LIQUID MEMBRANE | Membrane Technology | Membrane


1. Abstract«««««««««««««««««05 2. Introduction to Liquid Membrane««««««05 3. Types of Liquid Membrane«««.«««..««..06 4. Liquid Membrane Setup«««.«««««««.08 5. Liquid Membrane Transport Mechanisms«««15 6. Liquid Membrane Transport Phenomenon««..17 7. Conclusion««««««««««««««««.22 8. Case Study««««««««««««««««23 9. Applications«««««..««««««««««27 10. References«««««««««««««..««.28



Membrane separation process forms an important part in many industries. This process had replaced many traditional separating processes. In this work, we discuss recent progress achieved in this field, focusing on gas and liquid separation using facilitated transport membranes. The main advantages of using a carrier species in a liquid membrane is to enhance the flux, the selectivity and the permeability of the transport. This is more advantages system than many of the separation processes.

Introduction to Liquid Membrane
What is Liquid Membrane?
A liquid membrane (LM) can be defined as a thin liquid film separating two liquid or gaseous phases and controlling the mass transfer between these phases. The main advantage of this kind of membrane is the higher solubility and diffusivity coefficients of compounds in a liquid medium than in a solid one. Addition of a carrier agent increases even more the permeability of the membrane. The permeation of a compound in a liquid membrane can be divided into the following steps: 1) sorption at the feed interface, 2) complexation reaction with the carrier, 3) diffusion of the species/carrier complex across the membrane, 4) decomplexation reaction at the permeate interface and 5) desorption of the species. After completing this cycle, the carrier diffuses back to the feed interface to complex more molecules. Using a counter transport it is even possible to permeate one compound against its concentration gradient. This occurs when two ions with the same total charge are transported in opposite directions, because the

Liquid Membrane Technology And Its Applications. 2

Immobilized Liquid Membrane (ILM).I. An ELM can be visualized as a bubble inside a bubble inside a bubble type of the system. while the other aqueous phase will receive the compounds that permeate the membrane (receiving phase). 2. Liquid membranes are relatively high in efficiency. Emulsion Liquid Membrane (ELM). then they just do not work. liquid membrane separation combines the solvent extraction process and solute recovery in a single step. are being looked into for industrial applications. and as such. The simplest liquid membranes consist in an organic phase that contains the carrier situated between two aqueous phases.L. Types Of Liquid Membrane: There are two basic types of liquid membranes 1. It is at this point that we run into the largest of problems. and if they are pushed out of the pores or ruptured in some way due to pressure differentials or turbulence. also called a Supported Liquid Membrane. with the use of carriers for the transport mechanism. One aqueous phase contains the compounds to be separated (feed phase).T. One of the benefits of using a liquid membrane is that liquid membranes are highly selective and. Stability: Liquid membranes require stability in order to be effective. NAGPUR complexation reaction that takes place in the membrane phase reduces the chemical potential of the permeating species. When the components are in an aqueous phase. The inside phase of the bubble is acting as a receiving phase while the Liquid Membrane Technology And Its Applications. 3 . specific molecular recognition can be achieved.

so caution must be taken so as not to exceed the maximum operation pressure. Liquid is held inside the support pores by capillary forces. In an ELM setup. Figure 2 shows a supported liquid membrane (SLM). The supported liquid membrane (SLM) is the most attractive for industrial separations involving gaseous or liquid solutes. A second emulsion is then prepared with the first emulsion and the feed phase. which consists of a micro porous support containing a liquid phase impregnated with the carrier. And that is a very brief model of what a LM is.T. with lots of microscopic pores in it. Supported liquid membranes may be prepared using microporous membranes of various geometries. a stable emulsion of the organic and receiving phase is prepared.I. and in that liquid there is organic liquid and the carrier liquid. Every one of these pores. as described by the Laplace-Young equation. Fig. 4 . This ILM takes things from one side of the rigid membrane and carries it to the other side through this liquid phase. Supported Liquid Membrane Liquid Membrane Technology And Its Applications.L. Pretty much what is there in some other kind of rigid membrane. there are large quantities of bubbles which are distributed uniformly in the system. The hollow fiber geometry is particularly advantageous because it allows much higher module packing densities than the flat sheet plate and frame modules or the tubular membrane modules. is filled with this liquid. 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. In this system. then. An ILM is much simpler to visualize. NAGPUR outside phase of the bubble is acting like the source phase and the bubble itself is acting like a separating skin. Another advantage is that hollow fiber modules require low investment and operating costs due to the reduced equipment requirements. Emulsified liquid membranes (ELM) are being used to solve the problem of low interfacial area and reproducibility.

4. Bulk Liquid Membrane. This membrane can be setup in coaxial cylinders and in U tube. different setups have been studied in an effort to increase the efficiency of the entire liquid membrane operation in industrial use. NAGPUR Liquid Membrane Setup Main aspects of setup While there are two basic types of liquid membrane. laboratories and in pilot scale. That is the organic membrane phase. 5. Thin Sheet Supported Liquid Membrane. The reason behind the slow speed is to maintain the stability. Liquid Membrane Technology And Its Applications.I.T. Two Hollow Fiber Supported Liquid Membrane. Emulsion Liquid Membrane. 1. A stirrer is provided in the form of magnetic stirrer with very low speed. 2. and some type of carrier which is dissolved in organic liquid is placed in the bottom of the tube.L. In Figure 1. 6. Hollow Fiber Supported Liquid Membrane. Spiral Wound Membrane. 3. a Utube cell and coaxial cylinder is used.Bulk Liquid Membrane This kind of membrane is used in universities. Two aqueous phases are placed in the arms of the U-tube. 1. The speed is kept nearly about 100 to 300 RPM. floating on top of the organic membrane. 5 . The transported amounts of materials which are transfer from source phase to receiving phase determined by the concentrations in the receiving phase.

L. An ELM can be visualized as a bubble inside a bubble inside a bubble type of the system. Because of all Liquid Membrane Technology And Its Applications. The membrane formed in this type of setup is very thin.T.Emulsion Liquid Membrane. 6 .I. 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. Bulk Liquid Membrane 2. NAGPUR Figure 1. there are large quantities of bubbles which are distributed uniformly in the system. The inside phase of the bubble is acting as a receiving phase while the 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.

e. Generally in this kind of system the volume ratio of source phase to that of receiving phase is very high. since in order to make the emulsion stable. and large source volumes cannot be used if we still want to maintain that large area per source phase volume ratio mentioned earlier. etc. The carrier is added in the organic fluid Liquid Membrane Technology And Its Applications. If. you have to break down the emulsion. Figure 2. the separation achieved to that point is destroyed. all that is required is for both the membrane solvent and the carrier molecule to be mildly hydrophobic. all having to do with the formation of the emulsion.I. At the same time this are used in various aspects and in large number. Anything effecting emulsion stability must be controlled. This type of membrane is supposed to be the most simple in design. 3. For stability. 2. Thin Sheet Supported Liquid Membrane. Ionic strengths. Figure 2 shows a simple ELM. and in order to replenish the carrier phase. Compared to the hollow fiber system. This is a difficult task. 1. This system has several disadvantages. This setup consists of a polymer film having number of pores. Emulsion Liquid Membrane. the volume ratio is not large.L. NAGPUR these factors the transport rate through the membrane are increased. pH. for any reason. 3. 7 . you have to work against the ease of breaking it back down.T. In order to recover the receiving phase. the membrane does not remain intact during operation. i. since the organic and receiving phase volumes are equal.

1. Inside that shell there are many thin fibers running the length of the shell in neat rows. A gentle stirring is provided for the proper mixing.I. 3. Figure 5 is a close up of the cross section of a single hollow fiber. 4. Thin Sheet Supported Liquid Membrane. Figure 4 represents this system. Leakage and contamination problem can be easilysolved. The source phase and receiving phase are separated by this kind of setup. The source/receiving phases are more easily recoverable than the emulsion system as both are transported through different system. NAGPUR and this fluid forms the membrane on the pores. Advantages. In this type of system the organic fluid with carrier are passed through the system and the pores of each fiber in the system is filled with that phase.L. The surface area and membrane thickness provide rapid transportation 2. When the source phase is passed through the hollow fibers and receiving phase is passed through the system. Figure 3. Liquid Membrane Technology And Its Applications. Hollow Sheet Supported Liquid Membrane The HSSLM can be visualized as a solid outer shell.T. The entire source and receiving phase are not in contact with the membrane at any given time 4. the carrier transport the source phase to receiving phase and receiving phase is removed from the side of the shell. 8 . In this type the system can be collapsed because of the evaporation of organic fluid or by creating large pressure drop across the system.

Liquid Membrane Technology And Its Applications. Hollow Fiber System must be cleaned between uses or there will be aqueous and contaminant buildup 3. High Capital Costs Figure 4. 1. NAGPUR Disadvantages.I.T. Figure 5. Very hydrophobic membrane solvents are required to maintain integrity 2. 4. Hollow Fiber Supported Liquid Membrane. Fouling are easily appeared in pores due to film effect. Close-up Cross Section of a Hollow Fiber. 9 .L.

one that looks something like the sketch in Figure 6. there is another setup. and the receiving phase in and out through another. 2. NAGPUR 5. with a stirred membrane phase in contact with both. Two Module Hollow Fiber Supported Liquid Membrane. . Advantages. Creation of a boundary layer slows system down as compared to either ELM or HFSLM 3.L. So the question remains . High Capital Costs Liquid Membrane Technology And Its Applications. 3.I. Fouling a problem 4..T. In an effort to work around one of the problems found in the HFSLM. Solvents with lower hydrophobic ties required Replacement of solvent and carrier is simple Relatively High Transport Rate Leakage and contamination are easily contained Disadvantages. The way this works is that the source phase is piped in through one channel of hollow fibers. 1. 10 . 4. 1. Transport rates dependant on amount of stirring of membrane phase 2.

a membrane.T. and a permeate channel. This type of membrane is a sort of intermediate step between the generic flat. a feed channel. wrapped around a perforated tube. NAGPUR Figure 6. which forces all the separated material towards that perforated tube in the center. at least in terms of surface area per unit volume and stability. Two Module Hollow Fiber Supported Liquid Membrane. another membrane. through which the effluent streams out of the membrane. laboratory membrane and the hollow fiber membrane. Spiral Wound Membrane The spiral wound membrane is essentially a flat membrane sandwich. 11 .I. 6.L. Liquid Membrane Technology And Its Applications. As one can see in Figure 7. that sandwich is actually four layers.

but in understanding those. Active Transport 3. Passive Transport Liquid Membrane Technology And Its Applications. From the above discussion it is clear that there are number of ways by which liquid membrane can be set up. active and passive transport.L. That's probably the best place to start because there are in fact two major categories of transport. NAGPUR Figure 7. Basic Diffusion 2. Spiral Wound Membrane.I.T. 1. But the main important thing that has to be discussed is how this mechanism takes place. 12 . Liquid Membrane Transport Mechanisms. we will notice that there are two stages involving diffusion. If we actually followed the stages of the cation transport. one should also understand the rules governing diffusion.

NAGPUR Rules Governing Diffusion Simple Diffusion The flux of a gas through a membrane under a concentration gradient in one dimention system is dictated by Fick's First Law. If we rewrite Fick's First law and begin to define the flux in terms of (a) the conjugate forces. 13 .I. and (c) the coupled chemical reactions.T. the flux may be negative and uphill transport is possible. then we end up with a function which look as In work done by Kedem and Caplan.L. (b) the coupled flux. Active Transport When talking of active transport. it was shown that if the sum of Ji×Xi + Jr×Xr is positive. we are most often referring to carrier kinetics which allow for transport against a concentration gradient. The flux for a species is therefore Liquid Membrane Technology And Its Applications. Passive Transport Passive transport is basically transport with the concentration gradient. driven by a difference in chemical potential.

3. 14 . the concentrations. There is also about fourteen different models for relating the flux of a metal ion through a membrane. Cation Transport Anion Transport Neutral Guest Transport Switchable Transport Liquid Membrane Technology And Its Applications. flux is directly proportional to the total carrier concentration in the membrane. Now then. and. the one big item to notice is that regardless of mechanism. In each of these systems. and the thickness of the membrane. these are really general break-downs. If you couldn't tell by that wonderful lead-in. 4. NAGPUR following Fick's Law. the four systems are 1.L. the math involved would take up too much room on my account. so I'll break down a few into a sentence or so. each of which has its own mechanisms and carrier types.T. One of these is the case where M+L ML which is diffused. Essentially what we get is that the transport ceases when the concentration in both phases becomes the same. the complexes formed are that charge-neutrality must be maintained. 2. more importantly. and can be expressed in terms of the diffusion coefficient. Liquid Membrane Transport Phenomenon Types of Transport There are four basic types of transport systems. but there is no way I will cover these.I. and the same equilibrium constant is applied to both interfaces.

Figure 8. as shown in Figures 8 and 9. either symport or antiport. 15 . which makes itself ready for another transport. Liquid Membrane Technology And Its Applications. In the symport configuration. This occurs in four stages. 4. 3. The release of that guest salt occurs at the Phase II interface of the membrane.I. At the Phase I interface of the membrane. 2. then 1.L. Cationic Symport. a neutral carrier moves the guest and co-transported anion together across the membrane. and the inner side of the membrane is in contact with Aqueous Phase II. The carrier diffuses back across the membrane. That complex diffuses across the membrane. NAGPUR Cation Transport Cation Transport can occur in either of two ways.T. the guest salt forms complex with the carrier. If the outer side of the membrane is in contact with Aqueous Phase I.

The carrier complex with the counter-transported ion diffuses back across the membrane. Cation-exchange reaction releases the guest cation to Phase II. 16 . anionic carrier has been used.L. Figure 9. At the Phase I interphase. NAGPUR Antiport transport is similar to symport transport but instead of neutral carrier.I. 3. The ion-pair diffuses across the membrane.T. Liquid Membrane Technology And Its Applications. 2. 4. the carrier tries to form a neutral complex with the guest cation. So the four stages are a slight bit different. Cationic Antiport. 1.

Figure 10. the only difference is that here cationic carrier is used instead of anionic carried in antiport configuration. Liquid Membrane Technology And Its Applications.T. anionic transport is similar in mechanism to the cationic transport.L. NAGPUR Anion Transport As summarized in Figure 10. 17 .I. Anionic Antiport and Symport Transport.

but they use a mechanism different that that shown in Figure 11. Oxygen and CO have been transported as gases through the liquid membrane. Switchable Transport The use of photochemistry and electrochemistry has recently been investigated in increasing the rates at which the carrier complexes dissociate. A sample of this is shown in Figure 12.T. 18 . Figure 11.I. the switchable transport system works in addition to the regular transport system. using various carriers. NAGPUR Neutral Guest Transport Neutral species are transported symport. but one can imagine coming up with exactly what is being down. which would therefore increase the transport rate. Transport of Neutral Guest. Essentially. and only the second step of the AC ± ereaction is accelerated.L. AC+ A + C+ Liquid Membrane Technology And Its Applications.

Liquid membranes have been investigated in many studies. given that solubility and diffusivity coefficients of compounds in a liquid medium are higher than those in a solid one. NAGPUR Figure 12. below which no facilitated transport occurs. Switchable Transport. Thus. On the other hand. The disadvantage of this type of membrane is the lack of stability due to the loss of solvent and carrier.T. 19 .L. a comparatively larger number of studies dealing with carrier fixed membranes can be found in the literature. Liquid Membrane Technology And Its Applications. Existing membranes have low selectivity for use in economically feasible process. Despite this feature. The main reason for this is the greater stability of the immobilized carrier.I. and there is a minimum carrier concentration. facilitated transport membranes have been used in many applications to increase permeability and selectivity simultaneously. the matrix must have sufficient segmental motion of the chains. Conclusion Membrane processes are an alternative to the traditional energy-intensive processes for some difficult separations.

was supplied to the lower compartment. filter diameter 142mm) were used as the support of the liquid membrane. after passing through mass flow controllers (Brooks Instruments. The main product. An aqueous solution of silver nitrate was prepared by dissolving silver nitrate in deionized water.L. permeate. the membrane filter could be used for 3-4 weeks with no change in separation and permeation properties. Flat Sheet Membrane Module Polyvinilydene diflouride (PVDF) flat sheet membranes (Durapore from Millipore. Once prepared. B. After being immersed in the carrier solution. was collected from the lower compartment and the secondary product. All tubing used to connect all parts of the setup was stainless steel (AISI 316). A back pressure regulator (BPR. Germany) was used on the retentate line to Liquid Membrane Technology And Its Applications. Carrier Solution Silver Nitrate (AgNO3. A combination of a heater and a cooler were used as the temperature control system. The experimental procedure is as follows. NAGPUR Case Study Immobilized Liquid Membrane for Propylene-Propane Separation A. D. 2. was collected from the upper compartment. the membrane filter was sandwiched between two compartments of the module. The feed gas was introduced to the upper compartment of the cell and the sweep gas. nitrogen. were mixed and entered the humidifier.I. model 5850S). 20 .T. Tescom. The humidified feed passes through a temperature control system and enters the membrane cell. Experimental Apparatus and Procedure The schematic diagram of the experimental setup is shown in Fig. Propylene and propane. Feed Gases Industrial grade propylene and industrial grade propane were used as feed gases and pure nitrogen was used as sweep gas. C. GR Pro Analysis) was used as the carrier of propylene. retentate.

Analysis The gas composition was determined by a Gas Chromatograph (Agilent 6890N) equipped with a Flame Ionization Detector (FID. Therefore. All the experimental data were obtained after an initial permeation period of 4-6 hr. 21 . During all experiments. and 50 m in length). the more the driving force for separation. the more the pressure on the feed sides.L. F. 0. Fig. more propylene was transported across the membrane and Liquid Membrane Technology And Its Applications. Increasing the pressure is in favor of absorption and decreasing the pressure is in favor of stripping.I. Hence. Thus. the more the absorbed propylene on the feed side.53 mm in diameter. the more the trans-membrane pressure. Agilent Technologies Inc. Facilitated transport is a combination of two processes: absorption (on the feed side) and stripping (on the permeate side).T. sweep gas was at atmospheric pressure. HP Al/S. The experiments were conducted at room temperature (298 5K). column. the complexed propylene is decomposed on the permeate side. Schematic diagram of the supported liquid membrane system E. Different mixtures of propylenepropane were used as feed gas. Due to the pressure difference between feed side and permeate side. Result And Discussion The effect of trans-membrane pressure and carrier concentration on membrane performance is shown in Figure. NAGPUR control the pressure of the system.

Performance of membrane system for the separation of 30:70 vol.L. propylene permeation occurs via two mechanisms: 1. most of the propylene molecules can react with carrier molecules and can transport across the membrane via facilitated mechanism. when more carriers are available in the membrane.I. In the absence of carrier (Ag+) in the membrane. Fickian diffusion and 2. In an immobilized liquid membrane with a constant carrier concentration and at constant trans-membrane pressure. in the former case.T. all of them cannot react with the carrier molecules and cannot transport across the membrane via facilitated mechanism. but in the latter case. propylene was permeated only via Fickian diffusion. Based upon facilitated transport mechanism. NAGPUR separation factor was increased. The reason is that.% propylene-propane mixture Liquid Membrane Technology And Its Applications. the separation factor was higher in comparison with the case when a large concentration of propylene was in the feed stream. When carrier was added to the membrane system. when a few concentration of propylene was in the feed stream. Hence. as more propylene molecules were in the membrane. 22 . more propylene can be transported along the membrane thickness and this will cause membrane to have a better separation performance. propylene was permeated via Fickian diffusion and facilitated transport. In facilitated transport membranes. separation factor in the former case is greater than in the latter case. Facilitation transport.

NAGPUR Performance of membrane system for the separation of 50:50 vol.% propylene-propane mixture Liquid Membrane Technology And Its Applications.I.% propylene-propane mixture Performance of membrane system for the separation of 70:30 vol.L. 23 .T.

In the recovery of metals from dilute solutions and for controlling certain problems in the oil well control industry. or other molecules naturally found in cell membranes can provide fast. 5. Glucose/Fructose Separation etc. 6. and almost continuous service for the researcher. It is used in various separation processes such as Propane/Propylene Separation.T. The most promising avenue for new uses of liquid membranes resides mainly in the biochemistry and biological fields. 24 . Separation of oxygen from the air to obtain highly oxygen enriched air. Liquid Membrane Technology And Its Applications. 2. efficient. Some possible uses for liquid membranes would be in the treatment of wastewater. 3.I. NAGPUR Applications of Liquid Membrane.L. 4. The use of carriers utilizing proteins. antibiotics. These types of Liquid Membrane are used in 1.

I. R Anupama and K Palanivelu 2. Engineering and Technology 47 2008. 5. Indian Journal of Chemical Technology Vol. Chemical Separations With Liquid Membranes Richard A. 12 July 2005.rpi. 25 . Journal of Membrane Science 280 (2006) 330±334. Douglas Way Liquid Membrane Technology And Its Applications. www. World Academy of Science. 4. NAGPUR References 1. Bartsch and Article written by Chris Pattillo 3.

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