Membrane separations

Membrane
• Membranes: Rate based processes rather equilibrium
based processes.
membrana: thin skin
conventional filters (like a coffee filter) but with much
finer mesh or much smaller pores to enable the
separation of tiny particles, even molecules.
Bladder is one of the oldest membrane used in ancient
period
Onion layer and skin is best examples for membranes
 Membrane
• A membrane can essentially be defined as a barrier that
separates two phases and selectively restricts the
transport of various chemicals. It can be homogenous or
heterogeneous, symmetric or asymmetric in structure,
solid or liquid, and can carry a positive or negative charge,
or be neutral or bipolar. Transport across a membrane can
take place by convection or by diffusion of individual
molecules, or it can be induced by an electric field or
concentration, pressure or temperature gradient. The
membrane thickness can vary from as little as 100 mm to
several millimeters.
 Definitions : Membrane separation system separates an influent
stream into two effluent streams known as the permeate and the
concentrate. The permeate is the portion of the fluid that has passed
through the semipermeable membrane, whereas the concentrate
stream contains the constituents that have been rejected by the
membrane.
• Feed or bulk solution : Generally contains macro and micro molecules
or different species.
• Retentate stream : retained by the membrane and containing both
material (rejected by membrane and would have not been rejected).
• Permeate: Passed through the membrane (contains less conc. Or less
molecules)
Schematic diagram:
Retentate (Max. of ‘A’ and min. of ‘B’)

Bulk Solution

Flux
Permeate (Max. of ‘B’ and min. of A )
 Applications
• Various applications have been commercialized in the fields of Chemical
Engineering, biotechnology and pharmaceutical
• The combination of molecular separation with a chemical reaction, or
membrane reactors, offers important new opportunities for improving the
production efficiency in biotechnology and in the chemical industry.
• It has established the applications in areas such as hydrogen separation,
the recovery of organic vapors from process gas streams, and the
selective transport of organic solvents, and it is creating new possibilities
for catalytic conversion in membrane reactors.
• It also provides a unique solution for industrial waste treatment and for
the controlled production of valuable chemicals.
• Since it deals with the smallest penetrants in the size spectrum, gas
separation requires extremely precise discrimination of size and shape—
often in the range of 0.2–0.3 Å—between permeated and rejected
species.
• Membrane contactors have proved to be efficient contacting devices, due
to their high area per unit volume that results in high mass transfer rates.
They are not only compact but also eliminate several of the problems
faced in conventional processes such as ion exchange, solvent extraction,
and precipitation.
• Few examples of industrial applications : Apple juice , Vegetable oil, Dairy
industry
Apple Juice
Residue

Brix is sugar
content
Aroma increase process

Pectin will be present in juice

which reduces the flux, to
break the pectin, pectinase
enzyme will be added

Membrane separation
Vegetable oil : Conventional and possible replacement
with membrane separation operations

Light blue colour boxes

are membrane
separation operation
replacements
Dairy Industry
• Classification : Based on driving force:
1) Pressure Driven
• Reverse Osmosis
• Nanofiltration
• Ultrafiltration
• Microfiltration
• Pervaporation
• Membrane gas separation
2) Concentration driven
• Dialysis
• Membrane Extraction
3) Electrical voltage
• Electrodailysis
4) Temperature difference
• Membrane distillation
S.No Membrane Process Particle size Molecular wt (Da) Particle characteristics
(mm)
1 Reverse Osmosis 0.0001 100 Ionic
2 Nanofiltration 0.0001-0.001 100-1000 Ionic to molecular
3 Ultrafiltration 0.001-0.1 1000-105 Molecular to macromolecular
4 Microfiltration 0.1-10 105-5x105 Macromolecular to cellular
5 Pervaporation <1 nm Gas/vapor molecules
6 Gas separation <1 nm Gas molecules
Membrane separation processes have numerous
industrial applications and provide the following
advantages:
 They offer appreciable energy savings;
 they are environmentally benign;
 the technology is clean and easy to operate;
 they replace conventional processes like filtration,
distillation, and ion exchange;
 they produce high-quality products; and
 they offer greater flexibility in system design.
Limitations
 Membrane types, Materials,
Preparation and characterization
Classification
• Nature of membrane
• Natural vs synthetic
• Structure of membrane
• Porous vs non porous
• Morphological characteristics
• Solid vs liquid
• Pore geometry
• Cylindrical vs modular vs sponge like
General classification of synthetic membranes

Synthetic
membrane

Asymmetric Thin film Electrically

Microporous Inorganic
composite charged

Isotropic
Anisotropic
Microporous membranes
• Similar to conventional filter
• Rigid and highly voided structure with randomly distributed and
interconnected pores.
• Pore dia. Is 0.01 to 10 mm
• Microporous membranes will retain all the particles above its rating
• Isotropic : The pores are uniform size throughout the membrane
• Anisotropic : The pores are change in size from one surface to
another
Asymetric Membrane
• Is probably a greatest break through in membranes R&D
• Asymetric membranes are characterized by a think skin on the surface
of the membrane. (0.1 to 1 micron)
• Porous sublayers acts as supported to the thin, fragile skin.
• These porous sublayers has minimal effect on separation
Skin

Porous Support
Thin Film Composite
• Similar to Asymetric membranes
• Composites have a thin dense polymer skin formed over a
microporous support film
• Primarily developed for RO and NF applications
• Successful production of these membranes requires a very finely
porous substrate to which the thin film can adhere
Electrically Charged membranes
• Ion Exchange membranes consisting of highly swollen gels carrying fixed
positive or negative charges.
• Mainly used in electrodialysis
• A membrane with fixed positively charged ions referred as an anion
exchange membranes because it binds anions in the surrounding fluid.
• A membrane with fixed negatively charged ions referred as an cation
exchange membranes because it binds cations in the surrounding fluid.
• The ion exchange membranes are non porous and is having a typical
functional group.
• Characteristics : ion conductivity, hydrophilicity and existence of fixed
carrier.
 Applications
Ion Conductivity Electro dialysis Concentration or desalination of electrolytes

Diffusional Dialysis Acid or Alkali recovery from waste

Fuel cell Hydrogen- Oxygen
Pervaporation Dehydration of water miscible organic solvents

Dehumidification Dehumidification of air and gases

Hydrophilicity Sensor Gas sensors (CO,NO) , medical (enzyme etc)

Fixed carrier (ion exchange group) Facilitated transport Removal of acidic gas
Inorganic membranes
• Known as ceramic membranes
• Can operate at elevated temperatures 500 -800 0C even some times
1000 0C .
• Much more resistance to corrosion and chemical attack

Applications :
• Air separation by mixed oxygen ionic and electronic conducting
ceramic membranes and molecular sieve carbon membranes
• Hydrocarbon separation by zeolite and silica membranes
• Carbon dioxide separation by silica or zeolite membranes
Membrane modules
• Basically four modules
• Plate and frame
• Tubular
• Spiral wound
• Hollow fiber

• The techno economic factors for selection, design and operation of

membrane modules include cost of supporting materials and enclosure
(pressure vessels), power consumption for pumping and ease of
replaceability.
Comparative characteristics

Characteristics Plate and frame Spiral wound Tubular Hollow fibre

pH range of tolerance in RO 4-7 4-7 4-7 4-10
Resistance to mechanical damage Good Good Good Good
Resistance to fouling Good Moderate Very Good Poor
Packing density 30-500 200-800 30-200 500-9000
Power consumption Good Good Poor Poor
Major applications Dialysis, RO, PV, Dialysis, RO, RO, MF Dialysis, RO,
UF, MF GP, UF, MF GP, UF

RO : Reverse Osmosis, PV : pervaporation, UF: Ultrafiltration , MF: Microfiltration, GP : gas permeation

Plate and frame filter or flat sheet
• Flat sheet modules have channel gaps ranging from 0.5 to 10 mm and
are of lengths ranging from 10 to 60 cm. The superficial Reynolds
numbers for flat sheet modules are in the laminar flow region;
• however, good mixing can be achieved when a screen is placed in the
feed channel.
• The pretreatment to 150 μm is recommended for flat sheet modules.
• With regard to packing density, energy consumption, and cost, flat
sheet modules lie in between tubular modules and spiral-wound
modules.
Major advantages
• Sheets can be quite close to one another to reduce the concentration
polarization , a phenomena which is detrimental to membranes
• They can be taken apart for cleaning

Permeate

Retentate

Feed
Tubular
Tubular modules are composed of a number of membrane tubes
assembled in a shell-and-tube arrangement. The membrane tubes are
usually made up of porous fabric or plastic support with selective
membranes on the inside.
The internal diameters of the tubes generally range from 5 to 25 mm,
and the tube lengths are in the range of 0.6 to 6 m.
 Characteristics
I. Due to their large internal diameters, these are capable of dealing
with the feed stream containing fairly large particles secondly they
can be easily cleaned by using either mechanical or chemical
methods;
II. They need large pumping capacity, because they are usually
operated under the turbulent flow conditions with the Reynolds
numbers greater than 10,000
III. They have the lowest surface area-to-volume ratio among all the
four membrane configurations. The holdup volumes of tubular
modules are also high, which need large floor space to operate.
 Hallow fiber
• These are “thin” tubular membranes in compact modules, but in the form of
self-support that enables them to withstand high backpressure.
• Normally, hollow fiber modules are composed of 50-3000 individual hollow
fibers, bundled and sealed together on each end
• The fiber diameters typically range from 0.2 to 3 mm
• For RO, which may be as thin as 0.04 mm and can withstand much higher
pressure.
• The fiber lengths range from 18 to 120 cm.
• In MF and UF, hollow fiber modules are operated in the inside-out mode with
selective skin layers on the inner sides of the fibers, while in RO, they are
operated in the outside-in mode with selective skin layers on both sides of the
fibers.
Characteristics
(1) they are recommended to operate with the Reynolds numbers in
the range of 500-3000, therefore, most of them are run in the laminar
flow region. At a pressure of maximum of 2.5 bar;
(2) Due to the combination of low cross flow rate and low pressure
drop, hollow fiber modules are one of the more economical modules in
terms of energy consumption;
(3) hollow fiber modules have the highest surface area-to-volume ratio
among all the four membrane configurations, and their holdup volumes
are low;
(4) because the fibers are self-supported, hollow fiber modules have
good backwash capacity and are hence easy to clean; and
(5) one distinct disadvantage of hollow fiber modules is that, their thin
fibers are susceptible to get blocked by the feed with large particles,
when they are operated in the inside-out mode. Therefore, the
pretreatment to reduce particle size to 100 μm is usually required for
hollow fiber modules
Spiral wound
1) Spiral-wound modules, two membrane sheets are separated by a
mesh-like spacer with the active membrane sides facing away.
2) Three edges of the two membrane sheets are glued together with
the fourth edge open to a perforated center tube for the permeate
removal. On the other two sides of “the envelope,” another two mesh-
like spacers with Thicknesses in the range of 0.563 mm are placed as
the feed channel spacers.
3) The whole assembly is rolled around the perforated center tube in a
spiral configuration.
Characteristics
(1) Spiral wound modules are operated in the turbulent flow region
because of the presence of feed spacers;
(2) due to the additional drag generated by feed spacers, the pressure
drop in spiral-wound modules is relatively high;
(3) spiral-wound modules have fairly high surface area volume ratio and
are the lowest in terms of capital cost, among all the four kinds
(4) suspended particles can easily block the mesh-like spacers and then
partially block the feed channel. Therefore, spiral-wound modules
require relatively clean feed that are with minimum content of
suspended particles.
5) The pretreatment to reduce suspended particles is needed for spiral-
wound modules.
Less common types/special modules
• Thin channel : feed stream flows through a narrow channel (velocity
152 – 762 cm/s)
• Parallel leaf type : mainly used in dairy industry
• Transversal flow capillary module : Mainly used in dialysis where
boundary layer effects must be controlled on the feed and permeate
side of the membrane
• Monolithic : 1 to 37 monolithic elements are assembled together in
module housing
• Cassette or flat spiral module : Cassette is used two different cross
flow membranes.
• Rotating disc module : Three way separation ( centrifugal force
separation and membrane separation)
Typical flow patterns
Membrane materials
• Many types of membrane materials extensively used in industry
• Broadly three major groups
• Rubbery Polymer : When the polymer operates at a temp. above the glass
transition temperature. Their behavior is essentially that of a viscous liquid.
These polymers have high fluxes of organics and low flux of water. Ex: Silicone
rubber, thiocynate, polyvinyal ammonium, Polydimethyl siloxane.
• Glassy polymer : When the polymer operates at a temperature lower than the
glass transition temperature. These are amorphous or crystalline. Segmental
motion of or rotation of polymeric molecules is restricted leading to
heterogeneity of polymer structure. Ex: Polycarbonate, cellulose acetate,
polysulphone .
• Ion Exchange membranes: Ion exchange membranes are essentially ion
exchange resins made in membrane form. Having ionic charge on polymeric
membrane. These are very selective for water.
Cellulose derivatives
• Cellulose or regenerated cellulose is the most important naturally occurring
polymer for membrane applications and best source is cotton linters which
contains highest concentration of alpha cellulose.
• Cellulose Nitrate(CN)(inorganic) and Cellulose Acetate (CA) (organic) are
two important cellulose derivatives.
• CN is first synthetic polymer utilized to produce filtration membranes
• CA is less inflammable and cheaper has overtaken the CN
• Cellulose triacetate (CTA) 42.3% of acetyl content and having pronounced
hydrophilicity which is useful in minimizing fouling of the membranes.
• CA is available with wide range of pore sizes and reasonably high fluxes .
• Disadvantages: Narrow temp range : 30-40 0C ,Low pH range : 3-6
• Poor resistance to Chlorine (Which may oxidize the CA and the pore size
may change)
Aromatic Polyamides (PA)
• Highly melting crystalline polymers (275 0C) with better thermal
stability. Higher resistance to solvents
• Optimum balance between processing and end-use properties are
achieved by randomizing the molecular structure through the use of
meta and para substituted monomers.
• PA is better than CA in pH tolerance.
• CA is better than PA in chlorine tolerance.
• Polyamide hydrazide, polyetheramide hydrazide, Crosslinked
polysulphonamide are examples
Polysulphone
• Polysulphone is a condensation product of bisphenol-A and
dichlorodiphenyl sulfone.
• High degree of molecular immobility, high rigidity, creep resistance
and dimensional stability.
• Wide range of operating temp. 75-125 0C
• pH range 1-10
• Fairly good chlorine resistance
• Wide range of pore sizes are available to use in UF and MF
• Widely used as a porous supports in thin film composite membranes
for RO.
Polyimides
• Polyimides are obtained by reaction of diamines with dianhydrides and
subsequent condensation of the resultant polyamic acid.
• Initially expected that this will work good for RO but due to less chlorine
resistance it didn’t work
• Now usage in gas separation membranes
Polytetraflouroethylene (PTFE)
• The monomer of PTFE is produced by dechlorination of dichloro
tetrafluoroethane or decarboxylation of sodium perfluoro-propionate
• PTFE is a straight chain , high crystalline polymer which gives considerable
strength.
• Stable to acids, alkalis, solvents
• Temp range -100 – 260 0C
• Extremely Hydrophobic and uses in the treatment of organic feed solutions
• Polycarbonate (PC)
• Derived from carbonic acid and bisphenol –A and mainly amorphous
• The nonplanner configuration of PC provides a large av. interchain
displacement and results the gas permeability is higher.
• PC are thermoplastics and can be extruded into various shapes such as
films and sheets.
• Copolymers of PC and polyethylene glycols (PEG) are suitable for making
hemodialysis membranes
• Use of silicone PC copolymers in membrane blood oxygenarators work is in
progress
• Polypropylene
• Polymerization of propylene will give PP
• Hydrophobic, relatively inert, can withstand moderately higher temp.
Inorganic membrane materials (IM)
• Large number of materials are available for the manufacture of IM
• Common membranes are made with Al, Si, Ti and Zr oxides
• Zeolite membranes and molecular sieves.
• More resistance to pH, temperature and corrosion
• But brittle in nature
• Used in Gas and vapour separation
• Fuel cells, oxygen sensors
Types of pores
Pore Width (nm) Major Application
Macropore  50 UF, MF and filtration
Mesopore 2 to 50 UF, NF
Micropore <2 NF
Supermicropore 0.7 to 2 RO, NF
Ultramicropore <0.7 RO, GS, dialysis
Ultrpore <0.35 RO, GS, dialysis
General methods of membrane manufacture
Methods :
Phase inversion methods
Track-etch method
Sol-get precipitation method
Interfacial polymerization
Melt pressing
Film stretching
Template Leaching
Ion Exchange membranes

Principles to be used
• Control the pore size & Control the pore size distribution at the surface layer
• Decrease the thickness of the surface layer
Phase inversion methods
• Flexible technique to obtain membranes with large sort of morphologies.

Precipitant
• Polymer and solvent is mixed and completely soluble (similar to LLE)
( Two pairs partially soluble LLE equilibrium)
• Homogenous solution of polymer and solvent (point A) is quenched in
precipitant.
• Addition of precipitant will move towards ABC path.
• At A , the solution is homogeneous/single phase and as the
precipitant added to the homogeneous solution the concentration
will move towards B (i.e. transition region ) and at ‘C’ solidification
starts (two phase region with solid membrane and other two liquid
phases in pores) and finally will move to point D where only
membrane and precipitant will be present.
• Phase inversion will be done by Solvent Evaporation and Thermal
inversion
• Solvent Evaporation
• The polymer is dissolved in a suitable volatile solvent and a swelling agent is
added.
• This solution is cast and allowed the solvent to evaporate , results in
increasing concentration of polymer at solution air interface.
• This results, formation of skin layer in asymmetric membrane.
• Once the skin layer forms the solvent evaporation will be slow. (similar to
drying phenomena)
• The swelling agent start separating as separate layer (two phase region)
(Polymer + solvent as concentrated phase and swelling agent as dispersed
phase)
• Further evaporating the solvent the polymer start aggregating to form a coat
around the swelling agent.
• This method is used for manufacture of CA, CTA, Polyamide membranes
Thermal Inversion
• The polymer solution is kept at high temperature so that all in single phase
• Followed by rapid cooling to split the solution into polymer rich and solvent
rich phases
• Results in gelation of polymer and its structure can be set by cooling below
the freezing point of solvent.
• The cooling is kept slow to get more homogeneous ultrastructure made up
of micro aggregates of polymers.
• Finally a second solvent is used to remove the (known as non solvent) 1st
solvent.
• The use of different solvents results in membranes of different pore size
and distribution.
• On completion of the solvent exchange the membrane is transferred to
desiccator where solvents are slowly evaporated.
• Poly propylene, poly ethylene and Poly olefins are made with this method