Unit 3 PDF

Advanced Separation Processes
(ASP)
UNIT 3: Membrane gas separations,
Pervaporation & Membrane reactor
Membrane gas separations, Fundamental mechanism, governing factors,

principle of designing of gas separator membrane using complete mixing
model. Gas separation membranes, applications of membrane gas separation.
Introduction to pervaporation: principle, membranes used and application.
Hybrid distillation-pervaporation system, Membrane Reactor: Concept &
working, Various types of membrane used for membrane reactor, Membrane
bioreactor.
4/3/2023 Dr. Swapna PANDA 2

What is Gas Membrane
Separation?
• Separation of a known component into

two product streams (known as the
permeate and reject, or retentate)
through a semi-permeable polymeric
membrane.
In case of gas separation by membranes, high pressure feed gas is
supplied to one side of the membrane and permeate comes out
normal to the membrane to the low pressure side.
Due of high diffusivity in gases, concentration gradient in the gas

phase normal to the membrane surface is small.
So, gas film resistance is neglected compared to membrane

resistance.
This means concentration in gas phase in a direction normal to

membrane is uniform whether gas stream flows parallel to the
surface or not.
There are various types of gas separation processes depending
upon the flow characterizations.
Since the permeate comes normal to the flow direction of the feed,
this is known as simple cross flow (Fig. 5a).
If there is complete mixing of the feed and permeate by an external

agent (stirrer or mixer), then the configuration is complete mixing
(Fig. 5b).
If feed and permeate are in the same direction, then the flow is
cocurrent flow (Fig. 5c).
If they are in opposite direction, then it is counter current flow

4/3/2023 (Fig. 5d). Dr. Swapna PANDA 5
Gas Separations Using Membranes
4/3/2023 Dr. Swapna PANDA

6
7
Industrial Uses?
• H2 Separation
– H /N
2 separation in ammonia plants & H2/hydrocarbon separation
2
in petrochemical applications
• N2/Air Separation
• CO2 & H2O removal from natural gas
• Organic vapor removal from air or N2 streams Inerting
• – Chemical industry products stored in inert atmosphere
– Reduces risk by removing O 2
Blanketing
• – Uses N 2 to ‘cover’ liquid
• Prevents vaporization
• Maintains atmosphere to reduce ignition potential
• Prevents oxidation or contamination by reducing exposure to
atmospheric air
Gas Separations Using Membranes
Current applications:
• Air separation - mainly N2 enriched air
• Natural gas treatment - acid gas removal
• H2 separation - H2 from hydrocarbons, ammonia purge, syngas
• Removal of vapors from mixtures with light gases (vapor separation)
Advantages:
• Low energy separation (no phase change)
• Reliable (no moving parts)
• Small footprint
Drawbacks:
• Incomplete separation (need higher selectivity)
• Low chemical/thermal stability (need more resistant matls.)

9
Advantages
Separation units smaller than other types

– Small footprint = good for operations such as offshore gas-processing
platforms
Environmentally friendly (no waste product) Wide operating
parameters (flexible)
Requires less energy than other separation processes (no phase change)
Very reliable
Lacks mechanical complexity – no supervision required (low operating cost)
Disadvantages
• Membrane founing - more frequent than other Membranes due to is configuration
(contaminated feed).
•Expensive - more so than other types available (fabrication method)
•Lack of research - less research done compared to other types of membrane

Ideal Membrane Characteristics
• High flux (high permeability, thin)

• High selectivity
• Tolerance to all feed components
• Mechanical stability
• Ability to be packaged in high surface area modules
• Excellent manufacturing reproducibility, low cost

11
12
Hollow Fiber Module
Contaminated Natural Gas CO2- rich permeate
(High Pressure) (Low pressure)
~5,000 m2/m3
Upgraded Natural gas

(High Pressure)
4/3/2023 D. Wang, et al., ACS Symp. Ser.,Dr.v.Swapna

744,PANDA
p. 107, 1999. 13
Natural Gas Purification
U.S. Pipeline Specifications1:

Amine Scrubber Component Specification
CO2 <2%
H 2O <120 ppm
H 2S <4 ppm
C3+ hydrocarbons 950-1050
Btu/ft3(STP)
Dew Point -20C
Inerts (N2, CO2, He, etc.) <4%
Potential membrane applications:

• Acid gas removal
• N2 removal
• Higher hydrocarbon removal
• Dehydration
Membrane Unit 1R.W. Baker, I.&E.C. Res., 41, 1393 (2002). 14
Why Crosslinking ??? Poly(ethylene oxide) [XLPEGDA]
CH 2 CH C [O CH 2 CH 2 ] O
14
C CH CH 2
OR
O O
PEO
Poly(ethylene oxide) diacrylate (PEGDA: Crosslinker)
O C
C C C
C C C
CH 2 CH C [O CH 2 CH 2 ] OR C O
n O C O C C O
O PEO
UV O PEO PEO
R=CH3; poly(ethylene glycol) methyl
O
ether acrylate (PEGMEA); n=8 PEO OR O
R=H; poly(ethylene glycol) acrylate O C O C
O C
(PEGA); n=7 C C C
C C C

Membrane Types
Dense membrane Asymmetric membrane
Permeability (inherent property) Permeance (normalized flux)
Ql P= Q
P=SD=
AP l PA
Where
A = Membrane surface area (cm2)
l = Thickness of dense membranes (cm)
P = Permeability of a membrane to gas i (barrer, 1barrer=110-10 cm3 (STP)-cm/cm2 sec
cm-Hg)
P = Trans-membrane pressure drop (cm-Hg)
Q = Volumetric flow rate of gas i at standard temperature and pressure (cm3 (STP)/s)
S = Solubility coefficient (cm3 (STP)/cm3 cm-Hg)
D = Diffusion coefficient (cm2/s)
4/3/2023 (P/l) = Permeance of an asymmetric membrane to gas i (GPU, 1GPU=110-6 cm3
Dr. Swapna PANDA 16
(STP)/cm2 sec cm-Hg)
Polysulfone - C27H22O4S
• Oxygen Permeability
– PA = 1.38
• Nitrogen Permeability
– PB = 0.239
• Selectivity
– α = PA/PB
– α = 1.38/0.238 = 5.8

In Gas separation

In Gas separation
Selectivity and retention

Fundamental mechanism of Gas
transport
• Knudson Diffusion
• Molecular Sieving
• Solution-Diffusion Molecular Sieving
(Permeation)

➢ Fundamental mechanism for Membrane gas separations:
Both porous and dense membranes can be used as selective gas separation barriers; Figure illustrates the mechanism
of gas permeation. Three types of porous membranes, differing in pore size, are shown in figure.
➢ If the pores are relatively large from 0.1 to 10 μm gases permeate the membrane by convective flow, and no
separation occurs.
➢ If the pores are smaller than 0.1 μm, then the pore diameter is the same size as or smaller than the mean free path
of the gas molecules. Diffusion through such pores is governed by Knudsen diffusion, and the transport rate of
any gas is inversely proportional to the square root of its molecular weight. This relationship is called Graham’s
law of diffusion.
➢ Finally, if the membrane pores are extremely small, of the order 5–20 A°, then gases are separated by molecular
sieving. Transport through this type of membrane is complex and includes both diffusion in the gas phase and
diffusion of adsorbed species on the surface of the pores (surface diffusion). These very small-pore membranes
have not been used on a large scale, but ceramic and ultra- microporous glass membranes with extraordinarily
high selectivities for similar molecules have been prepared in the laboratory.
Types of Motion of molecules through a barrier
1) Permeation:
a) Dissolution of permeating molecules in the membrane

b) Diffusion of dissolved molecules
c) Desorption of penetrant molecules to the downstream side.
2) Knudsen diffusion (d/λ < 0.2):
Single gaseous molecules diffuse under rarefied conditions so that the mean free path is longer than the
pore diameter. P is constant Molecules collide with the wall. Due to low selectivity, Knudsen diffusion
in membranes is not commercially attractive (average distance an object will move before collision).
3) Convection (d/λ > 20): Viscous flow through the pores of ultrafiltration and microfiltration.
transport • Solution-Diffusion
1) Permeation:
a) Dissolution of permeating molecules in the membrane

b) Diffusion of dissolved molecules
c) Desorption of penetrant molecules to the downstream side.

where Ji is the flux of component “i” (g/cm2·s), pio and pil are the partial pressure of the
component “i” on either side of the membrane, l is the membrane thickness, Di is the
permeate diffusion coefficient, and KiG is the Henry’s law sorption coefficient
(g/cm3·pressure).
➢The ratio Di/Dj is the ratio of the diffusion coefficients of the two gases and can be viewed as
the mobility selectivity, reflecting the different sizes of the two molecules. The ratio Ki/Kj is
the ratio of the sorption coefficients of the two gases and can be viewed as the sorption or
solubility selectivity, reflect in the relative condensabilities of the two gases.
➢In all polymer materials, the diffusion coefficient decreases with increasing molecular size,
because large molecules interact with more segments of the polymer chain than do small
molecules.
➢Glassy Polymers
➢Rubbery polymers,

Glassy polymers
• are characterized by their high stiffness and amorphous non-crystalline
structure and higher solubility coefficient.
• These properties make them size selective in their dense form and also
mechanically sufficiently resistant to exist as porous flat film or hollow fibre
membranes.
Rubbery polymers
Generally have higher diffusion coefficients than glassy polymers (above Tg, glass transition temperature)
In rubbery polymers, the sorption selectivity term is usually dominant, permeability increases with increasing
permeate size, and larger molecules permeate preferentially. Therefore, when used to separate organic vapor from
nitrogen, rubbery membranes preferentially permeate the organic vapor.
• TG refers to the glass transition temperature whereas TM refers to the
melting temperature.
• The terms TG (or Tg) and TM (or Tm) give two important parameters of polymers.
• These are temperatures at which the texture of polymer changes.
The key difference between TG and TM polymers is that the TG describes

the conversion of the glassy state into rubbery state whereas the TM
describes the conversion of the crystalline state into an amorphous
state. Therefore, as another important difference between TG and TM
polymers, we can say that the TG describes the conversion of the phase
of matter (solid to rubbery phase) but, the TM does not describe the
conversion of the phase of matter (solid to solid).
Thermosetting plastic: Plastics
which do not get deformed or
softened on heating when mold
once, are called thermosetting
plastics. Bakelite and melamine are
the examples of thermosetting
plastics. epoxy, silicone,
polyurethane and phenolic.
Thermoplastics…
polyethylene, polypropylene,
polyvinyl chloride, polystyrene,
polyethylenetheraphthalate,
polycarbonate, polybenzimidazole,
nylon, Teflon

Fundamental mechanism of
Gas transport • Solution-Diffusion

Gas Transport in Polymers:
Solution-Diffusion Model
4/3/2023 J. Membr. Sci., 107,

Dr. Swapna PANDA1-21 (1995)
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A membrane is defined:
as a selective barrier that allows certain components in a mixture to pass through, but
rejects others, thus achieving a separation.
Solution-diffusion mechanism:
Permeability (P) = Solubility (Sapp) x Diffusivity (Dapp) or Mobility factor
DENSE
Ql
P = S •D =
MEMBRANE
AP SORPTION
DESORPTION
DIFFUSION
l
Materials Design Approach
PA = SA DA S A DA
 A/B =
S B DB
• Traditional membrane materials
• Glassy polymers
• Designed to be strongly size-sieving
• Low permeability
• High selectivity due to high diffusion selectivity
• Upon plasticization, selectivity decreases, sometimes strongly
• H2 selective in H2/CO2 separations
• Our approach
• Rubbery polymers
• Designed to be strongly solubility-selective
• High permeability
• Selectivity derives primarily from high solubility selectivity
• Upon plasticization, separation properties can increase in
4/3/2023 some cases (CO2/H2) Dr. Swapna PANDA
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Permeability (P) = Solubility (Sapp) x Diffusivity (Dapp)
• Sapp is a thermodynamicparameter
• Penetrant condensibility, polymer-penetrant interactions and free
volume in glassy polymer matrices affect Sapp
Dapp is a kinetic parameter

Dapp is proportional to the frequency at which gaps of sufficient
volume open next to a penetrant and allow it to make a diffusive
jump.
Penetrant size, chain packing, polymer chain segment mobility
4/3/2023 and cohesive energy Dr.ofSwapna
thePANDA
polymer govern Dapp. 33
DENSE
MEMBRANE
Permeability P = S D =
Ql
AP
SORPTION
DESORPTION
Ideal Selectivity  = PA/PB = (DA/DB)( SA/SB)
Or Permselectivity DIFFUSION
diffusion solubility
selectivity selectivity
l
Kinetics Thermodynamics
Selectivity in mixed gases  = (yA/yB) / ( xA/xB)
Molar fraction of Molar fraction of

Components A and B at Components A and B at
Downstream Upstream
transport • Molecular Sieving

Permselectivity of selected rubbery and
glassy polymers
For most of these pairs, the diffusion

selectivity is greater than unity, but there
are some exceptions for CO2/O2 and
CO2/N2, which reflect subtle shape
issues that become important when the
sizes are similar.
The important point is to see the much

greater diffusion selectivity for O2/N2 and
CO2/CH4 in polysulfone than in the two
rubbery polymers; this translates into
greater permselectivity of the glassy
material than of the rubbery ones.
In most cases, PA/PB > 1 since the kinetic issue overpowers the thermodynamic one for most A and
B in the case of glassy polymers.
Membrane materials:
Ceramic and zeolite membranes:
Ceramic and zeolite membranes have begun to be used for a few commercial applications just for a few years back. So, these
membranes are all multi-layer composite structures formed by coating a thin selective ceramic or zeolite layer onto the
micro porous support layer.
Ceramic membranes are prepared by the sol-gel technique, zeolite membranes are prepared by direct crystallization in
which the thin zeolite layer is crystallized at high pressure and temperature directly onto the micro porous support.
Composite membrane with a very thin palladium (Pd)/ silver (Ag) layer:
Thin layer of palladium on tantalum or vanadium support film and porous substrates, such as ceramic or stainless steel is
being use for many applications of gas separation. tantalum and vanadium are quite permeable to hydrogen so possibility of
getting more hydrogen that is why they are being used.
These membranes are quite permeable at high temperature, reduced materials cost and improved mechanical strength.
Palladium membranes are for hydrogen permeation and silver membranes for oxygen permeation because their
permeability
4/3/2023 inside these membrane materials is very high
Dr. Swapna PANDA 37
Hydrogen permeation through metal membrane:
First the hydrogen molecule, will absorb on the membrane surface where it dissociates into hydrogen atoms. In
next step, each individual hydrogen atoms loses its electron to the metal lattice and diffuses through the lattice as
an ion. In the last step, Hydrogen atoms emerging at the permeate side of the membrane re-associate to form
hydrogen molecule and then desorb and complete the permeation process.

Polymer materials:
Most gas separation processes require that selective membrane layer to be extremely thin to achieve economic flux.
Composite membranes with glassy thin selective layers with high flux are good, the micro porous support layer can be a
tough glassy material to provide strength.

Factors affecting Gas permeation
– Temperature
– Pressure
– Plasticization
– Permanent condensability
– Polymer crystallinity

Temperature dependence
Diffusion of gases through polymeric membranes is related to activation energy. Thus the
temperature dependence of D, S and P can be described by the following Arrhenius relationships.

– Gas diffusion coefficient increases with increase in
Temperature
– Since diffusivity and solubility coefficient are functions of
temperature so, the separation factor is also a function
of temperature.

Pressure dependence

Plasticization

Permanent condensability

Polymer crystallinity

Temperature:
• Gas diffusion coefficients are generally increased with increasing temperature right when the polymer does not
undergo thermally induced morphological rearrangement such as crystallization about the temperature range of
interest.
• Both diffusivity and solubility coefficients are temperature dependent.
• The selectivity also sensitive to change in temperature.
• The increased segmental motion at higher temperature reduces the ability of polymer to discriminate between the
penetrance of different physical dimensions thereby resulting in a diffusivity selectivity loss.
Pressure:
• large variation of permeability may occur with the change in pressure of permeant contacting with the polymer.
• A few typical patterns of response can be observed in permeability versus pressure relationships.
• For the permeation of an organic vapor into rubbery polymer, permeability increases linearly with increasing pressure.
For low sorbing penetrants such as helium or nitrogen in rubbery or glassy polymers, diffusion and solution become
independent of gas pressure.
• So, a decreasing trend of permeability with increasing pressure is typically observed with highly soluble gases such as
carbon dioxide and glassy polymers.
Plasticization pressure:
Plasticization pressure is usually defined as the pressure at which an increase in permeants occurs. So, at such feed pressure
the gas concentration in the polymer material disrupts the chain packing. The polymer matrix swells and the segmental
mobility of the polymer chain increases, this results in an increase in gas diffusivity and induces increase in permeability the
polymer is highly plasticized by the penetrant, the diffusion coefficient may become a function of time. This non-ideal
behavior is explained by the free volume theory. Free volume theory of diffusion suggests that molecules can only diffuse
through free volume in a molecular matrix.
Permeant condensability: In general, gas solubility and polymers increase with increasing gas condensability, so,
condensability can be measured as the gas critical temperature or the normal boiling point, diffusion coefficients of
permeants are found to decrease with increasing size of permeants. So, diffusion coefficient in polymers are also sensitive to
permeant shape, shape also plays a very important role. So, a linear or oblong permeant molecule such as carbon dioxide
exhibit high diffusivity than those of spherical molecular shape of equivalent molecular volume such as methane. Specific
interactions between gas and polymer molecules also affect gas solubility, gases such as carbon dioxide which has a
quadrupole moment are generally more soluble in polar polymers.
Polymer crystallinity: Crystallinity in polymers tends to reduce both permeant solubility and diffusivity thereby reducing
permeability which is usually undesirable. And polymer cross-linking reduces polymer segmental mobility, therefore
diffusion coefficients of the penetrant gas typically decreases with an increase in the degree of cross-linking in the polymer.
So, in lower molecular weight polymers chains are more mobile and penetrant diffusivity decreases with increasing
molecular weight.
Principle of designing of gas separator membrane using
complete mixing model
✓ Complete mixing model (Designing of Membrane w.r.t. area requirement):
✓ Conceptually the complete mixing model is similar to stirred tank reactor (CSTR).
✓ In this model, the reject or residue and the product or permeate compositions are assumed to be equal to
their respective uniform composition in the chamber. (uniform mixing)
✓ Assume isothermal conditions and negligible pressure drop in the feed and permeate stream.
✓ It is also assumed that the effects of the total pressure and/or composition of the gas are negligible and that
the permeability of each component is constant. This means there would be no interaction between two
components. (ideally)
✓ The difference partial pressures of a component in between two compartments are the driving force its
permeation.
4/3/2023 Schematic diagram is represented Dr.
inSwapna
below figure:
PANDA 49
Separation Factor is represented as :

Substituting Qp =𝜃 Qf from equation (7) in equation (9) and solving for membrane area Am
• In flux equation (1), if certain total molar flow rate of a component through the membrane specified, then
selecting a membrane material with high permeability will result in the decrease the required membrane
area.
• Gas permeability increases with increase in temperature. Therefore, increasing the temperature for a given
flux will also decrease the membrane area.
• But commonly used polymeric membrane do not allow high temperature feeds and feed temperatures are
normally below 100 °C. Heating the feed stream may result in substantial damage of the membrane.
• Thinner the membrane higher the permeation, and low area required for desired purpose.
Applications of membrane gas separations:
Membrane gas separation modules operates on the basis of selective permeation. These kinds of technologies take advantage of the fact that gases dissolve and
diffuse into polymeric materials. If a pressure differential is set up on opposing sides of a membrane film, transport across the film (permeation) will occur. The
product of solubility coefficient and a diffusion coefficient determines rate of permeation. Very small molecules (He and H2) permeates very fast as compare to
the larger molecules. Highly soluble molecules will give higher diffusion as compared to less soluble molecules. Based on these various applications of
separation can be achieved:
Recovery of hydrogen from tail gases: Hydrogen separation from tail gases is one of the early application areas of membranes. This includes cases like recovery
of hydrogen from ammonia purge stream, separation/recovery of hydrogen from various refinery streams or separation of hydrogen from CO-H2 syn-gas in order
to adjust the composition for a particular use. The membrane used in these applications is polysulphone hollow fibers. The production of ultrapure hydrogen by
palladium membranes is used in semiconductor industries. One mole of palladium can absorb six moles of hydrogen. When palladium alloy is stretched into the
film, and a hydrogen pressure gradient is applied, the transport of hydrogen takes place.
Removal of carbon dioxide: Most oil and gas application involve removal of CO2 from natural gas components. When a natural gas stream containing CO2 is fed
to a membrane, the CO2 will permeate the membrane at a faster rate than the natural gas components. Thus, feed stream is separated into a CO2 rich, low
pressure stream and a CO2 depleted from high pressure natural gas stream. Removal of CO2 from the flue gas can be also accomplished by membrane
separation processes. Membrane processes are generally more energy efficient and easier to operate than the adsorption process. Many microporous inorganic
membranes developed in recent times, shown very good permeability for CO2 over nitrogen at low pressure.
Separation of oxygen and nitrogen: Both oxygen and nitrogen gas find wide application in various sector of chemical process industries. One of the application
of Oxygen/nitrogen separation is to produce oxygen enriched gas that is used in biomedical application as an oxygenator. Oxygen enriched gas is also used in
furnaces for improvement of combustion by the way of increasing the flame temperature. Nitrogen is used as inert gas blanketing, purging the pipelines, inerting
applications on the offshore production platform and for creating controlled atmosphere for food preservation. Traditionally nitrogen separation is carried out
by cryogenic process and also by PSA (pressure swing adsorption). But the membrane system appears promising to produce nitrogen of 95% to 99.5% purity.
Silicon-polycarbonate block polymer is a typical membrane material is used for this purpose. Oxygen enrichment can be carried out by a dimethyl
siloxane/bisphenol.
Dehydration of Air: In dehydration process, compressed air is allowed to pass through a dryer system which consists of hollow fiber membranes. These
membranes are chemically or physically post treated to adjust the pore size and spore size distribution. Such systems are operated at 2069 kPa and produce dry
air of 0 °C dew point from the feed air of 40 °C dew point.
Helium recovery from natural gas:
The concentration of He in natural gas varies from 0.055 to 1.55%. helium in its liquid stat provides excellent cryogenic environment needed for cry-preservation of
biological materials. It is also chemically inert and provides inert atmosphere for controlled growth of semiconductor crystals. The conventional cryogenic
separation of helium is highly energy intensive process. The membrane used for recovery of He is generally hollow fiber modules. A typical hollow fiber contains up
to 2,70,000 individual fibers. Compressed gas pass through four stage permeation process. In first stage concentration of He increased from 0.05% to 1.4%. The
He enriched gas is again compressed and passed through a second stage where the He concentration is increased to 3.3% to 8.1%. After another compression
followed by removals of CO2, the helium containing gas undergoes two more concentration stages. In these stages concentration of He raised up to 72% to 90%. In
the final stage concentration of He achieved up to 99.99%. This process requires 40% of the energy needed in conventional process.
Separation of hydrocarbon from air: The permeabilities of the hydrocarbons with larger molecules sizes are lesser than gas molecules of smaller sizes. Rubbery
polymers are most suitable for the recovery of highly concentrated hydrocarbon vapors from the air.
Biogas processing: Membranes can be used to recover methane from biogases such as landfill gas. Such gas is typically 40 to 45% CO2, 0.5 to 1.0%, trance
contaminants and 50-56% CH4. In this process gas is collected, compressed and the after any necessary pre-treatment, contacted with membranes. The
membrane process produces an enriched methane fuel gas at the elevated feed pressure and low-pressure CO2 by product.
NGL recovery- Dew point adjustment: Raw natural gas often saturated with propane, butane and higher hydrocarbons. Separation of these components is
desirable o economic grounds; the hydrocarbons have more value as recovered natural gas liquids (NGLs) than as fuel. In addition, reducing higher hydrocarbons
and water in the gas is necessary to prevent the formation of hydrocarbon liquids and hydrates in pipelines. Membranes can be used to bring raw material gas to
pipeline quality by removing water and higher hydrocarbons. A simple economical membrane system can lower the dew point of gas by 20 to 30°C. Removal VOL
(volatile organic liquids) from the air of exhaust streams VOC removal Desiccation

Pervaporation Membrane
Separation

Introduction to pervaporation:
• It is an energy efficient combination of membrane permeation and evaporation (Permeation

+ Evaporation = Pervaporation) This led to a high degree of separation along with high
permeation rates.
• The process was yet to be commercialized until 1982 when Germany installed a
pervaporation plant to separate water from concentrated alcohol solutions.
• This method applied to remove limitation of azeotrope formation between water-ethanol.

Distillation is extremely complex when the concentration of the separating components is
similar in the liquid and vapor phase, called the azeotropic point.
• Distillation alone cannot perform any further separation beyond the azeotropic point.
• Pervaporation continues to evolve as a feasible separation technology for many different

applications.
Basic principle:
Pervaporation is a membrane separation
process which uses a dense polymeric
membrane for selective permeation of one
or more components form a liquid mixture.
In this process, liquid mixture is kept in direct

contact with one side of the membrane and
permeated product is removed in the form
of vapor.
The mass flux is brought about by

maintaining the downstream partial pressure
lower than a saturation pressure, either by a
vacuum on the permeate side or introducing
a carrier gas.

There are two steps in pervaporation process:
1) Evaporation process:
In this process, the temperature of the feed liquid is elevated to the point where a saturated vapor is
formed. When feed enters, the saturated vapor comes in contact with the membrane.
2) Diffusion of vapors across the membrane (Mass transfer process):
In the second step, the vapor diffuses from the feed side, across the membrane to the permeate side.
A condenser is installed on the permeate side to create a pressure lower than the feed side.
The second step can be defined as the ration of the components in the permeate vapor to the ration of
the components in the feed vapor.
✓ The vapor permeate is at least partially condensed to produce a liquid product. Any incondensable
vapor is purged from the system.
✓ The mass flux is due to the continuous adsorption on the one side of the membrane and desorption on
the other side. The membrane operates by a solution diffusion mechanism.
✓ The polymer becomes highly swollen on the liquid side and dries on the vapor side the diffusivity
varies across the membrane.
✓ Because of evaporation process this pervaporation operation achieved nearly isothermal conditions.
which is beneficial when it comes to economic point of view.
Advantages of pervaporation:
• Separation of close boiling organic solvents using distillation or liquid-liquid extraction is difficult as
the components have similar properties with respect to each other.
• In recent years, the use of pervaporation technology for the separation of organic mixtures has great
importance because of the following advantages:
1. With the following low temperature and pressure involved, in pervaporation, it often has cost and
performance advantages for the separation of azeotropic mixtures and mixtures of components with
close boiling points.
2. This technology minimizes thermal degradation of heat sensitive products, such as flavor essences.
3. Energy consumption is reduced for hybrid systems.
4. No entrainer (foreign component) is required.
5. Due to molecular design of the membrane system even small units can operate economically.
6. Pervaporation uses no sorbents which must be generated.
7. Pervaporation is continuous and offers immediate recovery of solvents and for industrial applications.
8. High degree of flexibility regarding the feed mixtures that may be accommodated, through put and
final product quality.
Membranes used in pervaporation:
✓ Hydrophobic membranes are often polydimethylsiloxane based where the actual separation
mechanism is based on the solution-diffusion model.
✓ Hydrophilic membranes are more widely available. The commercially most successful pervaporation
membrane system to date is based on polyvinyl alcohol.
✓ More recently also membranes based on polyimide have become available.
✓ To overcome the intrinsic disadvantages of polymeric membrane systems ceramic membranes have been
developed over the last decade. These ceramic membranes consist of nano-porous layers on top of a
macroporous support. The pores must be large enough to let water molecules pass through and retain any
other solvents that have a larger molecular size such as ethanol. As a result, a molecular sieve with a pore
size of about 4 Å is obtained. The most widely available member of this class of membranes is that based
on zeolite A.
✓ Alternatively, to these crystalline materials, the porous structure of amorphous silica layers can be
tailored
4/3/2023 towards molecular selectivity. These membranes
Dr. Swapna PANDAare fabricated by sol-gel chemical processes.
66
Applications of pervaporation:
Dehydration of alcohol or manufacturing of absolute alcohol (Hybrid distillation pervaporation system):
❑ Pervaporation finds its most important application in the dehydration of ethyl alcohol. A fermentation broth
usually contains 5 to 10% of ethanol.
❑ In conventional process, it is concentrated and dehydrated by distillation. Still concentration achieved through
distillation is only 95%.
❑ Ethanol forms an azeotrope with water and ethyl alcohol concentration of 95.6%, and distillation becomes
ineffective at removing the trace amount of water.
❑ Azeotropic distillation with some additives, normally either cyclohexane or benzene, may be useful for
dehydration but energy consumption of this process is very high.
❑ As result, pervaporation which was developed by GFT in Germany in 1970s has been an attractive and
economic alternative.
❑ They use an asymmetric composite membrane of there layers. There is a non-woven polyester support on
which a polyacrylonitrile (PAN) or polysulphone UF membrane is casted.
❑ On the top of the UF membrane layer is cast an ultrathin (0.1 mm) layer of cross-linked poly-vinyl alcohol
(PVA).
❑ The hydrophilic PVA layer allows preferential permeation of water through it and leaves dehydrated alcohol as
the retentate.
❑ A flow diagram of a combine distillation and pervaporation
4/3/2023 Dr. Swapna PANDA for the dehydration of alcohol is as shown.67
Other Applications
2. Control of ethanol concentration in fermenter:
Establish a continuous fermentation process, the ethanol concentration within the fermentation vessel must
be kept at 5% by weight or lower. Pervaporation has been used to maintain the necessary ethanol
concentration in the broth. The advantage of using pervaporation in such a system include the ease of
processing the clean, nearly pure ethanol extracted from the fermentation vessel and a higher fermentation
capacity or the reduction in fermenter size and costs.
3. Recovery of methanol from MTBE process:
MTBE is produced by reacting methanol with isobutene over an acidic ion exchange catalyst. The isobutane
conversion up to 95% could be achieved by keeping methanol to isobutane ration slightly higher than one.
Additional 4 to 5% conversion is possible by using excess methanol in feed mixture. But excess methanol
causes the problem of separation, because of formation of azeotropes. Pervaporation can remove methanol
from reactor effluent thereby reducing the methanol concentration from 5 to 2%, which can be fed to a
debutanizer column without causing formation of azeotrope.
Other Applications
4. Separation of ethylene glycol-water mixture:
Ethylene glycol production involves hydrolysis of ethylene oxide with excess of water. The resultant stream is a
dilute aqueous solution containing ethylene glycol in the concentration range of 10-15%. Water is removed I a
series of multiple effect evaporator, followed by distillation to get glycol. Pervaporation may be applied for the
production of ethylene glycol-water mixture to either selectively permeate the minor component ethylene glycol
through a glycol selective membrane leaving water as retentate or the selectively permeate water through a
hydrophilic membrane and concentrate ethylene glycol as retentate.
5. Concentration and recovery of flavor and fragrance:
Pervaporation is used to recover any lost juice during evaporation. The vapor from the evaporation process is
further processed using pervaporation. Membrane system can also be used to recover natural flavor and
fragrance compounds produced in a wide variety of food processing applications. 6. Removal of VOC from water:
Volatile organic compounds (VOC) are common contaminants in wastewater and contaminated ground water.
Pervaporation is considered as an alternative technology for removal of volatile organic compounds from
contaminated water. The volatile organic compounds contained in the liquid phase are adsorbed onto the
membrane and diffuse through to the other side where they are draw off by a vacuum. The organics and some
water which posses through the membrane are condensed, the condensed permeate often separates into an
aqueous and an organic phase, offering industrial applications
4/3/2023 Dr. Swapna PANDA the possibility of recovering the organic fraction.
70
Factors affecting pervaporation:
Feed composition and concentration: A change in the feed composition directly affects the sorption
phenomena at the liquid membrane interface. As the diffusion of the components in the membrane is
dependent on the concentration of the components the permeation characteristics hence dependent on the
feed concentration as well.
Feed and permeate pressure: The driving force in the pervaporation is the partial pressure difference of the
components. The permeate pressure is directly related to the activity of the components at the downstream
side of the membrane. For higher permeate pressures, the feed pressure influences the pervaporation
characteristics.
Temperature: As the temperature of the feed increases, the permeation rate generally follows on Arrhenius
equation. The selectivity is strongly dependent on the temperature in most cases a small decrease in
selectivity is observed with increasing temperature.
Concept and working of membrane reactor:
➢ Membrane reactors combine reaction with separation to increase conversion.
➢ One of the products if a given reaction is removed from the reactor through the membrane, forcing the
equilibrium of the reaction “to the right” (Le chatelier’s principle), so that more of that product is produced.
➢ A membrane reactor is a device that utilizes the properties of a membrane to improve the efficiency of chemical
or biochemical reactions. It is mainly applied in catalytic and enzymatic reactions.
➢ In membrane reactor the membrane is used as a contactor that separates the catalyst from the reaction
medium.
➢ In second type of membrane reactor, the membrane shows the selective mass transport properties, and is used
to shift the equilibrium of a chemical reaction by selectively removing the reaction products.
➢ The third type of membrane reactor combines the membrane contactor and separation function such as in
enzyme catalyzed de-esterification reactions. (The following 3 types MR are sued).

Membrane reactors are of two types:
(1) Inert membrane reactor and (2) catalytic membrane
reactor. The inert membrane reactor allows catalyst
pellets to flow within the reactions on the feed side.
In this kind of membrane reactor, the membrane does

not participate in the reaction directly; it simply acts as a
barrier to the reactants and some products.
A catalytic membrane reactor (CMR) has a membrane

that has either been coated with or is made of
a material that contains catalyst which means that
membrane itself. Participates in the reaction.
✓ Advantages and disadvantages of membrane reactor:

✓ Advantages of membrane reactor:
✓ Compact in design
✓ High efficient quality
✓ High volumetric load possible
✓ Less sludge production
✓ Less space requirement
✓ Possible to convert from existing conventional active
sludge4/3/2023
purification Dr. Swapna PANDA 74
Various modules used for
✓ Operation costs are lower
✓ Complete bacterial removal membrane reactor:
✓ Possibility of reuse of treated waste water for
irrigation purposes or as a process water
✓ Less fouling compared to other membrane There are basically four types of membrane
modules available.
Disadvantages of membrane reactor:
a) Plate and Frame
❑ High capital cost
b) Tubular
❑ Limited data on membrane shelf life
c) Spiral wound
❑ High cost of membrane replacement
d) Hollow fiber
❑ Aeration limitations
❑ Energy cost

Depending on the application, one of the above listed modules is selected.
✓ Plate and frame module are similar to the plate and frame filter press with a series of flat membrane
✓ sheets.
✓ In plate and frame module sheets can be quite close to one another to reside concentration
✓ polarization.
✓ The benefit of using plate and frame module is that they can be taken apart for cleaning purpose.
✓ Tubular module resembles a shell ad 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.
✓ Tubular module operated with simple pre-treatment of feed.
✓ In tubular module, module area to module space ration is small.
✓ The advantage of using tubular module is that, it is mechanically cleaned by forcing a sponge ball
✓ through the tubes.
✓ The spiral wound module is formed from a plate and frame sheet wrapped around a center collection pipe.
✓ The feed flows through a feed spacer, parallel to the central tube, whereas the permeate flows through the permeate
space, spirally perpendicular to the feed flow direction.
✓ Spiral wound elements are most commonly manufactured with flat sheet membrane of either cellulose di-acetate or tri-
acetate.
✓ Spiral wound is compact and having high membrane packing density.
✓ In hollow fiber module, the fiber wall has a structure of the asymmetric membrane and the active skin layer being placed to
the feed side.
✓ In hollow fiber module, the permeate water flow per unit area of membrane is low and therefore, the concentration
polarization is not high at the membrane surface.
✓ Hollow fiber membranes can be designed for circulation, dead-end and single pass operations.
What are membrane bioreactors (MBRs)?
❖ Membrane filtration has a major role in water and wastewater treatment, which is superior to the
conventional water technologies with a proven better performance and more efficient economics. For more
than the last 10 years MBRs have emerged as an effective secondary treatment technology by using
membranes in the range of MF and UF.

✓ A Membrane bioreactor (MBR) processes are mainly used for wastewater treatment (WWT)
by using microfiltration (MF) or ultrafiltration (UF) and integrating them with a biological
process like a suspended growth bioreactor. The membranes are employed as a filter
removing the solids which are developed during the biological process, which gives a clear
and pathogen free product.
✓ A membrane bioreactor is essentially a replacement in the conventional activated sludge

(CAS) system for the settlement tank for solid/liquid separation.
✓ The MBR gives to the end user improved process control and much better product water
quality.
✓ Schematic of conventional activated sludge process (top) and external (side stream)
membrane bioreactor (bottom) can be found from the following figure:

Process.
Applications of membrane reactor: 1) Food and beverage − high in organic loading
❖ Used in biochemical processing 2) Petroleum industry − exploration, refining and petrochemical sectors
3) Pharmaceutical industry – have active pharmaceutical ingredients (APIs)
❖ In petrochemical applications
4) Pulp and paper industry − high levels of suspended solids, COD and BOD
❖ In environmental pollution control 5) Textile industry effluent − re-biodegradability, toxicity, FOG content and color
❖ For wastewater treatment 6) Landfill leachate − wide variety of dissolved and suspended organic and
❖ For hydrogen production inorganic compounds
❖ For seawater desalination 7) Ship effluents − legislative requirements and space restrictions
❖ In pharmaceutical industries 8) Industrial versus municipal treatmen
❖ In textile industries
References
• Coker, D.T., Prabhakar, R. and Freeman, B. Gas

•
Separation Using Polymers. Chemical Engineering
Education. Winter 2003. 60-67.
•
• Membranes For Gas Separation. Chemical &
• Engineering News.
•
• October 03, 2005. Volume 83: Number 40. 49-57.
• http://www.cheresources.com/blanketzz.shtml
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Advanced Separation Processes

Membrane gas separations, Fundamental mechanism, governing factors,

4/3/2023 Dr. Swapna PANDA 2

• Separation of a known component into

Due of high diffusivity in gases, concentration gradient in the gas

So, gas film resistance is neglected compared to membrane

This means concentration in gas phase in a direction normal to

If there is complete mixing of the feed and permeate by an external

If they are in opposite direction, then it is counter current flow

4/3/2023 Dr. Swapna PANDA

4/3/2023 Dr. Swapna PANDA

Separation units smaller than other types

•Expensive - more so than other types available (fabrication method)

•Lack of research - less research done compared to other types of membrane

• High flux (high permeability, thin)

4/3/2023 Dr. Swapna PANDA

Upgraded Natural gas

4/3/2023 D. Wang, et al., ACS Symp. Ser.,Dr.v.Swapna

U.S. Pipeline Specifications1:

Potential membrane applications:

4/3/2023 Dr. Swapna PANDA 15

Dense membrane Asymmetric membrane

Permeability (inherent property) Permeance (normalized flux)

4/3/2023 Dr. Swapna PANDA 17

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Selectivity and retention

4/3/2023 Dr. Swapna PANDA 19

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a) Dissolution of permeating molecules in the membrane

2) Knudsen diffusion (d/λ < 0.2):

a) Dissolution of permeating molecules in the membrane

4/3/2023 Dr. Swapna PANDA 23

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The key difference between TG and TM polymers is that the TG describes

4/3/2023 Dr. Swapna PANDA 28

4/3/2023 Dr. Swapna PANDA 29

4/3/2023 J. Membr. Sci., 107,

Dapp is a kinetic parameter

Selectivity in mixed gases  = (yA/yB) / ( xA/xB)

Molar fraction of Molar fraction of

4/3/2023 Dr. Swapna PANDA 35

For most of these pairs, the diffusion

The important point is to see the much

4/3/2023 Dr. Swapna PANDA 38

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• Both diffusivity and solubility coefficients are temperature dependent.

• The selectivity also sensitive to change in temperature.

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• It is an energy efficient combination of membrane permeation and evaporation (Permeation

• This method applied to remove limitation of azeotrope formation between water-ethanol.

• Pervaporation continues to evolve as a feasible separation technology for many different

In this process, liquid mixture is kept in direct

The mass flux is brought about by