A NEW THIN-FILM COMPOSITE SEAWATER REVERSE OSMOSIS MEMBRANE

J.E. CADOTTE, R.J. PETERSEN, R.E. LARSON and E.E. ERICKSON

FilmTee Corporation, 15305 Minnetonka Boulevard, Minnetonka, Minnesota 55343, USA

ABSTRACT
During the past year a new thin- film composite reverse osmosis membrane that
shows excellent potential for single-pass seawater operation has been developed.
This membrane, designated FT-30, is formed by depositing a proprietary thin
polymer coating on a microporous polysulfone support layer.
Membrane samples, tested at an operating pressure of 1000 psi with synthetic
seawater, yielded fluxes of about 30 gallons per square foot per day (gfd) and
salt rejections as high as 99.6 percent. At 800 psi the flux dropped to 23 gfd
with Little decrease in salt rejection. Membrane tested with other raw waters,
including tapwater at a pressure of 50 psi and brackish waters at ZOO-600 psL,
also provided excellent results. The membrane appears to be suitable for a
variety of applications, ranging from water conditioning to single-pass seawater
operation.
Other important performance characteristics of the new membrane are that it
appears to be chlorine-resistant (not damaged by chlorine concentrations of
100 ppm in three-day immersion tests), can be operated over a wide range of pR
(3-ll), is resistant to compaction, and can operate at tempreatures as high as
60C without damage.

INTRODUCTION
During the past ten years significant advances hove been made in reverse
osmosis technology, including: 1) membrane casting methods, 2) chemi.cal modifi-
cations of cellulose acetate polymers to obtain specific membrane properties,
3) module configurations, and more recently 4) nonpolysaccharide membrane
development. The nonpolysaccharide membranes have exhibited significant
advantages over polysaccharides in such areas of performance as flux, salt
rejection, stability, and microbiological resLstance.
Currently, several nonpolysaccharide reverse osmosis membranes are commercially
available_ These include aromatic polyamides, aromatic polyhydrazides, poly-
benaimidazolone (PBSL), polyepiamine/amide, and polyepiaminefurea. Laboratory
25
26 ?xlnm!EBThL

and pilot plant development is underway on other membranes including poly-

ethyleneiminefurea (NS-lOO), sulfonated polyfurane (NS-ZOO), polybenzimidazole

(PBS), and polypiperazine isophthalamide.

It cannot be said that any currently commercial membrane system fully meets
the requirements of the reverse osmosis industry. Asymmetric cellulose acetate
membranes all suffer a problem of compaction and gradual flux decline over their
lifetimes_ 3Cn addition, they have low chemical resistance, making them
sensitive to possible system upsets (pR too high or too low), and they are
highly susceptible to biological attack. Cellulose triacetate is characterized
by low initial membrane flux such that its primary commercial form is as a

hollow fiber (which allows for high membrane surface area to achieve high overall
throughput of water). Quaternized cellulose triesters, in addition to the
compaction problem, suffer significant losses in salt rejection by hydrolysis or
other degradative processes after approximately six months in service.
Aromatic polyamide and polyhydrazide membranes, commercially available in
hollow fiber form, suffer two main difficulties: lack of chlorine resistance
and high susceptibility to fouling by colloidal materials in water. In addition,
these membranes are asymmetric in their hollow fiber form and are thereby
temperature-limited (maxims recommended use temperature of 43OC).
The polyepiamine/amide thin-film composite membrane and its urea counterpart
show excellent flux and salt rejection properties. A key difficulty with these
membranes is their complete lack of resistance to chlorine in the feedwater.
Among the experimental membranes under development, the NS-100 and NS-200
membranes also suffer from lack of chlorine resistance. Also, the NS-200
membrane has shown considerable variability in flux and long-term stability
during development work at various companies,
Although significant advances have been made, a continuing need exists for
improved reverse osmosis membranes, inclsding improvements in water flux and salt
rejection, compaction resistance, resistance to free chlorine and other oxidizing
agents, stability over a wide pII range, wet-dry reversibility, stability in
storage (particularly dry storage), and stability at higher temperatures. All
membranes that are currently couanercially available fall short in some of the
above areas. Important economic benefits in the desalting cf both seawater and
brackish waters would arise from membrane improvements, including lower operating
costs, higher resistance to system upsets, and greater ease of operation and
maintenance. FilmTec Corporation has developed a new membrane-the FT-30-
which shows improvements over the state of the art in most of the above criteria.
The FT-30 membrane is of the thin-film composite configuration and is non-
cellufosic. It can tithstand temperatures of up to 100C, is chlorine resistant
(72 hours in a 3.00ppm chlorine water solution), is stable over a broad pH range
(3-Xl), and has good flux and salt rejection characteristics (30 gfd and up to
99.6% for seawater at 1000 psi)_ Test results are presented in this paper.
CADornETAJ; 27

TECRNECAL APPRi3AcH TO THIN-FILM COMPOSITE MEMBUANE FABRICATION

In l.967,microporous polysulfone supporti film was first produced and reported
by North Star Research Institute in conjunction with work on ultrathin cellulose
acetate reverse osmosis membranes (ref. 1). Polysulfone microporous films are
asymmetric in nature with pores generally less than 200 2 on the air side and up
to 40,000 g on the glass side. These films, unt2ke the porous backing of the
asymmetric reverse osmosis membranes, are relatively resistant to pressure
compaction, can be dried, and are resistant to bioiogical and chemical
degradation. Beginning in 1970, research efforts at North Star were devoted to
formation of salt barrier layers in situ on these polysuMone supports by
chemical condensation processes. This research resulted in the NS-100 membrane
in 1971 (ref. Z), the NS-200 membrane in 1973 (ref. 3), and the NS-300 membrane
in 1977 (ref. 4). Work on the latter membrane is continuing at FilmTec
Corporation under the direction of the former North Star staff members.
To illus%rate the approach involved in these membranes, a microporous poly-
sulfone support film was prepared by casting a liquid film of polysulfone
solution (159,w/v in dimethylformamide, cast on a glass plate for laboratory use
or on a non-woven fabric support for eLement production), and by quenching it in
water. Handmade sheets of support film used in the work described here were S
inches by 20 inches in size. These sheets were washed in water and cut into
3-inch-diameter circles. The membrane was then formed by interfacial polymeri-
zation on the glossy surface of the 3-inch disk, and tested in high-pressure
test celis as described later.
The great advantage of the composite-membrane fabrication technique is that it
allows the deveLopment and successful handling of extremely thin layers of
barrier materials from almost any conceivable chemical combination. Any of a
number of brittle, weak, insoluble, crosslinked, or otherwise intractable polymer
systems can be generated in situ on the polysulfone surface, and most of the
handling problems that would otherwise occur can be avoided. Furthermore, these
compositions are present in such minute thicknesses that water flux is greatly
enhanced. Polymer systems can be maximized for salt rejection characteristrcs
while maintaining economically attractive fluxes.
This approach proved itself earlier through the development of the "NS"
membrane series. Several other membrane systems have since been explored that
approached the first two in terms of saLt rejection, which is the most critical.
parameter in achieving a seawater conversion membrane. However, only in the past
two years,with development of the FT-30 membrane system, has research begun to
pay off in the development of a chJ.orine-reslstanr reverse osmosis membrane with
salt rejections high enough for seawater conversion applicatious. The tests on
this membrane are described below.
28 CADOTTEETAL

EXPERIMENTAL EQUIPMENT
Tests on 3-inch-diameter coupons to determine tbe intrinsic performance of
the membrane were carried out in the reverse osmosis test loop developed at
North Star (ref. 5). The major components of the systemwere a 20-liter
reservoir, a model 2L&-144B Milton Roy pump, an accumulator (surge tank), a beat
exchanger, six stainless steel test cells, a LOO-mesh high-pressure filter, a
needle valve for system pressure control, and a rotameter-type flow meter. The
test cells were machined from AIST 316 stainless steel. Mechanical support for
the membrane was supplied by a f-inch-diameter sintered stainless steel plate,
$-inch thick. A nonwoven polyester support (HollyTex 83361, Eaton-Dikeman Co.,
it. Holly Springs, Pennsylvania) was placed between the porous plate and the
membrane-support composite to protect the membrane from the rough surface of the
plate. A seal was obtained with a 1.75-inch (I.D.) O-ring. The channel height
of the feed solution chamber was 0.05 inch.
The test cells were connected in series and the recovery for each membrane
sample was about 0.1 percent. With this low recovery, concentration polarization
effects were minimized and a true measure of the intrinsic performance of the
membrane could be approached_

REVERSE OSMOSIS PROPERTIES OF FT-30 MEMBRANE

Effects of Feedwater Pressure
The effects of pressure were determined using a 3.5 percent synthetic seawater
(made from "Sea-Salt", Lake Products Co., St. Louis, Missouri) at 2SC over a
pressure range of 400 to 1000 psi. The effects on water flux and salt rejection
are shown in Figure 1, As might be anticipated, a linear relationship exists
between flux and pressure over the measured range. The salt rejection curve has
the approximate form of a hyperbola, reaching a horizontal asymptote of 99.4
percent rejection at about 1000 psi. As also indicated in Figure 1, a rejection
of 98.8 percent was still maintained when the Pressure dropped to 600 psi. This

PRESSURE (~8)

FHXIRE 1. WATER t-%.:1X AND SALT itEJECTION AS A FIGURE 2. WATER FLUX AND SALT RE.SECTIOH AS A
FUhCTION OF PPESSUPE FUNCTION OF TEM?ERWURE
CADOTTE ET AL 29

suggests that the PT-30 membrane has potential for S&q&-paSS seawater perform-
ance at pressures lower than 800 psi, The rejection falls off precipitously at
pressures below 600 psi.

Effects of Feedwater Temperature

The effects of feedwater temperature on membrane performance are shown in
Figure 2. The data were obtained using 3.5 percent synthetic seawater at 1000 psi.
The temperature effec& on salt rejectfon and water flux is reversible, As
the temperature of the feedwater was increased, the rejection decreased and the
flux showed a strong increase. When the seawater temperature was returned to
near the standard test conditions (to 22oC), the membrane properties returned to
their normal values, showing no permanent degradation. The data for salt
rejection show that the membrane fell below the minimum desired performance for
seawater rejection of 99-3 percent at a temperature of 27OC. A Further increase
in temperature caused the rejection to drop at a decreasing rate to about 98.9
percent at 60C. The ffux increased at a Linear rate as the temperature
increased and reached a value of 73 gfd at 60C.

Effects of Feedwater Brine Concentration

The effects of brine concentration change on mtnnbrane performance are shown
in Figure 3. The data were obtained at 1000 psi using synthetic seawater at
concentrations of 0.5 percent to 8 percent at a temperature of 25OC: The water
flux dropped from 59 gfd at 0.5 percent to about 7.5 gfd at 8 percent salt
concentration. Rejection decreased from 99.4 percent to 97.8 percent over the
same range.
Similar tests were made using pure sodium chloride over the same concentration
range, pressure, and temperature. These tests indicated that there were no
significant differences between pure sodium chloride solutions and synthetic
seawater feeds for the FT.-30.

- .._
. 2 1.
BRINE &CEhTII;,T,OS t=:

FICUPES. WATER FLUX AND S4l.T REJECTlOS As , FlCURE4. WATER CtUX AND SALT PWECTlOZI A!3 A
FUXCTIO~ OF BRShE CONCESTR4TTION FUNCTIOS OF .li
30 CADurrEETAL

Effects of Feedwater pH
The FT-30 membrane is resistant to acid or base hydrolysis. Several tests
were made in which the membrane was immersed in 1 percent hydrochloric acid, 1
percent sodium phosphate, or 1 percent sodium hydroxide for an hour at the
boiling point. Subsequent reverse osmosis tests in synthetic seawater showed
either no loss in membrane flux and salt rejection or only a slight effect.
In a number of flov tests, the membrane was tested at various pH levels in
both synthetic seawater and sodium chloride. The tests were started at a
neutral pH of 7. Hydrochloric acid was added to lower the pH in steps to a low
value of 3. The pH vas then adjusted upward in steps through the neutral range
again to a value of 11, and then back to 7. Shown in Figure 4 are data taken on
a typical membrane at a pressure of 500 psi for 0.5 percent sodium chloride
feedwater. The data indicate that the water flux is fairly constant over the
entire pH range, showing a slight increase with increasing PH. The salt
rejection reached a peak of 99.5 percent at a pH near 8. In several tests the
pH was lowered to 2, which caused a drastic decrease in salt rejection. Data at
pH values below 5 tended to scatter widely, and the nature of the cume is
estimated. A decrease also occurred when the pH was raised past 11 to 12. In
both cases no major effects were noted on the membrane water flux. upon cycling
to an acid condition (pH 3) then to an alkaline condition (pH 11) and back to
neutral, the flux and salt rejection returned closely to their original values,
indicating that no permanent change in the membrane occurred.

Effects of Feedwater Pressure for a 0.5 Percent Sodium Chloride Solution

The effects of feedvater pressure at a salt concentration of 0.5 percent at
25OC are shown in Figure 5. The figure indicates a linear relationship between
water flux and pressure over the entire pressure range, while the salt
rejection holds constant at pressures above about 250 psi. These data suggest
that the FT-30 membrane should perform well in the brackish water range and offer
a potential high flux capability at fairly low pressures_

FICIJPES. WATER FLUX AND SALT REJECTION AS A

FUNCTION OF PRESSURE
t2luxmm ET AL 31

COMMENTS ARD CORCLUSIONS

The FT-30 membrane has demonstrated in small-scale laboratory studies that it
possesses high flux and salt rejection characteristics, and further, that it
possesses excellent chemical stability. In particular, it has demonstrated
chlorine resistance in immersion tests w%th 100 ppm hypochlosite. This has been
confirmed in 72-hour exposures to nominally 100 ppm hypochlorite in reverse
osmosis test loop trials aswell, though hypochlorite levels varied widely in
the test loop due to natural consumptive processes. The membrane is also
resistant to residual chlorine in tapwater over test periods of up to 2000 hours.
The l?T-30 membrane appears to have a pE operating range of about 4 to 11,
Eowever, exposures to pR values beyond these limits can be tolerated. In fact,
cleaning of membrane surfaces with 1 percent hydrochloric or phosphoric acid
has been carried out in long-term laboratory tests with exceIlent results.
Roiling of membrane samples usually improved salt rejection while maintaining or
improving flux as well.
Further tests are underway on the FT-30 membrane, both in the form of small
disks and spiral-vound elements. Applications are being explored for this
membrane where its high flux, chlorine resistance, and microbiological stability
are beneficial.

REFERENCES
I L-T, Rozelle, J-E, Cadotte, R.D. Corneliussen, and E.E. Erickson, Development
of New Reverse Osmosis Membranes for Desalination, Office of Saline Water
Research and Development, Report No. 359, U.S. Dept. of the Interior,
Washington, D.C. 20240, 1968.
2 L.T. Rozelle, S.E. Cadotte, K.E. Cobiaa, and C.V. Kopp, in S. Sourirajan (Ed_),
Reverse Osmosis and Synthetic Membranes, National Council Canada, Ottawa, 1977,
Ch. 12, p. 249.
3 3.E. Cadotte, C V. Kopp. K.E. Cobian, and L.T. Rozelle, In Situ-Formed
Condensation Polymers for Reverse Osmosis Membranes: Second Phase, Report No,
PB-234198, National Technical Information Service, Springfield, VA, June 1974.
4 J-E. Cadotte, H.J. Steuck, and R.J. Petersen, Research on In Situ-Formed
Condensation polymer for Reverse Osmosis Membranes, National Technical
Information Service, Springfield, VA, March 1978.
5 L.T. Rozelle, 3-E. Cadotte, B.R. Nelson, and C.V. Kopp, Ultrathin Membranes
for Treatment of Waste Effluents by Reverse Osmosis, Vol. 22, 1973, p. 223.