/s-m -Pa
r capillary radius, n
R gas constant
Re Reynolds number a t w a l l defined as r,v p/u

w
Re a x i a l Reynolds number
z

T absolute temperature, K
v r a d i a l v e l o c i t y a t w a l l , m/s
rw
x = mole f r a c t i o n of more permeable component on tube s i d e
y = mole f r a c t i o n of more permeable component on s h e l l s i d e
z = a x i a l coordinate measured from bottom of column, m
Z = t o t a l column h e i g h t , m
Greek L e t t e r
u = v i s c o s i t y of ga mixture
TT = 3.14159 •••
3
p = gas d e n s i t y , kg/m
Subscripts
1 = more-permeable component
2 = less-permeable component
B = at bottom of column
i = inside
o = outside
r = ratio
T = a t top o f column
w = at c a p i l l a r y w a l l
z = axial direction
Abstract
Engineering aspects of "the continuous membrane column," an

i n n o v a t i o n in membrane s e p a r a t i o n technology are d i s c u s s e d . The
gaseous permeation cell is no longer regarded as a s i n g l e stage,
but r a t h e r as a continuous cascade. The membrane column e x p l o i t s
the countercurrent p l u g - f l o w o p e r a t i o n of modern gas permeators.
By maximizing the amount of permeation relative to product stream

flow r a t e s , a strong internal r e f l u x a c t i o n is created. Thus, a

b i n a r y feed mixture can be introduced to the membrane column, and
n e a r l y complete s e p a r a t i o n can be achieved on a continuous b a s i s .
Experiments were conducted w i t h a permeator composed of 35
silicone rubber capillaries (pressurized internally). Results
are presented f o r the b i n a r y systems O2-N2 (air), CO2-N2, CO2-O2,
and the multicomponent system CO2-CH4-N2. Particular attention
is given t o s e p a r a t i o n of the CO -CH -N2 mixture in a s t r i p p e r ,
2 4
c o n d i t i o n s f o r observing composition minima in the e n r i c h i n g

s e c t i o n , inherent s i m u l a t i o n difficulties in modeling the membrane
column, variation of experimental parameters, and local HMU vari-
ation along the column.
Literature Cited
1. Blaisdell, C.T.; Kammermeyer K Chem Eng Sci., 1973 28

1249.
2. Thorman, J.M.; Rhim, H.; Hwang, S.T. Chem. Eng.Sci.,1975,

30, 751.
3. Ohno, M.; Morisue, T.; Ozaki, O.; H e k i , H.; Miyauchi, T.

Radiochem. Radioanal. L e t t . , 1976, 27, 299.
4. S t e r n , S.A.; Onorato, F.J.; Libove, C. AIChE J., 1977, 23,

567.
5. Thorman, J.M.; Hwang, S.T. Chem. Eng. Sci., 1978, 33, 15.
6. Pan, C.-Y.; Habgood, H.W. Can. J. Chem. Eng., 1978b, 56,

210.
7. Antonson, C.R.; Gardner, R.J.; King, C.F.; Ko, D.Y.

Ind. Eng. Chem. Process Des. Develop, 1977, 16, 463.
8. Blaidell, C.T.; Kammermeyer, K. AIChE J., 1972, 18, 1015.
9. Pan, C.-Y.; Habgood, H.W. Ind. Eng. Chem. Fundam., 1974, 13

323.
10. S t e r n , S.A.; Mullhaupt, J.T.; G a r e i s , P.J. AIChE J., 1969,

15, 64.
11. S t e r n , S.A.; Fang, S.-M.; Jobbins, R.M. J . Macromol. Sci.-

Phys., 1971, B 5 ( 1 ) , 41.
12. S t e r n , S.A.; Fang,S.-M.; Frisch, H.L.; J. Polymer. Sci.,

1972, Part A-2, 201.
13. Fang,S.-M.; S t e r n , S.A.; F r i s c h , H.L: Chem. Eng.Sci.,1975,

30, 77.

14. Ohno, M.; Morisue, T.; Ozaki, O.; M i y a u c h i , T. J . Nucl. Sci.

Technol., 1978a, 15, 411.
15. Ohno, M.; Morisue, T.; Ozaki, O.; Miyauchi, T. J . N u c l . Sci.

Technol., 1978b, 15, 376.
16. Ohno, M.; Ozaki, O.; S a i t o , H.; Kimura, S.; M i y a u c h i , T.

J . Nucl. Sci. Technol., 1977, 14, 589.
17. S o u r i r a j a n , S.; Agrawal, J.P. "Reverse Osmosis in S y n t h e t i c

Membranes," S. S o u r i r a j a n (Ed.), N a t l . Res. C o u n c i l Can.,
1977, Chapter 26.
18. H i g a s h i , K.; D o i , H.; S a i t o , T.; Energ. N u c l . , 1970, 17, 98.
19. Rainey, R.H.; C a r t e r Blumkin ORNL-4522

Oak Ridge N a t i o n a
20. Yamamoto, I . ; Kanagawa, A.; J. N u c l . Sci. Technol., 1975,

12, 120.
21. H i g a s h i , K.; Miyamoto, Y. J . N u c l . Sci. Technol., 1976, 13,

30.
22. Pan. C.-Y.; Habgood, H.W. Can.J.Chem. Eng., 1978a, 56,

197.
23. Gardner, R.J.; Crane, R.A.; Hannan, J.F. Chem. Eng. Prog.,
1977, 73(10), 76.
24. Knieriem, M. Jr. Hydrocarbon P r o c e s s i n g , 1980, 59(7), 65.
25. Hwang, S.-T.; Kammermeyer, K. "Membranes in Separations,"

W i l e y - I n t e r s c i e n c e , New York, 1975.
26. Meares, P. (Ed.) "Membrane Separation Processes," E l s e v i e r ,

New York, 1976.
27. Thorman, J.M. "Engineering Aspects of C a p i l l a r y Gas Perme-

a t o r s and the Continuous Membrane Column," Ph.D. T h e s i s ,
U n i v e r s i t y of Iowa, Iowa City, Iowa, 1979.
28. Hwang, S.-T.; Thorman, J.M.; AIChE J., 1980, 26, 558.
29. Hwang, S.-T.; Thorman, J.M.; Yuen, K.M. Sep.Sci.Technology,

1980, 15(4), 1069.
30. B e c k e t t , R.; Hurt, J . "Numerical C a l c u l a t i o n s and

A l g o r i t h m s , " McGraw-Hill, New York, 1967.

17
Chemically Resistant Asymmetric Membranes
Made from PVA for the Separation of Organic
Solvents and Phenols from Aqueous Solutions
S. P E T E R and R . S T E F A N
Lehrstuhl für Technische Chemie, Universität Erlangen-Nürnberg,
Egerlandstrasse 3, D-8520 Erlangen, West Germany
The i n c r e a s i n g q u a n t i t i e s o f industrial wastes r e q u i r i n g

treatment are becomin
demands on t h e quality
be discharged o r r e c y c l e d . The effluents r e q u i r i n g purification
f r e q u e n t l y c o n t a i n a wide variety o f compounds w i t h differing
p r o p e r t i e s . G e n e r a l l y t h e c o n c e n t r a t i o n s o f these organic and
i n o r g a n i c p o l l u t a n t s may range between 0 , 5 and 5% by weight,
o f t e n making an expensive treatment o f industrial wastes
necessary. Reverse osmosis could p o s s i b l y become an attractive
a l t e r n a t i v e t o the classical s e p a r a t i o n processes such as
distillation, e x t r a c t i o n , evaporation e t c . , which are c u r r e n t l y
in use. Reverse osmosis may be used t o increase t h e concentra-
tion of t h e compounds present in the wastes so t h a t t h e i r
r e e x t r a c t i o n w i t h the aid o f classical s e p a r a t i o n methods
becomes economical. A l s o it can be used as a step in the
treatment o f wastes before d r a i n off.
The differing p r o p e r t i e s o f t h e compounds present in
industrial e f f l u e n t s r e q u i r e membranes that are s t a b l e a g a i n s t
the s o l v e n t s in q u e s t i o n . Futhermore, the membranes have t o
be sufficiently permeable. Thermal stability and durability
over a wide pH range (1-14) are a l s o r e q u i r e d a s well as a
sufficiently high selectivity w i t h regard t o the compounds t o
be separated. The demand o f general stability against solvents
is met by c r o s s - l i n k e d membranes.
M a t e r i a l used
For t h e i n v e s t i g a t i o n s reported here p o l y v i n y l a l c o h o l

(PVA) and i t s d e r i v a t i v e s such as p o l y v i n y l a c e t a t e , p o l y v i n y l
ether e t c . were used a s the b a s i c polymeric m a t e r i a l s . These
compounds can e a s i l y be converted i n t o polymeric analogues [ l ] .
I t was shown i n an e a r l i e r work [ 2 ] t h a t PVA-membranes w i t h
an asymmetrical s t r u c t u r e can be obtained by phase-inverted
p r e c i p i t a t i o n s i m i l a r t o the method o.f Loeb and S o u r i r a j a n [ 3 ] .
These membranes can a l s o be rendered i n s o l u b l e i n water by
0097-6156/81/0154-0281$05.00/ 0

c r o s s - l i n k i n g [4]*. The f o l l o w i n g substances were mainly used:

PVA w i t h a h y d r o l y s i s grade o f 98% and a m o l e c u l a r weight o f
9.0 000, P o l y v i n y l a c e t a t e w i t h a molecular weight o f 110 000,
p o l y v i n y l b u t y r a t e w i t h a molecular o f 7000 and 12-16% o f f r e e
OH-groups.
Method o f producing the membranes
F i l m s were c a s t from the polymer s o l u t i o n and a f t e r t h a t

immersed i n a p r e c i p i t a t i o n bath. The asymmetric membranes
obtained are s o l u b l e i n water and have t o be made i n s o l u b l e
by c r o s s ^ - l i n k i n g . During the c r o s s - l i n k i n g r e a c t i o n s the
asymmetric s t r u c t u r e produced by the phase-inverted p r e c i p i t a -
t i o n must remain unchanged. T h i s can be performed by t r e a t i n g
the asymmetric membrane i n a f i x i n g bath o f an a c i d i c s a l t
s o l u t i o n . A f t e r t h i s treatment c r o s s - l i n k i n i p o s s i b l b
organic and inorgani
asymmetry.
C r o s s - l i n k i n g renders the membranes i n s o l u b l e i n water;
a d d i t i o n a l l y , the r e t e n t i o n of the organic compounds i s improved.
The best r e s u l t s were obtained f o r the c r o s s - l i n k i n g e i t h e r by
using both organic and i n o r g a n i c reagents together i n one step
or by a p p l y i n g them one a f t e r another. C r o s s - l i n k i n g by means
of metal s a l t s can e q u a l l y w e l l precede o r f o l l o w the t r e a t -
ment w i t h an organic reagent.
P r o p e r t i e s o f the membranes
The i n f l u e n c e o f d i f f e r e n t c r o s s - l i n k i n g reagents on the

p r o p e r t i e s o f the membranes was i n v e s t i g a t e d by reverse osmosis
experiments. A procedure f o r preparing the membranes was
devised t h a t y i e l d e d membranes o f medium r e t e n t i o n o f phenol
a g a i n s t an aqueous phenol s o l u t i o n o f 2 g / l i t r e a t pH 13.
The membranes were always prepared i n e x a c t l y the same way.
Thus the i n f l u e n c e o f the d i f f e r e n t c r o s s - l i n k i n g agents could
be compared b e t t e r than under optimum c o n d i t i o n s o f p r e p a r a t i o n .
A f t e r c r o s s - l i n k i n g by means o f organic compounds, some o f the
membranes were a d d i t i o n a l l y t r e a t e d w i t h a s o l u t i o n c o n t a i n i n g
Cr(III)-salts [5].
The osmotic p r o p e r t i e s of the membranes were t e s t e d a t
room temperature and a pressure d i f f e r e n c e o f 50 bar. Phenol
r e t e n t i o n and product f l u x were measured.
The s t a b i l i t y o f the membranes obtained a g a i n s t v a r i o u s
s o l v e n t s was i n v e s t i g a t e d by immersing the membranes i n the
s o l v e n t concerned a t 40°C f o r about three weeks. A f t e r t h a t
t h e i r mechanical and osmotic p r o p e r t i e s were t e s t e d again and
compared w i t h t h e i r p r o p e r t i e s before t h e treatment. The r e s u l t s
of the experiments are shown i n t a b l e I . The s t a b i l i t y o f the
membranes subjected t o c r o s s - l i n k i n g by an organic reagent i s
very s a t i s f a c t o r y . A d d i t i o n a l treatment w i t h C r ( I I I ) s o l u t i o n s

17. PETER AND STEFAN Chemically Resistant Asymmetric Membranes 283
Table I : Chemical s t a b i l i t y o f PVA-membranes i n o r g a n i c and

i n o r g a n i c solutions- a t 40°C
Membrane; lompo- Membrane
s o l v e n t mixtures type I reactant jsition-f type
I II X In
CH OH-C H OH-H 0 25:25 :50
3 2 5 2
weight%
DMSO- C H OH-H O 60:30 :10
2 5 2
DMSO- C H O H 50:502 5 HCOOH 98-100

DMSO- DMF 75:25 l
60:30:10 CH COOH
DMSO-C H OH-FA 2 5
3
100
DMSO-CH OH-FA 60:30:10
3 NaOH
20
C H OH-H 0
2 5 2 50:50
25:75
75:25
100:1 HNO 3
12
isopropyl S0:b6 100
benzene
alcohol-H o 2 25:75
100
75:25 toluene
100:1 100
xylene
dioxane- EÔ 50:50 phenole 3,5
25:75
c r e s o l (o,m,p) 7
75:25
100:1 pyridine 6
DMSO - H 0 2 50:50 formaldehyde 35
25:75
isobuty-
75:25
100:1 -methy1-ketone 100
DMF H0 2
50:50
25:75 1 = s t a b l e , no change i n
75:25
membrane p r o p e r t i e s
100:1
2 = not s t a b l e
eyelohecanone 50:50
- H 0 2
25:75 3 = d e s t r u c t i o n o f membrane
75:25 Type o f membrane I = PVA,
100:1 c r o s s - l i n k e d by o r g a n i c
formamide 50:50 compounds
- H 0 2
25:75 Type o f membrane I I = PVA,
75:25 c r o s s - l i n k e d by o r g a n i c
100:1 compounds and t r e a t e d w i t h
Cr(III)
CH OH-H 0
3 2 50:50
25:75 + Concentrations r e f e r t o
75:25 aqueous s o l u t i o n s .
100:1

increases the s t a b i l i t y as w e l l as the phenol r e t e n t i o n as i s

shown l a t e r .
In F i g . 1 the phenol r e t e n t i o n of membranes c r o s s - l i n k e d
i n s a t u r a t e d s o l u t i o n s of d i c a r b o x y l i c a c i d s i s represented
as a f u n c t i o n of the number of carbon atoms of the d i c a r b o x y l i c
acid. The s o l u b i l i t y of the d i c a r b o x y l i c a c i d s i n water
i s a l s o represented. As can be seen the a l t e r n a t i n g behavior
f
of homologous s e r i e s w i t h the number of carbon atoms i s

r e f l e c t e d i n the phenol r e t e n t i o n of the c r o s s - l i n k e d membranes.
The r e s u l t s of the i n v e s t i g a t i o n are s p e c i f i e d i n t a b l e I I .
Besides the r e t e n t i o n of phenol, the r e t e n t i o n of Na S was, 2
s i m i l a r l y measured. The t a b u l a t e d v a l u e s are mean v a l u e s f o r

the membranes obtained from about 3 separate t r i a l s . The
r e p r o d u c i b i l i t y of the^ measurements amounts to about 2% f o r the
2
r e t e n t i o n and 0,003 m /(m d) f o r the product f l u x . The a d d i t i o n a l
treatment of the membranes i n C r ( I I I ) s a l t s o l u t i o n s caused a
notable improvement i n
p r a c t i c a l l y unaltered.
The behavior of membranes c r o s s ^ l i n k e d by v a r i o u s ketones
was i n v e s t i g a t e d i n the same way. These membranes possess
e x c e p t i o n a l l y good mechanical p r o p e r t i e s . Moderate values f o r
f l u x and phenol r e t e n t i o n were found (see t a b l e I I I ) . Since
the o b j e c t o n l y was to compare d i f f e r e n t c r o s s - l i n k i n g reagents,
no f u r t h e r attempt was made t o improve the f l u x and the r e t e n -
tion.
Table IV g i v e s the r e t e n t i o n and product f l u x f o r membranes
c r o s s - l i n k e d by d i c a r b o n y l compounds i n presence of v a r i o u s
aqueous s o l u t i o n s of phenol, sodium s u l f i d e , p y r i d i n e and
ammonia. The strong c o n c e n t r a t i o n dependence of the r e t e n t i o n
i n the presence of phenol and the dependence of the f l u x on the
s o l u t e i s i n t e r e s t i n g . Membranes w i t h 95% r e t e n t i o n f o r phenol
3 2
a t f l u x e s of about 0.100 m /(m d) can be e a s i l y obtained.
In biotechnology, the products concerned are removed from
aqueous s o l u t i o n by e x t r a c t i o n w i t h methylacetate, b u t y l a c e t a t e ,
i s o b u t y l methyl ketone e t c . The remaining aqueous substrate i s
s a t u r a t e d w i t h the e x t r a c t i o n s o l v e n t s . Sometimes t h i s causes
problems w i t h regard t o environmental r e g u l a t i o n s . Table V
shows t h a t the s o l v e n t s can be remored almost e n t i r e l y by
reverse osmosis. The concentrate c o n s i s t s of two phases,
namely, the s o l v e n t saturated w i t h water and the water
s a t u r a t e d w i t h s o l v e n t . These can be separated by means of a
s e t t l e r . The water phase i s r e c i r c u l a t e d to the reverse osmosis.
The s a t u r a t e d s o l u b i l i t y i n Water a t room temperature i s
19 000 m g / l i t r e f o r i s o b u t y l methyl ketone, 3300 m g / l i t r e f o r
b u t y l acetate and 9 500 m g / l i t r e f o r methyl acetate. As the
r e s u l t s i n t a b l e V show, the r e t e n t i o n f o r isobutyl-methyl
ketone increases w i t h i n c r e a s i n g c o n c e n t r a t i o n . T h i s r e s u l t i s
remarkable, as g e n e r a l l y a decrease i n r e t e n t i o n i s observed
with increasing concentration.

PETER AND STEFAN Chemically Resistant Asymmetric Membranes 285
Figure 1. Concentration of carboxylic acid and retention of the PVA membrane:

( ) concentration of acid in the cross-linking solution; ( ) retention on 0.2
wt %, phenol, pH =13.

to
oo
ON
Table I I : PVA-Membranes C r o s s - l i n k e d by D i c a r b o x y l i c Acids and C r ( I I I ) s o l u t i o n
3
r 1
Number o f Retention [%] Product F l u x m
C-atoms i n .m d_
molecule A c i d MW Cr (III) phenole ammonia phenole ammonia
2000 [5H] 2400 [5H; 2000 2400
2 Oxalic Acid 90.04 - 58 0.070
+ 65 0.066
3 Malonic A c i d 104.06 - 25 0.120
+ 38 0.250
4 Succinic Acid 118,OO - 66 0.078
+ 74 0.060
5 Glutaric Acid 132,11 - 45 0.105
+ 69 10 0.075 0. 119
6 Adipic Acid 146,14 - 58 0.090
+ 65 0.080
7 Pimelic Acid 160,17 - 58 0.105
+ 66 0.080
8 Suberic Acid 174,19 - 63 0.100

+ 69 20 0.075 0. 200
9 Azelaic Acid 188,22 - 40 0.130
+ 46 25 0.105 0. 220
10 Sebacic A c i d 207,25 - 64 0.080
+

70 IO 0.075 0. 300
Ap = 50 bar T 25°C
in
W
Table I I I : PVA membranes c r o s s - l i n k e d by ketones
phenole content o f feec

C-atoms mole f r a c t i o n o f
L J
K E T O N E in MW ketone i n the 20CO 1 pH 13
molecule cross-linking
L
solution R [%] PR 2j
m d
acetophenone 8 120.14 0.138 59 100

propiophenone 9 134.17 0.124 69 185
benzylmethylketone 9 134.17 0.124 46 100
butyrophenone 10 148.20 0.112 73 100
acetone 3 58.08 0.286 60 26

ethylmethylketone 4 72.10 0.230 68 80
iso-butylmethylketone 6 lOO.16 0.166 63 96
eyelohexanone 6 98.14 0.169 59 420

dimethylcyclohexanone 8 126.20 0.132 66 74
diacetyl 4 86.09 0.193 69 32

benzil 14 210.22 0.079 63 62

acetylacetone 5 100.11 0.166 61 268
benzoylacetone 10 162.18 0.102 56 m
Ap = 50 bar T = 25°C
to
oo
00
Table IV: membranes c r o s s - l i n k e d by d i c a r b o n y l compounds
u
Dicarbonyl o
m R E T E N T I O N [%] P R O D U C T F L U X [-y-]
compound
i n the cross- CD
l i n k i n g so- > phenole a pH 13 Na S

2 P y r i - NH
3
phenole a t pH 13 Na S
2 P y r i - NH
3
i—i
lution o o dine dine
w ft 485 2000 30000 400 13000 2400 485 2000 30000 400 130CO 2400
H0 2
66 26 17 70 85 40
glyoxal PVA DMS0,H Q 2
70 96 30 8 60 90 120 140
CH OH H 03 f 2
62 78 24 14 80 95 100 90
H0 2
97 95 66 96 53 28 70 150 75 80 70 80
glutar- PVA DMSO,H 0 2 99 97 57 93 56 30 85 90 82 82 65 90
dialdehyde CH OH,H 0 99
3 2 99 81 50 30 60 70 97 90 110
PVB C H OH,DMI
2 5 55 140
PVAC CH OH, 3 33 300
CH COCH 3 3

H 63 38 36 10 55 80 100 320
2°
adipic- PVA DMSO,H 0 2 65 50 32 80 70 140
aldehyde CH OH,H 03 2 80 63 35 60 65 125

Ap = 50 bar T = 25°C cone, [^-j
17. PETER AND STEFAN Chemically Resistant Asymmetric Membranes 289
Table V Separating performance bf PVA c r o s s - l i n k e d membranes

for certain solvents
ISOBUTYL METHYL KETONE N-BUTYL- METHYLACETATE DMSO

ACETATE
19 OOO SSL 9 OOO SSL 3 300 53. 9 500 *5. 6 4oo sa 40 OOO ^ \
R PR R PR R PR R PR R PR R PR
70 90 35 120 75 80 35 IOO 45 105 60 200
Ap = 50 bar t = 25°C R [%] PR [ — ^ — 1

md
Table VI g i v e s the r e t e n t i o n and product f l u x of a PVA cross-

l i n k e d membrane f o r the organic and i n o r g a n i c compounds i n
e f f l u e n t from a coking p l a n t .
Several membranes w i t h good v a l u e s f o r the r e t e n t i o n o f
organic and i n o r g a n i c compounds were i n v e s t i g a t e d by reverse
osmosis experiments w i t h the e f f l u e n t s from the manufacture
of organic intermediate products. The composition o f the
e f f l u e n t s were complex w i t h a n a l y s i s a s f o l l o w s :
Type B pH = 9 TOC 14 OOO [mg/1]

COR 40 800
BOD^ 1 900
i o n concentration D 51 000
Type C pH = 8 TOC 14 600
COR 40 400
BOD,, 6 OOO
ion concentration 67 725
The t e s t s were c a r r i e d out under the f o l l o w i n g c o n d i t i o n s :

a) a t room temperature and 50 bar and 85 bar r e s p e c t i v e l y
b) a t 42°C and 50 bar.
Each t e s t l a s t e d a week. I n a l l cases no change i n the r e t e n t i o n
or f l u x was observed during the experiment. The f o l l o w i n g
r e t e n t i o n values were obtained a t a product f l u x o f about
2
20 l i t r e / ( m d ) and were found t o be independent o f the pH
value o f waste:
phenolic compounds 60-90%

TOC 60-70%
2
SO " 76-82%

to
O
Table V I : Retention and product f l u x w i t h regard t o organic and i n o r g a n i c compounds

of c r o s s - l i n k e d PVA-membranes i n waste water from a coke p l a n t
F e e d c o k e r y w a s t e w a t er
m
RET E N T I 0N [%] R m PR [ 2 ]
PRODUCT
md
Type o f phenolic sulphide ammonia ammonia i n
+ FLUX +
OH-groups free ammonia p h e n o l i c OH-groups
3
membrane salts
isooo [SSL] 12000 [SSL] 5000 [SSL] [ ™ ] 4500 [3&]
65000 [SSL]
I 67 14 54 24 0.048 77 0.292
II i 58 14 62 21 0.043 72 0.415
III 66 17 56 26 0.450 69 0.860

IV 57 10 62 15 0.080 59 0.432
V 18 0.961 35 6.262

+ p h e n o l i c OH-groups i n phenol e q u i v a l e n t s
Ap = 50 bar T = 25°C
17. P E T E R AND STEFAN Chemically Resistant Asymmetric Membranes 291
A f t e r the i n v e s t i g a t i o n i n t o the h a n d l i n g and the a c t i o n

of the most important reagents has been completed, f u r t h e r
r e s e a r c h can be done t o improve those methods t h a t are most
promising. I n i t i a l t r i a l s have r e s u l t e d i n membranes g i v i n g
a f l u x o f 1 m /(m d) and a phenol r e t e n t i o n o f 70% f o r a
3
phenol c o n c e n t r a t i o n o f 2 g / l i t r e a t pH = 1 3 . Membranes c r o s s -
l i n k e d by d i c a r b o n y l compounds have been found t o possess h i g h
thermal s t a b i l i t y ; r e t e n t i o n and product f l u x remained u n a l t e r e d
a f t e r one week o f t e s t i n g i n an phenol s o l u t i o n o f 2 g / l i t r e
a t 50°C. I t i s worth remarking w i t h regard t o the treatment
of e f f l u e n t s discharged a t h i g h temperature, t h a t the thermal
s t a b i l i t y o f these membranes makes heat r e c y c l i n g by means o f
reverse osmosis a p o s s i b i l i t y .
T h i s work was supported by the M i n i s t e r i u m f u e r Forschung
und Technologie (BMFT) o f the German F e d e r a l Government.
Abstract:
Asymmetrical membranes were initially produced from

p o l y v i n y l a l c o h o l s o f suitable m o l e c u l a r weight u s i n g phase
-inverted precipitation. They were then t r e a t e d w i t h a c i d s o l u -
t i o n s o f sodium formate and sodium a c e t a t e . The asymmetrical
s t r u c t u r e was stabilised as a result o f the slight cross
linking of the polymers produced. A cross-linked membrane so
prepared can then be made i n s o l u b l e in water and permanent
in the presence o f s o l v e n t s by f u r t h e r c r o s s - l i n k i n g . T h i s was
e f f e c t e d by treatment w i t h v a r i o u s compounds c o n t a i n i n g one
or two aldehyde groups o r w i t h one or more c a r b o x y l groups
(saturated and unsaturated d i c a r b o x y l i c and tricarboxylic
a c i d s ) ; in this wayiswas p o s s i b l e t o m a i n t a i n the primary
asymmetry completely. The chemical activity, c h a i n l e n g t h and
c h a i n s t r u c t u r e o f the individual compounds used r e s u l t e d
in different degrees of c r o s s - l i n k i n g o f the polyvinyl a l c o h o l s
in the membran. The c r o s s - l i n k e d membranes produced have good
chemical, mechanical and thermal durability in an pH - range
of 1 - 1 4 . The membranes have been t e s t e d in reverse-osmosis
experiments in aqueons s o l u t i o n s o f phenols, methyl i s o b u t y l
ketone, a c e t i c a c i d e s t e r s e t c . The r e t e n t i o n and p e r m e a b i l i l y
p r o p e r t i e s in the presence o f the above-mentioned s o l v e n t s
are r e p o r t e d .
Literature Cited
1) F. K a i n e r , P o l y v i n y l a l k o h o l e , Ferdinand Enke V e r l a g
Stuttgart (1949)
2) S.Peter, N. Hese, R. S t e f a n , D e s a l i n a t i o n , 1 9 (1976)
1 6 1 - 1 6 7 ; S. P e t e r , R. S t e f a n , Proc. 6 th I n t . Symp.
Fresh Water from the Sea, V o l . 3 (1978) 2 3 9 - 2 4 6 ;
3) S. Loeb, S. S o u r i r a j a n , Advanced Chem. S e r i e s 38 (1962) 1 1 7 .
4) DOS 2441 311 ( 1 9 7 4 ) ; DOS 27 30 528 (1977)
5) N. Hese, T h e s i s (1976) Erlangen

18
Solute Preferential Sorption in Reverse Osmosis
1 1
J. M . D I C K S O N and D O U G L A S R. LLOYD
Department of Chemical Engineering, Virginia Polytechnic Institute and
State University, Blacksburg, VA 24061
Since the e a r l y days of research in reverse osmosis (RO), it

has been recognized t h a t , in comparison to the s e p a r a t i o n of salt
solutions, certain solute exhibi behavior
A typical example is th
phenol s o l u t i o n s when u s i n g c e l l u l o s e acetate membranes; i . e . , the
permeate stream is more concentrated in phenol than is the feed
stream. This anomalous behavior can be accounted f o r by p o s t u l a t i n g
that s o l u t e s such as phenol are preferentially a t t r a c t e d t o or
preferentially sorbed by the c e l l u l o s e acetate membrane m a t e r i a l .
I t is t o t h i s t o p i c of s o l u t e preferential s o r p t i o n in reverse
osmosis that t h i s paper is dedicated. Specifically, this discussion
will i n v o l v e a d e s c r i p t i o n of s o l u t e preferential s o r p t i o n , an
overview of the literature i n the area, and finally a p r e s e n t a t i o n
of some recent work on the removal of aromatic hydrocarbons from
water. The s i g n i f i c a n c e of t h i s work is a t l e a s t two-fold. From
a practical p o i n t of view the c l a s s e s of s o l u t e s which demonstrate
preferential attraction to the membrane m a t e r i a l tend to be organic
compounds and the removal and recovery of these s o l u t e s from water
is environmentally and economically important. From a t h e o r e t i c a l
p o i n t of view an understanding of the phenomena i n v o l v e d is
e s s e n t i a l t o the achievement of a fundamental d e s c r i p t i o n of the
RO process. Although t h i s paper deals s o l e l y w i t h aqueous
s o l u t i o n s and c e l l u l o s e acetate membranes, it is important t o
recognize that the concepts discussed can be extended to i n c l u d e
other membrane m a t e r i a l s and non-aqueous systems.
Solute P r e f e r e n t i a l S o r p t i o n
At t h i s p o i n t , i t i s important t o d e s c r i b e e x a c t l y what i s
meant by s o l u t e p r e f e r e n t i a l s o r p t i o n and the consequences that
r e s u l t from t h i s s i t u a t i o n . Consider f i r s t the c l a s s i c a l case of
the s e p a r a t i o n of aqueous NaCl s o l u t i o n s by c e l l u l o s e acetate
membranes. I n t h i s instance the membrane m a t e r i a l has a stronger
a f f i n i t y f o r the s o l v e n t than i t has f o r the s o l u t e . The r e s u l t
1
Current address: Department of Chemical Engineering, University of Texas, Austin,
TX 78712.
0097-6156/81/0154-0293$05.50/0

i s the e x i s t e n c e of e s s e n t i a l l y pure water on the surface of and

w i t h i n the membrane. This water i s subsequently transported
through the membrane i n the RO process. While t h i s d e s c r i p t i o n
holds t r u e f o r a number of s o l u t e s ( i n p a r t i c u l a r i o n i z e d s o l u t e s ) ,
there are c e r t a i n s o l u t e s which e x h i b i t anomalous behavior. I n
such cases the membrane m a t e r i a l has a stronger a f f i n i t y f o r the
s o l u t e than f o r the s o l v e n t . The r e s u l t may be p i c t u r e d as the
establishment of a sorbed l a y e r of s o l u t e which may subsequently
be transported through the membrane. The consequence of the
s o l u t e being p r e f e r e n t i a l l y sorbed i s that the observed performance
behavior i s d i f f e r e n t than i n the case of water p r e f e r e n t i a l
s o r p t i o n . The main d i f f e r e n c e s i n performance can be summarized
as f o l l o w s :
For the case of water p r e f e r e n t i a l s o r p t i o n -
i ) i n c r e a s i n g the operating pressure u s u a l l y increases
separation
i i ) the decrease i
i s due to the osmotic pressure of the s o l u t i o n
i i i ) s e p a r a t i o n i s always p o s i t i v e
i v ) s e p a r a t i o n increases w i t h decreasing pore s i z e on the
membrane s u r f a c e .
However, f o r the case of s o l u t e p r e f e r e n t i a l s o r p t i o n -
i ) i n c r e a s i n g the operating pressure u s u a l l y decreases
separation
i i ) the permeate f l u x i s l e s s than the pure water f l u x , even
when the osmotic pressure e f f e c t s are n e g l i g i b l e
i i i ) s e p a r a t i o n may be p o s i t i v e , zero, or negative depending
on the s o l u t e and the s p e c i f i c operating c o n d i t i o n s
i v ) s e p a r a t i o n may e x h i b i t a maximum, a minimum, or both w i t h
decreasing pore s i z e on the membrane s u r f a c e .
The l i s t of s o l u t e s that are known to be p r e f e r e n t i a l l y sorbed
by c e l l u l o s e acetate membranes i n c l u d e s many a l c o h o l s , phenols,
un-ionized c a r b o x y l i c a c i d s and hydrocarbons ( 1 ) . Although s o l u t e
p r e f e r e n t i a l s o r p t i o n i s a common occurrence w i t h a number of
important aqueous organic systems l i t t l e experimental or
q u a n t i t a t i v e work has appeared i n the l i t e r a t u r e . The purpose
of the current work i s to r e c t i f y t h i s s i t u a t i o n .
L i t e r a t u r e Review
A number of models have been developed over the years to

d e s c r i b e reverse osmosis. These models i n c l u d e the s o l u t i o n -
d i f f u s i o n model, the f i n e l y porous model, and the p r e f e r e n t i a l
s o r p t i o n - c a p i l l a r y flow model. I n each case, the model was
o r i g i n a l l y developed based on the s e p a r a t i o n of aqueous,salt
s o l u t i o n s . The a p p l i c a t i o n of each of these models to systems
which e x h i b i t anomalous behavior w i l l be discussed i n t h i s s e c t i o n .
S o l u t i o n - D i f f u s i o n Model (2). I n t h i s model, the s o l u t e and

solvent are transported through the membrane by f i r s t d i s s o l v i n g

18. DICKSON AND LLOYD Solute Preferential Sorption 295
i n the homogeneous s k i n l a y e r and then d i f f u s i n g through i t . Thus,

p e r m e a b i l i t y i s the product of the s o l u b i l i t y and the d i f f u s i v i t y
of the compound i n the membrane m a t e r i a l . The o r i g i n a l attempts
to apply t h i s model to the phenol-water system were made by
Lonsdale et a l . ( 3 ) . Phenol was found t o be r e a d i l y s o l u b l e i n
the c e l l u l o s e a c e t a t e membrane and the d i f f u s i v i t y of phenol i n
c e l l u l o s e a c e t a t e was approximately the same as that of water.
The r e s u l t was negative s e p a r a t i o n i n RO a p p l i c a t i o n . The
s o l u t i o n - d i f f u s i o n model i n i t s e x i s t i n g form proved to be
i n s u f f i c i e n t to q u a n t i t a t i v e l y d e s c r i b e the negative s e p a r a t i o n .
Therefore, the authors suggested the development of a coupled
f l o w model ( i . e . the s o l u t e f l u x i s coupled to the water f l u x ) .
Subsequent attempts to develop such a model met w i t h o n l y moderate
success (*\_). Anderson e t a l . (5) conducted s t u d i e s that
p a r a l l e l e d the work of Lonsdale. The emphasis was placed on
s e p a r a t e l y measuring e q u i l i b r i u s o r p t i o d diffusio
c o e f f i c i e n t s f o r the s o l u t
a t t r i b u t e d the negativ s e p a r a t i o g
the phenol and the c e l l u l o s e a c e t a t e membrane m a t e r i a l . Pusch
e t a l . (6) a l s o studied the s e p a r a t i o n of phenol and water.
D i a l y s i s and s o r p t i o n experiments were performed, and the r e s u l t s
were c o n s i s t e n t w i t h the n e g a t i v e s e p a r a t i o n observed i n RO. The
decrease i n water f l u x i n the presence of phenol was a t t r i b u t e d
to the decrease i n membrane water content under these c o n d i t i o n s .
F i n e l y Porous Model. I n t h i s model, s o l u t e and s o l v e n t

permeate the membrane v i a pores which connect the h i g h pressure
and low pressure faces of the membrane. The f i n e l y porous model,
which combines a v i s c o u s f l o w model and a f r i c t i o n model (7,8),
has been developed i n d e t a i l and a p p l i e d to RO data by Jonsson
(9-12). The most recent work of Jonsson (12) t r e a t e d s e v e r a l
organic s o l u t e s i n c l u d i n g phenol and o c t a n o l , both of which
e x h i b i t s o l u t e p r e f e r e n t i a l s o r p t i o n . I n h i s paper, Jonsson
compared s e v e r a l models i n c l u d i n g that developed by S p i e g l e r and
Kedem (13) (which i s e s s e n t i a l l y an i r r e v e r s i b l e thermodynamics
treatment), the f i n e l y porous model, the s o l u t i o n - d i f f u s i o n
i m p e r f e c t i o n model (14), and a model developed by Pusch (15).
Jonsson i l l u s t r a t e d that the f i n e l y porous model i s s i m i l a r i n form
to the Spiegler-Kedem r e l a t i o n s h i p . Both models f i t the data
e q u a l l y w e l l , although not w i t h t o t a l accuracy. The Pusch
model has a s i m i l a r form and proves to be l e s s a c c u r a t e , w h i l e
the s o l u t i o n - d i f f u s i o n i m p e r f e c t i o n model i s even l e s s a c c u r a t e .
In a l l models, the l a r g e s t discrepancy between the p r e d i c t e d
performance and the experimental data occurred when negative
s e p a r a t i o n was observed. Jonsson concluded that the f i n e l y porous
model i s p r e f e r r e d over the a l t e r n a t i v e s , although the Pusch
r e l a t i o n s h i p i s e a s i e r to use and y i e l d s reasonable r e s u l t s i n most
cases.
P r e f e r e n t i a l S o r p t i o n - C a p i l l a r y Flow Model. An a l t e r n a t i v e
approach to those mentioned above has been presented by

S o u r i r a j a n (16) and i s i l l u s t r a t e d s c h e m a t i c a l l y i n Figure 1. I n

t h i s approach the c e l l u l o s e acetate membranes are considered t o be
porous. Separation i s j o i n t l y governed by the p r e f e r e n t i a l
s o r p t i o n of one of the c o n s t i t u e n t s of the s o l u t i o n a t the
membrane-solution i n t e r f a c e , and the number, s i z e , and s i z e
d i s t r i b u t i o n of the pores on the membrane s u r f a c e . I n the case
of s a l t s o l u t i o n s , water i s p r e f e r e n t i a l l y sorbed. This means
that a sharp c o n c e n t r a t i o n gradient e x i s t s i n the v i c i n i t y of the
membrane m a t e r i a l , l e a d i n g to a l a y e r of almost pure water on the
surface of the membrane. Applying pressure allows t h i s pure water
to be c o n t i n u o u s l y withdrawn through the membrane pores. Smaller
pore s i z e leads t o higher s e p a r a t i o n . This s i t u a t i o n of water
p r e f e r e n t i a l s o r p t i o n i s a p p l i c a b l e t o most s a l t s o l u t i o n s and
many organic s o l u t e s . The t r a n s p o r t of these s o l u t i o n s i s
q u a n t i t a t i v e l y described by the Kimura-Sourirajan a n a l y s i s (16,17).
With t h i s model, i t i s p o s s i b l t p r e d i c t s o l u t s e p a r a t i o d
f l u x f o r many systems whic
(17,18).
However, some s o l u t e s e x h i b i t a strong a t t r a c t i o n t o the
membrane m a t e r i a l and are t h e r e f o r e p r e f e r e n t i a l l y sorbed compared
to the s o l v e n t water. This can lead t o p o s i t i v e , zero, or negative
s e p a r a t i o n depending on both the magnitude of the a t t r a c t i v e
f o r c e s and the m o b i l i t y of the s o l u t e a t the solution-membrane
i n t e r f a c e ( r e l a t i v e to the m o b i l i t y of water i n t h i s r e g i o n ) . Both
the p o l a r and nonpolar character of the s o l u t e may be important
i n the s e p a r a t i o n process. Consider the case of a p o l a r s o l u t e .
Since the c e l l u l o s e acetate membrane m a t e r i a l has a net proton
acceptor nature ( 1 ) , any p o l a r compound i s a t t r a c t e d t o the
membrane s u r f a c e . The more p o l a r the compound the stronger the
a t t r a c t i o n . When the s o l u t e i s more p o l a r than the s o l v e n t , as i s
the case i n phenol-water systems, the s o l u t e i s p r e f e r e n t i a l l y
sorbed by the membrane. [Note: the p o l a r nature of a compound can
be c o n v e n i e n t l y and q u a n t i t a t i v e l y expressed by the T a f t number
(1,19).] Since the s o l u t e and the s o l v e n t are both p o l a r , a
strong i n t e r a c t i o n e x i s t s between the two s o l u t i o n components.
This i n t e r a c t i o n allows the s o l u t e t o be r e l a t i v e l y mobile i n the
v i c i n i t y of the pore, and thus i t can be c a r r i e d through the pore
w i t h the water, r e s u l t i n g i n negative s e p a r a t i o n .
On the other hand, f o r a hydrocarbon s o l u t e such as benzene,
the nonpolar f o r c e s predominate. The c e l l u l o s e acetate membrane
m a t e r i a l has a nonpolar character due t o i t s carbon backbone.
This nonpolar character r e s u l t s i n the a t t r a c t i o n of nonpolar
s o l u t e s . Since the s o l u t e has l i t t l e p o l a r c h a r a c t e r , i t i s more
s t r o n g l y immobilized on the membrane s u r f a c e than i s water. Thus,
the s o l v e n t passes through the membrane r e l a t i v e l y f a s t and
p o s i t i v e s e p a r a t i o n i s observed. The s t r e n g t h of t h i s nonpolar
a t t r a c t i o n , q u a n t i t a t i v e l y represented by the modified Small's
number CI,20), w i l l , i n p a r t , determine the extent of s e p a r a t i o n .
The presence of p r e f e r e n t i a l l y sorbed s o l u t e on the membrane
surface w i l l block or impede the flow of the s o l v e n t water. This

18. DICKSON A N D LLOYD Solute Preferential Sorption 297
pore b l o c k i n g e f f e c t r e s u l t s i n the permeate f l u x f o r feed

s o l u t i o n s , even d i l u t e s o l u t i o n s of n e g l i g i b l e osmotic p r e s s u r e ,
being l e s s than the f l u x observed f o r a pure water feed under
s i m i l a r o p e r a t i n g c o n d i t i o n s ; i . e . , permeate f l u x (PF) i s l e s s
than pure water f l u x (PWF) .
The advantage of the p r e f e r e n t i a l s o r p t i o n - c a p i l l a r y flow
approach to r e v e r s e osmosis l i e s i n i t s emphasis on the mechanism
of s e p a r a t i o n at a molecular l e v e l . This knowledge i s u s e f u l when
i t becomes necessary to p r e d i c t membrane performance f o r unknown
systems. A l s o , the approach i s not r e s t r i c t e d to the s o - c a l l e d
" p e r f e c t " , d e f e c t - f r e e membranes, but encompasses the whole range
of membrane pore s i z e . U n t i l r e c e n t l y , the a p p l i c a t i o n of a
q u a n t i t a t i v e model to the case of s o l u t e p r e f e r e n t i a l s o r p t i o n
has been m i s s i n g . Attempts to change t h i s s i t u a t i o n have been
made by Matsuura and S o u r i r a j a n (21) by using a m o d i f i e d f i n e l y
porous model. In a d d i t i o thi
(9-12), a Lennard-Jones
to d e s c r i b e the membrane-solute i n t e r a c t i o n . This model i s
discussed elsewhere i n t h i s book.
Separation of Aromatic Hydrocarbons
In t h i s paper, the removal of two aromatic hydrocarbons,

benzene and toluene, from water i s i n v e s t i g a t e d . Toluene can be
shown to be more nonpolar than benzene by comparing the m o d i f i e d
Small's numbers (1,), which are 549 and 425 ( c a l cm )^/mol
for toluene and benzene, r e s p e c t i v e l y . The greater nonpolar
character of toluene ( i n d i c a t e d by the l a r g e r m o d i f i e d Small's
number) suggests t h a t , i n comparison to benzene, toluene w i l l be
more s t r o n g l y a t t r a c t e d to the membrane, and t h e r e f o r e w i l l e x h i b i t
lower m o b i l i t y . The r e s u l t i s that under i d e n t i c a l o p e r a t i n g
c o n d i t i o n s the s e p a r a t i o n of toluene from water should be greater
than the s e p a r a t i o n of benzene from water. The v a l i d i t y of t h i s
assumption i s checked i n the present study. I n a p r e v i o u s study
of these s o l u t e s , data was reported f o r a s i n g l e feed c o n c e n t r a t i o n
(22). The e f f e c t of feed c o n c e n t r a t i o n on membrane performance
i s examined i n t h i s work.
The q u a n t i t a t i v e treatment of the data generated i n the present
study w i l l i n i t i a l l y be based on a set of equations r e c e n t l y
reported (23). These equations, which have proven to be adequate
for d i l u t e p-chlorophenol-water systems, are as f o l l o w s :
(1)
PWF
N A = K 2 X A 2 P (2)
X
A2 = X
A3 +
< A1 X _ X
A3> e x pF
P ( / P>k (3)

(4)
ref AB AB,ref
The nomenclature i s d e f i n e d i n the Legend of Symbols s e c t i o n
a t the c o n c l u s i o n of t h i s paper and i s i l l u s t r a t e d i n F i g u r e 1.
Equation 1 i s an e m p i r i c a l r e l a t i o n which d e s c r i b e s the extent
of pore b l o c k i n g , expressed by the pore b l o c k i n g f a c t o r 1-(PF/PWF).
In the case of the RO s e p a r a t i o n of a d i l u t e s o l u t e - c o n t a i n i n g feed
stream i n which there i s no pore b l o c k i n g by the s o l u t e , the f l u x
of the permeating stream i s equal to the f l u x obtained f o r a s i m i l a r
experiment i n which the feed stream i s pure water ( i . e . , permeate
f l u x (PF) equals pure water f l u x (PWF)). In t h i s case, the f l u x
r a t i o PF/PWF i s u n i t y and the pore b l o c k i n g f a c t o r 1-(PF/PWF) i s
zero. Conversely, when the pores are completely blocked PF i s
zero, and thus, the pore b l o c k i n g f a c t o r i s u n i t y . Equation 1
i n d i c a t e s t h a t the pore b l o c k i n f a c t o i p r o p o r t i o n a l t th
c o n c e n t r a t i o n of the boundar
This r e l a t i o n s h i p w i l l b Equatio
e m p i r i c a l r e l a t i o n which r e l a t e s s o l u t e f l u x (NA) to both X^2
(again r a i s e d to a power of n j ) and the o p e r a t i n g pressure
( r a i s e d to a power of n2). The exponents rii and n2,as w e l l as the
proportionality factors and K 2 , are f u n c t i o n s of pore s i z e and
the nature of the s o l u t e . Equation 3, which a l l o w s the
c a l c u l a t i o n of X ^ from experimental data, i s based on a simple
" f i l m " theory f o r mass t r a n s f e r and i s d e r i v e d elsewhere (17,23).
Equation 4 a l l o w s the mass t r a n s f e r c o e f f i c i e n t on the feed
s i d e , k, to be c a l c u l a t e d f o r any s o l u t e based on the value
obtained f o r a r e f e r e n c e s o l u t e ( u s u a l l y sodium c h l o r i d e ) i n the
same t e s t c e l l . The p o s s i b i l i t y of u s i n g equations of t h i s form
f o r aromatic hydrocarbon s o l u t i o n s w i l l be examined i n t h i s paper.
Experimental
The c e l l u l o s e a c e t a t e membranes used were batch 316(0/25) -

type membranes (24) made by the general Loeb-Sourirajan technique
(25). The s i x f l a t c a s t membranes were shrunk at d i f f e r e n t
temperatures (from 68 to 85°C) p r i o r to l o a d i n g the membranes i n t o
the r e v e r s e osmosis t e s t c e l l s . This treatment a d j u s t s the average
surface pore s i z e of each membrane so t h a t a range of p o r o s i t i e s
could be s t u d i e d . A p r e p r e s s u r i z a t i o n at a pressure of 11 720 kPa
f o r 2 hours was used to s t a b i l i z e the membranes f o r subsequent
use a t pressures of 6900 kPa or lower. ( A l l pressures l i s t e d are
gauge pressure.)
The general experimental procedure was s i m i l a r to that r e p o r t e d
i n the l i t e r a t u r e (25). The s i x flow type reverse osmosis c e l l s
were connected i n s e r i e s and were c o n s t r u c t e d i n a design s i m i l a r
to that r e p o r t e d by S o u r i r a j a n (25). The c e l l s were placed i n a
constant temperature box and the system was c o n t r o l l e d to
25 ± 1°C. The feed f l o w r a t e was maintained constant at 400

ml/min. For each experiment, the pure water f l u x (PWF) and the
permeate f l u x (PF) were measured. I n a d d i t i o n , the s o l u t e
c o n c e n t r a t i o n was determined i n the feed and permeate s o l u t i o n s and
the s e p a r a t i o n , f , was c a l c u l a t e d as
m
f =T " 3 m
m
(5)
l
where m^ and 1113 are the feed and permeate m o l a l i t i e s r e s p e c t i v e l y .
For d i l u t e s o l u t i o n s t h i s can be approximated as
^ _ ppml - ppm3 (6)
ppml
where ppml and ppm3 are the feed and permeate c o n c e n t r a t i o n s
expressed i n p a r t s per m i l l i o n . The s o l u t e c o n c e n t r a t i o n s f o r
benzene and toluene samples were analyzed u s i n g an Oceanography
I n t e r n a t i o n a l C o r p o r a t i o n T o t a l Carbon A n a l y z e r The sodium
c h l o r i d e s o l u t i o n s wer
C o n t r o l D i f f e r e n t i a l Refractomete y
Meter. The water used was d e i o n i z e d and d i s t i l l e d and a l l other
chemicals were a n a l y t i c a l reagent grade.
R e s u l t s and D i s c u s s i o n s
Membrane C h a r a c t e r i z a t i o n . The s i x c e l l u l o s e a c e t a t e membranes

were c h a r a c t e r i z e d according t o the sodium c h l o r i d e performance
data. These data are presented i n Table I . A c t u a l experiments
were repeated a t r e g u l a r i n t e r v a l s i n order t o monitor the membrane
changeând the i l l u s t r a t e d data represent the average of nine
t e s t s . Since the s o l u t e t r a n s p o r t parameter D^M/KS f o r sodium
c h l o r i d e , and hence l n C*N Cl> remained e s s e n t i a l l y constant over
a
the experimental time p e r i o d i t can be assumed that the membrane

pore s i z e remained constant. The q u a n t i t y l n C* -^ i s r e p r e s e n t a t i v e
NaC
of the average pore s i z e on the membrane s u r f a c e and i s independent

of the s o l u t e under c o n s i d e r a t i o n (26). B r i e f l y , a decrease i n
the v a l u e o f l n C*NaCl i n d i c a t e s a decrease i n the average pore
s i z e . The v a l u e s of l n C * N c i f o r the membranes t e s t e d cover a
a
wide range of s u r f a c e pore s i z e , thereby maximizing experimental

design. The pure water p e r m e a b i l i t y constant A tended t o decrease
over the p e r i o d of s e v e r a l experiments; t h i s decrease was a t t r i b u t e d
to membrane compaction. This change i n A v a r i e d from a 10%
decrease f o r the membranes of l a r g e s t pore s i z e t o a 5% decrease
f o r the membranes of s m a l l e s t pore s i z e . The r a t e o f compaction
f o r these hydrocarbon s t u d i e s was s l i g h t l y h i g h e r than would
normally be observed f o r s a l t s o l u t i o n experiments. This
a c c e l e r a t e d decrease i n A may be the r e s u l t of the d e t r i m e n t a l
e f f e c t that h i g h i n t e r f a c i a l c o n c e n t r a t i o n of organics have on the
c e l l u l o s e a c e t a t e . The average s e p a r a t i o n and the permeate f l u x
f o r aqueous NaCl s o l u t i o n s measured under the i n d i c a t e d c o n d i t i o n s
are a l s o l i s t e d i n Table I .

TABLE I
a
C h a r a c t e r i z a t i o n and Performance of the C e l l u l o s e Acetate Membranes
F i l m Number
1 2 3 4 5 6
Pure water p e r m e a b i l i t y constant, A,

2 4
(mol H 0)/(m s k P a ) , x l O
2 0.7051 0.8547 1.268 1.868 2.331 2.487
S o l u t e t r a n s p o r t parameter,
(D /K6 m / s X l 0 ? 0.6914 1.342 2.846 8.653 29.69 66.15
AM >NaCl> >
l n C -13.25 -12.59 -11.84 -10.73 -9.49 -8.69
*NaCl
Mass t r a n s f e r c o e f f i c i e n t , k,
6
m/s, x l O 28.3 38.2 38.5 44.0 47.0 29.3
Solute Separation, % 98.8 98.1 97.0 93.5 82.8 61.7

3
Permeate f l u x , — ^ — , xlO 7.43 9.05 13.27 19.38 24.41 25.80
2
m s
3 2

a) F i l m area, 1.443 x l O m ; o p e r a t i n g pressure 6900 kPa; feed c o n c e n t r a t i o n 10 000 ppm NaCl;
temperature 25°C; feed f l o w r a t e 400 ml/min.
18. DICKSON AND LLOYD Solute Preferential Sorption 301
Benzene - Water Reverse Osmosis Data. The e x p e r i m e n t a l l y

determined performance f o r the s e p a r a t i o n of benzene and water a t
four d i f f e r e n t pressures i s i l l u s t r a t e d i n Figures 2 through 5.
The s e p a r a t i o n and pore b l o c k i n g f a c t o r observed f o r s e v e r a l
d i f f e r e n t feed concentrations are p l o t t e d as a f u n c t i o n of the
membrane pore s i z e , l n C * N c i . Although there i s s c a t t e r i n the
a
data, i t i s p o s s i b l e t o observe trends that apply c o n s i s t e n t l y i n

Figures 2 through 5. As the pore s i z e decreases the s e p a r a t i o n
i n c r e a s e s . As the feed c o n c e n t r a t i o n i n c r e a s e s , the s e p a r a t i o n
i n c r e a s e s . The extent of t h i s c o n c e n t r a t i o n e f f e c t i s s m a l l f o r
the membranes of l a r g e pore s i z e , and increases w i t h decreasing
pore s i z e u n t i l the greatest i n f l u e n c e i s observed f o r the membrane
of s m a l l e s t pore s i z e . I n a l l cases, the extent of pore b l o c k i n g
increases l i n e a r l y w i t h decreasing pore s i z e . I n a d d i t i o n ,
i n c r e a s i n g the feed c o n c e n t r a t i o n increases the extent of pore
blocking.
The e f f e c t of s o l u t
i l l u s t r a t e d by e x t r a c t i n g the data f o r any given membrane from
the curves i n Figures 2 through 5, and r e p l o t t i n g the data i n the
form of s e p a r a t i o n as a f u n c t i o n of s o l u t e c o n c e n t r a t i o n i n the
feed stream. T y p i c a l r e s u l t s are shown i n Figure 6. This
r e l a t i o n s h i p c l e a r l y i l l u s t r a t e s that s e p a r a t i o n increases w i t h
i n c r e a s i n g c o n c e n t r a t i o n , e v e n t u a l l y l e v e l i n g o f f a t a constant
v a l u e . This p l o t a l s o a l l o w s the comparison of s e p a r a t i o n a t
d i f f e r e n t pressures. For the range of pressures 690 to 3450
kPa, the s e p a r a t i o n increases w i t h decreasing pressure, which i s
c o n s i s t e n t w i t h the general behavior of p r e f e r e n t i a l l y sorbed
s o l u t e systems as discussed above and w i t h the data p r e v i o u s l y
obtained (1). However, the data f o r 6900 kPa does not f o l l o w
t h i s trend and i n d i c a t e s that s e p a r a t i o n passes through a
minimum w i t h i n c r e a s i n g pressure. This behavior w i l l be
i n v e s t i g a t e d i n more d e t a i l i n the f u t u r e .
The trends i n Figures 2 to 6 a r e c o n s i s t e n t w i t h the
q u a l i t a t i v e f e a t u r e s of s o l u t e p r e f e r e n t i a l s o r p t i o n discussed
e a r l i e r i n t h i s paper. The permeate f l u x i s lower than the pure
water f l u x due to pore b l o c k i n g . This e f f e c t i s enhanced by e i t h e r
decreasing the pore s i z e or i n c r e a s i n g the feed c o n c e n t r a t i o n .
Both of these f a c t o r s l e a d to a r e l a t i v e increase i n the s o l u t e
content of the pore and thus, to r e s t r i c t e d water t r a n s p o r t through
the pore. Since the s o l u t e i s r e l a t i v e l y immobile a t the membrane
s u r f a c e , p o s i t i v e s e p a r a t i o n i s observed. Both i n c r e a s i n g the
feed c o n c e n t r a t i o n and decreasing the pore s i z e l e a d to higher
s e p a r a t i o n . The a d d i t i o n a l s o l u t e r e t a i n e d on the h i g h pressure
s i d e must a l s o be r e l a t i v e l y immobile. I t i s hypothesized that
benzene can be sorbed i n m u l t i p l e l a y e r s which are bound to the
membrane. The l a y e r s i n the immediate v i c i n i t y of the membrane
m a t e r i a l / p o r e w a l l are s t r o n g l y bound to the membrane. The s t r e n g t h
of the a t t r a c t i o n f o r c e decreases as the d i s t a n c e between each
subsequent l a y e r and the membrane surface i n c r e a s e s .

BULK FEED SOLUTION UNDER

"OPERATING GAUGE PRESSURE P
-CONCENTRATED BOUNDARY SOLUTION
Â2 -PREFERENTIALLY SORBED INTERFACIAL FLUID
-DENSE MICROPOROUS MEMBRANE SURFACE

LESS DENSE MICROPOROUS TRANSITION
"MEMBRANE LAYER
-SPONGY POROUS MEMBRANE
P R O D U C T S O L U T I O N AT
ATMOSPHERIC PRESSURE
Â3
Figure 1. Schematic of RO transport under steady-state conditions (16)
0.4 —
J I I -L
I I I I L_
-13 -12 -II -10 -9
l n C
NaCI
Figure 2. Effect of feed concentration on the RO performance for the benzene-

water system. Operating conditions: membrane material = CA; membrane area =
3 2
1.443 X IO' m , In C* obtained at 6900 kPa; feedflowrate = 400 mL/min;
Nam
T = 25°C; operating pressure = 690 kPa. Curve a (O) 20.6 ppm; Curve b (%)
31.7 ppm; Curve c O 54.0 ppm; Curve d (^) 96.0 ppm.

DICKSON AND LLOYD Solute Preferential Sorption 303

water system. The operating conditions are identical to those of Figure 2 except
that the operating pressure = 1725 kPa. Curve a (O) 18.0 ppm; Curve b (%) 29.8
ppm; Curve c O 49.0 ppm; Curve d (U) 98.8 ppm.


ppm; Curve c (Q) 44.8 ppm; Curve d (^) 54.5 ppm; Curve e (A) 92.6 ppm.

DICKSON A N D LLOYD Solute Preferential Sorption 305

80 -
0 20 40 60 80
FEED CONCENTRATION (ppm BENZENE)
Figure 6. Effect of feed concentration and operating pressure on separation for

the benzene-water system. Data illustrated for the CA membrane with In C* i NaC
= -13.25. Curve a (O) 690 kPa; Curve b (%) 1725 kPa; Curve c O 3450 kPa;
Curve d ( | ) 6900 kPa.

The r e s u l t s observed f o r the benzene-water system can be

compared to those observed f o r the p-chlorophenol-water system. I n
the l a t t e r case, higher feed concentrations and s m a l l e r pore s i z e
l e a d to lower s e p a r a t i o n ( 2 3 ) . As discussed e a r l i e r i n t h i s r e p o r t ,
t h i s d i f f e r e n c e i n behavior i s c o n s i s t e n t w i t h the d i f f e r e n c e s
i n m o b i l i t y of the two s o l u t e s . With both benzene and
p-chlorophenol, i n c r e a s i n g the c o n c e n t r a t i o n i n c r e a s e s the amount
of s o l u t e bound t o the membrane pore w a l l . Since the p-chlorophenol
i s more h i g h l y hydrated i t can move through the pore w i t h the water,
which decreases the s e p a r a t i o n . For benzene, the s o l u t e i s
r e l a t i v e l y immobilized, and w i t h i n c r e a s i n g c o n c e n t r a t i o n more and
more of the pore i s occupied w i t h immobilized s o l u t e . The r e s u l t
i s higher s e p a r a t i o n . Thus, i t appears that the s e p a r a t i o n and
pore b l o c k i n g f a c t o r a r e both c o n t r o l l e d by the r e l a t i v e amount of
immobilized s o l u t e i n the pore. This r e l a t i v e q u a n t i t y of s o l u t e
can be increased by i n c r e a s i n th feed c o n c e n t r a t i o t fixed
pore s i z e o r by decreasin
c o n c e n t r a t i o n . As c o n c e n t r a t i o ,
s o l u t e assumes a p o s i t i o n i n sorbed l a y e r s which are i n c r e a s i n g l y
f a r from the membrane s u r f a c e . Thus, the a t t r a c t i o n f o r c e s exerted
by the membrane m a t e r i a l on the s o l u t e are p r o g r e s s i v e l y l e s s , and
the a d d i t i o n a l s o l u t e i s not so t i g h t l y bound. The r e s u l t i s the
permeation of a p o r t i o n of the concentrated boundary l a y e r .
Therefore, there i s a l e v e l i n g o f f i n s e p a r a t i o n w i t h i n c r e a s i n g
concentration.
C o r r e l a t i o n of X A 2 w i t h Pore B l o c k i n g f o r Benzene-Water Data.

The b l o c k i n g of the pores on the membrane surface by the
p r e f e r e n t i a l l y sorbed s o l u t e , which was discussed q u a l i t a t i v e l y
i n the preceding s e c t i o n , i s now t r e a t e d more q u a n t i t a t i v e l y .
Equation 4 was used to estimate the a p p r o p r i a t e k value f o r each
c e l l . The d i f f u s i v i t y of the s o l u t e i n water was estimated by
the method of Wilke and Chang ( 2 7 ) , and the d i f f u s i v i t y of sodium
c h l o r i d e i n water used was 1 . 6 0 x 10~" cm /s ( 2 6 ) . Then X A 2
5 2
was c a l c u l a t e d f o r each run from Equation 3 . F i g u r e 7 i l l u s t r a t e s

the r e l a t i o n s h i p between 1 -(PF/PWF) and X A 2 - W i t h i n the s c a t t e r
of t h i s data, i t i s reasonable to use a s t r a i g h t l i n e through the
o r i g i n f o r a l l s i x membranes. This data corresponds to an n i value
of 1 . 0 i n Equation 1 . The K j v a l u e s , obtained by l e a s t squares
a n a l y s i s of the data i n F i g u r e 7 , a r e p l o t t e d i n Figure 8 as a
f u n c t i o n of l n C * N C l * This r e l a t i o n s h i p can be described by the
a
equation
Ki = -2189 l n C* N a C 1 - 12840 (7)
For the membranes used i n t h i s study, ¥L\ v a r i e d from 6 x 1 0 t o 3
1 6 x 1 0 . I t should be noted that F i g u r e s 7 and 8 i n c l u d e d data

3
from a l l pressures t e s t e d and t h e r e f o r e Equation 7 w i l l p r e d i c t

K i f o r a l l pressures and c o n c e n t r a t i o n s w i t h i n the range s t u d i e d .
The i n v e r s e dependence of on l n C*NaCl r e f l e c t s the increased

LO
00
o

importance of s o l u t e pore b l o c k i n g f o r the membranes of s m a l l e r pore

s i z e , E q u a t i o n 7, t h e r e f o r e , can be used to estimate the extent of
pore b l o c k i n g that w i l l be caused by p r e f e r e n t i a l l y sorbed benzene.
This e s t i m a t i o n can be performed by simply conducting experiments
w i t h NaCl-water systems to determine the l n C*NaCl value f o r the
membrane i n use. The a p p l i c a t i o n of Equation 7 to aqueous
systems c o n t a i n i n g benzene p l u s a s o l u t e such as NaCl w i l l be
explored i n f u t u r e s t u d i e s .
Toluene-Water Reverse Osmosis Data. Data f o r the reverse

osmosis s e p a r a t i o n of aqueous toluene s o l u t i o n s a t 3450 kPa
and three d i f f e r e n t c o n c e n t r a t i o n s , u s i n g the same s i x membranes
as above, a r e i l l u s t r a t e d i n Figure 9. These r e s u l t s are
q u a l i t a t i v e l y s i m i l a r t o those f o r the benzene s t u d i e s . That i s ,
s e p a r a t i o n and extent of pore b l o c k i n g i n c r e a s e w i t h both i n c r e a s i n g
c o n c e n t r a t i o n and decreasin size studie
i n v e s t i g a t e the e f f e c t s
C o r r e l a t i o n of XA2 w i t h Pore B l o c k i n g f o r Toluene-Water Data.

An a n a l y s i s s i m i l a r t o that used f o r the benzene data was a p p l i e d
to the toluene data to i n v e s t i g a t e pore b l o c k i n g as a f u n c t i o n of
c o n c e n t r a t i o n . Figure 10 i l l u s t r a t e s t h i s r e l a t i o n s h i p f o r a l l
s i x membranes. The data f o r membranes 5 and 6 can be approximated
by a s t r a i g h t l i n e ; t h e r e f o r e , n\ was s e t to 1.0 i n Equation 1.
For the other f i l m s , a l e a s t squares parameter e s t i m a t i o n was
a p p l i e d and the n\ and K j values generated. The r e s u l t s are
i l l u s t r a t e d i n F i g u r e 11, where K j ( p l o t t e d as l n K^ f o r convenience)
and ni are shown as f u n c t i o n s of l n C*NaCl» F o r t n e
r e g i o n of
l n C * N d l e s s than -10.5 both n^ and K^ i n c r e a s e w i t h l n C*NaCl«
a
3
Above t h i s value n i and K j l e v e l o f f a t 1.0 and 40 x 1 0 ( i . e . ,
l n K i = 10.6), r e s p e c t i v e l y . This r e s u l t i s s i m i l a r to that
obtained p r e v i o u s l y i n p-chlorophenol s t u d i e s (23) , where n i was
found to l e v e l o f f a t l n C*^ n^ values greater than -12.0.
a(
In general, the s e p a r a t i o n and pore b l o c k i n g data f o r the

toluene-water system are c o n s i s t e n t w i t h those obtained f o r the
benzene-water system. P o s i t i v e s e p a r a t i o n occurs, and the general
trends of i n c r e a s i n g s e p a r a t i o n and pore b l o c k i n g w i t h i n c r e a s i n g
c o n c e n t r a t i o n and decreasing pore s i z e are observed. This i s not
s u r p r i s i n g s i n c e toluene and benzene are s i m i l a r i n s t r u c t u r e .
However, based on the modified Small's number f o r these s o l u t e s ,
as discussed e a r l i e r i n t h i s paper, i t would be expected that toluene
would be more s t r o n g l y sorbed by the membrane than i s the benzene.
I f t h i s i s t r u e , then a t otherwise i d e n t i c a l c o n d i t i o n s toluene
should demonstrate greater pore b l o c k i n g and higher s e p a r a t i o n
than benzene. Curve c_ i n Figure 9 f o r toluene and curve a i n
Figure 4 f o r benzene a r e a t the same pressure and approximately
the same molar c o n c e n t r a t i o n . I n a l l cases, the expected r e s u l t
i s found. For example, f o r membrane 2, the separations are 41%
and 9% and the pore b l o c k i n g f a c t o r s are 0.30 and 0.08 f o r
toluene and benzene, r e s p e c t i v e l y . Thus, the modified Small's

K.xlO"
Figure 8. Correlation ofK of Equation t
1 with membrane pore size (In C* ci) Na
for separation of the benzene-water sys-

tem In C .
8 0
6
i-
<
OC 6 0
& a
W 40 1-
UJ
Z
W 20
_J
O
0
-12 -II
l n c
NaCI
Figure 9. Effect of feed concentration on the RO performance for the toluene-

ppm; Curve c (Q) 20.8 ppm.

DICKSON A N D LLOYD Solute Preferential Sorption 311
Figure 10. Correlation of the pore-blocking factor, 1-(PF/PWF), and the bound-
ary layer concentration of toluene, X . The operating conditions are the same as
A2
in Figure 9 with Membranes 1 (*), 2 (Q), 3 (A), 4 (A), 5 (O), and 6 (M) as
designated in Table I.
Figure 11. Correlation of In K j and n t
of Equation 1 with membrane pore size

(In C* ci) for separation of the toluene-
Na
NaCl water system

number i s a u s e f u l t o o l f o r q u a l i t a t i v e l y p r e d i c t i n g d i f f e r e n c e s
i n the reverse osmosis performance f o r toluene-water and
benzene-water systems.
Conclusions
In c o n c l u s i o n , s e v e r a l important p o i n t s of t h i s work should

be r e i t e r a t e d . An understanding and q u a n t i t a t i v e d e s c r i p t i o n of
s o l u t e p r e f e r e n t i a l s o r p t i o n i s imperative to the advancement
of a fundamental knowledge of the s e p a r a t i o n mechanism and to the
a p p l i c a t i o n of reverse osmosis. For the systems s t u d i e d ,
i n c r e a s i n g the feed c o n c e n t r a t i o n was found to i n c r e a s e s e p a r a t i o n
and decrease permeate f l u x . This behavior can be contrasted to the
case of water p r e f e r e n t i a l s o r p t i o n where both s e p a r a t i o n and
permeate f l u x would remain constant f o r these d i l u t e
c o n c e n t r a t i o n s . The r e s u l t s f o r the benzene s t u d i e s and the
toluene s t u d i e s were s i m i l a
f l u x decreased w i t h i n c r e a s i n
pore s i z e . The benzene s t u d i e s showed a minimum i n s e p a r a t i o n
w i t h i n c r e a s i n g pressure. At s i m i l a r experimental c o n d i t i o n s
the toluene system showed higher s e p a r a t i o n and lower f l u x than
the benzene system. This observation i s c o n s i s t e n t w i t h the
d i f f e r e n c e i n the nonpolar character of the s o l u t e s as expressed
by the Small's number. Further work i s needed i n order to
improve the q u a n t i t a t i v e understanding of systems which e x h i b i t
solute p r e f e r e n t i a l sorption.
Legend of Symbols
A = pure water p e r m e a b i l i t y constant, mol H2O/

2
(m s kPa)
2
D^g = d i f f u s i v i t y of A i n B, m /s
D K( =
AM/ 5 s o l u t e t r a n s p o r t parameter, m/s
f = separation
k = mass t r a n s f e r c o e f f i c i e n t , m/s
Ki,K 2 = p r o p o r t i o n a l i t y f a c t o r s defined i n Equations
1 and 2, r e s p e c t i v e l y
ln C*N d a = r e l a t i v e measure of the membrane pore s i z e
mi = concentration, m o l a l i t y
ni,n 2 = exponents defined i n Equations 1 and 2,
respectively
2
NA = s o l u t e f l u x , mol/(m s)
P = operating pressure, kPa gauge
2
PF = permeate f l u x , kg/(m s ) '

ppm = c o n c e n t r a t i o n , p a r t s per m i l l i o n
2
PWF = pure water f l u x , kg/(m s)
X = c o n c e n t r a t i o n , mole f r a c t i o n
3
p = s o l u t i o n d e n s i t y , kg/m
Subscripts
1 = feed s o l u t i o n
2 = boundary l a y e r s o l u t i o n
3 = permeate s o l u t i o n
M = membrane phase
A = solute
B = solvent
ref = referenc
Acknowledgements
The authors wish t o thank The Engineering Foundation f o r t h e i r

support of t h i s research and the N a t u r a l Sciences and Engineering
Research C o u n c i l of Canada f o r the s c h o l a r s h i p support of one of
the authors (JMD).
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314 SYNTHETIC MEMBRANES*. HF AND UF USES
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19
Estimation of Interfacial Forces Governing the
Reverse-Osmosis System: Nonionized Polar
Organic Solute-Water-Cellulose Acetate
Membrane
TAKESHI MATSUURA, Y U T A K A TAKETANI, and S. SOURIRAJAN
Division of Chemistry, National Research Council of Canada,
Ottawa, Ontario K1A 0R9 Canada
This extends the previous work (1) i n which the Lennard-

Jones type surface p o t e n t i a l f u n c t i o d th frictional f u n c t i o
r e p r e s e n t i n g the interfacial
molecule from the membran por
and s o l v e n t t r a n s p o r t through a pore t o c a l c u l a t e data on
membrane performance such as those on s o l u t e s e p a r a t i o n and the
ratio of product r a t e to pure water permeation r a t e in reverse
osmosis. I n the previous work (1) parameters i n v o l v e d in the
Lennard-Jones type and frictional f u n c t i o n s were determined by a
trial and e r r o r method so that the s o l u t i o n s in terms of s o l u t e
s e p a r a t i o n and (product rate/pure water permeation r a t e ) ratio
fit the experimental data. I n t h i s paper the potential f u n c t i o n
is generated by using the experimental high performance liquid
chromatography (HPLC) data in which the r e t e n t i o n time represents
the a d s o r p t i o n and d e s o r p t i o n e q u i l i b r i u m of the s o l u t e a t the
solvent-polymer i n t e r f a c e .
The frictional f o r c e is expressed by a f u n c t i o n of the ratio
of a d i s t a n c e a s s o c i a t e d w i t h steric r e p u l s i o n a t the i n t e r f a c e ,
to the pore r a d i u s . The frictional f u n c t i o n increases s t e e p l y
w i t h increase in the latter ratio. The method of c a l c u l a t i n g
reverse osmosis s e p a r a t i o n data by u s i n g the surface potential
f u n c t i o n and the frictional f u n c t i o n so generated, i n c o n j u n c t i o n
w i t h the t r a n s p o r t equation is illustrated by examples i n v o l v i n g
c e l l u l o s e acetate membranes of different p o r o s i t i e s and 40
nonionized organic s o l u t e s in s i n g l e s o l u t e aqueous s o l u t i o n
systems.
Experimental
HPLC Experiments. The l i q u i d chromatograph model ALC 202 of

Waters A s s o c i a t e s f i t t e d w i t h a d i f f e r e n t i a l refractometer was
used i n t h i s work. The method of column p r e p a r a t i o n and the
general experimental technique used were the same as those
reported e a r l i e r (2). A l l experiments were c a r r i e d out a t the
l a b o r a t o r y temperature (23-25°C). The s o l v e n t (water) flow r a t e
0097-6156/81/0154-0315$06.00/0

3
through the column was f i x e d a t 0.27 cm /min. The pressure drop
through the column was 1034kPa(=150psi)/ft. F o r t y s o l u t e s
i n c l u d i n g a l c o h o l s , p o l y a l c o h o l s , phenols, ketones, e t h e r s ,
aldehydes, e s t e r s , amines, amides, n i t r i l e s and nitrocompounds
were i n j e c t e d i n t o the column which was made from c e l l u l o s e
acetate Eastman E-398 polymer. I O U L of sample s o l u t i o n ( s o l u t e
c o n c e n t r a t i o n i n the range 1~10%) was i n j e c t e d i n t o the column,
and the r e t e n t i o n time f o r each s o l u t e was determined. R a f f i n o s e
whose r e t e n t i o n time was the l e a s t , was used as the unretained
component to e s t a b l i s h the p o s i t i o n of s o l v e n t f r o n t . The
r e t e n t i o n time measurements were d u p l i c a t e d and the average
values obtained were used f o r computations; i n most cases, the
r e s u l t s of d u p l i c a t e d measurements were i d e n t i c a l . I t was
already e s t a b l i s h e d (2) that changes i n column l e n g t h , p a r t i c l e
s i z e , packing d e n s i t y of column m a t e r i a l , s o l v e n t v e l o c i t y
through the column, o p e r a t i n g pressure and sample s i z e d i d not
a f f e c t the r e t e n t i o n tim
otherwise i d e n t i c a l experimenta
Reverse Osmosis Experiments. This work makes f u r t h e r use of

reverse osmosis data a l r e a d y reported w i t h respect to membranes
made from c e l l u l o s e acetate Eastman E-398 polymers (3,^,5^,60.
Data on amides, n i t r i l e s and nitrocompounds were newly added i n
t h i s work. The experimental d e t a i l s are b r i e f l y as f o l l o w s .
Each membrane was subjected to an i n i t i a l pure water pressure of
2068kPa gauge(=300psig) f o r about 2h p r i o r to subsequent use i n
reverse osmosis experiments a l l of which were c a r r i e d out a t
1724kPa gauge(=250psig) and a t l a b o r a t o r y temperature (23-25°C).
For purposes of membrane s p e c i f i c a t i o n s i n terms of pure water
2
p e r m e a b i l i t y constant A ( i n kg-mol of HÔ/m »s«kPa) and s o l u t e
t r a n s p o r t parameter (D^/KS) ( t r e a t e d as a s i n g l e q u a n t i t y , m/s),
aqueous feed s o l u t i o n s c o n t a i n i n g 3500 ppm of NaCl were used ( 7 ) .
Data on A and (D^/KS) thus obtained are l i s t e d i n Table I w i t h
respect to a l l membranes used i n t h i s work together w i t h
experimental reverse osmosis data of sodium c h l o r i d e s o l u t e . In
a l l other experiments, the s o l u t e concentrations i n the aqueous
feed s o l u t i o n s were so low (0.001 to 0.006 molal) that the
osmotic pressures i n v o l v e d were n e g l i g i b l e compared to the
o p e r a t i n g pressure. In each experiment, the f r a c t i o n s o l u t e
s e p a r a t i o n defined as:
^ _ s o l u t e c o n c e n t r a t i o n i n f e e d - s o l u t e c o n c e n t r a t i o n i n product
s o l u t e c o n c e n t r a t i o n i n feed
membrane permeated product r a t e (PR) and pure water permeation

r a t e (PWP) i n g/h f o r the e f f e c t i v e area of membrane surface used
2
(=13.2 cm i n t h i s work) were determined a t the s p e c i f i e d
o p e r a t i n g c o n d i t i o n s . A l l reverse osmosis experiments were f o r
s i n g l e s o l u t e systems. The c o n c e n t r a t i o n s of sodium c h l o r i d e
were determined using a c o n d u c t i v i t y b r i d g e ; the c o n c e n t r a t i o n s
of organic s o l u t e s were determined by a Beckman t o t a l carbon

19. MATSUURA ET AL. Interfacial Forces Governing the RO System 317
analyzer Model 915A. Data on s p e c i f i c a t i o n s and performances o f

a l l f i l m s used i n t h i s work are given i n Table I .
Theoretical
In the e a r l i e r work (1) transport equations were developed

on the b a s i s of surface force-pore flow model i n which a surface
p o t e n t i a l f u n c t i o n and a f r i c t i o n a l f u n c t i o n are incorporated.
The r e s u l t s can be b r i e f l y summarized as f o l l o w s :
D e f i n i n g the f o l l o w i n g dimensionless q u a n t i t i e s ,
P = r/R (1)
CA(P) = CA (P)/C 3 A 2 (2)
<HP) = u (ri6x B??
B A
T ( 3 )
3 = n / R C ( 4 )
1 * A B A2
p p T c
&2 = ( i- o)/? A2 <
$(p) = *(r)/RT (6
the s o l u t e s e p a r a t i o n , f , on the b a s i s of the boundary concentra-
c a n e
t i o n , c^2> k c a l c u l a t e d by
f [exp(a(p))/i + | e x p ( a ( p ) - l ) | | a(p)pdp
f' = 1 - ^ ^ (7)
f a(p)pdp
The dimensionless r a d i a l v e l o c i t y p r o f i l e , expressed by a(p) i s

obtained by s o l v i n g the d i f f e r e n t i a l equation
2
d a(p)
e i i i e l C 4 < p ) 1
dp f 4 r^^( - " )( - )
-(b(p)-l)a(p)C (p)/e A i = 0 (8)
where
C (p)
A = exp(a(p))+ |exp(a(p))-l| (9)
w i t h boundary c o n d i t i o n s :
= 0 when p = 0 (10)
dp
and
a(p) = 0 when p = 1 (11)

a
Table I . Experimental Reverse Osmosis D a t a f o r the System NaCl-HÔ and Glycerol-HÔ Using Porous
C e l l u l o s e Acetate Membranes and Parameters C h a r a c t e r i z i n g Membranes
F i l m No. 1 2 3 4 5 6 7 8 9 10 11 12 13 14
7 2
A x l O , kg-mol/m .
1.726 1.544 2.955 3.485 2.044 2.513 1.622 3.559 3.430 2.810 1.728 1.535 3.438 5,189
s.kPa
D k6 x 1 0 ?
( AM/ >NaCl > 2.515 2.772 10.15 25.75 3.302 6.759 2.230 18.36 25.13 9.833 2.195 2.877 26.81 62.81
m/s
k x 106 m s 22.6 21.1 35.0 40.0 26.0 30.6 22.0 40.6 39.5 33.5 23.0 21.1 39.5 45.0
NaCl > /
(PWP), g/h 25.45 22.77 43.57 51.38 30.14 37.06 23.91 52.47 50.57 41.43 25.48 22.64 50.70 76.51
NaCl experimental
b b b b b b b b b
data
(PR), g/h 20.40 18.90 34.40 42.20 28.18 34.34 22.23 49.09 46.67 36.00 21.53 20.49 43.84 66.64
Solute s e p a r a t i o n , 93.5 92.2 85.8 74.0 93.4 89.4 94.4 81.3 75.5 85.6 94.3 91.9 73.0 62.0
%
Glycerol experi-
0
mental d a t a 82.9 82.8 75.0 60.2 82.5 79.2 83.2 66.2 60.6 75.6 83.3 82.7 59.5 40.0
Solute s e p a r a t i o n ,
%
Pore r a d i u s , A 7.36 7.48 8.61 9.39 7.62 8.24 7.20 9.14 9.37 8.57 7.20 7.54 9.42 10.09
Solutes s t u d i e d Alcohols Ketones, E s t e r s , Ethers Amides, N i t r i l e s , N i t r o -
compounds

Operating pressure, 1724 kPa gauge (=250 p s i g )
3
Flow r a t e , 400 cm /min
2
E f f e c t i v e membrane area, 13.2 cm .

Sodium c h l o r i d e c o n c e n t r a t i o n i n feed, 0.026 m o l a l unless otherwise s t a t e d ,
k" Sodium c h l o r i d e c o n c e n t r a t i o n i n feed, 0.06 m o l a l .

C
* G l y c e r o l feed c o n c e n t r a t i o n i n feed, 0.002 m o l a l , (PR)~(PWP),
Table I Continued
F i l m No. 15 16 17 18 19 20 21 22 23 24
7 2
A*10 , kg-mol/m <s*kPa 4.263 1.564 2.291 3.198 3.917 2.593 4.338 1.546 2.271 3.219
( D / k 6 ) 1 0 ? m / s 58.64 2.319 7.610 13,09 29.63 17.50 61.43 2.371 7.199 13.06
AM NaCl * •
X 1 0 6 m / s 45.00 21.4 28.5 37.1 44.1 31.4 45.0 21.0 28.2 37.3
âCl •
(PWP), g/h 62.86 23.05 33.78 47.16 57.78 38.24 63.96 22.80 33.48 47.46
NaCl experimental data
(PR), g/h 60.36 21.63 31.64 44.65 54.51 36.15 60.53 21.58 31.69 44.92
Solute s e p a r a t i o n , % 61.8 94.0 87.3 84.6 74.8 77.2 61.0 93.8 87.8 84.7
0
G l y c e r o l experimental data
Solute s e p a r a t i o n , % 43.3 82.9 78.3 74.3 58.0 63.9 41.8 83.1 78.6 71.3
0
Pore r a d i u s , A 9.98 7.36 8.35 8.66 9.47 9.24 10.04 7.30 8.31 8.86

Solutes s t u d i e d P o l y a l c o h o l s , Carbohydrates Phenols, A n i l i n e s

A l l symbols used are d e f i n e d a t the end of the paper. The r a t i o

of product r a t e to pure water permeation r a t e , (PR)/(PWP), i s
obtained from the r e l a t i o n .
1
(PR)/(PWP) = if a(p)pdp/(3 /83 ) 2 1 (12)
In the above equations the dimensionless p o t e n t i a l f u n c t i o n

expressing the s o l u t e - p o r e w a l l surface i n t e r a c t i o n can be
w r i t t e n as
D
( 10 when 1-p <, —
*(p) = J 3
= R
D
(13)
-8/R when 1-p > R
3 —
(1-p)
i n a non-dimensional form, p a r t i c u l a r l y f o r the organic s o l u t e s
f o r which Lennard-Jones type i n t e r f a c i a l p o t e n t i a l f u n c t i o n i s
a p p l i c a b l e . F u r t h e r , b(p) was w r i t t e n i n the previous work (JL)
using a non-dimensional f r i c t i o n a l f u n c t i o n i n the form
io u , 5
e when 1-p 1
b(p) = (14)
E/R , . . D
exp — when 1-p > r>
1-p &
In eq 13 and 14, D i s the d i s t a n c e between the polymer s u r f a c e
and the s o l u t e mclecule a t which $(p) becomes very l a r g e , and E
i s the f r i c t i o n a l f o r c e constant f o r the t r a n s p o r t of s o l u t e
through the pore. As i t i s c l e a r from eq 14 the f r i c t i o n a l f o r c e
i s a f u n c t i o n of D. Therefore, b and D a r e d i r e c t l y r e l a t e d .
F u r t h e r , s i n c e the d i s t a n c e D i s a s s o c i a t e d w i t h s t e r i c r e p u l s i o n
at the i n t e r f a c e , and s i n c e the l a t t e r d i r e c t l y p a r a l l e l s the
e f f e c t i v e s i z e of the s o l u t e molecule concerned, i t i s reasonable
to c o n s i d e r that D i s a f u n c t i o n of the e f f e c t i v e s i z e of the
s o l u t e molecule. Therefore, both D and b can be r e l a t e d to the
e f f e c t i v e s i z e of the s o l u t e molecule. For the purpose of
mathematical a n a l y s i s , the l o c a t i o n of a molecule i n s i d e a pore
may be considered as the l o c a t i o n of the center of the molecule,
assuming s p h e r i c a l shape f o r the molecule. Therefore, the lowest
l i m i t i n g d i s t a n c e D a t which s u r f a c e r e p u l s i o n f o r the molecule
i s the h i g h e s t i s a c t u a l l y the r a d i u s of the molecule i t s e l f ,
since i t cannot be any c l o s e r to the membrane s u r f a c e . F u r t h e r ,
f o r n o n i o n i c s o l u t e s which are s u b j e c t to s h o r t range hydrogen
bonding and/or d i s p e r s i o n f o r c e s of a t t r a c t i o n and r e p u l s i o n , the
a c t u a l d i s t a n c e D cannot be too f a r d i f f e r e n t from the r a d i u s o f
the molecule. Therefore, as a matter of p r a c t i c a l approximation
the d i s t a n c e D i s considered i d e n t i c a l to an e f f e c t i v e r a d i u s of
the molecule f o r purposes of a n a l y s i s i n t h i s work.

I t has to be noted that f o r the s o l u t i o n of eq 7 and 8

together w i t h boundary c o n d i t i o n s given by eq 10 and 11, only
pore r a d i u s , R, and parameters B, D and E are necessary. The
other q u a n t i t i e s i n v o l v e d i n the above equations are a l l a v a i l -
able i n terms of the experimental c o n d i t i o n s used. In other
words, the s o l u t e s e p a r a t i o n , f ' , which i s d e f i n e d on the b a s i s
i s
of the boundary c o n c e n t r a t i o n c ^ s t r i c t l y a function of
v a r i a b l e s R, B, D and E under a given s e t of operating c o n d i t i o n s .
In eq 7, s o l u t e s e p a r a t i o n was defined on the b a s i s o f
a s
boundary c o n c e n t r a t i o n c ^ >
c —c
A 2 A 3
f = (15)
C
A2
In order to r e l a t e the above s o l u t e s e p a r a t i o n to that on the

b a s i s o f feed c o n c e n t r a t i o
C C
Al" A3
A 1 A J
f = (16)
C
A1
the f o l l o w i n g equation based on the b a s i c t r a n s p o r t equation
e s t a b l i s h e d e a r l i e r (7)
C
A2 = C
A3 + ( c
Ar A3C ) e X p
( 3
lH 17
< >
can be employed using the f a c t that the molar d e n s i t y remains

e s s e n t i a l l y constant f o r the present system. In eq 17, v i s the g
l i n e a r v e l o c i t y of the permeate s o l u t i o n through the membrane,

which i s e s s e n t i a l l y the same as v ^ = A ( P ^ - P ) / c f o r d i l u t e 0
s o l u t i o n s . Furthermore, from previous work the mass t r a n s f e r

c o e f f i c i e n t k can be represented as a f u n c t i o n of pure water
p e r m e a b i l i t y constant, A, as shown i n Figure 1 ( 8 ) . Combining
eq 15, 16 and 17 we o b t a i n
f
(18)
f +\ (1
which equation r e l a t e s f defined by eq 15 to f d e f i n e d by eq 16.
A n a l y s i s of High Performance L i q u i d Chromatography (HPLC) Data
On the b a s i s of a n a l y s i s of r e t e n t i o n time data obtained

from l i q u i d chromatography experiments reported e a r l i e r (9) the
existence o f i n t e r f a c i a l water i s assumed a t the s o l u t i o n polymer
i n t e r f a c e and the e q u i l i b r i u m c o n c e n t r a t i o n of s o l u t e between
s t a t i o n a r y - and mobile-phases i s regarded as that between

i n t e r f a c i a l - and bulk-water phases. This model i s s c h e m a t i c a l l y

described i n Figure 2. Expressing average concentration of
s o l u t e i n the i n t e r f a c i a l r e g i o n as c ^ and the concentration of
s o l u t e i n the b u l k s o l u t i o n phase c ^ , the e q u i l i b r i u m constant
K can be w r i t t e n as
K' = — (19)
C
Ab
I t i s f u r t h e r assumed that the e q u i l i b r i u m constant f o r is

the same as that of o r d i n a r y water and i s u n i t y . Then, K' f o r
other s o l u t e s can be c a l c u l a t e d from the r e l a t i o n (9)
[V] - [V]
v' - R Vmin
7 ( 2 0
"Tv ! =17]
L L
Vwater Vmi
s
where [VR] i s the experimental r e t e n t i o n volume, [v$}\jater ^
tv«] of D 0 and [vX] . i s [v£] of a reference s o l u t e , r a f f i n o s e
o
. K L K mm #K ' .
i n t h i s p a r t i c u l a r system, which e x h i b i t s the lowest r e t e n t i o n
volume among s o l u t e s i n j e c t e d ( 9 ) . From eq 20, values of K' f o r
water and reference s o l u t e are one and zero, r e s p e c t i v e l y . Using
the e q u i l i b r i u m constant defined by eq 20, r e t e n t i o n volume [v^]
f o r any s o l u t e can be given by
[ V ] [ V ] + K V ( 2 1 )
R " P m -in ' c
K mm K s
where V represents the volume o f s t a t i o n a r y phase water and i s
g
equal to the volume of the i n t e r f a c i a l water i n t h i s case. I n

eq 20, the value o f K' may be equal t o , greater than o r l e s s
than u n i t y depending on d e t a i l s of concentration gradient i n the
i n t e r f a c i a l r e g i o n . Further, the i n t e r f a c i a l "water l a y e r t h i c k -
ness, t . i n Figure 2, evaluated i n the previous work (9) to be
9.5A f o r c e l l u l o s e acetate E-398 polymer m a t e r i a l , i s used i n
t h i s work.
Since membrane pore surface and the chromatography packing
surface a r e both made out of the same polymer m a t e r i a l , i d e n t i c a l
i n t e r f a c i a l forces have to govern both membrane t r a n s p o r t and
chromatography e q u i l i b r i u m . The only d i f f e r e n c e between the two
systems i s that i n the l a t t e r case, there i s no e f f e c t of s o l u t e
movement ( k i n e t i c e f f e c t ) on the r e t e n t i o n volume data, and
therefore the i n t e r f a c i a l f o r c e governing the chromatography
e q u i l i b r i u m may be represented only by surface p o t e n t i a l working
on the s o l u t e , which may be expressed by a Lennard-Jones type
equation.
The e q u i l i b r i u m constant, K', can be r e l a t e d to the Lennard-
Jones type p o t e n t i a l f u n c t i o n as f o l l o w s . The concentration
p r o f i l e of the s o l u t e a t polymer-solution i n t e r f a c e may be
described s c h e m a t i c a l l y as shown i n Figure 3a and 3b.

Figure 1. Effect of the PWP constant on the mass-transfer coefficient for sodium
chloride
BULK SOLUTION
"A
'4.
Figure 2. Equilibrium of solute between

interfacial water and bulk solution

Using the p o t e n t i a l f u n c t i o n , cj>, as. a f u n c t i o n of the

d i s t a n c e from the polymer s u r f a c e ,
10RT when d<D
•(d) = J (22)
-B
-7f RT when d>D
d
(dimensionless p o t e n t i a l f u n c t i o n eq 13 was d e r i v e d from eq 22),
and Boltzmann's law, s o l u t e c o n c e n t r a t i o n i n the range 0<d<D i s
e f f e c t i v e l y equal to zero (because the l o c a t i o n of s o l u t e
molecule i s assumed to be j t s geometric center) and increases
e a t anc t n e n
d i s c o n t i n u o u s l y to °Ab * g r a d u a l l diminishe
according to the f u n c t i o n a
3
exp(B/D ) (23)
u n t i l i t f i n a l l y reaches the b u l k c o n c e n t r a t i o n ,
According to d e f i n i t i o n , surface excess, T, can be c a l c u -
l a t e d by
D
r = f (0-c )d(d> +/ ic exp(B/d )-c }^(d)
A b A b
3
A b (24)
D ^ D
water
where D denotes the e f f e c t i v e r a d i u s of a s i n g l e water

w a t e r
molecule (=0.87A ( 1 0 ) ) . Since there e x i s t s e f f e c t i v e l y no water,

and t h e r e f o r e no s o l u t i o n , between d=0 and d = D integration w a t e r
s t a r t s from ? i n eq 24, where the c o n c e n t r a t i o n i n excess o f

w a t e r
the bulk c o n c e n t r a t i o n i s i n t e g r a t e d from d = D to d=«>. w a t e r
Supposing t h i s excessive amount of s o l u t e i s compressed i n the

r e g i o n of i n t e r f a c i a l water, whose thickness i s t ^ (see Figure 3)
and averaged out, the r e s u l t becomes,
7 +C
A i " 77 Ab
1
d ( d ) + e x ( B / d 3 ) c d w
/
y
<-<w / 1
Kb p - Ab}1
water ?
= +c A b (25)
1
Using eq 19

D
00
3
(-l)d(d) + f (exp(B/d )-l)d(d)
K' = J: + !
1
3
•(5-5 w a t e r ) +/ (exp(B/d )-l)^(d)
+ 1 (26)
t.
l
Eq 26 i n d i c a t e s that the e q u i l i b r i u m constant K' i s uniquely
r e l a t e d to parameters B and D which c h a r a c t e r i z e the Lennard-
Jones type p o t e n t i a l f u n c t i o n
Frictional Function
I t i s a w e l l accepted concept that the movement of the

molecule i s r e s t r i c t e d i n the pore of diameters which are
comparable to those of s o l u t e molecules. Many groups have
attempted so f a r to describe the r e s t r i c t e d molecular motion i n
s m a l l pores q u a n t i t a t i v e l y . Even though the degree of r e s t r i c -
t i o n depends on the distance o f the s o l u t e molecule from the pore
w a l l (11), i t has been common i n the l i t e r a t u r e to express the
f r i c t i o n a l f o r c e as a f u n c t i o n of the r a t i o of the molecular
r a d i u s t o the pore r a d i u s , designated as X.
In t h i s work, A i s defined as
D
X =i (27)
c o n s i d e r i n g D equal to the e f f e c t i v e molecular r a d i u s f o r

p r a c t i c a l purpose. According to eq 27, X and hence b are both
independent of the p o s i t i o n of the s o l u t e molecule i n the pore.
Faxen suggested that the reduced d i f f u s i v i t y i n f i n e pores
( D ) r e s u l t i n g from an increased f r i c t i o n a l drag on the s o l u t e
M
which i s i n the p r o x i m i t y of s o l i d w a l l s can be expressed by (12)
= 1 - 2.104A + 2.09X - 0.95X (28)

AB
Since the f r i c t i o n a l f u n c t i o n b can be w r i t t e n as
b = 1 / ( D /D._) (29)
m AD
b i s r e l a t e d to the q u a n t i t y X by

3 5
i = 1 - 2.104X + 2.09X - 0.95X (30)
b
2
When combined w i t h a s o l u t e r e p u l s i o n f a c t o r (1-X) eq 30 was
found v a l i d i n the range of X below 0.2 using membranes whose
pore s i z e s ranged from 45 to 300A (.13) . S a t t e r f i e l d , C o l t o n and
P i t c h e r on the other hand studied r e s t r i c t e d d i f f u s i o n i n h e t e r -
ogeneous s o l i d almina bead c a t a l y s t s which possessed a pore
r a d i u s of 16A, by unsteady d i f f u s i o n and observed a more severe
r e s t r i c t i o n of the s o l u t e d i f f u s i o n i n the pore (14).
When there i s no i n t e r a c t i o n between s o l u t e and the pore
w a l l , e f f e c t i v e d i f f u s i v i t y i n the pore could be expressed by
l o
*10 ( D
eff / I )
AB )
" " ° - 3 7
" 2
- 0 X ( 3 1 )
D / D 4 2 7 1 0 2 X
eff AB " °- * " '°
When there i s strong i n t e r a c t i o n between s o l u t e and the pore

w a l l and the former i s s t r o n g l y adsorbed to the l a t t e r , the
D i s e v e n l e s s t n a n t n e
r a t i o , ff/°A > e B quantity obtained by eq
Though t h e i r includes the e f f e c t of t o r t u o s i t y and does

not denote the d i f f u s i v i t y i n the pore i n a s t r i c t sense of the
d e f i n i t i o n , the f r i c t i o n a l f u n c t i o n can be w r i t t e n , i n analogy
to eq 29, as
2 0 X
0.427 x i o ' (32)
Eq 32 i m p l i e s that the f r i c t i o n a l f u n c t i o n includes a l s o the

e f f e c t of t o r t u o s i t y .
In Figure 4, 1/b described by eq 30 and 32 are both
i l l u s t r a t e d w i t h an experimental c o r r e l a t i o n of S a t t e r f i e l d e t
a l . , when there i s a strong i n t e r a c t i o n between s o l u t e and the
pore w a l l , i n the form of the c o r r e l a t i o n shown by Lane and
1
R i g g l e (15). Obviously S a t t e r f i e l d s c o r r e l a t i o n l i e s f a r below
T
that of Faxen. While Faxen s equation can w e l l demonstrate the
f r i c t i o n a l drag i n the range of X<0.2 (13) i t i s o b v i o u s l y
underestimating the r e d u c t i o n i n pore d i f f u s i v i t y i n the range
of higher X v a l u e s , p a r t i c u l a r l y when there i s a solute-pore
1
w a l l i n t e r a c t i o n . S a t t e r f i e l d s c o r r e c t i o n seems to be b e t t e r
r e p r e s e n t i n g the r e l a t i o n s h i p between 1/b and X. I n an attempt
to make the best use of both c o r r e l a t i o n s , a new f u n c t i o n was
1 1
generated, i n which both Faxen s and S a t t e r f i e l d s c o r r e l a t i o n s
were combined. The new f u n c t i o n thus synthesized i s a l s o
i l l u s t r a t e d i n F i g u r e 4. I t has to be noted that the value 1/b

Figure 4. Correlation of 1/X vs. 1/b

i n the higher range of X resembles more S a t t e r f i e l d * s e x p e r i -

mental data on s o l u t e s under i n t e r a c t i o n f o r c e from the pore
w a l l . The new f u n c t i o n can be expressed as
3 5
1 - 2.104X + 2.09X - 0.95X when X<0.22
!
(3
2 3
1/(44.57 - 416.2X + 934.9X + 302.4X ) when X>0.22
Eq 33 was used throughout t h i s work i n order to represent the
e f f e c t of X on b.
E f f e c t of S i z e o f Water Molecule on Solvent Transport through
Pore
When the s i z e of the pore i s comparable to the molecular

s i z e , the e f f e c t o f s o l v e n
ignored. I n a pore ther
water molecule cannot enter due to i t s c o l l i s i o n onto the pore
w a l l . This area i s i l l u s t r a t e d i n Figure 5 as the area
surrounded by c o a x i a l c i r c l e s of r a d i i R-^ and R 2 . The q u a n t i t y
R
R
2" 1 c o r r e s
P o n d s to the molecular r a d i u s of water ( D w a t e r
=
0. 87A i n t h i s work). The pore r a d i u s used i n the P o i s e u i l l e

equation should be, t h e r e f o r e , the s m a l l e r r a d i u s designated by
R^. On the other hand, the i n t e r a c t i o n f o r c e expressed by a
p o t e n t i a l f u n c t i o n such as eq 13 or the f r i c t i o n a l f u n c t i o n such
as eq 39 a r e exerted throughout the l a r g e r pore r a d i u s R 2 .
These two r a d i i have to be s t r i c t l y d i s t i n g u i s h e d . F o l l o w i n g the
previous work, the pore r a d i u s used i n the P o i s e u i l l e equation,
1. e. R]_, i s defined as the pore r a d i u s and t h i s d e f i n i t i o n i s
used throughout t h i s work.
C a l c u l a t i o n of Pore Radius of Membrane. By choosing an

a p p r o p r i a t e r e f e r e n c e s o l u t e the pore r a d i u s of the membrane can
be c a l c u l a t e d i n the f o l l o w i n g way:
Step 1. Using the d i f f u s i v i t y of the r e f e r e n c e s o l u t e a t
i n f i n i t e d i l u t i o n and the Stokes equation
kT
D 3 4 )
AB " 6 ^ <
where k, T, U and r are the Boltzmann gas constant, a b s o l u t e

A
temperature, s o l u t i o n v i s c o s i t y ( v i s c o s i t y of pure water i n t h i s

case) and the s o l u t e r a d i u s , r e s p e c t i v e l y , c a l c u l a t e r ^ . Solute
r a d i u s , r ^ , thus obtained i s considered equal to D of the
reference s o l u t e f o r purposes o f a n a l y s i s .
Step 2. Using eq 26 and data on K' from l i q u i d chromatography
experiment determine B. Use t . = 9.5A and D = 0.87A i n

Step 3. Assume R-^ as pore r a d i u s , d e f i n e d by F i g u r e 5, and

c a l c u l a t e X by eq 27 where D i s s e t equal to R£ = R-^ + 9 t e r * w a
Then c a l c u l a t e b by eq 33. This b i s used as a constant through-

out the e n t i r e range of p i n eq 7-9.
anc D V ec
Step 4. Assume * calculate l 17- The value of k
found i n F i g u r e 1 as a f u n c t i o n of A l i s t e d i n Table I i s used i n
this calculation.
Step 5. C a l c u l a t e dimensionless parameters 3-^ and $2 from eq 4
and 5 using data on o p e r a t i n g pressure and c ^ obtained above.
The v i s c o s i t y data of pure water can be used f o r n. X i s A B
c a l c u l a t e d from the r e l a t i o n
RT
X
AB - 5- (35)
AB
where D^g i s the d i f f u s i v i t

that R i n eq 4 correspond
Step 6. Combine eq 8, 9 and 13 and solve the d i f f e r e n t i a l eq 8
w i t h boundary c o n d i t i o n s eq 10 and 11 u s i n g D, B, b, 3^ and $2
obtained i n steps 1, 2, 3 and 5. R i n eq 13 must be Ri + 5 « w a t e r
Step 7. Since a ( p ) , as f u n c t i o n of p, i s now known, f can be

c a l c u l a t e d from eq 7.
Step 8. Use £' c a l c u l a t e d above i n eq 15 and c a l c u l a t e using
the value of c ^ obtained i n step 4. When agrees w i t h the
value assumed i n step 4, f ' i s regarded as v a l i d , i n which case
go to the next step. Otherwise go back to step 4 and repeat.
Step 9. Using f ' obtained above c a l c u l a t e f from eq 18. I f i t
agrees w i t h the experimental s e p a r a t i o n data, R-^ assumed i n step
3 i s regarded as the f i n a l s o l u t i o n and the pore r a d i u s i s thus
determined. Otherwise go back to step 3 and repeat the e n t i r e
procedure.
G l y c e r o l was chosen as the reference s o l u t e and the pore
r a d i u s R± was determined f o r a l l the membranes used i n t h i s
study. The experimental r e s u l t s on g l y c e r o l s e p a r a t i o n and the
pore r a d i u s , R-^, so c a l c u l a t e d are both l i s t e d i n Table I .
The q u a n t i t i e s l n R^ and ln(PWP) were then subjected to
l e a s t squares a n a l y s i s . As a r e s u l t , i t was found that
ln(PWP) = -3.12 + 3.2 l n R

(36)
3 , 2
or (PWP) = 0.04 R
Assuming the number of pores i s equal f o r a l l membranes i n v o l v e d

i n t h i s work, eq 36 i n d i c a t e s that the pore flow i s very much
l i k e P o i s e u i l l e flow as assumed i n the e n t i r e scheme of t h i s
calculation.

C a l c u l a t i o n of Molecular Radius of S o l u t e s . The membranes

of s m a l l e s t pore s i z e s ( f i l m s 1, 7, 11, 16 and 22) were then
chosen and the c h a r a c t e r i s t i c constants D and B, d e s c r i b i n g the
i n t e r f a c i a l a t t r a c t i v e p o t e n t i a l f u n c t i o n , were determined f o r
each s o l u t e i n v o l v e d i n t h i s work from experimental r e s u l t s of
reverse osmosis and l i q u i d chromatography. The method used was
as f o l l o w s :
Step 10. Assume s o l u t e r a d i u s D.
Step 11. Same as step 2 b e f o r e , c a l c u l a t e B.
Step 12. R^ i s now known f o r the membrane under c o n s i d e r a t i o n ;
c a l c u l a t e b.
c
Step 13. Same as step 4 b e f o r e , assume c^g and c a l c u l a t e ^ 2 *
Step 14. Same as step 5 b e f o r e , c a l c u l a t e 3i and $2«
Step 15. Same as step 6 b e f o r e , c a l c u l a t e a(p) as a f u n c t i o n of
P.
Step 16. Same as step 7 b e f o r e o b t a i f '
Step 17. Same as step 8
the value assumed i n step , g step , g
to step 13.
Step 18. C a l c u l a t e f from £'. I f i t agrees w i t h experimental f ,
D assumed i n step 10 i s regarded as the f i n a l s o l u t i o n . Other-
wise, go back to step 10.
By the method described above D and B were c a l c u l a t e d f o r a l l
s o l u t e s i n v o l v e d except the reference s o l u t e g l y c e r o l . In Table
I I , D and B are l i s t e d together w i t h e q u i l i b r i u m constant
obtained by l i q u i d chromatography data. For comparison molecular
r a d i u s , r , c a l c u l a t e d from eq 34 i s a l s o l i s t e d u s i n g e x p e r i -
A
mental D^B data a v a i l a b l e i n the l i t e r a t u r e . The agreement

between D and r ^ i s s u r p r i s i n g l y good f o r most of the s o l u t e s
except e t h y l a c e t a t e , phenol and r e s o r c i n o l f o r which D values
c a l c u l a t e d by combination of reverse osmosis and l i q u i d chroma-
tography data were s i g n i f i c a n t l y smaller than r ^ . I t must be
noted that D was evaluated without any reference to r ^ . There-
f o r e , t h i s agreement t e s t i f i e s the v a l i d i t y of surface force-pore
flow model f o r reverse osmosis t r a n s p o r t , and a l s o the form of
the p o t e n t i a l f u n c t i o n and p a r t i c u l a r l y that of the f r i c t i o n a l
f u n c t i o n b. Figure 6 and 7 i l l u s t r a t e the p o t e n t i a l f u n c t i o n s
f o r two s p e c i a l cases where the s o l u t e i s s t r o n g l y r e j e c t e d from
the membrane pore (solute=glucose) and the s o l u t e i s s t r o n g l y
adsorbed onto the membrane pore w a l l ( s o l u t e = t - b u t y l i - p r o p y l
ether).
Reverse Osmosis Separation of Various Organic Solutes Using

Membranes of D i f f e r e n t P o r o s i t i e s . Since R^ f o r a l l membranes,
B and D f o r a l l s o l u t e s i n v o l v e d i n t h i s work are now a v a i l a b l e
(Table I and I I ) , i t i s p o s s i b l e to c a l c u l a t e the s o l u t e separa-
t i o n , f , f o r a l l membranes other than those used f o r the d e t e r -
mination of B and D and f o r a l l s o l u t e s other than the reference
solute.
The c a l c u l a t i o n i s s t r a i g h t from step 3 to step 9 described

T a b l e I I . D i f f u s i v i t i e s of S o l u t e s , E q u i l i b r i u m C o n s t a n t s
C a l c u l a t e d from HPLC Data and C h a r a c t e r i s t i c C o n s t a n t s
D e f i n i n g I n t e r f a c i a l F o r c e s f o r the System C e l l u l o s e
A c e t a t e (Eastman E-398) - Water
b
D
AB X l
° >9 m 2 / s C
D, B,
Solute K' r
A'
a t 25°C o o 3
A A i
Methanol 1 69 1.077 1 85 1 45 8.31
Ethanol 1 19 1.474 2 03 2 05 21.54
1-Propanol 1 15 2.385 2 15 2 12 37.77
2-Propanol 1 08 1.564 2 45 2 26 38.40
1-Butanol 1 05 a
4.705 2 10 47 .27
2-Butanol 1 05 a
3.154 2 45 62.15
2-Methyl-l-propanol 0 80 4.205 2 75 3 05 95.57
2-Me thy1-2-p ropano1 0 73 1.897 3 67 3 35 134.3
1-Hexanol
Acetone
M e t h y l e t h y l ketone 1 08 4.307 1 92 1. 9 2 35.87
M e t h y l i s o p r o p y l ketone o 943 a
7.923 2 45 83.67
M e t h y l i s o b u t y l ketone 0 853 a
15.69 2 45 97.88
Cyclohexanone 0 883 a
10.59 2 72 120.8
D i i s o p r o p y l ketone 0 786 a
28.46 2 62 131.7
Methyl a c e t a t e 1 19 a
4.821 1 73 27.88
Ethyl acetate 1 02 7.308 1 83 2. 39 36.41
Ethyl propionate 0 91 a
14.33 1 88 45.63
Ethyl b u t y l ether 0 834 a
6.333 2 53 86.45
E t h y l t - b u t y l ether 0 834 a
20.44 5 30 901.2
I s o p r o p y l t - b u t y l ether 0 767 a
11.72 5 60 918.2
Propionamide 1 09 1.410 1 98 2 24 19.13
Acetonitrile 1 66 4.128 1 78 1 47 28.49
Propionitrile 1 32 a
7.436 1 78 34.20
Nitromethane 1 48 a
8.077 1 80 36.00
a
1-Nitropropane 1 22 28.15 2 05 65.76
Phenol 1 16 75.21 1 71 2 10 45.39
Resorcinol 0 89 55.87 1 73 2 74 45.16
Aniline 1 01 a
46.46 1 80 48.98
Dimethyl a n i l i n e 0 816 a
47.9-7 2 50 125.8
1,2-Ethanediol 1 16 0.692 2 20 2 11 -16.82
Glycerol 1 06 0.513 2 30 2 30 -52.30
2,3-Butanediol 0 994 a
0.846 2 75 -11.97
Xylitol 0 815 a
0.308 3 30 -135.0
1,2,6-Hexanetriol 0 796 a
0.667 2 82 -16.95
D-Sorbitol 0 739 a
0.205 4 64 -180.2
D-Glucose 0 67 0.180 3 36 3 66. -203.1
D-Fructose 0 758 a
0.205 4 51 -181.8
Sucrose 0 52 -o 5 11 4 67 -343.2
Maltose 0 49 ~0 4 98 4 98 -346.0
From Wilke-Chang equation (16).
M o l e c u l a r r a d i u s was c a l c u l a t e d by eq 34 o n l y when measured

d i f f u s i v i t y d a t a were a v a i l a b l e i n the l i t e r a t u r e .
C
* From l i t e r a t u r e (17,18).
D i f f u s i o n c o e f f i c i e n t s were c o n v e r t e d to v a l u e s a t 25°C by
eq 34.
d.
Data o b t a i n e d from d i f f u s i o n i n benzene.

Figure 6. Potential curve of interfacial force for the system CA (E-398) material-
water-glucose and an imaginary solute

MATSUURA ET AL. Interfacial Forces Governing the RO System 333
Figure 7. Potential curve of interfacial force for the system CA (E-398) material-
water-t-butyl-iso-propyl ether

above without any assumption i n values of R-^, B, and D. The

c a l c u l a t e d s e p a r a t i o n data so obtained versus experimental values
are p l o t t e d i n Figure 8. A t o t a l of 140 data p o i n t s obtained are
crowded along the diagonal l i n e , i n d i c a t i n g the good agreement
between c a l c u l a t e d and experimental v a l u e s . This r e s u l t again
t e s t i f i e s the v a l i d i t y of the surface force-pore flow model, and
a l s o the form of the p o t e n t i a l f u n c t i o n of the i n t e r f a c i a l f o r c e
working on the s o l u t e and the f r i c t i o n a l f u n c t i o n a f f e c t i n g
d i f f u s i o n i n membrane pores.
E f f e c t of P o t e n t i a l Function on Solute Separation. As shown

i n Figures 6 and 7, glucose i s s t r o n g l y r e p e l l e d from the membrane
pore w a l l as the r e s u l t of the p o s i t i v e p o t e n t i a l working i n the
e n t i r e range of the d i s t a n c e of s o l u t e from the pore w a l l , w h i l e
t - b u t y l i - p r o p y l ether i s s t r o n g l y adsorbed onto the pore w a l l as
the r e s u l t of the deep negative value of the p o t e n t i a l i n the
v i c i n i t y of the i n t e r f a c e
has the same molecular r a d i u
adsorbed onto the pore w a l l ; then what k i n d of s o l u t e s e p a r a t i o n
w i l l take place as the reverse osmosis performance data w i t h a
p a r t i c u l a r membrane p o r o s i t y ? In order to answer t h i s question
the e f f e c t of o p e r a t i n g pressure on f and (PR)/(PWP) f o r glucose
s o l u t e and f o r an imaginary s o l u t e , whose D and B are each equal
3
to 3.36A and 500A , as i n d i c a t e d by the dotted l i n e i n Figure 6,
was c a l c u l a t e d and the r e s u l t i s i l l u s t r a t e d i n F i g u r e 9 f o r the
membrane whose pore s i z e , R^, i s 7.36A.
The r e s u l t obtained c l e a r l y shows the e f f e c t of the
p o t e n t i a l f u n c t i o n on the reverse osmosis experimental data. The
f o l l o w i n g three conclusions can be reached immediately from
Figure 9.
1. The imaginary s o l u t e w i t h a high a d s o r p t i o n c a p a c i t y to the
membrane pore w a l l shows s i g n i f i c a n t l y l e s s separations than
glucose.
2. Data on (PR)/(PWP) f o r the imaginary s o l u t e i s a l s o s i g n i f i -
c a n t l y l e s s than u n i t y w h i l e that f o r glucose i s e s s e n t i a l l y
u n i t y i n d i c a t i n g considerable pore b l o c k i n g i n the former system.
3. As pressure increases the s e p a r a t i o n of the imaginary s o l u t e
tends to decrease w h i l e that of glucose tends to i n c r e a s e . A l l
the above r e s u l t s are e n t i r e l y c o n s i s t e n t w i t h experimental
r e s u l t s discussed i n the previous work (_1) .
Conclusion
In t h i s work HPLC experimental data were combined w i t h

surface force-pore flow model to determine the parameters
i n v o l v e d i n the surface p o t e n t i a l f u n c t i o n and the f r i c t i o n a l
f u n c t i o n which represent the surface f o r c e working on the s o l u t e
molecule a t the p o l y m e r - s o l u t i o n i n t e r f a c e i n the membrane pore.
The use of the p o t e n t i a l and f r i c t i o n a l f u n c t i o n s so
obtained enables one to c a l c u l a t e the s o l u t e s e p a r a t i o n f o r each
s o l u t e s t u d i e d under a given o p e r a t i n g c o n d i t i o n . The good

0 20 40 60 80 100
SOLUT
Figure 8. Comparison of calculated and experimental solute separation for vari-

ous undissociated polar organic solutes. Membrane material, CA (E-398); operat-
3
ing pressure = 1724 kPa gauge (250 psig); feed flow rate = 400 cm /min; dilute
solution systems.
CL
1.0
a.
2 _l I L
0
100
R
l = 7.36 x I 0 " ' ° m
80
- D = 3.36 x I 0 " ' ° m ^(GLUCOSE)
B = -203.1 x I O " m 30 2
D = 3.36xl0" m , 0
\ (IMAGINARY
B = 5 0 0 . 0 x l 0 - 3 0 3 J SOLUTE m
<
&
UJ
40
to
LxJ
I—
3
o
if)
1 1 1 1 1 1 1 1 1 1 1 1
50 100
2
PRESSURE x l O " , kPa
Figure 9. Effect of pressure on the (PR)/(PWP) ratio and solute separation of

glucose and an imaginary solute. Membrane material, CA (E-398); membrane pore
3 3
radius = 7.36 A; feed flow rate = 400 cm /min; feed concentration = 1 mol/m .

agreement between the c a l c u l a t e d and experimental values t e s t i f i e s

the v a l i d i t y of the model used and the forms of p o t e n t i a l as w e l l
as f r i c t i o n a l f u n c t i o n s .
I t was a l s o shown that the change of reverse osmosis p e r f o r -
mance data of a p a r t i c u l a r s o l u t e w i t h the change i n pore s i z e of
the membrane and the experimental operating c o n d i t i o n such as
operating pressure depends s i g n i f i c a n t l y on the r e l a t i v e magni-
tude of the d i s t a n c e a s s o c i a t e d w i t h the s t e r i c r e p u l s i o n a t the
i n t e r f a c e and the q u a n t i t y r e p r e s e n t i n g the a f f i n i t y of the
s o l u t e molecule to the polymer s u r f a c e .
The f r i c t i o n a l f u n c t i o n which was described as a f u n c t i o n of
the r a t i o of the distance a s s o c i a t e d w i t h the s t e r i c r e p u l s i o n a t
the i n t e r f a c e to the pore r a d i u s , however, i s s t i l l an a p p r o x i -
mation a t most, though i t i s convenient t o use, due to i t s
s i m p l i f i e d form. A more appropriate f u n c t i o n a l form i n c l u d i n g
both s t e r i c r e p u l s i o n and i n t e r f a c i a l a f f i n i t y e f f e c t s on the
r e s t r i c t e d motion of th
yet to be developed. A
is called for.
Nomenclature
2
A =
pure water p e r m e a b i l i t y constant, kg-mol HLO/m s kPa
B =
constant c h a r a c t e r i z i n g p o t e n t i a l f u n c t i o n , m^
b =
f r i c t i o n a l f u n c t i o n defined by eq 33
=
dimensionless s o l u t e c o n c e n t r a t i o n defined by eq 2
c =
molar c o n c e n t r a t i o n of s o l u t i o n , mol/m^
c^ =
molar c o n c e n t r a t i o n of s o l u t e , mol/m
C =
AB roolar^concentration of s o l u t e i n the bulk s o l u t i o n ,
mol/m
c = m a r
Ai ol c o n c e n t r a t i o n of s o l u t e i n the i n t e r f a c i a l
s o l u t i o n , mol/nr*
D = distance a s s o c i a t e d w i t h s t e r i c r e p u l s i o n a t the
interface, m
=
9water molecular r a d i u s of water, m
D =
AB d i f f u s i v i t y of s o l u t e i n water, n r / s
D ffe = e f f e c t i v e d i f f u s i v i t y of s o l u t e i n the pore i n c l u d i n g
t o t u o s i t y f a c t o r , m^/s 2
D m = e f f e c t i v e d i f f u s i v i t y of s o l u t e i n the pore, m/s
D K(
( AM/ 5) = s o l u t e t r a n s p o r t parameter ( t r e a t e d as a s i n g l e
q u a n t i t y ) , m/s
d = distance between pore w a l l and the center of s o l u t e
molecule, m
E = constant c h a r a c t e r i z i n g f r i c t i o n a l f u n c t i o n , m
f = f r a c t i o n s o l u t e s e p a r a t i o n based on the feed
concentration
f' = f r a c t i o n s o l u t e s e p a r a t i o n based on the s o l u t e
c o n c e n t r a t i o n i n the boundary phase
K' = e q u i l i b r i u m constant between concentrations of i n t e r -
f a c i a l s o l u t i o n - and bulk s o l u t i o n phase

k = mass t r a n s f e r c o e f f i c i e n t f o r s o l u t e on high pressure

s i d e of membrane, m/s
k = Boltzmann constant
P. = operating pressure, Pa when used i n eq 5, kPa when
used w i t h A
P = atmospheric pressure, Pa when used i n eq 5, kPa when
used w i t h A
(PR) = membrane permeated product r a t e f o r given area of
membrane s u r f a c e , g/h
(PWP) = pure water permeation r a t e f o r given area of membrane
s u r f a c e , g/h
R = pore r a d i u s , m
R R = p o r e r a
l' 2 ^ i i defined i n Figure 5, m o r A when used i n
eq 36
R = gas constant
r = r a d i a l distance i n c y l i n d r i c a l coordinate m
r^ = molecular r a d i u
T = absolute temperature
t± = thickness o f i n t e r f a c i a l water l a y e r , m
Ug = v e l o c i t y of s o l v e n t i n the pore, m/s
[VR] = chromatography r e t e n t i o n volume, m^
V G = volume of s t a t i o n a r y phase water, m^
v s = permeation v e l o c i t y of product s o l u t i o n , m/s
v* = pure water permeation v e l o c i t y , m/s
Greek L e t t e r s
a = dimensionless q u a n t i t y d e f i n e d by eq 3
$1 = dimensionless q u a n t i t y defined by eq 4
=
$2 dimensionless q u a n t i t y defined by eq 5
T = surface excess, mol/m^
6 = l e n g t h of c y l i n d r i c a l pore, m
n = s o l u t i o n v i s c o s i t y , Pa*s
X = q u a n t i t y d e f i n e d by eq 27
p = dimensionless q u a n t i t y d e f i n e d by eq 1
$ = dimensionless q u a n t i t y defined by eq 6
<j> = p o t e n t i a l f u n c t i o n of f o r c e exerted on s o l u t e
molecule by pore w a l l , J/mol
=
XAB q u a n t i t y defined by eq 35
Subscripts
1 = b u l k feed s o l u t i o n
2 = concentrated boundary s o l u t i o n on the high pressure
s i d e of membrane
3 = membrane permeated product s o l u t i o n on the low
pressure s i d e of membrane

Acknowledgments
The authors a r e g r a t e f u l to A.G. Baxter f o r h i s v a l u a b l e

a s s i s t a n c e i n the progress of these i n v e s t i g a t i o n s . One of the
authors (Y.T.) thanks the N a t i o n a l Research C o u n c i l of Canada f o r
the award of a p o s t d o c t o r a l research a s s o c i a t e s h i p .
Literature Cited
1. Matsuura, T.; S o u r i r a j a n , S. Ind. Eng. Chem., Process Des.

Dev., ( i n p r e s s ) .
2. Matsuura, T.; Blais, P.; S o u r i r a j a n , S. J. A p p l . Polym. Sci.,
1976, 20, 1515.
3. Matsuura, T.; S o u r i r a j a n , S. J. A p p l . Polym. Sci., 1971, 15,
2905.
4. Matsuura, T.; S o u r i r a j a n S J. A p p l Polym Sci., 1972 16
1663.
5. Matsuura, T.; S o u r i r a j a n
1043.
6. Matsuura, T.; Baxter, A.G.; S o u r i r a j a n , S. Ind. Eng. Chem.,
Process Des. Dev., 1977, 16, 82.
7. S o u r i r a j a n , S., "Reverse Osmosis"; Academic: New York, 1970;
Chap. 3.
8. Rangarajan, R.; Matsuura, T.; Goodhue, E.C.; S o u r i r a j a n , S.
Ind. Eng. Chem., Process Des. Dev., 1976, 15, 529.
9. Matsuura, T.; S o u r i r a j a n , S. J. Coll. I n t .Sci.,1978, 66,
589.
10. Robinson, R.A.; Stokes, R.H., " E l e c t r o l y t e S o l u t i o n s " , 2nd
ed.; Butterworths: London, 1959; p. 13.
11. Anderson, J.L.; Quinn, J.A. Biophys. J., 1974, 14, 130.
12. Faxen, H. Kolloid Z., 1959, 167, 146.
13. Beck, R.E.; S c h u l t z , J.S. Biochim. Biophys. A c t a , 1972, 255,
253.
14. Satterfield, C.N.; C o l t o n , C.K.; P i t c h e r , W.H., Jr.
A.I.Ch.E.J., 1973, 19, 628.
15. Lane, J.A.; R i g g l e , J.W. Chem. Eng. Progr. Symposium Ser.,
1959, 55 (24) 127.
16. W i l k e , C.R.; Chang, P. A.I.Ch.E.J., 1955, 1, 264.
17. N a t i o n a l Research Council of the United States of America,
" I n t e r n a t i o n a l Critical Tables of Numerical Data", V o l . V,
First ed.; McGraw-Hill: New York, 1929.
18. L a n d o l t - B o e r n s t e i n , "Zahlenwerte und Funktionen aus Physik-
Chemie-Astronomie Geophysik und Technik", 6th ed., V o l . 2,
No. 5; Springer: Berlin, 1969.
Issued as NRC No. 18590

20
Reverse-Osmosis Separations of Alkali Metal
Halides in Methanol Solutions Using Cellulose
Acetate Membranes
B R I A N A . F A R N A N D and F . D . F . T A L B O T
Department of Chemical Engineering, University of Ottawa, Ottawa
T A K E S H I M A T S U U R A and S. S O U R I R A J A N
Division of Chemistry, National Research Council of Canada, Ottawa
Virtually all reverse osmosis separations have been made

w i t h water as the majo
aqueous salt s o l u t i o n s
literature (1, 2 ) . While separations in nonaqueous s o l u t i o n
systems have been i n v e s t i g a t e d (3, 4, 5 ) , no organized study o f
such systems has been made and there are no r e p o r t s in t h e
literature of u s i n g reverse osmosis t o separate i n o r g a n i c s a l t s
in nonaqueous s o l u t i o n s . F o r these reasons, the reverse osmosis
s e p a r a t i o n of alkali metal h a l i d e s in methanol s o l u t i o n s u s i n g
porous c e l l u l o s e acetate membranes has been s t u d i e d in this work.
Previous work w i t h aqueous s o l u t i o n systems has been
s u c c e s s f u l in t r e a t i n g both completely i o n i z e d salts as well as
incompletely i o n i z e d salts (2, 6 ) . T h i s work i n c o r p o r a t e s both
of these cases in methanol s o l u t i o n s and uses the Kimura-
Sourirajan a n a l y s i s f o r t h e treatment of reverse osmosis data
(7). The surface excess f r e e energy parameters (-ΔΔ/RT) for t h e
ions and ion p a i r s i n v o l v e d were determined by the methods
e s t a b l i s h e d earlier ( 8 ) . The predictability of membrane
performance by the use o f data on f r e e energy parameters obtained
in this work has been t e s t e d .
Removal of d i s s o l v e d i n o r g a n i c i m p u r i t i e s from methanol is
of i n t e r e s t from the p o i n t of view of utilization of methanol as
an a l t e r n a t i v e t o conventional fuels. Reports show that t h e
c o r r o s i o n r a t e of metal alloys used f o r t u r b i n e s and fuel
t r a n s p o r t a t i o n is g r e a t e r in methanol than in water in t h e
presence of t r a c e s of c h l o r i n e and sodium ions (9, 1 0 ) . F u r t h e r ,
i o n complexes in t r a c e q u a n t i t i e s have been observed in methanol
and there is concern that they could alter the r e a c t i o n kinetics
f o r processes which use methanol as a feedstock o r r e a c t i o n
medium (11). Methanol t h a t is used as a feedstockinthe
p r o d u c t i o n o f s i n g l e cell p r o t e i n could be sterilized as well as
purified of heavy metals by reverse osmosis which can be
i n t e g r a t e d in the d e s i g n of these processes.
0097-6156/81/0154-0339$05.25/0

Table I . P h y s i c a l P r o p e r t i e s of L i C l - M e t h a n o l S o l u t i o n s
mol fraction TT b
ÂB
3
x 10 kPa 2
m /s x 10 1 0
mol f r a c t i o n basis
0 0 12.07 1.000
1.0 71 7.74 .496
2.0 155 7.65 .384
3.0 235 8.02 .333
4.0 318 8.47 .304
5.0 403 8.93 .285
6.0 495 9.37 .273
7.0 592 9.79 .265
8.0 675
9.0 755
10.0 839 10.95 .251
11.0 925 11.29 .250
12.0 993 11.68 .248
a
from (14)
b
from (15)
Table I . - Cont'd
P h y s i c a l P r o p e r t i e s of L i B r - M e t h a n o l S o l u t i o n s
ÂB Y ±
mol fraction 7T
x 10 3
kPa 2
m /s x 10 1 0
mol f r a c t i o n basis
0 0 12.56 1.000
1.0 71 8.05 .496
2.0 155 7.96 .384
3.0 235 8.35 .333
4.0 318 8.81 .304
5.0 403 9.29 .285
6.0 495 9.75 .273
7.0 592 10.19 .265
8.0 675 10.61 .259
9.0 755 11.02 .254
10.0 839 11.39 .251
11.0 925 11.75 .250
12.0 993 12.15 .248
a
from (16)

20. FARNAND ET AL. RO Separations of Alkali Metal Halides 341
Table I . - Cont'd
P h y s i c a l P r o p e r t i e s of NaCl-Methanol S o l u t i o n s
a b
mol f r a c t i o n TT ÂB Y + >

2
x 103 kPa m /s x 10 1 0
mol f r a c t i o n b a s i s
0 0 13.17 1.000
1.0 74 7.25 .428
2.0 155 7.17 .332
3.0 241 7.33 .285
4.0 327 7.51 .257
5.0 406 7.68 .239
6.0 488 7.89 .226
7.0 558 8.09 .217
8.0 648
9.0 725
10.0 803 8.69 .202
a
from (17)
b
from (18)
c
from (19)
d
from (15)
Table I . - Cont'd
P h y s i c a l P r o p e r t i e s of NaBr-Methanol Solutions
b 0AB
mol f r a c t i o n TT
3
x IO kPa m2/ s x 10 1 0
0 0 13.37 1.000
1.0 86 12.09 .658
2.0 181 11.31 .581
3.0 282 10.98 .536
4.0 385 10.73 .504
5.0 488 10.54 .479
6.0 594 10.39 .459
7.0 690 10.27 .442
8.0 795 10.17 .427
9.0 898 10.09 .414
10.0 1001 - .403
12.0 1203 - .382
14.0 1408 - .365
16.0 1613 - .350
18.0 1818 - .337

from (18)
b
from (19)
Table I . - Cont'd
P h y s i c a l P r o p e r t i e s of KI-Methanol S o l u t i o n s
ÂB Y± A
mol f r a c t i o n
2
x 10 3
kPa m /s x iolO mol f r a c t i o n b a s i s
0 0 15.20 1.000
1.0 74 13.02 .545
2.0 150 11.95 .472
3.0 230 11.40 .428
4.0 306
5.0 394
6.0 466 10.64 .355
7.0 538 10.34 .338
8.0 613 10.14 .324
9.0 696 9.85 .311
10.0 780 9.59 .300
a
from (14)
b
from (20)
Table I . - Cont'd
P h y s i c a l P r o p e r t i e s of CsCl-Methanol S o l u t i o n s
b ÂB Y+ A
mol f r a c t i o n TT
2
x 10 3
kPa m /s x 10 1 0
0 0 14.98 1.000
1.0 74 7.89 .428
2.0 155 7.81 .332
3.0 241 7.98 .285
4.0 327 8.18 .257
5.0 406 8.36 .239
a
from (21)
b
from (15)

Table I . - Cont'd
L i m i t i n g D i f f u s i o n C o e f f i c i e n t s of A l k a l i
M e t a l H a l i d e s i n Methanol
Solute ÂB
2
m /s x 10l0
LiCl 12.07
LiBr 12.56
NaCl 13.17
NaBr 13.37
Nal 14.03
KF
KC
KBr 14.41
KI 15.20
RbCl 14.33
CsCl 14.98
CsBr 15.16
Table I I . Bulk S o l u t i o n Free Energy of S o l v a t i o n f o r

A l k a l i M e t a l and H a l i d e Ions i n Methanol
Solutions
Ion Crystallographic
radius
nm kJ/mol
+
Li 6.0 481.9 a
481.9 b
Na+ 9.5 385.5 385.5

K+ 13.3 314.3 314.3
Rb+ 14.8 289.1 289.0
Cs+ 16.9 249.3 247.2
F" 13.6 _ _
CI" 18.1 305.9 -
Br"
I-
19.5
21.6
282.8
253.5
-
—
a
from (22)
b
from (23)

Experimental
Twelve a l k a l i metal h a l i d e s were used i n s i n g l e s o l u t e

methanol s o l u t i o n systems with c e l l u l o s e acetate batch 316
(10/30) membranes at pressures of 1725 kPa gauge (250 psig) and
3450 kPa gauge (500 p s i g ) ( 1 ) . The membranes were heat t r e a t e d
i n water and then solvent exchanged to methanol by immersion i n
s u c c e s s i v e l y concentrated methanol-water s o l u t i o n s . A f t e r a pure
methanol immersion had been completed, the membranes were loaded
i n t o c e l l s and subjected to pressures of 120% of the subsequent
operating pressures f o r one h o u r . The apparatus used was the
same as reported e a r l i e r with the a d d i t i o n of a temperature
c o n t r o l l e r to keep the temperature of the feed s o l u t i o n at
25 ± 0 . 5 ° C ( 2 ) . The concentrations of the feed s o l u t i o n s
i n v o l v e d were i n the range of 0.005 m to 0.45 m and the o p e r a t i n g
pressure was e i t h e r 172
(500 p s i g ) . A l l experiment
3
flow r a t e of 490 c m / m i n . For each experiment, pure solvent
permeation r a t e s (PSP) and product r a t e s (PR) as w e l l as s o l u t e
s e p a r a t i o n (f) defined as:
f - feed m o l a l i t y - permeate m o l a l i t y
^ feed m o l a l i t y
were determined. A n a l y s i s of the c o n c e n t r a t i o n of the v a r i o u s

s a l t s i n both the feed and the permeate s o l u t i o n s was by e i t h e r
e l e c t r i c a l conductance or atomic a b s o r p t i o n spectroscopy.
Results and D i s c u s s i o n
P h y s i c a l P r o p e r t i e s . The c a l c u l a t i o n of osmotic pressure

r e q u i r e s values of the s o l v e n t ' s thermodynamic a c t i v i t y f o r each
solution. The s o l u t e mean a c t i v i t y c o e f f i c i e n t s , y
+9 are
reported i n the l i t e r a t u r e and t h e i r transformation"to
solvent a c t i v i t i e s was made by use of the Gibbs-Duhem r e l a t i o n
(12). The d i f f u s i o n c o e f f i c i e n t , ^^g* was determined f o r each
s o l u t e by the Nernst-Haskel equation (13). These are presented
i n Table I along with osmotic p r e s s u r e s . The f r e e energy of
s o l v a t i o n f o r the b u l k s o l u t i o n (Ac7g) f o r each i o n considered and
the d i s s o c i a t i o n constant ( i £ ) of r e l e v a n t s a l t s are given i n
D
Tables I I and I I I r e s p e c t i v e l y .
Basic Transport E q u a t i o n s . The Kimura-Sourirajan a n a l y s i s

of experimental reverse osmosis data leads to the f o l l o w i n g b a s i c
t r a n s p o r t equations (2, 1_, 8) :
A = <im ( 2 )
M B • S • 3600 • P K
'

N = A • (P - TT
2 + TT ; 3 (3)
AM 1 ^ A Q
AM I A3 , v v \ (4)
(5)
A l l symbols are d e f i n e d at the end of the paper. In the range

of s o l u t i o n concentrations used i n t h i s work, the molar d e n s i t y
of s o l u t i o n , o i s e s s e n t i a l l
9
25°C) so that 0 ^ = 0 2 = 0 3
become:
A3
X KO
1
A2 A3
A3
A2 A 3
= k • a • (l-X.J • l n (l y ) (7)
U x
Ar A y 3
Using equations 2, 3, 6, and 7, one can c a l c u l a t e the values of

A ÂM/£6, and k f o r each membrane f o r each set of experimental
3
(PSP), (PR), and / data corresponding to s p e c i f i e d experimental

conditions.
For the case of completely d i s s o c i a t e d u n i v a l e n t s a l t s i n
s o l u t i o n the s o l u t e t r a n s p o r t parameter (ÂM./K6) has been shown
to be (2):
n
where l £|j ci represents the p o r o s i t y of the membrane s u r f a c e ,
a
s u b s c r i p t i represents the ions i n v o l v e d and AAG i s the surface

excess f r e e energy of s o l v a t i o n d e f i n e d as:
AA6 = AGT - A£ (9)

I B
where A£ i s the f r e e energy of s o l v a t i o n and the s u b s c r i p t s I

and B represent the membrane-solution i n t e r f a c e and the bulk
s o l u t i o n phase r e s p e c t i v e l y .

I t i s known t h a t i n methanol s o l u t i o n s , s o l u t e s i n v o l v i n g
monovalent i o n s , even i n low c o n c e n t r a t i o n s , are subject t o
s i g n i f i c a n t i o n p a i r formation (28a). For s o l u t i o n systems
i n v o l v i n g both ions and i o n p a i r s , eq. (8) becomes ( 6 ) :
•AAg
m =mc* aC1 +
+ (l-a) (10)
where the s u b s c r i p t IP represents t h e i o n p a i r and a represents

the degree of d i s s o c i a t i o n defined as (28b):
2
A2
(11)
(l-a)
where K-Q i s t h e i o n i c
ionic activity coefficient
-3 + A 2
+ 43 (12)
where
•j
(13)
F i g u r e 1 gives the c o r r e l a t i o n of a w i t h 3 . I t should be

noted that f o r s m a l l values of X^* & i s
l a r g e and approaches
u n i t y which corresponds t o complete d i s s o c i a t i o n .
C o r r e l a t i o n of k w i t h A. Values of the mass t r a n s f e r

c o e f f i c i e n t k were determined by reverse osmosis experiments w i t h
NaCl-methanol s o l u t i o n s a t 0.15 m u s i n g s e v e r a l membranes, of
d i f f e r e n t s u r f a c e p o r o s i t i e s . The p l o t of k versus A i n F i g u r e
2 gives a l i n e a r c o r r e l a t i o n which can be expressed by the
relation.
0.9201 04 x i o * + 12.17) x i o " (14)
To o b t a i n values of k a t other concentrations and a l s o f o r

d i f f e r e n t s o l u t e s , the Schmidt-Sherwood c o r r e l a t i o n f o r constant
Reynold's number was used (29):
n 2/3
AB
k = k (15)
ref (
W ref

FARNAND ET AL. RO Separations of Alkali Metal Halides
Figure 2. Mass-transfer coefficient with pure solvent permeability for 0.15m NaCl
and 1725 kPa

where i s the d i f f u s i v i t y of the s o l u t e A i n the solvent B

and the s u b s c r i p t " r e f " r e f e r s to the data f o r NaCl at 0.15 m
and 25°C.
(-AAG/RT)ifor Ions. The f o l l o w i n g r e l a t i o n s h i p s have been

d e r i v e d and discussed elsewhere (2):
1 = -1 _ ^B
(16)
B,i B B
J L = zk _ _I (17)
AAG.
(v. +A
i I)
The q u a n t i t i e s E and A are constants f o r each c l a s s of i o n s , and

Eft and Ag have been determined by a l i n e a r p l o t of 1/A£g w i t h
the P a u l i n g i o n i c radius i n F i g u r e 3 which gave # and A B B
values of 656.5 kJ^nm-mol"! and 0.0753 nm r e s p e c t i v e l y f o r the

c a t i o n s and 492.9 kJ-nm-mol""! and -0.0180 nm r e s p e c t i v e l y f o r the
h a l i d e i o n s . These are compared to those f o r water i n Table IV.
Using eq. (18), eq.(8) may be w r i t t e n as:
(19)
L A
V B/X
Reverse osmosis experiments were performed with 12 s a l t s and

four membranes and the r e s u l t s obtained are given i n Table V.
These r e s u l t s were used to o b t a i n values f o r (D^/K6)^ x" • + T h e
4 A + a n d A
unknown q u a n t i t i e s l n C * , (^J^M "' ^ I ^ M » ^ I ^ X " »
a C 1 ^ I^X"
were determined by r e g r e s s i o n a n a l y s i s and are g i v e n i n Table I V .
They were used to determine values of (-AAc7/RT) f o r d i f f e r e n t i
ions which are compared to those f o r aqueous s o l u t i o n s i n Table

VI.
(-AA£/RT)jp f o r Ion P a i r s . For the case where i o n p a i r s

had a s i g n i f i c a n t e t t e c t , eq. (10) was used i n p l a c e of eq. (19).

FARNAND ET AL. RO Separations of Alkali Metal Halides 349
Table I I I . Values of D i s s o c i a t i o n Constant,

Kfi, f o r Various Ion P a i r s
Ion P a i r ^D Ref.
LiCl .01059 (24)

LiBr .0105
NaCl .00412
NaBr .003996 (26)
KI .004058 (26)
CsCl .004539 (27)
Table IV. Values of Born Equation Parameters,

C e l l u l o s e Acetate (Eastman E-398)
E
h A
B i i A
Ion Class , , 9 i - i - l m2
kJ«nm«mol
T x
nm x 10^ kJ-nm«mol
n T
nm x 10^ v
A l k a l i Metal 656.5 7.53 665.6 7.81

C a t i o n , Methanol
H a l i d e Anion, 492.9 -1.80 492.9 -1.80

Methanol
A l k a l i Metal 761.5 8.9 824.7 9.76

Cation, Water
H a l i d e Anion, 504.2 -2.0 477.4 -2.30

3
Water
a
from (2)

Table V . Separations and Permeation Rates f o r Some A l k a l i

Metal Halide S a l t s
Membrane
1 2 5 6
Solute Run
Number (PR) (PR) f (PR) / (PR)
LiCl 39 21.50 .802 5.20 .831 20.05 .806 3.17 .876

LiBr 41 21.78 .782 5.20 .829 20.42 .789 3.11 .888
NaCl 13 21.22 .589 5.32 .729 20.21 .631 3.31 .803

NaCl 27 21.67 .613 5.25 .718 20.12 .622 3.24 .775
NaCl 28 21.66 .612 5.22 .720 20.28 .619 3.24 .783
NaBr 38 21.92 .56 20.43 .577 3.22 .764
Nal 12 21.39
KF 50 22.01 .603 5.26 .706 20.39 .614 3.23 .774

KC1 42 21.62 .461 5.15 .606 20.11 .470 3.14 .678
KBr 43 21.76 .435 5.15 .577 20.21 .443 3.15 .642
KI 44 21.49 .432 5.05 .563 19.89 .419 3.08 .623
Kl 45 21.68 .411 5.14 .560 20.18 .428 3.15 .622
RbCl 15 21.41 .455 5.31 .623 20.09 .464 3.24 .732
CsCl 14 21.59 .437 5.35 .612 20.15 .456 3.27 .670

CsBr 46 21.59 .415 5.06 .566 19.94 .415 3.11 .623
Operating p r e s s u r e , 1724 kPa gauge; Feed s o l u t i o n , 0.005 m;

Product r a t e s are g/h f o r 1.32 x 10-3 2 membrane s u r f a c e .
m
Table V I . Values of (-AAG/RT).
Ion r
i> Methanol Water
nm (-AAG/RT)i
+
Li 6.0 -1.36 5.77
Na+ 9.5 -0.427 5.79
K+ 13.3 0.033 5.91
Rb+ 14.8 0.138 5.86
Cs+ 16.9 0.244 5.72
F" 13.6 -2.34 -4.91
ci- 18.1 -1.71 -4.42
Br" 19.5 -1.58 -4.25
I" 21.6 -1.41 -3.98
a from (2)

5.0
r., nm
Figure 3. Born Equation for alkali metal and halide ions—bulk-phase free energy
of solvation in methanol solutions
Table V I I . Values of
Average a, f o r
Ion P a i r 0.15 m feed,
determined at
NaCl 0.73 -1.295

NaBr 0.80 -0.343
KI 0.85 5.175
CsCl 0.82 1.706
LiCia =a.o -
LiBr a
^1.0 -
Kj) i s so l a r g e that a i s considered as

u n i t y f o r the c o n c e n t r a t i o n ranges
used i n t h i s work.

Reverse osmosis experiments were performed w i t h the same

membranes that were used p r e v i o u s l y a t concentrations where t h e
formation of i o n p a i r s was s i g n i f i c a n t . The values of
(-AAG/RT)^ f o r the unassociated ions t h a t were determined
p r e v i o u s l y were used i n eq. (10) w i t h the values of ln(ÂM/#6)
f o r the a s s o c i a t e d i o n experiments t o o b t a i n the values of
7
(-AAG/R2)-j-p presented i n Table V I I .
P r e d i c t a b i l i t y o f Membrane Performance. New membranes were

placed i n the c e l l s as before and an experiment was done w i t h a
reference s o l u t e (NaCl). With the use of the t r a n s p o r t equations
(eq. (2), (3), (6), and (7)) and the c o r r e l a t i o n of k w i t h A,
eq. (14), ( ^ A M / Z 6 ) NaC1 was determined. The a p p r o p r i a t e
(AAc7/RZ ) s were used from Table VI t o determine C$ ci f o r each
7
i
f
a
membrane. C a l c u l a t i o n s o f (Pi?) and / f o r s e v e r a l s a l t s a t

v a r i o u s concentrations and mad d dt
the experimental r e s u l t
summarized i n F i g u r e 4 ,
s a t i s f a c t o r y agreement between p r e d i c t e d and experimental
r e s u l t s obtained i n d i c a t e s the p r a c t i c a l u t i l i t y o f the
c o r r e l a t i o n s and parameters generated i n t h i s work.
Comparison of Water and Methanol S o l u t i o n s . Comparison of

7
(-AAG/R2 ) i f o r i o n s i n both water and methanol s o l u t i o n s can be
7
made by u s i n g (-AAG/R20 + and (-AA&/R2 )
Na as references f o r
the a l k a l i metal c a t i o n s and h a l i d e anions r e s p e c t i v e l y . These
have been p l o t t e d i n F i g u r e 5 w i t h the l y o t r o p i c numbers f o r
each i o n . Figure 5 shows that w i t h respect to h a l i d e ions the
! T ! 7
c o r r e l a t i o n of l y o t r o p i c number w i t h [ (-AAG /R2 ) -(-AA6 /R5 ) -]
i cl
i s both l i n e a r and i d e n t i c a l f o r both s o l v e n t s , whereas t h e

corresponding c o r r e l a t i o n s w i t h respect t o a l k a l i metal c a t i o n s
are d i f f e r e n t . I n p a r t i c u l a r , w i t h respect t o these l a t t e r i o n s ,
7 ! 7
the change of [ (-AA6^/R!Z ) -(-AA6 /R5 ) +] w i t h l y o t r o p i c number i s
i Na
g r e a t e r i n methanol s o l u t i o n s than i n aqueous s o l u t i o n s . T h i s

means that f o r a given membrane, the v a r i a t i o n s i n s o l u t e
s e p a r a t i o n f o r a l k a l i metal h a l i d e s a l t s w i t h common anions i s
much l e s s i n aqueous s o l u t i o n s than i n methanol s o l u t i o n s , which
i s c o n s i s t e n t w i t h experimental r e s u l t s . F u r t h e r , i n the case
of methanol s o l u t i o n s , t h e s o l u t e s e p a r a t i o n i n c r e a s e s w i t h
i n c r e a s e i n l y o t r o p i c number f o r the a l k a l i metal c a t i o n s e r i e s
and decreases w i t h an i n c r e a s e i n l y o t r o p i c number f o r the
halide series.
The l y t o r o p i c number f o r an i o n i s a fundamental
physicochemical parameter which expresses i t s r e l a t i v e tendency
f o r e l e c t r o n t r a n s f e r (30) which i s a l s o the b a s i s f o r
p r e f e r e n t i a l s o r p t i o n a t i n t e r f a c e s f o r aqueous s o l u t i o n s
i n v o l v i n g p o l a r s o l u t e s (31). Since t h e l y o t r o p i c s e r i e s i s
v a l i d i n many f i e l d s of p h y s i c a l chemistry i n c l u d i n g s o l v a t i o n ,

FARNAND ET AL. RO Separations of Alkali Metal Halides 353
E (-AAG/RT),
i
Figure 4. Separation in methanol solutions with surface excess free energy of

solvation at 0.005m and 1725 kPa
LYOTROPIC NUMBER
Figure 5. Comparison of the surface excess free energies for alkali metal and
halide ions for aqueous and methanol solutions

Table V I I I . Experimental and Product Rates,

( P i ? ) , at 0.15 m and 1725 kPa
f (PR)
Membrane Run Solute Exptl Calcd Exptl Calcd a
7 32 NaC
38 CsC
40 LiCl .817 .813 5.65 5.52 1.00
41 LiBr .780 .792 5.75 5.50 1.00
42 NaBr .605 .590 6.04 5.77 .80
47 KI .323 .304 5.94 6.89 .87
8 32 NaCl .658 .636 4.61 4.31 .74

38 CsCl .471 .392 4.99 5.03 .83
40 LiCl .848 .831 4.08 4.06 1.00
41 LiBr .817 .812 4.17 4.05 1.00
42 NaBr .639 .619 4.37 4.22 .80
47 KI .361 .330 4.39 5.02 .87
9 32 NaCl .639 .641 3.65 3.41 .74

38 CsCl .417 .407 3.94 3.95 .83
40 LiCl .836 .835 3.22 3.22 1.00
41 LiBr .805 .816 3 .30 3.21 1.00
42 NaBr .625 .623 3.47 3.33 .80
47 KI .349 .335 3.43 3.95 .87
11 32 NaCl .655 .673 3.60 3.40 .74

38 CsCl .431 .434 3.97 3.98 .84
40 LiCl .850 .853 3.20 3.24 1.00
41 LiBr .822 .835 3.31 3.22 1.00
42 NaBr .649 .655 3.47 3.32 .80
47 KI .381 .367 3.48 3.95 .87

Table I X . Experimental and C a l c u l a t e d Separation, /,

and Product Rate, (PR), at 3450 kPa
Concn (PR)
Membrane Run Solute m Exptl Calcd Exptl Calcd a
7 16 LiCl .4586 .801 .816 9.17 7.61 1.00

22 LiCl .4930 .790 .796 8.25 7.34 1.00
14 LiBr .4093 .768 .802 9.88 8.49 1.00
24 LiBr .2617 .821 .816 11.10 10.20 1.00
11 NaBr
26 NaBr
8 16 LiCl .4586 .835 .852 6.71 5.64 1.00

22 LiCl .4930 .828 .838 6.10 5.40 1.00
14 LiBr .4093 .814 .841 7.29 6.30 1.00
24 LiBr .2617 .856 .853 8.21 7.59 1.00
11 NaBr .3853 .616 .615 8.50 8.65 .73
26 NaBr .2686 .676 .613 8.15 7.95 .75
9 16 LiCl .4586 .820 .839 5.38 4.57 1.00

22 LiCl .4930 .815 .819 4.86 4.40 1.00
14 LiBr .4093 .800 .836 5.79 5.01 1.00
24 LiBr .2617 .840 .842 6.53 6.07 1.00
11 NaBr .3853 .600 .591 6.73 7.04 .73
26 NaBr .2686 .661 .590 6.45 6.17 .75
11 16 LiCl .4586 .839 .854 5.51 4.73 1.00

22 LiCl .4930 .835 .832 5.05 4.49 1.00
14 LiBr .4093 .816 .846 5.99 5.24 1.00
24 LiBr .2617 .861 .853 6.71 6.27 1.00
11 NaBr .3853 .617 .621 6.91 7.18 .73
26 NaBr .2686 .684 .619 6.72 6.51 .75
12 16 LiCl .4586 .748 .792 4.54 3.95 1.00

22 LiCl .4930 .737 .766 4.16 3.85 1.00
14 LiBr .4093 .729 .887 4.84 3.78 1.00
24 LiBr .2617 .771 .790 5.47 5.11 1.00
11 NaBr .3853 .515 .517 5.42 6.10 .73
26 NaBr .2686 .571 .517 5.34 5.51 .75

7
s o r b a b i l i t y , and s u r f a c e t e n s i o n , the c o r r e l a t i o n of (-AA&/R2 )^
w i t h l y o t r o p i c number r e f l e c t s the s e p a r a t i o n of ions i n
reverse osmosis.
Conclusions
The physicochemical c r i t e r i a approach t o reverse osmosis

separations i n v o l v i n g the surface excess f r e e energy of
s o l v a t i o n f o r i o n i z e d and nonionized s o l u t e s has been
demonstrated by t h i s work t o i n c l u d e nonaqueous s o l u t i o n s . The
parameters and c o r r e l a t i o n s presented i n t h i s work permit the
p r e d i c t i o n of reverse osmosis separations and permeation r a t e s
f o r d i f f e r e n t a l k a l i metal h a l i d e s f o r c e l l u l o s e acetate
OEastman E-398) membranes of d i f f e r e n t s u r f a c e p o r o s i t i e s from
only a s i n g l e s e t of experimental data f o r a sodium c h l o r i d e -
methanol reference feed s o l u t i o system
Abstract
Reverse osmosis separations of 12 alkali metal h a l i d e s in

methanol s o l u t i o n s have been s t u d i e d u s i n g c e l l u l o s e acetate
membranes of different s u r f a c e porosities. Data f o r s u r f a c e
excess f r e e energy parameters for the ions and ion pairs
i n v o l v e d have been generated for the above membrane m a t e r i a l
- s o l u t i o n systems. These data o f f e r a means of p r e d i c t i n g the
performance of c e l l u l o s e acetate membranes in the reverse
osmosis treatment of methanol s o l u t i o n s i n v o l v i n g the above ions
from only a s i n g l e s e t of experimental data.
Nomenclature
A = pure s o l v e n t p e r m e a b i l i t y constant (mol s o l v e n t ) •

1
m'^s'l-kPa" -.
= c o n s t a n t
^NaCl d e f i n e d i n eq. ( 8 ) , m/s.
o = molar c o n c e n t r a t i o n of s o l u t i o n , mol/nr*.
AAB =
d i f f u s i v i t y o f s o l u t e A i n s o l v e n t B, m /s.
2
ÂM/X6 = s o l u t e t r a n s p o r t parameter, t r e a t e d as a s i n g l e
v a r i a b l e , m/s.
E = constant i n m o d i f i e d Born equation, kJ*nm*mol~-'-.
/ = f r a c t i o n of s o l u t e s e p a r a t i o n , defined i n eq. ( 1 ) .
AG = f r e e energy of s o l v a t i o n , kJ/mol.
AAG = s u r f a c e excess f r e e energy of s o l v a t i o n , kJ/mol.
Kj) = i o n i c d i s s o c i a t i o n e q u i l i b r i u m constant based on
mol f r a c t i o n .
k = mass t r a n s f e r c o e f f i c i e n t on the high pressure s i d e
of the membrane, m/s.
= molecular weight of s o l v e n t B.
2
Nft = s o l v e n t f l u x through membrane, mol-nT . - l . s
P - o p e r a t i n g pressure, kPa.

(PR) = product permeation r a t e through a given membrane

area, g/h.
(PSP) = pure solvent permeation r a t e through a g i v e n
membrane area, g/h.
3 1
R = gas constant, 8.314 x 1 0 " J - K ^ M H O I " .
= P a u l i n g c r y s t a l l o g r a p h i c r a d i u s of i o n i , nm.
S = e f f e c t i v e membrane s u r f a c e area, m . 2
T = system temperature, K.
= m
ZA ° l f r a c t i o n of t o t a l ( d i s s o c i a t e d and
u n d i s s o c i a t e d ) s o l u t e A.
Greek L e t t e r s
a = degree of i o n i c d i s s o c i a t i o n .
3 = d e f i n e d i n eq. (13).
Y + = mean i o n i
A = constant
^ = osmotic pressure of s o l u t i o n , kPa.
Subscripts
1 = bulk s o l u t i o n or feed s o l u t i o n , i . e . 3^1•

2 = concentrated boundary s o l u t i o n on the high pressure
s i d e of the membrane, i . e . Â2«
3 = membrane permeated s o l u t i o n on the low pressure
s i d e o f the membrane, i . e . Â3-
A = p e r t a i n i n g t o the s o l u t e .
B = p e r t a i n i n g t o the solvent or bulk s o l u t i o n phase.
I = membrane-solution i n t e r f a c e ,
i = i o n of type i .
IP = ion pair.
+, - = c a t i o n i c and a n i o n i c , r e s p e c t i v e l y .
Acknowledgement
The authors are t h a n k f u l f o r the t e c h n i c a l a s s i s t a n c e o f

A. Baxter and f o r the a n a l y t i c a l work of V. Clancy, G. Gardner,
and H. MacPherson. T h i s work r e c e i v e d f i n a n c i a l support from
the N a t i o n a l Science and Engineering Research C o u n c i l of
Canada and from a research c o n t r a c t with the N a t i o n a l Research
C o u n c i l of Canada. One of the authors (B.F.) thanks the
Province of Ontario f o r the award of a s c h o l a r s h i p .
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24. S k a b i c h e v s k i i , P . A . Russ. J. Phys. Chem., 1975, 49, 181.
25. E v e r s , C.; Knox, G. J. Amer. Chem. Soc., 1951, 73, 1739.
26. C u s s l e r , E.; Fuoss, R. J. Phys. Chem., 1967, 71, 4459.
27. Kay, R . ; Hawes, J. J. Phys. Chem., 1965, 69, 2787.
28. Robinson, R . A . ; Stokes, R . H . " E l e c t r o l y t e S o l u t i o n s " ,
2nd. E d . ; Butterworths: London, 1959;
(a) p . 401;
(b) p . 396.

29. Matsuura, T.; S o u r i r a j a n , S. J. A p p l . Polym.Sci.,1973,

17, 1043.
30. McBain, J.W. "Colloid Science"; Heath Co.: Boston,
1950; p. 131.
31. S o u r i r a j a n , S.; Matsuura, T. "Reverse Osmosis and
S y n t h e t i c Membranes", S o u r i r a j a n , S., Ed.; N.R.C.
Canada: Ottawa, 1977; p. 11.
Issued as NRC No. 18591

21
Ultrafiltration and Hyperfiltration in the Pulp and
Paper Industry for By-Product Recovery and
Energy Savings
PER H. CLAUSSEN
Niro Atomizer, Inc., 9165 Rumsey Road, Columbia, MD 21045
The development work w i t h regard t o a p p l i c a t i o n of DDS-RO(1)

membrane filtration system
pulp and paper i n d u s t r
1972.
Both l a b and pilot trials were s u c c e s s f u l and a Norwegian
patent (2) was granted f o r s e p a r a t i o n of l i g n o s u l f o n a t e from
spent sulfite l i q u o r (SSL) by ultrafiltration ( U F ) .
In 1974 a major Norwegian manufacturer of lignin products
s t a r t e d r e g u l a r p r o d u c t i o n of U F - l i g n o s u l f o n a t e s . The p l a n t has
been expanded s e v e r a l times and today the p r o d u c t i o n is some
thousand tons per year of product.
A c o o p e r a t i o n agreement was made in 1973 between DDS-RO and
the F i n n i s h Pulp and Paper Research Institute w i t h the aim t o
develop products and processes on the b a s i s o f membrane filtra-
tion of e f f l u e n t s from the pulp and paper i n d u s t r y . The cooper-
a t i o n w i t h Dr. Kaj Forss' s e c t i o n a t FPPRI has been very
s u c c e s s f u l . For i n s t a n c e , through an extensive development pro-
gram UF has been found t o be a f e a s i b l e t o o l f o r the p r e p a r a t i o n
of lignin f o r the Karatex (3) plywood binder. This adhesive,
which is made from ultrafiltered spent sulfite l i q u o r (SSL) o r
kraft b l a c k l i q u o r (KBL), can be used f o r partial replacement of
the much more expensive petroleum based phenol-formaldehyde r e s i n
i n plywood and other wooden boards.
The Swedish Company EKA and DDS-RO have worked together on a
2-year l a r g e s c a l e pilot o p e r a t i o n in a Swedish k r a f t mill for
c o l o r removal from c a u s t i c e x t r a c t i o n bleach e f f l u e n t by UF (4).
The r e s u l t s of the program were s u c c e s s f u l both w i t h regard
to c o l o r removal efficiency, reliability and membrane lifetime
and the first full s c a l e installation will be made t h i s year in
Japan.
With the i n c r e a s i n g f u e l p r i c e s , it becomes more and more
important t o f i n d energy efficient c o n c e n t r a t i o n methods f o r
industrial e f f l u e n t s . H y p e r f i l t r a t i o n (HF).also c a l l e d r e v e r s e
osmosis is in s e v e r a l cases the most f a v o r a b l e method.
Toten S u l p h i t e Mill in Norway r e a l i z e d t h i s in 1976 when a
0097-6156/81/0154-0361$05.00/0

a demand f o r a d d i t i o n a l water removal c a p a c i t y occurred, and

they i n s t a l l e d a HF-system. Over the years s u b s t a n t i a l f u e l
savings have been made.
So f a r t h i s paper has been d e a l i n g w i t h the past. The t a b l e
below shows the s i t u a t i o n today w i t h regards to DDS-RO i n s t a l l a -
t i o n s i n the pulp and paper i n d u s t r y .
2
At the end of 1980 about 30,000 f t . of membrane area of
DDS make w i l l be i n o p e r a t i o n i n t h i s i n d u s t r y .
By-product c a p a c i t y w i l l be 15,000-20,000 tons per year of
product s o l i d s by UF.
Water removal c a p a c i t y i s approximately 100,000 g a l l o n s per
day.
2
Main Features of the Systems. The 450 f t . h o r i z o n t a l mounted
2
module UF 35-42 and the 300 f t . v e r t i c a l module HF 40-28 are
the key components of th
and 3.
Both the UF and the HF systems are m u l t i s t a g e continuous
p l a n t s according to the concept on f i g u r e 4.
Process c o n t r o l concept i s simple but e f f i c i e n t and r e l i a b l e ,
w i t h thermostatic c o n t r o l of supply of steam or c o o l i n g water to
the heat exchangers and f l o w / s o l i d s c o n c e n t r a t i o n c o n t r o l e i t h e r
on b a s i s of i n - l i n e refractometer at the end of the system or
r a t i o c o n t r o l between feed and concentrate flow.
F i g u r e 5 i s showing a t y p i c a l U F - i n s t a l l a t i o n i n the pulp
and paper i n d u s t r y at Iggesund K r a f t M i l l i n Sweden. Figure 6
i s showing the H F - i n s t a l l a t i o n at Toten S u l p h i t e m i l l i n Norway.
Membranes of v a r i o u s polymer m a t e r i a l s are used i n the UF
systems a l l o w i n g o p e r a t i n g temperatures up to 190°F and pH from
0 to 14, which i s f a v o r a b l e when o p e r a t i n g on p u l p i n g e f f l u e n t s
that e i t h e r are i n the upper or the lower end of the pH-range
and w i t h temperatures c l o s e to the l i m i t s f o r the system.
The systems a l s o a l l o w c l e a n i n g w i t h strong a l k a l i n e or a c i d
chemicals, a l s o oxydants as H 2 O 2 and NaOCl which i n some cases i s
necessary to keep the membranes s u f f i c i e n t l y clean i n the long
run.
For HF c e l l u l o s e acetate membranes are used s e t t i n g l i m i t s
f o r temperature, 85°F, as w e l l as f o r pH, 2.5 to 8.0. S t i l l with
those l i m i t a t i o n s i t i s p o s s i b l e to keep the systems at an accept
ably high performance l e v e l f o r extensive periods of time, when
o p e r a t i n g on spent s u l p h i t e l i q u o r .
A proper p r e f i l t r a t i o n of the l i q u i d s i s r e q u i r e d and i s
mainly done i n a s e l f - c l e a n i n g r o t a r y drum f i l t e r w i t h a 25micron
web.
A p p l i c a t i o n s , Experience. U l t r a f i l t r a t i o n of SSL. This process-

ing has been going on on a r e g u l a r commercial b a s i s s i n c e 1974
f o r manufacture of l i g n o s u l f o n a t e products w i t h a l i g n o s u l f o n a t e
content i n the 90%+ range ( 5 ) . Not only the l i g n o s u l f o n a t e
content of the product i s of importance, o f t e n a l s o the molecular

21. CLAUSSEN UF and HF in the Pulp and Paper Industry 363
Yr. I n s t a l l e d System Country Product

1974-1979 UF Norway Lignosulfonates
1976 HF Norway NH4-SSL
1978 UF N.America Lignosulfonates
1978 HF Canada Ca-SSL
Under C o n s t r u c t i o n
1980 UF Finland Kraft liquor
1980 UF Finland Lignosulfonates
1980 UF Japan Kraft bleach effluent
Larger P i l o t Plants
1978 UF Sweden Kraft bleach effluent
1980 H
1980 H
Figure 1. DDS-Ro installations in the pulp and paper industry
2
Figure 2. The 450-ft horizontally mounted UF module UF 35-42

2
Figure 3. The 300-ft vertical HF mod-
ule HF 40-28

CLAUSSEN UF and HF in the Pulp and Paper Industry 365
Figure 4.
Figure 5. Typical UF installation at Iggesund Kraft Mill in Sweden

weight d i s t r i b u t i o n of the l i g n o s u l f o n a t e , F i g u r e 7, i s showing

the molecular weight d i s t r i b u t i o n of the l i g n o s u l f o n a t e i n SSL
and i n the two f r a c t i o n s from UF, the concentrate and the f i l -
t r a t e ( 6 ) . The l i g n o s u l f o n a t e s from UF are mainly used as
dispersants.
I t took a few years before the modules, the membranes, pre-
treatment and membrane c l e a n i n g procedures were s u f f i c i e n t l y
developed, but today the UF systems operate as s t e a d i l y and r e -
l i a b l e as other u n i t o p e r a t i o n s i n t h i s i n d u s t r y .
The process concept i s simple and energy e f f i c i e n t , the
pumps are the only moving p a r t s . No chemicals r e q u i r e d f o r the
o p e r a t i o n except f o r minor q u a n t i t i e s of harmless c l e a n i n g agents.
Membrane c l e a n i n g frequency i s mainly once every one or two
days.
L i f e t i m e expectancy, based on l a t e s t experience i s one year
+.
UF i s made on bot
Pekilo-fermented l i q u o r Kaj Forss et a l (6) found a 50% h i g h e r
production c a p a c i t y f o r a UF system of a given s i z e and a given
product composition compared w i t h UF of the unfermented l i q u o r .
The d i a f i l t r a t i o n water requirement was 55% l e s s f o r the fermen-
ted l i q u o r .
Further d e t a i l s from the above mentioned o p e r a t i o n s cannot
be d i s c l o s e d as the i n v o l v e d companies, due to the competitive
s i t u a t i o n , p r e f e r to give out as l i t t l e i n f o r m a t i o n as p o s s i b l e .
UF of K r a f t Black L i q u o r . L i g n i n from k r a f t b l a c k l i q u o r has f o r

years been used to a l i m i t e d extent as extender f o r b i n d e r s i n
v a r i o u s board products.
With the r a p i d l y i n c r e a s i n g p r i c e s and the o u t l o o k of i n s u f -
f i c i e n t s u p p l i e s of PF r e s i n i n the f u t u r e , there i s a growing
i n t e r e s t f o r l i g n i n f o r such a p p l i c a t i o n s .
An extensive development program i n F i n l a n d , conducted by
Dr. Kaj F o r s s , has shown that UF i s a simple, e f f i c i e n t and i n e x -
pensive method f o r t a i l o r i n g a l i g n i n product f o r t h i s purpose.
By s e l e c t i o n of the proper membrane and p r o c e s s i n g para-
meters, i t i s p o s s i b l e i n a simple way to get a product w i t h the
content- of l i g n i n and molecular weight d i s t r i b u t i o n r e q u i r e d f o r
an a c t i v e binder i n g r e d i e n t which combines c h e m i c a l l y w i t h PF
r e s i n f o r plywood.
So f a r , a 40% replacement of PF r e s i n has been made without
change i n the p r o p e r t i e s of the plywood.
S u c c e s s f u l u l t r a f i l t r a t i o n / d i a f i l t r a t i o n has been made on
15% TDS l i q u o r from pulp washers, as w e l l as 30% TDS l i q u o r from
t a l l o i l soap skimming. I t appears from Figure 8, that f o r a
l i g n i n product w i t h a l i g n i n content i n the 80-90% range, based
on product s o l i d s , the p r o d u c t i o n c a p a c i t y of a system of a given
s i z e i s almost the same i n the two cases, but the 30% l i q u o r r e -
q u i r e s more water to get to the same l i g n i n content.

Figure 6. HF installation at Toten Sulfite Mill in Norway
Figure 7. Molecular-weight distribution of lignin in SSL and UF concentrate and

filtrate

The f i r s t i n d u s t r i a l s c a l e i n s t a l l a t i o n w i l l come on stream

towards the end of t h i s year i n F i n l a n d .
H y p e r f i l t r a t i o n - P r e c o n c e n t r a t i o n of SSL. P r e c o n c e n t r a t i o n of SSL
has been going on s i n c e 1976 a t Toten S u l p h i t e M i l l i n Norway and
s i n c e 1978 at Reed's L i g n o s o l P l a n t i n Quebec, Canada.
This method of c o n c e n t r a t i n g weak l i q u o r s i n combination
w i t h evaporation i s becoming more and more a t t r a c t i v e w i t h the
rapid increasing fuel prices.
F i g u r e 9 showing energy requirement f o r v a r i o u s evaporator
systems compared w i t h h y p e r f i l t r a t i o n , i n d i c a t e s c l e a r l y the ad-
vantage of water removal by h y p e r f i l t r a t i o n .
F i g u r e 10 i s showing the energy savings that can be achieved
by combining HF w i t h an e x i s t i n g evaporator system f o r SSL at a
given s i t u a t i o n .
By i n t e g r a t i o n o
50% which should more tha
the same time, r e l i e v e the steam b o i l e r or make more steam f o r
other operations a v a i l a b l e .
For incremental increases i n water removal c a p a c i t y , HF i s ,
i n most cases, the f a v o r a b l e o p e r a t i o n , due to the energy
e f f i c i e n c y and the p o s s i b i l i t y of adding modules stepwise accord-
ing to the i n c r e a s i n g demand f o r c a p a c i t y .
T h i s f a c t has been taken advantage of at Toten and Reed.
F i g u r e 11 i s showing some of the e s s e n t i a l f e a t u r e s from
those two HF p l a n t s .
Both p l a n t s a r e using CA-membranes and d e s p i t e that pH i s
on the lower s i d e of the acceptable pH-range, at Toten o c c a s i o n -
n a l l y below pH2 on average, membrane l i f e t i m e of one year + i s
experienced.
There have been some f o u l i n g problems i n the systems caused
by p i t c h - c o n t a i n i n g small f i b e r s and calcium s u l f i t e . Improved
pretreatment and membrane c l e a n i n g procedures are the keys to
the b e t t e r performance of the systems.
Power consumption f o r the systems i s i n the range 3.5-4.5
Kwh per 1,000 l b s . of water removal.
Membrane c l e a n i n g frequency has been 2-6 times a week f o r
the two systems.
Composition of f i l t r a t e i s not much d i f f e r e n t from that of
an evaporator condensate.
The U l t r a s e p Color Removal Process f o r C a u s t i c E x t r a c t i o n Bleach

E f f l u e n t . An extensive l a r g e s c a l e p i l o t p l a n t program was
c a r r i e d out by the Swedish company, EKA, at Iggesund K r a f t M i l l
i n Sweden, using a f o u r - s t a g e , continuous DDS-RO u l t r a f i l t r a t i o n
system f o r t h i s a p p l i c a t i o n .
The system has been i n continuous o p e r a t i o n f o r about two
years, s e p a r a t i n g 10% of the t o t a l c a u s t i c e x t r a c t i o n e f f l u e n t ,
approximately 100 GPM, i n two f r a c t i o n s , 4 GPM of concentrate
c o n t a i n i n g 90% of the c o l o r and 96 GPM c o n t a i n i n g 10% of the
color.

CLAUSSEN UF and HF in the Pulp and Paper Industry 369
C 0 N T E N T 0 F
Q3 ^ tt- NA.-LIGNIN IN PRODUCT, PRODUCT CAPACITY
A N D
b§ o < ^ DIAFILTRATION WATER REQUIREMENT DURING THE
C 0 U R S E 0 F T M E
tt(L I o < J SEPARATION.
CC CO -.rr .W
£ \ i £ o w • INITIAL TDS 15%
40 50 60 70 80
% PRECIPITABLE LIGNIN OF PR00UCT SOLIDS
Figure 8. UF of KBL. Content of NA-lignin in product, product capacity, and

diafiltration water requirement during the course of the separation.
E n e r g y - E f f i c i e n t C o n c e n t r a t i o n by HF (RO)
Common energy requirements f o r e v a p o r a t o r s and HY systems:
System B t u p e r 1,000 l b s , o f water

removal
1 e f f e c t w i t h vapor r e c o m p r e s s i o n 50,000
6 stage m u l t i p l e e f f e c t evaporator 215,000
Hyperfiltration 15,000
Figure 9. Energy efficient concentration by HF (RO)

4 STAGE ME EVAPORATION A COMPARED WITH COMBINATION OF

4 STAGE ME EVAPORATION AND HYPERFILTRATION B
ENERGY
56 MILL. BTU/HR
4 STAGE
SSL CONCENTRATE
A. EVAPORATOR
200,000 LbS/HR. 36,400 L B S / H R
10% TDS ME 5 5 % TDS
ÊVAPORATION
163,600 LbS/HR
ENERGY ENERGY
B. SSL HYPE
?00.000 LBS/HR. FILTRATION 110,00 36,40
18 2 % TDS 5 5 % TDS
>0% T D S ME
FILTRATE EVAPORATION
90.000 L B S . / HR 73.600 LBS/HR
Figure 10. Energy requirement for water removal. Four-stage ME evaporation,

A, compared with a combination of the four-stage ME evaporation and HF, B.
Features Toten Reed
I n s t a l l a t i o n year 1976 1978

S i z e s q . f t . membrane a r e a 4215 4817
Configuration 4 stage cont. 4 stage cont.
Product N H 4 - S S L pH 2-2.5 Ca-SSL pH 3-3.5
% TDS f e e d 6-10 10 - 12
% TDS c o n c e n t r a t e 12 18
Maximum feed r a t e GPM 88 132
Max f i l t r a t i o n r a t e GPM 44 44
Avg. f i l t r a t i o n r a t e a t
max. f e e d 15 13
Nominal power consumption
approx. Kw. 75 90
Nominal power concumption
Kwh p e r 1000 l b s . f i l t r a t e 3.4 4.0
No.of membrane r e p l a c e m e n t s 3 1
Figure 11. Features of the HF plants at Totel and Reed as of August 15, 1980

PRE-BLEACHED PULP
Effluent 6000 TT?

Total Solids 40 tons
Total Chloride 7 tons
Color Pt 70 tons
COD 12 tons
BOD 4 tons
3
Concentrate 250 m
Solids 18 tons
Chloride 1 ton
Color Pt 63 tons
COD 8 tons
BOD 2 tons
3
Permeate 5750 m
Solids 22 tons
(12 tons org.)
(10 tons NaCl)
Chloride 6 tons
Color Pt 7 tons
COD 4 tons
BOO 2 tons
Figure 12. Ultrasep system for color removal. Materials balance for 600 tons of
kraft pulp.

F i g u r e 12 i s showing the d i s t r i b u t i o n of other e s s e n t i a l

substance; f o r i n s t a n c e , BOD, COD, c h l o r i d e and TDS i n the two
fractions.
The o p e r a t i o n ran smoothly w i t h few major problems. Membrane
c l e a n i n g frequency was, on average, once every three weeks.
D i f f e r e n t membranes were used; the l a s t set was i n continuous
o p e r a t i o n f o r more than 8,000 hours without s i g n i f i c a n t change
i n performance.
This process i s found to be competitive to e x i s t i n g c o l o r
removal processes, both w i t h regard to economy and c o l o r removal
efficiency.
To which degree i t i s going to be u t i l i z e d i s depending on
what k i n d of r e g u l a t i o n s there w i l l be w i t h regard to emmissions
from b l e a c h p l a n t s . However, the f i r s t i n d u s t r i a l i n s t a l l a t i o n
of i t s k i n d w i l l be made t h i s year i n Japan.
ABSTRACT. Membrane filtration

than five years on a commercial s c a l e in the pulp and paper in-
dustry. Continuous, m u l t i - s t a g e p l a t e and frame based systems
are being used f o r purification, and molecular distribution
c o n t r o l of l i g n o s u l f o n a t e from spent sulfite l i q u o r and precon-
c e n t r a t i o n of weak spent sulfite l i q u o r before evaporation.
Larger s c a l e , long term pilot operations w i t h the s i m i l a r
systems f o r s e p a r a t i o n of lignin from k r a f t b l a c k l i q u o r and
c o l o r removal from bleach p l a n t e f f l u e n t s are going on success-
a d v i s i n g new and comprehensive a p p l i c a t i o n s f o r membrane
filtration process in this i n d u s t r y . The aspect of saving
fossile energy is a common f e a t u r e of most such operations as
hyperfiltration i s typical low energy c o n c e n t r a t i o n method and
the lignin products in many cases r e p l a c e petroleum based chemi-
cals.
Literature Cited
1. DDS Modules, U.S. Patent 3,872,015, GB patent 1,390,671,

Italy patent 978,747, S w i t z e r l a n d patent 542,639, New
Zealand patent 169,679.
2. L. Janzen, P.H. Claussen, Norway patent 127,545, Swiss
patent 560,289, P o r t u g a l , France, Brazil, Italy patents.
3. K. F o r s s , A. Fuhrman, Karatex adhesive, F i n l a n d patent
167,647, U.S. patent 4,105,606. Patents GDR, A u s t r i a , GB,
Hungary, e t c .
4. J . Manson, EKA AB Sweden. Proceedings from I n t e r n a t i o n a l
Pulp Bleaching Conference i n Toronto, June, 1979.
5. P.H. Claussen, Pulp and Paper Canada, March, 1978.
6. K. F o r s s , R. Kokkonen, H. Sirelius, P.E. Sagfors, Pulp
and Paper Canada, December, 1979.

22
Pressure-Independent Ultrafiltration—Is It Gel
Limited or Osmotic Pressure Limited?
1
D A N I E L R. T R E T T I N and M A H E N D R A R. D O S H I
Environmental Sciences Division, The Institute of Paper Chemistry,
Appleton, WI 54912
Ultrafiltration i n v o l v e s the p r e s s u r e - a c t i v a t e d s e p a r a t i o n
of chemical species whic
a membrane. Solute r e t e n t i o
e x c l u s i o n , that is, a s i e v i n g - t y p e of mechanism and s o l v e n t
passes through by pore flow. As an initially homogeneous solu-
tion is p r e s s u r i z e d over a s e l e c t i v e membrane, s o l v e n t permeates
through w h i l e r e j e c t e d s o l u t e accumulates in the vicinity of the
membrane. The net result is a l a y e r of s o l u t i o n adjacent to the
membrane surface of substantially greater s o l u t e c o n c e n t r a t i o n
than that of the bulk s o l u t i o n . This phenomenon of concentra-
t i o n polarization always operates to reduce the s o l v e n t permea-
t i o n r a t e which may become pressure independent in some cases.
In the ultrafiltration of macromolecular s o l u t i o n s , a l a r g e
number o f i n v e s t i g a t o r s have observed that as pressure is in-
creased, permeate f l u x first increases and then remains more o r
l e s s pressure independent. B l a t t , e t al. (1970), among o t h e r s ,
argued that one of the reasons f o r the observed pressure inde-
pendence could be due to the formation of a g e l l a y e r on the
membrane s u r f a c e . The permeate r a t e in t h i s case may be expressed
as:
I I AP - ATT N ,
K\ p (R + R ) ( 1 )
m g
where R and R are the h y d r a u l i c r e s i s t a n c e s o f the membrane and
m g
gel l a y e r r e s p e c t i v e l y , AP and ATT represent the a p p l i e d pressure
and osmotic back pressure and y i s the permeate v i s c o s i t y . I n
the case of pressure independent u l t r a f i l t r a t i o n of macromolecular
s o l u t i o n s , i f the a p p l i e d pressure i s much greater than the
osmotic pressure d i f f e r e n c e across the membrane, and s i n c e the
gel r e s i s t a n c e i s g e n e r a l l y s u b s t a n t i a l l y greater than that of a
membrane, Eq. (1) can be s i m p l i f i e d t o :
1
Current address: Union Camp Corporation, Franklin, VA 23851.
0097-6156/81/0154-0373$09.25/0

AP AP » ATT
v
w " UR ' R » R m
g g
Any i n c r e a s e i n pressure a f t e r the occurrence of g e l formation
merely i n c r e a s e s g e l t h i c k n e s s and hence R^ so that the permeate
f l u x remains e s s e n t i a l l y independent of pressure.
There could be other p o s s i b i l i t i e s f o r the observed pressure
independence. We know t h a t , i n the absence of g e l formation,
i n c r e a s e i n the a p p l i e d pressure r e s u l t s i n the i n c r e a s e i n
s o l u t e c o n c e n t r a t i o n at the membrane s u r f a c e . I f osmotic pres-
sure i s q u i t e s e n s i t i v e to the changes i n s o l u t e c o n c e n t r a t i o n ,
i t i s p o s s i b l e that an i n c r e a s e i n AP gives r i s e to p r o p o r t i o n a l
i n c r e a s e i n Air so that the net d r i v i n g f o r c e , (AP - ATT) remains
v i r t u a l l y constant. From Eq. ( 1 ) , then, the permeate r a t e i n
the absence of g e l formatio
due to osmotic pressure l i m i t a t i o n . Other phenomena, f o r

example, solute-membrane i n t e r a c t i o n s may give r i s e to pressure
independent permeate r a t e .
Gel p o l a r i z e d u l t r a f i l t r a t i o n was r e c e n t l y analyzed f o r
cross flow and u n s t i r r e d batch c e l l systems by T r e t t i n and Doshi
(1980 a,b). We have shown i n these papers that the w i d e l y used
f i l m theory does not p r e d i c t the l i m i t i n g f l u x a c c u r a t e l y . The
o b j e c t i v e of t h i s paper i s to d e r i v e an e x p r e s s i o n f o r the perme-
ate f l u x when the pressure independent u l t r a f i l t r a t i o n of macro-
molecular s o l u t i o n s i s osmotic pressure l i m i t e d . We w i l l a l s o
attempt to d i s t i n g u i s h between g e l and osmotic pressure l i m i t e d
u l t r a f i l t r a t i o n of macromolecular s o l u t i o n s .
The e f f e c t of osmotic pressure i n macromolecular u l t r a f i l t r a -
t i o n has not been analyzed i n d e t a i l although many s i m i l a r i t i e s
between t h i s process and reverse osmosis may be drawn. An
e x c e l l e n t review of reverse osmosis research has been given by
G i l l et a l . (1971). I t i s g e n e r a l l y found, however, that the
simple l i n e a r osmotic p r e s s u r e - c o n c e n t r a t i o n r e l a t i o n s h i p used
i n reverse osmosis s t u d i e s cannot be a p p l i e d to u l t r a f i l t r a t i o n
where the c o n c e n t r a t i o n dependency of macromolecular s o l u t i o n s
i s more complex. I t i s a l s o reasonable to assume t h a t v a r i a b l e
v i s c o s i t y e f f e c t s may be more pronounced i n macromolecular u l t r a -
f i l t r a t i o n as opposed to reverse osmosis. S i m i l a r l y , because
of the r e l a t i v e l y low d i f f u s i v i t y of macromolecules compared
to t y p i c a l reverse osmosis s o l u t e s (by a f a c t o r of 100), con-
c e n t r a t i o n p o l a r i z a t i o n e f f e c t s are more severe i n u l t r a f i l t r a -
tion.
An e a r l y work c o n s i d e r i n g osmotic pressure i n the u l t r a -
f i l t r a t i o n of macromolecular s o l u t i o n s was done by B l a t t , et a l . ,
(1970), who employed a theory which had been developed f o r cross
flow reverse osmosis systems. They e s s e n t i a l l y suggested t h a t
the f i l m theory r e l a t i o n s h i p given by Eq. (2) could be s o l v e d
simultaneously w i t h Eq. (1) to p r e d i c t permeate r a t e s , where the

22. TRETTIN AND DOSHI Pressure-Independent UF 375
value of k was determined from a Leveque-type s o l u t i o n of the

convective d i f f u s i o n equation n e g l e c t i n g t r a n s v e r s e v e l o c i t y .
c - c
|v | = k
1 1 w
ln cw - c p
o p (2)
Presented data were not analyzed i n terms of t h i s model, however,

because i t was f e l t that macromolecular s o l u t i o n s g e n e r a l l y had
very low osmotic p r e s s u r e s .
Goldsmith (1971) p o i n t e d out that developed osmotic p r e s -
sures f o r macromolecular s o l u t i o n s were not n e c e s s a r i l y neg-
l i g i b l e . The u l t r a f i l t r a t i o n of Carbowax 20M (polyethylene oxide)
and various Dextrans was s t u d i e d i n t h i n channel and tube flow
as w e l l as s t i r r e d batch c e l l h turbulen d lamina flo
regimes were considered
Eq. (2) and the phenomenologica p Eq (1)
Rg = 0. From Eq. (1) i t was p o s s i b l e to c a l c u l a t e an average
value of ATT where R , the membrane r e s i s t a n c e , AP, and e x p e r i -
m
mental f l u x Iv I were known. The average value of c could be

1 1 &
w w
e x t r a c t e d from a known osmotic pressure r e l a t i o n s h i p , and an
experimental value of k_could f i n a l l y be found from Eq. ( 2 ) .
Experimental values of k were compared to t h e o r e t i c a l values to
estimate molecular d i f f u s i o n c o e f f i c i e n t . The d i f f e r e n c e between
the experimental and the l i t e r a t u r e value of the d i f f u s i o n
c o e f f i c i e n t was a t t r i b u t e d to the c o n c e n t r a t i o n dependency of
v i s c o s i t y and d i f f u s i o n c o e f f i c i e n t .
K o z i n s k i and L i g h t f o o t (1972) modeled the u l t r a f i l t r a t i o n of
bovine serum albumin (BSA) through a r o t a t i n g d i s k . Concentra-
t i o n dependent v i s c o s i t y and d i f f u s i v i t y were assumed, and the
one-dimensional convective d i f f u s i o n equation, which was coupled
to the a p p r o p r i a t e Navier-Stokes equation, was s o l v e d n u m e r i c a l l y .
Osmotic pressure data of Scachard et: a l . (1944) were used.
Numerical p r e d i c t i o n of f l u x agreed very w e l l w i t h experimental
r e s u l t s f o r the r o t a t i n g d i s k . T h e i r model was extended to
other flow geometries, such as t u b u l a r and t h i n channel, where
average values of v i s c o s i t y and d i f f u s i v i t y were used. The con-
v e c t i v e d i f f u s i o n equation i n t h i s case was s o l v e d through
s i m i l a r i t y t r a n s f o r m a t i o n . The p u b l i s h e d data of B l a t t , _et a l . ,
(1970) were analyzed i n terms of the developed model but agree-
ment was not good.
M i t r a and Lundblad (1978) s t u d i e d the t h i n channel u l t r a -
f i l t r a t i o n of immune serum g l o b u l i n (ISG) and human serum albumin
(HSA) . Data were i n t e r p r e t e d u s i n g the f i l m theory r e l a t i o n s h i p
of:
v 1 = A In v (c /c ) C3)
w w o

where m u l t i p l e r e g r e s s i o n techniques were employed to s o l v e f o r

the value of the constants A, B, and c . The value of c was
* ' w w
assumed to equal the corresponding c o n c e n t r a t i o n at which the
developed osmotic pressure approximately e q u a l l e d the a p p l i e d
system pressure. Agreement of data w i t h the general model was
not good, the c a l c u l a t e d value of A e x h i b i t i n g a 21% standard
d e v i a t i o n . Large a x i a l pressure drops along the t h i n channel at
the h i g h e r v e l o c i t i e s s t u d i e d may be a p a r t i a l e x p l a n a t i o n of
the discrepancy.
Leung and P r o b s t e i n (1979) s t u d i e d the u l t r a f i l t r a t i o n of
macromolecular s o l u t i o n s i n steady s t a t e , laminar channel f l o w .
The convective d i f f u s i o n equation was s o l v e d by an i n t e g r a l meth-
od. A p a r a b o l i c c o n c e n t r a t i o n p r o f i l e was assumed. The osmotic
pressure r e l a t i o n s h i p of V i l k e r (1975) f o r 0.15M s a l i n e BSA s o l u -
t i o n s a t pH 4.5, and a
e a r l y i n t e r p o l a t i n g th
g e l and d i l u t e s o l u t i o n c o n c e n t r a t i o n l i m i t s were used. The
determination of t h i s d i f f u s i v i t y r e l a t i o n s h i p has been o u t l i n e d
i n a previous paper [ P r o b s t e i n , et a l . (1979)]. The i n t e g r a l
s o l u t i o n was checked i n the l i m i t i n g case of a l i n e a r osmotic
p r e s s u r e - c o n c e n t r a t i o n r e l a t i o n s h i p and constant d i f f u s i v i t y w i t h
B r i a n ' s (1966) f i n i t e d i f f e r e n c e s o l u t i o n f o r reverse osmosis
systems. Thin channel u l t r a f i l t r a t i o n data were acquired by
Leung and P r o b s t e i n using BSA i n 0.10M acetate s o l u t i o n at pH 4.7.
1
A discrepancy emerges i n the use of V i l k e r s osmotic p r e s -
sure r e l a t i o n s h i p , however. In an e a r l i e r paper, P r o b s t e i n ,
et a l . , (1979) determined the g e l l i n g ( s o l u b i l i t y l i m i t ) concen-
t r a t i o n of BSA i n 0.10M acetate s o l u t i o n (pH 4.7) to be 34 g/100
cc. We have determined the value to be approximately 38.5 g/100
cc [ T r e t t i n and Doshi (1980b)]. I t i s c l e a r from F i g . 5 t h a t
V i l k e r has determined osmotic pressures f o r BSA i n 0.15M s a l i n e
s o l u t i o n s (pH 4.5) up to c o n c e n t r a t i o n s of 48 g/100 cc. This
f i n d i n g suggests the e f f e c t of b u f f e r type i s s u b s t a n t i a l i n
i n f l u e n c i n g s o l u t e s o l u b i l i t y l i m i t s and most probably s o l u t i o n
osmotic pressure. Therefore, i t i s h a r d l y a d m i s s i b l e to use
1
V i l k e r s s a l i n e b u f f e r osmotic pressure data to i n t e r p r e t the t h i n
channel u l t r a f i l t r a t i o n data of BSA i n acetate b u f f e r without
f u r t h e r c o n f i r m a t i o n of the e f f e c t of b u f f e r type.
The preceding review has shown that although many advances
have been made i n the understanding of macromolecular u l t r a f i l t r a -
t i o n , some very fundamental questions s t i l l remain unanswered.
For i n s t a n c e , the establishment of when an u l t r a f i l t r a t i o n process
i s osmotic pressure l i m i t e d or g e l l i m i t e d needs to be more c l e a r -
l y d e f i n e d . In macromolecular u l t r a f i l t r a t i o n s o l u t i o n osmotic
pressure i s o f t e n a s t r o n g f u n c t i o n of moderate-to-high s o l u t e
c o n c e n t r a t i o n (c ) due to the i n c r e a s e d importance of the second
and t h i r d order v i r i a l terms i n the F l o r y equation [Brandup and
Immergut (1967), B i l l m e y e r (1971)]. In t h i s event, the u l t r a -
f i l t r a t i o n f l u x may be l i m i t e d by the osmotic pressure and/or

by the formation of a g e l l a y e r depending on the nature of the

s o l u t e and o p e r a t i n g c o n d i t i o n s . The determination of a f l u x -
l i m i t i n g cause i s the primary concern of t h i s paper.
T h e o r e t i c a l Development
Consider the u n s t i r r e d batch c e l l geometry shown i n F i g . 1

where the general s o l u t e mass balance equation of
|£_ |v |
1
w
1
|£- D 9 2 /8y
c
2
W
dt dy
a p p l i e s . I t i s i m p l i c i t l y assumed i n the d e r i v a t i o n of Eq. (4)

that the s o l u t i o n densit diffusio coefficien indepen
dent of s o l u t e c o n c e n t r a t i o n
The appropriate boundary and i n i t i a l c o n d i t i o n s are:
at y = 0 ;. c = c ( t ) (5)
w
iv I c R = D
-| w| w 9y'
f | y = 0
(6)
w
y -> °°, c = c for a l l t (7)

o
t + 0 , c = C q for a l l y (8)
where
R = 1 - c /c
p w
The phenomenological equation of permeate v e l o c i t y i s
| v j = MP il-§); A = ^- (9)
m
where
ATT = TT - TT (10)
w p
I f osmotic pressure i s r e l a t e d to s o l u t e concentration by a cubic
equation:
2 3
TT = b c + b i c
0 + b c 2


then
ATT B c w AP [1 + a i c w + a 2 c/]
where
2
B = Mo , a i = b l - ^ R ^ a 2 = b 2 (3-3R R ) + ( 1 2 )
n r
b 0 b 0
Our o b j e c t i v e i s to d e r i v e an e x p r e s s i o n f o r the permeate

v e l o c i t y when u l t r a f i l t r a t i o n i s osmotic pressure l i m i t e d . We
r
therefore, introduce equivalent w a l l concentration, ^ > f °
which the osmotic pressur
the asymptotic case, as ATT approaches A P , the permeate v e l o c i t y
w i l l approach zero, Eq. ( 9 ) , and from Eq. (11) we have:
1 = B c (1 + a i c + a 2 c *) (13)
wa wa wa
Equation (13) i s then the d e f i n i n g equation f o r c ^ . We w i l l use

c as a c h a r a c t e r i s t i c c o n c e n t r a t i o n i n making l o c a l concentra-
wa
t i o n dimensionless. Time, d i s t a n c e and v e l o c i t y are expressed i n
dimensionless forms by a proper combination of a c h a r a c t e r i s t i c
v e l o c i t y AAP and d i f f u s i o n c o e f f i c i e n t , D:
Eq. (4) may be transformed to
80 80 = 8 0 Z
(15)
W
8T 3Z 8^
where the boundary c o n d i t i o n s of Eq. (5)-(8) become
R w e =
" w all n d6)
z=0
17
e(t>0) = 5£1 = e <>
C W
wa

C
6 (0,z) = 0 (T,~) = -°- = e ( 1 8 )
c o
wa
and Eq. (9) may be r e w r i t t e n as
2 2
w = 1 - Be 9 (1 + a i c 0 + a c 2 0 ) (19)
wa w wa w wa w
I n t r o d u c i n g the s i m i l a r i t y coordinate
1
x = Z/WT) /* (20)
Equations (15)-(18) become [6(T,Z) => 0(T,X)]
Z U W T ;
^ T
8T ' 8X 8X2
- 2 /T R w 0 w - || | (22)
x=0
0 (T,0) = 0 , 0 (T,») = 6 (23)
The s i m i l a r i t y t r a n s f o r m a t i o n , Eq. (20), used here i s gen-

e r a l l y a p p l i e d to o b t a i n s m a l l time s o l u t i o n . However, i n the
case of g e l p o l a r i z e d u l t r a f i l t r a t i o n , T r e t t i n and Doshi (1980 b)
have used such s i m i l a r i t y t r a n s f o r m a t i o n to o b t a i n an expression
f o r the l i m i t i n g permeate v e l o c i t y . We have, t h e r e f o r e , used
s i m i l a r i t y t r a n s f o r m a t i o n to evaluate osmotic pressure l i m i t e d
permeate v e l o c i t y . In the case of g e l p o l a r i z e d u l t r a f i l t r a t i o n ,
c^ = c = constant and consequently, Eq. (21) to (23) can be
g
s o l v e d by c o n s i d e r i n g 0 as a f u n c t i o n of x only and by s e t t i n g w
0 # 5
T as a constant. However, i n the osmotic pressure l i m i t i n g
case considered here, c i s a f u n c t i o n of time. We can s o l v e Eq.
w
5
(21) to (23) i n the form of a power s e r i e s i n T ° * :
f2(x) (24)
6 -- f ( x ) ++
fl f
0 * f / ,+
fi(?)
2 T
,
f

then
e w = i + ^ + i ^ > + ... (25)
where
lim 6 = f (O) = 1
0 (26)
W
->oo
T
Substituting for 0 i n Eq. (19) and r e a r r a n g i n g y i e l d s :
w / T = Sifi(O) + I f y r + (27)
where
2 3
Bi = - (1 + B a i c + 2B a 2 c ) C28)
wa wa
The value of B remains to be determined.

2
S u b s t i t u t i n g f o r 0 and w/~T i n Eq. (21) and c o n s i d e r i n g terms

of c o e f f i c i e n t T° only gives
! T
-2xf 0 - 2Bi f i ( 0 ) f 0 = fo" (29)
T
-2R [ B i f i ( 0 ) ] f ( 0 ) = f o ( 0 ) 0 (30)
3 1
f (°°) = 0
0 ( )
o
f„(0) = 1 (32)
Equation (29) may be i n t e g r a t e d to y i e l d

00
6 = 1 + Ii exp [ 6 i f i ( 0 ) ] 2 2
/ 2
exp (-5 ) d £ (33)
0
Bl fi(0)
where
5 = x + 3! f!(0) (34)

o r , more simply,
2(6 -l) o
Ii = 72 C35)
1 W
/TT exp (^-^- ) e r f c
where V 0 - . /rk
_w = Bi f i ( 0 )
2
Considering the w a l l boundary c o n d i t i o n of Eq. (30), Eq. (35)
becomes
i-e
(36)
R/r
In a s i m i l a r manner as p r e v i o u s l y , consider c o e f f i c i e n t s of
1 2
T" ' only i n Eq. (21)
?
fi" + 2fi (x + B i f i ( 0 ) ] + 2 f i
(37)
2B 2 I i exp [-(x + 23i 2

fi(0)x)]
1 2
Considering the c o e f f i c i e n t s o f x"" / f o r the w a l l boundary con-
d i t i o n of Eq. (22) y i e l d s
2
-2R ( B i f i ( 0 ) + g ) = f!'(()) (38)
2
where
Bl f i ( 0 ) = I /2R ; 2 f2(oo) = o (39)
The s o l u t i o n f o r f i i s :
r
2
f i =[fi(0) + B 2 I i /r? / e x p ( r ) e r f c ( r ) d r ~ ]
(40)
exp w exp(-r )
4

where r = x + y-, and
l i m f i = 0, lim f x = fi(0) = Ii
x -> 00
x -> 0 2R3i (41)
r -> oo
Evaluating the f i r s t d e r i v a t i v e o f Eq. (40) at x = 0 gives
f (0)
f
= -26a f!*(()) + 32 I i A exp M*-J erfc^) (42)
The w a l l boundary c o n d i t i o n o f Eq. (38) may be equated to Eq. (42)

to y i e l d a r e l a t i o n s h i p f o r the value o f 3 namely
6 = B (0)(l-R) (43)
2
(R-l) + 0
S u b s t i t u t i n g f o r 62 i n Eq. (27), n e g l e c t i n g terms s m a l l e r than

1 2
T- / yields
w / r = 3i fi(0) fi(0)(R-D (44)

/r[(R-l)+6 ]
o
The dimensionless permeate v e l o c i t y w i l l be p r o p o r t i o n a l to

- 1 2
T / when
r: > y fi(0)(R-l) _ Ii(l-R)

(45)
[(R-D+e ] o 2R 3 i [ ( R - i ) + e ] Q
Equation (45) i s w r i t t e n i n dimensional form as
D V (1-R) 7
t » w (46)
2
(A AP) |3i| [ ( R - l ) + QJ
I f the c r i t e r i o n suggested i n Eq. (46) i s met, s o l u t e con-

c e n t r a t i o n at the membrane surface w i l l be approximately equal to
the asymptotic v a l u e , c . The s o l u t e c o n c e n t r a t i o n d i s t r i b u t i o n
wa
can be d e s c r i b e d by a s i n g l e independent v a r i a b l e , x. The problem
then becomes analogous to the g e l p o l a r i z e d u l t r a f i l t r a t i o n case
s o l v e d i n T r e t t i n and Doshi (1980b). I n t h i s same paper, an
i n t e g r a l method s o l u t i o n i s a l s o d e r i v e d . A p l o t of c a l c u l a t e d
values o f V v s . 0o which s a t i s f y Eq. (36) i s g i v e n i n F i g . 2 f o r
w —

v a r i o u s values of R. An unpublished work of V i l k e r (1975) has

r e c e n t l y come to our a t t e n t i o n where a s i m i l a r concept i s p r e -
sented.
An analogous treatment to the u n s t i r r e d batch c e l l may be
performed f o r the t h i n channel system where
u ^ - | | |£ v - D^f (47)
3 £ w' dy 1
8y2
and the boundary c o n d i t i o n s are
at y = 0 c = c (x) (48)
|v | c
W w
y = 0
3
, c> = c for a l l x C50)
o
2- 0, c = c for a l l y 51
<>
A diagram of the t h i n channel system i s shown i n F i g . 3.

Transforming Eq. (47) to dimensionless form, we f i n d
t _ |9 _ w |i = 14 (52)
dz
z w
3A 3z2
where
V
A Ap | w| A
z y w =
= — » A~AP '
2 53
/ , (A A P ) x . 3D < >
= c / c
wa' X =
 D ' h A AP
and assuming a J_inerarized axial velocity p r o f i l e , namely,
3
The boundary c o n d i t i o n s of Eq. (48)-(51) become

TRETTIN AND DOSHI Pressure-Independent UF 385
Figure 3. Thin-channel crossflow system

C (x) rets
( 5 6 )
e (x,o) - * - -
C W
wa
(0,z) = eCA.co) = C o / C w a = Q q ^
Equation (19) remains unchanged except that 6 i s now a f u n c t i o n

w
of X i n s t e a d o f T .
2 2
w = 1 - Be 6 (1 + otic 6 + a c 0 ) (19)
wa w wa w wa * 2 TT
I n t r o d u c i n g the s i m i l a r i t y , analogou
batch c e l l problem, Eq. ( 2 0 ) ,
Equations (52), (55)-(57) become [0 (A z) => 0 (A,n)]
3 0 1 3
* i n -u ^ A / , 80 2
80 r t - v
Q
3 A n (n + w ( ^ - j ) (59)
10 i w " 8n I (60)
n =o
0(A,O) = 0 w ( 6 1 )
The corresponding g e l p o l a r i z e d u l t r a f i l t r a t i o n problem,
where c = c = constant, i s s o l v e d by T r e t t i n and Doshi (1980a)
w g
0(A,°°) = 0 Q ) ( 6 2
by c o n s i d e r i n g 0 as a f u n c t i o n o f r| o n l y . I n the osmotic p r e s -
sure l i m i t e d case, as we have done f o r the u n s t i r r e d batch c e l l ,
we expand 0 i n the f o l l o w i n g form:
e = g 0 ( n ) + + _
(63)

e w = i + ^ + ^ + ... ( 6 4 )
where
65
l i m 6 = g (0) = 1 w 0 ( >
X -> 00
S u b s t i t u t i n g f o r 0 i n Eq. (19) and rearranging y i e l d s
l / 3 66
w X = S i g i ( 0 ) + - j ^ y + ... < >
1 3
S u b s t i t u t i n g f o r 0 and w A / i n Eq. (59) and c o n s i d e r i n g
0
terms of c o e f f i c i e n t A onl give
l/3
- n 2
go 1
-(f) B i giCO) T
go = go" (67)
1/3
-(f) P i g i ( 0 ) go(0) R = go'(0) (68)
( a 3 )
g 0 = G (69)
O
?
go(0) = 1 ( °)
Equation (67) may be i n t e g r a t e d using the boundary c o n d i t i o n s o f

Eq. (69)-(70) to y i e l d
0 - 1
T 2
1 1
"-
/ exp [- (\ n + W n)] d n 3
tt
(71)
0 J w
where
f
- W R = g CO) = I i
w 0 ( 7 2 )
Considering the w a l l boundary c o n d i t i o n of Eq. ( 6 8 ) , Eq. (71)

becomes

1 -
W = 0 0
w (73)
3
R J exp [- (y n + w w n ) ] dn
0
-1/3
Without c o n s i d e r i n g c o e f f i c i e n t s of A ' , we may develope
an approximate r e l a t i o n s h i p d e f i n i n g the parameters which i n -
fluence the rate at which an asymptotic w a l l concentration i s
reached. From Eq. (64)
e = w ... ( 7 4 )
Therefore, for c y c ,
w ^ wa'
3
W
or simply,
D w
x » ,, (76)
h(AAP)3 -[BTJ ;
From Eq. (76) i t can be seen that the membrane pure solvent
f l u x (A AP) has a l a r g e e f f e c t i n determining the required chan-
c
n e l length to reach an asymptotic w a l l concentration ( c ^ ^ a ^ * W
u >
since = ^ , i t may be seen that hydrodynamic shear at the
membrane surface i s a l s o an important f a c t o r and Eq. (76)
becomes:
2
° Y (77)
<\J 'w
x
3 (A AP)
> y 3
When the c r i t e r i o n of Eq. (46) f o r the u n s t i r r e d batch c e l l ,

or Eq. (77) f o r the cross flow p a r a l l e l p l a t e system, i s s a t i s -
f i e d , i t i s p o s s i b l e to make the s i m p l i f y i n g assumption o f con-
stant w a l l concentration (c c ). Consequently, Eq. (36)
7
, w ^ wa
becomes
(78)
where
2
V = w /if = Iv I ( 4 t / D ) V (79)
w w

f o r the u n s t i r r e d batch c e l l and Eq. (73) becomes

00
c —- c
wa
C80)
-^-f- = w w / exp [ - ( | n 3
+ w w n)] d n
where
1/3
h x (81)
W = v 1 1
D 2
w w
f o r the cross flow p a r a l l e l p l a t e system.

An i n t e g r a l method s o l u t i o n of Eq. (78) has been d e r i v e d by
T r e t t i n and Doshi (1980b) and may be represented as
c -c c -c
wa o wa p (82)
Ki
w c -c c -c
wa p o p
where
K i = 2 m / ( n i + 1)
(83)
and
1/2
/c - c \ //c - c \ 2 ^c -c
wa _p_] [ ( wa p'
ni = Ic - c [C - c + 8 wa p 1
(84)
V o p o p Vo °p C
S i m i l a r l y , the s o l u t i o n of Eq. (80) f o r the p a r a l l e l p l a t e

system has been d e r i v e d by T r e t t i n and Doshi (1980a) and i s
represented as
1/3
c -c c -c
wa o wa p
w = K (85)
w c -c 2
c -c
wa p o P
where
2
K 2 = 2n /(n 2 2 + D O * + 2)
(86)
and
1/2
C C
wa p\
n 2 = + 24 c - c (87)
° P,

In both i n t e g r a l method s o l u t i o n s the value o f D and s o l u t i o n

density are assumed constant. A d d i t i o n a l l y , as shown i n T r e t t i n
and Doshi (1980a, b ) , both i n t e g r a l method s o l u t i o n s agree very
w e l l w i t h t h e i r corresponding exact s o l u t i o n s . Note that i f one
wants to c a l c u l a t e o r W^, i n t e g r a l method r e s u l t s , Equations
(82)-(87) a r e convenient w h i l e f o r the c a l c u l a t i o n o f the
c
asymptotic w a l l c o n c e n t r a t i o n , > exact s o l u t i o n , Equations
w a
(78)-(81) are convenient.

In u n s t i r r e d batch c e l l u l t r a f i l t r a t i o n , the value o f |v |
i s t y p i c a l l y very s m a l l and t h e r e f o r e d i f f i c u l t to measure
i n s t a n t a n e o u s l y . I t i s p o s s i b l e , however, to a c c u r a t e l y measure
eluded permeate volume (AV) as a f u n c t i o n o f time. Therefore,
upon i n t e g r a t i o n , Eq. (79) becomes
AV = 2
t w
where
A = the t r a n s p o r t s u r f a c e area o f membrane
T = time of permeat c o l l e c t i o n
T
AV = / A t |v^| dt = eluded permeate volume i n time T.
o
When accumulated permeate volume i s measured a t three consecutive
times ( T i , T 2 , T ) , i t i s p o s s i b l e to w r i t e
3
A V 2 - A Vi = T2 /1 2
- 1
T1 / 2
( .
1 2 J
A V 3 - A Vi T3 / 1 2
- Ti / ^
I f sample times are s e l e c t e d such t h a t T2 = 2 T i , T3 = 4Ti an

accuracy of data may be checked:
In a l l batch c e l l experiments, data a c c e p t a b i l i t y l i m i t s were

e s t a b l i s h e d as ± 3% o f the 0.4142 v a l u e . Acquired data which
were not w i t h i n these l i m i t s were d e l e t e d .
As o u t l i n e d i n T r e t t i n and Doshi (1980b), a c o r r e c t i o n must
be made to the e x p e r i m e n t a l l y measured value o f AV t o a d j u s t f o r
the permeate c o l l e c t e d d u r i n g the i n i t i a l p e r i o d o f f i l t r a t i o n
when c < c o r c . Although the d u r a t i o n o f t h i s r e g i o n i s
&
w wa g
s m a l l , i t occurs at a time when permeate f l u x i s g r e a t e s t and i s

t h e r e f o r e necessary to c o r r e c t f o r . Experimentally c o l l e c t e d
permeate may be adjusted as f o l l o w s
91
AV = AV - AV C )
exp corr
S u b s t i t u t i n g f o r AV i n Eq. (88) and r e a r r a n g i n g y i e l d s
AV
R
—iff =2A V (D/4) / + 1 2
AV (1/T / ) 1 2 (92)
1/ 2 t w corr
or
AV
exp
172 _T Jlim corr
T
AV
By p l o t t i n g T T / 2 vs. 1/T / 1 2
and e x t r a p o l a t i n g t o i n f i n i t e time
(T), we can minimize the e f f e c t s o f the i n i t i a l r e g i o n where c^
1 2
i s not constant, and determine the t r u e value o f AV/T / [or
1 2
( A V / T / ] ^ ) as p r e d i c t e d by Eq. (88).
I t i s important to d i g r e s s momentarily t o d i s c u s s i n f u r t h e r
AV
1 2
d e t a i l the i n t e r p r e t a t i o n of the ? y ? v s . 1/T / p l o t .
T Since
both models presented i n T r e t t i n and Doshi (1980a, 1980b) were
d e r i v e d e x p l i c i t l y f o r the constant w a l l c o n c e n t r a t i o n boundary
c o n d i t i o n , and i n p a r t i c u l a r f o r g e l p o l a r i z a t i o n , the q u e s t i o n
a r i s e s as to the d i f f e r e n c e between g e l p o l a r i z e d behavior and
constant w a l l c o n c e n t r a t i o n (osmotic pressure e q u i v a l e n t ) behav-
i o r . The major s i m i l a r i t y between the two processes o f g e l p o l a r -
i z e d and osmotic pressure e q u i v a l e n t u l t r a f i l t r a t i o n i s that the
s o l u t e c o n c e n t r a t i o n a t the membrane s u r f a c e i s constant w i t h
respect to time, as i n the u n s t i r r e d batch c e l l case, o r a x i a l
A V
ex
p o s i t i o n , as i n the cross flow case. Therefore, a p l o t o f • fy\ T
vs. w i l l be l i n e a r i n the u n s t i r r e d batch c e l l case. The

major d i f f e r e n c e between the two processes i s t h a t i n g e l p o l a r -
i z e d u l t r a f i l t r a t i o n , not only i s the w a l l c o n c e n t r a t i o n constant
but i t i s a l s o independent of a p p l i e d pressure. This i s n o t true
of osmotic pressure e q u i v a l e n t u l t r a f i l t r a t i o n where w a l l concen-
AV e
'1/S?
1 2
t i o n i s pressure dependent. Therefore, i n a t VS* 1/T /
p l o t , g e l p o l a r i z a t i o n i s i n d i c a t e d by an i n t e r s e c t i o n o f

AV
v a r i a b l e AP l i n e s (at constant c ) a t the same value o f exp,
o LT Ti / 2 J l i m . A / z
A process which i s osmotic pressure l i m i t e d w i l l i n t e r s e c t

AV
X
at a d i f f e r e n t value o f i / ^ f o r each a p p l i e d pressure t e s t e d .
T
As can be seen, the u n s t i r r e d batch c e l l technique represents a

unique method f o r c h a r a c t e r i z i n g macromolecular s o l u t i o n s as t o
the pressure range i n which g e l p o l a r i z a t i o n occurs. One must be
cautious i n using the batch c e l l technique, however, t o s e l e c t
AP increments which are l a r g e enough to cause a d i s c e r n i b l e
change i n the value o f c This i s p a r t i c u l a r l y t r u e i n cases
wa
where s o l u t i o n osmotic pressure i s a s t r o n g f u n c t i o n o f concen-
tration.
With the u l t r a f i l t r a t i o n o f macromolecular s o l u t i o n s i n
cross flow systems suc
u s u a l l y the procedure t
s t a t e . Therefore, Eq. (81) may be i n t e g r a t e d to give
2 1/3
D (94)
= 1.5
h L
2
D 1/3
1.5 s W (95)
where Iv wI *= average permeate f l u x

1 l
and Q = s L v 1 = average v o l u m e t r i c permeate r a t e

1
p w
An analogous r e l a t i o n s h i p to Eq. (93) can be w r i t t e n t o account
f o r i n i t i a l e f f e c t s where c ^ c :
w <
exp + (1/L 2 / 3
)
iQpl (96)
lim corr
In a l l u l t r a f i l t r a t i o n systems reported i n the l i t e r a t u r e , aver-

age v o l u m e t r i c f l u x r a t e s at c o n s e c u t i v e l y i n c r e a s i n g lengths
along the conduit are not measured. As a r e s u l t i t i s not p o s s i -
2
ble to p l o t L 2/3
0 /V^ vs.
_
1/L r .
and
?i
extrapolate to i n f i n i t e length
to f i n d the t r u e value o f Therefore, i n the i n t e r -

lim
p r e t a t i o n o f the a v a i l a b l e cross flow u l t r a f i l t r a t i o n data, the

c o r r e c t i o n term, to a f i r s t order approximation, i s n e g l e c t e d .

This i s a reasonable assumption f o r the cross flow system i n which
the l e n g t h of the i n i t i a l r e g i o n may be s m a l l i n comparison to the
t o t a l conduit l e n g t h . The reason i s t h a t , u l i k e the batch c e l l
system where average f l u x i s 2 orders of magnitude l e s s than
pure s o l v e n t f l u x , average f l u x i n cross flow systems i s only 10
times l e s s than pure solvent f l u x .
Experimental Procedure
Bovine serum albumin (BSA) (Sigma Chemicals — Cohn f r a c t i o n

V) was s e l e c t e d as a s o l u t e m a t e r i a l to be s t u d i e d i n batch c e l l
u l t r a f i l t r a t i o n . The j u s t i f i c a t i o n of t h i s choice was based on
the f a c t that BSA has been used by previous i n v e s t i g a t o r s ; t h e i r
work would o f f e r a source of comparison to our r e s u l t s [ B l a t t ,
et a l . (1970), K o z i n s k
(1977, 1979), P r o b s t e i
and M i t r a and Lundblad (19 78)]. S o l u t i o n s of BSA d i s c u s s e d i n
t h i s paper were prepared i n aqueous 0.15M NaCl and adjusted to pH
7.4. Sodium azide of 200 ppm c o n c e n t r a t i o n was added as a pre-
s e r v a t i o n and f i n a l s o l u t i o n s were f i l t e r e d through a 0.8 ym
M i l l i p o r e f i l t e r to remove u n d i s s o l v e d s o l u t e . A l l s o l u t i o n s
were r e f r i g e r a t e d at 10°C p r i o r to use and s o l u t i o n s which had
aged more than 2 weeks, or showed a p p r e c i a b l e sedimentation, were
discarded. Solute c o n c e n t r a t i o n was determined by u l t r a v i o l e t
l i g h t a b s o r p t i o n w i t h a spectrophotometer a t the a b s o r p t i o n peak
of 280 nm.
U l t r a c e n t r i f u g e experiments were performed i n our l a b o r a t o r y
w i t h BSA s o l u t i o n s u s i n g the o p t i c a l procedure of Longsworth
(1952) and Creeth (1955) as o u t l i n e d by T o s t e v i n (1966). A
l i m i t a t i o n of t h i s method i s that only low s o l u t e concentrations
may be s t u d i e d due to r e f r a c t i o n f r i n g e merging a t higher con-
c e n t r a t i o n s (> 0.01 g/cc).
The l i t e r a t u r e contains numerous experimental determinations
of the mutual d i f f u s i o n c o e f f i c i e n t of BSA i n v a r i o u s b u f f e r
s o l u t i o n s [Creeth (1952), Charlwood (1953), K e l l e r , et a l . (1971),
Doherty and Benedek (1974), P h i l l i e s , _et a l . (19 76)]. The range
of reported d i f f u s i o n c o e f f i c i e n t at low c o n c e n t r a t i o n i s D =
7 2
5 . 5 — 7.Ox 10 cm /sec. However, values at h i g h e r concentra-
t i o n s show considerable s c a t t e r as p o i n t e d out by Shen and
P r o b s t e i n (1977). P h i l l i e s , e t a l . (1976) have s t u d i e d BSA s o l u -
t i o n d i f f u s i v i t y i n 0.15M NaCl aqueous systems over the pH range
of 4.3 — 7.6. Their data taken w i t h i n the h i g h e r pH and concen-
t r a t i o n ranges have been i n t e r p r e t e d by P r o b s t e i n , e t a l . (1979)
7 2
to y i e l d an average value of 6.7 x 10 cm /sec. Both Creeth
(1952) and Charlwood (1953) have reported the d i f f u s i v i t y o f d i -
7 2
l u t e BSA_solutions to be w i t h i n the range of 6.6 x 10 cm /sec to
7 2
7.1 x 10 cm /sec at 25°C. T h e i r data a l s o show that the e f f e c t s
of pH and b u f f e r type upon the d i f f u s i o n c o e f f i c i e n t are n e g l i g i -
b l e . The value of the d i f f u s i o n c o e f f i c i e n t f o r 0.15MNaCl BSA

7 2
s o l u t i o n (pH 7.4) was determined t o be 6.91 x 10 cm /sec from
our u l t r a c e n t r i f u g e experiments a t 23.5°C. I t has been shown by
T r e t t i n and Doshi (1980b) t h a t t h i s value i s reasonably constant
over a wide range o f c o n c e n t r a t i o n i n the u l t r a f i l t r a t i o n of
s a l i n e BSA s o l u t i o n s .
Batch c e l l experiments were performed i n s t a i n l e s s s t e e l
pressure c e l l s manufactured by the Gelman F i l t e r Company. The
2
average membrane area e q u a l l e d 15.62 cm and the t o t a l c e l l volume
3
was approximately 230 cm . The batch c e l l s were a f f i x e d to a
support i n t e g r a l w i t h the b u i l d i n g s t r u c t u r e t o prevent extraneous
v i b r a t i o n . The room temperature was c o n t r o l l e d w i t h i n the range
of 21-24°C. T o t a l permeate volume was g r a v i m e t r i c a l l y measured
as a f u n c t i o n of time f o r p e r i o d s as l o n g as 24 hours. C e l l p r e s -
5 5 2
sure was v a r i e d from 2.76 x 1 0 - 17.24 x 1 0 N/m (40 t o 250
psi).
The m a j o r i t y of experiment
t a t e membranes (5,000 —
Systems. Several experiments were a d d i t i o n a l l y conducted u s i n g
n o n c e l l u l o s i c (X-117) and p o l y s u l f o n e membranes a l s o from UOP.
Both n o n c e l l u l o s i c membranes performed as w e l l as the c e l l u l o s e
acetate membrane, y i e l d i n g s o l u t e r e j e c t i o n s g r e a t e r than 95%.
In T r e t t i n and Doshi (1980b), a p l o t o f 0.15M s a l i n e BSA

s o l u t i o n data (pH 7.4) was presented showing that above 6.89 x
5 2
10 N/m a p p l i e d p r e s s u r e , a g e l l a y e r may have formed upon the
membrane s u r f a c e . This graph has been reproduced i n F i g . 4 of
5 2
t h i s paper w i t h a d d i t i o n a l data taken at 2.76 x 1 0 N/m and 4.14
5 2 5 2
x 1 0 N/m . At c e l l pressures o f 6.89 x 1 0 N/m o r g r e a t e r , the
presence of g e l p o l a r i z a t i o n (pressure independence) i s i n d i c a t e d
AV
1 2 00
by the i n t e r s e c t i o n o f t / ? v s . 1/T / p l o t s as T -> f o r two
T
d i f f e r e n t pressures at constant b u l k s o l u t i o n c o n c e n t r a t i o n . When

the data a t lower pressures are examined, they do not i n t e r s e c t
AV
at the same value of as the h i g h e r pressure data. It is
L —I l i m
i n t e r e s t i n g to note, however, t h a t the lower pressure data p l o t s
are l i n e a r , i n d i c a t i n g constant w a l l c o n c e n t r a t i o n . The w a l l
c o n c e n t r a t i o n i n t h i s case corresponds approximately to the
osmotic pressure e q u i v a l e n t (c ) of the a p p l i e d p r e s s u r e .
Osmotic pressure l i m i t e d u l t r a f i l t r a t i o n data were analyzed
by u s i n g Eq. (92) and the osmotic pressure data o f V i l k e r (1975)
T
f o r 0.15M S a l i n e BSA s o l u t i o n s at pH 7.4. V i l k e r s data are
reproduced i n F i g . 5 f o r BSA i n both 7.4 and 4.5 pH 0.15M s a l i n e
s o l u t i o n . The comparison between theory and experiment i s q u i t e
good as shown i n Table I where the value o f D was taken as 6.91 x
7 2
10 cm /sec.

A- 10.34*10 N/m
5 2
O- 6 89x10 N/m
s 2
--'J C=1 03g/100cc
Q
•-4 14x10 N/m

s 2
V-2.76x10 N/m
s 2
. - C=1.03g/100cc
o
J7- - '
o 1000 -f ----O-(c =2.17 0
/100cc
___--o- ^ A-\ g
__
7 C=2 08 0
g/IOOcc
^ - — C=5 15g/100cc
0
_ C=5 10g/100cc
0
- - - -O^ " - - A- - -
C ^5 08g/100cc
0
6 8
1/2 3
(1/T ) xio (sec-V ) 2
Figure 4. Unstirred batch cell UF of 0.15M NaCl BSA solution (T = 21 °-24°C,

pH 7.4) at various solute concentrations and applied pressures

Vincent L Vilker
Figure 5. Solution osmotic pressure vs. solute concentration: 0.15M NaCl BSA
solution (21)

TABLE I
0.15M SALIN
Experimental Theoretical
c c AP x l O - 5
c 1
[AV/T / ] 2 1 2
[AV/T / ],. *
o P 2
wa lim lim R
[g/lOOcc] [g/lOOcc] [N/m ] [g/lOOcc] [mL-sec / J -1 2
[mL-sec / ] -1 2
a
1.030 0.0033 2.76 40.45 0.1137 0.1127 0.989
1.030 0.0042 4.14 44.20 0.1248 0.1164 0.931
2.080 0.0058 2.76 40.45 0.0792 0.0752 0.949
2.140 0.7090 2.76 40.45 0.0897 0.0917 1.02
2.170 0.3472 4.14 44.20 0.0880 0.0847 0.964
5.080 0.0603 4.14 44.20 0.0455 0.0461 1.01
1 2
theoretical [AV/T / ! .
'lim
1 2
experimental [ A V / T / ] . * n
lim

In order t o add i n s i g h t i n t o the time r e q u i r e d to reach an

asymptotic w a l l c o n c e n t r a t i o n i n the batch c e l l , we can c a l c u l a t e
the value o f t from Eq. (46).
V (1-R)
w
t » (A AP) 2 (46)
I Si I[(R-i) + e ] o
where we have assumed the value of R t o equal 0.990. The approxi-

mate r e l a t i o n s h i p o f
4 2 2 3
1.42 x I O c - 8.96 x 1 0 c + 17.74 c ,
25 £c< 40 g/100 cc (97)
2
where TT = [N/m ], c = [g/100 c c ]
i s used to c a l c u l a t e | 3 i |
Table I , we f i n d 6 = 2.5 0 , Fig , w
The c a l c u l a t e d value o f i s found to equal 4.20, and A =

9
5.0 x 10 i s specified. Therefore,
N-sec
t » 0.264 seconds (98)
which i s indeed a very short time p e r i o d t o reach the asymptotic

?
w a l l c o n c e n t r a t i o n a t the membrane s u r f a c e . V i l k e r s pH 7.4 data
were l i n e a r l y e x t r a p o l a t e d t o h i g h e r pressures where we have
5 2
experienced g e l p o l a r i z a t i o n . At 6.89 x 1 0 N/m , the e x t r a p o l a -
t i o n i n d i c a t e s a value o f c equal t o 54 g/100 cc. This i s i n
wa
reasonable agreement w i t h our, and K o z i n s k i and L i g h t f o o t ' s
(1972), determination of 58.5 g/100 cc ( g e l concentration) con-
s i d e r i n g the accuracy o f the e x t r a p o l a t e d value and the r e l a t i v e
i n s e n s i t i v i t y of the model t o s m a l l changes i n c » wa
The cross f l o w , t h i n channel data o f P r o b s t e i n , e t a l . ,

(1978) and M i t r a and Lundblad (1978) were analyzed i n terms o f the
?
osmotic pressure e q u i v a l e n t model u s i n g V i l k e r s osmotic pressure
data f o r 0.15M S a l i n e BSA s o l u t i o n s (pH 7.4). Although M i t r a and
Lundblad d i d not study BSA d i r e c t l y , but r a t h e r human serum a l -
bumin (HSA), i t was f e l t that s u f f i c i e n t s i m i l a r i t y e x i s t e d be-
tween the two s o l u t e s that an approximate comparison u s i n g BSA
parameters could be made [Scatchard, e t a l . (1944)]. Data were
i n t e r p r e t e d t h e o r e t i c a l l y u s i n g the r e l a t i o n s h i p o f Eq. (94). I n
the a n a l y s i s of P r o b s t e i n , e t a l . , data, the c i t e d values o f h =
0.19 cm (channel h a l f width) and L = 43 cm (channel length) were
f
used. S i m i l a r l y , i n the a n a l y s i s o f M i t r a and Lundblad s 0.15M
S a l i n e HSA s o l u t i o n (pH 6.9) data, the c i t e d values of h = 0.019
cm and L = 76 cm were used. The value o f D was taken to be 6.91
7 2
x 10 cm /sec i n a l l c a l c u l a t i o n s and s o l u t e r e j e c t i o n at the

membrane s u r f a c e was assumed to be complete. The i n t e r p r e t a t i o n

T
of P r o b s t e i n , et a l . and M i t r a and Lundblad s data are shown i n
Tables I I and I I I , r e s p e c t i v e l y . The data of M i t r a and Lundblad
which were a c q u i r e d at a x i a l v e l o c i t i e s above 65.56 cm/sec were
not considered due to h i g h pressure drops along the t h i n channel
length.
I t i s i n t e r e s t i n g to note i n Table I I t h a t , although theo-
r e t i c a l p r e d i c t i o n of f l u x agrees w e l l w i t h experimental values
5 2
at a p p l i e d pressures above 1.0 x 10 N/m , at lower pressures
experimental f l u x i s s u b s t a n t i a l l y over p r e d i c t e d by theory.
This o b s e r v a t i o n may be e x p l a i n e d i n terms of the approximate
r e l a t i o n s h i p of
2
D Y W
w w L* (77)
x » 3
3(A AP)
w
At low pressures and h i g h a x i a l v e l o c i t i e s , the r a t i o of —^p)T
i s l a r g e , and t h e r e f o r e longer a x i a l d i s t a n c e s are r e q u i r e d to
reach an asymptotic w a l l c o n c e n t r a t i o n . When these i n i t i a l d i s -
tances, where c^ < c > are a p p r e c i a b l e , the osmotic pressure
wa
e q u i v a l e n t model does not apply and the i n t e g r a l method or numer-

i c a l technique employed by Leung and P r o b s t e i n (1979) may have to
5 2
be used. I t i s shown by the 0.689 x 10 N/m data i n Table I I
that p r o g r e s s i v e l y b e t t e r agreement w i t h theory i s obtained as
shear r a t e i s decreased. This o b s e r v a t i o n i s c o n s i s t e n t w i t h Eq.
(77).
In Table I I I , experimental f l u x i s c o n s i s t e n t l y o v e r p r e d i c t -
ed t h e o r e t i c a l l y by approximately 5%. This discrepancy may be
due to the use of BSA s o l u t i o n parameters (D, TT) to i n t e r p r e t
HSA s o l u t i o n data.
Previous workers [Shen and P r o b s t e i n (1977, 1979), Prob-
s t e i n , et a l . (1978, 1979)] have i n t e r p r e t e d g e l p o l a r i z a t i o n of
5 5 2
BSA s o l u t i o n s to occur between 2.76 x 10 and 4.14 x 10 N/m ap-
p l i e d system pressure based upon f l u x _vs. pressure p l o t s . Our
batch c e l l work has shown that g e l p o l a r i z a t i o n of s a l i n e BSA
5 2
s o l u t i o n s does not occur at pressures below 6.89 x 10 N/m .
This apparent discrepancy may be r e s o l v e d i n the f o l l o w i n g man-
ner. In F i g . 6, we p l o t the value of W , which i s d i r e c t l y pro-
w
p o r t i o n a l to f l u x , vs_. AP, the a p p l i e d pressure. The value of
W^ i s c a l c u l a t e d from Eq. (94) f o r the t h i n channel system u s i n g
the a p p r o p r i a t e value of c ^ at each s p e c i f i c a p p l i e d pressure.
a
1
The value of c i s determined from V i l k e r s s a l i n e BSA s o l u t i o n
wa
data (pH 7.4). In F i g . 6 i t can be seen that at low AP, the
d W
w
value of ~j~"j£p i s l a r g e and s h a r p l y decreases to a s m a l l value at

TABLE I I
THIN CHANNEL UF OP 0.15M S A L I N E BSA SOLUTIONS

(pH 7.4) - PROBSTEIN, e t a l . (1978)
Experimental theoretical
o
c 100 L* AP xi0" ?
c
wa
 |v
1
w1
| xlO 4
Iv
1
w
| xlO"
[g/100 c c ] [cm] [N/m ] 2

[g/100 cc] [cm/sec] [cm/sec] [cm,/ s e c ] R
a
1.74 0.490 2.76 40.34 34 5 6.38 5 .87 0.920
1,76
1.78 4.19 1.10
1.80 11 .5 3.67 4,.01 1.09
1.87 0.075 5,.8 3.04 3 .14 1.03
1. 74 2.13 2.07 37.33 34 .5 6.10 5.68 0.931
1,76 23 .0 4.71 4 .93 1.05
1.80 11.5 3.67 3..88 1.06
1 ,87 0.325 5 ,8 3.04 3 .04 1.00
1. 74 6.53 1.38 32.83 34..5 5.58 5..36 0.961
•!.. 76 23.0 4.56 4..66 1.02
1.78 17..3 4.06 4..22 1.04
1.80 11..5 3.60 3..66 1.02
L.87 1.00 5.1I 2.96 2..86 0.966
1.78 6.82 1.03 30.50 17.,3 3. 79 4.,08 1.08
1.80 11..5 3.33 3.,53 1.06
1-87 2.15 5 A] 3.04 2.,77 0.911
i . 74 60.0 0.689 26.00 34.,5 3.60 4.,81 1.34
1.76 23..0 3.25 4.,18 1.29
1.78 17..3 3.15 .i..78 1.20
1.80 11..5 2.90 3..28 1.13
1.87 9.10 5..8 2.40 2. 57 1.07

TABLE I I I
THIN CHANNEL UF OF 0.15M SALINE HSA SOLUTIONS (pH 6.9)-MITRA AND

5 2
LUNDBLAD (1978), AP =- 1.72 x l O N/m , c = 35.33 g/100 cc
Experimental Theoretical
c 1 xlO 4
| xlO"
o
g/100 cc] [cm/sec J
3.83 33.70 6.25 6.95 1.11
A > 5 33.70 5.63 6.23 1.11
6.05 33.70 5.00 5.30 1.06
7.83 33.70 4.17 4.43 1.06
9.43 33.70 3.54 3.8 3 1.08
3.25 49.86 8.25 8.63 1.05
4.66 49.86 7.29 7.09 0.973
6.75 49.86 5.00 5.61 1.12
8.66 49.86 4.58 4.68 1.02
10.63 49.86 3.92 3.94 1.01
13.41 49.86 2.92 3.13 1.07
3.44 65.56 9.38 9.18 0.979
4.09 65.56 8.33 8.36 1.00
7.12 65.56 6.46 5.92 0.916
9.25 65.56 4.79 4.86 1.01
1.04 Av

5 2
values of AP above 3.0 x 1 0 N/m . This behavior i s c h a r a c t e r i s -
t i c o f a c t u a l experimental p l o t s . In f a c t , the d i f f e r e n c e i n
5 5 2
p r e d i c t e d W between AP values of 2. 76 x 1 0 and 4.14 x 1 0 N/m
w
i s only 5%. I t i s our c o n t e n t i o n that a p l o t o f f l u x v s . AP does
not n e c e s s a r i l y i n d i c a t e the presence o f g e l p o l a r i z a t i o n a t the
p o i n t where f l u x appears t o become independent o f a p p l i e d p r e s -
sure. The s m a l l f l u x change behavior as a f u n c t i o n o f pressure
may be due s o l e l y to the s o l u t i o n osmotic p r e s s u r e . The pressure
5 2
range o f 2.76-4.14 x 1 0 N/m i s too narrow to y i e l d an accurate
i n t e r p r e t a t i o n of g e l p o l a r i z a t i o n w i t h an average e r r o r l e s s than
d W
w
5%. Table IV gives the c a l c u l a t e d value o f as a f u n c t i o n of
AP f o r v a r i o u s values of C . The e x p e r i m e n t a l l y observed behavior
q
of h i g h c o n c e n t r a t i o n s o l u t i o n s reaching a p l a t e a u r e g i o n a t
s m a l l e r values o f AP a
i s e x p l a i n e d by the f a c t t h a t the value o f ^ ^ decreases ( a t

constant AP) as the s o l u t i o n c o n c e n t r a t i o n i n c r e a s e s .
Conclusions
I t i s t h e o r e t i c a l l y shown f o r the u n s t i r r e d b a t c h c e l l t h a t ,
i n l i m i t i n g cases, the assumption o f constant w a l l (membrane) con-
c e n t r a t i o n w i t h respect to time may be made even i n the absence
of g e l formation. Although the assumption of constant w a l l con-
c e n t r a t i o n i s s i m i l a r i n both g e l and osmotic pressure l i m i t e d
u l t r a f i l t r a t i o n , i t i s important t o recognize that i n g e l
p o l a r i z e d u l t r a f i l t r a t i o n , w a l l c o n c e n t r a t i o n i s a l s o pressure
independent s i n c e i t corresponds t o the s o l u t e s o l u b i l i t y l i m i t .
This i s not the case i n osmotic pressure l i m i t e d u l t r a f i l t r a t i o n
where c^ i s approximately equal to the c o n c e n t r a t i o n a t which the
developed osmotic pressure at the membrane s u r f a c e equals the
a p p l i e d system p r e s s u r e . C r i t e r i a are presented — Eq. (46) f o r
the u n s t i r r e d batch c e l l and Eq. (77) f o r the p a r a l l e l p l a t e
system — to e s t a b l i s h the v a l i d i t y o f the constant w a l l concen-
t r a t i o n (osmotic pressure e q u i v a l e n t ) assumption i n osmotic p r e s -
sure l i m i t e d u l t r a f i l t r a t i o n .
When the assumption o f constant w a l l c o n c e n t r a t i o n i s j u s t i -
f i e d , data f o r the u n s t i r r e d batch c e l l and t h i n channel systems
may be i n t e r p r e t e d using models presented i n T r e t t i n and Doshi
(1980a, 1980b). Such an a n a l y s i s i s performed where agreement i s
shown to be very good between theory and osmotic pressure l i m i t e d
u l t r a f i l t r a t i o n experiments.
I t i s f u r t h e r shown t h a t the c u r r e n t p r a c t i c e o f p l o t t i n g
permeate f l u x vs. AP i n macromolecular c r o s s - f l o w u l t r a f i l t r a t i o n
may l e a d to s e r i o u s m i s i n t e r p r e t a t i o n of g e l p o l a r i z a t i o n . I t i s
t h e r e f o r e recommended that s o l u t i o n s be s t u d i e d i n the u n s t i r r e d

PRE-GEL REGION GEL POLARIZATION

REGION
C 0 =1.0g/KX) cc
Co =2.0g/KX) cc
C =4.0g/100cc
o
—, , ( , , ,
1.0 20 30 4.0 5.0 6.0 7.0
A P*10' (N/m )
5 2
Figure 6. W w vs. AP thin-channel crossflow system. Values of C w a calculated

from Figure 5 for various applied pressures.
TABLE IV
J
|- VERSUS AP ~ THIN CHANNEL SYSTEM
(FROM FIG. 6)
5
AP x l 0 ~ d AP d Ap d A?
2
[N/m ] (c = 1.0 g/100 cc.) (c = 2.0 g/100 cc) (c = 4.0 g/100 cc)
o o o
0.58 1.15 1.00 0.90
L.00 0.62 0.55 0.45
1.65 0.37 0.31 0.26
2 60 0.22 0.18 0.16
4.45 0.10 0.09 0.08
6.89 0.07 0.06 0.05

batch c e l l p r i o r to study i n c r o s s - f l o w systems i n order to

determine the pressure at which g e l p o l a r i z a t i o n a c t u a l l y occurs.
In previous work, pressure independent f l u x i s assumed to be due
to the presence of g e l p o l a r i z a t i o n even at low p r e s s u r e s .
Probably, the g e l p o l a r i z a t i o n i s the exception r a t h e r than the
r u l e i n most i n d u s t r i a l - t y p e a p p l i c a t i o n s . Obviously, more care
must be taken i n s o l u t e and s o l u t i o n c h a r a c t e r i z a t i o n w i t h regard
to the i n t e r p r e t a t i o n of u l t r a f i l t r a t i o n data.
Acknowled gment s
The authors express t h e i r g r a t i t u d e to the member companies

of The I n s t i t u t e of Paper Chemistry f o r t h e i r support of the
graduate program.
P o r t i o n s of t h i s work were used by one of the authors (DRT)
as p a r t i a l f u l f i l l m e n t f th requirement f o th Ph.D degre
at The I n s t i t u t e of Pape
Nomenclat ure
A = membrane c o e f f i c i e n t = — — i— /
u R \N-sec /
m ^
2
A^, = membrane t r a n s p o r t s u r f a c e area (cm )
3
Bo = constant as d e f i n e d by Eq. (13) (cm /g)
b = osmotic pressure constant as d e f i n e d by Eq. (11)
3
/ N-cm \
bi = osmotic pressure constant as d e f i n e d by Eq. (11)
(h • W )
b2 = osmotic pressure constant as d e f i n e d by Eq. (11)
3N 3
/N /fcm , \
*W )
3
c = s o l u t e c o n c e n t r a t i o n (g/cm ) unless otherwise noted
2
D = s o l u t e d i f f u s i o n c o e f f i c i e n t (cm /sec)
d^ = h y d r a u l i c diameter (cm)
h = channel h a l f h e i g h t (cm)
I i , I2 = constants of i n t e g r a t i o n
Ki = dimensionless constant d e f i n e d by Eq. (92)
K2 = dimensionless constant d e f i n e d by Eq. (95)
k = mass t r a n s f e r c o e f f i c i e n t (cm/sec)
k = average mass t r a n s f e r c o e f f i c i e n t (cm/sec)
L = channel l e n g t h (cm)
ni = dimensionless constant d e f i n e d by Eq. (93)
n2 = dimensionless constant d e f i n e d by Eq. (96)

Q = S L |V | = average v o l u m e t r i c permeate r a t e (cm /sec)

P w
W
. w
r = x + —
„ _ theoretical flux
R = r a t i o of : ^ • -•,
a experimental f l u x
 d^p
R = Reynolds number =
e y
R = solute rejection c o e f f i c i e n t = 1- c /c
J
p w
Sc = Schmidt number = y/Dp
5 = w i d t h of membrane (cm)
kd
Sh = average Sherwoo
t = time (sec)
T = time p e r i o d (sec)
u = a x i a l v e l o c i t y (cm/sec)
 = average a x i a l v e l o c i t y (cm/sec)
|v^| = average permeate v o l u m e t r i c f l u x (cm/sec)
|v^| = permeate v o l u m e t r i c f l u x (cm/sec)
V = dimensionless p o s i t i v e f l u x constant f o r batch c e l l
W
[Eq. (91)]
= dimensionless p o s i t i v e permeate f l u x constant f o r
t h i n channel [Eq. (94)]
w = dimensionless permeate f l u x d e f i n e d by Eq. (16)
x = a x i a l d i s t a n c e coordinate (cm)
x = s i m i l a r i t y coordinate d e f i n e d by Eq. (22)
y = t r a n s v e r s e d i s t a n c e coordinate (cm)
z = dimensionless t r a n s v e r s e d i s t a n c e d e f i n e d by Eq. (16)
Greek L e t t e r s
oti, a 2 = osmotic pressure constants d e f i n e d by Eq. (13)

2
cc ( cc
g
3i = constant d e f i n e d by Eq. (30)
Ti> T2 = osmotic pressure v i r i a l c o e f f i c i e n t s
= w a l l shear r a t e (1/sec)
6 = mass boundary l a y e r t h i c k n e s s (cm)
5 = d e f i n e d by Eq. (36)
ri = s i m i l a r i t y coordinate f o r t h i n channel system d e f i n e d
by Eq. (65)
6 = dimensionless s o l u t e c o n c e n t r a t i o n d e f i n e d by Eq. (16)

X = dimensionless a x i a l d i s t a n c e coordinate d e f i n e d by
Eq. (60)
N—s ec
y = solution viscosity o—
2
TT = s o l u t i o n osmotic pressure (N/m )
3
p = s o l u t i o n d e n s i t y (g/cm )
T = dimensionless time as d e f i n e d by Eq. (16)
(J) = dimensionless constant d e f i n e d by Eq. (60)
2
AP = a p p l i e d h y d r o s t a t i c pressure (N/m )
3
AV = t o t a l permeate volume (cm )
ATT = TT - TT = s o l u t i o n osmotic pressure d i f f e r e n c e
w p
between w a l l c o n c e n t r a t i o n s o l u t i o n and permeate
2
(N/m )
Subscripts
g = of g e l
m = o f membrane
o = o f bulk s o l u t i o n
p = o f permeate s o l u t i o n
w = at w a l l p o s i t i o n
wa = of asymptotic s o l u t i o n
1, 2, 3 = a t measurement times
exp = e x p e r i m e n t a l l y measured
corr = correction
Abstract
In macromolecular ultrafiltration, as pressure is i n c r e a s e d ,

permeate flux first i n c r e a s e s and then in a l a r g e number o f
cases l e v e l s out and remains more o r l e s s pressure independent.
This could be due to the i n c r e a s e in s o l u t e c o n c e n t r a t i o n a t the
membrane s u r f a c e such that e i t h e r g e l formation occurs o r the
corresponding osmotic pressure approaches the a p p l i e d p r e s s u r e .
L i m i t i n g f l u x f o r the g e l p o l a r i z e d case was r e c e n t l y analyzed
f o r cross flow and u n s t i r r e d batch cell systems by Trettin and
Doshi (1980,a, b ) . In t h i s paper we have analyzed the osmotic
pressure l i m i t e d ultrafiltration for the two systems. Our un-
stirred batch cell data and the literature cross flow data agree
q u i t e w e l l w i t h the theory. We have f u r t h e r shown t h a t an un-
stirred batch cell system can be used t o determine whether p r e s -
sure independent ultrafiltration of macromolecular s o l u t i o n is gel
or osmotic pressure limited. Other causes f o r the observed p r e s -
sure independence may be present but a r e not considered in t h i s
paper.

Literature Cited
Blatt, W. F., A. D r a v i d , A. S. M i c h a e l s , and L. Nelsen, " S o l u t e

Polarization and Cake Formation in Membrane Ultrafiltration:
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Science and Technology, J . E. Flinn, ed. p. 47, Plenum P r e s s ,
New York, N.Y. (1970).
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E d i t i o n , I n t e r s c i e n c e , New York (1967).
Brandrup, J., and E. H. Immergut, "Polymer Handbook," I n t e r -

s c i e n c e , New York (1967).
B r i a n , P. L. T., in D e s a l i n a t i o n by Reverse Osmosis, U. Merten,

editor, MIT P r e s s Cambridge Mass. p 161 (1966)
Charlwood, P. A., " E s t i m a t i o Heterogeneity

Measurements," J. Phys. Chem., 57, 125 (1953).
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P r o t e i n S o l u t i o n s . An Assessment o f the Accuracy o f the
Method," Biochem. J., 51, 10 (1952).
Creeth, J . M., " S t u d i e s of Free D i f f u s i o n in L i q u i d s w i t h the

Rayleigh Method," J. Am. Chem. Soc., 77, 6428 (1955).
D e i s s l e r , R. G., " A n a l y s i s o f Turbulent Heat T r a n s f e r , Mass Trans-

fer, and Friction i n Smooth Tubes a t High P r a n d t l and Schmidt
Numbers," NACA Report No. 1210 (1955).
Doherty, P., and G. B. Benedek, "The E f f e c t o f Electric Charge

on the D i f f u s i o n of Macromolecules," J . Chem. Phys., 61,
5426 (1974).
Gill, W. N., L. J . Derzansky, and M. R. Doshi, "Convective D i f -

f u s i o n in Laminar and Turbulent Hyperfiltration (Reverse
Osmosis) Systems," in Surface and Colloid Science, Volume 4,
E. M a t i j e v i c , ed., p. 261, Wiley and Sons, New York, N.Y.
(1971).
Goldsmith, R. L., "Macromolecular Ultrafiltration with Micro-

porous Membranes," Ind. Eng. Chem., Fundam., Volume 10,
No. 1, p. 113 (1971).
Keller, K. H., E. R. Canales, and S. I . Yum, "Tracer and Mutual

D i f f u s i o n C o e f f i c i e n t s o f P r o t e i n s , " J . Phys. Chem., 75,
379 (1971).

K o z i n s k i , A. A., and E. N. L i g h t f o o t , " P r o t e i n Ultrafiltration:

A General Example of Boundary Layer Filtration," AIChE J.,
Volume 18, No. 5, p. 1030 (1972).
Leung, W. F., and R. F. P r o b s t e i n , "Low Polarization in Laminar

Ultrafiltration of Macromolecular S o l u t i o n s , " Ind. Eng.
Chem., Fundam., Volume 18, No. 3, p. 274 (1979).
Longsworth, L. G., " D i f f u s i o n Measurement, a t 1°, o f Aqueous

S o l u t i o n s o f Amino A c i d s , P e p t i d e s , and Sugars," J . Am.
Chem. Soc., 74, 4155 (1952).
M i c h a e l s , A. S., "New Separation Technique f o r the CPI," Chem.

Eng. P r o g r e s s , Volume 64, No. 12, p. 31 (1968).
M i t r a , F., and J. L. Lundblad "Ultrafiltration o f Immune Serum

G l o b u l i n and Human
S t u d i e s , " Separatio
No. 1, p. 89 (1978).
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in P r o t e i n S o l u t i o n s at High Concentrations: A Study o f
Q u a s i e l a s t i c L i g h t S c a t t e r i n g Spectroscopy," J . Chem.
Phys., 65, 1883 (1976).
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filtration," Ind. Eng. Chem. Prod. Res. Develop., Volume
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of Macromolecular S o l u t i o n s at High Polarization in Laminar
Channel Flow," D e s a l i n a t i o n , Volume 24, p. 1 (1978).
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F l u x in Laminar Ultrafiltration o f Macromolecular S o l u t i o n s , "
Ind. Eng. Chem., Fundam., Volume 16, No. 4, p. 459 (1977).
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Cambridge, Mass. (1975).

23
Polymer Solute Rejection by Ultrafiltration
Membranes
L E O S Z E M A N and M I C H A E L W A L E S
Abcor, Inc., 850 Main Street, Wilmington, MA 01887
Ultrafiltration membranes are used, both on industrial s c a l e

as w e l l as in l a b o r a t o r i e s
s e p a r a t i o n and c o n c e n t r a t i o
ble m a t e r i a l s .
R e j e c t i o n o f the s o l u t e (or dispersed c o l l o i d ) is, together
w i t h permeate flux, one of the two key performance parameters of
any ultrafiltration membrane. The values of rejection coeffi-
cients are o f crucial importance in many a p p l i c a t i o n s of ultra-
filtration. The o b j e c t i v e o f this c o n t r i b u t i o n is t o consider
and analyze the i n d i v i d u a l f a c t o r s a f f e c t i n g rejection o f polymer
s o l u t e s by ultrafiltration membranes. The f a c t o r s that will be
considered i n c l u d e steric rejection ( s i e v i n g ) , s o l u t e velocity
l a g and solute-membrane interaction.
Our a n a l y s i s e x p l o i t s h e a v i l y a model concept of a s p h e r i c a l
s o l u t e in a cylindrical capillary and we do not want t o dispute
the simplicity o r inadequacy inherent i n this model. However, we
want t o demonstrate that even w i t h i n the framework of this ideal-
ized model, u s e f u l p r e d i c t i o n s about the membrane rejection
behavior can be made.
We are not going t o d i s c u s s here the e f f e c t s of f o u l i n g
(adsorption) o r of electrostatic charge, even if we have t o bear
in mind that these may be overwhelmingly important in many situa-
tions. The d i s c u s s i o n will a l s o consider only a case of a pre-
ponderantly convective s o l u t e transport w i t h a negligible contri-
bution due t o diffusion.
Steric Rejection
In h i s w e l l known d e r i v a t i o n of a formula f o r s t e r i c r e j e c -
t i o n , J . D. Ferry (1) a r r i v e d i n 1936 a t a simple r e l a t i o n
between the s o l u t e r e j e c t i o n c o e f f i c i e n t , R 2 , and the s o l u t e t o
pore diameter r a t i o , A, where
R
2
0097-6156/81/0154-041l$06.00/0

3 2
R = 1-4 / ($-3 )dB = ( X ( 2 - X ) ) ; f o r X<1 (lb)
2
o -
and
R 2 = 1 f o r X>1 (lc)
These r e l a t i o n s can be used as rough estimates of s t e r i c

r e j e c t i o n , i f the s o l u t e and membrane pore dimensions are known.
The d e r i v a t i o n i s based on a s t r i c t l y model s i t u a t i o n (see
Figure 1) and a long l i s t of necessary assumptions can be w r i t t e n .
Apart from the s i m p l i f i e d geometry (hard sphere i n a c y l i n d r i c a l
pore), i t was a l s o assumed that the s o l u t e t r a v e l s a t the same
v e l o c i t y as the surrounding l i q u i d , that the s o l u t e c o n c e n t r a t i o n
i n the a c c e s s i b l e p a r t s of the pore i s uniform and equal t o the
c o n c e n t r a t i o n i n the feed
l i q u i d i s Newtonian, d i f f u s i o n a
port i s n e g l i g i b l e (pore P e c l e t number i s s u f f i c i e n t l y h i g h ) ,
c o n c e n t r a t i o n p o l a r i z a t i o n and membrane-solute i n t e r a c t i o n s are
absent, e t c .
Solute V e l o c i t y Lag
In g e n e r a l , a sphere moving through a c y l i n d r i c a l pore

does not move w i t h the same v e l o c i t y as the surrounding f l u i d .
Consequently, the formula ( l b ) has t o be c o r r e c t e d f o r t h i s
e f f e c t . I n 1975, Paine and Scherr (2) c a l c u l a t e d drag coef-
f i c i e n t s k , k i which weight the c o n t r i b u t i o n s of the sphere and
2
f l u i d v e l o c i t i e s t o the drag f o r c e F:
F = -6TTTVL (k v
2 2 - kivx) (2)
The drag c o e f f i c i e n t s k]^ and k are both a f u n c t i o n of X and 3

2
(dimensionless d i s t a n c e of sphere's center from the pore's a x i s ) .

The dependence of k]^ and k on 3 can be neglected without too
2
much e r r o r (2) and the r a t i o of k i / k can be considered t o depend

2
only on X.
In a steady-state s i t u a t i o n , the drag f o r c e has to be zero
and a constant s o l u t e v e l o c i t y l a g can be described by an equa-
tion:
vo k-. 2
— = i~ = exp (-0.7146X ) (3)
V k
l 2
The right-hand s i d e of Equation (3) was obtained by a l e a s t -

2
square f i t of a f u n c t i o n (exp (-°cX) on the values of k]^ and k 2
reported by Paine and Scherr (2) f o r d i f f e r e n t values of X.

f
Paine and S c h e r r s values represent a r i g o r o u s t h e o r e t i c a l s o l u -
t i o n f o r a c e n t e r - l i n e motion of a r i g i d sphere i n s i d e a
c y l i n d r i c a l tube. Applying t h i s c o r r e c t i o n , we can then w r i t e

23. ZEMAN AND WALES Polymer Solute Rejection 413
for solute rejection:

2 2
R 2 = 1 - ( 1 - ( A ( 2 - A ) ) ) exp (-0.7146A ) (4)
The magnitude of the s o l u t e v e l o c i t y l a g c o r r e c t i o n i s shown

i n F i g u r e 2. As seen, f o r a r i g i d sphere i n a c y l i n d e r , t h i s
c o r r e c t i o n i s not too l a r g e . N e v e r t h e l e s s , we w i l l keep c o n s i d -
e r i n g i t i n f u r t h e r d i s c u s s i o n s . The c o r r e c t i o n c a l c u l a t e d from
Equation (16b) of Anderson and Quinn ( 7 ) , a p p l i c a b l e f o r A<0.4,
i s i n agreement w i t h our r e s u l t s .
P o l y d i s p e r s e Solute
The s o l u t e hindrance c o e f f i c i e n t , W , i s d e f i n e d as
2
For a p o l y d i s p e r s e polymer s o l u t e , both W and R are f u n c t i o n s

2 2
of the s o l u t e molecular weight, M . I f f ( M ) i s the s o l u t e

2 2
d i f f e r e n t i a l weight d i s t r i b u t i o n s and W(M ) the_ corresponding

2
hindrance, the average r e j e c t i o n c o e f f i c i e n t , R i s d e f i n e d 2
through:
M (A=1)
2
R 2 = 1- / W (M ) f (M ) dM
2 2 2 2 (6)
o
and the r e l a t i o n between A and M 2 i s u s u a l l y of the form:
* b
A =f- M (7)
r l 3
2
where a, b are constants and r i s the membrane pore r a d i u s . The

3
d i f f e r e n t i a l weight d i s t r i b u t i o n f u n c t i o n i s e i t h e r known from

the experiment or i t has to be approximated by some t h e o r e t i c a l
f u n c t i o n . We have considered a case of p o l y d i s p e r s e dextran
s o l u t e s w i t h the values of constants i n Equation ( 7 ) , a = 0.3069
and b = 0.47. For a r v a l u e of 75A (close to Nuclepore 150A
3
f i l t e r ) , the comparison was done between r e j e c t i o n c o e f f i c i e n t s

c a l c u l a t e d from M data alone and from the a c t u a l dextran molecu-
w
l a r weight d i s t r i b u t i o n data s u p p l i e d by the producer (Pharmacia

Fine Chemicals). The r e s u l t s are shown i n Table I . I t i s seen
that c a l c u l a t i o n of the r e j e c t i o n c o e f f i c i e n t from the M value 2w
alone leads to an overestimate of r e j e c t i o n .

STERIC REJECTION—J.D. FERRY, 1936
Figure 1. Schematic of a spherical solute in a cylindrical pore
Figure 2. Effect of solute velocity lag with solute rejection as a function of X. The
line without symbols is calculated from Equation lb, the line with triangles is from
Equation 4, and the circles are calculated from Equation 16b of Anderson and
Quinn (1).

Table I
E f f e c t o f Solute Polydispersity
From
From
Experimental
Dextran 2,w 2,n 2,w MWD
T-10 10,500 6,400 0.330 0.326

MO TT
M
2,n
T-40 39,500 29,500 0.769 0.698
= 1 - 3 4
M
2,n
T-70 68,500 40,300 0.925 0.803
vk^ ~ 1-70
2,n
We can a l s o assume a t h e o r e t i c a l form of the d i s t r i b u t i o n

f u n c t i o n such as the log-normal (Wesslau) d i s t r i b u t i o n . I n t h i s
case
1 L 2
exp (( ^ -) l n ( ^ = — )
9
2a 0
2,m
(8)
f (M ) 9
a M • V^TT
2 2
n 2,w 0.5 N
(9)
2,n
and
M = M e x p( } (10)
2,m 2,n 2"
The e f f e c t o f s o l u t e p o l y d i s p e r s i t y ( a ) on r e j e c t i o n i s shown
2
i n F i g u r e 3. These curves were c a l c u l a t e d again f o r dextrans

of d i f f e r e n t M , but t h i s time a log-normal d i s t r i b u t i o n was
2 w
assumed f o r f ( M ) . Equation (6) was solved n u m e r i c a l l y . I t i s

2
seen again that i n c r e a s i n g the s o l u t e p o l y d i s p e r s i t y leads t o a

decrease i n the r e j e c t i o n c o e f f i c i e n t .
Membrane Pore Size Distribution
With the exception of membranes prepared by s p e c i a l t e c h -

niques (such as t r a c k - e t c h i n g ) , a d i s t r i b u t i o n of membrane pore

r a d i i has to be assumed f o r u l t r a f i l t r a t i o n membranes. Equations

f o r s o l u t e and s o l v e n t f l u x have then to i n c o r p o r a t e the e f f e c t
of membrane pore s i z e d i s t r i b u t i o n s dN/d^. The solvent f l u x
f o r an ensemble of pores obeying the P o i s e u i l l e equation i s :
00
4
TTAP / r o dN/dro dro 0 /
4
* i ,— » " • i ni <">
and the s o l u t e f l u x through these pores i s :
00
C 2 ) F ,AP / W r / 2 f dr 3
J x 10 (14)
2 krr 3
The c o n c e n t r a t i o n
C- p =— (15)
J
' l
and the average s t e r i c hindrance, W , i s 2
C 0
W 2 = 1^2 (16a)
:
2,F
Then, combination of Equations (13), (14), (15) and (16a)

yields:
oo
f TT 4 d N
A
W r d r
r 2 3 d7 ? 3 3
W2 = 1 - R 2 = -~ (16b)
°r 4 dN .
3
o 3
Equation (16b) d e s c r i b e s the e f f e c t of membrane pore r a d i u s d i s -

t r i b u t i o n on s o l u t e r e j e c t i o n . In the absence of a v a i l a b l e exper-
imental data on wet asymmetric u l t r a f i l t r a t i o n membranes w i t h
pore r a d i i s m a l l e r than 100A, we have to r e s o r t t o the use of an
assumed t h e o r e t i c a l d i s t r i b u t i o n f u n c t i o n .
As an example, we choose again the log-normal (Wesslau) d i s -
tribution function:
1 r
-
z
3
exp ( ( - 2 a 2) l n (^-)
|N . 1 hS- f (17)
3 A •a r 3 3 /2TT
where r are the median v a l u e and

3
m the standard d e v i a t i o n o f
l n r , r e s p e c t i v e l y . We r e d e f i n e A t o become X , where
3 m

r
2
A =- s — (18)
3,m
The s t e r i c hindrance, W , i s d e f i n e d by Equations (4) and (5) and
2
f o r the purposes of numerical c a l c u l a t i o n s i t can be expressed as

a l e a s t s q u a r e - f i t t e d polynomial
k=4
W = E A, A** (19)
2 m
k=0 ^
s a t i s f y i n g c o n d i t i o n s of W = 1 a t A = 0 and W = 0 a t A = 1.
2 m 2 m
The c o e f f i c i e n t s A^ are given i n Table I I .
Coefficient
0 1
1 0.04152060
2 -5.2303573
3 6.2893776
4 -2.1005409
Numerical s o l u t i o n of Equations (16b), (17) and (19) then a l l o w s

c a l c u l a t i o n of R as a f u n c t i o n of A and a . The r e s u l t s are
2 m 3
shown i n F i g u r e 4. I t i s seen t h a t membranes w i t h pore s i z e

d i s t r i b u t i o n s y i e l d r e j e c t i o n curves that are l e s s steep than
those c a l c u l a t e d f o r membranes w i t h uniform pore s i z e . Passage
of s o l u t e occurs even f o r A > 1.0. m
Presence of Holes
From a p r a c t i c a l p o i n t of view, t h i s i s a very common and a

very important problem. Holes may o r i g i n a t e from d e f e c t s i n
membrane backings, inhomogeneities i n the c a s t i n g s o l u t i o n s , a i r -
borne dust p a r t i c l e s , e t c . For s i m p l i c i t y , l e t us consider a
membrane area t h a t contains N pores of r a d i u s r and N holes of
f 3
r a d i u s r . Water f l u x , J-^ through t h i s membrane i s given by:

3
4 1 4 2 4
= (N r 3 +N r 3 ) x 1 0 " (20)
The s o l u t e f l u x through t h i s membrane i s given by:
J =
2 ((1- R 2 ) N r * N ' ;*) C
3 + r 2 f F . **** " 1 0 2 4
(21)
8n i 1 3

Figure 4. Effect of membrane pore-size distribution. R . is calculated as a func-

2
tion of A m and a . 3

where R i s r e j e c t i o n of the h o l e - f r e e membrane, and the hole i s

2
assumed to have a zero r e j e c t i o n c o e f f i c i e n t f o r the s o l u t e . The

c a n e
r e j e c t i o n c o e f f i c i e n t of t h i s d e f e c t i v e membrane, R êf ^ 2
c a l c u l a t e d as
J R
2 2
22
R
2,def = 1
" -7 ~ ' 1\~ < >
J C
1 2.F 1 + « ( ! 3 j
r
3
where
N
(23)
N
To i l l u s t r a t e t h i s e f f e c t
r
o » o
3 = 40A and r ^ = 1000A (O.lu). The c a l c u l a t e d r e j e c t i o n curve
(dashed l i n e ) i s shown i n Figure 5 and compared to that of a h o l e -
f r e e membrane ( f u l l l i n e ) . In the s o l u t e s i z e range of i n t e r e s t ,
the R = 1 p l a t e a u ( q u a n t i t a t i v e r e j e c t i o n of the s o l u t e ) i s
2
never achieved. R e j e c t i o n curves of t h i s s o r t are very commonly

encountered i n p r a c t i c e .
Van der Waals A t t r a c t i v e Forces
In the d e r i v a t i o n of J . D. F e r r y ' s formula, Equation ( l b ) , i t

was assumed that the s o l u t e c o n c e n t r a t i o n w i t h i n the a c c e s s i b l e
part of the membrane pore i s uniform and equal to C F . Obviously 2 >
t h i s assumption cannot hold i f we are to acknowledge the presence

of i n t e r a c t i v e forces between the s o l u t e and the pore w a l l (mem-
brane) . Here we w i l l concentrate only on the e f f e c t of Van der
Waals forces but analogous treatments could be developed f o r
other i n t e r a c t i v e p o t e n t i a l s ( e l e c t r o s t a t i c , e t c . ) .
We f i r s t consider an atom w i t h i n a c y l i n d r i c a l o r i f i c e i n the
membrane (component 3) of r a d i u s r = 1 i n t e r a c t i n g w i t h a 3
c y l i n d r i c a l volume element d V at a d i s t a n c e x (see Figure 6a).

3
The p o t e n t i a l energy of i n t e r a c t i o n (Van der Waals a t t r a c t i o n ) i s

-p N dV f
atom-3 M 6
3 0
x
t
where <* i s the i n t e r a c t i o n constant.
I n t e g r a t i o n over i n f i n i t e space o u t s i d e of the o r i f i c e ( i n
c y l i n d r i c a l coordinates y i e l d s
t
-2p„ N oc oo oo TT
* ,n\ 3 a - r dr QCD ay
I f f
r f
$ - Q (6 ) = 7Z ~ io f o
a t o m 3 M 2 2 3
" 3 y=0 r - l o)=0(y + r + B - 2 r 3 cosa))
1
-2p N cc
= ^ • I (6 ) (25)
M3

Figure 5. Effect of holes. Rejection curve calculated for a membrane with 40-A
radius pores ( ) and for the same membrane containing 1000-A holes ( ) at
7
a frequency of « = 3 X 10~ hole per pore.

the t r i p l e i n t e g r a l I (3 ) i n Equation (25) can be approximated

by:
?
I (3 ) = exp(exp(exp 1.5260$'-0.4637))) (26)
T
where 3 denotes the dimensionless r a d i a l p o s i t i o n of the atom.
We can now a l s o i n t e g r a t e over the s o l u t e sphere w i t h a r a d i u s
X (Figure 6b). For now, we assume that the s o l u t e i s made of the
same m a t e r i a l as the membrane ( p = P ; M = M^). 2 3 2
f P N TT/2
X , TT
*snhere-3
S p h e r e J
( 3
t A ) =
" 8
" < M
/
/ I (3 ) s sinGdsdedcJ)
/
3 cf>=0 6=0 s=0

Po N 0
8 # I lA 27
' " ^ > <>
and
2
= (s sin 2 2
0 + 3 -23s sin0 s i n ( ) ) ) 1/2
(28)
The c l u s t e r of constants i n Equation (27) can be s i m p l i f i e d by

u s i n g the Hamaker constant, H 3 3 :
P N 17
3 a 2 •
H33 = ( - V - ) 2 2
- (29)
and t h e r e f o r e
* (B,A) = H 3 3 ' I (B X) f (30)

TT
The f a c t that the s o l u t e (component 2) and the membrane (component

3) a r e made from two d i f f e r e n t m a t e r i a l s separated by the solvent
(component 1) w i l l be r e f l e c t e d by the use of a composite Hamaker
constant.
1/2 1/4 2
(31)
H
213 = ( H
11 - 22(H
V >
The energy of i n t e r a c t i o n f o r a s p h e r i c a l s o l u t e of r a d i u s X
i n a s o l v e n t - f i l l e d i n f i n i t e c y l i n d r i c a l pore w i t h a r a d i u s 3=1
and a t a r a d i a l p o s i t i o n 3 i s t h e r e f o r e
* (3'X) = ^ H 2 1 3 I (3'X) (32)

TT
The s o l u t e c o n c e n t r a t i o n p r o f i l e w i t h i n the a c c e s s i b l e p a r t of the

pore w i l l be determined by the Boltzmann d i s t r i b u t i o n law.

Figure 6b. Schematic of a spherical solute within the pore

23. Z E M A N AND WALES Polymer Solute Rejection 423
C 2 = C exp (-$/kT)
2 (33)
o -14
The value o f kT considered (25 C) i s 4.12 x 10 e r g .
R a d i a l d i s t r i b u t i o n o f s o l u t e molecules i n the pore does not
change the average s o l u t e c o n c e n t r a t i o n i n the pore and t h e r e f o r e
,2 _ I"* - $
Tr(l-A) C 2 j F = C -2ir / exp
2 ( dg, (34)
wherefrom:
2
_ C (1-A)
(35)
c
2 =
" 2 * i=r
/ e x p ( " T j ) 6 dg
Equations (32), (33) an

f u n c t i o n o f B and A f o r d i f f e r e n t values of H 3 (Hamaker con 2
s t a n t ) . Due t o the complexity o f c a l c u l a t i o n ( e v a l u a t i o n o f two

t r i p l e i n t e g r a l s ) , t h i s i s best done on a computer. T y p i c a l r e -
s u l t s of computer c a l c u l a t i o n s are shown i n F i g u r e 7. The e f f e c t
of Van der Waals a t t r a c t i v e f o r c e s w i l l lead t o an accumulation of
s o l u t e molecules near the w a l l s f o r s m a l l values of A but a t l a r g e
values of A , the p o s i t i o n s c l o s e t o the pore a x i s s t a r t being pre-
ferred.
The value o f H ^3 chosen i n our c a l c u l a t i o n i s r a t h e r l a r g e .
2
The expected magnitude of Hamaker constants would be between 2 x

13 1
1 0 " - 5 x l O " ^ erg depending on the " h y d r o p h i l i c i t y " o f both the
s o l u t e and the membrane.
To c a l c u l a t e r e j e c t i o n c o e f f i c i e n t s , we use the formula
/ 1-A
J
R 9 = 1 -£ / C (B-B ) dB9 (36)
1 C
2,F o 1
that accounts f o r the presence of a c o n c e n t r a t i o n gradient w i t h i n

the a c c e s s i b l e part o f the pore. R e j e c t i o n curves c a l c u l a t e d
from Equations (32), (33), (35) and (36) are shown i n F i g u r e 8.
I t i s seen t h a t the e f f e c t i s most pronounced below A = 0.7 and
i t s magnitude depends on the value o f the r e s p e c t i v e Hamaker
constant. The r e j e c t i o n c o e f f i c i e n t i s increased by the a t t r a c -
t i v e f o r c e s between the s o l u t e and the membrane.
I t i s t o be expected that f o r l a r g e values o f H, a d s o r p t i o n
a l s o occurs and the pore dimensions are changed correspondingly.
The e f f e c t s of adsorbed s o l u t e l a y e r s may be very important, but
these were not considered i n our a n a l y s i s o f the solute-membrane
interaction effects.

424 SYNTHETIC MEMBRANES HF AND UF USES
Figure 7. Example of calculated concentration profiles for the value of H i 2 3 = 1.5

X 10~ erg and different values of A and f$
13

Concentration Polarization
T y p i c a l r e s u l t s of an u l t r a f i l t r a t i o n experiment a l s o r e -
f l e c t the presence of c o n c e n t r a t i o n p o l a r i z a t i o n . This phenom-
enon, i . e . accumulation of s o l u t e i n f r o n t of the membrane, was
described i n great d e t a i l by others (Refs. 3, 4 ) . A consequence
of c o n c e n t r a t i o n p o l a r i z a t i o n i s a strong dependence of measured
r e j e c t i o n c o e f f i c i e n t s on transmembrane f l u x e s . An i l l u s t r a t i o n
of the e f f e c t i s presented i n Figure 9, which shows the measured
"apparent" r e j e c t i o n c o e f f i c i e n t s (R ) as a f u n c t i o n of transmem-
a
brane f l u x f o r two water-soluble polymers (Tetronic 707 and

Carbowax 4000). I t i s c l e a r from F i g u r e 9 that i f we want t o
minimize the e f f e c t s of c o n c e n t r a t i o n p o l a r i z a t i o n , we have to
conduct experiments at very low values of transmembrane f l u x .
Theory of S t e r i c R e j e c t i o
The experimental r e s u l t s are going to be presented i n d e t a i l

elsewhere and only a b r i e f p r e s e n t a t i o n w i l l be given below.
The p r e d i c t i v e power of Equation (4) was t e s t e d w i t h defined
polymeric s o l u t e s and track-etched Nuclepore f i l t e r s .
The polymers used were: l i n e a r polyethylene oxides, (Carbo-
waxes s u p p l i e d by Union Carbide C o r p o r a t i o n ) , and Dextran T
f r a c t i o n s , (Pharmacia Fine Chemicals). For Carbowaxes, the
s o l u t e r a d i i used i n c a l c u l a t i o n s were mean r a d i i of g y r a t i o n
c a l c u l a t e d from molecular weights v i a the Flory-Fox equation and
u s i n g the Mark-Houwink constants given i n reference (5). For
n o n - l i n e a r dextrans, we used the Stokes r a d i i c a l c u l a t e d from
molecular weights using the c o r r e l a t i o n of data reported by
Granath and K v i s t (6). Both types of polymer have very narrow
d i s t r i b u t i o n s of molecular weight. The s o l u t e r a d i i are summa-
r i z e d i n Table I I I .
Table I I I
Solute R a d i i
Solute M w (Daltons) R a d i u s ( & }
Carbowax 4000 4,010 25.4 Mean r a d i u s

Carbowax 6000 7,000 34.6 of g y r a t i o n
Dextran T10 10,500 23.8
Stokes
Dextran T40 39,500 44.4
Radius
Dextran T70 68,500 57.5
Nuclepore f i l t e r s used have s t r a i g h t - t h r o u g h pores w i t h

diameters s p e c i f i e d by Nuclepore Corporation as 150, 300 and 500A.
These are the s o - c a l l e d " r a t e d " pore diameters and they represent

Figure 8. Effect of solute-membrane interaction on rejection. Rejection curves

13
calculated for H = 0, H = 0.8 X IO' erg, and H = 2.0 X iO' erg.
213 213
13
213
1.0 THEORY - = K
— e (Brian's Model)
1-R a 1- Rl
(dalM
tWons)Q(GPM)(cm/s) iR
k
R
3
O OTetronic 707 12000 3.5 6.4xl0' 0.97
ACarbowax 4000 3500 1.7 3.7xl0" 0.83 3
0.5 V Membrane: ABC0R HFM 100
0 100 200 300 400 500 600 700 800 900 1000
FLUX (J), GFD
Figure 9. Effect of concentration polarization. Theoretical curves calculated for
the values of R i and k specified in the figure. Experimental data for Tetronic 707
(O) and Carbowax 4000 (A) ultraflltered through the ABCOR HFM 100 mem-
brane.

23. ZEMAN AND WALES Polymer Solute Rejection All
the maximum v a l u e . According to Nuclepore l i t e r a t u r e , the a c t u a l

pore s i z e s should not vary more than +0% to -20% from the r a t e d
values.
For each f i l t e r - s o l u t e combination, A was c a l c u l a t e d as a
r a t i o of the s o l u t e r a d i u s to the " r a t e d " pore r a d i u s . The p r e -
d i c t e d value of the r e j e c t i o n c o e f f i c i e n t was then c a l c u l a t e d from
Equation (4). The comparison between the p r e d i c t e d values and
those a c t u a l l y measured w i t h Carbowaxes 4000 and 600 i s shown i n
F i g u r e 10a and b, r e s p e c t i v e l y . The measurements were c a r r i e d
out at s e v e r a l values of AP i n order to assess the importance of
c o n t r i b u t i o n from c o n c e n t r a t i o n p o l a r i z a t i o n .
Using the GPC a n a l y s i s of feed and permeate s o l u t i o n s (Figure
11 a,b), we a l s o c a l c u l a t e d a p a r t of the s o l u t e r e j e c t i o n curve
for the given f i l t e r s . The example of such a curve i s a Carbowax
r e j e c t i o n curve f o r Nuclepore 150% (diameter) f i l t e r (Figure 11c).
The agreement between experimenta predictio
Equation (4) ( s o l i d l i n e
A s i m i l a r t e s t was performed w i t h Dextran T f r a c t i o n s and
Nuclepore 150&, 300&, 500X (diameter) f i l t e r s . The r e s u l t s are
summarized i n F i g u r e 12. The experimental p o i n t s were obtained
both from s i n g l e s o l u t e measurements (+ - r e j e c t i o n of T10 and
T70 by the 150& f i l t e r ) and from a n a l y s i s of the GPC t r a c e s ( F 1 ~
500& f i l t e r , A-300& f i l t e r , o-1508 f i l t e r ) . The agreement
between the experimental data and the p r e d i c t i o n of Equation (4)
( s o l i d l i n e ) i s again s u r p r i s i n g l y good, c o n s i d e r i n g the crude-
ness of assumptions i n v o l v e d i n i t s d e r i v a t i o n .
Simultaneous R e j e c t i o n Measurements
The GPC a n a l y s i s of feed and permeate s o l u t i o n i s i d e a l l y

s u i t e d f o r r a p i d simultaneous r e j e c t i o n measurements. S i m u l t a -
eous r e j e c t i o n i s of great importance i n u l t r a f i l t r a t i o n p r a c t i c e .
As an example, we show here a simultaneous measurement of r e j e c -
t i o n of p r o t e i n s and of l a c t o s e i n whey u l t r a f i l t r a t i o n (Figure
13). The membrane used was the ABCOR HFK membrane and the feed
s o l u t i o n had a t y p i c a l composition of a p a r t i a l l y concentrated
whey stream. The feed ( ) and the permeate (- - -) s o l u t i o n s
were analyzed by GPC (Waters 1-125 columns) w i t h simultaneous
anc
monitoring of uv absorbance ( A 2 8 0 ) * °^ r e f r a c t i v e index
d i f f e r e n c e (ARI). The a n a l y s i s shows a q u a n t i t a t i v e r e j e c t i o n
(R=100%) of a l l whey p r o t e i n s and a very low r e j e c t i o n (R=8%)
of l a c t o s e .
Conclusions
According to our a n a l y s i s , the predominant e f f e c t c o n t r o l l i n g

r e j e c t i o n of polymeric s o l u t e s by uncharged u l t r a f i l t r a t i o n mem-
branes i s the s t e r i c f a c t o r determined by the v a l u e of parameter
A.
The c o n t r i b u t i o n s to r e j e c t i o n from hydrodynamic l a g , Van der
Waals a t t r a c t i o n between the s o l u t e and the membrane can be r e -
garded as of r e l a t i v e l y minor importance.

N150A
^ N500A
10 20 30 40
AP(psi)
N150A
N300A
A
N500A
"S TT
10
4,
20
1
30
i
40
L
AP(psi)
Figure 10. R(%) as a function of A P for Nuclepore 150 A (Q), Nuclepore 300 A
(A), and Nuclepore 500 A ([7]): (a) 0.1 Carbowax 4000; (b) 0.1 Carbowax 6000.
Solid lines show theoretical predictions according to Equation 4.

R(%)
o /
40 o /
20
1
10
1
20 30 40 50
RADIUS OF G Y R A T I O N (A)
Figure 11. Measured apparent rejection of polyethylene oxide (Carbowax) at AP

= 50 psi: (a) GPC trace of a blend solution containing 0.02% of each Carbowax
1000, 1400, 1540, 4000, and 6000; (b) GPC trace of a permeate obtained by UF
at AP == 50 psi through Nuclepore 150 A membrane; (c) apparent rejection calcu-
lated from GPC traces shown in a and b, (Q), as a function of solute radius of
gyration. The solid line shows theoretical prediction according to Equation 4.

Figure 12. Measured apparent rejection of dextrans by Nuclepore filters calcu-

lated from GPC traces as a function of A. Points calculated from Nuclepore 150 A
(O), 300 A (A), and 500 A ([J) traces. The solid line shows theoretical prediction
according to Equation 4. Rejection coefficients measured for single dextran frac-
tions (T10 and T70) and the Nuclepore 150 A filter are shown also (+).

AR.I.
20 15
—ELUTION VOLUME, ML
Figure 13. Simultaneous rejection measurement by GPC. The GPC profiles: ARI
trace (upper,) and A o trace (lower) for whey feed and permeate obtained by UF
28
through the ABCOR HFK membrane. The peak labelled IgG corresponds to whey
immunoglobulines; peaks labelled oc and /3 correspond to oc -lactalbumin and /3-lac-
toglobulin, respectively.

The t y p i c a l u l t r a f i l t r a t i o n r e s u l t s w i l l r e f l e c t e f f e c t s of
the r e s p e c t i v e s i z e d i s t r i b u t i o n s of both the s o l u t e and the mem-
brane pores, as w e l l as o f c o n c e n t r a t i o n p o l a r i z a t i o n . A l l of
these e f f e c t s should be expected to lower the membrane r e j e c t i o n
coefficient.
Acknowledgement
We thank Mr. Michael Morin of ABCOR, INC. f o r i n v a l u a b l e help

i n performing the computer c a l c u l a t i o n s .
L i s t of Symbols
2
A Membrane area, cm
A^ Coefficient
a Constant i n Equation ( 7 ) , A d a l t o n
b Constant i n Equation ( 7 ) , dimensionless
-3
C^ F Solute c o n c e n t r a t i o n i n the feed, g cm
-3
C^ p Solute c o n c e n t r a t i o n i n the permeate, g cm
f(M«) Solute d i f f e r e n t i a l molecular weight distribution,
1
dalton'
F Viscous drag f o r c e , dyne
H Hamaker constant, e r g
I Integrals
Solvent f l u x , cm s ^
-2 -1
J 2 Solute f l u x , g cm s
k Mass t r a n s f e r c o e f f i c i e n t , cm s ^ (Figure 9)
k Boltzmann constant, e r g °K
k^,k^ Drag c o e f f i c i e n t s , dimensionless

o
1^ Pore l e n g t h , A
M^ Solute molecular weight, d a l t o n
M^ Number average s o l u t e molecular weight, d a l t o n

M 0 Weight average s o l u t e molecular weight, d a l t o n

z,w
Membrane polymer molecular weight, d a l t o n
-2
N Number of pores per u n i t membrane area, cm
» -2
N Number of holes per u n i t membrane area, cm
N^ Arogadro number, mole ^
r D i s t a n c e , cm
o
r^ Solvent molecule r a d i u s , A
r^ Solute r a d i u s
r^ Membrane pore r a d i u s , A
R or R^ Solute r e j e c t i o n c o e f f i c i e n t , dimensionless
R Apparent r e j e c t i o n c o e f f i c i e n t , dimensionless
a
s D i s t a n c e , cm
o
T Absolute temperature, K
v- Solvent v e l o c i t y , cm s ^
v^ Solute v e l o c i t y , cm s ^
3
V Volume, cm
W^ Solute hindrance c o e f f i c i e n t , dimensionless
x D i s t a n c e , cm
y D i s t a n c e , cm
?
<* N /N
? 6
« Van der Waals i n t e r a c t i o n constant, erg cm
6 R a d i a l p o s i t i o n of s o l u t e i n the pore, dimension-
less
f
g (3 f o r a s i n g l e atom, dimensionless
Solvent v i s c o s i t y , p o i s e
9 Angle, r a d i a n

X r ^ / r ^ , dimensionless
P2 Solute d e n s i t y , g cm ^
-3
Membrane polymer d e n s i t y , g cm
a 2 Standard d e v i a t i o n of l n r , dimensionless
2
0^ Standard d e v i a t i o n of l n r ^ , dimensionless
c|> Angle, r a d i a n
$ Van der Waals i n t e r a c t i o n energy, e r g
0) Angle, r a d i a
Subscripts
1 Solvent
2 Solute
3 Membrane
Literature Cited
1. F e r r y , J. D., Chem. Rev., 1936, 18, 373
2. Paine, P. L.; Scherr, P., B i o p h y s i c a l J., 1975, 15, 1087
3. B r i a n , L. T., " D e s a l i n a t i o n by Reverse Osmosis", Merten, U.,

Ed., The MIT P r e s s , Cambridge, Massachusetts, 1966, 101
4. B l a t t , W. F.; David, A.; M i c h a e l s , A. S.; Nelsen, L., "Mem-

brane Science and Technology", F l i n n , J . E., Ed., Plenum
P u b l i s h i n g C o r p o r a t i o n , New York, 1970, 47
5. Ring, W., Cantow, H. J., H o l t r u p , H., European Polymer J.,

1966, 2, 151
6. Granath, K. A.; K v i s t , B. A., J. Chromatogr., 1967, 28, 69-81
7. Anderson, J. L.; Quinn, J. A., Biophys. J., 1974, 14, 130-150

24
Recent Applications of Dynamic Membranes
C R A I G A . B R A N D O N — C A R R E , Inc., Seneca, SC 29678
J. L E O GADDIS—Department of Mechanical Engineering, Clemson University,
Clemson, SC 29631
H . G A R T H SPENCER—Department of Chemistry, Clemson University,
Clemson, SC 29631
The systematic i n v e s t i g a t i o n o f dynamically-formed membranes

began w i t h t h e formatio
the Oak Ridge N a t i o n a
tion membrane most o f t e n used in subsequent a p p l i c a t i o n s has been
prepared by s e q u e n t i a l d e p o s i t i o n s o f zirconium IV hydrous oxide
f o l l o w e d by poly(acrylic acid) on a s u i t a b l e porous support
under pressure and cross f l o w c o n d i t i o n s . Although not compet-
itive w i t h t h e conventional hyperfiltration membranes f o r de-
salination, the resulting hyperfiltration (RO) membrane possesses
p r o p e r t i e s d e s i r e d f o r some industrial a p p l i c a t i o n s . (2) It is
s u i t a b l e f o r a p p l i c a t i o n s r e q u i r i n g high temperature during
e i t h e r o p e r a t i o n , c l e a n i n g , or sterilization and for those in
which a charged membrane is advantageous.
Results from two s t u d i e s i n v o l v i n g high volume recovery of
multicomponent process e f f l u e n t s are presented here as illustra-
t i o n s o f recent a p p l i c a t i o n s o f hyperfiltration membranes in a
t u b u l a r c o n f i g u r a t i o n supported by porous s t a i n l e s s steel. The
first is a l a b o r a t o r y s e p a r a t i o n o f dyes from a s a l i n e dye
manufacturing process e f f l u e n t and t h e second a pilot renovation
of wash water from a dye range f o r reuse.
The general p r o p e r t i e s o f r e p r e s e n t a t i v e dynamically-formed
membranes are provided in Table I .
Separation o f Dye Manufacturing Process E f f l u e n t
In a t y p i c a l dye s y n t h e s i s t h e dye i s s a l t e d - o u t o f t h e
r e a c t i o n s o l u t i o n and captured on a f i l t e r press. The dye
f i l t r a t e i s normally d i l u t e d w i t h f i l t e r washings and other
water sources t o as much as (100:1) (water: dye f i l t r a t e ) ,
t r e a t e d , and discharged from t h e p l a n t . The authentic samples
of dye f i l t r a t e used i n t h i s study were h i g h l y c o l o r e d , near
n e u t r a l l i q u i d s w i t h high s a l t concentrations (5 t o 20 weight
percent) and a t o t a l organic carbon (TOC) c o n c e n t r a t i o n o f
about 0.5 percent.
0097-6156/81/0154-0435$05.00/0

Table I . CARRE, Inc. Membrane S p e c i f i c a t i o n s
Ultrafiltration Hyperfiltration
ZOSS ZOPA
Flow Geometry Tubular Tubular
Membrane Support stainless steel (3l6£) stainless steel

(3l6£)
Membrane M a t e r i a l zirconium oxide zirconium oxide

polyacrylate
Method o f Replace- i
ment solution solution
Prefiltration hO mesh screen 1+0 mesh screen

Requirement
Pressure Limitation g r e a t e r than 1000 greater than 1000

psig psig
Temperature greater than greater than

Limitation 100°C (212°F) 100°C (212°F)
pH Range 2-13 U-ll
P e r m e a b i l i t y with 0 . 1 t o O.k 0.05 - 0.07

Test S o l u t i o n @
100°F
8 200°F O.k t o 1 . 2 0.2 - 0.3
S a l t Rejection"^ 5 - 20% 80 - 90%
Test S o l u t i o n 1000 mg/l o f NaNO^ i n water

Flux equals P e r m e a b i l i t y times pressure
Examples: ( l ) ZOSS Membrane at 1000 p s i g at 100°F
F l u x = 0 . 2 5 x 1000 = 250 g a l l o n s / d a y / f t c
(2) ZOPA Membrane at 1000 p s i g at 200°F

Flux = 0 . 2 5 x 1000 = 250 g a l l o n s / d a y / f t ^
Flux with wastewater must be measured.

24. BRANDON ET AL. Dynamic Membranes 437
F o u r f l u i d s were s t u d i e d : f i l t r a t e s f r o m t h e m a n u f a c t u r e
o f (a) "basic y e l l o w C I U 8 0 5 ^ , i n d o l e t y p e ; (b) a c i d y e l l o w C I
1 3 9 0 6 , a z o - t y p e ; ( c ) a c i d b l u e CI 6 2 0 5 5 a n t h r a q u i n o n e t y p e ; a n d
5
(d) an e q u a l m i x t u r e o f t h e a b o v e , t e r m e d " c o m p o s i t e " . T a b l e I I

i d e n t i f i e s the s t r u c t u r e s o f the product dyes. Test f l u i d s
r a n g i n g i n d i l u t i o n f r o m 2 : 3 t o 1 0 0 : 1 were u s e d .
A need e x i s t s t o f r a c t i o n a t e t h e s o l u t e s i n t h e dye f i l t r a t e
i n t o r e t a i n e d o r g a n i c and p a s s e d i n o r g a n i c s a l t f r a c t i o n s . The
passage o f simple e l e c t r o l y t e s occurs through u l t r a f i l t r a t i o n
membranes a n d i o n - e x c l u s i o n h y p e r f i l t r a t i o n membranes a t a h i g h
salt concentration. B o t h t y p e s o f dynamic membranes were t e s t e d .
The dynamic u l t r a f i l t e r had b e e n o b s e r v e d t o r e t a i n c o l o r
i n s p e n t dye s o l u t i o n s , b u t i t s c o l o r r e t e n t i o n u s i n g t h e s e d i -
l u t e d dye f i l t r a t e s ( 1 0 0 : 1 ) was n e g l i g i b l e and no q u a n t i t a t i v e
r e s u l t s are presented. A d e s c r i p t i o n o f the experiments and
preliminary results usin basi yello U805^ d composit
f i l t r a t e s has been p u b l i s h e d
hyperfilter using aci yello
f i l t r a t e s are d e s c r i b e d here. T h e p r o p e r t i e s o f t h e dye f i l -
t r a t e s are p r o v i d e d i n Table I I I .
The e f f e c t s o f p e r t i n e n t o p e r a t i n g p a r a m e t e r s on t h e s e p -
a r a t i o n p r o c e s s were m e a s u r e d . Most e x p e r i m e n t s were p e r f o r m e d
a t 5 . 2 MPa (750 p s i ) . D e l i b e r a t e e x c u r s i o n s i n t e m p e r a t u r e were
made t o measure t h i s e f f e c t and p r o v i d e a means o f c o m p e n s a t i n g
t h e f l u x d a t a f o r t e m p e r a t u r e and r e p o r t i n g a l l c o m p a r i s o n d a t a
a t U5°C. The s e p a r a t i o n o f s o l u t e s was a n t i c i p a t e d t o depend
on c o n c e n t r a t i o n and pH and t h e s e e f f e c t s were d e t e r m i n e d
systematically.
Two e x p e r i m e n t a l p r o c e d u r e s were c a r r i e d o u t . In the f i r s t ,
a 1 0 0 : 1 ( w a t e r and dye f i l t r a t e ) d i l u t i o n was c o n c e n t r a t e d t o
o n e - t e n t h i t s i n i t i a l v o l u m e . R e j e c t i o n b a s e d on c o l o r a b s o r b -
ance {hlO nm) and e l e c t r i c a l c o n d u c t i v i t y , f l u x , p r e s s u r e ,
t e m p e r a t u r e , a n d c r o s s f l o w r a t e were m e a s u r e d a t i n t e r v a l s
during the concentration experiment. I n the second, a s l i g h t l y
d i l u t e d dye f i l t r a t e ( 2 : 3 ) was u s e d and t h e h y p e r f i l t r a t i o n a t
s t e a d y s t a t e was e v a l u a t e d a s i n t h e f i r s t p r o c e d u r e . The t e s t
was r e p e a t e d a t d i l u t i o n s r e a c h i n g ( 1 0 0 : 1 ) , w i t h pH and t e m p e r -
ature excursions a t a d i l u t i o n o f 3 : 1 .
The v a r i a t i o n o f f l u x w i t h t e m p e r a t u r e f o r a l l t h e f l u i d s
i s shown i n F i g u r e 1 . Each t r e n d i s reasonably c o r r e l a t e d b y
J = J q exp[-2,500 ( i - i )] [1]
o
where J Q i s t h e f l u x a t T = 3l8K ( i +5°C). T h e v a r i a t i o n o f f l u x

Q
and r e j e c t i o n s w i t h pH i s shown i n F i g u r e s 2 a n d 3 f o r t h e t w o
fluids.

Table I I . S t r u c t u r e s o f Product Dyes
Product Dye Structure
Basic Yellow,
CI hQ05k
CH 3
O^NJ-CHIN-N—^>-0
I I
C h U C H
3
Acid Yellow,
CI 13906
f
S 0 2 N H 2 C O - N H - O " N a
A c i d Blue,
CI 62055
0 N H

Table I I I . P r o p e r t i e s o f Dye F i l t r a t e s
Property A c i d Y e l l o w , CI 13906 A c i d B l u e , CI 62055

(mg/L) (mg/L)
CI" 116,000 12,600
TDS 217,000 111,000
COD lU,200 Hl,900
Alkalinity 6,l80 21,800
E q u i v a l e n t NaCl 177,000 50,000

(by c o n d u c t i v i t y )
pH 9.1 9.3
Cr 0.3k 0.20
Cu Q.kh 760.
Ni 1.73 0.63
Zn 0.63 0.87
Hg 17.8 13.8

2- 9 3• 3
103/T
Figure 1. Effect of temperature on membraneflux:P = 5.2 MPa (750 psi)

24. BRANDON E T A L . Dynamic Membranes 441
H 1 . 1 1 A I A •
•6
r
.4
° 6° •
.2 O • conductivity
I 9
I L i i I i
0
1 0 5 Jo
(m/s)
_l I I I 1 L_
PH
Figure 2. Rejection (r) and flux (J ) dependence on pH for the acid yellow CI
0
13906 filtrate: solid points at conductivity (LJ = 0.026 S/cm and open points at
L = 0.06 S/cm; P = 5.2 MPa (750 psi).

• •
pH
Figure 3. Rejection (r) and flux (J ) dependence on pH for the acid blue CI 62055
0
filtrate: conductivity (L) = 0.042 S/cm; P = 5.2 MPa (750 psi).

The dependence of the r e j e c t i o n s on the concentration i s o f

primary i n t e r e s t . The r e j e c t i o n s and f l u x dependence on concen-
t r a t i o n (represented by the c o n d u c t i v i t y of the feed) i s shown i n
Figures h and 5 f o r the two f l u i d s . The most s i g n i f i c a n t feature
i s the d i f f e r e n c e i n r e j e c t i o n based on absorbance (A) and t h a t
based on c o n d u c t i v i t y ( L ) , i . e . , the d i f f e r e n c e i n r e j e c t i o n o f
the c o l o r e d organic dye s a l t s and the simple s a l t s (the major
c o n t r i b u t o r t o the c o n d u c t i v i t y ) . The membrane e f f e c t i v e l y con-
centrates the c o l o r w i t h r e j e c t i o n , r ^ , g r e a t e r than 0.9 ôr
most data w h i l e passing simple s a l t s w i t h r e j e c t i o n , r ^ , l e s s
than O.k at high c o n c e n t r a t i o n . This r e s u l t suggests the de-
pendence of the s e p a r a t i o n f a c t o r , ajjj, where
L
a'A
l [2]
on c o n c e n t r a t i o n d i f f e r s f o r the two f l u i d s . As shown i n Figure

6, increases w i t h concentration f o r the a c i d y e l l o w CI 13906
f i l t r a t e but remains n e a r l y constant f o r the a c i d blue CI 62055
f i l t r a t e . The r e j e c t i o n o f c o l o r i s coupled w i t h t h a t of con-
d u c t i v i t y i n the l a t t e r f i l t r a t e but not i n the former. These
r e j e c t i o n s are uncoupled i n the b a s i c y e l l o w CI kQO^h f i l t r a t e .
(3_) I n c r e a s i n g i o n i c s t r e n g t h decreases the i o n - e x c l u s i o n
e f f e c t i v e n e s s of charged membranes. The r e s u l t s i n d i c a t e t h a t the
c o l o r e d components of the a c i d blue f i l t r a t e behave as a simple
e l e c t r o l y t e , w h i l e the l a c k of a r e d u c t i o n i n the c o l o r r e j e c t i o n
of the other two f l u i d s suggests the c o l o r e d species are e i t h e r
l a r g e r or aggregated so t h a t t h e i r r e j e c t i o n s are independent of
i o n i c s t r e n g t h . The dye f i l t r a t e s contained c o l o r e d species i n
a d d i t i o n t o the product dye. This was determined by s e p a r a t i n g
the c o l o r e d species by l i q u i d chromatography and comparing the
e l e c t r o n i c s p e c t r a of each c o l o r e d e l u t i o n band w i t h the p u r i f i e d
product dyes. Thus conclusions f o r the d i f f e r e n c e i n behavior
cannot be based on the product-dye s t r u c t u r e s .
I n summary, the dynamically-formed u l t r a f i l t e r d i d not
separate c o l o r e d compounds from the s a l t . The dynamically-
formed h y p e r f i l t e r e f f e c t i v e l y r e t a i n e d the c o l o r e d compounds
w h i l e p r o v i d i n g low r e j e c t i o n of the s a l t . Because the s a l t
r e j e c t i o n was low i n the concentrated s o l u t i o n s r e s u l t i n g i n low
osmotic pressure d i f f e r e n c e s , the f i l t r a t i o n of concentrated
s o l u t i o n s w i t h high i o n i c strengths could be accomplished at
the r e l a t i v e l y low o p e r a t i n g pressure o f 5-2 MPa (750 p s i ) .
Renovation of Dye Range Wash Water f o r Reuse
A p r o j e c t i s i n progress t o demonstrate the c l o s e d - c y c l e

operation of a production dye range. The cooperative agreement
w i t h LaFrance I n d u s t r i e s i n v o l v e s the Environmental P r o t e c t i o n

1 A
A > A k 1
a b s o r b a n c e
%> -
o O
1 1 1
•
•
-
•
0 i l 1 i
0 .02 .04 .0 6 .08 .10
C o n d u c t i v i t y ( S/cm)
Figure 4. Rejection (v) and flux (J ) vs. conductivity for the acid yellow CI 13906
0
filtrate: P = 5.2 MPa (750 psi).

BRANDON ET AL. Dynamic Membranes 445
1.0
A
.8
.6
r
.4 O
O
.2 con ducti vity
I l_
0
10° J 0
(m/s)
O
• o
0 .02 .04 .06 -08

Conductivity (s/cm)
Figure 5. Rejection (r) and flux (J ) vs. conductivity for the acid blue CI 62055
0
filtrate:filledsymbols represent the concentration procedure; open symbols the dilu-

tion procedure; P = 5.2 MPa (750 psi).
30 I
o
O y e l l o w
A blue
o
O
10
* \
O A
A
o i I I
D .1 .2 .3 >4
L
Figure 6. Dependence of the separation factor « A on the conductivity (L) of the
feed

Symposium ACS
Synthetic In
FLUX, GAL/FT /DAY
DIRECT
ACRYLIC
BLEACH
DIRECT
ACRYLIC
DISPERSED
DIRECT
ACRYLIC
DISPERSED
DIRECT
ACRYLIC
ACRYLIC
ACRYLIC
DIRECT
AUTOMOTIVE
ACRYLIC
DIRECT
ACRYLIC
DIRECT
DIRECT
DIRECT
AUTOMOTIVE
ACRYLIC
DIRECT
ACRYLIC
BLEACH
DCRECT
DIRECT
DIRECT
DIRECT
ACRYLIC
DIRECT
ACRYLIC
DISPERSED
DIRECT
REACTTVE
DIRECT
S3Sn 3fl QNV 3H :S3NVHaiA[3P\[ 3U3H1NAS 9yJ7
Q a

W w
CJ CJ CJ CJ CJ CJ
H H Bi H H H H
1
PRnrFQc CJ J
u CJ
u CJ J i—
J1 W
w UC J -• JJ a
w uCJ ^ j^jcjr: - J CCJ J J CC JJ CC JJ C J S J J J U U C J C J C J H J C J ^ W C J H C J
W >- w w >< a- W >•« W >- w w
T Y P F ttia: a; w< «
BS B
os! « B Bi: B
B£J LCOO B S B : as S B: E- B
Bii B
BiS BBS
S B Bi
i c
BSi a: H « K u « BS 2 Bi B S &d B S co Bi < BS
u CJ i—i CJ CJ CJ CJ
Q ec Q Q Q < < Q < Q
<d Q < O
a Q O < < C < « C Q Q G < Q <
< < a o < < < <

TEST SEQUENCE
Figure 7. Membrane performance summary data for a dynamic HF membrane—Module 453

Agency, Department o f Energy, and Department of I n t e r i o r . The

o b j e c t i v e s of t h e p r o j e c t are t o d e s i g n , i n s t a l l , and operate a
f u l l - s c a l e c o m m e r c i a l l y - a v a i l a b l e h y p e r f i l t r a t i o n system at L a -
France and t o demonstrate i t s p r a c t i c a l i t y . Phase I , the design
phase, has been completed, (k) The second phase, t h e equipment
i n s t a l l a t i o n , i s i n progress. Some data obtained i n Phase I
demonstrating t h e performance c h a r a c t e r i s t i c s o f the dynamic
h y p e r f i l t r a t i o n membrane u s i n g t h i s multicomponent feed up t o
high (96 percent) recovery are presented and d i s c u s s e d here.
The o b j e c t i v e s , process d e s c r i p t i o n , recovery concept, and reuse
e v a l u a t i o n have been r e p o r t e d . ( 2 , U )
F i g u r e 7 provides i n f o r m a t i o n ~ d e s c r i b i n g the performance o f
a dynamic membrane ( Z r ( l V ) o x i d e - p o l y a c r y l a t e ) . The feeds are
range wash water e f f l u e n t s from s i n g l e dye runs. F l u x and r e -
j e c t i o n s at i n i t i a l (0) and f i n a l ( 0 . 9 5 ) r e c o v e r i e s are provided.
The i n i t i a l f l u x i s u s u a l l h i g h 50 t 120 g f d decreasin
during the concentratio
range, at 5 - 5 2 MPa (80 p s i ) performanc chang
during these experiments r e f l e c t s t h e e f f e c t s of both time and
c o n c e n t r a t i o n . The " s a l t p o i n t " f l u x obtained u s i n g a % / l i t e r
s a l t s o l u t i o n a f t e r a hot water wash was normally higher than
the i n i t i a l f l u x obtained u s i n g the wash water feed. The c o l o r
r e j e c t i o n i s o f major concern. A s u i t a b l e product f o r washing
i s expected i f t h e c o l o r r e j e c t i o n i s 0 . 9 7 f o r the cumulative
product o f a 0 . 9 5 recovery h y p e r f i l t r a t i o n . The c o l o r r e j e c t i o n s
are g e n e r a l l y 0 . 9 9 at 0 . 9 5 r e c o v e r y , w i t h low r e j e c t i o n s occur-
r i n g at 0 . 0 recovery f o r some dye mixtures used on a c r y l i c f a b r i c
C o n d u c t i v i t y r e j e c t i o n s normally f a l l i n t h e 0 . 7 0 - 0 . 8 5 range.
The major v a r i a t i o n i n performance among t h e v a r i o u s dye
types was t h e low i n i t i a l c o l o r r e j e c t i o n f o r s e v e r a l a c r y l i c
process wash e f f l u e n t s . Subsequently i t has been found t h a t
these r e j e c t i o n s can be r a i s e d t o acceptable l e v e l s by i n c r e a s i n g
the pH s l i g h t l y . The c o l o r r e j e c t i o n i s normally h i g h f o r d i r e c t ,
a c i d / d i r e c t and d i s p e r s e dye wash water e f f l u e n t s .
Although the dye f o r m u l a t i o n s vary w i t h t y p e , shade, and hue,
they c o n t a i n a t h i c k e n e r (gum), v a r i o u s s u r f a c t a n t s , and i n some
cases s o l v e n t s , i n a d d i t i o n t o t h e dyes. Only about 15 percent
of t h e dye i s i n t h e wash water, w h i l e most of t h e a u x i l i a r y
chemicals are present.
F i g u r e 8 shows t h e f l u x and c o n d u c t i v i t y and c o l o r r e j e c t -
ions f o r a dynamic membrane at v a r i o u s recovery l e v e l s u s i n g
mixtures of t h e range wash water e f f l u e n t s . The temperature and
pressure e f f e c t s on f l u x are pvovided i n Figures 9 and 1 0 .
Table IV g i v e s t h e r e s u l t s f o r s e v e r a l a n a l y s i s procedures of
the h y p e r f i l t r a t i o n c o n c e n t r a t i o n and permeate at three d i f f e r e n t
recovery l e v e l s . The r e j e c t i o n s based on t h e a n a l y s i s types are
provided i n F i g u r e 11. Concentration has l i t t l e e f f e c t on the
r e j e c t i o n s of the c o n s t i t u e n t s t e s t e d .

UNKNOWN R E C O V E R Y
O M E M B R A N E WASH
••• WITHOUT F R E S H FEED
— WITH F R E S H FEED
<T~ r <r<r
OOa-UTjMD-O-^j^D
-> S O L SOLID P O I N T S INDICATE

£j N a N 0 R E F E R E N C E DATA
3
V CONDUCTIVITY
VELOCITY (FPS) • COLOR
L 18
8
8 |
1 8
1 1 .1S!.
• r M1 •• 1 " r
Y °
i i 1 1 1 i
300 400 500 700 750
O P E R A T I N G TIME (HOURS)
Figure 8. Product flux, conductivity and color rejection, and recovery profile for
a dynamic HF membrane—Module 452
800 PSI
5 -
, 3.0 _|_ 3.1

TEMP ( °K x I O ) 3
60 50
TEMP (°C)
Figure 9. Flux vs. temperature for a dynamic HF membrane—Module 452

50U
200 400 600 800 1000 1200 1400

PRESSURE (PSI)
Figure 10. Flux vs. pressure for a dynamic HF membrane—Module 452
Recovery
Figure 11. Rejections in terms of analysis for dye range composite effluent

Table IV. Chemical Analyses o f Concentrate and Permeate f o r a Dynamic H y p e r f i l t r a t i o n Membrane;
Module U52.
Recovery L e v e l 25% 15% 2^%
Sample Type Concen. Perm. Concen. Perm. Concen. Perm. Concen. Pern
COD, mg/L U70 k6 1320 69 U270 180 336 2k
Conductivity 315 67 815 162 1700 255 395 86

uS/ cm
pH 7.0 6.9 7.2 5.1 5.6 7.7
Hardness, mg/t 29 0 8U 0 232 2.5 18 0
Dissolved Solids, ^59 1*2 1330 122 3280 250 U87 U5

mg/£
T o t a l S o l i d s , mg/£ U70 51 1360 12k 3330 250 k9k h5
V o l a t i l e S o l i d s , mgill 288 37 791 52 2150 118 281 18
Suspended S o l i d s , 11 9 30 2 50 0 7 0
mg/l
0.00U 0.010 _# _*
Chromium, mg/£ 0, .020 0.003 0.3U0 0.027

I r o n , mg/£ 0. .560 0.015 1.900 0.02U 1.300 0.016 _*
Calcium, mg/£ 2,
.800 0.037 31.20 0.23 U0.00 0.U3 k.00 0.0175
Magnesium, mg/t k, .780 0.2^0 10.60 0.29 31. U0 0.76 2.87 0.030

* Not analyzed
The gum was suspected to make a major contribution to the

flux decline. Experiments using a solution containing only a
gum, a guar gum similar to that used in the process, confirmed
this hypothesis. An additional experiment in which the guar gum
was transformed into a gel by the addition of sodium tetraborate
at pH 8 was performed. The flux declined further when the gel
was formed and then increased when the pH was lowered to 6 to
redissolve the gum.
The evidence from these experiments and long term exper
iments at constant recovery indicates the gum present in the
dye formulation accounts for most of the flux decline. This
significant, but modest, decline is cost acceptable for the
system. However, work continues to understand the mechanism of
this fouling and establish preventive measures.
In summary, economically acceptable fluxes and technically
acceptable rejections hav bee obtained i pilot studie usin
hot dye range wash wate
Abstract
Dynamically-formed hyperfiltration membranes of the ZrO · 2
polyacrylate type on porous stainless steel were used in two

high volumetric recovery applications. The first is the separ
ation of dyes from a saline dye manufacturing process effluent
and the second the renovation of wash water from a dye range
for reuse. The dependence of the performance characteristics on
recovery is described and discussed. Separation factors (dye
from salt) in the first system are large and increase with
concentration in two cases, but not in a third. Acceptable
rejections and fluxes for reuse of the wash water were obtained
to recoveries of 0.96 in the second system. The fluxes are
concentration dependent.
List of Symbols
J Flux, gallons per (foot) per day (gfd), or m/s
J Q Flux at 318K (i+5°C)
T Temperature (K)
T 0 Reference temperature 3l8K
r^ Rejection based on absorbance at hlO nm
r-j^ Rejection based on conductivity
Separation factor
L Conductivity S/cm or yS/cm
Acknowledgements
Major contributions to this work were made by a number of
people representing government agencies and industries. The
authors gratefully acknowledge the cooperation and assistance

24. BRANDON ET AL. Dynamic Membranes
of Verona D y e s t u f f s D i v i s i o n , Mobay Chemical Corporation and

e s p e c i a l l y Dr. Harshad Vyas, Manager of the Ecology Department.
The cooperation and a s s i s t a n c e of the s t a f f at LaFrance I n d u s t -
r i e s i s a l s o p a r t i c u l a r l y acknowledged: P e r r y Lockridge and
Charles Smith and s e v e r a l maching operators and l a b o r a t o r y
technicians.
Support f o r the f i r s t p r o j e c t was provided by USEPA under
Grant 805002010; T. E. P o l l a c k and T. M. K e i n a t h p r i n c i p a l i n -
v e s t i g a t o r s and S. C. Wilson p r o j e c t d i r e c t o r . The second
p r o j e c t i s an interagency program No. S805182 b e n e f i t i n g from
the guidance of Max S a m f i e l d , Sarah A l l e n and Robert Mournigham
USEPA; John Rossmeissel, DOE: and Frank Coley, D0I.
References
1. Marcinkowsky, A. E. Kraus K A. Phillips, H O Johnso ,

J. S.; Shor, A. J.
2. Brandon, C. A. C l o s e d - c y c l e T e x t i l e Dyeing: F u l l - s c a l e
Hyperfiltration Demonstration; presented at the Fifth
Clemson Membrane Separation Technology Conference, Clemson
U n i v e r s i t y , Clemson, S.C. May 12-14, 1980.
3. Gaddis, J. L.; Spencer, H. G.; W i l s o n , S. C. AIChE Symp.

Ser. 90, 1979, 75, 156.
4. Brandon, C. A. Closed-cycle Textile Dyeing: F u l l - s c a l e

Hyperfiltration Demonstration (Design); EPA-600/2-80-055,
March, 1980.

INDEX
A Amino acid aqueous solution of

tomato juice, membrane per
Acid formance on At
aqueous solution of tomato juice, Aromatic hydrocarbons from water,
membrane performance on .... At separation of 297
blue C I 62055 nitrate, rejection and Asymmetric P V A membranes, chem
flux vs. conductivity for 445/ ically resistant 281-291
blue C I 62055 filtrate, rejection and Attractive forces, V a n der Waals 419
flux dependence on p H for .... 442/ Average rejection coefficient 413
-precipitated soy protein, modifica Axial filter 177/
tion of ultraflltered vs 134 Axial filtration 176
whey 3
yellow C I 13906 filtrate, rejectio
and flux vs. conductivity of diluted glucan fermenter broth
yellow C I 13906 filtrate, rejection through Nuclepore filters,
and flux dependence on p H for 441/ fluxes in 180/
Acroflux at a rotational speed of 2,000 rpm .. 186/
cartridge in a housing, schematic of 238/ screened feed for 183/
cartridge hydrodynamics, testing of 242 unscreened feed for 182/
module, hydrodynamics of 243
module, operation and hydro-
dynamic analysis of 239 B
vs. permeate rate, channel pressure
drop of 246/ Bag filter system for pretreatment
log-log plot of 244/ prior to an oily waste application 232/
Additive(s) Baking performance of meringue
on membranes for hemofiltration, batter 139
effects of 48 Base balance 159
solvents in membrane formation, Batch cell geometry 378/
role of partially water-soluble 51 Batch cell U F 393
solvents, relationship between mem 0.15M saline B S A solution (pH
brane performance and water 7.4) data— 397*
solubility of 49/ unstirred 390
Alcalase, standard hydrolysis curve of 0.15M N a C l B S A solution, .... 395/
for soy isolate and 152/ Beer, removal of the alcohol in 36
Alcohol in beer, removal of 36 Benzene, correlation of pore blocking
Alcohol, H F plant for removal of 33/ factor and boundary layer con
Alkali metal halide(s) centration of 308/
in methanol, limiting diffusion Benzene-water
coefficients of 343* data, boundary layer concentration
in methanol solutions using C A and pore blocking for 307
membranes, R O separations R O data 301
of 339-359 system, effect of feed concentration
salts, separations and permeation and operating pressure on
rates for 350* separation for 306/
Alkali metal and halide ions system, effect of feed concentration
Born equation for 351/ on the R O performance
in methanol solutions, bulk solution for 302/-305/
free energy of solvation for .... 343* Biomass removal 186/
for water and methanol solutions, by microscreens 181
surface excess free energies for 353/ Biopolymer uses 171
457

Biopolymers from fermentation C

broths, separation of 171-192
C O 0 - C H 4 - N 2 , shell-side composition
Bleach effluent, Ultrasep color
profiles for 264/
removal process for caustic
C 0 - N mixture in continuous-mem
extraction 368 2 2
brane column, shell-side compo

Blood
sition profile minimum for 272/
bag, schematic for a membrane 113/
C O 2 - N 2 system in an enricher, com
bag, schematic of the transport
position of minima for 269/
cell that holds 113/
enzymatic decoloration of 150/ C O 2 - O 2 mixture, shell-side composi
process for decoloration of tion profile of continuous-mem
slaughterhouse 145 brane column for 261/
Born equation for alkali metal and CsCl-methanol solutions, physical
halide ions 351/ properties of 342*
Born equation parameter values 349* C A (see Cellulose acetate)
Boundary layer Calf serum and BSA, osmotic
concentration pressure for 91/
of benzene, correlation of pore Calf serum, protein diffusivities
blocking factor and 308/ calculated from U F data for 104*
and pore blocking for benzene
water data 30
and pore blocking for toluene- ,
water data 309 tration of 285/
of toluene, correlation of pore C A R R E , Inc. membrane specifications 436*
blocking factor and 311/ Casting
modulus, equations for uniform conditions 47*
wall flux 81/ dope 213
modulus in fully developed region, composition, guidelines to an
asymptotic limit of 85/ optimum 47*
theory 77 on membrane formation, effects
for rejection experiments across of component ratio in 51
imperfect membranes 77 on glass plates 213
Bovine serum albumin (BSA) 375 on machine 213
in buffer solutions, diffusion solutions, formulation of 213
coefficient of 393 Caustic extraction bleach effluent,
in large E N K A bundle, J vs. P for 102/
v
Ultrasep color removal process
solution(s) for 368
(pH 7.4) data—batch cell, Cellulose acetate (CA) 45-60
0.15M saline 397* Eastman E-398 polymers 316
solution osmotic pressure vs. membrane(s)
solute concentration— characterization 299
0.15M N a C l 396/ and performance 300*
thin-channel U F of 0.15M saline 400* DDS 800, typical flux decay with 25/
unstirred batch cell U F of and a module for hemofiltration,
0.15M N a C l 395/ development of 45-60
U F of 375 R O data for the N a C l - H 0 and
2
Br0rup, H F of whey in Denmark 32/ glycerol-H 0 system using

2
Broth(s) porous 318*-319*

microscreening of scleroglucan 191 R O separations of alkali metal
from a scleroglucan fermentation, halides in methanol solu
laboratory tests of axial filtra tions using 339-359
tion on 178 -water-*-butyl /so-propyl ether,
treatment, fermentation and 173 interfacial force for 333/
after treatment, photomicrographs -water-glucose and an imaginary
of culture 175/ solute, potential curve of inter
B S A (see Bovine serum albumin) facial force for the system 332/
Bulk-solution free energy of solvation Cellulosic hollow fibers, solute
for alkali metal and halide ions in rejection by 75-108
methanol solutions 343* Cellulosic hollow fibers, U F rates by 75-108

INDEX 459
Channel pressure drop of acroflux vs. Continuous-membrane filtration

permeate rate 246/ system 365/
Cheddar cheese whey 38r Cottage cheese whey on membrane
Cheese production by UF 27 fouling in UF, effects of chemical
p-Chlorophenol-water system 307 treatments of 39
Clean-in-place (CIP) system 228 Cottage cheese whey, RO of 39
unit, RO system with 232/ Countercurrent dialyzer set-up 64/
Cloudiness of wine 18 Critical extraction ratio (E )
c 87/
Cocurrent dialyzer set-up 64/ Cross-linking and membranes 282
Colloid oncometer, Gambro high-flux Crossflowfiltercartridge, Gelman
dialyzer linear regression pleated 177/
measured by 68* Crossflow UF system, thin-channel .... 385/
Color removal process for caustic Cryopreserved RBCs, dialysis proc-
extraction bleach effluent, essing of 109-117
Ultrasep 368 Cryoprotective agents, new method
Color removal, Ultrasep system for ... 371/ for adding and removing 112
of continuous-membrane column, Culture broth after treatment, photo-
shell-side (low-pressure side) .. 270 micrographs of 175/
minimum(a) Cummins Engine Company 229
for C0 -N system in an enriche
2 2
of continuous-membrane column
for 0 -N system in an enricher 269/
2 2
waste water testing 230
profile minimum for C0 -N mix- 2 2
Cuprophanfiberbundles, properties of 90*
ture in continuous-membrane Curve fitting 128/
column 272/ and the T4/A membrane 129*
profile(s) shell-side Cyclohexanone content
to bottom product composition, in/of additive solution
sensitivity of stripper 272/ membrane cross-section for
for C0 -CH -N ,
2 4 2 264/ of 32 wt % 54/
of continuous-membrane column of 40 wt % 54/
for C 0 - 0 mixture 2 2 261/ of 50 wt % 55/
to feed composition, sensitivity of 273/ of 60 wt % 55/
variation with comparable cut of 68 wt % 56/
and variable column length 275/ of 25 wt % of dope, membrane
Concentration polarization 425 thickness vs 52/
effect of 426/ membrane performance vs 52/
Conductivity Cyclohexanone/water, numerical data
for the acid blue CI 62055 filtrate, on cyclohexanone and water for 53*
rejection and flux vs 445/
for the acid yellow CI 13906 fil- D
trate, rejection and flux vs 444/
and color rejection for a dynamic DAF (dissolved air flotation) 234
HF membrane 449/ Daicel HemoFresh 59
dependence of the separation factor 445/ structure of the developed module
Continuous-membrane column(s) for hemofiltration 57/
composition minima of 267 Dairy Denmark 31
engineering aspects of 259-279 Dairy industry
local variation of NMU and HMU development center in 34/
within a section of 268/ industrial application of HF in
modeling of 268/ the food and 27-36
multicomponents systems 260 industrial application of UF in
numerical simulation of 270 the food and 27-36
parameter variation of 274 DDS
performance of 262*-263* -865 CA membrane, desalination of
schematic of 261/ ISSPH by HF on 147*
shell-side composition 270 development 36
C 0 - 0 mixture, profile
2 2 261/ 800 membranes, rejection measured
profile minimum for C0 -N 2 2 for nitrogen, polyphenols and
mixture in 272/ sugars with 24*

DDS (continued) Dicarboxylic acids and Cr(III) solu

800 membranes, typical flux decay tion, P V A membranes cross-
with C A 25/ linked by 286*
-Nakskov 35/, 36 Dicarboxylic acids, phenol retention of
plate-and-frame R O membrane membranes cross-linked in satu
systems 209/ rated solutions of 284
- R O installations in the pulp and Diffusion coefficient of B S A in buffer
paper industry 363/ solutions 393
D E (diatomaceous earth) 230 Diffusivities of solutes 129*
Decoloration of blood, enzymatic 150/ Dissociation constant values for ion
Decoloration of slaughterhouse blood, pairs 349*
process for 145 Dissociation as a function for uni
Deglycerolization 109 valent salts 347/
residual glycerol left in R B C s after 115/ Dissolved air flotation ( D A F ) 234
schematic of the laboratory Dope cashing 213
set-up for 115/ composition, guideline to an
Denmark, Br0rup H F of whey in 32/ optimum 47*
Denmark proteins 30/ on membrane formation, effects of
Desalination of ISSPH 145 component ratio in 51
by H F on a DDS-865 C A
membrane 147
Dextrans by Nuclepore filters, meas filtrates, properties of 439*
ured apparent rejection of 430/ -manufacturing-process effluent,
DH-value, ISSPH with a fixed 149 separation of 435
Diacel Chemical Industries, L t d 1 range composite effluent, rejections
Dialysate at 265 mosm, composition in terms of analysis for 450/
of 114* range wash water for reuse,
Dialysate osmolality, exponential renovation of 443
decay of 114* structures of product 438*
Dialysis processing of cryopreserved types, variation in performance
RBCs 109-117 among 448
Dialyzer(s) Dynamic membrane
high-flux formation 240
Gambro HF
linear regression measured by conductivity and color rejection
colloid oncometer 68* for 449/
nonlinear regression deter flux vs. temperature for 449/
mined by regression 68* product flux for 449/
at random U F rates, in vivo recovery profile for 449/
data for 1.36 m 2
72* recent applications of 435-453
at zero U F rate, in vivo data
2
for 1.36 m 69* E
pressure control of U F rate
during hemodialysis with . .61-74 E (critical extraction ratio)
c 87/
RP-610 69* for R = 0.5 and P E = 0.5, errors
at random U F rates, in vivo incurred by choice of 87/
data for 1.0 m 2
72* Energy efficient concentration by H F 369/
RP-610 ; 73 Energy requirement for water removal 370/
schematic of apparatus used for test 94/ Engineering aspects of the continuous-
set-up, cocurrent 64/ membrane column 259-279
set-up, countercurrent 64/ Enzymatic
U F rate and solute rejection for test 92 decoloration of blood 150/
Diatomaceous earth (DE) 230 hydrolysis, characteristics of 133
Dicarbonyl compounds, P V A mem modification of proteins, application
branes cross-linked by 288* of membrane processes during 135*
Dicarbonyl compounds, retention and Enzyme consumption 151
product flux for membranes Enzyme losses, compensation for 166
cross-linked by 284 Equilibrium constants for solvents 322

INDEX 461
Exponential decay of dialysate Flow (continued)

osmolality 114* resistance and gel layer concentra
Externally wound membranes 194 tion for ovalbumin, relation
features of 194 ships between 123/
tubular resistance and gel layer concentra
elements tion for P V A 224, relation
in modular assemblies 193-205 ships between 123/
modular assembly housing 202 Flux(es)
structural materials for 200 in axial filtration of diluted glucan
systems, sealants for 199 fermentor broth through N u
systems, support structures for .... 198 clepore filters 180/
behavior with P A 300 poly amide
composite membranes, typical 25/
decay with C A D D S 800 mem
branes, typical 25/
Faxen's correlation 326 effect of temperature on membrane 440/
Feed experiments, rejection vs 93
concentration and operating pres measurement, volumetric 90
sure on separation for the ben for T 4 / A membrane experimental 124/
zene-water system effec
concentration on the R O perform
ance for the benzene-water vs. pressure for a dynamic H F
system, effect of 302/-305/ membrane 450/
screened 185/ for P V A 224 aqueous solutions 124/
for axial nitration 183/ rejection and
unscreened 184/ vs. conductivity for the acid blue
for axial nitration 182/ C I 62055 filtrate 445/
Fermentation vs. conductivity for the acid
broth, separation of biopolymer yellow C I 13906 filtrate ... 444/
from 171-192, 174/ dependence on p H for the acid
and broth treatment 173 blue C I 62055 filtrate 442/
inhibition of malo-lactic 19 dependence on p H for the acid
Fermentor sample of laboratory-pro yellow C I 13906 filtrate .... 441/
duced glucan after various treat solute 417
ments, viscosities of 174/ vs. temperature for a dynamic H F
Feta cheese 27 membrane 449/
production by U F , economy in 28/ uniform-wall- 100
U F process for 28/ water 48,417
Filter, axial 177/ Foam stability 139
Filter cartridge, Gelman pleated vs. the number of free NH -groups for
2
crossflow 177/ highly functional soy protein .. 143/

Filtration, axial 176 Food and dairy industry, industrial
on broth from a scleroglucan fer application of H F in 27-36
mentation, laboratory tests of .. 178 Food and dairy industry, industrial
of diluted glucan fermentor broth application of U F in 27-36
through Nuclepore niters, Fouling, membrane
fluxes in 180/ models 41
at a rotational speed of 2,000 rpm .. 186/ studies on whey 39
screened feed for 183/ in U F effects of chemical treatments
unscreened feed for 182/ of cottage cheese whey on 39
Finely porous model for R O 295 in whey R O 37-44
Fining agents 18 Fouling, whey pretreatments to reduce 40
Flat-sheet microporous R O membrane 237 Fraction solute separation 316
Flow Fractionation, effect of gel layer on 119-132
condition, dependence of the mem Free
brane rejection on 249/ energies for alkali metal and halide
rate of oil emulsions in silica ions for water and methanol
membranes 248 solutions, surface excess 353/

Free (continued) G l y c e r o l - H 0 system using porous

2
energy of solvation for alkali metal C A membranes, R O data for the

and halide ions in methanol N a C l - H 0 and
2 318*-319*
solutions, bulk-solution 343* Glycerol left in R B C s after deglycer
energy of solvation, surface excess olization, residual 115/
for ion pairs 348 G P C , simultaneous rejection measure
values for 351* ment by 431/
for ions 348
values for 350* H
separation in methanol solutions
with 353/ HC1 casein whey 38*, 40
water and methanol solutions, Hamaker constant 421
comparison of 352 Helical membrane element 195/
Freon measured by IR, hydrocarbon Helical winding process 200
extractables with 243 Hemodialysis 45
Frictional function 325 controlling U F during 61
Frozen R B C s using current processing with high-flux dialyzers, pressure
methods, advantages of 110 control of U F rate during 61-74
Frozen R B C s using current processing Hemofilter as a function of blood feed
methods, disadvantages o
, require propertie
G
new 46*
Gambro high-flux dialyzer Hemofiltration
linear regression measured by col Daicel HemoFresh, structure of the
loid oncometer 68* developed module for 57/
nonlinear regression determined by development of C A membrane and
regression 68* a module for 45-60
at random U F rates, in vivo data effects of additives on membranes
for 1.36 m 2
72* for 48
at zero U F rate, in vivo data for membrane preparation for 47
1.36 m2
69* membrane, separation character
Gel istics of 59
layer U F membrane development for 46
concentration HemoFresh, Daicel 59
for ovalbumin, relationships structure of the developed module
between flow resistance for hemofiltration 57/
and 123/ H F (see Hyperfiltration)
of P V A 224 121/ H F M 180, membrane 23*
relationships between flow High-flux dialyzer
resistance and 123/ Gambro
and the resistance of 119 linear regression measured by
on fractionation, effect of 119-132 colloid oncometer 68*
ovalbumin 129* nonlinear regression determined
on rejection of 119-132 by regression 68*
polarization 121/ at random U F rates, in vivo
2
equation 120 data for 1.36 m 72*
theory for ultrafiltration 41 pressure control of U F rate during
-polarized U F 374 hemodialysis with 61-74
rejection of solutes by 127 RP-610 69*
Gelman pleated crossflow filter at random U F rates, in vivo
2
cartridge 177/ data for 1.0 m 72*
Glucan fermentor broth through at zero U F rate, in vivo data
2
Nuclepore filters, fluxes in axial for 1.36 m 69*
filtration of diluted 180/ High-performance liquid chromatog
Glucan after various treatments, vis raphy (HPLC) 315
cosities of fermentor sample of data, analysis of 321
laboratory-produced 174/ experiments 315

INDEX 463
HMU Hyperfiltration (HF) (continued)

efficiency 267 -preconcentration of SSL 368
within a section of continuous- the pulp and paper industry, U F
membrane column, local varia and 361-372
tion of N M U and 268/ systems, main features of the U F
variation, local 267 and 362
Hollow fibers, solute rejection by systems, membrane development,
cellulosic 75-108 production, and use in 207-219
Hollow fibers, U F rates by and water removal 368
cellulosic 75-108 of whey 33/
H P L C (see high-performance liquid in Denmark, Br0rup 32/
chromatography)
Human serum albumin (HSA) 375
solutions, thin-channel U F of I
0.15M saline 401*
thin-channel U F of ISG and 375 Ibaragi plant of Kagome Co. Ltd.,
Hydrocarbon extractables with freon semicommercial equipment built
measured by I R 243 at 11/
Hydrocarbons from water, separation Iggesund Kraft M i l l in Sweden U F
of aromatic 29
Hydrolysate bitterness 14
Hydrolysates, low molecular protein .. 134 and HSA, thin-channel U F of 375
Hydrolysis Insulin in saline, rejection vs. J for .... 101/
v
characteristics of enzymatic 133 Interfacial forces governing R O sys

curves for soy protein isolates 137/ tem, estimation of 315-338
in a membrane reactor, continuous Ion(s)
protein 148 pairs, dissociation constant values
in a membrane reactor, develop for 349*
ment of a kinetic model for pairs, surface excess free energy
protein 155 of solvation for 348
Hydrostatic pressure, transmembrane 62 values 351*
Hyperfiltration (HF) 27-36 surface excess free energy of
on a DDS-865 C A membrane, solvation for 348
desalination of ISSPH by 147* values 350*
energy efficient concentration by .... 369/ ISG (see Immune serum globulin)
during enzymatically modified pro Isoelectric soluble soy protein
tein production, application hydrolysates (ISSPH) 144
of 133-169 desalination of 145
in the food and dairy industry, by H F on a DDS-865 C A
industrial 27-36 membrane 147*
installation at Toten Sulfite M i l l in with a fixed DH-value 149
Norway 367* H F of 146/
of ISSPH 146/ processing data regarding 147*
processing data regarding 147* on the membrane reactor,
membrane, dynamic production of 153*
chemical analyses of concentrate
and permeate for 451*
conductivity and color rejection K
for 449/
flux vs. pressure for 450/ Kl-methanol solutions, physical
flux vs. temperature for 449/ properties 342*
membrane performance summary Kagome Co. Ltd., semicommercial
data for 446/-447/ equipment built at Ibaragi plant
product flux for 449/ of 11/
recovery profile for 449/ Ketones, membranes cross-linked by .. 284
2
module H F 40-28, 300 ft vertical .. 364/ PVA 287*
plant for removal of alcohol 33/ Kraft black liquor (KBL) 361
plants at Totel and Reed as of lignin from 366
August 15, 1980, features of .. 370/ U F of 366/, 369/

464 SYNTHETIC MEMBRANES! HF AND U F USES
L Membrane(s) (continued)
Laminar channel flow, U F of macro column(s), continuous (continued)
molecular solutions in steady- composition minima of 267
state 376 engineering aspects of 259-279
Lennard-Jones type interfacial local variation of N M U and
potential function 320 H M U within a section of .... 268/
Lignin from K B L 366 modeling of 268/
Lignin in SSL and U F concentrate and multicomponents systems of 260
filtrate, molecular-weight numerical simulation of 270
distribution of 367/ parameter variation of 274
Lignosulf onates from U F 366 performance of 262*-263*
Limiting diffusion coefficients of alkali schematic of 261/
metal halides in methanol 343* shell-side composition profile
Linear regression measured by colloid minimum for C 0 2 - N 2
oncometer, Gambro high-flux mixture in 272/

dialyzer 68* shell-side (low-pressure side)
Lithium bromide-methanol solutions, composition of 270
physical properties of 340* cross-linked
Lithium chloride-methanol solutions by dicarbonyl compounds reten
physical properties of 340
Low molecular protein hydrolysate
in saturated solutions of dicar
M boxylic acids, phenol reten
Macromolecular solutions in steady- tion of 284
state, laminar channel flow, cross-linking and 282
U F of 376 cross-section for cyclohexane con
Macromolecular U F , effect of osmotic tent of additive solution
pressure in 374 32 wt % 54/
Malo-lactic fermentation, inhibition of 19 40 wt % 54/
Mass balance 119 50 wt % 55/
considerations 158 60 wt % 55/
equation for a solute 83 68 wt % 56/
Mass transfer coefficient(s) development, production, and use in
for ovalbumin, comparisons of 123/ H F systems 207-219
with pure solvent permeability 347/ of different porosities, R O separa
constant, correlation of 346 tion of various organic
for P V A 205, comparisons of 123/ solutes using 330
for sodium chloride, pure water dynamic H F
permeability constant on 323/ chemical analyses of concentrate
Membrane(s) and permeate for 451*
blood bag, schematic for 113/ conductivity and color rejection
boundary layer theory for rejection for 449/
experiments across imperfect .. 77 performance summary data
CA for 446/-447/
characterization 299 product flux for 449/
and performance 300* recovery profile for 449/
desalination of ISSPH by H F element, helical 195/
on a DDS-865 147* externally wound 194
and a module for hemofiltration, features 194
development of 45-60 tubular
nonionized polar organic solute- elements
water- 315-338 in modular assemblies ...193-205
R O data for the N a C l - H 0 and
2
modular assembly
glycerol-H 0 system using
2
housing 202
porous 318*-319* structural materials for 200
capillary 21* systems, sealants for 199
column(s), continuous systems, support structures for 198
for C 0 - 0 mixture, shell-side
2 2
filtration system, continuous- 365/
composition profile of 261/ flux, effect of temperature on 440/

INDEX 465
Membrane(s) (continued) Membrane(s) (continued)

formation P V A (continued)
dynamic 240 production 282
effects of component ratio in properties 282
casting dope on 51 reactor
role of partially water soluble continuous protein hydrolysis in 148
additive solvents in 51 development of a kinetic model
fouling for protein hydrolysis in .... 155
models 41 equations used in engineering
studies on whey 39 calculations of 154
in U F , effects of chemical treat process, variables in 151
ments of cottage cheese production of ISSPH on 153*
whey on 39 total yield calculations on 153*
for hemofiltration, effects of addi recent applications of dynamic .435-453
tives on 48 rejection on the flow condition,
H F M 180 23* dependence of 249/
P A 300 24* RO
performance calculation of pore radius of 328
on aqueous solution of tomato development 212
juice
acid 4
amino acid 4* filtration system, plate-and-frame 208
sugar 3* flat-sheet microporous 237
vs. cyclohexanone content in the fouling in whey 37-44
additive solution 52/ in the future 218
and membrane thickness, rela in a 35-cm module 217/
tionship between 50/ pore, position of water molecule
predictability of 352 in 332/
and water solubility of additive production 215
solvents, relationship scheme 217/
between 49/ system for the U F of oil
pore-size distribution 415 emulsions 237-258
effect of 418/ thin-film composite 218
PRs for 354* utilization 215
preparation for hemofiltration 47 separation characteristics of the
presence of holes in 417 developed 57/
processes during enzymatic modifi separation characteristics of the
cation of proteins, application hemofiltration 59
of 135* silica
processes in must and wine dynamically formed 242
treatment 17-26 formation 245
processing of whey 38 flow rate of oil emulsions in 248
PVA performance with oil emulsions .. 248
chemically resistant asym specifications, C A R R E , Inc 436*
metric 281-291 T4/A 126/
concentration of carboxylic acid curve fitting and 129*
and phenol retention of 285/ experimental fluxes for 124/
cross-linked thickness vs. cyclohexanone content
for certain solvents, separating in the additive solution of 25
performance of 289* wt % of dope 52/
by dicarbonyl compounds 288* thickness vs. water solubility of
by dicarboxylic acids and additive solvents 50/
Cr(III) solution 286* UV
by ketones 287* characterization of 122
in waste water from a coke development for hemofiltration .. 46
plant, retention and prod of a 3% oil emulsion with a
uct flux of 290* dynamically formed silica . 249/
in organic and inorganic solutions polymer solute rejection by ... 411-434
at 40°C, chemical stability of 283* Meringue batter, baking performance of 139

466 SYNTHETIC MEMBRANES! HF AND U F USES
Methanol, limiting diffusion coeffi Oil emulsion(s) (continued)

cients of alkali metal halides in .. 343/ with a dynamically formed silica
Methanol solutions membrane, U F of a 3% 249/
bulk-solution free energy of solva effects of concentration and time on 250
tion for alkali metal and halide R O membrane system for the
ions in 343/ UF 237-258
comparison of surface excess free silica membrane performance with 248
energy of solvation water and 352 in silica membranes, flow rate of .... 248
surface excess free energies for U F trials of silica dynamic mem
alkali metal and halide ions branes with Paxomus B B 251/
for water and 353/ Oily and organic chemical waste treat
with surface excess free energy of ment using R O 221-236
solvation, separation in 353/ Oily waste application, bag filter
Michaelis-Menten equation for com system for pretreatment prior to .. 232/
petitive inhibition 164 Organic solutes using membranes of
Microporous R O membrane, flat-sheet 237 different porosities, R O separa
Microscreen(s) 176 tion of various 330
effluents, polishing of 187 0rum plant 29/
flow pattern 177/ Osmolality exponential decay of
Microscreening of scleroglucan
Middle molecule hypothesis 6
Midpoint approximation 84 for calf serum and B S A 91/
Modular assembly(ies) 202 as a function of serum protein con
externally wound tubular membrane centration, measurement of .... 93
elements in 193-205 limited, permeate velocity when
multi-element 202 U F is 379
Modules, advantages of rotary 203 in macromolecular U F , effect of .... 374
Molecular weights of solutes 129/ vs. solute concentration—0.15M
Multicomponent systems, modeling .... 265 N a C l B S A solution, solution . 396/
Must of tomato juice 5/, 6
ultrafiltrate fluxes 23/ Ovalbumin
and wine treatment, membrane comparisons of mass transfer coeffi
processes in 17-26 cients for 123/
and wine treatment, role of sulfur gel layer 129/
dioxide in 18 relationships between flow resist
Myoglobin in saline, rejection vs. Jv
ance and gel layer concentra
for 96/ tion for 123/
N
P
N M U difficulty of separation 267
N M U and H M U within a section of P A 300 membrane(s) 24/
continuous-membrane column, polyamide composite, typical flux
local variation of 268/ behavior with 25/
Nonionized polar organic solute- rejection measured for nitrogen,
water-CA membrane 315-338 polyphenols, and sugars with .. 24/
Nonlinear regression determined by Paper industry, D D S - R O installations
regression, Gambro high-flux in the pulp and 363/
dialyzer 68/ Paper industry, U F and H F in the
Nuclepore filters, measured apparent pulp and 361-372
rejection of dextrans by 430/ Patient monitoring system 66/
Pazomus B B oil emulsion, U F trials of
silica dynamic membranes with .. 251/
O
Peclet number 78
0 - N system in an enricher, compo
2 2 Permeate flux (PF) 298
sition minimum for 269/ Permeate velocity when U F is
Oil emulsion(s) osmotic-pressure limited 379
concentration, permeate flow rate Permeation rates for alkali metal
vs. batch 252/ halide salts, separations and 350/

INDEX 467
Plate-and-frame R O membrane Pore (continued)

filtration system 208 blocking (continued)
Plate-and-frame R O membrane sys factor (continued)
tems, configuration of DDS 209 and boundary layer concentra
Pleated tion of toluene, correla
channel, cross-section of 238/ tion of 311/
crossflow filter cartridge, Gelman .. 177/ for toluene-water data, bound
crossflow molude, silica membrane in 252/ ary layer concentration
U F module 176 and 309
Plugging of millipore by polymer solu -size distribution, membrane 415
tions under 15 psig pressure 179/ effect of 418/
Plugging tests results 190/ radius 329
p H for the acid blue C I 62055 nitrate, of the R O membrane, calcula
rejection and flux dependence on 442/ tion of 328
p H for the acid yellow CI 13906 fil of solutes, calculation of the
trate, rejection and flux depend molecular 330
ence on 441/ Potential function on solute separa
Phenol retention of membranes cross- tion, effect of 334
linked in saturated solutions of P R (see Product rate)
dicarboxylic acids 28
Phenol retention of the P V A mem
brane, concentration of carbox- Preconcentration of SSL, H F - 368
ylic acid and 285/ Preferential sorption-capillary flow
Phosphates, spiral-wound U F R O model for R O 295
system for oily waste con Pressure
taminated with 233/ control of U F rate during hemodi
Polar organic solute, comparison of alysis with high-flux dialyzers 61-74
calculated and experimental drop of hemofilter as a function of
solute separation for various blood feed rate, U F rate and .. 58/
undissociated 335/ -independent U F 373-409
Polarization, concentration 425 rejection of Vitamin B vsi 2 128/
effect of 426/ transmembrane hydrostatic 62
Polyamide composite membranes, flux Product rate(s)
behavior with P A 300 25/ for membranes 354*
Polydisperse solute 413 to pure water permeation rate
Polydispersity, effect of 415* ((PR)/(PWR)) 320
solute 418/ ratio and solute separation of
on rejection 415 glucose and an imaginary
Polyethylene oxide, measured appar solute, effect of pressure on 335/
ent rejection of 429/ solute separation and 355*
Polymer(s) Product flux
C A Eastman E-398 316 of cross-linked P V A membranes in
flexibility 53 waste water from a coke plant,
modification of 212 retention and 290*
production of new 212 for a dynamic H F membrane 449/
selection of new 212 for membranes cross-linked by di
solute rejection by U F carbonyl compounds, retention
membranes 411-434 and 284
solutions under 15 psig pressure, Protein(s)
plugging of millipore by 179/ application of membrane processes
Polyphenoloxidase and wine quality .. 18 during enzymatic modification
Pore of 135*
blocking concentration, measurement of
for benzene-water data, bound osmotic pressure as a function
ary layer concentration and 307 of serum 93
factor 298 Denmark 30/
and boundary layer concentra diffusivities calculated from U F data
tion of benzene, correla for calf serum 104*
tion of 308/ hydrolysates, low molecular 134

468 SYNTHETIC MEMBRANES! H F A N D U F USES
Protein(s) (continued) Red blood cells (RBCs) 109-117

hydrolysis in a membrane reactor, using current processing methods,
continuous 148 advantages of frozen 110
hydrolysis in a membrane reactor, using current processing methods,
development of a kinetic disadvantages of frozen Ill
model for 155 after deglycerolization, residual
production, application of U F glycerol left in 115/
during enzymatically dialysis processing of cryo-
modified 133-169 preserved 109-117
U F experiments 100 freezing 109
rejection coefficients for 89 Reflux enricher, effect of column
in tubes 86 length on enrichment in a total .. 273/
whey 31 Rejection
Proteolytic modification of ultraflltered characteristics of tomato juice solutes 2
soy protein isolate, laboratory coefficient(s)
method for 137/ average 413
Pulp and paper industry, D D S - R O calculation of 423
installations in 363/ as a function of transmembrane
Pulp and paper industry, U F and pressure measured apparent 428/
H F in 361-37
Pure
solvent permeability constant, cor measured apparent 430/
relation of mass transfer coeffi effect of
cient with 346 gel layer on 119-132
water flux (PWF) 298 on holes 420/
water permeability constant on mass solute-membrane interaction on 426/
transfer coefficient for sodium solute polydispersity on 415
chloride 323/ Spiegler-Kedem equation 76
P V A membrane(s) experiments
chemically resistant asymmetric 281-291 data from 97/
concentration of carboxylic acid across imperfect membranes,
and phenol retention of 285/ boundary layer theory for .. 77
cross-linked in saline, working equation for .. 82
for certain solvents, separating solute reflection coefficient
performance of 289/ measured in 99/
by dicarbonyl compounds 288/ on the flow condition, dependence
by dicarboxylic acids and Cr(III) of the membrane 249/
solution 286/ and flux
by ketones 287/ vs. conductivity for the acid blue
in waste water from a coke plant, CI 62055 filtrate 445/
retention and product flux of 290/ vs. conductivity for the acid
in organic and inorganic solutions yellow C I 13906 444/
at 40°C, chemical stability of 283/ dependence on p H for the acid
production 282 blue C I 62055 filtrate 442/
properties 282 dependence on p H for the acid
P V A 224 224 yellow C I 13906 filtrate 441/
aqueous solutions, fluxes for 124/ intrinsic salt 247
comparisons of mass transfer coeffi vs /„ in saline 95/, 96/
cients for 123/ for insulin 101/
gel layer concentrations of 121/ for myoglobin 96/
relationships between flow resist vs. J in serum
r 94/, 95/
ance and 123/ measured for nitrogen, polyphenols,
P W F (pure water flux) 298 and sugars with DDS 800
membranes 24/
R measured for nitrogen, polyphenols,
and sugars with P A 300
Radial velocity profile, dimensionless 317 membranes 24/
Recovery profile for a dynamic H F measiirement(s), simultaneous 427
membrane 449/ by G P C 431/

INDEX 469
Rejection (continued) Reverse osmosis (RO) (continued)

of polyethylene oxide, measured in must treatment, potentialities for 20/
apparent 429/ oily and organic chemical waste
relationship between solute perme treatment using 221-236
ability of Vitamin B i and
2 130/ preferential sorption-capillary
of solutes, effect of serum on 98 flow model for 295
of solutes by gel 127 separation of various organic solutes
steric 411 using membranes of different
and experimental results, theory porosities 330
of 425 separations of alkali metal halides
in terms of analysis for dye range in methanol solutions using
composite effluent 450/ C A membranes 339-359
for test dialyzers, U F rate and solute 92 solute preferential sorption in ... 293-314
of T O C 250 solution-diffusion model for 294
by U F membranes, polymer system(s)
solute 411-434 with a CIP unit 232/
of Vitamin B vs. pressure
i2 128/ at Cummins 231/
vs. volume flux plots of 128/ estimation of interfacial forces
of Vitamin B 130/ governing 315-338
vs. volumetric flux experiment
Retention and product flux of
cross-linked P V A membranes in wound U F 233/
waste water from a coke plant ... 290/ performance for the benzene-
Retention and product flux for water, effect of feed con
membranes cross-linked by centration on 302/-305/
dicarbonyl compounds 284 performance for the toluene-
Reverse osmosis (RO) 1-16 water, effect of feed con
-concentrated tomato juice centration on 310/
benzene-water 301 tubular 193
development of a system by 1-16 transport under steady-state
for the N a C l - H 0 and glycerol-
2
conditions 302/
H 0 system using porous
2
ultrafiltration ( R O / U F ) 222
C A membranes 318/-319/ equipment 223/
quality of 16/ generalized view of 223/
solute retention values of 16/ system, criteria for 222
toluene-water 309 of whey 39
experiments 316 cottage cheese 39
finely porous model for 295 Reynolds number 77
laboratory apparatus, scheme of .... 25/ R O (see Reverse osmosis)
in the marketplace, mechanism of.. 225/ R O / U F (see Reverse osmosis/
membrane(s) ultrafiltration)
calculation of pore radius of 328 Rotary module(s) 197/
development 212 advantages of 203
procedure 214/ flow diagram for 204/
review 208,214/ RP-610 dialyzer 73
exchange in a 35-cm module 217/ high-flux 69/
flat-sheet microporous 237 at random U F rates, in vivo
2
fouling in whey 37-44 data for 1.0 m 72/
in the future 218
pore, position of water molecule S
in 332/
production 215 Saline, rejection vs. J in
v 95/, 96/
scheme 217/ for insulin 101/
system for the U F of oil for myoglobin 96/
emulsions 237-258 Saline, working equations for rejection
systems, configuration of D D S experiments in 82
plate-and-frame 209/ Salt(s)
thin-film composite 218 degree of dissociation as a function
utilization 215 for univalent 347/

470 SYNTHETIC MEMBRANES! HF AND UF USES
Salt(s) (continued) Silica membrane(s) (continued)

rejection, intrinsic 247 dynamically formed 242
solute transport parameter for formation 245
dissociated univalent 345 properties of 250/
Satterfield's correlation 326 U F of 3% oil emulsion with 249/
Scleroglucan broths, microscreening of 191 flow rate of oil emulsions in 248
Scleroglucan fermentation, laboratory performance with oil emulsions 248
tests of axial nitration on in a pleated crossflow module 252/
broth from 178 long-term U F performance of .... 252/
Screened feed 185/ Silica, permeate rate vs. circulation
for axial filtration 183/ time of dispersion of 246/
Sealants for externally wound tubu Simultaneous rejection measurements 427
lar membrane systems 199 by G P C 431/
Separating performance of P V A - Slaughterhouse blood, process for
cross-linked membranes for decoloration of 145
certain solvents 289* Sodium bromide-methanol solutions,
Separation(s) physical properties of 341/
for the benzene-water system, Sodium chloride
effect of feed concentration - H 0 and glycerol-H 0 system
and operating pressure o
characteristics of the develope
membrane 57/ -methanol solutions, physical
characteristics of the hemofiltra properties of 341/
tion membrane 59 pure water permeability constant
effect of solute concentration on .... 301 on mass transfer coefficient
factor 443 for 323/
on conductivity, dependence of. 445/ Solids removal efficiencies for various
in methanol solutions with surface media, volatile suspended 188/
excess free energy of solvation 353/ Solute(s)
and permeation rates for alkali concentration profile at the poly
metal halide salts 350/ mer solution interface 327/
solute 344 diffusivities of 129/
fraction 316 flux 417
of the toluene-water system 311/ hindrance coefficient 413
Sepralator 226, 227/ between interfacial water and bulk
cross-sections of 227/ solution equilibrium of 323/
Serum mass, balance equation for 83
protein concentration, measure -membrane interaction on rejec
ment of osmotic pressure as a tion, effect of 426/
function of 93 molecular weights of 129/
rejection vs. /„ in 94/, 95/ polydisperse 413
on rejection of solutes, effect of .... 98 polydispersity, effect of .415/, 418/
:
SHC (standard hydrolysis curve) for on rejection 415

soy isolate and alcalase 152/ within the pore, spherical 422/
Shell-side composition profile(s) cylindrical 414/
to bottom product composition, preferential sorption 293
sensitivity of stripper 272/ in R O 293-314
for C 0 - C H - N
2 4 2 264/ radius© 425/
to feed composition, sensitivity of .. 273/ calculation of the molecular pore 330
minimum for C 0 - N mixture in
2 2 reflection coefficient measure in
continuous membrane column 272/ rejection experiments 99/
variation with comparable cut and rejection
variable column length 275/ by cellulosic hollow fibers 75-108
Shell-side (low-pressure side) com effect of serum on 98
position of continuous membrane by gel 127
column 270 measurement 90
Silica membrane(s) relationship between permeability
dynamic, with Pazomus B B oil of Vitamin B and
1 2 130/
emulsion, U F trials of 251/ for test dialyzers, U F rate and .... 92

INDEX 471
Solute(s) (continued) Soy protein(s) (continued)

retention, tomato juice 2 modification of ultraflltered vs.
values of RO-concentrated \6t acid-precipitated 134
separation 317,344 process combinations for produc
effect of concentration on 301 tion of modified 138/
effect of potential function on .... 334 Spent sulfite liquor (SSL) 361
fraction 316 HF-preconcentration of 368
and P R 355/ U F of 362
for various undissociated polar and U F concentrate and filtrate,
organic solutes, comparison molecular-weight distribution
of calculated and experi of lignin in 367/
mental 335/ Spherical solute within the pore 422/
Stokes radii of 129/ cylindrical 414/
transport parameter for dissoci Spiegler-Kedem rejection equation ... 76
ated univalent salts 345 Spiral-wound U F R O system for oily
velocity lag 412 waste contaminated with phos
effect of 414/ phates 233/
-water-CA membrane, non SSL (see Spent sulfite liquor)
ionized polar organic 315-338 Standard hydrolysis curve (SHC) for
Solution-diffusion model for R
Solution osmotic pressure vs. solute
concentration—0.15M N a C l conditions, R O transport under .... 302/
B S A solution 396/ equations 157
Solvation for alkali metal and halide quasistationary conditions of 163
ions in methanol solutions, bulk- stability of 160
solution free energy of 343/ substrate-product balance in 160
Solvation, surface excess free energy of Steric hindrance 417
for ion pairs 348 Steric rejection 411
values 351/ and experimental results, theory of 425
for ions 348 Stokes radii of solutes 129/
values 350/ Stripper shell-side composition pro
separation in methanol solutions file to bottom product composi
with 353/ tion, sensitivity of 272/
water and methanol solutions, Subsrate-product balance 159
comparison of 352 in steady state 160
Solvent(s) Sugar aqueous solution of tomato
equilibrium constants for 322 juice, membrane performance on 3/
in membrane formation, role of Sulfur dioxide in must and wine
partially water soluble additive 51 treatment, role of 18
permeability, mass transfer coeffi Support paper 213
cient with pure 347/ Surface excess free energies for alkali
transport through pore, effect of metal and halide ions for water
water molecule size on 328 and methanol solutions 353/
Soy isolate and alcalase, standard Surface excess free energy of solvation
hydrolysis curve for 152/ for ion pairs 348
Soy protein(s) values 351/
highly functional 134 for ions 348
foam stability vs. the number of values 350/
free N H groups for
2 143/ separation in methanol solutions
whipping expansion vs. the num with 353/
ber of free N H groups for . 143/
2 water and methanol solutions,
hydrolysates, whipping expansions comparison of 352
vs. degree of hydrolysis for .... 138/ Sweet whey 37
isolate(s)
hydrolysis curves for 137/ T
laboratory method for proteolytic
modification of ultraflltered 137/ T 4 / A membrane 126/
by U F in pilot plant, production curve fitting and 129/
of 135/ experimental fluxes for 124/

Thin-channel Totel and Reed as of August 15, 1980,

crossflow U F system 385/ features of the H F plants at 370/
flow, schematic of 241/ Toten Sulfite M i l l 361
pressure drop of acroflux vs. per in Norway, H F installation at 367/
meate rate, log-log plot of .... 244/ Transmembrane
UF hydrostatic pressure 62
of ISG and H S A 375 pressure, measured apparent rejec
of 0.15M saline B S A solutions .. 400* tion coefficients as a function
0.15M saline H S A solutions 401* of 428/
Thin-film composite R O membranes . 218 transport properties 75
Thin-film theories 78 Transport
T O C (see Total organic carbon cell that holds the blood bag,
analysis) schematic of 113/
Toluene, correlation of pore blocking equations, basic 344
factor and boundary layer con properties, transmembrane 75
centration of 311/ Tubular membrane
Toluene-water externally wound
data, boundary layer concentration elements
and pore blocking for 309 in modular assemblies 193-205
R O data 30
system, effect of feed concentra
tion on the R O performance systems, sealants for 199
for 310/ systems, support structures for .. 198
system, separation of 311/ R O systems 193
Tomato juice Turbulence burst model 42
concentration
experiments, performance of the U
semicommercial equipment Ultraflltered vs. acid-precipitated soy
in 12 protein, modification of 134
on the pressure drop of the Ultraflltered soy protein isolate, labo
juice, effect of 9/ ratory method for proteolytic
on pressure drop, influence of .... 15/ modification of 137/
observation 13/ Ultrafiltrate fluxes, must 23*
system by R O , development of .. 1—16 Ultrafiltration (UF) 27-36
system, four types of 11/ batch cell 393
the viscosity observed at 20 °C, unstirred 390
effect of 9/ of 0.15M N a C l B S A solution. 395/
water flux and 6 of B S A 375
water flux as the function of If, 14/ cheese production by 27
flow velocity on water flux, effect economy in Feta 28/
of 8/, 14/ data for calf serum, protein dif-
membrane performance on aqueous fusivities calculated from 104*
solution of as defined in the marketplace,
acid 4* mechanism of 225/
amino acid At diafiltration processing data 141*
sugar 3* effect of osmotic pressure in
osmotic pressure of 5/, 6 macromolecular 374
pressure observation 13/ during enzymatically modified pro
quality of RO-concentrated 16* tein production, application
solute retention 2 of 133-169
values of RO-concentrated 16* equipment, schematic of 20/
solutes, rejection characteristics experiments
of 2 protein 100
velocity on water flux, effect of 6 for proteins in tubes 86
viscosity 6, 8/ rejection coefficients for 89
water flux as the function of typical data from 103*
pressure of If flux as a function of time 25/
Total organic carbon analysis (TOC) 242 in the food and dairy industry,
rejection of 250 industrial application of 27-36

INDEX 473
Ultrafiltration (UF) (continued) Ultrafiltration (UF) (continued)

gel polarization theory for 41 thin-channel
gel-polarized 374 of ISG and H S A 375
during hemodialysis, controlling .... 61 of 0.15M saline B S A solutions .. 400*
and H F in the pulp and paper and of 0.15M saline H S A solutions .. 40i*
paper industry 361-372 system, crossflow 385/
and H F systems main features of .... 362 trails of silica dynamic membranes
index 62 with Pazomus B B oil emulsion 251*
as a function of time, in vivo 70/ of whey 29/, 31
in vivo value of 65 Ultrasep color removal process for
installation at Iggesund Kraft caustic extraction bleach effluent 368
M i l l in Sweden 365/ Ultrasep system for color removal 371/
of K B L 366, 369/ Uniform-wall-flux 100
lignosulf onates from 366 Unscreened feed 184/
of macromolecular solutions in for axial filtration 182/
steady-state, laminar channel Unstirred batch cell U F 390
flow 376 of 0.15M N a C l B S A solution 395/
membrane(s)
characterization of 122
development for hemofiltratio
polymer solute rejection b
module, pleated 176
2 Velocity lag, solute 412
module U F 35-42, 450 ft hori
effect of . 414/
zontal mounted 363/
Velocity profile, dimensionless radial.. 317
monitoring system 66/
Viscosities of fermentor sample of
in must treatment, potentialities for 20/
laboratory-produced glucan
of a 3 % oil emulsion with a
after various treatments 174/
dynamically formed silica
Viscosity, tomato juice 6, 8/
membrane 249/
observed at 20°C, effect of con
of oil emulsions, R O membrane
centration on 9/
system for 237-258
Vitamin
is osmotic-pressure limited, per
B vs. volume flux, plots of
meate velocity when 379
rejection of 130/
performance of a silica membrane
B i vs. pressure, rejection of 128/
in a pleated crossflow module, 2
B12 and rejection, relationship be

long-term 252/
tween solute permeability of .. 130/
in pilot plant, production of soy
Volatile suspended solids removal
protein isolate by 135/
efficiencies for various media 188/
plant, continuous 32/
Volume flux
pressure-independent 373-409
plots of rejection vs 128/
process for Feta cheese 28/
plots of rejection of Vitamin B vs. . 130/
rate(s)
prediction 67
by cellulosic hollow fibers 75-108
Volumetric flux experiments, rejec
during hemodialysis with high-
tion vs 93
flux dialyzers, pressure
Volumetric flux measurement 90
control of 61-74
and pressure drop of hemofilter
as a function of blood feed W
rate 58/
and solute rejection for test Wall flux boundary layer modulus,
dialyzers 92 equations for uniform 81/
with time at various fixed trans Waste
membrane hydrostatic treatment using R O , oily and
pressures, decay of 70/, 71/ organic chemical 221-236
R O system for oily waste con treatment system at Whitestone 228
taminated with phosphates, water from a coke plant, retention
spiral-wound 233/ and product flux of cross-
simple means of controlling 63 linked P V A membranes in .... 290*
of SSL 362 water testing at Cummins 230

474 SYNTHETIC MEMBRANES! H F A N D U F USES
Water Whey (continued)

flux 48,417 pretreatments to reduce
effect of tomato juice flow fouling 40
velocity on 6, 8/, 14/ production 38
as the function of pressure of properties 37
tomato juice 7/ proteins 31
as the function of tomato juice RO 39
concentration If, 14/ of cottage cheese 39
and tomato juice concentration . 6 membrane fouling in 37-44
and methanol solutions, compari sweet 37
son of surface excess free of U F of 29/, 31
solvation 352 Whipping expansion(s) 136
and methanol solutions, surface vs. degree of hydrolysis for soy
excess free energies for alkali protein hydrolysates 138/
metal and halide ions for 353/ vs. the number of free N H groups
2
molecule size on solvent transport for highly functional soy

through pore, effect of 328 protein 143/
removal, energy requirement for .... 370/ Whitestone Chemical Co 226
removal, H F and 368 waste treatment system at 228
separation of aromatic hydrocar
bons from 29
solubility of additive solvents, weight 49/
membrane thickness vs 50/ Winding geometry 201/
solubility of additive solvents, rela Winding process, helical 200
tionship between membrane Wine
performance and 49/ cloudiness of 18
Whey quality, polyphenoloxidase
acid 37 and 18
cheddar cheese 38/ treatment, membrane processes in
concentration of 36 must and 17-26
HC1 casein 38/, 40 treatment, role of sulfur dioxide
H F of 33/ in must and 18
in Denmark, Br0rup 32/
membrane
fouling studies on 39
fouling in U F , effects of chemical
treatment of cottage cheese 39 Zr(IV)oxide-polyacrylate, perform
processing of 38 ance of 448

(ACS Symposium Volume 154) Albin F. Turbak (Eds.) - Synthetic Membranes - Volume II. Hyper - and Ultrafiltration Uses-American Chemical Society (1981)

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(ACS Symposium Volume 154) Albin F. Turbak (Eds.) - Synthetic Membranes - Volume II. Hyper - and Ultrafiltration Uses-American Chemical Society (1981)

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Synthetic Membranes:

In Synthetic Membranes: Volume II; Turbak, A.;

Albin F. Turbak, EDITOR

Based on the 20th Anniversary

Symposium honoring Drs. Loeb and

Sourirajan sponsored by the

Cellulose, Paper, and Textile

Division at the Second

Chemical Congress of the

North American Continent,

Las Vegas, Nevada,

August 25-29, 1980.

ACS SYMPOSIUM SERIES 154

AMERICAN CHEMICAL SOCIETY

In Synthetic Membranes: Volume II; Turbak, A.;

American Chemical Society

T h e citation of trade names and/or names of manufacturers in this publication is not to be

PRINTED I N T H E UNITED STATES O F AMERICA

In Synthetic Membranes: Volume II; Turbak, A.;

M . Joan Comstock Series Editor

David L. Allara James P. Lodge

Kenneth B. Bischoff Marvin Margoshes

Donald D. Dollberg Leon Petrakis

Robert E. Feeney Theodore Provder

Jack Halpern F. Sherwood Rowland

Brian M . Harney Dennis Schuetzle

W. Jeffrey Howe Davis L. Temple, Jr.

James D. Idol, Jr. Gunter Zweig

In Synthetic Membranes: Volume II; Turbak, A.;

In Synthetic Membranes: Volume II; Turbak, A.;

T his volume is the result of a symposium honoring Drs. Sidney Loeb

I.T.T. Rayonier, Inc. ALBIN F . TURBAK

Eastern Research Division

In Synthetic Membranes: Volume II; Turbak, A.;

In Synthetic Membranes: Volume II; Turbak, A.;

T wenty years ago two researchers laboring diligently at the University

In Synthetic Membranes: Volume II; Turbak, A.;

There have been man

Tomato j u i c e . D i l u t e d canned tomato paste was used f o r l a b -

In Synthetic Membranes: Volume II; Turbak, A.;

.Membranes. Three d i f f e r e n t grades of.DAICEL's c e l l u l o s e

Apparatus and equipment. For l a b o r a t o r y experiments, two to

In Synthetic Membranes: Volume II; Turbak, A.;

Table I MEMBRANE PERFORMANCE ON SUGAR AQUEOUS SOLUTION

DRS-•97 DRS--95 DRS--90

NaCl .47 98 .6 1.31 95 .4 1 .71 90.0

The sugar content of raw tomato j u i c e i s about 4.5% R e f r a c -

Loss (%) = 100-Retention (%) (4)

Table I I demonstrates a l l the membranes t e s t e d have amino

In Synthetic Membranes: Volume II; Turbak, A.;

Table I I MEMBRANE PERFORMANCE ON AMINOACID AQ. SOLN.

SERINE 10.1 99.6 99.1 97.6

Table I I I MEMBRANE PERFORMANCE ON ACID AQ. SOLUTION

DRS--97 DRS--95 DRS--90

As t o water f l u x , DRS-90 membrane showed the h i g h e s t value

In Synthetic Membranes: Volume II; Turbak, A.;

Figure 2. Osmotic pressure of tomato juice

In Synthetic Membranes: Volume II; Turbak, A.;

Water f l u x . Secondly, the e f f e c t s of f a c t o r s which were an-

I f there were not a pressure drop along w i t h feed f l o w ! I f

In Synthetic Membranes: Volume II; Turbak, A.;

JUICE CONCENTRATION (REFRACTIVE INDEX)

Figure 3. Water flux as a function of tomato juice concentration observed by using