FACULTY OF ENGINEERING DEPARTMENT OF CHEMICAL ENGINEERIN

MEMBRANE SEPARATION

SUPERVISOR: ALI HOSAIN

By ; KUBRA EDRIS RASUL

MAY 2020
Contents
Introduction ............................................................................................................................... 3

Theory ......................................................................................... Error! Bookmark not defined.

Industrial Applications of Membrane Separation Processes…………………………………………………6

Advantages and Disadvantages, Challenges of Membrane Separations………………………………9

Tayps of membran separation process and mechanism caracterization……………………………..12

Membran caracterization ........................................................................................................ 18

Characterization of Dense, Homogeneous Membranes ......................................................... 19

Characterization of Charged Membranes................................................................................ 22

Electrochemical Impedance Spectroscopy (EIS)…………………………………………………………………………22

Membrane Module Selection………………………………………………………………………………………………………24

Membrane configuration ……………………………………………………………………………………………………………25

Membrane performance and governing equations………………………………………………………………….27

Designing a Membrane System……………………………………………………………………………………………………28

Membrane cleaning methods……………………………………………………………………………………………31

References ............................................................................................................................... 33

2
Introduction

Membrane separation processes have a very important role in the separation industry.
Nevertheless, they were not considered technically important until the mid-1970s.
Membrane separation processes differ based on separation mechanisms and size of the
separated particles. The widely used membrane processes include microfiltration,
ultrafiltration, nanofiltration, reverse osmosis, electrolysis, dialysis, electrodialysis, gas
separation, vapor permeation, pervaporation, membrane distillation, and membrane
contactors. All processes except for pervaporation involve no phase change. All processes
except (electro) dialysis are pressure driven. Microfiltration and ultrafiltration is widely used
in food and beverage processing (beer microfiltration, apple juice ultrafiltration),
biotechnological applications and pharmaceutical industry (antibiotic production, protein
purification), water purification and wastewater treatment, the microelectronics industry,
and others. Nanofiltration and reverse osmosis membranes are mainly used for water
purification purposes.

Figure (1)

Dense membranes are utilized for gas separations (removal of CO2 from natural gas,
separating N2 from air, organic vapor removal from air or a nitrogen stream) and sometimes

3
in membrane distillation. The later process helps in the separation of azeotropic
compositions reducing the costs of distillation processes.

THEORY

Membrane separation processes is very essential in the separation industry. The processes is
conducted without heating and thus use less energy than conventional thermal separation
process which are distillation, sublimation or crystallization. Membrane is a selective
barricade that allows the separation of some species in a fluid by combination of filtering and
adsorption diffusion method. Separation is completed by selectively permeating one or more
components of a stream through the membrane whilst hindering the channel of one or other
components. Membrane separation also detach components over a huge range of particle
sizes and molecular weight which is from macromolecular material (starch and protein) to
monovalent ions.

Membrane processes can be described by a feed stream that is divided into 2 which are
retentate and permeate. The most universal process can be portrayed by the following Figure
(2)

Figure (2)

4
The retentate is the part of the feed that does not passage through the membrane, whilst the
permeate is that part of the feed that can pass through the membrane. The elective "sweep"
is a gas or liquid that is used to assist eliminate the permeate. The significance of the
component in membrane separation is known as the solute. The solute can be held on the
membrane and eliminate in the retentate or passed through the membrane in the permeate.
Membrane can perform separations by three different mechanisms

By having holes or pores which are of such a size that certain species can pass through and
others cannot. This mechanism is called size exclusion.

By selective retardation by the pores when the pore diameters are close to molecular
sizes. This mechanism is called pore flow.

By dissolution into the membrane, migration by molecular diffusion across the membrane,
and re-emergence from the other side. This is called solution diffusion.

The separation process is merely physical and the permeate and retentate can be used. Cold
separation is one of a membrane technology that is extensively used in the biotechnology
and pharmaceutical industries. Moreover, the advantage of using membrane is it allows
separation to occur which is impractical by thermal separation processes. For instance, it is
unachievable to separate the components of azeotropic liquids or solutes which form
isomorphic crystals by distillation or recrystallization. However, it is possible with the used
of membrane technology. Influenced by the different types of membranes, the selective
separation of certain individual component or mixture components is practical. Example of
essential applications in our daily life is the manufacture of drinking water by reverse
osmosis, filtration in the food industry and many more.

The choice of synthetic membranes for the aimed separation process is basically based on
few conditions. Membranes have to deliver optimum mass transfer area to process huge
amounts of feed stream. The selected membrane must contain high selectivity (rejection)
properties for certain particles; it has to repel fouling and with high mechanical stability.
Besides, it is also can be recycled and have low production costs.

5
 Industrial Applications of Membrane Separation

Processes

Reverse Osmosis

Desalination of brackish water

Treatment of wastewater to remove

impurities
Treatment of surface and ground water
Concentration of foodstuff
Removal of alcohol from beer and wine,
figure (3)

Figure (3)

Dialysis

Separation of nickel sulphate from sulphuric acid

Haemodialysis - removal of waste metabolites,

excess body water, and restoration of electrolyte
balance in blood, figure (4)

Figure (4)

6
 Electro dialysis

Production of table salt from seawater

Concentration of brines from reverse osmosis
Treatment of wastewater from electroplating
Demineralisation of cheese whey
Production of ultrapure water for
semiconductor industry, figure (5)

Figure (5)

Microfiltration

Sterilisation of drugs
Clarification of biological stabilisation of beverages
Purifications of antibiotics
Separation of mammalian cells from a liquid, figure (6)

Ultrafiltration

Pre-concentration of milk before making cheese figure (6)

Clarification of fruit juice
Recovery of vaccines and antibiotics from fermentation broth
Color removal from Kraft black liquor in paper-making

7
 Pervaporation

Dehydration of ethanol-water azeotropes

Removal of water from organic solvents
Removal of organics from water, figure (7)

Figure (7)

Gas Permeation

Separation of CO2 or H2 from methane and other

hydrocarbons
Adjustment of the H2/CO ratio in synthesis gas
Separation of air into nitrogen- and oxygen-enriched
streams
Recovery of helium
Recovery of methane from biogas , figure(8)

figure(8)

Liquid Membranes

Recovery of zinc from wastewater

Recovery of nickel from electroplating solutions, figure
(9)

Figure (9)

8
 Figure (10), types of membrane

Membrane processes have a number of advantages and disadvantages compared to

alternative means of performing separations.

Advantages and Disadvantages, Challenges of Membrane

Separations

Membrane processes have a number of pluses and minuses compared to alternative means
of performing separations.

9
 • The advantages include:

Because membrane processes can separate at the molecular scale up to a scale at which
particles can actually be seen, this implies that a very large number of separation needs
might actually be met by membrane processes.

Membrane processes generally do not require a phase change to make a separation (with
the exception of pervaporation). As a result, energy requirements will be low unless a great
deal of energy needs to be expended to increase the pressure of a feed stream in order to
drive the permeating component(s) across the membrane.

Membrane processes present basically a very simple flow sheet. There are no moving
parts (except for pumps or compressors), no complex control schemes, and little ancillary
equipment compared to many other processes. As such, they can offer a simple, east-to-
operate, low maintenance process option.

Membranes can be produced with extremely high selectivities for the components to be
separated. In general, the values of these selectivities are much higher than typical values for
relative volatility for distillation operations.

Because of the fact that a very large number of polymers and inorganic media can be
used as membranes, there can be a great deal of control over separation selectivities.

Membrane processes are able to recover minor but valuable components from a main
stream without substantial energy costs.

Membrane processes are potentially better for the environment since the membrane
approach require the use of relatively simple and non-harmful materials.

10
 • The disadvantages include:

Membrane processes seldom produce 2 pure products, that is, one of the 2 streams is
almost always contaminated with a minor amount of a second component. In some cases, a
product can only be concentrated as a retentate because of osmotic pressure problems. In
other cases the permeate stream can contain significant amount of materials which one is
trying to concentrate in the retentate because the membrane selectivity is not infinite.

Membrane processes cannot be easily staged compared to processes such as distillation,

and most often membrane processes have only one or sometimes two or three stages. This
means that the membrane being used for a given separation must have much higher
selectivities than would be necessary for relative volatilities in distillation. Thus the trade-off
is often high selectivity/few stages for membrane processes versus low selectivity/many
stages for other processes.

Membranes can have chemical incompatibilities with process solutions. This is especially
the case in typical chemical industry solutions which can contain high concentrations of
various organic compounds. Against such solutions, many polymer-based membranes (which
comprise the majority of membrane materials used today), can dissolve, or swell, or weaken
to the extent that their lifetimes become unacceptably short or their selectivities become
unacceptably low.

Membrane modules often cannot operate at much above room temperature. This is
again related to the fact that most membranes are polymer-based, and that a large fraction
of these polymers do not maintain their physical integrity at much above 100 oC. This
temperature limitation means that membrane processes in a number of cases cannot be
made compatible with chemical processes conditions very easily.

Membrane processes often do not scale up very well to accept massive stream sizes.
Membrane processes typically consist of a number of membrane modules in parallel, which
must be replicated over and over to scale to larger feed rates.

11
 Membrane processes can be saddled with major problems of fouling of the membranes
while processing some type of feed streams. This fouling, especially if it is difficult to remove,
can greatly restrict the permeation rate through the membranes and make them essentially
unsuitable for such applications.

TYPES OF MEMBRANE SEPARATION PROCESSES,

MECHANISMS OF SEPARATION

Membrane processes may be classified according to the types of membranes used. With
porous membranes, for example, a distinction is made between microfiltration and
ultrafiltration, depending on the pore sizes and particle sizes involved. As an extension to
this, reverse osmosis is sometimes called hyper filtration and indeed theories have been
developed, such as the "preferential sorption-capillary flow" model of Sourirajan,l in which
separation is considered to take place via pores with dimensions in the range of molecular
sizes. Another common way of classifying the membrane processes is according to the
exerted driving force. In nonporous (tight) membranes, which are used in, for example,
reverse osmosis, dialysis, pervaporation, vapour permeation, and gas separation, different
driving forces or phase conditions are applied (see Table 1). Various models2 suggest
fundamental differences between the separation mechanisms of these processes in tight
membranes. Such differences, however, exist only if we consider the conditions outside the
membranes. Within the membranes the transport mechanisms are identical for the
processes mentioned. This has been shown in theoretical studies of Cheng H. Lee3 and the
author4 and has been confirmed experimentally by the latter with mixtures of
hydrocarbons. Because of its importance this subject will be considered more closely in this
book.

12
 1. POROUS MEMBRANES

In micropore membranes (pore sizes between about 200-3000 nm) viscous flow (Poiseuille
flow) takes place under the influence of a pressure gradient as a driving force. The
permeating molecules collide with each other, thus exerting mutually a frictional force. As a
consequence all molecules pass the pores with the average drift velocity independent of
their size, shape, or mass. Therefore, transport through micro porous membranes is
nonseparative on a molecular base for liquids as well as for gases. 5 At pore sizes below
about 5 nm, large molecules such as polymers can be retained from a solution. Then the
process is called ultrafiltration. Apart from the "sieving" action of such membranes,
separation of molecules by size and shape also takes place by steric hindrance at the
entrance of the pores and by frictional resistance in the pores, both effects increasing with
the ratio of the molecular diameter (a) to the pore diameter (d). Pappenheimer6 took these
effects into account and derived for the effective cross-sectional area of a pore (Aef) the
following expression: Aef= Ao {(1 - a/d) 2 [1 - 2.104(a/d) + 2.09(a/d) 3 - 0.95(a/d) 5]} (2.1)

In which Ao is the real cross-sectional area of the pore. For mixtures of spherical molecules
with molecular weights of 100 and 600, respectively, we calculated the relationship
between permeate and retentate composition, depending on the cutoff molecular weight of
the ultrafiltration membranes, assuming the permeation rate of the permeants is
proportional to Aef and to their volume fraction in the retentate. From the results, shown in

13
figure (11), it is clear that, despite the large differences between the sizes of the molecules
and the cutoff molecular weights of the membranes under consideration, selectivities of
even 3 can be expected solely for geometrical reasons. By accounting also for the
concentration gradients, caused by this selective transport, even larger selectivities are
found. 7 Apart from the previously mentioned separation mechanisms of porous
membranes, use can also be made of "Knudsen flow" selectivity, if the pore diameters are
smaller than the mean free paths of the molecules to be separated; or, if the surface-to-
volume ratio of the pores is large enough to favour surface flow, preferential adsorption can
be applied. According to Budtov e/ al., 8 viscous flow of gases is observed in capillaries at
pore sizes above about 10-3 cm and "Knudsen flow" at pore sizes below about 10-6 cm. At
intermediate pore sizes both types of flow occur simultaneously. In the case of "Knudsen
flow," the chance that a permeating molecule will collide inside the pore with another
molecule is negligibly small with respect to the chance of it colliding with the pore wall.
Hence the permeating molecule will pass that pore at its own molecular speed, which is
inversely proportional to the square root of its molar mass.5 Although the resulting
"Knudsen" selectivity is generally low, this principle does have at least one interesting
application: that of separating hydrogen from mixtures with hydrocarbons in, for example,
the dehydrogenation process, in which porous ceramic membranes9 are used. In this way

the chemical

Figure (11). Molecular separation with porous membranes.

14
Equilibrium is shifted toward higher conversions, thus reducing considerably capital and
operating costs. At pore sizes below, say, 3 nm, the surface area of the pores is so large with
respect to the volume of the pores that the average residence time of a molecule on the
pore wall becomes noticeable. Then at least part of the transport takes place along the pore
surface. In such a process, which is called surface flow, transport of those compounds which
are adsorbed preferentially is enhanced. For instance, in a reverse osmosis experiment
performed on a hydrocarbon mixture, consisting of residual mineral oil, methyl ethyl
ketone, and toluene (weight ratio 1: 1: 1) at 20oe, the selectivity in favour of the solvent
mixture compared to the oil amounted to 20 with a Vycor glass membrane (pore size 3 nm),
10 while according to Eq. (2.1) a selectivity of about 3 would be expected. In this experiment
preferential sorption of the solvents took place onto the strongly polar pore surfaces. On
increasing the temperature to 800e the selectivity dropped to below 3 on account of the
decrease in preferential adsorption. Specific interactions can also be utilized for breaking
emulsions. A very strong emulsion of a concentrated aqueous H2S04 solution (droplet size
10, um) in an alkylate fraction, stabilized with a dispersant, can easily be broken by a micro
porous glass fibre membrane with an acrylic binder. 11 The acid phase coagulates onto the
polar glass fibres and the oil phase onto the hydrophobic polymeric binder. Both phases
were found to pass the membrane at an average flux of 10 m3j (m2 • bar· day). A well-
known process is the concentration of oil-in-water emulsions by hydrophilic (cellulose
acetate or ceramic) membranes. The overpressure is kept below the capillary pressure so
that only water can pass, a concentrated oil-in-water emulsion being retained. Another
application of such interactions is membrane distillation.12 In this process an aqueous
solution of a nonevaporating substance at higher temperature and clean condensate at
lower temperature is kept separated by a micro porous hydrophobic membrane at pressure
drops below the capillary pressure. Under such conditions only water vapour can pass
through the membrane from the solution and condense into the condensate phase. In this
way very pure (boiler feed) water is obtained, while waste heat can be used because of the
large membrane surface area per unit module volume which can be installed, permitting
low temperature gradients across the membranes. A process of membrane distillation in
reverse is vapor separation by capillary condensation, introduced and commercialized by
the Japanese membrane manufacturer Mitshubishi. Preferential condensation of the

15
component of larger activity (or concentration) takes place in the pores of the membrane.
The condensed liquid in the pores is evaporated on the

Permeate side by evacuation. Mitshubishi claims that a selectivity of more than 200 in favor
of water relative to ethanol can be achieved in this way. The development of porous
membranes, which was originally focused on polymeric materials, nowadays shows
increasing application of ceramics. Total sales of ceramic membranes are expected to grow
by 30% annually, for the most part at the expense of polymeric membranes.13 the strong
hydrophilic character of ceramics renders them eminently suited for treating aqueous
solutions and emulsions. Their high thermal and chemical stability warrants their application
at high temperatures and under severe corrosive conditions such as, for example, in
dehydrogenation reactors for equilibrium shift.9 the possibility of handling mixed oxides is
encouraging the development of catalytic ceramic membranes. 14 Catalytic activity can also
be introduced by impregnation of ceramic membranes.15 this technique can also be used to
build-in active groups into the pore surfaces for enhancing preferential adsorption, thus
improving the selectivity of membrane separation. A quite new development is the
preparation of membranes from molecular sieves, which potentially have extremely high
selectivities. Preliminary investigations with "carbon molecular sieve membranes" have
been performed by Koresh and Sofer. 16 They prepared such membranes by pyrolysis and
thermal treatment of polymeric hollow fibers. High gas selectivities were indeed observed
with some of these membranes; the reproducibility of the membrane production is still very
poor, however. The preparation of Zeolite membranes, although mentioned in the patent
literature, 17 is still far from technical realization.

2. LIQUID MEMBRANES

Unsupported liquid membranes have been invented by N. N. Li. 18 In fact they consist of a
very stable emulsion of an aqueous solution of a reagent and an immiscible hydrocarbon
phase, the latter liquid being the continuous phase. By gentle stirring this emulsion is
contacted with an aqueous phase, containing components which have to be removed.
These components dissolve in the resulting oil drops and diffuse through to the contained
aqueous solution droplets, where they are neutralized or converted by the reagent present.
Sometimes a complexing agent is added to the oil phase. The process is then called

16
mediated or facilitated transport; otherwise it is called nonmediated transport. After
reaction the reagent containing oily emulsion, which is stabilized by the addition of
dispersants or emulsifiers, is separated from the aqueous phase and broken, for example by
means of the aforementioned microporous membrane with hydrophilic and hydrophobic
arrays,l1 in order to recover the various ingredients supplied. In later developments
microporous polymer membranes were impregnated with a liquid containing a complexing
agent19 that was immiscible with at least one of the contacting phases. This "supported
liquid membrane" seems technically to be more feasible. The main problems are losses of
the impregnation liquid into the contacting phase(s) (membrane instability), low permeant
fluxes, sensitivity to overpressure due to irregular pore size distributions of the polymeric
membranes, and fouling of the liquid phases with surface-active contaminants.

3. TIGHT MEMBRANES

An important category of membranes is represented by nonporous (tight) polymeric

membranes, because they are applied in many membrane separation processes. In all these
processes the permeants are sorbed into the membrane material under the influence of
their thermodynamic potential and pass it as a result of a driving force exerted. The various
processes are distinguished by the applied driving forces and by the phase condition(s) of
the permeants. Let us consider these processes. In pervaporation the feed is in the liquid
phase; the permeants are evaporated by evacuation. The driving force is the activity
gradient of the individual permeants across the membrane, which corresponds to the
gradient in partial vapor pressure of those components. In vapor permeation the driving
force is also the gradient in partial vapor pressure. However, the feed is supplied as a vapor.
Therefore, no heat supply is needed for evaporating the permeants as is required in
pervaporation. Membrane separation of gas mixtures resembles vapor permeation, the
driving force being the gradient of the partial pressure of the gases involved. With reverse
osmosis the driving force is also a pressure gradient, but the feed (retentate) as well as the
permeate are liquids. In this process the permeants are transported in the direction of
increasing concentration. As a consequence, the osmotic pressure of the individual
permeants must be overcome, which limits the application of reverse osmosis to dilute

17
solutions of the retained compounds. Also with dialysis (osmosis) the feed is a liquid mixture
or solution. The permeants are diluted at the permeate side by means of a so-called
sweeping solvent. Hence, in dialysis the driving force is a concentration gradient. If the
boiling point of the permeants is much lower than that of the sweeping liquid, so that they
can be separated by flashing and/or stripping from the latter, the dialysis process is called
pertraction.

4. SELECTION OF MEMBRANE SEPARATION PROCESSES AND MECHANISMS

Although the review of the membrane processes and separation mechanisms in the
previous sections is far from complete, it shows that the possibilities of the membrane
separation technique are almost unlimited. The mechanisms used in the processes of
Section 1 and in the liquid membranes (especially with mediated transport, see Section 2)
are all different and are very specific for those processes; for more information the reader is
referred to the relevant literature (see also the references). In this book we restrict
ourselves to transport in tight (polymeric membranes), which covers the majority of those
processes in which separation takes place on a molecular scale. It will be shown that all
these processes can be described by the same physical model.

Membrane Characterization

Membrane processes can cover a wide range of separation problems with a specific
membrane being required for every problem. Membranes may differ significantly in their
structure and consequently in their functionality. To know what membrane to use in a
particular separation process, different membranes must be characterized in terms of
structure and mass transport properties. Because very different membranes are used,
different techniques are required for characterization.

Membrane characterization is a very important part of membrane research and

development because the design of membrane processes and systems depends on reliable
data relating to membrane properties.

18
The following sections briefly discuss the following:

Characterization of Porous Membranes

Characterization of Dense, Homogeneous Membranes

Characterization of Charged Membranes

• Characterization of Porous Membranes

Porous micro- or ultrafiltration membranes are generally characterized in terms of
their trans-membrane flux, pore size, pore size distribution, and molecular mass cut-
off.

1. Electron Microscopy

The structure of porous membranes can be determined by electron microscopy. Scanning

Electron Microscopy (SEM) gives an especially clear picture of membrane structure and
requires minimum sample preparation; however, resolution is limited to about 50-nm.
Higher resolution can be obtained with Transmission Electron Microscopy (TEM), but
sample preparation is significantly more complex and the structure is not nearly as clear as
that obtained by scanning electron microscopy.

2. Bubble-Point Test

The "bubble-point" test is a simple method for determining the maximum pore size of a
membrane. One side of the membrane is filled with liquid such as water, although i-
propanol is often used as the standard liquid. If the other side of the membrane is exposed
to air at a certain pressure, air bubbles will penetrate through the pores of the membrane
when the radius of the air bubble is equal to the radius of the pore. The pressure needed to
penetrate a pore is inversely proportional to pore size. Thus, penetration occurs first
through the largest pores. When the pressure is increased further, pores with smaller
diameters are also penetrated.

19
The basic principle of the bubble point method is shown in the Figure (12).

Figure (12)

Because the surface tension between water and air is rather high, high pressure is required
for the determination of small pores. In practice, pore sizes between 0.1 and 10 mm are
determined by hydrostatic pressures of 1500 - 15 kPa. The main application of the bubble-
point test is to determine pinholes and leaks in micro- and ultrafiltration membranes and
modules.

3. Filtration Tests

In filtration tests, trans-membrane flux and membrane solute retention are determined. To
avoid the influence of concentration polarization or any other boundary layer phenomenon,
the trans-membrane flux is generally measured as a function of applied hydrostatic pressure
with ultra-pure water.

Membrane flux often decreases with time during the filtration test due to compaction of the
membrane structure under pressure. A compaction factor has been defined, which is

20
determined from the slope of the curve obtained when the trans-membrane flux at
constant pressure is plotted versus time on a semi-logarithmic scale.

Unfortunately, the fluxes measured with ultra-pure water, at least in ultra- and
microfiltration, often bear little relation to those obtained with solutions containing
macromolecules or suspended particles.

4. Molecular Weight Cut-Off

Many membranes, especially those used in ultrafiltration, are also characterized in terms of
their molecular mass cut-off. Here, the rejection of a given membrane for various molecular
mass components is determined in filtration tests. Rejection is plotted versus molecular
mass and the resulting curve describes the membrane's solute retention properties.
Components with a diameter smaller than the smallest pores pass through the membrane
unhindered; all components with a diameter smaller than the largest pores but larger than
the smallest pores are rejected in proportion to the pore size distribution of the membrane.

The retention R is a dimensionless number expressed simply as:

Where cF and cP are the solute concentration in the feed and permeate respectively. The
value of R varies between 100% (complete retention of the solute) and 0% (solute and
solvent pass through the membrane freely).

Some commercial membranes have a very narrow pore size distribution and thus a sharp
molecular mass cut-off. Others have a wider pore size distribution and therefore a more
diffuse cut-off.

• Characterization of Dense, Homogeneous Membranes

Dense membranes are normally used to perform separations on a molecular level. As such,
the chemical nature and morphology of the polymeric membrane and the extent of
interaction between the polymer and the permeate are important factors to consider.

21
Characterization methods used with porous membranes need to be supplemented with
other procedures. One of the simplest method of characterizing these membranes is to
determine the membrane permeability towards gases and liquids. Various physical methods
can be used to characterize the parameters that affect the permeability, such as the glass
transition temperature and polymer crystallinity (degree, size and shape).

• Characterization of Charged Membranes

The methods used to determine the structural properties of ion-exchange membranes are
similar to those used for characterizing other polymer membranes. These methods are also
supplemented by various electro kinetic parameters such as the zeta potential and surface
charge density.

Because ion-exchange membranes are used mainly in separation processes with electrical
potential driving forces, their permeability and selectivity are determined under
experimental conditions closely related to their practical use, and their properties are
expressed in terms commonly used in electrochemistry (e.g. electrical resistance, ion-
transfer numbers, charge densities).

Electrochemical Impedance Spectroscopy (EIS)

Electrochemical impedance spectroscopy is a relatively new non-destructive technique for

characterizing membranes in terms of its electrical properties. The method involves the
measurement of the electrical impedance of a membrane system over a wide range of
frequencies (1 - 10,000 Hz).

Impedance measurements are made by injecting an alternating current (ac) of known

angular frequency (w) and small amplitude (IO) into the system. As a result, an electrical
potential difference (voltage) is developed across the membrane. The amplitude (VO) and
phase difference (F) of the developed voltage are then measured. This is achieved through
comparison with a complex electrical circuits within the impedance spectrometer.

22
The EIS method is useful in determining the electrical properties of heterogeneous
membrane system (e.g. those composed of a thin skin on a porous support) as it permits the
evaluation of contribution of each layer separately. The basic set-up is shown schematically
in Figure x-xx for a simple 1-membrane system.

A membrane separates the container into 2 chambers, and both are filled with an
electrolyte (e.g. potassium chloride solution). The electrodes are immersed as shown.
Current is injected via the electrodes.

To determine the impedance requires the measurement of the potential difference (and
phase) of the potential developed across the "system", which in this case includes not only
the membrane but also the solution in contact with the membrane (including the unstirred
layer of solution at the membrane surface), plus the electrode-solution interface
impedances which are in series with it.

A further complication arises if the potential developed is measured using the same
electrodes used to inject the current, for then we must also include the impedance of the
double layer which is present between the electrodes and the aqueous solution. The
impedance of the electrode-solution double layer is strongly dependent on the frequency,
especially at low frequencies; and its effect can be very large. The use of 2-electrode
impedance measurement method is best confined to high frequencies.

This problem can be eliminated through the use of 4-electrodes system for impedance
measurement because it allows only the electrical potential developed between the voltage
electrodes to be measured. The potentials developed at the current-injecting electrodes
need not be considered. Another advantage of the 4-electrode system is that the voltage
electrodes may be placed arbitrarily close to the membrane. A typical 4-eletrodes set-up is
shown in Figure x-xx. Now the membrane "system" being considered consists of the
membrane itself, plus the unstirred layers on both sides of the membrane, and the
electrolyte between the 2 voltage electrodes.

23
Membrane Module Selection

The types of modules generally used in some of the major membrane processes are listed in
the Table 2.

Table2, Membrane Technology and Applications

The choice of the most suitable membrane module type for a particular membrane
separation must balance a number of factors, as shown in the Table 3.

Table 3, Membrane Technology and Applications

24
These factors are briefly discussed below.

Cost (which is always important) is difficult to quantify because the actual price of the
same module design varies widely depending on the application. Generally, high-pressure
modules are more expensive than low-pressure or vacuum modules.

Concentration polarization is a particularly important factor in liquid separation

such as reverse osmosis and ultrafiltration. In gas separations, concentration polarization is
more easily controlled. Hollow fine-fiber modules are notoriously prone to fouling and
concentration polarization and can be used in reverse osmosis applications only of extensive
and costly feed solution pre-treatment removes all particulates. These fibers cannot be used
in ultrafiltration applications at all.

Another factor is the ease with which various membrane materials can be fabricated into a
particular module design. Almost all membranes can be formed into plate-and-frame, spiral-
wound and tubular modules, but many membrane materials cannot be fabricated into
hollow fine fibers or capillary fibers.

Finally, the suitability of the module design for high-pressure operation and the relative
magnitude of pressure drops on the feed and permeate sides of the membrane can be
important factors.

Membrane configuration

• Tubular
• Spilar wound
• Hollow fiber
• Plate and frame

25
Figure (13). Tubular element Figure (14). Spilar wound element

Figure (15). Plate and frame element Figure (16). Hollow fiber element

26
Membrane performance and governing equations

The selection of synthetic membranes for a targeted separation process is usually based on
few requirements. Membranes have to provide enough mass transfer area to process large
amounts of feed stream. The selected membrane has to have high selectivity (rejection)
properties for certain particles; it has to resist fouling and to have high mechanical stability.
It also needs to be reproducible and to have low manufacturing costs. The main modelling
equation for the dead-end filtration at constant pressure drop is represented by Darcy's law:

Where Vp and Q are the volume of the permeate and its volumetric flow rate respectively
(proportional to same characteristics of the feed flow), μ is dynamic viscosity of permeating
fluid, A is membrane area, Rm and R are the respective resistances of membrane and
growing deposit of the foulants. Rm can be interpreted as a membrane resistance to the
solvent (water) permeation. This resistance is a membrane intrinsic property and is
expected to be fairly constant and independent of the driving force, Δp. R is related to the
type of membrane foulant, its concentration in the filtering solution, and the nature of
foulant-membrane interactions. Darcy's law allows for calculation of the membrane area for
a targeted separation at given conditions. The solute sieving coefficient is defined by the
equation:

Where Cf and Cp are the solute concentrations in feed and permeate respectively. Hydraulic
permeability is defined as the inverse of resistance and is represented by the equation:

27
Where J is the permeate flux which is the volumetric flow rate per unit of membrane area.
The solute sieving coefficient and hydraulic permeability allow the quick assessment of the
synthetic membrane performance.

Designing a Membrane System

When designing a filtration system you must first specify your permeate (product) flow rate
and the flux of your membrane along with the membrane area of your selected unit.
Number of units can be found using the following equation

Where Q_p is the permeate flow rate, f is the flux, and S_E is the area of the selected
membrane.

Once you have also specified a recovery, you can choose a number of stages (series
membranes as opposed to parallel). Generally if the desired recovery is below 50%, the
separation can be done in one stage. Recoveries higher than this are generally best done
with 2 stages. More stages can be used to achieve very high recoveries but these are rare.
Once you have chosen a number of stages, you can use the following equations to
determine the number of membranes in each stage

Where Y is the recovery and n is the number of stages and R is the staging ratio. N_E_i is the
number of membrane elements in stage i.

Membrane cleaning methods

Membrane technology

There are several different membrane cleaning methods, such as forward flush, backward
flush and air flush.

28
 • When forward flush is applied, membranes are flushed with feed water or
permeate forward. The feed water or permeate flows through the system more
rapidly than during the production phase. Because of the more rapid flow and the
resulting turbulence, particles that are absorbed to the membrane are released
and discharged. The particles that are absorbed to membrane pores are not
released. These particles can only be removed through backward flushing.

• Backward flush is a reversed filtration process. Permeate is flushed through the

feed water side of the system under pressure, applying twice the flux that is used
during filtration. When the flux has not restored itself sufficiently after back
flushing, a chemical cleaning process can be applied.

• During a chemical cleaning process, membranes are soaked with a solution of

chlorine bleach, hydrochloric acid or hydrogen peroxide. First the solution soaks
into the membranes for a number of minutes and after that a forward flush or
backward flush is applied, causing the contaminants to be rinsed out.

• A newer cleaning method is the so-called air flush or air/ water flush. This is a
forward flush during which air is injected in the supplier pipe. Because air is used
(while the water speed remains the same), a much more turbulent cleaning
system is created.

Forward flush

When forward flush is applied in a membrane, the barrier that is responsible for dead-end
management is opened. At the same time the membrane is temporarily performing cross-
flow filtration, without the production of permeate.
The purpose of a forward flush is the removal of a constructed layer of contaminants on
the membrane through the creation of turbulence. A high hydraulic pressure gradient is in
order during forward flush.figure(17)

29
 Figure (17)

Backward flush

When backward flush is applied the pores of a membrane are flushed inside out. The
pressure on the permeate side of the membrane is higher than the pressure within the
membranes, causing the pores to be cleaned. A backward flush is executed under a
pressure that is about 2.5 times greater than the production pressure.
Permeate is always used for a backward flush, because the permeate chamber must
always be free of contagion. A consequence of backward flush is a decrease in recovery of
the process. Because of this, a backward flush must take up the smallest possible amount
of time. However, the flush must be maintained long enough to fully flush the volume of a
module at least once .figure(18)

figure(18)

30
Air flush or air/ water flush

Fouling on the membrane surface needs to be removed as effectively as possible during

backward flush. The so-called air flush, a concept developed by Nuon in cooperation with
DHV and X-flow, has proved to be very useful to perform this process. Using air flush
means flushing the inside of membranes with an air/ water mixture.
During an air flush air is added to the forward flush, causing air bubbles to form, which
cause a higher turbulence. Because of this turbulence the fouling is removed from the
membrane surface.
The benefit of the air flush over the forward flush is that it uses a smaller pumping
capacity during the cleaning process. Figure (19)

Figure (19)

Chemical cleaning

When the above-mentioned cleaning methods are not effective enough to reduce the flux
to an acceptable level, it is necessary to clean the membranes chemically.
During chemical cleaning chemicals, such as hydrogen chloride (HCl) and nitric acid
(HNO3), or disinfection agents, such as hydrogen peroxide (H2O2) are added to the
permeate during backward flush. As soon as the entire module is filled up with permeate,
the chemicals need to soak in. After the cleaning chemicals have fully soaked in, the
module is flushed and, finally, put back into production.

31
Cleaning methods are often combined. For example, one can use a backward flush for the
removal of pore fouling, followed by a forward flush or air flush.
The cleaning method or strategy that is used is dependent on many factors. In practise,
the most suitable methods is determined by trial and error (practise tests), figure (8) is
industrial reverse osmosis membrane cleaning. Figure (20)

Figure (20)

32
Reference

1. H. S. Ong, Challenges ahead for Singapore’s water supply. Seminar on Ensuring

Singapore’s Water Supply: Options and Issues Shangri-la Hotel, 10–11 Nov. (1997).

2. M. Joel, E. O. Peter, and R. W. Mark, Water Treatment Membrane Process McGraw-Hill

Company, New York, 1996, pp. 17.1–17.31.

3. S. Judd and B. Jefferson (eds.), Membrane for Industrial Wastewater Recovery and Re-use
Elsevier Advanced Technology, Oxford, 2003.

4. J. P. Chen, S. L. Kim, and Y. P. Ting, Optimization of feed pretreatment for membrane

filtration of secondary effluent. Journal of Membrane Science 219 27–45 (2003).

5. S. L. Kim, J. P. Chen, and Y. P. Ting, Study on feed pretreatment for membrane filtration of
secondary effluent. Separation & Purification Technology 29 171–179, 2002.

6. R. D. Letterman (ed.), Water Quality and Treatment, A Handbook of Community Water

Supplies 5th ed., McGraw-Hill, New York, 1999.

7. W. S. W. Ho and K. K. Sirkar (eds.), Membrane Handbook Chapman & Hall, New York,
1992.

8. Singapore Public Utilities Board. Singapore Water Reclamation Study, Expert Panel
Review and Findings. Singapore (2002).

9. T. Matsuura, Progress in membrane science and technology for seawater desalination—a

review. Desalination 134 47–54 (2001).

33