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27 December 2015 3
Dr. Saeed GUL, Department of Chemical Engineering, UET Peshawar, Pakistan
Introduction
since the 1960s a new technology using synthetic membranes for
process separations has been rapidly developed by materials
scientists, physical chemists and chemical engineers.
27 December 2015 4
Dr. Saeed GUL, Department of Chemical Engineering, UET Peshawar, Pakistan
Classification Of Membrane Processes
27 December 2015 5
Dr. Saeed GUL, Department of Chemical Engineering, UET Peshawar, Pakistan
Size of Materials Retained, Driving Force,
and Type of Membrane
Size of materials
Process Driving force Type of membrane
retained
0.1 - 10 µm Pressure difference
Microfiltration Porous
microparticles (0.5 - 2 bar)
1 - 100 nm Pressure difference
Ultrafiltration Microporous
macromolecules (1 - 10 bar)
0.5 - 5 nm Pressure difference
Nanofiltration Microporous
molecules (10 - 70 bar)
< 1 nm Pressure difference
Reverse Osmosis Nonporous
molecules (10 - 100 bar)
< 1 nm
Nonporous or
Dialysis molecules Concentration diff.
microporous
< 1 nm Electrical potential Nonporous or
Electrodialysis
molecules difference microporous
< 1 nm
Pervaporation Concentration diff. Nonporous
molecules
< 1 nm Partial pressure diff.
Gas Permeation Nonporous
molecules (1 - 100 bar)
Membrane < 1 nm
Partial pressure diff. Microporous
Distillation molecules
27 December 2015 6
Dr. Saeed GUL, Department of Chemical Engineering, UET Peshawar, Pakistan
Examples of Applications and Alternative
Separation Processes
Process Applications Alternative Processes
Sedimentation,
Microfiltration Separation of bacteria and cells from solutions
Centrifugation
Separation of proteins and virus,
Ultrafiltration Centrifugation
concentration of oil-in-water emulsions
Separation of dye and sugar, Distillation,
Nanofiltration
water softening Evaporation
Distillation,
Desalination of sea and brackish water,
Reverse Osmosis Evaporation,
process water purification
Dialysis
Dialysis Purification of blood (artificial kidney) Reverse osmosis
Crystallization,
Electrodialysis Separation of electrolytes from nonelectrolytes
Precipitation
Pervaporation Dehydration of ethanol and organic solvents Distillation
Absorption,
Hydrogen recovery from process gas streams,
Gas Permeation Adsorption,
dehydration and separation of air
Condensation
Membrane
Water purification and desalination Distillation
Distillation
27 December 2015 7
Dr. Saeed GUL, Department of Chemical Engineering, UET Peshawar, Pakistan
Examples of Applications
This chapter is primarily concerned with the pressure driven
processes, microfiltration (MF), ultrafiltration (UF), nanofiltration
(NF) and reverse osmosis (RO).
These are already well-established large-scale industrial processes.
For example, reverse osmosis is used world-wide for the
desalination of brackish water, with more than 1,000 units in
operation.
Plants capable of producing up to 105 m3/day of drinking water are
in operation.
it is now standard practice to include an ultrafiltration unit in paint
plants in the car industry.
The resulting recovery of paint from wash waters can produce
savings of 10–30 per cent in paint usage, and allows recycling of
the wash waters.
27 December 2015 8
Dr. Saeed GUL, Department of Chemical Engineering, UET Peshawar, Pakistan
The Nature of Synthetic Membranes
Membranes used for the pressure-driven separation processes,
microfiltration, ultrafiltration and reverse osmosis, as well as those
used for dialysis, are most commonly made of polymeric
materials.
Initially most such membranes were cellulosic in nature.
These are now being replaced by polyamide, polysulphone,
polycarbonate and a number of other advanced polymers.
These synthetic polymers have improved chemical stability and
better resistance to microbial degradation.
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Dr. Saeed GUL, Department of Chemical Engineering, UET Peshawar, Pakistan
Membrane Synthesis
Membranes have most commonly been produced by a form of phase
inversion known as immersion precipitation
This process has four main steps:
1. The polymer is dissolved in a solvent to 10–30 per cent by mass
2. The resulting solution is cast on a suitable support as a film of
thickness, approximately 100 µm
3. The film is quenched by immersion in a non-solvent bath,
typically water or an aqueous solution
4. The resulting membrane is annealed by heating
The third step gives a polymer-rich phase forming the membrane,
and a polymer-depleted phase forming the pores. The ultimate
membrane structure results as a combination of phase separation
and mass transfer, variation of the production conditions giving
membranes with different separation characteristics.
27 December 2015 10
Dr. Saeed GUL, Department of Chemical Engineering, UET Peshawar, Pakistan
The Nature of Synthetic Membranes
27 December 2015 11
Dr. Saeed GUL, Department of Chemical Engineering, UET Peshawar, Pakistan
The Nature of Synthetic Membranes
27 December 2015 12
Dr. Saeed GUL, Department of Chemical Engineering, UET Peshawar, Pakistan
The Nature of Synthetic Membranes
Polymeric membranes are most commonly produced in the form of
flat sheets, but they are also widely produced as tubes of diameter
10–25 mm and in the form of hollow fibres of diameter 0.1–2.0 mm.
A significant recent advance has been the development of
microfiltration and ultrafiltration membranes composed of inorganic
oxide materials. These are presently produced by two main
techniques:
1. deposition of colloidal metal oxide on to a supporting material
such as carbon, and
2. as purely ceramic materials by high temperature sintering of spray-
dried oxide microspheres.
Other innovative production techniques lead to the formation of
membranes with very regular pore structures. Zirconia, alumina and
titania are the materials most commonly used.
27 December 2015 13
Dr. Saeed GUL, Department of Chemical Engineering, UET Peshawar, Pakistan
The Nature of Synthetic Membranes
27 December 2015 17
Dr. Saeed GUL, Department of Chemical Engineering, UET Peshawar, Pakistan
General Membrane Equation
The general membrane equation is an attempt to state the factors
which may be important in determining the membrane permeation
rate for pressure driven processes. This takes the form:
27 December 2015 18
Dr. Saeed GUL, Department of Chemical Engineering, UET Peshawar, Pakistan
General Membrane Equation
For microfiltration and ultrafiltration membranes where solvent flow
is most often essentially laminar through an arrangement of
tortuous channels, this is analogous to the Carman–Kozeny equation
used in conventional filtration
27 December 2015 19
Dr. Saeed GUL, Department of Chemical Engineering, UET Peshawar, Pakistan
The Concept of Cross-Flow Microfiltration
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Dr. Saeed GUL, Department of Chemical Engineering, UET Peshawar, Pakistan
Membrane Fouling
In practice, the membrane
permeation rate falls with
time due to membrane
fouling; that is blocking of
the membrane surface and
pores by the particulate
materials, as shown in
Figure. The time-dependence of membrane
permeation rate during cross-flow filtration:
The rate of fouling depends on (a) Low cross-flow velocity, (b) Increased
the nature of the materials cross-flow velocity, (c) Backflushing at the
bottom of each “saw-tooth”
being processed, the nature of
the membrane, the cross-flow
velocity and the applied
pressure.
27 December 2015 23
Dr. Saeed GUL, Department of Chemical Engineering, UET Peshawar, Pakistan
Membrane Fouling
Ideally, cross-flow microfiltration would be the pressure-driven
removal of the process liquid through a porous medium without the
deposition of particulate material.
The flux decrease occurring during cross-flow microfiltration shows
that this is not the case.
If the decrease is due to particle deposition resulting from incomplete
removal by the cross-flow liquid, then a description analogous to that
of generalized cake filtration theory, should apply. The general
Membrane Equation (GME) may then be written as:
27 December 2015 24
Dr. Saeed GUL, Department of Chemical Engineering, UET Peshawar, Pakistan
Membrane Fouling
If all filtered particles remain in the cake, may be written as:
where e is the void volume of the cake and ds the mean particle diameter
27 December 2015 25
Dr. Saeed GUL, Department of Chemical Engineering, UET Peshawar, Pakistan
Membrane Fouling
Combing and
gives
27 December 2015 28
Dr. Saeed GUL, Department of Chemical Engineering, UET Peshawar, Pakistan
Ultrafiltration
Ultrafiltration is one of the most widely used of the pressure-
driven membrane separation processes.
The solutes retained or rejected by ultrafiltration membranes are
those with molecular weights of 103 or greater, depending mostly
on the MWCO of the membrane chosen.
The process liquid, dissolved salts and low molecular weight
organic molecules (500–1000 kg/kmol) generally pass through the
membrane.
The pressure difference applied across the membrane is usually in
the range 0.1–0.7 MN/m2 and membrane permeation rates are
typically 0.01–0.2 m3/m2 h.
In industry, ultrafiltration is always operated in the cross-flow
mode.
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Dr. Saeed GUL, Department of Chemical Engineering, UET Peshawar, Pakistan
Ultrafiltration
Concentration Polarization
The separation of process liquid and solute
that takes place at the membrane during
ultrafiltration gives rise to an increase in solute
concentration close to the membrane surface,
as shown in Figure.
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Dr. Saeed GUL, Department of Chemical Engineering, UET Peshawar, Pakistan
Ultrafiltration
Concentration Polarization
At steady state, the rate of back-diffusion will be equal to the rate of
removal of solute at the membrane, minus the rate of solute leakage
through the membrane:
Or:
27 December 2015 31
Dr. Saeed GUL, Department of Chemical Engineering, UET Peshawar, Pakistan
Ultrafiltration
Concentration Polarization
If it is further assumed that the membrane completely rejects the
solute, that is, R = 1 and Cp = 0, then:
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Dr. Saeed GUL, Department of Chemical Engineering, UET Peshawar, Pakistan
Ultrafiltration
Concentration Polarization
or for tubular systems:
27 December 2015 34
Dr. Saeed GUL, Department of Chemical Engineering, UET Peshawar, Pakistan
Ultrafiltration
Concentration Polarization
For both laminar and turbulent flow it is clear that the mass
transfer coefficient and hence the membrane permeation rate may
be increased, where these equations are valid, by increasing the
cross-flow velocity or decreasing the channel height.
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Dr. Saeed GUL, Department of Chemical Engineering, UET Peshawar, Pakistan
Ultrafiltration
Gel Polarization
The boundary-layer theory applies to mass-transfer controlled systems
where the membrane permeation rate is independent of pressure, for
there is no pressure term in the model.
In such cases it has been proposed that, as the concentration at the
membrane increases, the solute eventually precipitates on the
membrane surface.
This layer of precipitated solute is known as the gel-layer, and the
theory has thus become known as the gel-polarization model proposed
by MICHAELS. Under such conditions Cw becomes replaced by a
constant CG the concentration of solute in the gel-layer, and:
30 December 2015 36
Dr. Saeed GUL, Department of Chemical Engineering, UET Peshawar, Pakistan
Reverse Osmosis
Osmosis is the spontaneous net movement of
solvent molecules through a semi-permeable
membrane into a region of higher solute
concentration, in the direction that tends to
equalize the solute concentrations on the two
sides.
Applying an external pressure to reverse the
natural flow of pure solvent, thus, is reverse
osmosis.
Osmotic pressure is the minimum pressure
which needs to be applied to a solution to
prevent the inward flow of water across a semi-
permeable membrane. It is also defined as the
measure of the tendency of a solution to take in
water by osmosis.
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Dr. Saeed GUL, Department of Chemical Engineering, UET Peshawar, Pakistan
Reverse Osmosis
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Dr. Saeed GUL, Department of Chemical Engineering, UET Peshawar, Pakistan
Transport Through RO & NF Membrane
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Dr. Saeed GUL, Department of Chemical Engineering, UET Peshawar, Pakistan
Transport Through RO & NF Membrane
From Fick’s law we can derive an expression for the flux of solvent
which can be expressed as follows
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Dr. Saeed GUL, Department of Chemical Engineering, UET Peshawar, Pakistan
Membrane Modules and Plant Configuration
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Dr. Saeed GUL, Department of Chemical Engineering, UET Peshawar, Pakistan
Tubular modules
Tubular modules are preferred for solutions containing suspended
solids and were amongst the first industrial designs.
The membranes are formed as tubes and are normally cast onto a
supporting porous substrate.
The tubes are not self-supporting and are normally inserted in a
perforated tube. The tubes are typically housed in a shell and tube
configuration.
The membranes are normally sealed by means of elastomeric
inserts at either end of the tube.
The permeate is collected in the shell side of the module.
Tubular modules are normally operated in the turbulent region
with a Reynolds number of >10,000 and fluid velocities in the
region of 2-6 m/s.
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Dr. Saeed GUL, Department of Chemical Engineering, UET Peshawar, Pakistan
Tubular modules
The tubes are usually 8-12 ft in
length
Tubular modules are preferred for
applications where sanitary
operation is of paramount
importance because the design
allows for easy cleaning and
sterilization
The main drawbacks of tubular
systems are the low surface to
volume ratio and the high liquid
hold-up. This limitation restricts the
concentration factor that can be
achieved in batch operation.
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Dr. Saeed GUL, Department of Chemical Engineering, UET Peshawar, Pakistan
Flat-Sheet Modules
Flat-sheet modules are similar in some
ways to conventional filter presses.
This consists of a series of annular
membrane discs of outer diameter 0.3
m placed on either side of
polysulphone support plates which
also provide channels through which
permeate can be withdrawn.
The sandwiches of membrane and
support plate are separated from one
another by spacer plates which have
central and peripheral holes, through
which the feed liquor is directed over
the surface of the membranes,
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Dr. Saeed GUL, Department of Chemical Engineering, UET Peshawar, Pakistan
Flat-Sheet Modules
The flow is laminar.
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Dr. Saeed GUL, Department of Chemical Engineering, UET Peshawar, Pakistan
Spiral-Wound Modules
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Dr. Saeed GUL, Department of Chemical Engineering, UET Peshawar, Pakistan
Hollow-Fibre Modules
Hollow-fibre modules, consist of bundles of
fine fibres, 0.1–2.0 mm in diameter, sealed in
a tube.
For RO desalination applications, the feed
flow is usually around the outside of the
unsupported fibres with permeation radially
inward, as the fibres cannot withstand high
pressures differences in the opposite
direction.
This gives very compact units capable of high
pressure operation, although the flow
channels are less than 0.1 mm wide and are
therefore readily fouled and difficult to
clean.
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Dr. Saeed GUL, Department of Chemical Engineering, UET Peshawar, Pakistan
Hollow-Fibre Modules
The flow is usually reversed for biotechnological applications so
that the feed passes down the centre of the fibres giving better
controlled laminar flow and easier cleaning.
This limits the operating pressure to less than 0.2 MN/m2 however,
that is, to microfiltration and ultrafiltration applications.
A single ultrafiltration module typically contains up to 3000
fibres and be 1 m long.
Reverse osmosis modules contain larger numbers of finer
fibres.
This is a very effective means of incorporating a large membrane
surface area in a small volume.
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Dr. Saeed GUL, Department of Chemical Engineering, UET Peshawar, Pakistan
Comparison Between Several
Membrane Modules
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Dr. Saeed GUL, Department of Chemical Engineering, UET Peshawar, Pakistan
Membrane modules can be configured
in various ways to produce a plant of
the required separation capability. A
simple batch recirculation system is
most suitable for small-scale batch
operation, but larger scale plants will
operate either as feed and bleed or
continuous single-pass operations.
In Feed and bleed system,the start-up
is similar to that in a batch system in
that the retentate is initially totally
recycled. When the required solute
concentration is reached within the
loop, a fraction of the loop is
continuously bled off.
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Dr. Saeed GUL, Department of Chemical Engineering, UET Peshawar, Pakistan
Feed into the loop is controlled at a rate equal to the permeate
plus concentrate flowrates.
The main advantage is that the final concentration is then
continuously available as feed is pumped into the loop.
The main disadvantage is that the loop is operating continuously at
a concentration equivalent to the final concentration in the batch
system and the flux is therefore lower than the average flux in the
batch mode, with a correspondingly higher membrane area
requirement.
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Dr. Saeed GUL, Department of Chemical Engineering, UET Peshawar, Pakistan
Continuous single pass. In such a system the concentration of the feed
stream increases gradually along the length of several stages of
membrane modules arranged in series as shown in Figure. The feed
only reaches its final concentration at the last stage. There is no
recycle and the system has a low residence time. Such systems must
however, either be applied on a very large scale or have only a low
overall concentration factor, due to the need to maintain high
cross-flow velocities to control concentration polarization.
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Dr. Saeed GUL, Department of Chemical Engineering, UET Peshawar, Pakistan
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Dr. Saeed GUL, Department of Chemical Engineering, UET Peshawar, Pakistan
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Dr. Saeed GUL, Department of Chemical Engineering, UET Peshawar, Pakistan
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Dr. Saeed GUL, Department of Chemical Engineering, UET Peshawar, Pakistan
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Dr. Saeed GUL, Department of Chemical Engineering, UET Peshawar, Pakistan
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Dr. Saeed GUL, Department of Chemical Engineering, UET Peshawar, Pakistan
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Dr. Saeed GUL, Department of Chemical Engineering, UET Peshawar, Pakistan
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Dr. Saeed GUL, Department of Chemical Engineering, UET Peshawar, Pakistan
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Dr. Saeed GUL, Department of Chemical Engineering, UET Peshawar, Pakistan
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Dr. Saeed GUL, Department of Chemical Engineering, UET Peshawar, Pakistan
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Dr. Saeed GUL, Department of Chemical Engineering, UET Peshawar, Pakistan
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Dr. Saeed GUL, Department of Chemical Engineering, UET Peshawar, Pakistan
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Dr. Saeed GUL, Department of Chemical Engineering, UET Peshawar, Pakistan