Membrane Separation

Membrane Separations
In membrane separation processes, a feed mixture consisting of a
mixture of two or more components is partially separated into:
Retentate (that part of the feed that does not pass through the
membrane)
Permeate (that part that does pass through the membrane).
Membrane
The main feature which distinguishes membrane separations form
other separation techniques is the use of another phase, the
membrane.
A semipermeable barrier (the membrane) is most often a thin,
nonporous, polymeric film, but may also be porous polymer,
ceramic, or metal material, or even a liquid, gel, or gas.
This membrane, or barrier, controls the relative rates of transport of
various species through itself and thus, gives one product depleted in
certain components and a second product concentrated in these
components.
Membrane

To maintain selectivity, the barrier must not dissolve, disintegrate, or

break.

In membrane separations:
i. The two products are usually miscible
ii. The separating agent is a semipermeable barrier,
iii. A sharp separation is often difficult to achieve.
Performance of Membrane
The performance of a membrane is defined in terms of two simple
factors:
1. Flux or permeation rate
2. Retention or selectivity

Ideally a membrane with a high selectivity or retention and with a

high flux or permeability is required.
Typically attempts to maximise one factor are compromised by a
reduction in the other
Industrial Membrane Separation Processes

Membranes are used for various separations:

Separation of mixtures of gases and vapours,
Miscible liquids (organic mixtures and aqueous/organic mixtures)
and
Solid/liquid and liquid/liquid dispersions
Dissolved solids and solutes from liquids
Types of membranes
1. Microfiltration membrane
2. Ultrafiltration membrane
3. Nanofiltration membrane
4. Reverse osmosis
5. Dialysis
6. Electrodialysis
7. Pervaporation
8. Gas permeation
9. Liquid membranes
Industrial Membrane Separation Processes
1) Reverse osmosis:
Desalinization of brackish water
Treatment of wastewater to remove impurities
Treatment of surface and groundwater
Concentration of foodstuffs
Removal of alcohol from beer

2) Dialysis:
Separation of nickel sulfate from sulfuric acid
Hemodialysis (removal of waste metabolites and excess body
water, and restoration of electrolyte balance in blood)
3) Electrodialysis:
Production of table salt from seawater
Concentration of brines from reverse osmosis
Treatment of wastewaters from electroplating
Production of ultra-pure water for the semiconductor industry
4) Microfiltration:
Sterilization of liquids, gases, and parenteral drugs
Clarification and biological stabilization of beverages
Bacterial cell harvest and purification of antibiotics
Recovery of mammalian cells from cell culture broth
5) Ultrafiltration:
Preconcentration of milk before making cheese
Clarification of fruit juice
Purification of recombinant proteins and DNA, antigens, and
antibiotics from clarified cell broths
Color removal from Kraft black liquor in papermaking
6) Pervaporation:
Dehydration of ethanolwater azeotrope
Removal of water from organic solvents
Removal of organics from water
7) Gas permeation:
Separation of CO2 or H2 from methane
Separation of uranium isotopes
Separation of air into nitrogen- and oxygen-enriched streams
Recovery of helium
Recovery of methane from biogas
8) Liquid membranes:
Recovery of zinc from wastewater in the viscose fiber industry
Recovery of nickel from electroplating solutions
Classification of membrane processes

Transport of selected species through the membrane is achieved

by applying a driving force across the membrane. This gives a
broad classification of membrane:
Driving force/mechanism (mechanical, chemical, electrical or
thermal work)
Particle size
Driving force/Mechanism
Particle Size
1. Microfiltration
Filters for membrane microfiltration (MF) are typically made from
thin polymer films with 'uniform' pore size and a high pore density of
approximately 80%.
The principle method of particle retention is 'sieving', although the
separation is influenced by interactions between the membrane
surface and the solution.
 The high pore densities of the filters generally mean hydrodynamic
resistance is relatively low and hence high flow rates of permeate per
square meter of membrane area per hour, m/h), result at modest
operating differential pressures up to 2 bar.

With symmetric membranes some degree of in-depth separation

could occur.

To counter-act this effect, asymmetric membranes, are used.

These entrap the particles almost exclusively at the surface (the

membrane skin) whilst still offering low hydrodynamic resistance.
This technique has also enabled inorganic membranes to be used in
several applications.
 Microfiltration is widely applied in a dead-end mode of operation.
In feed, particles accumulate on the surface forming a layer of
retained solid or a filter cake
The effect of a build-up of solid particle cake on the membrane
surface can be reduced by the use of cross flow, or tangential
flow.
Fouling
Adsorption phenomena can play an important role in fouling for
example hydrophobic membranes (eg PTFE) generally show a
greater tendency to foul, especially by proteins.
Another disadvantage of hydrophobic membranes is that water
will not generally flow through the structure at low pressure
unless they are pretreated prior to use with for example alcohol.
Microfiltration membranes will require cleaning at some stage in
use.
This may involve using appropriate chemicals and thus the
membrane material must exhibit appropriate chemical resistance
to reagents.
2. Ultrafiltration

Ultrafiltration similar to microfiltration in operation,

It uses asymmetric membranes to carry out 'tighter' filtrations.
The membrane top-layer pore size is in the range of 0.05 m to 1
nm. Hence, it is used for separating extremely small particles and
dissolved molecules from fluids.
Materials ranging in size from 1,000 to 1,000,000 molecular
weight are retained by ultrafilter membranes while salts and water
will pass through.
Colloidal and particulate matter can also be retained.
 Ultrafiltration membranes are often operated in a tangential flow
mode.
Feed material sweeps tangentially across the upstream surface of
the membrane as filtration occurs - thereby maximizing flux rates
and filter life.
These systems offer the advantage of long life because ultrafilter
membranes can be repeatedly regenerated with strong cleaning
agents.
Performance

Commercial UF membranes are asymmetric, with a thin skin

some 0.1 to 1 micron thick, of fine porous texture exposed to the
feed side.
This skin is supported on a highly porous layer some 50 to 250
micron thick.
It combines to give the unique requirement of high permeability
and permselectivity.
Performance

Most UF membranes are polymeric, inorganic, ceramic

membranes.
Typical membrane materials are polysulfone, polyethersulfone,
polyacrylonitrile, polyimide, cellulose acetate, aliphatic
polyamides and ceramics, e.g. zirconium and aluminium oxides.
The principle of operation of ultrafiltration is analogous to
microfiltration and is based on "fine sieving".
The value of permeability constant K for UF membranes is much
smaller than that for microfiltration membranes, in the general
range of 0.1-10 m/day.
1. The values of flux increases with
temperature.
2. For water the recirculation rate (cross
flow velocity) will have little, if any,
effect on flux rate.
3. With real process fluids where build
up of solutes at the membrane surface
induce concentration factors which
reduce membrane flux.
4. Optimisation between cross flow
velocity and membrane length may
then be necessary.
 In ultrafiltration membrane performance is defined in terms of its
ability to retain certain molecules of a specific size.

Values of rejection are not absolute values for any single

membrane or solution.
Rejection coefficients vary with molar mass of solute.
R vary from 0 to 1.0 over one (tight membrane) or two or greater
(loose) membrane orders of magnitude in molar mass, for any one
membrane.
Pore Size Selection
Ultrafiltration membranes are rated in terms of their Nominal
Molecular Weight Cut-off (NMWC).
Flux declines with time, even with "clean" water. The influence of
time on the rate of flux decline may, however, be insignificant
compared to the effect of concentration.
A rapid flux decline, while processing a stream in total recycle (ie
no concentration) indicates either the circulation rate is too low or
foulants are present.
Concentration factors (Cv) in membrane systems:
4. Reverse Osmosis

Reverse osmosis/hyperfiltration is a process to remove low

molecular weight solutes, e.g., microrganic salts, small organic
molecules ( glucose for example) from a solvent, typically water.

It is a pressure driven process aimed at the separation of ionic

solutes and macromolecules from aqueous streams.

Such species are of similar molecular size and of a size

comparable to the wide range of pore spaces in the polymeric RO
membrane. Membrane pore size is of the order of 10nm and
lower.
Mechanism
 With ionic species the membrane exerts an electrostatic free
energy barrier against ionic movement into the membrane.
Thus the mobility of ionic species in the membrane is much less
than that of the water molecules.
For organic species of non ionic solutes the separation is
determined by:
The affinity of solute with the membrane
Their molecular weight.

The non-ionic species are usually taken up by the membrane and

separation is only achieved because of their relative low mobility
in the membrane compared to that of water
 The particle size range for applications of RO is approximately
0.0001 to 0.001 micron (1 to 10 A).

Application of Reverse Osmosis include:

Desalinization of brackish water
Treatment of wastewater to remove impurities
Treatment of surface and groundwater
Concentration of foodstuffs
Removal of alcohol from beer
Performance Criteria
The major objective is to primarily remove water or perhaps
another solvent from a solution to produce a more concentrated
product and/or a 'pure' water stream.
Thus the permeate water flow and any passage of salts or solutes
are the key performance indicators.
The flux depends upon the membrane permeability, the pressure
driving force and the osmotic pressure difference across the
membrane p, according to
J = K. (p - )
K= membrane permeability (5*10 -3 to 5*10 -5 m/h.bar)
p= pressure driving force
p =Osmotic pressure difference
 The flow of water through the membrane will invariably carry
solute(s) with it to a lesser or greater degree. This solute flux, Js is
proportional to the solute concentration difference across the
membrane Cs i.e.,
Js = Ks Cs (mol/m2.h)
Ks = solute permeability coefficient (5*10-3 to 10-4 mh-1).

The values of permeabilities of water and solute are both

inversely proportional to the membrane (or membrane skin)
thickness and proportion to the appropriate diffusivity of water or
of a solute.
 Reverse osmosis typically operates at high pressure from 20 to 100
bar, much higher than ultrafiltration.
The values of both permeabilities effectively determines the retention
of the membrane, which can be expressed as:

In reverse osmosis an increase in the operating pressure raises the

water flux, and also causes an increase in quality of the permeate as
the solute passage through the membrane falls.
The attraction of high pressure is both a higher water productivity
and improved water quality, which is of course at the expense of
increased cost.
Membrane performance
The performance of RO membranes depends on
Temperature
Membrane material and thickness
Membrane compaction

Temperature:
Temperature affects both water flow and osmotic pressure.
The permeability coefficient increases with temperature. The
osmotic pressure also increases with temperature therefore
tending to decrease flux.
 Membrane Material:
The product flow and salt rejection are dependent on membrane
material, membrane thickness.
Typical salt rejections are greater than 90% for brackish water
and greater than 99% for seawater.
Membrane compaction
It is caused by creep deformation of polymeric membranes with
time and depends upon material, pressure and temperature.
Increasing pressure and temperature, increases the tendency to
Creep.
The effect is more pronounced in asymmetric homogeneous
membranes.
3. Nanofiltration
Nanofiltration is similar to RO and is a pressure driven process
applied in the area between the separation capabilities of RO
membranes and UF membranes, that is in the separation of ions from
solutes such as small molecules of sugars.
Membranes can be formed by interfacial polymerisation on a porous
substrate of polysulphone or polyethersulphone.
Nanofiltration is used when high sodium rejection, typical of RO, is
not needed but where other salts such as Mg and Ca (ie divalent ions)
are to be removed.
The molecular weight cut off the NF membrane is around 200.
Typical rejections are (5 bar, 2000ppm solute) 60% for NaC1, 80%
for calcium bicarbonate and 98% for magnesium sulphate, glucose
and sucrose.
 These have applications in the processing of salty cheese wheys
(diafiltration) and pharmaceutical preparations.
Some other specific applications are removal of colour, removal
of TOC and trihalomethane precursors form surface water,
removal of hardness, radium and TDS from well waters
Pervaporation
Separate a mixture of two or more miscible liquids into more
concentrated products of the constituents.
 Methods of producing reduced pressure:
- pumping under reduced pressure
- stream of carrier gas
Pervaporation involves simultaneous heat and mass transfer.
Principal of separation depends on the solubility or diffusivities of
the constituents in the membrane.
Steps
i. Partitioning (selective sorption) of the feed constituents
into the retentate side of the "swollen" membrane
ii. Selective diffusion of penetrants through the membrane
iii. Desorption of the permeate at the membrane surface into
the vapour phase

Separation Factor:
Vapor Permeation
Vapor permeation is a membrane process for the separation of
saturated mixed vapor, with no change of phase involved in the
operation.
Operation in the vapor phase virtually eliminates the effect of
concentration polarization prevalent in liquid phase separation
such as pervaporation.
Vapor permeation can be used to separate a vapor from either
non-condensable gases or mixtures of vapor compounds.
Membranes are non-porous and materials are similar to those
of pervaporation.
A potential application is the use in a hybrid separation with
distillation
Thermopervaporation
Thermal driving force is used instead of vacuum induced
driving force.

Methods: High rates of condensation on permeate side of

membrane.
Liquid Membranes

Liquid membrane is used to describe a process of separation

which does not reply on inherent characteristics of a thin, solid
barrier.
The closest equivalent non-membrane separation process is liquid
extraction
Liquid membrane processes are referred to as liquid pertraction,
carrier mediated extraction and facilitated transport.
Principal of Liquid membrane process

Membrane phase in most of the applications is an organic

liquid although aqueous based membranes can be used for
separation of organic solutions
Features of liquid membranes

Molecular diffusion in liquids is generally several orders of magnitude

faster than in solids e.g. polymer membranes.
Pertraction can be intensified by eddy diffusion in the mobile membrane
phase.
Liquid membranes can be designed to be highly selective to specific solutes
A maximum driving force can be created, thus multistage processes
commonly used in liquid extraction are not needed
The organic phase, which contains the liquid membrane carrier can be
selected from a wide range of inert, insoluble and harmless organic liquids
Relatively small quantities of carrier are needed and therefore highly
selective, relatively expensive agents can be used.
Pertraction System
Classification:
- methods with phase dispersion
- methods without phase dispersion
Electrodialysis