DESALINATION

ELSEVIER Desalination 153 (2002) 355-360

www.elsevier.com/locate/desal

Developments in membrane technology for water treatment

Bjarne Nicolaisen
Business Development, CrossJow Membrane Business, Osmonics, Inc., 760 Shadowridge Drive, fista, CA 92083, US4
Tel. + I (760) 5983335; Fax f I (760) 5983334; email: bnicolaisen@osmonics.com

Received 26 March 2002; accepted 10 April 2002

Abstract

Membrane technology is widely accepted as a means of producing various qualities of water from surface water,
well water, brackish water and seawater. Membrane technology is also used in industrial processes and in industrial
wastewater treatment, and lately membrane technology has moved into the area of treating secondary and tertiary
municipal wastewater and oil field produced water. In many cases one membrane process is followed by another
with the purpose of producing water of increasing purity and quality for various purposes. One type of membrane
may thus enhance the fimction of another to meet goals ranging from disposal of wastewater to production of
drinking water from unexpected sources. In this way membrane technology offers the possibility of managing the
total water resources in a region, which is of special interest in geographical areas where the natural water resources
are scarce. The spiral wound membrane element configuration is the most widely used due to its high packing
density and relatively low price. This paper will describe some technological advance in the area of innovative new
membranes and application concepts for spiral wound membrane elements. Spiral wound elements span the four
commonly defined membrane technologies, which are microfiltration (0.01-O microns), ultrafiltration (500-
100,000 Da), nanofiltration (100-500 Da), and reverse osmosis (up to 100 Da). A sandwich consisting of two
membrane sheets with an inserted permeate carrier is glued together and to complete the membrane package a feed
spacer is inserted between the opposing membrane surfaces. The membrane package is wound around a perforated
central tube through which the permeate exits the element. The physical shape of a membrane element is secured by
applying a suitable outer wrap. The physical and chemical properties ofthe various materials, including the membrane,
are chosen according to the operating parameters. The typical reverse osmosis elements have limitations with respect
to temperature (45(Z), pH value (2-lo), silt density index (less than 3 SDI), chlorine (dechlorination mandatory)
and several other parameters. This is acceptable for conventional pure water applications, but for more complex
membrane applications these limitations must be diminished or removed. Advanced materials and material science
have been applied to the membranes, materials and construction of spiral wound elements. This effort has resulted

Presented at the EuroMed 2002 conference on Desalination Strategies in South Mediterranean Countries:
Cooperation between Mediterranean Countries of Europe and the Southern Rim of the Mediterranean.
Sponsored by the European Desalination Society and Alexandria University Desalination Studies and Technology
Center, Sharm El Sheikh, Egypt, May 4-6, 2002.

00 II-91 64/02/$- See front matter 0 2002 Elsevier Science B.V. All rights reserved
PII: SOOll-9164(02)01127-X
356 B. Nicolaisen /Desalination 153 (2002) 355-360

in elements with improved operating parameters and wider areas of applications. A host of new membrane applications
have been made possible and there is no limit in sight, except that new applications must rest on a profitable
foundation for the user. Scarcity of water, environmental requirements and the simple logic of reusing water instead
of discharging it are conditions, which call for increased use of membrane technology in a multitude of applications.

Keywords: Membrane; Well water; Brackish water; Surface water; Seawater; Secondary waste water; Tertiary waste
water; Produced water

1. Well water, brackish water and surface water

Fouling of the membrane surface during opera-
tion diminishes the productivity of the membrane
and in the case of a continued fouling condition
the salt rejection will suffer. Fouling mainly stems
from three sources, namely particles in the feed
water, buildup of sparsely soluble minerals and
byproducts of growth of microorganisms. All of
these conditions require frequent cleaning, which
is expensive and leads to shorter service life of
the membrane elements. Especially when more
than one fouling condition prevails, the membrane
can be irreversibly fouled, in which case correction
of the condition and replacement of the membrane
elements is the only solution. In general, the feed
to membranes should not contain suspended solids,
and adequate pretreatment of the feed is mandatory
to a well functioning membrane plant. Sparsely
soluble minerals are mainly, silica, barium and
contributors to hardness. Growth of micro-
organisms is most pronounced in the temperature
range of 30-45C, which ironically is the
prevailing operating temperature for membrane
plants throughout the Middle East countries.
Reverse osmosis membranes are sensitive to
mineral fouling, which occurs when the solubility
product of a material is exceeded in the boundary
layer formed on the membrane surface during
operation. The concentration in this boundary
layer can be twice as high as in the bulk solution,
if the crossflow of the feed stream is inadequate.
Several ways have been suggested to diminish
mineral fouling, including various post-treatment
methods to change the electrical charge of the
membrane surface, which is then believed to repel
certain species. However, only moderate success
has been achieved following this avenue. The
cellulose acetate membrane, which has largely
been replaced by thin-film polyamide membrane,
still seems to offer the best fouling resistance [ 11.
A recent study [2] suggests that the single most
important factor in preventing mineral fouling as
well as fouling caused by microorganisms is the
smoothness of the membrane surface. The
conclusion is that if there are no crevices in the
surface of the membrane, no material will be
deposited there, because the boundary layer
formation becomes less pronounced and the
crossflow will be able to remove it at a faster rate
than it can be deposited.
Most reverse osmosis membranes in use today
are thin-film polyamide membranes formed on
top of another membrane, usually a polysulfone
ultrafiltration or microfiltration membrane, called
a substrate (Fig. 1). The surface morphology of
the substrate determines the smoothness of the
resulting membrane sandwich. A smoother and
less fouling prone membrane can be made by
inserting an additional membrane layer between
the polysulfone and thin-film layers, or by designing
a polysulfone membrane with a smooth surface
to begin with. Both methods have proved their
value through results in practical applications. These
concepts have been used in the design of the new
line of DuraslickTM low fouling elements from
Osmonics.
In some cases naturally occurring water, for
instance from artesian wells, have a temperature
exceeding that, which is normally considered
feasible for reverse osmosis membranes. The
water can be cooled down, often at great expense,
to allow reverse osmosis treatment, but in most
 B. Nicolaisen /Desalination
ermeate Collectbn Mat
Feed Channel
cases such projects fall by the wayside for econo-
mical reasons in areas where water is much needed.
Lately, reverse osmosis elements tolerating
operating temperatures up to 80C have been
developed and commercialized. Operating a reverse
osmosis plant at temperatures in the 50-80C
range also alleviates the risk of growth of micro-
organisms, which can cause severe fouling of the
membrane surface. The line of DurathermTM high
temperature elements from Osmonics offers the
possibility of operating a membrane plant at high
temperature or sanitizing a plant occasionally at
90C to keep growth of microorganisms under
control.
2. Seawater
With only 3% of all available water on the
planet being fresh water, seawater is the most
abundant available source of drinking water and
water for industrial use in many regions, and
reverse osmosis is the dominant technology for
production of drinking water. Seawater reverse
osmosis membranes work at higher operating
pressures than membranes used for brackish water,
because the osmotic pressure of the dissolved
minerals in seawater must be exceeded before
pure water is produced. Seawater has a relatively
high hardness, which sets a limit for the recovery
by reverse osmosis at 30-50%, limited by the
osmotic pressure and depending on the actual
153 (2002) 355-360 357
Fig. 1. The spiral wound element.
hardness and salt content in the pretreated seawater.
This means that only one third to half of the
pretreated seawater ends up as drinking water.
This is especially pronounced in countries bordering
on the Persian Gulf, where the salt content is as
high as 46,000 ppm with associated high hardness.
Often the recovery rate of a seawater reverse
osmosis plant in this region is only 30-35%.
Work performed by the Saline Water Conversion
Corporation (SWCC) [3] in Saudi Arabia, using
a multi-valent ion specific nanofiltration membrane
with some salt rejection, has shown that due to
removal of hardness with the associated reduction
in scaling potential and reduction of the salt
content in the nanofiltration permeate, which is
used as feed for a subsequent reverse osmosis step,
the overall recovery can be increased significantly.
Due to the overall decrease in operating pressure
a sizeable reduction in energy consumption and
overall operating costs also results. It is to be
expected that this concept will gain in use in con-
nection with reverse osmosis treatment of seawater
in general.
Reverse osmosis only account for 10% of the
fresh water production in the Middle East countries.
The rest relies on evaporation technology. Similar
to reverse osmosis membranes, evaporators are
prone to mineral scaling and they typically operate
at only 70-80% of their design capacity, but
contrary to reverse osmosis membranes they are
impervious to the salt content in the feed. The
358 B. Nicolaisen / Desalination 153 (2002) 355-360

permeate from a multi-valent ion specific nano-
filtration membrane with a salt rejection as low
as possible would provide the ideal seawater feed
for multi-effect distillation and multi-stage flash
evaporators, which would then be able to gain at
least 25% in capacity by operating closer to the
design capacity. The overall economy of using
evaporation of seawater would also be greatly
improved due to fewer cleanings and therefore
longer equipment life.
The Desal@-5series of multi-valent ion specific
nanofiltration membranes from Osmonics provide
membranes for pretreatment of seawater for both
reverse osmosis and evaporation.
3. Oil field produced water
In 1998, Osmonics acquired Membrex, which
had developed the UltraFilic@membrane for use
in its spinning disc device, the WasteWizard@aimed
at recovering alkaline cleaners in the metal finishing
industry. Oil and other organic contaminants are
also rejected by the membrane in the process. The
challenge now arose to develop this membrane
for use in spiral wound membrane elements,
which had been accomplished in the M-series of
membranes from Osmonics.
The UltraFilic membrane is a modified poly-
acrylonitile (PAN) membrane, falling in the area
between ultrafiltration and microfiltration. It is
characterized by an A-shaped, asymmetric pore
structure, as opposed to the normal V-shaped
isotropic pore structure seen for MF membranes.
Hydrophilicity can be measured as the contact
angle between the membrane surface and a drop
of water placed on the surface of the membrane.
Most membrane materials exhibit a contact angle
between 30 and 1lo, whereas the UltraFilic mem-
brane has a very small contact angle of only 4
(Fig. 2). This characteristic combined with the
asymmetric pore morphology results in extra-
ordinary separation characteristics for oil, grease
and other organic materials from aqueous solutions.
The modification also provides the membrane
with resistance to many organic solvents. Further-
more, in an appropriate spiral wound element
construction the M-series membrane can operate
at temperatures up to 85C in the pH range of 2-
10. At the present time two pore sizes, namely
0.01 and 0.06 micron (approximately) are available.
The M-series membrane is uniquely suited for
applications where organic materials must be
separated from water. Among the most promising
applications for the UltraFilic membrane is

Water
M-Series
ContactAngle

Membrane

Contact

I
,,* ,080 660 46o i 44o j >30
Angle 4 f
v-b Increasing Hydrophlllclty p
Okphobic: Oleophobic:

I
- -
Repels Water Lower Flux pr Foot Repels Water Higher Flux per Foot
Absorbs Oil Dlfflcult to Clean Absoti Oil Easier to Clean
Fouls with Free Oils Not Fouled by Free Oils

Fig. 2. M-series membrane, comparative hydrophilicity.

 B. Nicolaisen / Desalination
treatment of onshore and offshore oil field produced
water. One of the methods to enhance the life and
productivity of oil wells is to inject water close
to or under the oil deposit and thus assisting in
pressing oil to the surface. This technology is used
in onshore and offshore oil exploration throughout
the world. The water used for injection must be
of a composition as close as possible to the naturally
occurring water in the oil bearing strata, or at least
have a composition which does not tend to block
the porous geological formation in which the oil
deposit is contained. Both naturally occurring
water and injected water finds its way to the
surface as water mixes with the oil as produced
water. As an oil field gets older, more and more
produced water will be present in the oil, and as
oil reservoirs gradually empty, more and more
water must be injected to enhance the oil pro-
duction. In some older oil fields, more than 90%
of the liquid brought to the surface is produced
water.
The produced water is often treated in hydro-
cyclones, which reduces the content of free oil
but is ineffective for removal of entrained oil. The
produced water often contains hardness in the
form of calcium, magnesium, iron and other salts,
which tend to block the oil containing strata, if it
is reinjected close to or under the oil deposit. The
result is that produced water must be disposed
of, often by injection at a distance from the oil
deposit, and new water must be prepared for
injection with the purpose of enhancing oil pro-
duction. In addition, produced water from wells
that are at a stage where water injection is not yet
required, may contain substances such as arsenic,
mercury and heavy metals, which makes disposal
problematic. Stricter environmental requirements
are being imposed all over the world, and in
offshore situations there is an increasing need to
clean the produced water prior to disposal to the
ocean.
The M-series membrane will, in many cases,
produce water, which can readily be used for
reinjection to enhance oil production; it will lower
the oil content to acceptable levels for disposal;
153 (2002) 355-360 359
and especially in offshore situations it will reduce
the level of many chemical species to levels allowing
disposal to the sea. In tandem with nanofiltration
and/or reverse osmosis treatment, water of an
acceptable composition for irrigation and other
purposes can be produced in onshore situations.
4. Secondary and tertiary wastewater
One of the potential sources for the supply of
water for various purposes in arid areas is recycling
of secondary and tertiary municipal and industrial
wastewater from biological treatment plants.
Membrane filtration of such water for reuse would
require either nanotiltration or reverse osmosis
treatment, but the pretreatment required has
hitherto rendered this approach uneconomical and
impractical.
Initial tests using the M-series UltraFilic mem-
brane may change this. After intensive testing, a
1 million gallon (260 m3) per day plant has been
installed at an air force base in the United States
and will be in operation shortly. The results in
this case and in several other situations, indicate
that permeate from the M-series membrane, which
is the feed to a subsequent reverse osmosis step,
has been pretreated sufftciently to allow the reverse
osmosis membrane to operate without appreciable
fouling. The resulting water is of a high quality,
which, if not for aesthetical reasons, could be reused
as drinking water.
When required the permeate from the M-series
membrane may be treated in a combination of sub-
sequent nanofiltration and reverse osmosis steps
to produce water of almost any desired quality.
5. Conclusions
Membrane technology has undergone a rapid
development as it pertains to most applications
and in particular as it pertains to water purification.
The last twenty years have witnessed new mem-
branes working at ever lower pressures and with
increasing salt rejection from the original cellulose
acetate membrane requiring 400 psi (28 bar) to
360 B. Nicolaisen /Desalination
modem polyamide thin-film membranes requiring
only 100 psi (7 bar) net driving pressure. Salt
rejection of the reverse osmosis membranes has
increased from 97.0 to 99.5%, with some special
membrane types exhibiting even higher salt rejec-
tions. Are we nearing the end of the possible and
will we have to accept todays standards in the
future?
The answer is that membrane technology will
continue to develop with huge benefits for the
user of membrane filtration equipment for water
purification. Material science and molecular
modeling are some of the tools, which are used in
the advancement of membrane technology. Net
driving pressures will continue to decrease. Salt
rejection will continue to increase, although they
are already close to 100%. Resistance of membrane
materials to oxidizing agents will increase to the
point that cleaning with chlorine is possible. The
tolerance for solvents and other aggressive chem-
icals will be improved. In short, the end is not in
153 (2002) 355-360
sight and membranes will claim an increasing role
in water purification to the advantage of our thirsty
humanity.
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