Membrane process

Gas seperations
Gas separation is a widely used technique in which the objective is the
separation of one or more gases from a mixture by use of a semi
permeable membrane.

Gas separation membranes allow one component in a gas stream to pass

through faster than the others. There are many different types of gas
separation membrane, including porous inorganic membranes, palladium
membranes, polymeric membranes and zeolites

Separation processes constitute an integral part of chemical industries for

isolation of products and recovery of reactants. Membrane methods of
separation are modern techniques which could reduce capital investment,
operating cost and process safety. Separation of binary gas mixtures is an
important unit operation in a large number of industries to recover
valuable gases and enable pollution control. Such separations are
currently undertaken by conventional technology viz., cryogenic
distillation, adsorption on solid surface and solvent absorption. Now
membranes are increasingly finding application for gaseous separations
and have exhibited tremendous potential. Large scale gas permeators
have already been employed in industrial sectors in the US and some
European countries. Membrane technology could compete as well as
compliment conventional separation techniques due to its
multidimensional character, which involves rapid mass transfer rate and
high selectivity towards a specific gas. Inherent advantages of membrane
gas separation process are as follows:
[Link] of operation and installation.
[Link] under mild conditions, for eg. air separation can be carried
out at lower pressure and ambient temperature rather than extreme
conditions in cryogenic distillation.
[Link] footprint and flexibility of operation due to compactness of
modules with huge reduction in consumption of electricity and fuel.
[Link] extra agents are required as compared to corrosive and polluting
amine solvents in absorption process.
[Link] mode of operation with partial or complete recycle of
retentate/permeate.

[Link] of integration with other separation units to constitute

effective hybrid processes for achieving improved economy and desired
purity levels.

Separation with Membranes

Separation of gases with membranes relies on the different affinities of
one or more gases towards the membrane material, causing one gas to be
permeate faster (or slower) than others.
The gas mixture is directed into a vessel and put in contact to the
membrane material which is at the interface with another vessel. The
mixture is allowed to diffuse into the second vessel under a pressure
gradient which promotes the mass transport through the membrane
separating the retentate (slower gas) from the permeate (faster gas).

Membranes for gas separation derived from their trade-off relationship

between permeability and selectivity for a required gas component. This
means that high permeable membranes have low selectivity, requiring
several run for a good separation, and highly selective membranes have
low permeability, meaning long operational times.

A simple sketch of gas separation by membrane is provided in the right

figure [Link] feed gets split into permeate stream and an unpermeate
stream also known as retentate.

Depending upon the application, either the permeate or retentate could be

the final product.

The membrane preferably allows one component of the feed stream to

pass through it due to preferential interaction and sorption combined
with higher diffusivity of the same component owing to differences in
molecular size.
 The lower the kinetic diameter, the higher the [Link] development
of a potential polymer is the key area of research in membrane
technology. The aim in the development of new membranes is to increase
the permeability and selectivity or increasing the permeability without
compromising the selectivity or enhancing the selectivity at constant
permeability.

THEORY OF GAS PERMEATION

The driving force for gas separation is partial pressure gradient which is
the product of total pressure and mole fraction. Most membranes used for
gas separation are [Link] 3. Principle of Gas Permeation and
Separation Separation takes place according to the morphology of the
membrane which is based on different transport mechanisms. Porous
polymer membranes have a pore size ranging from 0.5 to 10 µm and non-
porous membranes with a polymer chain gap of 10-3 to 10-4µm induced
by thermal vibration. Depending on the porosity of the membrane matrix,
various transport

mechanisms including Poiseuille (viscous) flow, Knudsen‟s diffusion,

molecular sieving, capillary condensation and solution–diffusion
mechanism for gas transport through membranes are proposed as
illustrated in Fig. 4. Porous membranes are used to separate the uranium
hexafluoro (UF6) isotope gas mixtures to isolate e radioactive U235
isotope. Mass Transfer through Porous Membranes Knudsen‟s diffusion
occurs in a porous membrane, whose pore sizes are smaller than the mean
free path of the gas molecules.
Fig. 4(a) reveals the transport of gases through porous membranes by
Knudsen diffusion mechanism. Gas molecules interact with the pore walls
much more frequently than colliding with one another which allows
lighter molecules to preferentially diffuse through pores. Knudsen‟s
diffusion principally takes place in membranes with a pore diameter in
the range of 50-100Å [ref hand book].Molecular sieving is primarily based
on the precise size exclusion and shape discrimination amongst various
gas molecules by the micropores of < 7Å in diameter as per Fig. 4 (b).
Mechanisms of Permeation in Nonporous Membranes

Transport of gases through nonporous polymeric membranes is usually

described by solution–diffusion mechanism (Fig. 4(c)) which consists of
three steps, (a) sorption of preferential permeate (solubility) at the
upstream surface of the membrane, (b) activated diffusion through the
membrane and (c) desorption at the downstream side. Solution-diffusion
mechanism is driven by a difference in thermodynamic activities existing
across the membrane and interacting forces working between membrane
material and permeating molecules. The activity difference causes a
concentration gradient that leads to diffusion in the direction of
decreasing activity as depicted in Fig. 4 (d). Carbon molecular sieve (CMS)
membranes and zeolites are the typical membranes dominated by
molecular sieving mechanism and give high separation performance.
Ratio of the gas molecular size to micropore diameter controls the
permeation rate. Permeability (P) is the capability of a membrane to
permeate gas molecules:

P=D×S
The ability of a membrane to separate two molecules, A to B, is the ratio of
their permeability, called as the membrane selectivity
For a binary gas mixture the selectivity can also be determined from a
molar concentration of the two gases in feed and permeate:

where y is the permeate concentration of the fast permeating gas and x is

its feed concentration.
Fig. 4. Mechanisms of Gas Permeation: (a) Knudsen’s Diffusion, (b)
Molecular Sieving, (c) Solution-Diffusion and (d) Detailed Overview of
Mass Transfer by Solution-Diffusion Gas permselectivity of a membrane
can be enhanced by facilitated transport which involves reversible
complexation and transport of permeant molecules across a membrane
through utilization of a carrier species. The carrier reacts with a
permeant molecule to form a labile complex. Within the membrane, the
carrier shuttles the permeant across the membrane boundaries to
downstream side where the carrier-gas molecule complex breaks allowing
the gas to flow into the permeate stream. When a feed mixture contains
only one species with which the carrier will react, the transport of that
particular species will be “facilitated” or carrier-mediated across the
membrane as illustrated in Fig.5. The driving force in facilitated transport
is a concentration gradient of permeant-carrier complexes across the
membrane. It has been found that olefin transport can be facilitated by
transition metal ions such as Cuprous and Silver ionswhich possess vacant
d-orbitals due to formation of a bond complex.

Fig. 5. Mechanism of Facilitated TransportGas separation using facilitated

transport is most commonly done with “immobilized liquid” membranes,
prepared by dissolving the carrier in an appropriate solvent to
impregnate an electrically neutral but rigid microporous polymer matrix.
Once formed, surface tension forces serve to hold the carrier molecules
inside the membrane.