A

Presentation
on

Membrane Technology
By
Dr. Ajit P. Rathod
Deptt. Of Chemical Engineering
Visvesvaraya National Institute of Technology, Nagpur
9th Sept. 2016
Dr. AJIT P. RATHOD
(Assistant Professor )

Education: Area of specialization:

BTech LIT Nagpur Heat Transfer, Membrane Separation Processes
MTech LIT Nagpur Adsorption, Biomass
PhD VNIT Nagpur
International/National Paper publications : 25
Experience: (14 yrs)
VNIT Nagpur International/National Conference : 25
JDIET Yavatmal
Book Chapter : 03
PhD Supervision:
Ongoing:1 Invited / Expert Lecture : 05

MTech Supervision: Consultancy Project :

Completed:1 Ongoing: 2
Ongoing:1
Patent : 01
• Developed membrane technology course for UG students and made them aware about new
research and its applications in the market
• Partial developed membrane technology lab
• Added new experiments in heat transfer lab
• Published research work on peer review international journal
• Participated in short term courses
• Presented research work on national conference and international conference
• Organized three one week self sponsored short term training program
• Reviewer of various journal such as Journal of Membrane Science, Brazilian Journal Of
Chemical Engineering etc.
• Filed one Indian patent
• Co-chaired the session on 7th December 2015 in World Research Journals Conference (WRC-
2015),Deira, Dubai (U.A.E)
• Judged Project/Paper presentation at various institute
• Delivered expert talk on ‘Enhancement of Esterification Reaction by Pervaporation Reactor’
on 6th February 2016 Short Term Training Program(STTP) on Advanced Separation
Processes 5th – 7th February 2016 Department of Chemical Engineering, NIT, Warangal
• Delivered expert talk on ‘Overview of Membrane Separation Technology’ on 19th December
2016 Short Terms Training Program (STTP) on New Trends in Industrial Waste Disposal and
Management” 17th-21st December 2015 Department of Chemical Engineering, SGGSIET,
Nanded
• Delivered expert talk on ‘Pervaporation: Principles and Applications’ on 30th March 2016
Department of Chemical Engineering, JDIET, Yavatmal
Why the need of
separation?
There are various separation processes used in the various process
industries. These processes with their
Corresponding separating agents are as follows:

Process Mass separating agent

Absorption Solvent
Stripping Stripping gas
Adsorption and Adsorbent
Ion exchange
Chromatography Adsorbent
Crystallization Heat removals
Distillation Heat
Drying Heat
Extraction Solvent
Membranes Membrane
OVERVIEW OF MEMBRANE
SEPARATION PROCESSES
 It is an indispensable part of downstream operation in
• Chemical
• Petrochemical
• Biochemical
• Food and Other allied process industries
 It is needed to achieve the goals of
• Enrichment
• Concentration
• Purification
• Refining and
• Isolation of any desired product from a mixture
Efficient separation processes are also required
to obtain high value products in the food and
pharmaceuticals industries

To supply communities and industry with high

quality water and

To remove and recover toxic or valuable

components from industrial effluents
The ability to analyze, synthesize and design
separation processes is considered to be a
distinctive core capability of a process
engineer.
Almost all kinds of separation can be
accomplished by exploiting the difference
between the matters to be separated:
• size,
• shape,
• vapor pressure,
• solubility and so on
Equilibrium and Rate Governed
Separation
Equilibrium separation
• Conventional separation processes such
as evaporation, distillation, extraction,
adsorption, and absorption
Rate governed separation
• Membrane separation
 What is a Membrane?
• A membrane is a selective barrier that permits
the separation of certain species in a fluid by
combination of sieving and diffusion
mechanisms
• Membranes can separate particles and
molecules and over a wide particle size range
and molecular weights
• This selectivity is utilized for separation.
• The selectivity is due to:
1. Size
2. Shape
3. Electrostatic charge
4. Diffusivity
5. Physicochemical interactions
6. Volatility
7. Polarity/solubility
 Basic Principle of Membrane
Separation

• Flux = Membrane permeability (Driving force)

Membrane Thickness
 Historical Development of Membranes
• Emerging technology
• During last 40 yrs, membranes have evolved from a laboratory
tool to industrial products
• 1748, 1887 first publication on osmosis
• 1907 devised a technique to prepare nitrocellulose membrane
• 1930 microporous membranes were commercially available
• During world war II, Milipore corporation(US)
• The golden age of membrane technology (1960-1980)
• In 1960 Loeb and Sourirajan- invented asymmetric integrally
skinned cellulose acetate RO membarne
• By 1980 – MF,UF,RO,ED were all established process.
• Mosanto prism membrane for H2 separation, Dow’s N2
separation from air, Cyanara and Separax system to co2 from
methane, inorganic membrane , nanofiltration membrane
 Classification of Membrane
Processes
Membrane for industrial separation can be broadly classified
1. Pressure Driven membrane process
• Reverse osmosis (RO)
• Nanofiltration (NF)
• Ultrafiltration (UF)
• Microfiltration (MF)
• Pervaporation(PV)
• Gas Separation(GS)

2. Concentration Gradient Driven membrane process

• Dialysis
• Membarne extraction

3. Electrical Potential Driven membrane process

• Electrodialysis(ED)
 The principal characteristics of various
commercialized membrane separation
processes
1. Separation goal
2. Nature of species retained(size of the species)
3. Nature of the species transported through membrane, electrolytic or
volatile
4. Minor or major species of feed solution transported through
membarne
5. Driving force
6. Mechanism for transport/selectivity
7. Phase of feed and permeate streams
 Advantages of membrane process
• Appreciable energy saving
• Clean technology with operational ease
• Replaces the conventional processes
• Recovery of high value products
• Greater flexibility in designing systems
• Hybrid process development
 Disadvantages
• Membrane fouling
• Upper solid limits
• Expensive
 MAJOR AREAS OF
APPLICATION
 Chemical Industry
a) Production of process water for industrial use
b) Waste water treatment
c) Desalting of food , acid and reactive dyes
d) Concentration of all types of dyes
 Pharmaceutical Industry
a) Concentration and purification of soluble
macromolecules such as plasma proteins, vaccines,
enzymes and yeasts
b) Process water as per USP standards
c) Endotoxin in free water
 Food and Dairy In Industry
a) Lactose and protein concentraction
b) Concentration of whole and skim milk
c) Lactose protein separation
d) Gelatin concentration
e) Papine enzyme concentration
f) Fractionation and concentration of egg albumin and
fish oils and proteins
g) Concentration of extracts of vanilla, lemon peel,
malt, etc.
 Biotechnology Industry
a) Enzyme concentration
b) Fermentation broth clarification
c) Separation of microsolutes like antibiotic and vitamins
d) Tissue culture reactor system

•
 Membrane separation processes:
Applications
• Product concentration, i.e. removal of solvent from
solute/s
• Clarification, i.e. removal of particles from fluids, a
special case being sterilization which refers to removal of
microorganisms from fluids
• Removal of solute from solvent, e.g. desalting,
desalination, demineralization, dialysis
• Fractionation, i.e. separation of one solute from another
• Gas separation, i.e. separation of one gas from another
• Pervaporation, i.e. removal of volatiles from non volatiles
(usually solvents)
 Choice for a certain kind of
membrane material
• Good permeability
• Chemical stability and compatibility
• Mechanical strength
• Resistance to fouling
• Amenability to casting in to a thin film
• Pore characteristics
Types of membrane

Sarvesh Gore
BT07CHE027
Types of Synthetic Membrane
 Types of membrane

• Microporous membrane
• Asymmetric membrane
• Thin film composite
• Electrically charged
• Inorganic membrane
Microporous membrane
Asymmetric membrane
Thin film composite
 Electrically charged
• These are basically ion exchange
membranes consisting of highly swollen
gels carrying fixed positive and negative
charges.
• Mainly used for electrodialysis.
• They can be dense or microporous. But
are most commonly very finely
microporous with pore walls carrying fixed
+ve and –ve ions
• A membrane with fixed positively charged
ions is referred to as anion exchange
membrane because it binds anions in the
surrounding fluid.
• Similarly , a membrane with fixed
negatively charged ions is called cation
exchange membrane.
• In this type , separation is mainly achieved
by the exclusion of ions of the same
charge as the fixed ions of membrane.
Schematic diagram of electrically charge
membrane
 The various characteristics of electrically
charged membrane are:

• Ion conductivity
• Hydrophilicity
• The existence of fixed carrier (ion
exchange group)
Applications
 Inorganic membrane
• This type of membrane is also known as
ceramic membrane.
• They generally have an asymmetrical
structure composed of at least two , but
mostly three , different porosity levels.
• In order to reduce the surface roughness ,
a mesoporous intermediate layer is often
applied before applying the active
microporous top layer.
Inorganic membrane
Advantages of inorganic membrane
• Thermal stability : usable at over 1000oC
• Chemical stability : resistant to chemical
attack
• Manufacturing flexibility : can be
manufactured according to conditions
maintained for separation process.
• Better than organic membranes for
commercial use.
• Offer sufficiently high permeance and
selectivity.
• Can be made into membrane module for
practical applications.
 Disadvantages
• It is relatively costlier.
• Manufacturing of porous ceramics in the
form of thin discs is difficult due to various
factors like scope of pore size , structural
stability of such thin discs (300 to 500
microns) and brittle nature of ceramic
material.
Ceramic membrane
 Manufacturing methods
• Particle dispersion and slip casting
• Phase separation and leaching
• Anodic oxidation
• Thin film deposition
 Applications
• Air separation by mixed oxygen ionic and
electronic conducting ceramic membranes
and molecular sieve carbon membranes.
• Hydrogen separation by metal , silica and
zeolite and proton-conducting ceramic
membranes.
• Carbon dioxide separation by silica or
zeolite membranes.
 MEMBRANE MODULES
 For practical applications membranes are installed
in a device, which is referred to as membrane
module.
 The membranes can be as flat sheets, tubes and
fine hollow fibers.
 For accommodating such shapes and structures,
different types of membrane modules are available.
 There are basically four different designs of
membrane modules which are most commonly
used.
These are:
1. Plate and frame
2. Tubular
3. Spiral wound
4. Hollow fiber
 Membrane element and
module
Membrane module refers to the device
which houses the membrane element:
•Stirred cell module
•Flat sheet tangential flow (TF) module
•Tubular membrane module
•Spiral wound membrane module
•Hollow fibre membrane module
 Stirred cell
Nitrogen/compressed air

Pressure gauge

Feed
Stirrer bar

Membrane

Permeate
collection Permeate/filtrate
chamber

Magnetic stirrer

•Research and small-scale manufacturing

•Used for microfiltration and ultrafiltration
•Excellently suited for process development
work
 Flat sheet tangential flow
module
Permeate

Feed Retentate

Permeate
Membranes

•Similar plate and frame filter press

•Alternate layers of membranes, support
screens and distribution chambers
•Used for microfiltration and
ultrafiltration
Spiral flow membrane module

•Flat sheet membranes are fused to form an

envelop
•Membrane envelop is spirally wound along with a
feed spacer
•Filtrate is collected within the envelope and piped
out
Tubular membrane module

Feed
Retentate

Pe rmeate (flow s radially)

•Cylindrical geometry; wall acts as the membrane

•Tubes are generally greater than 3 mm in diameter
•Shell and tube type arrangement is preferred
•Flow behaviour is easy to characterise
Hollow fibre membrane module

•Similar to tubular membrane module

•Tubes or fibres are 0.25 - 2.5 mm in diameter
•Fibres are prepared by spinning and are potted within the
module
•Straight through or U configuration possible
 Membrane modules

Type Fluid flow Membrane Mass Hold-up Special remarks

regime area /module transfer volume
volume ratio coefficient
TF flat Laminar- Low Low to Moderate Easily
sheet turbulent moderate dismantled and
cleaned.
Spiral Laminar Moderate Low Low Low TMP only.
wound

Hollow Laminar- High Low to Low Susceptible to

fibre turbulent moderate fibre blocking.

Tubular Turbulent Low Moderate Moderate Flow pattern

to high to high easy to
characterise.
Flow patterns in membrane
module
 The techno-economic factors for the
selection, design and operation of membrane
modules include cost of supporting materials and
enclosure (pressure vessels), power consumption
in pumping and ease of replaceability.
 Basic features of the above membrane
modules are their major advantages are
discussed briefly in the following:
 PLATE AND FRAME:
These are similar to plate and frame press with a
series of flat membrane sheets. The plate and frame
module has several variations. The most common one
consists of thin plastic plates covered on both sides by
membrane, which are sealed around the edge to
prevent leakage. The plate sometimes resemble
phonograph record in that their flat surface contains
small grooves through which the permeate flows
after passing through the membrane.
 MAJOR ADVANTAGES:
• Sheets can be quite close to one another
to reduce concentration polarization, a
phenomenon which is detrimental to
membrane.
• They can be taken apart for cleaning
purposes.
 TUBULAR
Tubular module resembles a shell and tube heat
exchanger, but the feed flows through the tubes.
Permeate passes through the wall of the tubes into the
shell side of the module. In some tubular modules,
the feed is supplies to the outside of the membrane
tube. Tubular devices consist of parallel bundles of
rigid walled, porous or perforated tubes. This module
contains up to 30 tubes.
Tubular modules are now generally limited to
ultrafiltration applications, for which the benefit of
resistance to membrane fouling due to good
fluid hydrodynamics outweighs their high cost.
Typically, the tubes consist of a porous paper or
fiberglass support with the membrane formed on
the inside of the tubes. In a typical tubular
membrane system a large number of tubes are
manifolded in series. The permeate is removed
From each tube and sent to a permeate
collection header.
 MAJOR ADVANTAGES:
• These can be operated with simple
pretreatment of feed.
• These can be mechanically cleaned by
forcing a sponge ball through the tubes.
• Membrane area/module space ratio is
small.
• Membrane contamination can be
minimized by high feed flow rate.
 SPIRAL WOUND
• Consists of large membrane envelope
rolled loosely
• Formed from plate and frame sheet
wrapped around centre collection pipe
• Density about 300-1000 m3/m2
• Diameter up to 4 cm
 MANUFACTURE
• Elements manufactured with flat sheet membrane of
either a cellulose diacetate and triacetate (CA) blend
or thin film composite
• Thin film composite membrane consists thin active
layer of one polymer cast on a thicker supporting
layer different polymer
• Exhibits higher rejection at lower operating pressure
than CA blends
• Materials may be polyamide, polysulfone, polyurea,
etc
 CONSTRUCTION
• Long flat sheets are laid in pile with spacers
and supports between sheets up to required
thickness
• Pile of sheet then rolled up to form cylinder
which is then inserted in cylindrical housing
vessel
• A permeate spacer is sandwiched between
two membranes
• Porous support side of membrane is faced to
the permeate spacer
 WORKING

• Feed flows through feed spacer, parallel to

central tube
• Permeate flows through permeate spacer,
spirally perpendicular to the feed flow
direction
• Feed flows axially on cylindrical module
• Permeate flows into central pipe
 ADVANTAGES
• High pressure durability:
Can withstand up to 1000 psi.
• Compactness:
Efficient utilization of floor space
• Low permeate pressure drop and membrane
contamination
• Minimum concentration polarization
• Minimum pressure drop at the permeate channel
 HOLLOW FIBER
• Consists of fibers with O.D. of 25-250 µm
and wall thickness of 5-50 µm
• Has structure of asymmetric membrane,
active skin layer being placed to the feed
side
• A bundle of hollow fibers mounted in a
pressure vessel, open end of U-shaped
fibers potted into head plate
 WORKING
• Input water under high pressure flows over
outside surface of fibers
• Permeated water then flows out through
base of fibers and collected as product
• If water flows inside fiber then product is
obtained outside of membrane
 PROPERTIES
• Permeate water flow per unit area of
membrane is low, hence less concentration
polarization at membrane surface
• Net result is hollow fiber units operate in a
non-turbulent or laminar regime
• Can be operated at up to 50 percent recovery
• Can be melt spun, wet spun or formed by
interfacial polymerization
 ADVANTAGES
• Modest energy requirement
• No waste product
• Large surface area per unit volume
• Flexible
• Can be designed for circulation, dead-end
and single pass operations
• Low cost
• Can not be used on corrosive substances
and high temperature conditions
COMPARISON
 GENERAL CHARACTERISTICS OF MEMBRANE MODULES
(Basic guidelines for selecting the right module geometry for a specific application)
Plate-and-
Characteristics Spiral Wound Hollow Fiber Tubular
Frame
Typical Packing Density
(ft2/ft3) 245 1830 21 150
(m2/m3) [800] [6000] [70] [500]
Required Feed Flow Rate
(ft3/ft2-s) 0.8-1.6 ~0.016 3-15 0.8-1.6
(m3/m2 -s) [0.25 - 0.50] [~0.005] [1.0 - 5.0] [0.25 - 0.50]
Feed Side Pressure Drop
(psi) 43 - 85 1.4 - 4.3 28-43 43-85
(Kg/m2) 3-6 0.1 - 0.3 2-3 3-6

Membrane Fouling Propensity High High Low Moderate

Ease of Cleaning Poor to good Poor Excellent Good

Typical Feed Stream Filtration 10 - 25 µ 5 -10 µ 10 - 25 µ

Not required
Requirement filtration filtration filtration
Recommended Clean dilute Very clean For high conc. in Laboratory
Applications streams such as streams such as dirty streams or work and
water for water. For UF/MF streams membrane
desalination. Not on dirty streams containing fouling evaluations.
good for high with built-in back chemicals, such as Good for high
concentration & wash system. dye desalting & viscous liquids.
fouling chemicals concentration
The glass-transition temperature Tg of a material
characterizes the range of temperatures over which this
glass transition occurs. It is always lower than the melting
temperature, Tm, of the crystalline state of the material, if
one exists.

Hard plastics like polystyrene and poly(methyl

methacrylate) are used well below their glass transition
temperatures, that is in their glassy state. Their Tg values are
well above room temperature, both at around 100 °C (212 °F).

Rubber elastomers like polyisoprene and polyisobutylene are

used above their Tg, that is, in the rubbery state, where they
are soft and flexible.
 Membrane material

Organic polymers Inorganics

• Polysulfone (PS) • -alumina

• Polyethersulfone (PES) • -alumina
• Cellulose acetate (CA) • Borosilicate glass
• Regenerated cellulose • Pyrolyzed carbon
• Polyamides (PA) • Zirconia/stainless steel
• Polyvinylidedefluoride • Zirconia carbon
(PVDF)
• Polyacrylonitrile (PAN)
Alpha cellulose
Cellulose acetate
 SELECTIVITY
• Retention:

cF  cP
R
cF
 SELECTIVITY
• Separation factor:

y A / yB
 A/ B 
x A / xB
Membrane preparation
• Polymer casting
– Precipitation from vapour phase
– Precipitation by evaporation
– Immersion precipitation
– Thermal precipitation

• Other methods
– Stretching
– Sintering
– Slip casting
– Leaching
– Track etching
 INTRODUCTION
– The use of membrane in chemical reactions is attracting
much more attention.
– Number of investigations have been concentrated on
applications of hydrogen membrane in reversible gas
phase reactions.
– Water permeable membranes to liquid phase reactions.
– Membrane technology enhance the conversion of
thermodynamically and kinetically limited reactions
through controlled removal of one or more reactants or
products from reaction mixture.
– Main functions of membranes are
1) immobilization of enzyme.
2) eliminating product inhibition.
3) recycling enzymes…etc.
 PREPARATION OF PVA
COMPOSITE CATALYTIC
MEMBRANE
• This procedure contains two steps:
• 1) Cross linked PVA (cross linked with
glutaraldehyde) dense active layer was coated
on the porous ceramic plate.
• 2) Zr(So)2.H2O, an inorganic solid acid which
was used as the esterification catalyst in this
experiment ,was immobilized on the dense
active layer.
MATERIAL USED IN PREPARATION:

1)Three kinds of PVA having a degree of

polymerization of 1750 + 50.
2)The porous ceramic plates.
3) Gutaraldehyde (GA) used as 50wt%
GA aqueous solution.
4)The deionized water.
5)Other chemicals used were A.R. grade
and used without further purification.
Dense active layer membrane preparation
conditions:

-Concentration of membrane 10% PVA water solution

making solution.
-Viscosity of membrane making 2.13-2.18 Pa s
Solution.
-Revolution speed of motor 750 rpm.
-Time of rotation 30 s.
-Drying time in membrane 24 h
making room.
-Heat-curing temperature 110°C.
-Heat-curing time 30 min.
Apparatus for preparing composite catalytic membrane:
(A)iron-shelf, (B) membrane making solution, (C) porous
ceramic
plate, (D) support plate, (E) variable-speed motor, (F) adjuster,
(G)input of 220 V stationary voltage
The working mechanism of the composite
catalytic membrane:

The working mechanism of the composite catalytic

membrane has been given as follow:

1) First, the acid and the alcohol have to sorbs and diffuse
into the catalytic layer toward the catalytic sites situated at
different depths, driven by their consumption by there
action at these sites.

2)The products of the reaction migrates differently from

the reaction sites toward the external phases according to
the directions of their driving forces.
In a general, the process is controlled by the
mass transfer of the ester and the water in the
first stage, then it is controlled by the water
mass transfer only until the reaction end. With
the increase of the temperature and the catalyst
concentration, the time of the first stage will
shorten.
 SUMMERY
• Membranes are widely used in chemical industries due to
their unique properties.
• Preparation of the poly(vinyl alcohol) (PVA)
composite catalytic membrane cross linked by
glutaraldehyde on porous ceramic plates is explained.
• Different conditions and materials for preparation are
explained.
• The cross-section morphology of membrane and
characterization of membrane can be obtained by SEM and
XPS method.
• This composite membrane is used in pervaporation method
for separation of water and ethanol..etc.
• Different difficulties can be overcome by using such
membranes.