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Abstract
Several commercial polymeric ultrafiltration membranes were screened for their performance with aqueous ethanol solutions. The method of conditioning the membrane has a major effect on solvent flux, membrane integrity and their pressure
ratings. Gradual solvent exchange with successively higher concentrations increased in small doses appears to work best with
completely miscible solvents such as those studied here (ethanolwater mixtures). Rapid solvent exchange between water and
high concentrations of alcohol disrupts the polymer matrix in many cases. The Darcy model was used to correlate the data and
it indicated that viscosity differences of the ethanol solutions could account for part of the variations in solvent flux with some
membranes. Exposure to organic solvents significantly reduces the pressure rating of the membranes. Several membranes
that provided acceptable rejection of ethanol-soluble proteins at low pressures (138 kPa, 20 psi) lose its properties at higher
pressures (413 kPa, 60 psi) if conditioned incorrectly, and vice versa. 2002 Elsevier Science B.V. All rights reserved.
Keywords: Ultrafiltration; Organic separations; Ethanol; Protein
1. Introduction
Organic solvents are being increasingly used in
extraction, purification and processing of pharmaceuticals, food, nutraceuticals and flavor compounds.
Membrane technology would be the method of choice
for separating the desired compounds and for recycling the solvent. However, almost all current applications of membrane technology are with aqueous
systems. The few nonaqueous applications discussed
in the literature usually deal with streams containing
organic compounds with concentrations only up to a
Corresponding author. Fax: +1-217-244-2455.
E-mail address: mcheryan@uiuc.edu (M. Cheryan).
1 Present address: James R. Randall Research Center, Archer
Daniels Midland Co., Decatur, IL, USA.
0376-7388/02/$ see front matter 2002 Elsevier Science B.V. All rights reserved.
PII: S 0 3 7 6 - 7 3 8 8 ( 0 1 ) 0 0 6 3 8 - X
76
(MWCO) membranes with methanol, ethanol and acetonitrile. Solvents with solubility parameters similar
to the membrane reportedly led to the greatest change
in flow resistance, but solvents with a similar solubility parameter but low hydrogen bonding capabilities
could disrupt the structure of anisotropic polysulfone
membranes to such an extent that a dramatic drop in
flow resistance is observed. Jaffrin and Charrier [7] observed an 80% drop in flux in 40% ethanol compared
to water in the manufacture of plasma proteins from
human serum. The reduction in flux was explained
by an increase in viscosity when ethanol was added
to water and the formation of a thicker polarization
gel layer due to lower back diffusion of the solutes in
40% ethanol. Gupta et al. [8] reported a 2535% drop
in UF flux when ethanol concentration was increased
from 20 to 30% with albumin in mineral (Carbosep)
membranes.
Most polymers used in manufacturing membranes
and/or their supports are first dissolved in organic solvents as part of their casting process. Consequently,
they could swell or dissolve in the solvent, leading to
unacceptable changes in solvent flux and solute separation. For example, of the 15 membranes screened
by Koseoglu et al. [4] for vegetable oil processing,
only 5 were found to be stable to hexane. Raman et al.
[9,10] tested 13 membranes for deacidification of
soybean oil of which only 6 were stable in methanol,
and only one was compatible with hexane. Kuk et al.
[11] reported significant degradation in membrane
performance on exposure to aqueous and anhydrous
ethanol solutions with cellulose acetate and composite reverse osmosis (RO) membranes with vegetable
oilsolvent mixtures. Koike et al. [12] screened 18
membranes (including some developed for gas separations) for separation of fatty acids and glycerides
from lipase hydrolysates of high oleic sunflower oil.
Cellulosic membranes gave good results but suffered
from poor long-term stability. Zwijnenberg et al.
[13] used prototype polyamide and cellulose-based
membranes for deacidification of vegetable oils in
acetone.
This paper reports on our studies on polymeric UF
membranes with ethanolwater solutions. The ultimate goal was to develop a process for the manufacture of zein, which is a hydrophobic, ethanol-soluble
protein in corn with a molecular weight of 22,000.
Zein has a variety of industrial uses, from fibers and
adhesives to chewing gums and biodegradable plastics [14]. The commercial application of this natural
polymer is limited by its high manufacturing cost, due
primarily to the high cost of separating and purifying
the zein from the ethanol extract and recovering the
ethanol solvent. Ultrafiltration could be used readily to
recover and purify the zein while simultaneously recycling the ethanol solvent [15]. The best solvent for extracting zein from corn is 70% (v/v) ethanol [16] and
thus our studies were limited to a maximum ethanol
concentration of 70% (v/v). This paper specifically focuses on the effect of conditioning on solvent flux and
rejection of zein.
77
Table 1
Ultrafiltration membranes selected for screening studies
Materiala
Membrane
MWCOb
Manufacturerc
Configurationd
Cellulose ester
Cellulose acetate
Regen. cellulose
Regen. cellulose
Compositee
Compositee
Compositee
PAN-m
PAN-based
PES-m
PES-m
PES
PES
PS
PS
PS
PS
PVDF
Type C
Cell
PLGC
YM10
U20S
G80
H051
MX25
U20T
Alpha
Omega
UFC
PES4H
UFP10
PS10
PM10
PM30
AN09
10000
10000
10000
10000
20000
5000
25000
20000
10000
10000
10000
10000
10000
10000
10000
30000
25000
Spectrum-Microgon
Pall Filtron
Millipore
Millipore
Koch
Osmonics
Osmonics
Osmonics
Koch
Pall Filtron
Pall Filtron
Hoechst
Hoechst
A/G Technology
Sartorius
Koch
Millipore
Osmonics
FS
FS
FS
FS
FS
FS
FS
FS
FS
FS
FS
FS
FS
HF
FS
HF
FS
FS
PAN: polyacrylonitrile, PES: polyethersulfone, PS: polysulfone, PVDF: polyvinylidine fluoride, Regen.: regenerated, m: modified.
Molecular weight cut-off from manufacturers specifications.
c A/G Technology, Needham, MA; Hoechst, Wiesbaden, Germany (through US Tech., Cincinnati, OH); Koch Membrane Systems,
Wilmington, MA; Millipore, Bedford, MA; Osmonics, Minnetonka, MN; Spectrum-Microgon, Laguna Hills, CA; Pall Filtron, Northborough,
MA; Sartorius, Edgewood, NY.
d FS: flat sheet, HF: hollow fiber.
e Composition is proprietary.
b
4.
5.
6.
7.
8.
Four methods of membrane conditioning were evaluated. The upper ethanol concentration was limited to
78
LP PT
(1)
1
PT
=
LP
J
(2)
79
Fig. 1. Effect of ethanol concentration and transmembrane pressure on flux of a modified PAN and cellulose ester membrane.
Membranes were conditioned using method 1.
80
81
Fig. 8. Resistance ratio plots for composite membranes. Membranes were conditioned using method 1.
82
molecular weight, viscosity, hydrophobicity and dielectric constant of the alcohol. Reddy et al. [23] observed lower flux of primary and secondary alcohols
with increase in molecular weight and hydrophobicity
of the solvent with a polyamide-polyphenylene sulfone membrane. There was no correlation with viscosity. Only Machado et al. [21] reported an increase in
flux with increase in solvent (acetone) mole fraction.
Their nonlinear exponential increase was thought to
be due to decreasing surface tension at higher acetone
concentrations.
3.3. Membrane swelling
Swelling of several polymeric membranes is shown
in Table 2. Except for two membranes (Alpha and
Omega), water resulted in higher degrees of swelling
by weight while 100% ethanol resulted in the least
weight-swelling. The polysulfone hollow fiber UFP10
showed the greatest degree of swelling in water
(211%) and in neat ethanol (94%). In general, the
dielectric constant of the solvent and difference in
solubility parameters of the polymer and solvent govern swelling behavior. Membrane swelling is higher
in polar solvents like water due to its high dielectric
constant ( = 80), and less with ethanol ( = 25)
and nonpolar solvents like hexane ( = 1.9). Musale
and Kumar [22] observed over 50% swelling by
weight with cross-linked chitosan-PAN membranes
Table 2
Weight swelling of polymeric UF membranesa
Material
Membrane
Water
70%
EtOH
100%
EtOH
Cellulose
Cellulose
Composite
Composite
Composite
PAN-m
PAN
PES-m
PES-m
PES
PS
PVDF
PVDF
Type C
Cell
U20S
G80
H051
MX25
U20T
Alpha
Omega
PES4H
UFP10
AN09
AF5
112.5
25.9
83.7
65.8
31.0
71.2
85.8
44.7
51.0
26.0
211.4
54.3
21.0
60.2
29.9
48.4
61.5
26.4
56.3
39.1
59.9
46.5
18.0
161.4
46.2
9.5
45.9
22.5
34.6
51.3
24.5
46.8
32.5
52.8
56.3
17.1
94.4
34.6
6.1
83
Table 3
Effect of methods of conditioning and pressure (kPa) on membrane permeability (LP ) with 70% ethanol solventa
Membrane
Method 1
Type C
Cell
PLGC
U20Sb
G80b
H051
MX25
Alpha
Omega
PES4H
PS10
AN09
a
b
Method 2
Method 3
Method 4
138
275
413
138
275
413
138
275
413
138
275
413
68
142
51
23
38
62
247
424
642
21
205
50
58
132
42
31
54
46
235
414
666
16
150
35
58
240
49
28
62
36
220
443
655
14
132
39
75
127
45
50
25
71
254
411
554
20
432
282
150
130
53
50
50
70
261
397
576
20
303
214
256
618
45
51
81
84
271
445
585
37
265
182
62
136
38
22
15
66
241
362
739
18
853
323
140
232
40
38
104
95
249
371
760
49
726
242
489
412
75
38
665
145
337
463
855
136
585
285
71
79
26
21
19
49
137
356
101
16
150
219
141
119
101
22
22
92
164
371
142
18
334
209
370
1112
278
42
21
428
179
655
483
126
445
214
Table 4
Effect of methods of conditioning and pressure (kPa) on membrane permeability (1015 m) and rejection (%) of proteina
Membrane
Method 1
LP
Type C
Cell
PLGC
U20Sb
G80b
H051
MX25
Alpha
Omega
PES4H
PS10
AN09
Method 2
Rejection
LP
Method 3
Rejection
LP
Method 4
Rejection
LP
138
275
138
275
138
275
138
275
138
275
138
275
138
275
138
275
56
63
42
N.D.c
8
34
41
70
45
22
114
63
46
55
29
9
15
34
39
68
N.D.
23
123
52
92
99
94
N.D.
87
96
98
99
78
88
90
79
97
94
95
93
96
92
99
98
N.D.
95
86
51
21
24
12
91
59
6
18
20
20
7
23
20
81
127
71
726
136
21
82
82
73
40
300
112
91
92
97
18
31
91
95
93
92
79
48
80
94
72
96
11
20
96
58
96
94
95
4
58
56
39
23
14
15
9
26
35
32
10
153
28
199
32
25
17
14
25
24
83
54
13
138
397
96
94
94
78
100
72
96
98
98
91
25
87
55
93
99
80
93
36
97
53
56
90
23
0
68
76
59
18
5
15
51
97
63
20
616
74
89
428
40
16
9
166
87
109
41
19
539
70
93
69
96
98
90
94
84
88
87
84
15
81
99
9
98
87
79
10
52
26
88
96
19
62
The protein was 5 g/l zein in 70% ethanol solvent. LP values were calculated from Eq. (1) (1015 m).
Pressures were 275 and 345 kPa.
c N.D.: not determined.
a
Rejection
84
Acknowledgements
This research was supported by the Illinois Corn
Marketing Board, Illinois Department of Commerce
and Community Affairs Bureau of Energy and Recycling, US Department of Agriculture through the
NRICGP program (Award No. 97-35504-4296) and
the Illinois Agricultural Experiment Station. Contributions of membranes by Koch Membrane Systems, Osmonics and Pall Filtron are gratefully acknowledged.
Analytical assistance was provided by Amanda D.
Popp and Melissa M. Stein. Useful discussions were
held with D.A. Musale, M. Balakrishnan, H. Yacubowicz and J. Yacubowicz.
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