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Liquid Membrane
Liquid Membrane
1. Abstract……………………………………………05
7. Conclusion………………………………………….22
8. Case Study…………………………………………23
9. Applications……………..…………………………27
10. References…………………………………..…….28
L.I.T. NAGPUR
Abstract
complexation reaction that takes place in the membrane phase reduces the
chemical potential of the permeating species.
One of the benefits of using a liquid membrane is that liquid membranes are
highly selective and, with the use of carriers for the transport mechanism, specific
molecular recognition can be achieved. Liquid membranes are relatively high in
efficiency, and as such, are being looked into for industrial applications. It is at this
point that we run into the largest of problems.
Stability:
Liquid membranes require stability in order to be effective, and if they are
pushed out of the pores or ruptured in some way due to pressure differentials or
turbulence, then they just do not work.
outside phase of the bubble is acting like the source phase and the bubble itself is
acting like a separating skin. In an ELM setup, there are large quantities of bubbles
which are distributed uniformly in the system.
Emulsified liquid membranes (ELM) are being used to solve the problem of
low interfacial area and reproducibility. In this system, a stable emulsion of the
organic and receiving phase is prepared. A second emulsion is then prepared with
the first emulsion and the feed phase. This configuration has the advantage of high
interfacial area between the phases with the drawback of a typical batch process
and the need to use other compounds to stabilize and break the emulsions.
An ILM is much simpler to visualize. Pretty much what is there in some other
kind of rigid membrane, with lots of microscopic pores in it. Every one of these
pores, then, is filled with this liquid, and in that liquid there is organic liquid and
the carrier liquid. This ILM takes things from one side of the rigid membrane and
carries it to the other side through this liquid phase. And that is a very brief model
of what a LM is.
The supported liquid membrane (SLM) is the most attractive for industrial
separations involving gaseous or liquid solutes. Figure 2 shows a supported liquid
membrane (SLM), which consists of a micro porous support containing a liquid
phase impregnated with the carrier. Liquid is held inside the support pores by
capillary forces, as described by the Laplace-Young equation, so caution must be
taken so as not to exceed the maximum operation pressure.
The membrane formed in this type of setup is very thin. As there are large
numbers of bubble and each bubble has its own identity the surface area per unit
volume of the bubble is very large as compare to any other system. Because of all
these factors the transport rate through the membrane are increased. Generally in
this kind of system the volume ratio of source phase to that of receiving phase is
very high.
For stability, all that is required is for both the membrane solvent and the carrier
molecule to be mildly hydrophobic. Compared to the hollow fiber system, the
volume ratio is not large, since the organic and receiving phase volumes are equal,
and large source volumes cannot be used if we still want to maintain that large area
per source phase volume ratio mentioned earlier. Figure 2 shows a simple ELM.
This system has several disadvantages, all having to do with the formation of
the emulsion.
phase are separated by this kind of setup. A gentle stirring is provided for the
proper mixing. In this type the system can be collapsed because of the evaporation
of organic fluid or by creating large pressure drop across the system.
Advantages.
Disadvantages.
Advantages.
Disadvantages.
From the above discussion it is clear that there are number of ways by which
liquid membrane can be set up. But the main important thing that has to be
discussed is how this mechanism takes place.
If we actually followed the stages of the cation transport, we will notice that
there are two stages involving diffusion. That's probably the best place to start
because there are in fact two major categories of transport, active and passive
transport, but in understanding those, one should also understand the rules
governing diffusion.
1. Basic Diffusion
2. Active Transport
3. Passive Transport
Active Transport
When talking of active transport, we are most often referring to carrier
kinetics which allow for transport against a concentration gradient. If we rewrite
Fick's First law and begin to define the flux in terms of (a) the conjugate forces, (b)
the coupled flux, and (c) the coupled chemical reactions, then we end up with a
function which look as
In work done by Kedem and Caplan, it was shown that if the sum of Ji×Xi + Jr×Xr
is positive, the flux may be negative and uphill transport is possible.
Passive Transport
There is also about fourteen different models for relating the flux of a metal
ion through a membrane, but there is no way I will cover these; the math involved
would take up too much room on my account, so I'll break down a few into a
sentence or so. If you couldn't tell by that wonderful lead-in, these are really
general break-downs. One of these is the case where
M+L ML
which is diffused, and the same equilibrium constant is applied to both interfaces.
Essentially what we get is that the transport ceases when the concentration in both
phases becomes the same, and, more importantly, flux is directly proportional to
the total carrier concentration in the membrane.
Types of Transport
There are four basic types of transport systems, each of which has its own
mechanisms and carrier types. In each of these systems, the one big item to notice
is that regardless of mechanism, the complexes formed are that charge-neutrality
must be maintained. Now then, the four systems are
1. Cation Transport
2. Anion Transport
3. Neutral Guest Transport
4. Switchable Transport
Cation Transport
Cation Transport can occur in either of two ways, either symport or antiport,
as shown in Figures 8 and 9. In the symport configuration, a neutral carrier moves
the guest and co-transported anion together across the membrane. This occurs in
four stages. If the outer side of the membrane is in contact with Aqueous Phase I,
and the inner side of the membrane is in contact with Aqueous Phase II, then
1. At the Phase I interface of the membrane, the guest salt forms complex
with the carrier.
2. That complex diffuses across the membrane.
3. The release of that guest salt occurs at the Phase II interface of the
membrane.
4. The carrier diffuses back across the membrane, which makes itself ready
for another transport.
1. At the Phase I interphase, the carrier tries to form a neutral complex with
the guest cation.
2. The ion-pair diffuses across the membrane.
3. Cation-exchange reaction releases the guest cation to Phase II.
4. The carrier complex with the counter-transported ion diffuses back across
the membrane.
Anion Transport
As summarized in Figure 10, anionic transport is similar in mechanism to
the cationic transport, the only difference is that here cationic carrier is used
instead of anionic carried in antiport configuration.
Switchable Transport
The use of photochemistry and electrochemistry has recently been
investigated in increasing the rates at which the carrier complexes dissociate,
which would therefore increase the transport rate. A sample of this is shown in
Figure 12, but one can imagine coming up with exactly what is being down.
Essentially, the switchable transport system works in addition to the regular
transport system, and only the second step of the
AC – e- AC+ A + C+
reaction is accelerated.
Conclusion
Case Study
B. Carrier Solution
Silver Nitrate (AgNO3, GR Pro Analysis) was used as the carrier of
propylene. An aqueous solution of silver nitrate was prepared by dissolving silver
nitrate in deionized water.
control the pressure of the system. During all experiments, sweep gas was at
atmospheric pressure. The experiments were conducted at room temperature
(298±5K). All the experimental data were obtained after an initial permeation
period of 4-6 hr.
E. Analysis
The gas composition was determined by a Gas Chromatograph (Agilent
6890N) equipped with a Flame Ionization Detector (FID, Agilent Technologies
Inc. column, HP Al/S, 0.53 mm in diameter, and 50 m in length).
Performance of membrane system for the separation of 30:70 vol.% propylene-propane mixture
Performance of membrane system for the separation of 50:50 vol.% propylene-propane mixture
Performance of membrane system for the separation of 70:30 vol.% propylene-propane mixture
References