Membrane Technology (CHE-

442)
Lecture-2

Instructor: Dr. Ayesha Raza​

School of Chemical and Materials Engineering (SCME)​
National University of Sciences and Technology (NUST),
Pakistan
 What is membrane???
A membrane is a selective barrier; it allows some things to pass through
but stops others. Such things may be molecules, ions, or other small
particles.
Membrane process: the feed stream is
divided into two streams
 retentate (concentrate) stream
 permeate stream
Either the concentrate or permeate stream is
the product
What is membrane???
What is membrane???
 Modes of Membrane

Modes of Membrane Processes

What is membrane???
What is membrane???
• Membrane distillation (MD) is a separation process that utilizes a
hydrophobic membrane to separate volatile components from a liquid
feed solution. It operates on the principle of vapor pressure
differences and is often used for desalination, wastewater
• Membrane distillation (MD) is a thermally driven separation process in
which separation is driven by phase change. A
hydrophobic membrane presents a barrier for the liquid phase,
allowing the vapour phase (e.g. water vapour) to pass through the
membrane's pores. The driving force of the process is a partial vapour
pressure difference commonly triggered by a temperature difference.
and concentration of solutions
 Membrane Modules
Membrane module-technical arrangement of the membranes is the core part of any membrane system to get good
separation productivity. Three major types of membrane modules include:
Plate and Frame Module
Plate and frame module comprises of stacked flat sheets of membranes separated by spacers and rubber gasket to prevent
any leakage.
Low packing density and high cost are the major limitations of this module. This type of module configuration is not
preferred for gas separation applications but commonly used for small scale electrodialysis and pervaporation systems.
Spiral-wound Module
Flat sheet membranes are utilized in spiral-wound module. It provides higher packing density relative to the plate and
frame configuration. Membrane envelops, each consists of two flat sheets of membranes with a spacer in between to give
mechanical strength, are wound around the central porous permeate collecting tube.
Hollow-fiber Module
Hollow fiber module comprises of a bundle of HF membranes, assembled in a high pressure vessel. Feed can enter from the
shell or the bore side.
Hollow-fiber configuration offers highest packing density compared to other modules. However, the major downside of this
module is high pressure drop at the bore side mainly in the case of large volume of permeating gas. Hence, for gas
separation shell side feeding is preferred to limit pressure drop.
The selection of module depends upon numerous factors for instance application, economics, ease of cleanliness,
scale of separation etc.
Membrane Classification
 Membrane materials

Materials for Membrane Synthesis

The choice of suitable material for membrane fabrication is very
challenging and highly depends upon the separation application. The
essential requirements of the membrane materials are
1. Good separation efficiency with reasonable permeation rate
2. Decent thermal and chemical stability
3. Economical and eco-friendly nature
4. Manufacturing reproducibility
5. Reasonable mechanical strength
 Membrane materials
polydimethylsiloxane (PDMS)
Rubbery Polymers Advantages
1. Easy to scale-up
Organic 2. Easy to fabricate
3. Low production cost
4. Cost friendly
cellulose acetate, polysulfone and polyimides
Glassy polymers Limitations
Membrane 1. Robeson trade-off
materials 2. Plasticization
3. Aging

Inorganic

Advantages Limitations
1. Good separation 1. Not economical
2. Excellent stability 2. Difficulty in reproduction 18
Robeson tradeoff
• The inverse relationship between permeability and selectivity of
the separating gases was observed by the Robeson in 1991 and
established the upper-bound limit which was modified in 2008.
He proposed that polymeric membranes have inverse
relationship between selectivity and permeability.
Membrane plasticization
The plasticization of the membrane occurs when highly condensable
gases like CO2, swells the polymer to an extend that lead to an
improvement in chains mobility and free volume. Subsequently,
reduces the separation selectivity of the resultant membrane.The
pressure corresponds to the bare lowest permeability is called as
plasticization pressure. This happening must be prevented to upgrade
the membrane performance and suitability for industrial use.

Aging
Physical aging of the polymer is referred to the changes associated
with the physical features of the polymer with time. It influences the
polymer packing density, crystallinity and free volume.
Consequently, separation performance of the membrane significantly
reduces with time.
 Approaches to Overcome the Constraints Associated with Organic and Inorganic Membranes

MMMs are considered as a promising strategy to counter the

challenges of polymeric membranes by incorporating inorganic
nanoparticles in the continuous phase of polymer matrix.These
membranes are likely to merge the benefits of the polymeric matrix
such as low cost and easy processability with the merits of the
inorganic components in terms of better permeability, selectivity and
good thermal stability. Inorganic particles incorporated in MMMs as
dispersed phase can be classified into two major groups.
1. Non-porous/ non-permeable fillers for instance silica and TiO2

2. Porous/permeable fillers for instance zeolites, like carbon nanotubes

and metal organic frameworks (MOFs)
Solution Blending
• It is a very simple approach to synthesize MMMs. It involves (1)
dissolution of polymer in a suitable solvent (2) incorporation of
nanoparticles in the prepared polymer solution followed by stirring to
uniformly disperse the added
In-situ polymerization
• This method includes the direct dispersion of the nanoparticles in a
monomer solution, followed by the polymerization. Under high
temperature, the functional groups attached on the surface of inorganic
ingredients generate the initiating radical, positive or negative charged
species. The common functional groups are carboxyl and hydroxyl. The
inorganic particles are connected with the polymeric chains by covalent
bonds [8].
Sol-gel method
• Sol-gel is considered as highly utilized technique for the synthesis of
 Technique Advantages Limitations
Solution blending  Simple  Agglomeration
 Well suited for of particles
different types of
inorganic materials
 Easy to control the
concentration of
inorganic material
In situ  Strong bonding  High processing
polymerization between temperature
nanoparticles and
polymer matrix
Sol gel method  Simple  Difficult to
 Moderate control
processing membrane
temperature porosity

Based upon the bonding between polymer matrix and nanoparticles,
MMMs are classified into two types.
1. MMMs in which polymer matrix and nanoparticles are connected by
primary bonds such as covalent bonds. This type of membrane
morphology can be obtained by in situ polymerization or sol gel
method.
2. MMMs in which polymer and inorganic nanoparticles are connected
by secondary bonds for example van der waals forces. Solution
blending is the common method use to get such types of
membrane structure
 Approaches to Overcome the Constraints Associated with Organic and Inorganic Membranes

Challenges of Mixed Matrix Membranes

Usually, the formation of defect free polymer-particle
interface is very challenging owing to the following
reasons.
1. Strong agglomeration tendency of particles
2. Poor adhesion between polymer matrix and
nanoparticles
3. Poor compatibility between matrix and dispersed
phase
4. Different thermal coefficient of the polymer and
particles.
 Approaches to Overcome the Constraints Associated with Organic and Inorganic Membranes

Approaches to Tackle Polymer-Particle Interface

1. Membrane casting temperature should be greater than the Tg of
the polymer.
2. Plasticizer can be added in the polymer solution to improve
polymer chains flexibility.
3. Functionalization of the inorganic particles to improve
compatibility between dispersed and matrix phase.
4. Priming method- use dilute polymer solution to coat the surface
of inorganic particles before dispersion into the bulk polymer.
5. Incorporation of a third element such as pnitroaniline (pNA) into
the dope solution to link the polymer chains with inorganic
particles.
 Approaches to Overcome the Constraints Associated with Organic and Inorganic Membranes

Polymer Blend Membranes

Polymer A Polymer B
Types of polymer blends
1. Miscible blends
• Both the polymers are miscible at molecular level and
connected by primary bonding such as hydrogen bonding.
Miscible blends exhibit single glass transition temperature.

2. Immiscible blends
• Heterogeneous blends that are unable to form a single phase
and there exist an interphase between both blend
components.

3.Partially miscible blends

• Also known as isotropic heterogeneous blends. Both blend

components are partially miscible into each other.
Consequently, the composition of the separated phases is
 Approaches to Overcome the Constraints Associated with Organic and Inorganic Membranes

Current Challenges of Polymer Blend Membranes

Apart from their advantages, major challenge of the
polymer blends is the blend miscibility at molecular level.
Usually for the gas separation applications, miscible
blends are more preferred
Membrane Classification
Symmetric vs Asymmetric Membranes
• Symmetric membranes can be termed as membranes in which separating layer and
support layer are undistinguishable because of the uniform composition and
structure in the direction of the membrane thickness.
• The productivity of these membranes can be enhanced by decreasing the membrane
thickness. But very thin stand-alone membranes are not mechanically strong enough
to withstand high operating pressure in many applications.
• Asymmetric membranes is comprised of thin skin film on a thick, porous support.
• Separation function is performed by the skin layer which is generally dense while the
mechanical strength is offered by the thick support to the fragile skin.
• Porous support does not give any transport resistance, so the permeation flux mainly
depends upon the skin layer thickness.
• If both distinguishable layers of the asymmetric membranes are made up of different
materials, then the resultant membranes are referred as “asymmetric composite
membranes”. These membranes offer the advantage of choosing the membrane
material based upon their intended functions such as the material for support layer is
selected on the basis of its chemical resistance and mechanical properties while for
the selection of skin layer material, major consideration is given to its separation
ability
Dense vs Microporous Membranes
• Surface of the dense membranes is free of pores and
voids.
• Separation performance of these membranes mainly
depends upon the inherent characteristics of the
membrane material, separating species and their
interactions with membrane.
• Microporous membranes exhibit interconnected porous
structure across the membrane thickness. Size of the
pores ranges from 0.01 to 10 microns, commonly
utilized in ultrafiltration and nanofiltration.