Feature 35

Filtration+Separation April 2007

Introduction to membranes:
Membrane
selection
n the second of a series of articles, Graeme Pearce looks at
I the factors influencing selection when choosing membranes
working with water and wastewater, aiming to provide an
understanding of the factors which influence the selection of
membrane material for commercial products

Water applications Membrane fabrication is now provided by products using PES and
PVDF.
Commercial membrane technology for water Commercial UF/MF membranes span the
and wastewater applications falls into two range from fully hydrophilic polymers Hollow fibre and capillary membranes can
broad categories. In the first category, reverse such as cellulose acetate (CA), to fully be made either by a phase inversion process
osmosis (RO) and nanofiltration (NF) is hydrophobic polymers such as polypropylene or by a stretching process (also known as
used for removing dissolved components (PP) and polyethylene (PE). Between the dry spinning) [1, 2]. UF membranes are
from water or wastewater feeds; in the two extremes, there is the polysulfone produced by phase inversion, whilst MF can
second, the membrane filtration process is (PS) / polyethersulfone (PES) family, be made by either process. Phase inversion
used for the removal of fine particulates. polyacrylontrile (PAN), and polyv inylidene has the advantage of enabling the pore
RO/NF is long established, and has evolved fluoride (PVDF). Though these polymers are size to be varied over a wide range with a
hydrophobic, membranes made from them structure that can be precisely controlled.
to a mature product offering in which most
can be modified to some extent through The phase inversion can be solvent based
products have similar membrane materials,
the use of additives, either as co-polymers, (the so called wet spinning process) or
module formats, and process design. Indeed,
pore formers, or by post treatment. To be temperature based (the Thermal Induced
standard spiral wound RO elements are often
cost effective in large scale applications, it Phase Separation (TIPS) process). In either
interchangeable, and system designs based on case, the membrane is formed by inducing
is important that the membrane polymer
products from one manufacturer may be able precipitation which occurs when the
is a commodity product of low or medium
switch to another. polymer solution containing the membrane
price. The earliest commercial products in
Membrane filtration has not developed the water and wastewater field were based on polymer is destabilized. For wet spinning,
interchangeable products, though a degree PS, CA, and PP, though most of the market the polymer or polymer solution needs to be
of commonality is beginning to emerge.
The existence of more choices in membrane
filtration is both due to the relative newness
of this application in water and wastewater
treatment, and due to the fact that the
optimum technical choice between different
approaches may be a close call, varying from
application to application. This paper will
consider the factors that have influenced
the development of the range of commercial
products currently available. Through an
examination of the pros and cons of the
alternatives, the reasons for the current
diversity of commercial products will be
explored and guidance will be provided for the
user in selecting the most suitable membrane
for their particular application. Figure 1. Comparison of physical stability - membrane materials (N.B. recent PAN improved (ref. Kiwa))
36 Feature
Filtration+Separation April 2007

strength and flexibility. PES has similar

Figure 2: Relative Hydrophilicity of Membranes
mechanical properties to those of PS.
Hydrophilic Hydrophobic
Figure 1 shows that PS and PVDF are the
CA PES PAN PVDF/ PS PE, PP
strongest polymers, whilst PVDF is more
CA is naturally hydrophilic flexible. Flexibility is highly desirable if air
PS, PES, PAN, and PVDF are naturally quite hydrophobic, but can be blended with additives and scour is used for the cleaning process, and
pore formers to make a moderately hydrophilic membrane PVDF is commonly used for formats which
rely on air use such as MBRs and outside
PE and PP are hydrophobic, and are difficult to modify feed configurations. More recent work by
Kiwa [8] has shown that different polymer
sources can affect the physical properties,
Figure 3: Pros and Cons of Different Membranes so the figure needs to be used with some
CA caution. Also, the membranes derived from
good permeability and rejection characteristics polymers can vary widely in their properties
according to the preparative conditions,
susceptible to hydrolysis
membrane dimensions etc. Thus for
limited pH resistance example, recent PAN membranes perform
chlorine tolerant and fouling resistant much better than indicated in the figure,
with significantly improved flexibility. The
PES, PVDF (PS, PAN)
Kiwa survey of field experience has shown
ability to modify properties through polymer blend that PVDF membranes have low fibre
good strength and permeability breakage rates, whereas the breakage rates
PVDF best for flexibility, and use with air scour for PES single fibre products are somewhat
higher (though still within end user
PES best for polymer blending and UF rating
requirements in most cases). A multi-bore
PE, PP PES product is cited with very low breakage
susceptible to oxidation rates.
limited blend capability In addition to mechanical properties,
chemical resistance is equally important.
soluble in a solvent that can be worked with to produce satisfactory MF membranes, Membrane processes have developed to allow
easily. The membrane polymer is dissolved though permeability may be low due to a degree of fouling, which is then reversed
in the solvent and subsequently precipitated low pore density, and the variation of by cleaning. Resistance to common cleaning
by contact with a non solvent. CA, PS/ membrane pore size may be much less than agents is therefore of great importance. In
PES, PVDF, and PAN all lend themselves the wet spinning process. Dry spinning broad terms, there are three groups of fouling
to wet spinning. In the TIPS process, the produces slit shaped pores, unlike the agents, and these foulants are best removed
precipitation of the membrane is induced by circular pores of wet spinning. Slit shaped by different cleaning agents:
a change in temperature, and this process pores give a wider pore size distribution • Organics – removed most effectively
can be used for PVDF membranes. (psd), and produce a less defined removal by caustic, but also removed by high
efficiency from the feed. PE can be made concentrations of chlorine and other
The solubility of PS/PES makes these
hydrophilic by post treatment, but although cleaning approaches are sometimes used
polymers ideal candidates for polymer blend
membranes since other polymers can be co- these membranes are used successfully in
membrane bioreactors (MBRs), they are • Inorganics – removed by mineral acids (eg
dissolved, allowing the hydrophilic properties
not used in conventional MF products. PP scale) or by citric acid (eg Fe or Mn)
of the finished membrane to be modified and
enhanced. An advantage of wet spinning is is used in MF products, but cannot be made • Biofouling – removed most effectively by
that pore size and other membrane properties hydrophilic. Cl2, but other oxidants or a pH change
can be widely varied, dependent on the may be used.
spinning conditions chosen. PS/PES can be Membrane properties
made hydrophilic with the appropriate blend The process of making the UF and MF
polymers [3,4], thereby gaining the advantage Table 1: PVDF vs PES Comparison
membranes has to control both the
of the hydrophilicity of CA, whilst avoiding Parameter PVDF PES
surface characteristics, and the supporting
the primary disadvantages of CA, namely
sub-structure. Polymers have to have Polymer cost Hi Med
biodegradability, and poor tolerance to
caustic cleaning chemicals. good mechanical properties, to produce UF rating Med Hi
membranes which combine burst and
Permeability Med Hi
PVDF membranes can be formed by wet collapse strength with a reasonable degree
spinning [5] and TIPS processes [6], but it of flexibility. Also, they need to have good Caustic Med Hi
is more difficult to modify since hydrophilic chemical resistance, tolerating a wide pH resistance
additives tend to lead to macrovoid range, and high chlorine concentrations, Chlorine Hi Med
formation and a weakening of the structure enabling rigorous cleaning to be conducted resistance
[7]. Accordingly, most commercial PVDF if necessary. In addition, thermal resistance Feed range Hi Med
membranes are relatively hydrophobic with should be good, so that moderate elevated
surface characteristics close to the unmodified Fibre breaks Nil - Lo Med *¹
temperatures can be used without affecting
polymer. the membrane properties or life. Figure Membrane Life Hi Med - Hi

Dry spinning is used for hydrophobic 1 from the Toray web site shows how the *¹ Fibre breakage experience refers to single bore
fibres
polymers such as PP and PE. It tends common polymers compare in terms of
 Feature 37
Filtration+Separation April 2007

Of the polymers discussed above, the PS/PES membrane is easily wetted, and this results The PS/PES family and PVDF are now
family has the widest chemical resistance, in easy commissioning procedures and high emerging as the dominant polymers of
and can tolerate a pH range from 1.5 to 13, permeabilities relative to the pore size. choice for the water industry. Both of these
as well as moderate chlorine levels. PDVF Ready wetting ensures that an air based polymer families have excellent properties
tolerates acids, but is limited to pH 11 with integrity test can be carried out without the for the products in which they are used. PS/
caustic. However, its major advantage is risk of drying out (repeated contact of air PES can have the advantage of producing
a very high tolerance to chlorine, which with a hydrophobic surface will lead to a a hydrophilic membrane, and achieving a
makes it ideal for MBRs. PVDF membranes progressive loss of wetting). good UF rating. Also, it has excellent all
tend to use chlorine cleaning in applications round chemical tolerance. PVDF is excellent
Secondly, the fouling constituents often
where PS/PES may opt for caustic. PAN has for strength and flexibility, with very high
present in surface water sources are organics,
similar pH tolerance to PVDF, combined Cl2 tolerance. It tends to produce a coarse
which readily attach to a hydrophobic
with a moderate chlorine tolerance
(probably similar to PS/PES).
surface. A hydrophilic surface tends to resist UF/fine MF rating. •
attachment due to absorption by organics, Contact:
CA is much more limited in its chemical and such a surface is referred to as a low Graeme Pearce
resistance, since its natural hydrophilicity fouling surface. Experimental work has [email protected]
makes it susceptible to hydrolysis in the shown that for a given membrane polymer
presence of acids below pH 4 and caustic and feed, a hydrophilic character has an References
above pH 8. It tolerates chlorine, but is advantage in resisting adsorptive fouling [9].
biodegradable which makes it sensitive to However, many factors influence fouling, [1] Basic Principles of Membrane
bacterial attack. Despite these limitations, both in the feed (eg ionic strength), and in Technology,
CA can be effectively used in applications the membrane (eg surface roughness, pore M Mulder, Enschede, The Netherlands,
where chemical cleaning requirements are density etc), so predicting the most suitable 1990
limited, such as groundwaters and some membrane for a particular application is not
[2] Membrane Formation and Modification,
surface waters. a straightforward exercise [10].
I Pinnau & B D Freeman (Ed), ACS
The polyolefin family, PP and PE, has A disadvantage of a hydrophilic membrane Symposium Series No. 744, Las Vegas, 1997
good tolerance to acid and caustic, but low is that robustness and longevity may not
[3] Microfiltration: membrane development
tolerance to chlorine, particularly in the be as good as for hydrophobic membranes.
and module design, H D W Roesink, PhD
case of PP. The lack of chlorine tolerance The most common example of a moderately
Thesis, University of Twente, Enschede, Nl,
is a major limitation in the water industry, hydrophobic membrane used commercially
1989
and this has limited the prospects for these is PVDF, and this is particularly known for
membranes. strength and long membrane life. Figure [4] Microstructures in phase inversion
2 shows the membrane polymers used in membranes Pt 2. Role of polymeric
In the early years of the water market, PS,
the water industry on a spectrum of the additives, R M Boom, I M Wienk, Th van
CA and PP were the major membranes,
relative hydrophilicity of the commercial den Boomgaard, C A Smolders, Journal of
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All of the membranes discussed in this
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A hydrophilic surface is one which is
different products and operating methods Kiwa
completely wetted by water, whilst on a
have developed to take best advantage of
hydrophobic surface, water forms beads or [9] Natural organic matter fouling of
the strengths of the various membranes.
droplets. The degree of hydrophilicity is low pressure systems, J Lozier, G Amy,
measured by the contact angle of the water Important properties for a membrane J Jacangelo, C Mysore, B Heijman,
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has some obvious advantages. Firstly, the product. Univ of New South Wales, Australia, 1999.