Membrane Separation

Processes
Chapter 8
 Whilst effective product separation is crucial to economic operation
in the process industries, certain types of materials are inherently
INTRODUCTION
difficult and expensive to separate. Important examples include:

1. Finely dispersed solids, especially those which are

compressible, and which have a density close to that of the
liquid phase, have high viscosity, or are gelatinous.

2. Low molecular weight, non-volatile organics or

pharmaceuticals and dissolved salts.

3. Biological materials which are very sensitive to their physical

and chemical environment.
 A membrane may be defined as “an interphase
separating two phases and selectively controlling the
transport of materials between those phases”. A
membrane is an interphase rather than an interface
Membrane because it occupies a finite, though normally small,
element of space. Human beings are all surrounded by a
membrane, the skin, and membranes control the
separation of materials at all levels of life, down to the
outer layers of bacteria and subcellular components.
 As discussed by LONSDALE(2), since the 1960s a new
technology using synthetic membranes for process
separations has been rapidly developed by materials
scientists, physical chemists and chemical engineers.
Membrane Such membrane separations have been widely applied
to a range of conventionally difficult separations. They
potentially offer the advantages of ambient temperature
operation, relatively low capital and running costs, and
modular construction.
CLASSIFICATION OF
Industrial membrane processes may be classified
MEMBRANE
PROCESSES
according to the size range of materials which they are

to separate and the driving force used in separation.

There is always a degree of arbitrariness about such

classifications, and the distinctions which are typically

drawn are shown in Table

CLASSIFICATION OF
MEMBRANE
PROCESSES
This Topic is primarily concerned with the pressure
driven processes
1. Microfiltration (MF)
2. Ultrafiltration (UF)
3. Nanofiltration (NF)
4. Reverse osmosis (RO).
 These are already well-established large-scale industrial processes.
CLASSIFICATION OF
MEMBRANE Reverse osmosis is used world-wide for the desalination of

PROCESSES
brackish water

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.

The use of reverse osmosis and ultrafiltration in the dairy industry

has led to substantial changes in production techniques and the
development of new types of cheeses and related products
CLASSIFICATION OF
Nanofiltration is a process, with characteristics
between those of ultrafiltration and reverse osmosis,
MEMBRANE
PROCESSES which is finding increasing application in
pharmaceutical processing and water treatment.

Electrodialysis is a purely electrically driven separation

process used extensively for the desalination or
concentration of brackish water.
CLASSIFICATION OF
MEMBRANE
PROCESSES
OF SYNTHETIC
Membranes used for the pressure-driven separation

MEMBRANES
THE NATURE
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.
 Membranes have most commonly been produced by a form
of phase inversion known as immersion precipitation. This
Synthesis of
Membranes 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, approximately100 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.

Synthesis of
Membranes Most microfiltration membranes have a symmetric pore
structure, and they can have a porosity as high as 80 per
cent. Ultrafiltration and reverse osmosis membranes
have an asymmetric structure comprising a 1–2 μm thick
top layer of finest pore size supported by a ∼100 μm
thick more openly porous matrix, as shown in Figure
Synthesis of
Membranes

Electron micrograph of a section of an asymmetric ultrafiltration membrane showing finely porous

“skin” layer on more openly porous supporting matrix
Synthesis of Another important type of polymeric membrane is the thin-

Membranes film composite membrane. This consists of an extremely thin

layer, typically ∼1 μm, of finest pore structure deposited on a
more openly porous matrix. The thin layer is formed by phase
inversion or interfacial polymerisation on to an existing
microporous structure. 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

Membranes oxide materials. These are presently produced by two main techniques:
Inorganic
Deposition of colloidal metal oxide on to a supporting material such
as carbon

As purely ceramic materials by high temperature sintering of spray-

dried oxide microspheres.
Zirconia, alumina and titania are the materials most commonly used.
The main advantages of inorganic membranes compared with the
polymeric types are their higher temperature stability, allowing steam
sterilisation in biotechnological and food applications, increased
resistance to fouling, and narrower pore size distribution.
 The pore structure of microfiltration membranes is relatively easy

Characterization to characterize, atomic force microscopy (AFM) and electron

microscopy (EM) being the most convenient methods and
Membrane allowing the three-dimensional structure of the membrane to be
Physical

determined.

Both the maximum pore size and the pore size distribution may
be determined.

A parameter often quoted in manufacturer’s literature is the

nominal molecular weight cut-off (MWCO) of a membrane. This is
based on studies of how solute molecules are rejected by
membranes.
 Physical
Characterization
Membrane
 The general membrane equation is an attempt to state the factors
which may be important in determining the membrane permeation
MEMBRANE
EQUATION
rate for pressure driven processes. This takes the form:
GENERAL
 Membrane equipment for industrial scale operation of microfiltration,
ultrafiltration and reverse osmosis is supplied in the form of modules.

CONFIGURATION
MODULES AND
The area of membrane contained in these basic modules is in the range
MEMBRANE

1–20 m2. The modules may be connected together in series or in parallel

PLANT
to form a plant of the required performance.

The four most common types of membrane modules are

1. Tubular

2. Flat sheet

3. Spiral wound

4. Hollow fiber
 Tubular modules are widely used where it is advantageous to have a

Tubular modules turbulent flow regime, for example, in the concentration of high solids
content feeds. The membrane is cast on the inside of a porous support
tube which is often housed in a perforated stainless steel pipe as shown
in Figure. Individual modules contain a cluster of tubes in series held
within a stainless steel permeate shroud. The tubes are generally 10–25
mm in diameter and 1–6 m in length. The feed is pumped through the
tubes at Reynolds numbers greater than 10,000. Tubular modules are
easily cleaned and a good deal of operating data exist for them. Their
main disadvantages are the relatively low membrane surface area
contained in a module of given overall dimensions and their high
volumetric hold-up.
Tubular modules
Tubular modules
Tubular modules
Tubular modules
 Flat-sheet modules are similar in some ways to conventional filter
presses. An example is shown in Figure. This consists of a series of
Flat-sheet
annular membrane discs of outer diameter 0.3 m placed on either side
modules 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, The flow is laminar. A
single module contains 19 m2 of membrane area. Permeate is collected
from each membrane pair so that damaged membranes can be easily
identified, though replacement of membranes requires dismantling of
the whole stack.
Flat-sheet
modules
Flat-sheet
modules
Flat-sheet
modules
 Spiral-wound modules consist of several flat membranes
Spiral-wound separated by turbulence promoting mesh separators and
modules formed into a Swiss roll, as shown in Figure. The edges of the
membranes are sealed to each other and to a central
perforated tube. This produces a cylindrical module which can
be installed within a pressure tube. The process feed enters at
one end of the pressure tube and encounters a number of
narrow, parallel feed channels formed between adjacent
sheets of membrane. Permeate spirals towards the
perforated central tube for collection.
Spiral-wound
A standard size spiral-wound module has a diameter of
modules some 0.1 m, a length of about 0.9 m and contains about
5 m2 of membrane area. Up to six such modules may be
installed in series in a single pressure tube. These
modules make better use of space than tubular or flat-
sheet types, although they are rather prone to fouling
and difficult to clean.
Spiral-wound
modules
Spiral-wound
modules
Spiral-wound
modules
Hollow-fiber
Hollow-fibre modules, shown in Figure , consist of bundles of fine
modules fibres, 0.1–2.0 mm in diameter, sealed in a tube. For reverse-
osmosis 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.
Hollow-fiber The flow is usually reversed for biotechnological applications so that
the feed passes down the centre of the fibres giving better
modules 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.
Hollow-fiber
modules
Hollow-fiber
modules
Hollow-fiber
modules