MEMBRANE SEPARATION

PROCESSES

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 INTRODUCTION
 Definition of membrane
 a thin barrier or film through which solvent and solutes are
selectively transported
 an interphase separating two phases and selectively
controlling the transport of materials between those phases

The separation process occurs when there are exist differences

in solubilities and diffusion rates through the membrane that
caused the driving force.

It can made by organic polymer or inorganic materials.

Types of membrane
 MEMBRANE STRUCTURE
From the morphological point of view, membranes can be categorised
into;
Porous membrane
 have tiny pores or pore networks within themselves
 achieve separation mechanically by size exclusion (i.e. sieving)
where the rejected material may be either dissolved or suspended
depending on its size relative to that of the pore.
Dense membrane
 do not have any pores and solute or solvent transport through
these take place by a solubilisation mechanism.
 relies to some extent on physicochemical interactions between
the permeating component and the membrane materials, and to
separation process having the highest selectivity
Continue…
From the structural point of view, membranes can be
categorised into;

Symmetrical structure
has a similar structural morphology
at all positions within it

asymmetrical structure
constituted of two or more structural
planes of non-identical morphologies
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 Microporous Membranes

 Behaves like a fibre filter

 Separates by a sieving mechanism determined by

the pore diameter and particle size

 Materials used to make membranes such as

ceramics, graphite, metal oxides, polymers

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 Homogeneous Membranes

 A dense film through which a mixture of chemical

species is transported under the driving force of
pressure, concentration, or electrical potential gradient
 Membrane phase itself may be solid or liquid

 Mass transport in homogeneous membranes occurs by

diffusion
 Permeabilities are low

 Homogeneous membranes should be as thin as

possible
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 Asymmetric Membranes
 Made up of porous regions that comprise the bulk of
the membrane and relatively thin dense regions
 Water permeability through these membranes is
dependent on the structure of the membranes
 Factors in determining the permeability:

a) Porous nature

b) Thickness and extent of the dense regions

c) Composition

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 Electrically Driven Membrane
 Electrical potential difference acts as the driving force

 Use the ability of charged ions or molecules to conduct

an electrical current
 Uncharged molecules are not affected by this driving
force
 Two types of membrane can be distinguished:

 cation-exchange membranes

 anion-exchange membranes

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 Electrically Driven Membrane(CONT’D)

The following concepts where ions are involved and ionic

membranes are used:
Electrodialysis require an electrical
Membrane electrolysis potential difference
Bipolar membranes as driving force
Fuel cells (convert chemical energy into electrical
energy)

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  Stirred cell module
• Uses flat sheet membrane element
 Flat sheet tangential flow (TF) module
• Uses flat sheet membrane element
 Spiral wound membrane module
• Uses flat sheet membrane element
 Tubular membrane module
• Uses tubular membrane element
 Hollow fibre membrane module
• Uses hollow fibre membrane element

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 Stirred cell
Nitrogen/compressed air

Pressure gauge

Feed
Stirrer bar

Membrane

Permeate
collection Permeate/filtrate
chamber

Magnetic stirrer

•Useful for small scale and research applications

•Used for UF and MF
•Provide uniform conditions near the membrane surface
14 •Useful for small-scale process development work
 Flat sheet tangential flow

•Design is similar to plate and frame filter

press
•Easily disassembled for cleaning and
replacement of defective membranes
•Can be used to filter suspended solids and
viscous fluids
•Relatively low packing density
•Used for UF, MF and NF
•Design calculations based on empirical
correlations

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 Spiral wound membrane module

•The spiral wound membrane

envelope)
•Feed flowing around the envelope
•Permeate collected inside envelope
•Design calculations are empirical
•High membrane packing density
•Low cost
•Unable to handle suspended solids
•Difficulty to clean
•Used for NF and UF

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 Tubular membrane module

•Several tubular membranes arranged as in a shell and tube type heat exchanger
•Feed stream enters the tube lumen
•Permeate passes through tube wall: collected on shell side
•Retentate collected at other end of tubes
•Low fouling, easy cleaning, easy handling of suspended solids and viscous fluids
and high transmembrane pressures
•High capital cost, low packing density, high pumping costs, and limited achievable
concentrations

17 •Used for all types of pressure driven separations

 Hollow fibre membrane module

 Similar in design to the tubular membrane i.e. shell and tube

configuration.
 Advantages: Low pumping power, very high packing density, and
ability to achieve high concentrations in the retentate
Disadvantages: Fragility of the fibres, inability to handle suspended
solids Used for UF, MF and dialysis

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CLASSIFICATION OF MEMBRANE PROCESS
 Microfiltration

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 Microfiltration
 process of retaining molecules typically in the size
range of 0.02 to 10μm
 pressure driven, micro-porous membrane process
used to retain matter such as colloids, small solid
particles, blood cells, yeast, bacteria, microbial cells
and large soluble macromolecules

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 Membrane Types
1. Relatively thick, high porosity of 80% to 85% cast
cellulose –ester membranes with open tortuous,
sponge like structure.
2. Thin, low porosity of minimal 10% polyester,
polycarbonate track-etch membrane of sieve like
structure with narrow distribution of straight
through cylinder like pores

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 Modes of Filtration
1. Dead-end (in-line) Microfiltration (DEF)

Feed

Particle-free permeate

 Batch, semi-continuous dilute solutions

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 Process
i. The solvent is forced under pressure through the
membrane.
ii. The matter larger than a certain size is retained
at the membrane.
iii. As the retained matter increases, the pressure
required to maintain the desired flow rate
increases or permeate flux will decrease.
iv. The process is then operated at either constant
pressure, constant flux or a combination of both

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 Modes of Filtration

2. Tangential-flow (cross flow)

Microfiltration (TFF)

 Large scale and continuous

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 Process
i. A fraction of the feed passes through the membrane

ii. A large retentate is recycled throughout the process

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 Ultrafiltration

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 Ultra-filtration (UF)

 Hydrostatic pressure forces a liquid against a semi

permeable membrane.
 Behave like a physical sieve.
 Highly porous membrane.
 Selectivity of separation determined by solute size.
 Used for separate solutes with molar mass within the
range 5kDa to 500kDa. (macromolecules)

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 Characteristics of ideal ultra-filtration membrane

 High hydraulic permeability to solvent.

 Sharp ‘retention, cut-off” properties.
 Good mechanical durability, chemical and thermal stability.
 Excellent manufacturing reproducibility and of manufacture.

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 Ultra-filtration equipment
-Larger hollow fibre of membranes.
-Internally pressurised.

Spiral wound modules

Flat sheet modules

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 Nanofiltration

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 Nanofiltration (NF)
 Nanofiltration is a liquid separation membrane
technology positioned between reverse osmosis (RO)
and ultrafiltration (UF).
 NF rejects solutes approximately 1 nanometre (10
angstroms) in size with molecular weights above 200
 NF has always been a difficult process to define and to
describe. Tight NF membranes are similar to RO
membranes, and loose NF membranes could probably
be classified as UF membranes

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 Comparison Between NF, UF and RO

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 REVERSE
OSMOSIS

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 Reverse Osmosis (RO)

 Also known as hyperfiltration.

 Reversed the normal osmotic flow of solvent.
Osmosis: Solvent diffuses across a membrane from a
solution with low concentration into a solution with a high
solute concentration
 Capable of separating a solvent from a solution by forcing
the solvent through a semipermeable membrane by
applying a pressure greater than the osmosis pressure of
the solute.
 Unlike freezing and evaporation, RO requires no phase
change .
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 Reverse Osmosis (RO)
 With nonvolatile solutes such as electrolytes, the osmotic
pressure builds up as the concentration of solute increases,
and the pressure required to force more water through the
membrane becomes impractically high once concentration
becomes too high.
 That is the osmotic pressure difference across the
membrane becomes too high for further concentration of
the solute to be practical.
 Hence, RO processes will only be practical for dilute
solutions

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 For diluted system,
 RO has to compete with adsorption, but RO is more likely
to be the choice for those applications where an aqueous
stream is too dilute.
 Since RO is usually involved in removing ionic materials
from aqueous streams, the competition at extremely low
concentrations is likely to come from ion exchange.
 When the contaminant is only a trace fraction of the total
electrolyte and a selective ion exchange material is
available that can concentrate the contaminant many-fold
by not removing the other bulk electrolyte, ion exchange
will have a significant advantages over RO.
 When all or most of the electrolyte must be removed and
the concentrations are above trace levels RO is likely to be
attractive
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 RO Application
 RO is used in various industries like food processing,
pharmaceutical, bio-industry and electronic industry.
 Its applications include
 polishing evaporator condensate before reuse
 Preconcentration of fruit juice before evaporator
 sugar recovery in candy making
 landfill leachate treatment
 water softening
 boiler feed water treatment
 nitrates removal
 Besides, RO process byproduct can be used as animal
feed, recovery of valuable solids and reuse of
41 sugars(byproduct).
 Electrodialysis

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  Electrodialysis refers to an electrolytic process for
separating an aqueous, electrolyte feed solution into a
concentrate or brine and a dilute or desalted water
(diluate) by means of electric field and ion-selective
membranes.

 Membrane-based separation process in which ions are

driven through an ion-selective membrane under the
influence of an electric field.

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  Four ion-selective membranes are of two types (C & A) arranged in an
alternating-series pattern.
 The cation-selective membranes (C) carry a negative charge, and thus
attract and pass positively charged ions (cations), while retarding
negative ions. The anion-selective membranes (A) carry a positive charge
that attracts and permits passage of negative ions (anions).
 Both types of membranes are impervious to water.
 Both anions and cations are concentrated in compartments 2 and 4, from
which concentrate is withdrawn, and ions are depleted in compartment 3,
44 from which the diluate is withdrawn.
  A direct-current voltage is applied (e.g., with a battery or
direct-current generator) across the anode and cathode.
Both electrodes are chemically neutral metals (inerts:no
oxidation and reduction occurred), with the anode being
typically stainless steel and the cathode typically platinum-
coated tantalum, niobium, or titanium.
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 Most widely used ion-exchange membranes for electrodialysis:
Electrically Charged Membranes

Cation-selective membranes containing negatively charged

group fixed to a polymer matrix (eg. polystyrene cross-linked
with divinylbenzene and sulfonated to produce fixed sulfonate, ,
anion groups).
Anion-selective membranes containing positively charged
groups fixed to a polymer matrix (eg. polystyrene cross-linked
contains quaternary ammonium group).
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  It consists of fixed anions, mobile cations (called
counterion) and mobile anions (called co-ions). The mobile
anions are almost completely excluded from the polymer
matrix by electrical repulsion, called the Donnan effect.
 Membranes are 0.2 – 0.5 mm in thickness and reinforced
with a screen to provide mechanical stability.
 commercial electrodialysis system is a large stack of
membranes patterned after a plat-and-frame configuration
47 that up to 100 to 600 cell pairs.
 Figure :Schematic of A Complete System
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 Applications:
 desalinization of brackish water in the salt concentration
range of 500 to 5,000 ppm.
 recovery of nickel and copper from electroplating rinse
water.
 deionization of cheese whey, fruit juices, wine, milk, and
sugar molasses.
 separation of salts, acids and bases from organic
compounds.

 cannot produce water with a very low dissolved-solids

content because of the high electrical resistance of dilute
solutions.
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