A P P L I C AT I O N N O T E
1
Nanofiltration Properties and Uses
Henia Yacubowicz, Jorge Yacubowicz
Koch Membrane Systems
Introduction
Modern crossflow filtration technology
has principally evolved during the last
thirty years, following the significant
advancements in polymer chemistry
over the same time. Today, a vast ma-
jority of crossflow filtration installa-
tions utilize polymeric membranes.
Virtually all commercial nanofiltration
membranes are polymeric.
Nanofiltration (NF) is a crossflow, pres-
sure driven process that is characterized
by a membrane pore size corresponding
to molecular weight cutoff of approxi-
mately 200 1000 dalton, and operating
pressures of 150 500 psi (10 34 bar).
NF is primarily used to separate low mo-
lecular weight organics and multivalent
salts from monovalent salts and water.
Starting in the late 1970s, NF mem-
brane processes gradually found their
way into industrial applications, and
serve as a viable alternative to more
traditional separation processes like
extraction, evaporation and distillation.
The first industrial systems using nano-
filtration membranes were installed
in 1978 using tubular membranes for
desalination of dyes and brighteners.
Nanofiltration membranes are manu-
factured using two preparation tech-
niques: polymer phase inversion
resulting in a homogeneous asymmet-
ric membrane, and interfacial polariza-
tion of a thin film composite layer on top
P U B L I S H E D in the September 2005 issue of Filtration+Separation Magazine (www.filtsep.com).
Reprinted with permission of Elsevier, Ltd.
of a substrate ultrafiltration membrane or
other porous substrate. Cellulose acetate
and sulfonated polysulfone are two com-
mon materials used for making homoge-
neous asymmetric NF membranes. Thin
film composite nanofiltration mem-
branes use crosslinked polyamide poly-
mers, reacted to carboxylic group or other
charged pendant. Substrate materials
commonly used for thin film composite
membranes are polysulfone (PS), poly-
ethersulfone (PES), polyvinyledene fluo-
ride (PVDF), polyacryloni trile (PAN),
and Polyether ether Ketone (PEEK). Re-
cent development of NF membranes with
exceptional stability in very low or high
pH, very high temperature, or organic
solvent media required membrane man-
ufacturers to seek new materials for
membrane manufacturing. The materials
used for these innovative membranes are
highly crosslinked, to allow long term
stability and practical membrane life in
aggressive environments. Nanofiltation
membranes have a slightly charged sur-
face. Most NF membranes are negatively
charged at neutral pH. This surface
charge plays a major role in the trans-
portation mechanism and separation
properties of NF membranes.
Industrial applications of nanofiltration
membranes are common in food and
dairy, chemical process, pulp and
paper, electronic and textile industries.
The primary application of nanofiltra-
tion membranes continues to be in
water treatment.
Most NF membranes are packed into spi-
ral wound elements; however, tubular,
hollow fiber and flat sheet/plate and
frame modules are also available.
Transport Mechanism
in Nanofiltration
Nanofiltration membranes are often cat-
egorized as loose reverse osmosis (RO)
membranes. The differences between the
two, however, are significant. The most
notable difference is the ability of NF
membranes to selectively reject divalent
ions, while passing monovalent ions. It
is a common belief that NF and RO
membranes do not have distinct pores,
as in ultrafiltration and microfiltration
membranes. Although recent studies
using Atomic Force Microscopy (AFM)
suggest that pores of NF membranes can
be viewed, most membrane scientists
choose to describe the pores as the dis-
tances between the polymer chains of the
membrane building material.
The mechanism of transport and
rejection of NF membrane is quite com-
plex and is still a point of debate between
scientists. Many models have been devel-
oped to identify the effect of different pa-
rameters on the transport mechanism and
1 This article is written for general information
purposes. The information contained here-
in should not be relied upon for specific facts
and circumstances and is not intended to
be a substitute for consultation with a mem-
brane technologist.
to predict the NF membrane perform-
ance. The two major schools are Sourira-
jans sorption surface-capillary flow
approach, and the solution-diffusion
theory. Sorption surface-capillary flow de-
scribes the preferential sorption of water
molecules in the membrane and the des-
orption of multivalent ions (by dielectric
forces) causing exclusion of charged
solutes, even smaller than the membrane
pores, from movement into the mem-
branes (Donnan exclusion). Effective
charge density, pore radii and the ionic
strength determine the rejection of mono-
valent ions, but generally speaking, for NF
membranes the rejection of monovalent
ions will be between 0 and 50%. Solution-
diffusion theory describes the membrane
as a porous film into which both water
and solute (ion) dissolve. The solute moves
in the membrane mainly under concen-
tration gradient forces, while the water
transport is dependent on the hydraulic
pressure gradient. The transport of the
solute through the membrane depends on
hindered diffusion and convection.
The transportation of a non-charged
solute through an NF membrane is con-
sidered to be determined by a steric
exclusion mechanism. Steric exclusion
applies to NF membranes as well as
ultrafiltration and microfiltration mem-
branes. A separation between two differ-
ent non-charged solutes is determined
predominantly by the difference in their
size and shape.
Parameters Affecting the
Performance of Nanofiltration
Membranes
When designing a nanofiltration process,
one should consider several operating
parameters. The most important operat-
ing parameters affecting the performance
of nanofiltration membranes are similar
to those for most crossflow filtration
processes:
Pressure. Pressure difference is the
driving force responsible for a nanofil-
tration process. The effective driving
pressure is the supplied hydraulic pres-
sure less the osmotic pressure applied
on the membrane by the solutes.
2
Nanofiltration provides good separa-
tion at net pressures of 150 psi (10
bar) or higher.
Temperature. Increasing the process
temperature increases the NF mem-
brane flux due to viscosity reduction.
The rejection of NF membranes is
not dependent significantly on the
process temperature.
Crossflow Velocity. Increasing the
crossflow velocity in an NF mem-
brane process increases the average
flux due to efficient removal of foul-
ing layer from the membrane surface.
However, the mechanical strength of
the membrane, and construction
of the element and system hardware
will determine the maximum cross-
flow velocity that can be applied.
Running a nanofiltration membrane
at too high a crossflow velocity may
cause premature failure of mem-
branes and modules.
pH. pH affects performance of nano-
filtration membranes in more than
one way. The charged sites on the NF
membrane surface (i.e. carboxylic
group, sulfonic group) are negatively
charged at neutral pH or higher, but
lose their charge at acidic pH. It is
well known that most NF and RO
membranes have lower rejection at
low pH, or after acid rinse. It should
be noted, however, that since differ-
ent membrane manufacturers use
different chemistries to produce their
thin film composite layer, the pH de-
pendency of a membrane should be
determined for each membrane type.
In addition to the effect of pH on the
membrane itself, pH can be respon-
sible for changes in the feed solution,
causing changes in membrane per-
formance. Two examples are change
of solubility of ions at different pH
regimes, causing different rejection
rate; and change in the dissociation
state of ions at different pH ranges.
Salinity. The effective pore radius of a
charged pore will increase as the ionic
strength of the surrounding liquid in-
creases. Therefore, the rejection of
monovalent ions will decrease as their
concentration in the feed solution in-
creases. The rejection of divalent ions
will be affected to a lower extent.
Uses of Nanofiltration
Membranes
Due to their unique separation properties
nanofiltration membranes are widely used
in industry. It is advantageous to use
nanofiltration membranes when:
It is not necessary to retain monova-
lent salts. Application of nanofiltration
can permit operation at lower pressure
and with less energy consumption.
A separation between low molecular
weight organic material and a mono-
valent salt is desired. Examples: sepa-
ration of lactose from ash; separation
of dyes from sodium chloride.
Purification of acids, bases or solvent
is being investigated, when the con-
taminants are in the nanofiltration
MWCO range.
A reduction in osmotic pressure is re-
quired, compared to reverse osmosis
membranes.
Nanofiltration membranes are applied in
water treatment, wastewater treatment
and in a variety of industrial applications.
Some applications of note are:
Polishing of conventional water treat-
ment and wastewater treatment systems.
Nanofiltration membranes are used for
removal of dissolved low molecular
weight organics and color from second-
ary effluent from biologically treated ef-
fluent. A large nanofiltration system was
installed to polish effluent in a paper
mill. The nanofiltration membranes
consistently remove over 90% of the
COD, 80% of the hardness and 90% of
the sulfates. In one district in the United
States, where river water is used for
water supply, a conventional treatment
comprising sedimentation, coagulation,
 flocculation, and mixed media filtra-
tion was installed. Due to significant
seasonal fluctuations in total dissolved
solids, the effluent from the water treat-
ment facility did not always supply
water at the desired quality. Nanofiltra-
tion polishing was proven to be the
most economical, effective and reliable
solution for the district, to produce
high quality water consistently and to
handle the fluctuations in feed quality.
Softening of seawater and brine
solutions. In the oil and gas industries,
seawater is often injected into offshore
oil wells to displace oil. Due to the high
sulfate content in the seawater and the
high barium and strontium content in
the wells, there is potential for signifi-
cant scaling and possible reservoir
souring. These scale deposits are a com-
mon problem. Conventional treatment
of this problem required the use of high
doses of antiscalants which is labor
intensive, economically inefficient,
technically difficult to control, and en-
vironmentally unfriendly. In the late
1970s, a membrane solution was intro-
duced: the use of nanofiltration to re-
move the sulfate from the seawater
before injection. The volumetric recov-
ery of the process is between 75% and
80%. The concentrate stream is re-
turned to the sea. Another application
where seawater is used as raw material
is the production of soda ash. In this
process, seawater is used as a source of
sodium chloride. Sulfates, as well as
hardness, need to be removed from the
seawater. Nanofiltration technology
was found to be economical and effec-
tive in removing hardness and sulfate
to the desired levels. The purification of
brine, the main raw material for chlo-
ralkali process, belongs to the same
family of applications. It should be
noted that sulfate ions are removed by
most negatively charged nanofiltration
membranes, however, in order to effec-
tively remove hardness from seawater a
tight NF membrane, in the 200 MWCO
range has to be used.
Nanofiltration membranes are widely
used in dairies to treat whey, a protein
byproduct of cheese making. Typically
whey is first treated with ultrafiltra-
tion (UF) membranes, to concentrate
the protein to a usable level. The UF
permeate, containing lactose and salts
is then processed with NF or RO
to concentrate and demineralize
the lactose solution. Other uses of
nanofiltration in dairies are whey pre-
concentration and whey protein de-
salination, and caustic and acid
recovery from CIP operation. NF is
often used in the last stage of an RO
system in dairies, to minimize os-
motic pressure and allow concentra-
tion to the desired level. In this case,
permeate from the NF stage is recy-
cled back, so that permeate quality is
not compromised.
Nanofiltration membranes are widely
used in the food industry, in applica-
tions such as gelatin concentration.
Traditionally, gelatin can be concen-
trated using ultrafiltration mem-
branes. The use of UF to concentrate
gelatin to medium and high concen-
tration can cause high losses, particu-
larly when low bloom gelatin is
processed. Recent developments of
NF membranes for moderate and
high temperatures allow gelatin man-
ufacturers to use them effectively, with
minimal to non-detectable losses.
Desalination of dyestuff. In the man-
ufacturing of liquid dye formulations,
it is important to obtain a liquid with
good shelf stability. In many cases
such stability is reached only when
organic impurities and residual salt
are removed from the reaction mix-
ture of the dye. Nanofiltration mem-
branes are used to desalt and
concentrate liquid dyes. A typical
membrane desalting process is a
combined concentration/diafiltration
procedure. During the diafiltration
step fresh water is added to the dye
and forced across the membranes to-
gether with salts and impurities.
This application is mostly served by
tubular nanofiltration membranes,
due to the high final dye concentra-
tion (20 40%) and the high viscosity
of the dye solution in this concentra-
tion range. It is worth noting that since
most liquid dyes are charged mole-
cules, this application exhibits under
certain conditions negative salt rejec-
tion rates, meaning that the concen-
tration of salt in the permeate is often
higher than the concentration of the
salt in the feed. Special care should be
given to the membrane selection and
process design and optimization, in
order to utilize this negative rejection
to reduce system size and diafiltration
water consumption.
Koch Membrane Systems (KMS) tu-
bular NF membranes are used for dye
desalination in a dye production facil-
ity in the US. The liquid dye solution is
first concentrated twofold, from 3% to
6% dye. Five volumes of diafiltration
water are then added to the feed tank
and removed through the permeate.
At the end of this step the dye solution
is further concentrated to around 20%
dye, before it is transferred for pack-
aging. As a result of the concentra-
tion/diafiltration process the dye to
salt ratio increases from 3:1 to 400:1 or
more. The rejection to sodium chlo-
ride is progressing from approximately
0% at the beginning of the process to
-100% (negative 100%) at the end of
the process.
Antibiotic, intermediates and peptide
recovery in organic solvents media.
The development of reliable solvent
stable nanofiltration membranes
opened the door for large new oppor-
tunities. Solvent extraction and other
solvent-media separation operations
are widely used in the pharmaceutical
industry. In 6-APA (6-Amino penicil-
lanic acid, MW 216) production large
volumes of solvent solution contain-
ing low concentrations of 6-APA in-
termediate are discharged to drain.
The first system to recover the 6-APA
from the discharge stream was in-
stalled in 1995. Since then more than
60% of the 6-APA manufacturers in
the world installed similar systems to
recover this high value substance from
3
 their wastewater. The feed solution
contains around 20% organic solvents,
and between 0.2 and 0.5% 6-APA. The
6-APA is concentrated up to 3 5% by
the nanofiltration membranes, and
then returned upstream to the extrac-
tion process. The solvent composition
may change from site to site, depend-
ing on the specific production process;
methanol, methylene chloride, and
Removal of dissolved solids from a
zero discharge paper mill. A unique
crossflow membrane application was
developed in a zero discharge paper
mill in the United States. Ultrafiltra-
tion membranes clarify/purify white-
water from the paper machine for
water reuse in showers in paper mak-
ing. The retentate from the UF mem-
branes is then processed by NF
Corporate Headquarters
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Wilmington, Massachusetts 01887- 3388
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ethyl acetate, are common solvents for
this application.
KMS NF solvent stable membranes typ-
ically exhibit rejection rates of 9598%,
resulting in small losses of product.
Caustic recovery from rayon fibers
manufacturing. In rayon manufactur-
ing, steeping is the process of immers-
ing the dissolving pulp in a solution of
sodium hydroxide of mercerizing
strength (17 20%). The purpose of
membranes, to dewater the concen-
Manufacturing Facilities
trate and to haul away the solids from
Wilmington, Massachusetts
the mill. NF technology was the mill San Diego, California
choice after UF technology proved Aachen, Germany
to loose too much solids, while
RO technology was found to operate International Contacts
at lower flux and higher pressure, Europe
leading to a more expensive unit. Koch Chemical Technology Group, Ltd.
Solids are concentrated by the NF Koch Membrane Systems Division
membranes from 5% to 20%, reduc- The Granary, Telegraph Street
ing the concentrate volume by a fac- Stafford ST17 4AT
tor of four. United Kingdom
Tel: +44 -178 - 527- 2500

this treatment is twofold: to produce Other applications include enzymes and Fax: +44 -178 - 522- 3149

alkali-cellulose (sodium cellulose) and
to remove soluble impurities from the
pulp. Large quantity of contaminated
concentrated sodium hydroxide can-
not be reused unless purified. Ad-
vanced nanofiltration membranes,
specially designed and produced to
operate in this harsh environment, are
utilized to remove hemicellulose,
lignin and other low molecular weight
organics from the sodium hydroxide
solution. Significant savings are
achieved, because the rayon manufac-
turer needs to purchase less fresh caus-
tic and discharges less wastes to the
waste treatment facility.
amino acids purification and concentra- Aachen, Germany
tion, glycol recovery, acid purification Lyon, France
from various sources, such as pickling Madrid, Spain
and plating baths and galvanization op- Milan, Italy
erations, recovery of precious metals Stafford, United Kingdom
from acidic streams, copper-EDTA and Wijnegem, Belgium
photoresist recovery in the electronic in-
Asia/Pacific
dustry, and uranium and gold recovery Beijing, China
from mining operations. Chennai, India
Melbourne, Australia
Applications of nanofiltration mem- Mumbai, India
branes have grown significantly as Shanghai, China
knowledge of their operation has ex- Singapore
panded. Well beyond its roots as loose
Latin America
RO, nanofiltration is now an integral
Sao Paulo, Brazil
step in many processes.
Middle East
Manama, Kingdom of Bahrain

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Application Note 011

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