OVERVIEW ABOUT MEMBRANE SEPARATION

BME 2015

Introduction
Membrane technology is a growing subject in a broad range of applications, from
industrial to medical applications. The main feature that is exploited is the ability of a
membrane to control the permeation rate of a chemical species trough the membrane.
In the first chapters, this review provides a general introduction to membrane
science, covering the basic topics to all membrane processes, such as types of membrane
and transport mechanisms. In the following chapters, the main industrial membrane
separation processes are reviewed, such as reverse osmosis, nanofiltration, ultrafiltration,
microfiltration, pervaporation and electrodialysis. In the last chapters a more considerate
attention is given to the reverse osmosis and nanofiltration processes, plus the recent
advancements of both.
Historical Development
In 1748 Abbe Nolet discovered the phenomenon of osmosis in natural membranes
and describes it as the permeation of water through a diaphragm [1]. Until the beginning
of XX century, membranes were only used as laboratory tools to develop physical and
chemical theories. Van Hoff in 1887 developed his limit law using membranes made by
Moritz Traube, Traube was the first to produce artificial semipermeable membranes by
putting droplets of glue in tannic acid. This kind of semipermeable membrane also was
used by Maxwell in developing the kinetic theory of gases.
Later in 1907 Bechhold introduced term ultrafiltration forcing solutions at
pressures up to several atmospheres through membranes prepared by impregnating filter
paper with acetic acid collodion nitrocellulose.
By the early 1930s microporous collodion semipermeable membranes were
commercially available recurring on Bechholds technique, in the next few years others
kinds of polymers were used like cellulose acetate for example. In 1950 Hassler
introduces the first concept of membrane desalination [1].

At World War II membranes were important to test the drinking water, because
water supplies in Europe had broken down, and lters to test for water safety were needed.
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These kind of filters were developed by the US Army, later Millipore Corporation
exploited the semipermeable membranes becoming the largest microltration membrane
producer.
Until 2003 there wasnt significant membrane separation industry, because
membranes were too slow, unselective, and expensive. Early 1960 Loeb-Sourirajan
developed a process that transformed membrane separation to an industrial process, these
membranes consisted in an ultrathin, selective surface lm on a much thicker and more
permeable microporous support, this kind of process uses the anisotropic reverse osmose,
and it was 10 times higher than that of any membrane available in the market, and made
reverse osmosis a new potentially method to desalt water.

The work of Loeb and Sourirajan with the economic financiation of Ofce of
Saline Water, resulted in the commercialization of reverse osmosis and at the same time
in the development of ultraltration, microltration and medical separation process. In
1945 W.J. Kolf

[6]

had demonstrated the rst articial kidney, only after 20 years the

technology was used on a large scale. Since then more than 800 000 people are sustained
by articial kidneys and also the development of the membrane blood oxygenator made
possible an open-heart surgery, helped millions of people. In 1966 Alex Zaffaroni
founded Alza, a company dedicated to the developing of membranes that controlled drug
delivery systems, improved the efciency and safety of drug delivery.

Between 1960 and 1980 the LoebSourirajan technique suffered some progresses
including interfacial polymerization and multilayer composite for making highperformance membranes. Using membranes with selective layers as thin as 0.1 m, largemembrane-area spiral-wound, hollow-ne-ber, capillary, and plate-and-frame modules
were developed, improving the membrane stability. In the 1980s Monsanto Prism
developed the membrane gas separation process in industrial scale, like the membrane for
hydrogen separation. Gas separation technology is expanding quickly, Cynara and
Separex produced membranes to separate carbon dioxide from natural gas, also
pervaporation systems for dehydration of alcohol are now available, and others
pervaporation applications are at the early commercial stage.

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OVERVIEW ABOUT MEMBRANE SEPARATION

BME 2015

Membrane Science Technology

Introduction
The primary characteristic that is exploited in membrane separation, is the ability
of a membrane to control the permeation rate of a chemical species. But the goal varies
according to the application. In controlled drug delivery the goal is to moderate the
permeation rate of a drug from a reservoir to the body, instead, in separation applications,
the goal is to allow one component of a mixture to permeate the membrane freely, while
hindering permeation of other components.
Types of Membranes
A membrane is nothing more than a discrete, thin interface that moderates the permeation
of chemical species. This interface may be molecularly homogeneous, that is, completely
uniform in composition and structure, or it may be chemically or physically
heterogeneous, for example, containing holes or pores of nite dimensions or consisting
of some form of layered structure [1].
The principal types of membrane are shown schematically in Figure 1 .1 and are
described briey below.

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OVERVIEW ABOUT MEMBRANE SEPARATION

BME 2015

Symmetrical membranes
Microporous Membranes
A microporous membrane is very similar in structure and function to a
conventional lter. It has a rigid, highly voided structure with randomly distributed,
interconnected pores. The difference between a conventional filter, are the extremely
small pores, ranging between 0.01 to 10 m in diameter. Therefore, particles larger than
the largest pores are blocked by the membrane [2]. Only molecules that differ considerably
in size can be separated effectively by microporous membranes, for example, in
ultraltration and microltration. Microporous membranes have much higher uxes than
nonporous membranes, being widely used in industrial processes.
Nonporous Membranes
This membranes consist of a dense lm through which permeants are transported
by diffusion under the driving force of a pressure, concentration, or electrical potential
gradient

[1]

. Nonporous membranes can separate permeants of similar size if their

concentration in the membrane material differs significantly. Therefore, the solubility of

the components of a mixture in the membrane material is directly related to their transport
rate within the membrane. However, these membranes are rarely used in industrial
processes because the transmembrane ux through these relatively thick membranes is
too low for practical separation processes. Thus, they are only used in laboratory work.
Sometimes, to improve the flux, these membranes have an anisotropic structure.
Electrically Charged Membranes
Electrically charged membranes are most commonly very nely microporous,
with the pore walls carrying xed positively or negatively charged ions, being referred to
as anion-exchange membrane and cation-exchange membrane, respectively.
Separation is accomplished by exclusion of ions of the same charge as the fixed
ions of the membrane structure.
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OVERVIEW ABOUT MEMBRANE SEPARATION

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Anisotropic Membranes
High transport rates are desired in membrane separation, for economic reasons,
therefore the membrane should be as thin as possible, since the transport rate of a species
through a membrane is inversely proportional to the membrane thickness.
Membrane fabrication technology limits manufacture of films to about 20 m
thickness. However, in the last 30 years there were major improvements to produce
anisotropic membrane structures. These membranes consists in an extremely thin surface
layer supported on a much thicker and porous substructure. The surface layer determines
the separation proprieties and permeation rates, while the substructure only provides
mechanical support.
Since the high fluxes provided by anisotropic membranes are so great, almost all
commercial processes use such membranes.
Ceramic and Metal Membranes
The majority of membranes used commercially are polymer-based, however other
materials like ceramic and metal are being investigated. Metal membranes are, for
example, being tested for the separation of hydrogen from gas mixtures. Also, ceramic
membranes are being used in ultrafiltration and microfiltration separations, where a
solvent resistance and thermal stability are required.

Membrane Processes

The four developed industrial membrane separation processes are microfiltration,

ultrafiltration, reverse osmosis, and electrodialysis, differing principally in the average
pore diameter of the membrane filter. Microfiltration membranes filter colloidal particles
and bacteria from 0.1 to 10 m in diameter, ultrafiltration membranes can be used to filter
dissolved macromolecules from 100 to 1000 . In reverse osmosis membranes, the
membrane pores are so small, from 5 15 in diameter, that they are within the polymer
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OVERVIEW ABOUT MEMBRANE SEPARATION

BME 2015

that form the membrane, the transport occurs via statistically distributed free volume
areas.

The difference between reverse osmosis, ultrafiltration and microfiltration is in

pore diameter, it produces important differences in the way the membranes are used. The
liquid ow through a pore (q) is given by Poiseuilles law as:
4

= 128
is the pressure difference across the pore, is the liquid viscosity and l is the pore
length.
The ux, per unit membrane area, is the sum of all the flows through the individual
pores, is given by:
4

= 128 (1.2)

Where N is the number of pores per square centimeter of membrane.

For membranes of equal porosity () the number of pores per square centimeter is
proportional to the inverse square of the pore diameter:
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OVERVIEW ABOUT MEMBRANE SEPARATION

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2

BME 2015

(1.3)

The ux is given by combining Equations (1.2) and (1.3):

J=

P
32

Fluxes are proportional to the square of these pore diameters, the permeance
(ux per unit pressure difference (J /_p)) of microltration membranes for example is
higher than that of ultraltration membranes, which is much higher than that of reverse
osmosis membranes. These differences signicantly impact the operating pressure.

Carrier Facilitated Transport

One of the most important industrial membranes to be developed is carrier

facilitated transport which employs liquid membranes containing a carrier agent.
Facilitated transport is concerned with the reversible and selective reaction between the
solute or component and the carrier. This reaction normally takes place throughout the
liquid membrane phase in the feed side, the carrier agent acts as a shuttle to selectively
transport one particular component from the feed and then diffuses across the membrane
to release the permeant on the product side of the membrane. Water is required on both
the feed and permeate side of the membrane for high selectivity to be observed, probably
as a consequence of the active participation of water in the chemical reactions that
enhances solubilities. Facilitated transport membranes can be used to separate gases and
metal ions (coupled transport). Membrane transport is then driven by a difference in the
gas partial pressure across the membrane to separate gases, or driven by ow of hydrogen
or hydroxyl ions to separate metal ions, the ion-exchange reaction occurs at a liquid-liquid
interface since metal ions are not soluble in the organic membrane phase.
One simple example is the hemoglobin, on the feed side hemoglobin reacts with oxygen
to form oxyhemoglobin, which then diffuses to product side, there the oxygen is liberated
and hemoglobin is re-formed. The hemoglobin then diffuses back to the feed side of the
membrane to repeat the process. In the coupled transport case one of the species moved
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OVERVIEW ABOUT MEMBRANE SEPARATION

BME 2015

against its concentration gradient, provided the concentration gradient of the other
species. In example, the carrier is an oxime that forms an organic soluble complex with
copper ions. On the feed side two oxime carrier molecules pick up a copper ion, liberating
two hydrogen ions at the same time. The copperoxime complex then diffuses to the
product side, where the higher concentration of hydrogen ions makes the reaction
reversed. The copper ion is liberated to the permeate solution, and two hydrogen ions are
picked up, then the reformed oxime molecules turns back to the feed side.

Facilitated transport carrier particular species, so extremely high selectivity

membranes are needed, however there is no commercial applications in this area because
there are problems with the physical and chemical instability of the liquid membrane and
the carrier agent. Some potential solutions have been studied to make carrier facilitated
transport viable in a commercial and industrial way.

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OVERVIEW ABOUT MEMBRANE SEPARATION

BME 2015

Transport Mechanisms
Introduction
There are two models that describes the mechanism of permeation in membranes,
the solution-diffusion model and the pore-flow model. Permeation in reverse osmosis and
pervaporation occurs by molecular diffusion and is described by the solution-diffusion
model, while the pore-flow model defines the microfiltration and ultrafiltration, as shown
in Fig. X. There are also an intermediate model, in which nanofiltration falls into.

Solution-Diffusion Model
Diffusion, the basis of the solution-diffusion model, is the process by which
matter is transported from one part of a system to another by a concentration gradient. In
an isotropic medium, the individual molecules are in random motion, with no preferred
direction. However, if there is a concentration gradient of permeate molecules in the
medium, a transport of mass will occur from the high to the low concentration region.
The pores, in this model, are tiny spaces between polymer chains caused by thermal
motion. So, the pores appear and disappear during the motion of permeants traversing
the membrane.
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OVERVIEW ABOUT MEMBRANE SEPARATION

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This phenomenon is theoretically described by Ficks law of diffusion, which

states
=

where is the flux of a component i (g/cm2s) and / is the concentration gradient

of a component i. The diffusion coefficient, (cm2/s) is a measure of the mobility of
the individual molecules.
In practical applications, high fluxes are achieved by creating large concentration
gradients in the membrane.

This model is universally well accepted and supported, since it provides simple
equations that accurately link the driving forces of concentration and pressure with flux
and selectivity. However, it has been unsuccessful at providing a connection between the
nature of the membrane material and the membrane permeation proprieties.

Pore-Flow Model

The pore-flow model is usually described by a pressure-driven convective flow

through very small pores. Separation occurs because one of the permeants is filtered from
some of the pores, while other permeants pass through. While the pores in the solutiondiffusion model vary from position and volume during the motion of the permeants, in
the pore-flow model the pores are large and fixed and do not fluctuate in position or
volume.
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OVERVIEW ABOUT MEMBRANE SEPARATION

BME 2015

The fundamental equation that describes this model is Darcys law, which is

where K is a coefficient regarding the nature of the medium, ci is the concentration of a

component i in the medium and dp/dx is the pressure gradient present in the porous
medium.

The pore-flow model is much less developed, compared to the solution-diffusion

model. There are many characteristics hard-to-compute that affect the permeation.
Measurements of permeation through ideal uniform-pore-diameter membranes made by
the nucleation track method are in good agreement with theory. Unfortunately,
industrially useful membranes have nonuniform tortuous pores and are often anisotropic
as well.

Intermediate Model
The intermediate zone between the previous models, seems to occur with
membranes with very small pores, ranging from 5 to 10 . Apparently this transition is
in the nanofiltration range, with membranes having good filtration to divalent ions and
organic solutes, but rejection to monovalent ions in the 20-70% range.
The transition from reverse osmosis membranes to ultrafiltration membranes is
shown in Figure X.

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OVERVIEW ABOUT MEMBRANE SEPARATION

BME 2015

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