Lecture No. 27 & Lecture No.

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Membrane separation – introduction - membrane separation methods - RO, nano-
filtration methods, equipments and applications.

Membrane separation - membrane separation methods - ultra filtration and macro-

filtration methods, equipments and applications.
(10.1, 10.2, 10.3.1, Example 10.1, 10.4.1, 10.4.2 upto equation 10.10 and its terms,
Example 10.4, 10.5.2)

Introduction:
In technology, a membrane is a thin film of material (most commonly, but not always,
a synthetic polymer) with selective permeability. Membrane-based separation processes make
use of this selective permeability. A considerable number of different membrane processes
have found industrial applications. In this chapter, we shall deal mainly with four: microfi
ltration (MF), ultrafi ltration (UF), nanofi ltration (NF) and reverse osmosis (RO). The
driving force for material transport through the membrane in those four processes is a
pressure difference. These processes are therefore called pressure-driven membrane
processes. Electrodialysis , in which the driving force is an electric field, has a number of
interesting applications in food processing.
In a membrane separation system, a fluid
containing two or more components is in contact
with a membrane that permits selected components
(for example, water in the fluid) to permeate more
readily than other components. The physical and
chemical nature of the membrane—for example,
pore size and pore-size distribution—affect the
separation of liquid streams.

The importance of biological membranes as selective barriers in cells and tissues is

well known. The property of selective permeability (perm-selectivity) of natural membranes
was discovered by the French physicist Abbé Nollet as early as 1748. The industrial
application of membranes, however, is a fairly recent field.

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 Microfiltration (MF) and ultrafiltration (UF) are genuine filtration processes where
particle size is practically the sole criterion for permeation or rejection. In contrast, reverse
osmosis (RO) membranes separate particles at molecular level and their selectivity is based
on the chemical nature of the particles. Nanofiltration (NF) is, in essence, a membrane
process similar to reverse osmosis.
The approximate ranges of separation and typical operation pressures for the
fourpressure-driven membrane processes are given in Table:

Tangential Filtration
The vast majority of industrial membrane processes are tangential (cross-flow)
filtration operations. Consider a tubular membrane module used for the microfiltration of an
aqueous suspension of solid particles.

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 The suspension flows inside the tube. Assume that the particles are larger than the
pores of the membrane and, therefore, only the continuous medium (water) passes through
the membrane. The fraction that passes through the membrane is called the ‘permeate’. The
material that is retained by the membrane is the ‘retentate’ . As the suspension flows inside
the tube, water is gradually removed and the suspension becomes progressively more
concentrated. As long as the axial flow rate inside the tube is sufficiently high, the solid
particles are carried along with the suspension and do not accumulate on the membrane
surface as a cake.
Just as in ordinary filtration, the driving force for the transport of the permeate
through the membrane is the pressure drop across the membrane, or the transmembrane
pressure difference, TMPD or ΔPTM . The pressure at the permeate side is practically
uniform. The pressure at side of the retentate decreases in the direction of the flow.
The transmembrane pressure difference is defined as:

where:
P1, P2 = retentate side pressure at the module inlet and outlet, respectively
P3 = permeate side pressure, assumed uniform.
Note: The notions developed above are valid for all the types of membrane processes.
Microfiltration was used only as an example.

Mass Transfer Through MF and UF Membranes

Solvent transport
Microfiltration and ultrafiltration are genuine filtration processes. The membranes
used in these processes are porous. Therefore, the transport of permeate through the
membrane follows the basic principles of flow through porous media.

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 For membrane filtration, Darcy’s law is written as follows:

J = LpΔPTM
Where,
J= permeate flux, m.s-1
Lp = hydraulic permeability, m.s-1 Pa-1.
The hydraulic permeability is an important characteristic of the membrane, because it
affects strongly the filtration capacity of the system.
What are the physical properties that determine the hydraulic permeability of
membranes? If the membrane is considered as a medium perforated by straight, parallel
capillaries of radius r, then the hydraulic permeability, based on Poiseuille’s law, is given by:

The application of the Poiseuille model to membranes has the same shortcomings as
its use for the prediction of the specific resistance of filter cakes. Nevertheless, with certain
corrections, the model is useful for approximate calculations of membrane permeability. Both
the porosity and the average radius of the pores can be determined by microscopy.

Example: A membrane for MF was examined microscopically and found to have

about 120000 pores with an average diameter of 0.8μm, per mm square of membrane surface.
It is desired to estimate the hydraulic permeability of the membrane to water, using the
Hagen–Poiseuille capillary model. The thickness of the membrane is 160μm. µ, viscosity of
water is

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 The membrane in a reverse-osmosis system allows water to
permeate whereas salts and sugars are rejected. Ultra filtration
membranes are useful in fractionating components by rejecting
macromolecules. In microfiltration, the membranes separate
suspended particulates.

Reverse osmosis membrane systems

It is well known that when a plant or an animal membrane is
used to separate two solutions of different solute concentrations,
pure water passes through the membrane. The movement of water
occurs from a solution with high concentration of water to a

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solution with low concentration of water, thus tending to equalize the water concentration on
the two sides of the membrane. This movement of water is generally referred to as osmosis.
Plant root hairs absorb water from the soil according to this phenomenon. Consider a solution
of water containing a solute. In Figure 11.6a, a semi permeable membrane separates the
solutions of the same solute concentration contained in chambers A and B. Since the
chemical potential of the solvent (water) is the same on both sides of the membrane, no net
flow of water occurs through the membrane. In Figure 11.6b, chamber A contains a solution
with a higher solute concentration than chamber B; that is, chamber A has lower water
concentration than chamber B. This also means that the chemical potential of the solvent
(water) in chamber A will be lower compared with that of chamber B. As a result, water will
flow from chamber B to chamber A. As seen in Figure 11.6c, this movement of water will
cause an increase in the volume of water in chamber A. Once equilibrium is reached, the
increased volume represents a change in head, or pressure, which will be equal to the osmotic
pressure. If an external pressure greater than the osmotic pressure is then applied to chamber
A, as shown in Figure 11.6d , the chemical potential of water in chamber A will increase,
resulting in water flow from chamber A to chamber B. The reversal in the direction of water
flow, obtained by application of an external pressure that exceeds the osmotic pressure, is
termed reverse osmosis.
A reverse-osmosis membrane system is used to remove water from a water–solute mixture by
application of external pressure. The membrane used in the reverse-osmosis system must be
permeable to water.In a reverse-osmosis system, water is the permeating material referred to
as “permeate,” and the remaining solution concentrated with the solutes is called “ retentate. ”

Mass Transfer in Reverse Osmosis

Basic concepts

The term ‘osmosis’ signifies the spontaneous transfer of water from a more dilute into
a more concentrated solution through a membrane. In order to stop osmotic transfer of water
into a solution, a certain pressure, called osmotic pressure, must be exerted against the
direction of the transfer. Application of a pressure stronger than the osmotic pressure causes
water transfer in the opposite direction, from the concentrated solution to the less
concentrated medium. This is the principle of ‘ reverse osmosis’.

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 Reverse osmosis (RO) is not a true filtration process, because the separation of
components is not based solely on the size of their particles. RO membranes are essentially
homogeneous, non-porous, gel-like materials. Therefore, theories of flow through porous
media (e.g. Darcy’s law) are not satisfactorily applicable to reverse osmosis. Different
models have been proposed for the selective mass transfer through RO membranes.

One model, the ‘preferential sorption–capillary flow’ theory (Sourirajan, 1970),

assumes that the surface of the membrane acts as a microporous medium that preferentially
adsorbs water and rejects the solute. The adsorbed water then penetrates the pores and is
transported by capillary flow towards the downstream face of the membrane.

Solvent transport in reverse osmosis

Like ultrafiltration and microfitration, reverse osmosis is a pressure-driven process

where the driving force for transport is the transmembrane pressure difference. In reverse
osmosis, however, the pressure difference must overcome the difference in osmotic pressure,
Δπ between the retentate and the permeate, in addition to the resistance of the membrane to
the transfer. The net available driving force is the ‘net applied pressure’

NAP defined as follows:

NAP = TMPD – Δπ

Solvent fl ux is given by the following expression (Baker, 2004)

JW = KW (TMPD - Δπ)

The osmotic pressure π (Pa) of ideal solutions is calculated with the help of van’t Hoff ’s
equation (Jacobus Henricus van’t Hoff, 1852–1911, Dutch chemist, 1901 Nobel Prize in
chemistry):

π = φCMRT = CRT/M
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where:

CM = molar concentration of the solution, kmol.m-3

R = gas constant = 8314 Pa.(kmol.m-3 )-1.K-1
T = absolute temperature, K
φ = a dimensionless constant, depending on the dissociation of the solute. For non-ionic
solutes such as neutral sugars, φ = 1.

Problem: What is the maximum theoretical concentration of orange juice attainable by

reverse osmosis at a TMPD of 5000 kPa? Assume that the juice behaves osmotically as a
solution of glucose (MW = 180) and that solute rejection is total.

Solution:
The maximum retentate concentration is that corresponding to an osmotic pressure equal to
the TMPD.

Membrane configurations
‘ Membrane configuration ’ refers to the geometry of the membrane and its position in space
in relation to the flow of the feed fluid and of the permeate. As most industrial membrane
installations are of modular design, membrane configuration also determines the manner in
which the membrane is packed inside the modules.

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Ultra filtration membrane systems:
Ultra filtration membranes have pore sizes
much larger than the reverse-osmosis
membrane. Ultra filtration membranes are
used primarily for fractionating purposes:
that is, to separate high-molecular weight
solutes from those with low molecular weight. Since the ultra filtration membranes have
larger pore sizes, the hydraulic pressures required as a driving force are much smaller when
compared with the reverse osmosis membrane systems.

Four main types of membrane configurations are used in the food industry. These are:
plate-and-frame, spiral wound, tubular and hollow-fiber configurations. The membrane
geometry is planar in the first two and cylindrical in the two others.
The desirable characteristics of a membrane configuration are:
 Compactness, i.e. the ability to pack as much membrane surface as possible into a
module of limited volume
 Low resistance to tangential flow (less friction, less energy expenditure, less pressure
drop along the retentate flow channel)
 No ‘ dead ’ regions, uniform velocity distribution
 High degree of turbulence at the retentate side, in order to minimize fouling and
promote mass transfer
 Easy cleaning and maintenance
 Low cost per unit membrane area.

Plate-and-Frame:The plate-and-frame membrane systems involve a large number of flat

membranes that are sandwiched together with the use of spacers. As shown in Figure, the
spacers provide the channels for flow. The membranes (usually 50 to 500 μm thick) are
bonded on a porous, inert matrix that offers little resistance to the fluid flow. The flow of feed
and retentate occur in alternate channels. This arrangement of membranes is very similar to
the plate heat-exchanger. The membranes may be square or circular, arranged in vertical or
horizontal stacks. Plate-and frame modules cannot withstand very high pressure and are
therefore limited to MF and UF duty. The
surface area to volume ratio of plate-and-
frame modules is not high.

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Tubular: The tubular design was the first
commercial design of a reverse osmosis
system. It resembles a shell-and-tube heat
exchanger. It consists of a porous tube
coated with the membrane material such
as cellulose acetate. Typically, feed
solution is pumped into the tube through
one end and forced in the radial direction
through the porous pipe and the membrane .Water drips from the outer surface of the
membrane while the concentrated stream “retenate” leaves through the outer end of the tube.
The tubes may have diameters in the range of 10 to 25 mm. Flow direction is usually inside-
out, i.e. the retentate flows inside the tubes and the permeate is collected at the shell-side.
This type of reverse-osmosis device is expensive to use for high volumetric flow rates, since
the membrane area is relatively small.

Spiral-Wound: This design can be

visualized as a composite of multi
layers. The two layers of membrane
are separated by a plastic mesh, and
on either side of the membrane is a
porous sheet. These five layers are
then spirally wound around a
perforated tube. The ends of the
rolled layers are sealed to prevent
mixing of feed and product streams.
The whole spiral assembly is housed in a tubular metal jacket that can withstand applied
pressures. Feed is pumped through the perforated tube on one side of the spiral wound roll.
Feed enters inside the plastic mesh. The feed then permeates the membrane in a radial
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direction and exits the membrane into porous layers. The permeate (water) transports through
the porous sheet in a spiral manner and leaves the assembly through the exit tube, whereas
the retentate leaves through the other end of the spiral-wound roll. Spiral wound membranes
are sold as cylindrical assemblies or cartridges, complete with central tube, spacers and
connections. Their surface area to volume ratio is high.
Hollow-Fiber: A hollow-fiber, made out of
aramid. Hollow-fibers, finer than human
hair, have an internal diameter of about 40
μm, and an external diameter of about 85
μm. Configurations are, in principle, similar
to the tubular setup. A large number of
hollow-fibers (several millions) are arranged
in a bundle around a perforated distributor
tube. In the reverse-osmosis system, the
fibers are glued with epoxy to either end.
These fibers provide extremely large surface
areas; thus, hollow fiber membrane systems
can be made very compact. Feed water is
introduced through the distributor pipe; the
permeate flows through the annular space of the fibers into the hollow bore of the fibers and
moves to the tube sheet end, discharging from the exit port. The retentate or brine stays on
the outside of the fibers and leaves the device from the brine port. Hollow fibers are used
mainly to purify water.
Most membrane systems in the food industry have been in dairy and fruit juice applications.
Other commercial applications include processing of coffee, tea, alcohol, gelatins, eggs, and
blood, and corn refining and soybean processing.

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