Fouling Membran Nano PDF

Separation and Purication Technology 63 (2008) 251263
Contents lists available at ScienceDirect
Separation and Purication Technology

journal homepage: www.elsevier.com/locate/seppur
Review
Drawbacks of applying nanoltration and how to avoid them: A review
b,1 , M. Nystrom
b,1
B. Van der Bruggen a, , M. Mantt
ari
a
K.U.Leuven, Department of Chemical Engineering, Laboratory for Applied Physical Chemistry and Environmental Technology, W. de Croylaan 46, B 3001 Leuven, Belgium
Lappeenranta University of Technology, Department of Chemical Technology, Laboratory of Membrane Technology and Technical Polymer Chemistry,
P.O. Box 20 FI-53851 Lappeenranta, Finland
b
a r t i c l e
i n f o
Article history:
Received 26 February 2008
Received in revised form 6 May 2008
Accepted 10 May 2008
Keywords:
Membrane ltration
Nanoltration
Fouling
Concentrates
Fractionation
Water treatment
Drinking water
Wastewater
a b s t r a c t
In spite of all promising perspectives for nanoltration, not only in drinking water production but also
in wastewater treatment, the food industry, the chemical and pharmaceutical industry, and many other
industries, there are still some unresolved problems that slow down large-scale applications. This paper
identies six challenges for nanoltration where solutions are still scarce: (1) avoiding membrane fouling,
and possibilities to remediate, (2) improving the separation between solutes that can be achieved, (3) further treatment of concentrates, (4) chemical resistance and limited lifetime of membranes, (5) insufcient
rejection of pollutants in water treatment, and (6) the need for modelling and simulation tools.
The implementation of nanoltration in the industry is a success story because these challenges can be
dealt with for many applications, whereas more research would result in many more possible applications.
It is suggested that these challenges should be among the main priorities on the research agenda for
nanoltration. This paper offers an overview of the state-of-the-art in these areas, without going into
details about specic observations in individual studies, but rather aiming at giving the overall picture
of possible drawbacks. This leads to suggestions which direction the nanoltration research community
should follow, and where research questions can be found. Evidently, the six identied challenges are
to some extent interrelated; mutual inuences are explained as well as possible solutions, or possible
pathways to solutions.
2008 Elsevier B.V. All rights reserved.
Contents
1.
2.
3.
4.
5.
6.
7.
8.
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Membrane fouling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Insufcient separation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Treatment of concentrates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Membrane lifetime and chemical resistance . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Insufcient rejection for individual compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Modelling and simulation of nanoltration . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
1. Introduction
The introduction of new technologies always involves transition
phenomena, such as unexpected start-up problems, discussions
between believers and non-believers, and research efforts leading
Corresponding author. Tel.: +32 16 32 23 40; fax: +32 16 32 29 91.

E-mail addresses: bart.vanderbruggen@cit.kuleuven.be (B. Van der Bruggen),
mika.manttari@lut. (M. Mantt

ari),
marianne.nystrom@lut. (M. Nystrom).
1
Tel.: +358 5 621 2192; fax: +358 5 621 2199.
1383-5866/$ see front matter 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.seppur.2008.05.010
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to fundamental understanding, suggestions for practical solutions

and technical improvements. Nanoltration was dened as a process intermediate between reverse osmosis and ultraltration that
rejects molecules which have a size in the order of one nanometer
[1]. It was introduced in the late 1980s, mainly aiming at combined
softening and organics removal [1]. Since then, the application
range of nanoltration has extended tremendously. New possibilities were discovered for drinking water production, providing
answers to new challenges such as arsenic removal [27], removal
of pesticides, endocrine disruptors and chemicals [811,6,12,13],
and partial desalination [1417]. Large plants were constructed, the
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B. Van der Bruggen et al. / Separation and Purication Technology 63 (2008) 251263
best documented example being the Mery-sur-Oise

plant in France,
which was started in the second half of the 1990s [18,19].
During the last decade, the interest in the use of membrane technology in general and nanoltration in particular has emerged in
wastewater treatment as well as drinking water and process water
production. This growth can be explained by a combination of (1)
growing demand for water with high quality, (2) growing pressure
to reuse wastewater, (3) better reliability and integrity of the membranes, (4) lower prices of membranes due to enhanced use, and (5)
more stringent standards, e.g., in the drinking water industry.
The number of applications for nanoltration increases steadily;
nevertheless, several challenges remain to be solved to allow the
use of nanoltration in more demanding applications. Drinking
water production, still the largest application of nanoltration in
terms of volumes, currently faces new challenges. The notion of
impeccable drinking water developed in the Water Quality 21
research programme in the Netherlands [20] and the growing concerns in the USA on the presence of emerging contaminants [21]
induced a shift towards less permeable, high rejection membranes,
which can be denoted as (low pressure) reverse osmosis membranes. For tight nanoltration membranes and reverse osmosis
membranes, knowledge on which solutes are removed to what
extent is needed.
The potential for nanoltration in wastewater treatment and
water reuse is noteworthy [2225], but hindered by unstabilities in
operation caused by membrane fouling. Extensive research projects
in which nanoltration was used for water reclamation have been
carried out; in the majority of these, membrane fouling was studied
as a potential problem. Industrial plants may be successful [26,27],
but their success depends on a thorough understanding of possible
interactions between the feed solution and the membrane, causing organic fouling, scaling, biofouling, or particulate fouling. When
wastewater is to be treated, the concentrate is usually another problem [28,29]. The discharge option is often compromised by the
increase of concentrations in the remaining fraction after membrane treatment. This can also be problematic for drinking water
production, when discharge is not possible or not allowed, or when
the yield is considered too low for a valuable, permit-protected
source such as groundwater.
The chemical processing industry and the pharmaceutical
industry are other potential beneciaries of nanoltration. Huge
savings could be obtained by implementing membrane technology; environmental benets due to reduced energy consumption
make nanoltration particularly attractive [30,31]. Drawbacks in
this area are of a different kind; for solvent ltration, one of the
emerging applications, these are mainly related to membrane stability and lifetime [32], and the lack of fundamental understanding
of the process performance that can be translated to modelling and
simulation tools [3336].
The food industry traditionally adopts new technologies relatively fast. The dairy industry was among the rst users of
nanoltration [37]. Nevertheless, the challenges in the food industry are high. Standards for food products are very high and emerging
applications, such as low fat products, low calories products, and
products suitable for special diets require more and improved
separations. Based on its potential to separate monovalent and multivalent ions, and to separate organic solutes with different size
from one another, nanoltration could be the promise for the future.
However, separation factors are often insufcient, which limits the
potential.
This review gives a systematic overview of reported impediments for nanoltration, and possible solutions to solve these
problems. Solutions may be directly suggested from the literature,
or can be derived from a critical assessment of the state-of-theart in nanoltration. Challenges that will be covered in this review
are (1) membrane fouling, its causes and possibilities to remediate, (2) separation between solutes that can be achieved, (3)
further treatment of concentrates, (4) chemical resistance of membranes, (5) insufcient rejection in water treatment, and (6) the
need for modelling and simulation tools. It must be stressed that
many applications are already running regardless of these suggested improvements. Nevertheless, one should be aware that more
can be done if the limitations can be overcome.
2. Membrane fouling
Fouling is one of the main problems in any membrane separation, but for nanoltration it might be even somewhat more
complex because of the interactions leading to fouling take place
at nanoscale, and are therefore difcult to understand [3844]. Its
negative consequences are obvious and include the need for pretreatment, membrane cleaning, limited recoveries and feed water
loss, and short lifetimes of membranes. In that sense, membrane
fouling is closely related to other problems such as concentrate
treatment and membrane stability and lifetime: a total control of
fouling would reduce the need for cleaning and would enhance the
permeate yield.
Foulants playing a role for nanoltration membranes can be
organic solutes, inorganic solutes, colloids, or biological solids
[45]. An extensive description of the consequences of fouling in
nanoltration can be found in the literature [46], including indices
describing the feed water fouling potential and the post factum
analysis by membrane autopsy. Boussu et al. [4749] extended the
study of membrane characteristics to prediction and interpretation of fouling caused by organic solutes, colloids and surfactants.
Fouling of organic solutes is thought to be mainly caused by adsorptive interactions with the membrane material [5052]. Fouling
and adsorption can be related to component properties, which is
reected by the correlation between the octanolwater partition
coefcient (log P) and adsorption; adsorption is also related to the
dipole moment and the water solubility [52]. Concerning the membrane characteristics, the hydrophobicity of the top layer is believed
to cause the most ux decline [53,54]. For charged organic compounds, electrostatic attraction or repulsion forces between the
component and the membrane inuence the degree of fouling. A
necessary condition for this is that the membrane surface charge is
large enough; otherwise hydrophobic forces overcome the electrostatic forces resulting in more fouling of hydrophobic membranes
[55].
Depending on the relative size of colloidal particles and membrane pores, colloidal fouling may occur either due to accumulation
of particles on the membrane surface and build-up of a cake or by
penetration within the membrane pores [5659]. It is assumed that
colloidal fouling is related to membrane roughness [60,61]: colloids
are thought to be preferentially transported into the valleys, which
results in valley clogging. In addition, surface hydrophobicity and
permeability also play a role [6264].
The size, charge and concentration of the colloids also inuence
fouling in nanoltration. An increase in colloid concentration leads
to an increase in fouling [58,63,6567]; a larger colloid size may
have either a negative [63] or a positive effect [56,68] on fouling in
comparison with smaller colloids.
Inorganic fouling is related to scaling, i.e., precipitation of salts
on the membrane surface [46]. Nanoltration membranes retain
ions, causing an increase of the concentration at the membrane
surface, which may exceed the solubility limit at a certain point
in the ltration module. The most common constituents of scale
are calcium carbonate, gypsum, barium/strontium sulphate and silica, although other potential scalants exist [46]. Scaling is a purely
thermodynamic process involving a phase change, which requires
a degree of supersaturation. In general, the point of saturation can

be estimated from the activities of the ions involved in the precipitation reaction; nevertheless, it is difcult to determine the critical
point of supersaturation.
Biofouling is a general problem with many membrane processes
and involves all biologically active organisms, mainly bacteria
and (in some cases) fungi [46]. Biofouling is a dynamic process
and involves the formation and growth of a biolm attached to
the membrane. The biolm may reduce the water ux and even
totally prevent water passage. For nanoltration of wastewater, the
biolms were found to have a thickness of 2030 m [69]. Biofouling is not a specic problem for nanoltration, in contrast to
scaling and adsorption of small organic solutes: these may (partly)
penetrate into the membrane, whereas bacteria are too large and
will remain in the supercial biolm. Nevertheless, it is suggested
[69,70] that the formation and accumulation of exopolymeric substances (EPS) is the real cause of ux decline when biofouling
occurs.
Classical solutions to fouling are the optimization of pretreatment methods and cleaning of membranes. Suggested
pretreatment methods often make use of other pressure driven
membrane separations such as ultraltration and microltration
[7173]; other options include ozonation or UV/H2 O2 oxidation,
adsorption (PAC) and occulation [74,75]. An extensive overview
of pretreatment methods can be found in the literature [76].
Cleaning of nanoltration membranes has become a research
area on itself [7779]. Nevertheless, in practical applications cleaning is usually considered in a very pragmatic way. Physical cleaning
may be a signicant part of the cleaning protocol and includes ushing (backush, forward ush, reverse ush), scrubbing, air sparging,
vibrations and sonication [46,80,81]. Membrane design and process
conditions may help in this by increasing the efciency of physical
cleaning, up to the point where direct nanoltration without pretreatment can be applied [82]. Chemical cleaning involves chemical
reactions such as hydrolysis, saponication, solubilisation, dispersion, chelation, and peptisation [83]. Membrane manufacturers
often develop specic cleaning strategies and products suitable for
their own membranes. However, it should be taken into account
that the cleaning protocol should also depend on the characteristics
of the feed solution. This leads to a wide variety of cleaning mixtures and protocols in the literature [8486]. In addition, enzymatic
cleaning may be considered [87].
Membrane modication is potentially the most sustainable
solution to obtain fouling-resistant membranes [77]. The idea is to
insert hydrophilic groups into a polymeric structure, so that the
overall material becomes more hydrophilic and thus less prone
to (organic) fouling. Ultraltration membranes are often taken as
starting point; a hydrophilic nanoltration membrane is obtained
by grafting [8890]. Nanoltration membranes can be modied by
ion beam irradiation in view of obtaining fouling-resistant membranes [91]. However, it is not clear to what extent the newly
obtained membranes are stable.
Colloidal fouling may be reduced by developing membranes
with lower surface charge or surface charge similar to that of
the foulant. Increasing the hydrophilicity may also be benecial
to reduce colloidal fouling. Surface roughness may also increase
membrane fouling by increasing the rate of attachment onto the
membrane surface [77]; it is accepted that membranes with a rough
surface are more prone to fouling than membranes with a smoother
surface [92]. Biological fouling can be reduced by the addition of,
e.g., silver nanoparticles in the membrane structure [93].
An intrinsic solution to the problem of membrane fouling could
be the concept of critical or sustainable ux [94]. The critical ux
is the maximal ux where fouling interactions remain reversible;
when operating below the critical ux, ux decline can be reversed
253
Fig. 1. Critical ux for paper mill efuent for a at sheet membrane module (temperature: 40 C, cross-ow velocity 2.7 m/s). Open circles: pressure increase; black
circles: pressure decrease; black squares: pressure decrease after the maximum
pressure.
by non-destructive measures. The critical ux concept has a sound

theoretical basis; it represents the shift from repulsive interaction
(dispersed matter-polarised layer) to attractive interaction (condensed matter-deposit) [94]. The concept of a sustainable ux
evolved from the critical ux theory and can be considered a generalisation: the sustainable ux is dened as the ux above which the
rate of fouling is economically and environmentally unsustainable.
The sustainable ux depends on hydrodynamics, feed conditions
and process time, and is therefore difcult to determine. Nevertheless, the understanding of this principles leads to guidelines for
operational conditions where fouling is minimal [95,96]. A typical
example is shown in Fig. 1 for paper mill efuent, where the pressure was stepwise increased and decreased; it can be clearly seen
that the critical ux in this case is around 50 l/m2 h.
3. Insufcient separation
Internationally, nanoltration has known a breakthrough since
the last decade in areas related to water treatment and drinking water production [97], where it is used for softening and
removal of pollutants (micropollutants such as pharmaceutically
active compounds, pesticides and other relatively small organic
solutes). Nanoltration can also be applied for more challenging
applications, involving fractionation rather than purication. It is
well known that nanoltration membranes can be used for salt fractionation [98101] since the rejection of monovalent salts is lower
than that of multivalent salts. An extreme case of charge-induced
separation is the observation of negative rejections of monovalent
ions in the presence of multivalent ions or polyelectrolytes [102].
Typically, the rejection of a divalent ion of the same charge as the
membrane is above 95%, whereas the rejection of a monovalent ion
of the same charge can be anywhere between 20 and 80% [103].
Thus, nanoltration membranes allow ion fractionation, which is
a signicant advantage and one of the reasons of the fast commercial growth of the process. Nevertheless, the separation factors
obtained with nanoltration are relatively modest, typically 510.
Many applications of ion separation can be found [104107]. A wellknown application is the separation of peptides based on charge
differences [108]. In the latter case, the solution pH is often the key
to control the desired separation.
254
Fig. 2. Typical sigmoidal rejection curve obtained for rejection of uncharged solutes
with a nanoltration membrane.
For uncharged solutes, however, (nanoltration) membranes are

characterised by a sigmoidal rejection curve (rejection as a function
of molar mass) [109], which results in an insufcient separation
between different compounds on the basis of molecular size. A
typical sigmoidal rejection curve is given in Fig. 2. Furthermore,
the separation depends on hydrophobicity and charge interactions
[110]. Therefore, the permeate contains molecules with variable
size, both below and above the claimed pore size of the membrane.
Either the permeate or the retentate is to be considered as a waste
fraction.
Fractionation using membranes (including nanoltration) is
considered by many authors, but usually in the sense that nanoltration is preceded by either ultraltration or microltration, or
followed by reverse osmosis [111114]. The fractions obtained in
this way are orders of magnitude different in molecular size, and
a ner fractionation (between solutes with size in the nanometer
range and below) is seldomly reported.
In the pharmaceutical industry, many possible applications of
fractionation in the nanorange are to be found. Pharmaceutically
active compounds and intermediates are often thermally labile
(which makes a distillative separation difcult or impossible), and
have to be separated from smaller or larger side products, remaining reagents and the solvent. A single membrane separation is often
insufcient to obtain the desired separation because it is impossible to retain one component completely and at the same time
allow a second component, slightly different in size or charge, to
pass completely. The incompleteness of the separation is a major
impediment for a wide application of membrane processes, including nanoltration. A multiple membrane passage may improve
the overall rejection but not the separation between different
individual compounds. Dialtration is sometimes a good solution
when product recovery is considered, such as in solvent exchange
[115], but is not applicable for separation of individual solutes. The
use of continuous counter current integrated membrane cascades
with recycle, in analogy with (conventional) separations based on
thermodynamic equilibrium (presented in Fig. 3), may allow better separations between individual compounds, or fractionation
of a mixture. This should allow realising any separation, i.e., to
obtain simultaneously a nearly complete rejection of component
A, and no removal of component B, slightly different in molecular
size (or any other parameter playing a role in transport through
the membrane). To this date the separation that can be attained
with a nanoltration cascade has not received much attention.
For gas separations with membranes, cascades have been studied and are well known as integrated separation processes [116].
For liquid separations there is no knowledge on cascades, apart
from some exploratory studies concerning module congurations
in reverse osmosis [117], which is a more or less similar idea. For
nanoltration, cascades have not been considered before; a multi-
Fig. 3. Schematic representation of the principle of a membrane cascade (adapted

from [116]).
step approach was recently suggested for purication of solvents

[118].
Fractionation is also of importance in the food industry. Again,
membranes are the key for these separations: the share of the
food industry is 2030% of the entire membrane market [119].
Nanoltration for food applications is the second largest after ultraltration [119]. Dairy applications were among the very rst where
nanoltration was used [120]. Using nanoltration, desalted lactose containing whey could be produced with a single process; ca.
40% of the salts in whey can be removed. By using dialtration, salt
removal can be even up to 90%. However, as previously stated, there
is a signicant product loss to permeate (lactose, in this case) when
dialtration is used. Another example is skim milk modication. A
precise control of the milk composition would open new possibilities in the area of tailor-made milk products; however, in spite of
the unsharp separation that can be achieved in one step, this seems
to be the rst and continuing success story of nanoltration [120].
In the sweetener industry, purication of xylose is an emerging application. This requires a challenging separation between
xylose and glucose, two compounds with only a slight difference in
molecular size and with similar properties such as, e.g., polarity. A
separation can be achieved, but it was shown to be extremely difcult [121]; the process is feasible when a single fraction (xylose) is to
be recovered with enhanced purity, but again, a sharp separation
is impossible using simple one-step solutions. Nanoltration can
be used more easily for separation of oligosaccharides [122124]
in combination with ultraltration, or even the separation of saccharides and salts (in dialtration mode) [125].
Nanoltration cascades can possibly also be used for purication of natural sweeteners. Stevia rebaudiana Bertoni is a plant
that contains very sweet steviol glycosides, of which stevioside
and rebaudioside A are the most abundant (Fig. 4). Stevioside and
rebaudioside A can be used as a natural sweetener in low doses
(maximum 200300 mg/day), without a signicant caloric value. It
Fig. 4. Chemical structure of stevioside.
is also safe for phenylketonuria patients who might be in danger

by consumption of large amounts of aspartame. High doses stevioside (7501500 mg/day) might be used in the treatment of the
metabolic syndrome (hypertension, diabetes type 2) [126].
It is obvious that food additives have to meet very strict requirements. During the isolation of the sweeteners from Stevia, safety
and sustainable techniques are needed. The use of solvents should
be avoided if possible. The sweeteners can be extracted with water.
After extraction, purication of the crude extract is needed to separate the products with a molecular mass between 800 and 1000
(sweetener fraction). This could in principle be done with nanoltration, but the separation that can be realised in this way results in
either a too low purity, or a large loss of the fraction between 800
and 1000. Nanoltration cascades are a possible solution to this. The
nal solution can be further concentrated by using reverse osmosis,
upon which the sweeteners can be crystallised.
4. Treatment of concentrates
The generation of a concentrate (or retentate) stream is an
intrinsic problem for pressure driven membrane processes, including nanoltration. For aqueous streams, the concentrate is often
an unwanted by-product of the purication process and has to be
discharged or further treated. This is per denition an unsolved
problem when the feed solution contains unwanted compounds
or a fraction that cannot be reused, since membranes only achieve
a separation and not a destruction or transformation. The composition of the concentrate is similar to the feed composition, but with
increased concentrations for components rejected by the membrane. The concentration factor CF can be calculated from the mass
balance for component i [29]:
Cr,i =
(Qf Cf,i ) (Qp Cp,i )

Qr
so that
CF =
Cr,i
Q
= f
Cf,i
Qr

1 (REC
Cp,i
Cf,i

,
where REC = recovery, Q = volumetric ow (l/h), C = concentration

(mg/l); the subscripts r, f, p and i refer to the retentate, the feed, the
permeate and the component used, respectively.
255
Additives such as anti-scalants (polyacrylates, polyacrylic acids,

polyphosphates) also end up in the concentrate; the addition of
sulphuric acid or hydrochloric acid inuences the pH of the concentrate. Chemical cleaning for removal of scaling, organic fouling
and biofouling from the membrane surface [79,127] results in
a (relatively small) additional waste stream, containing cleaning
chemicals such as acids (phosphoric acid or citric acid), bases
such as sodium hydroxide, complexing agents such as EDTA, polyacrylates, sodium hexametaphosphate) and disinfectants (H2 O2 ,
NaOCl).
Possibilities to treat or to discharge the concentrate [29] include
reuse, further treatment by removal of contaminants, incineration,
direct or indirect discharge in surface water, direct or indirect discharge in groundwater, and landlling.
Reuse is the most attractive option, but only applicable in few
cases where the concentrated fraction is the desired product, such
as in the food industry. The beverage industry uses a concentration step prior distribution, allowing to reduce the volume and the
related costs. Water is added at the point of usage; although some
avours may be lost, this method is generally used as the most efcient solution. Nanoltration is a cheap concentration method, used
as an alternative for reverse osmosis when salt permeation is not a
problem. The permeate is relatively pure water that can be used or
treated as a waste fraction. The concentrate is further dehydrated
to obtain a viscous liquid ready for distribution. Nanoltration is
applied to this purpose in several applications [128,129]. Other
examples in food processing where the concentrate can be reused
are to be found in the dairy industry, as already discussed. Nanoltration is used for the recovery of organic nutrients in so-called
second cheese whey [130]. The whey is processed by nanoltration to recover a rich lactose fraction in the concentrate and a
process water with a high salt content in the permeate. It should
be concluded that the challenge of obtaining a good separation is
intrinsically interconnected with the concentrate problem.
An example of a closed cycle in wastewater treatment can be
found in the tanning industry, where nanoltration is used for
the recuperation of chromium from exhausted chromium baths
[131134]. A combination of ultraltration and nanoltration can
then be used to recycle the tanning baths a concentration of Cr (III)
is obtained in the concentrate fraction; the concentrate can directly
be reused for retaining baths or further concentrated by precipitation (at high pH, addition of NaOH required) and dissolution (in a
concentrated sulphuric acid solution). The nanoltration permeate
contains a high chloride concentration, because monovalent ions
are almost not retained by the nanoltration membrane. This is an
advantage when the permeate is reused in pickle baths (saving in
chemicals to be added). The permeate is then a side product that
can be reused as a rinsing water, or discharged.
An integrated treatment system has been considered for water
reuse in a textile company based on nanoltration, in which the
concentrate generated from purication of exhausted dye baths
is entirely recycled by systematically separating all constituents
[135]. Nanoltration is applied after a classical wastewater treatment, and produces high-quality process water. The idea of a
zero-discharge system in the textile industry was already suggested
by a combination of chemical, biological and membrane processes,
but appeared to be quite challenging [136]. A combination of membrane processes was suggested for design of new productive cycles
[137], a concept now adopted in the terminology of process intensication. At present, the use of membrane processes in the textile
industry is still limited to one-step designs, which solves the problem of fresh water supply but not the waste (water) problem, since
the pollutant load is unchanged after concentration.
An integrated approach should comprise two main steps [135]:
removal of the organic fraction (dyes, additives), and removal of
256
the inorganic fraction (salts). After a pretreatment using microltration, the removal of the organic fraction can be done by
nanoltration using a membrane with low salt rejection at a high
temperature, close to the temperature of the dye bath. The permeate fraction contains a large fraction of inorganics; the organic
fraction should be low. The concentrate is mainly organic in nature.
Membrane distillation can be applied to separate the organic fraction from water, taking advantage of the elevated temperature of
the feed. The distillate is recycled to the nishing process; the
remaining organic fraction has an added value by utilizing its
energy content in an incineration process. The energy yield makes
up for the loss of energy by losses in the different treatment steps.
The nanoltration permeate feeds a second nanoltration unit,
where salts are retained using a relatively tight nanoltration
membrane with high salt rejection. The permeate from the second nanoltration unit is pure enough for reuse as process water.
The concentrate is a salt solution, comparable to the brine from
desalination processes, and can be used for salt production in a
membrane crystallizer [138]. The combination of all these membrane processes results in a zero-discharge system with energy
recuperation. A detailed description and calculation of this system
can be found in the literature [135].
If reuse of the concentrate is not feasible, further treatment can
be necessary before discharge. Two options for further treatment
can be distinguished: (a) further concentration, and (b) removal
of specic components by a proper choice of a selective treatment method. The rst option leads to a sludge or solid waste
that has to be reused (if possible), landlled (if necessary after
solidication/stabilisation or a similar pretreatment to avoid leaching of contaminants), or incinerated. The second option leads to
a (treated) wastewater, that has to be reused (if possible) or discharged in surface water (direct or indirect via sewage systems) or
in groundwater.
Concentrates resulting from drinking water production are a
special case. A distinction should be made between groundwater
and surface water. Nanoltration is not often used for production
of drinking water from groundwater, because (a) groundwater is
almost exclusively used when a source of good quality, not requiring extensive further (membrane) treatment, is available, and (b)
the concentrate that is generated is a large waste fraction, expensive and technically challenging to dispose of. For surface water,
nanoltration is a valuable option when the concentrate can easily
be discharged. A study in the Netherlands [139] revealed that disposal of the concentrate is a serious problem, especially in those
cases where no large surface water is present. In general, concentrate disposal as such was feasible, as long as a limited number of
parameters such as sulphate, chloride, phosphate, iron and antiscalant were under control.
Other factors than the volume and composition that have to
be taken into account are legal requirements such as allowances
and conditions; cost of further treatment; local factors such as the
proximity and size of a wastewater treatment plant, the presence of
surface water or open land, soil characteristics and geological structure; exibility of the disposal method in case of an expansion of the
existing plant; and public acceptance. Release of micropollutants to
the concentrate was also mentioned as a risk [140].
5. Membrane lifetime and chemical resistance

Membrane lifetime and chemical resistance of nanoltration
membranes is related to the occurrence of fouling (and therefore,
the need for cleaning), and the application of nanoltration in
demanding circumstances such as in solvent resistant nanoltration. These are well-known problems for nanoltration and other
membrane processes, and their impact is usually studied from a

pragmatic point of view, i.e., as a solution to specic ltration
problems. This includes the choice of membrane materials, operating conditions, energy consumption, cleaning chemicals, permeate
yield and overall environmental impact.
For aqueous applications, membrane lifetime depends signicantly on the cleaning frequency and the overall strategy against
membrane fouling. Applications where fouling requires frequent
cleaning often face a faster membrane deterioration, because cleaning agents also damage the membrane to some extent. This has
resulted in various cleaning protocols proposed by membrane
manufacturers, as explained above. Examples of these cleaning protocols can be found in the literature [46,8487]. Alkaline cleaning
[46] is essential for the removal of organic foulants, or inorganic
colloids coated by organics from the surface of the membrane and
from the pores of the membrane. It was found that ca. 50% of all
foulants are organic in nature [141], therefore, alkaline cleaning
is the rst measure to be taken in general. In most cases a high
pH is obtained by using sodium hydroxide and sodium carbonate; this is often combined with a anionic or nonionic surfactant
allowing to emulsify fat containing particles and to prevent foulants
from adhering to the surface. Alkaline cleaning requires a pH often
above the window of chemical resistance of the membrane, which
is possible by limiting the contact time with the cleaning solution.
Nevertheless, repetition of alkaline cleaning may damage the membrane. The outcome may be positive as well: increased uxes and
unchanged rejections were observed after alkaline cleaning [142].
Acid cleaning [46] follows the same principles, using nitric acid,
citric acid, phosphonic acid or phosphonic acid to obtain a low pH
(12) The purpose in this case is the removal of scale, since precipitated salts are more soluble at low pH. Again, this requires going
outside the applicable pH window for a short time, which determines the membranes lifetime in the long run. Enzymatic cleaning
can be applied in more mild conditions, but can only be applied
for specic foulants (often polysaccharides as excretion products
of biofoulants). Finally, biocides may be necessary to destroy biofoulants; these products are mainly based on oxidation (chlorine,
ozone) and therefore also attack the membrane to some extent.
This is usually indicated by the manufacturer as a maximal chlorine
tolerance.
A solution where membrane deterioration is completely absent
does not exist. However, a good strategy should minimise the
impact of cleaning by using well-chosen cleaning agents, tailored
for the specic application. This usually requires trial-and-error.
It must be pointed out that in this procedure, the only parameter is usually the cleaning efciency by the water ux recovery,
the clean water ux recovery or the change in membrane resistance [46]. Considerations about membrane lifetime are not usually
taken into account, although the importance is known and recognised. Membrane autopsy could help in making the optimal choice,
especially when biofouling is the problem [143]. Inorganic foulants
(scale) can be determined by ICP-MS [144]; determination of the
specic nature of organic foulants is difcult, although in many
cases conclusions can be made, especially when some information about the possible foulants is available. This is, for example,
the case for determination of EPS deposits [145], NOM [146], trace
contaminants [147] and even organic deposits in general [148].
Compatibility of polymeric membranes with a wide range of
organic solvents for solvent resistant nanoltration is a new and
even more challenging issue in discussions about membrane lifetime. Membranes can be made more stable by, e.g., increasing the
degree of crosslinking of the polymeric top layer [149], by using
alternative membrane materials such as poly(organophosphazene)
[150], crosslinked poly(urethanes) [151], lled PDMS [152], and
polyimide [153], or by improving more common materials such
257
Table 1
Solvent resistant nanoltration membranes and membrane characteristics as specied by the manufacturers
Membrane
N30F
NF-PES-010
MPF-44
MPF-50
Desal-5-DK
Desal-5-DL
SS-030505
SS-169
SS-01
HITK-1T
StarMem-120
StarMem-122
StarMem228
a
b
c
d
e
f
g
h
i
j
k
l
m
n
o
p
q
Manufacturer
a
Nadir
Nadira
Kochd
Kochd
Osmonicsh
Osmonicsh
SolSepj
SolSepj
SolSepj
HITKo
METp
METp
METp
Material
PES
PES
PDMS
PDMS
PA
PA
k
k
k
TiO2
PI
PI
PI
MWCO (Da)
400
1000
250
700
150300
150300
g
g
g
g
200
220
280
Tmax ( C)
95
95
40
40
90
90
90
150
150
g
60
60
60
L (l/h m2 bar)
b
1.01.8
510b
1.3b
1.0f
5.4b
9.0b
1.0l
10l
10l
5b
1.0q
1.0q
0.26q
R (%)
7090c
3050c
98e
g
98i
96i
>90m
95m
97n
g
g
g
g
Nadir Filtration GmbH, Wiesbaden, Germany.

Pure water permeability.
4% lactose (MW 342).
Koch Membrane Systems, Wilmington, MA, USA.
5% sucrose (MW 342).
Methanol permeability.
Not specied.
GE Osmonics, Vista, CA, USA.
MgSO4 .
SolSep BV, Apeldoorn, The Netherlands.
Covered by secrecy and non-analysis agreement.
Ethanol permeability.
MW 500 in ethanol.
MW 1000 in acetone.
Technische Keramik, Hermsdorf/Thuringen,
Hermsdorfer Institut fur

Germany.
Membrane Extraction Technology, London, UK.
Toluene permeability.
as poly(acrylonitrile) [154]. An overview of solvent resistant

nanoltration materials can be found in the literature [32,155];
commercially available membranes are summarised in Table 1
[156].
Solvent resistant nanoltration is successful even on large scale
in many applications [31]. Nevertheless, its success depends on
a careful analysis of the separation problem, a good membrane
choice and small-scale testing. Recurrent problems are dissolution, deformation or swelling of the membrane. Swelling values
of up to 170% have been reported [157]. It has been shown that
swelling follows very complex mechanisms and may be signicantly inuenced by pressure, which indicates that compaction
plays a secondary role. The properties of the solvent itself determine
the degree of swelling for a given membrane. For example, it was
observed that for mixtures of xylene and heptane with methanol,
ethanol or propanol, reduced swelling occurred as the concentration of alcohol increased [157]. Other studies describe the changes
in performance as complex solventsolutemembrane interactions
[158] involving pore solvation (and solute solvation) rather than
swelling. These approaches may explain the dynamic behaviour of
polymeric membranes when applied in organic solvents; however,
it is not clear to what extent swelling shortens the membranes
lifetime. Nevertheless, it can be assumed that swelling may lead to
membrane deterioration in the long run.
Changes in the membrane performance or instability of polymeric membranes in organic solvents is not always visible [159].
Even when there was no apparent interaction between membrane
and solvent (damage), membrane properties might have changed.
Pore sizes may have changed, or the hydrophobic (hydrophilic)
character of the membranes may have shifted towards a more
hydrophilic (hydrophobic) one. An early study of nanoltration
membranes assumed to be stable in at least some organic solvents
[159], three out of four rst generation membranes showed visible defects after exposure to one or more organic solvents (Fig. 5),
and the characteristics of all four membranes changed notably after

exposure to the solvents. Therefore, stability of polymeric membranes in organic solvents is a very relative concept: the membrane
might look unchanged, but membrane characteristics could have
changed to a certain extent, ranging from a slight difference to a
total loss of selectivity.
The development of ceramic nanoltration membranes for
applications in organic solvents may solve the problems of swelling,
changes in performance, and limited lifetime, due to their superior chemical resistance. Ceramic membranes are substantially
more expensive, but this may be compensated by higher uxes
(especially at high temperatures) and the prolonged lifetime.
However, only few ceramic nanoltration membranes are commercially available today, in spite of the good performance of
Fig. 5. Effect of exposure to a range of organic solvents (methylene chloride,

n-hexane, ethyl acetate, ethanol, acetone) of a rst generation solvent resistant
nanoltration membrane.
258
these membranes. Hydrophilic ceramic nanoltration membranes

in asymmetric multilayer congurations have been successfully
developed since the late 1990s [160162]. These consist of an open
porous support, mesoporous interlayers, and defectless microporous top layers made of (hydrophilic) alumina, zirconia or titania.
Attempts have been made to make these ceramic membranes
hybrophobic, so that ltration of non-polar solvents would be feasible. However, this is work in progress and needs to be further
developed.
6. Insufcient rejection for individual compounds
Being regarded as low pressure reverse osmosis membranes
in the 1980s, nanoltration had the advantage of lower energy
consumption due to higher uxes, resulting from a more loose
membrane structure with more free volume in the polymer.
Reduced cost for applications where complete rejection of (mainly)
ions was not necessary has paved the way to many applications
of nanoltration. However, one of the new trends in water treatment is the demand for complete absence of all possible pollutants,
even at ultra-low concentrations. This may be a subjective customer
criterion not necessarily based on risks or toxicity, but it is a reality that has to be recognised. It is to some extent related to new
advances in analytical chemistry, allowing detection of pollutants
at concentrations in the range of ng/l, but the trend can also be
seen for suspicious compounds such as nitrate. International standards for nitrate ranging from 10 mg/l (USEPA) to 50 mg/l (EU)
are based on possible health effects for infants under 6 months
(methemoglobinemia). Having a stomach pH above 4 (which causes
a partial reduction of nitrate to nitrite), they might suffer from
lack of oxygen in their blood due to reaction of hemoglobine with
nitrite. Nitrate itself does not pose any risk; no clear health effects
can be observed [163]. Nonetheless, nitrates remain on the list
of unwanted species in (drinking) water; removal techniques are
considered in many studies. Since nitrate is a monovalent ion, it
can only partially be removed by nanoltration [164168]. Therefore, reverse osmosis membranes are often preferred to ensure a
(nearly) full removal of nitrate. This may be unnecessary, but on
the other hand, synergetic toxicity effects may occur in combination with, e.g., pesticides [170], and some effects may be unknown
[163] so that the precaution principle can be defended. Table 2
shows nitrate rejection values from the literature obtained with
typical nanoltration membranes. Although these rejections would
Table 2
Experimental nitrate rejections for typical nanoltration membranes
Membrane
Nitrate rejection (%)
Reference
NF90
HG19
SX10
SV10
SX01
BQ01
MX07
NF70
NF45
UTC-20
UTC-60
MPS44
NF70
Desal
ESNA-1 LF
NF
NF90
OPMN-K
OPMN-P
9498
9
32
28
25
12
8
76
16
32
11
90 50
90 85
60 33
7580
6580
8595
2550
4070
[169]
[168]
[168]
[168]
[168]
[168]
[168]
[167]
[167]
[167]
[167]
[166]
[166]
[166]
[165]
[164]
[164]
[164]
[164]
depend on the experimental concentrations, it can be concluded

that all membranes with the exception of NF90 have moderate
nitrate rejections. Nanoltration for lowering nitrate concentrations to some extent, in combination with another objective such
as softening or NOM removal, is certainly feasible, but if nearly
complete nitrate removal is wanted, nanoltration is not the appropriate process.
An even more challenging pollutant is boron. Boron is an important micronutrient for plants, animals and humans, although the
range between deciency and excess is narrow [171]. In aqueous
environments (i.e., neutral pH) boron is mainly present as boric
acid, which is mostly undissociated and therefore only partially
rejected even by reverse osmosis membranes. In acid conditions (at
pH values between 3 and 4.5), boron can be removed by nanoltration based on charge interactions [172]. This was investigated
for liquid waste streams in coal-red power plant, which contain
a wide spectrum of trace elements, most of which originate in the
coal and remain in the y ash or bottom ash when the coal is burned.
Another study, for removal of boron from chemical landll leachate,
used high pH values (around 11) and also obtained good results,
although the rejection for nanoltration was relatively low compared to reverse osmosis [173]. Under neutral conditions, boron
can only be removed as a complex. Complexation of boron with
mannitol allows a good removal with nanoltration membranes
[171]. Nevertheless, for most applications, boron is not a target compound, but it is monitored as a species of interest with a very low
concentration by preference. A comparison of different treatment
trains would yield a disadvantage for nanoltration, if boron is a
(possible) problem.
For organic micropollutants, rejections with nanoltration may
range from high to low. Organic micropollutants are a very
broad class of compounds, comprising natural and synthetic hormones; industrial pollutants such as phthalates, alkylphenols,
bisphenol-A, PCBs (polychlorinated biphenyls), PAHs (polyaromatic hydrocarbons), NDMA (N-nitrosodimethylamine) and MTBE
(methyl tertiarybutyl ether); pesticides; pharmaceuticals; personal
care products and disinfection by-products (DBPs) [174]. It is not
always clear which are the most important compounds to look at;
a recent study made an attempt to dene priority compounds in
view of drinking water production, based on maximum observed
concentrations in surface water, toxicity and production volumes
[175]. A large variation of physico-chemical parameters can be
found among these various types of micropollutants, and because
some of these parameters have a signicant inuence on rejection,
the removal of micropollutants from aqueous solution can be very
different from component to component. Modelling and prediction
of rejections is still difcult (see also next section), so that extensive experimental research has to be carried out to assess removal
of individual micropollutants. A qualitative appraisal of rejections
was obtained through a classication of compound/membrane
combinations [176]. A further semi-quantitative assessment of the
rejection of organic compounds in aqueous solution was derived in
an attempt to quantify the range of rejections that can reasonably
be expected based on a limited number of parameters [174]. This
classication can be used for practical conclusions. Both studies
[174,176] are based on up to ten classes of compounds. Parameters used for this classication are molecular weight, molecular
weight cut-off of the membrane, pKa (solute charge) and log Kow
(hydrophobicity). It was shown that the lowest rejection should be
expected for uncharged hydrophobic compounds with low molar
mass, which can be explained by the absence of steric hindrance
effects and electrostatic interactions. Examples are 2-naftol, 4phenylphenol, estradiol, ibuprofen, uoranthene and bisphenol-A,
estradiol, estrone, atrazine, simazine, diuron, and isoproturon. For
these compounds, a rejection decrease as a function of time, due
to adsorption in the membrane matrix, was observed, which may

lead to misinterpretations: observed rejections may be overestimated when the time of measurement was not sufciently long
[177].
Micropollutants from other classes, however, have also been
identied as problematic compounds. It should be understood that
the classication is not absolute: membrane pore sizes are usually
unknown, and when they are known, they represent an effective
pore size, dependent on the determination method. Furthermore,
molar mass is not a good measure for the size of a solute; it is
a pragmatic parameter because of its availability, but may yield
wrong conclusions. The (largely unknown) interplay between steric
hindrance, charge repulsion and hydrophobic interactions are a further complication. A typical example is NDMA: this is a relatively
hydrophilic solute, but has a low molar mass, which leads to low
rejections in nanoltration. Research into the removal mechanisms
playing a role in the nanoltration process can help to improve
the insights into the removal of the organic pollutants, which may
contribute to the development of better barriers, even if other pollutants should arise in the drinking water sources. This requires
a better understanding of interactions between solutes and membranes involved in transport through the membrane, development
of model equations and their translation to a simulation tool that
can be used to provide realistic predictions of concentrations in
permeates.
7. Modelling and simulation of nanoltration

Modelling the performance of a nanoltration membrane comprises two aspects: ux prediction and rejection prediction. These
two allow full understanding of a lab-scale membrane module.
Scaling up to larger installations requires that changes along the
ltration module are taken into account, i.e., the inuence of the
permeate yield. This can be done by taking concentration increases
into account [178].
Different models have already been proposed for the description of the ux through a (nanoltration) membrane. For relatively
porous nanoltration membranes, simple pore ow models based
on convective ow can be used. The HagenPoiseuille model
and the Jonsson and Boesen model, which are commonly used
for aqueous systems permeating through porous media, such as
microltration and ultraltration membranes, take no interaction
parameters into account, and viscosity is the only solvent parameter. Nevertheless, these expressions are usually sufcient for use
in nanoltration, because they basically express the fundamental
Darcys law (ux proportional to pressure gradient) with an empirical proportionality constant, the permeability. The latter parameter
is not expressed as a function of membrane characteristics, as it is
done in other processes, because some parameters (porosity, pore
size) are difcult to measure or even doubtful as concept in nanoltration.
Two aspects remain to be modelled: the inuence of membrane
fouling on ux, and prediction of uxes for organic solvents. Not
much work has been done on modelling of fouling in nanoltration.
For surfactants, a correlation has been proposed [179], although it
was recommended not to replace experimental testing by the proposed equation. A more general model, based on characteristics
of individual models, was proposed for aqueous solutions containing well-known organic solutes [51]. In most applications, however,
the feed composition is unknown, so that models are not helpful. In
these circumstances, it may be better to use a pragmatic approach
by using estimates of ux decline to be expected. Practical measures to minimise ux decline and membrane fouling were already
discussed in a previous section.
259
In contrast with aqueous solutions, the HagenPoiseuille or

Jonsson and Boesen equation are insufcient to describe the
performance of solvent resistant nanoltration membranes. A
resistance-in-series model based on convective transport of the solvent for the permeation of pure solvents and solvent mixtures can
be used [180]:
J=
P
[(c l ) + f1 ] + f2
where f1 and f2 are solvent independent parameters characterising

the nanoltration and ultraltration sublayers, a solvent parameter, c the critical surface tension of the membrane material and l
the surface tension of the solvent. This model takes solvent viscosity
and the difference in surface tension between the solid membrane
material and the liquid solvent into account. However, this model
is developed for hydrophobic membranes, but seems inadequate
for the description of uxes through hydrophilic membranes [181].
A further disadvantage is that for each solventmembrane combination an empirical parameter has to be determined as a
measure for the interaction between a solvent and the membrane
material.
Polymeric nanoltration membranes can also be described by a
solution-diffusion mechanism, possibly corrected for the inuence
of convective transport [34]. A description of solvent transport in
this case is necessarily based on the solution-diffusion (SD) model
[182]. With respect to ux modelling of organic solvents, a possible
equation would be [183]:
J
V 1
m

n m
This model is based on solvent viscosity, the molar volume

Vm (as a measure for the molecular size), the surface tension of
the solid membrane material and a sorption value (as a measure for membranesolvent interactions). An alternative equation
[184] is:
J
Vm

where is the difference in surface tension (mN/m), is the

dynamic viscosity (Pa s), and Vm is the solvent molar volume
(m3 /mol).
It is evident that these models for describing uxes in solvent
resistant nanoltration have not yet converged; more experience is
needed before a translation to a universal model can take place.
Transport of solutes through nanoltration membranes can be
described by the equations of Spiegler and Kedem, which combine
both diffusive and convective effects:
Js = L (P )
Jc = Ps x
dc
+ (1 )Js c
dx
leading to an expression for the rejection R:

R=
(1 F)
1 F
1
with F = exp
Ps
Js
The permeability Ps is a measure of the transport of a molecule

by diffusion. The reection coefcient of a given component is the
maximal possible rejection for that component (at innite solvent
ux). Various models have been proposed for the reection coefcient [185188]. If a lognormal distribution can be assumed for
the pore size, a molecule may permeate through every pore that is
larger than the diameter of the molecule [188]. The reection curve
260
can then be expressed as:

=
0
rc
1
1
exp
Sp 2 r

2
(ln(r) ln(r ))
2Sp2
dr
with rc = dc /2. This equation comprises two variables, Sp and r ,

where Sp is the standard deviation of the distribution. This standard deviation is a measure for the distribution of the pore sizes. r
is a mean pore size, namely the size of a molecule that is retained
for 50%.
This relatively simple case for uncharged solutes in water
already reects the difculties in developing a reliable and generally applicable model for nanoltration. When rejections in organic
solvents are considered, the problem is even larger, given the
complex interactions between solutes, solvents and membranes,
leading to differences in solvation and therefore also in effective
size. The rejection of organic solutes in water is inuenced by
partitioning effects [189,190], and sorption in the membrane was
assumed to be one of the factors that govern the selectivity of membranes towards small organic molecules. Therefore, quantitative
sorption data are crucial for understanding this effect [191]. For
ion rejection in water, many models have been developed [192],
but these calculations tend to become so complex that a simple
translation to a simulation tool is not straightforward. Model-based
tools to design membrane processes for new industrial applications or to optimise existing membrane installations are needed,
and in spite of all efforts in unravelling ux and separation phenomena, these tools are not yet available. An ambitious attempt to
use MaxwellStefan equations and all current knowledge to come
to a predictive model led to the conclusion that much depended on
tting parameters and not on physically relevant parameters [193],
so that further research is needed if a generally applicable simulation tool is envisaged. Membrane manufacturers often develop
their own simulation tool, but this is based on empirical rejection
and ux data and cannot be applied for other than standard congurations, membranes or solutions. For electrolytes in water, an
interesting approach to simulation has been the NANOFLUX tool
[194]. Nevertheless, further extension of this tool or development
of new tools will be the major key to industrial implementation of
nanoltration.
8. Conclusions
It is clear that nanoltration still has to grow more in terms
of understanding, materials, and process control. Regardless of
reviewed drawbacks, NF is widely used in industry and special
properties of the NF membranes make possible novel separations that are difcult or expensive to achieve with other
separation methods. Furthermore, the potential of nanoltration in industrial application is still underdeveloped because
of these drawbacks. In anticipation of new insights and generally applicable solutions, using nanoltration with the current
knowledge will offer a considerable lead to more conservative
players. Practical problems requiring a pragmatic solution are
membrane fouling and the need for cleaning (and, related to
this, membrane lifetime). A number of options have been proposed; using the expertise of a membranologist, feasible solutions
can be elaborated for many applications. Applications where
an enhanced separation between solutes is required, or a complete removal of contaminants, can be solved by using novel
process congurations or by selecting an adequate membrane.
On the long run, process control can be obtained by translating insights in transport to models, and then translating these
models into simulation tools. A number of attempts in this direction have proven to be successful, and further extension of these
would allow prediction of the process performance in all circumstances.

In summary, it can be stated that further implementation of
nanoltration will go hand in hand with the elaboration of the
research objectives mentioned. In that sense, it can be expected
that large steps forward will be made during the coming decade.
Acknowledgements
The Fund for Scientic Research Flanders (FWO-Vlaanderen) is
gratefully acknowledged for a travel grant (B. Van der Bruggen).
NanoMemPro is acknowledged for nancial support.
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Separation and Purication Technology 63 (2008) 251263

Contents lists available at ScienceDirect

Separation and Purication Technology

Drawbacks of applying nanoltration and how to avoid them: A review

Corresponding author. Tel.: +32 16 32 23 40; fax: +32 16 32 29 91.

mika.manttari@lut. (M. Mantt

to fundamental understanding, suggestions for practical solutions

best documented example being the Mery-sur-Oise

a degree of supersaturation. In general, the point of saturation can

by non-destructive measures. The critical ux concept has a sound

For uncharged solutes, however, (nanoltration) membranes are

Fig. 3. Schematic representation of the principle of a membrane cascade (adapted

step approach was recently suggested for purication of solvents

Fig. 4. Chemical structure of stevioside.

is also safe for phenylketonuria patients who might be in danger

(Qf Cf,i ) (Qp Cp,i )

where REC = recovery, Q = volumetric ow (l/h), C = concentration

Additives such as anti-scalants (polyacrylates, polyacrylic acids,

5. Membrane lifetime and chemical resistance

membrane processes, and their impact is usually studied from a

Nadir Filtration GmbH, Wiesbaden, Germany.

Hermsdorfer Institut fur

as poly(acrylonitrile) [154]. An overview of solvent resistant

and the characteristics of all four membranes changed notably after

Fig. 5. Effect of exposure to a range of organic solvents (methylene chloride,

these membranes. Hydrophilic ceramic nanoltration membranes

Nitrate rejection (%)

depend on the experimental concentrations, it can be concluded

to adsorption in the membrane matrix, was observed, which may

7. Modelling and simulation of nanoltration

In contrast with aqueous solutions, the HagenPoiseuille or

where f1 and f2 are solvent independent parameters characterising

This model is based on solvent viscosity, the molar volume

where is the difference in surface tension (mN/m),  is the

leading to an expression for the rejection R:

The permeability Ps is a measure of the transport of a molecule

can then be expressed as:

with rc = dc /2. This equation comprises two variables, Sp and r ,

would allow prediction of the process performance in all circumstances.

[46] A.I. Schafer,

Fouling in nanoltration, in: A.I. Schafer,

[59] J. Warczok, M. Ferrando, F. Lopez, C. Guell,

[76] J. Tanninen, L. Kamppinen, M. Nystrom,

in: A.I. Schafer,

[84] M. Luo, Z. Wang, Complex fouling and cleaning-in-place of a reverse osmosis

Inuence of process con[96] M. Nystrom,

[99] J. Tanninen, M. Mantt

[140] L.D. Nghiem, A.I. Schafer,

H. Martin, J. Nuortila-Jokinen, M. Nystrom,

[147] L.D. Nghiem, A.I. Schafer,

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where is the difference in surface tension (mN/m), is the