Membrane Separation Processes - Technology The development of ion exchange membrane some forty years ago paved the

way for the membrane separation technology. Since then due to a whole lot of technological innovations, especially in the area of new materials, membrane technologies have been established as very effective and commercially attractive options for separation and purification processes. What is a Membrane? The membrane can be defined essentially as a barrier, which separates two phases and restricts transport of various chemicals in a selective manner. A membrane can he homogenous or heterogeneous, symmetric or asymmetric in structure, solid or liquid, can carry a positive or negative charge or be neutral or bipolar. Transport through a membrane can be effected by convection or by diffusion of individual molecules, induced by an electric field or concentration, pressure or temperature gradient. The membrane thickness may vary from as small as 100 rnicron to several mms. Membrane Separation Technology A membrane separation system separates an influent stream into two effluent streams known as the permeate and the concentrate. The permeate is the portion of the fluid that has passed through the semi-permeable membrane. Whereas the concentrate stream contains the constituents that have been rejected by the membrane. Membrane separation process enjoys numerous industrial applications with thefollowing advantages: Appreciable energy savings Environmentally benign Clean technology with operational ease Replaces the conventional processes like filtration, distillation, ion-exchange and chemical treatment systems Produces high,quality products Greater flexibility in designing systems. Types of Membranes The proper choice of a membrane should he determined by the specific application objective: particulate or dissolved solids removal, hardness reduction or ultra pure water production, removal of specific gases/chemicals etc. The end-use may also dictate selection of membranes for industries such as potable water, effluent treatment, desalination or water supply for electronics or pharmaceutical manufacturing. The following section explains the types of membranes commonly used. Microporous Membranes The membrane behaves almost like a fibre filter and separates by a sieving mechanism determined by the pore diameter and particle size. Materials such as ceramics, graphite, metal oxides, polymers etc. are used in making such membranes. The pores in the membrane may vary between 1 nm-20 microns. Homogeneous Membranes This is a dense film through which a mixture of molecules is transported by pressure, concentration or electrical potential gradient. Using these membranes, chemical species of similar size and diffusivity can be separated efficiently when their concentrations differ significantly. Asymmetric Membranes An asymmetric membrane comprises a very thin (0.1-1.0 micron) skin layer on a highly porous (100-200 microns) thick substructure. The thin skin acts as the selective membrane. Its separation characteristics are determined by the nature of membrane material or pore size, and the mass transport rate is determined mainly by the skin thickness. Porous sub-layer acts as a support for the thin, fragile skin and has little effect on the separation characteristics. Electrically Charged Membranes These are necessarily ion-exchange membranes consisting of highly swollen gels carrying fixed positive or negative charges. These are mainly used in the electrodialysis. Liquid Membranes A liquid membrane utilizes a carrier to selectively transport components such as metal ions at relatively high rate across the membrane interface. Membrane Modules

Schematic diagrams of plate and frame membrane module and spiral-wound membrane module The membranes can he cast as flat sheets, tubes and fine hollow fibres. For accommodating such shapes and structures, different types of membrane modules are available. The last decade of membrane and module development has lessened the effects of physical compaction and has brought forth spiral membrane modules capable of operating at pressures in excess of 800 psig (55.2 bar). 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. The following membrane modules are largely used for industrial applications:

Spiral wound module: Consists of large consecutive layers of membrane and support material rolled up around a tube Maximizes surface area Less expensive, however, more sensitive to pollution. Tubular membrane: The feed solution flows through the membrane core and the permeate is collected in the tubular housing. Generally used for viscous or bad quality fluids. System is not very compact and has a high cost per m2 installed Hollow fiber membrane: The modules contain several small (0.6 to 2 mm diameter) tubes or fibers. The feed solution flows through the open cores of the fibers and the permeate is collected in the cartridge area surrounding the fibers. The filtration can be carried out either “inside-out” or “outside-in”
Membrane Separation Processes Various types of membrane separation have been developed for specific industrial applications. Some of the widely used processes are discussed hereunder: Schematic diagrams of plate and frame membrane module and spiral-wound membrane module Reverse Osmosis (RO)

Formally, reverse osmosis is the process of forcing a solvent from a region of high solute concentration through a semipermeable membrane to a region of low solute concentration by applying a pressure in excess of the osmotic pressure. [The osmotic pressure Π of a dilute solution can be approximated using the Morse equation (named after Harmon Northrop Morse):[2]
Π = iMRT,

where

i is the dimensionless van 't Hoff factor M is the molarity R=0.08206 L · atm · mol-1 · K-1 is the gas constant T is the thermodynamic (absolute) temperature

This equation gives the pressure on one side of the membrane; the total pressure on the membrane is given by the difference between the pressures on the two sides. Note the similarity of the above formula to the ideal gas law and also that osmotic pressure is not dependent on particle charge. This equation was derived by van 't Hoff. Osmotic pressure is an important factor affecting cells
• Hypertonicity is the presence of a solution that causes cells to shrink. The solution may or may not have a higher osmotic pressure than the cell interior since the rate of water entry will depend upon the permeability of the cell membrane. Hypotonicity is the presence of a solution that causes cells to swell. The solution may or may not have a lower osmotic pressure than the cell interior, since the rate of water entry will depend upon the permeability of the cell membrane. Isotonic is the presence of a solution that produces no change in cell volume.

The membranes used for reverse osmosis have a dense barrier layer in the polymer matrix where most separation occurs. In most cases the membrane is designed to allow only water to pass through this dense layer while preventing the passage of solutes (such as salt ions). This process requires that a high pressure be exerted on the high concentration side of the membrane, usually 2–17 bar (30–250 psi) for fresh and brackish water, and 40–70 bar (600– 1000 psi) for seawater, which has around 24 bar (350 psi) natural osmotic pressure that must be overcome. This process is best known for its use in desalination (removing the salt from sea water to get fresh water), but since the early 1970s it has also been used to purify fresh water for medical, industrial, and domestic applications. Osmosis describes how solvent moves between two solutions separated by a semipermeable membrane to reduce concentration differences between the solutions. When two solutions with different concentrations of a solute are mixed, the total amount of solutes in the two solutions will be equally distributed in the total amount of solvent from the two solutions. Instead of mixing the two solutions together, they can be put in two compartments where they are separated from each other by a semipermeable membrane. The semipermeable membrane does not allow the solutes to move from one compartment to the other, but allows the solvent to move. Since equilibrium cannot be achieved by the movement of solutes from the compartment with high solute concentration to the one with low solute concentration, it is instead achieved by the movement of the solvent from areas of low solute concentration to areas of high solute concentration. When the solvent moves away from low concentration areas, it causes these areas to become more concentrated. On the other side, when the solvent moves into areas of high concentration, solute concentration will decrease. This process is termed osmosis. The tendency for solvent to flow through the membrane can be expressed as "osmotic pressure", since it is analogous to flow caused by a pressure differential.

In reverse osmosis, in a similar setup as that in osmosis, pressure is applied to the compartment with high concentration. In this case, there are two forces influencing the movement of water: the pressure caused by the difference in solute concentration between the two compartments (the osmotic pressure) and the externally applied pressure.

Applications Water and wastewater purification:- Rain water collected from storm drains is purified with reverse osmosis water processors and used for landscape irrigation and industrial cooling in Los Angeles and other cities, as a solution to the problem of water shortages. Drinking water purification:- Around the world, household drinking water purification systems, including a reverse osmosis step, are commonly used for improving water for drinking and cooking. Dialysis:- Reverse osmosis is similar to the technique used in dialysis, which is used by people with kidney failure. Food Industry:- In addition to desalination, reverse osmosis is a more economical operation for concentrating food liquids (such as fruit juices) than conventional heat-treatment processes. Hydrogen production:- For small scale production of hydrogen, reverse osmosis is sometimes used to prevent formation of minerals on the surface of electrodes and to remove organics from drinking water

Disadvantages
Household reverse osmosis units use a lot of water because they have low back pressure. As a result, they recover only 5 to 15 percent of the water entering the system. The remainder is discharged as waste water. Because waste water carries with it the rejected contaminants, methods to recover this water are not practical for household systems. Waste water is typically connected to the house drains and will add to the load on the household septic system. An RO unit delivering 5 gallons of treated water per day may discharge 40 to 90 gallons of waste water per day to the septic system. [3] Large scale industrial/municipal systems have a production efficiency of closer to 48% because they can generate the high pressure needed for RO filtration.

Nanofiltration (NF) Nanofiltration is a form of filtration that uses

membranes to separate different fluids or ions. NF is typically referred to as "loose" RO due to its larger membrane pore structure as compared to the membranes used in RO, and allows more salt passage through the membrane. Because it can operate at much lower pressures, and passes some of the inorganic salts, NF is used in applications where high organic removal and moderate inorganic removals are desired. NF is capable of concentrating sugars, divalent salts, bacteria, proteins, particles, dyes and other constituents that have a molecular weight greater than 1000 daltons.

Membranes used for NF are of cellulosic acetate and aromatic polyamide type having characteristics as salt rejections from 95% for divalent salts to 40% for monovalent salts and an approximate 300 molecular weight cut-off (MWCO) for organics. An advantage of NF over RO is that NF can typically operate at higher recoveries, thereby conserving total water usage due to a lower concentrate stream flow rate. NF is not effective on small molecular weight organics, such as methanol. Pervaporation Pervaporation is a method for the separation of mixtures of liquids by partial vaporization through a nonporous or porous membrane. The name of this membrane-based process is derived from the two basic steps of the process, firstly the permeation through the membrane by the permeate, then its evaporation into the vapor phase. This process is used by a number of industries for several different processes, including purification and analysis, due to its simplicity and in-line nature.The membrane acts as a selective barrier between the two phases, the liquid phase feed and the vapor phase permeate. It allows the desired component(s) of the liquid feed to transfer through it by vaporization. Separation of components is based on a difference in transport rate of individual components through the membrane.Typically, the upstream side of the membrane is at ambient pressure and the downstream side is under vacuum to allow the evaporation of the selective component after permeation through the membrane. Driving force for the separation is the difference in the partial pressures of the components on the two sides and not the volatility difference of the components in the feed.The driving force for transport of different components is provided by a chemical potential difference between the liquid feed/retentate and vapor permeate at each side of the membrane. The retentate is the remainder of the feed leaving the membrane feed chamber, which is not permeated through the membrane. The chemical potential can be expressed in terms of fugacity, given by Raoult's law for a liquid and by Dalton's law for (an ideal) gas. It should be noted that during operation, due to removal of the vapor-phase permeate, the actual fugacity of the vapor is lower than anticipated on basis of the collected (condensed) permeate.Separation of components (e.g. water and ethanol) is based on a difference in transport rate of individual components through the membrane. This transport mechanism can be described using the solution-diffusion model, based on the rate/ degree of dissolution of a component into the membrane and its velocity of transport (expressed in terms of diffusivity) through the membrane, which will be different for each component and membrane type leading to separation. Pervaporation is a very mild process and hence very effective for separation of those mixtures which cannot survive the harsh conditions of distillation. Solvent Dehydration: dehydrating the ethanol/water and isopropanol/water azeotropes

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Continuous water removal from condensation reactions such as esterifications to enhance conversion and rate of the reaction. Membrane introduction mass spectrometry Removing organic solvents from industrial waste waters. Combination of distillation and pervaporation/vapour permeation Concentration of hydrophobic flavour compounds in aqueous solutions (using hydrophobic membranes)


Dialysis
Dialysis is the movement of molecules by diffusion from high concentration to low concentration through a semi-permeable membrane. Only those molecules that are small enough to fit through the membrane pores are able move through the membrane and reach equilibrium with the entire volume of solution in the system. Once equilibrium is reached, there is no further net movement of the substance because molecules will be moving through the pores into and out of the dialysis unit at the same rate. By contrast, large molecules that cannot pass through the membrane pores will remain on the same side of the membrane as they were when dialysis was initiated. To remove additional unwanted substance, it is necessary to replace the dialysis buffer so that a new concentration gradient can be established. Once the buffer is changed, movement of particles from high (inside the membrane) to low (outside the membrane) concentration will resume until equilibrium is once again reached. With each change of dialysis buffer, substances inside the membrane are further purified by a factor equal to the volume difference of the two compartments. Factors that affect the completeness of dialysis include (1) dialysis buffer volume, (2) buffer composition, (3) the number of buffer changes, (4) time, (5) temperature and (6) particle size vs. pore size.

Gas separation Gas mixtures can be effectively separated by synthetic membranes. For other methods see adsorption, absorption, cryogenic distillation. Membranes are employed in: • • • • • separation of hydrogen from gases like nitrogen and methane recovery of hydrogen from product streams of ammonia plants recovery of hydrogen in oil refinery processes separation of methane from biogas enrichment of air by oxygen for medical or metallurgical purposes removal of water vapor from natural gas removal of CO2 from natural gas removal of H2S from natural gas removal of volatile organic liquids (VOL) from air of exhaust streams desiccation Usually nonporous polymeric membranes are utilized. There, vapours and gases are separated due to their different solubility and diffusivity in polymers. Polymers in glassy state, generally more effective for separation, predominantly differentiate in diffusivity. Small molecules of penetrants move among polymer chains according to the formation of local gaps by thermal motion of polymer segments. Free volume of the polymer, its distribution and local changes of distribution are of the utmost importance. Then diffusivity of a penetrant depends mainly on the size of its molecule. Porous membranes can also be utilized for the gas separation. The pores diameter must be smaller than the mean free path of gas molecules. Under normal condition (100 kPa, 300 K) it is about 50 nm. Then the gas flux through the pore is proportional to molecules velocity i.e. inversely proportional to square root of the molecule mass. It is known as Knudsen diffusion. Gas flux through a porous membrane is much higher than through nonporous one – 3 to 5 orders of magnitude. Separation efficiency is moderate – hydrogen passes 4 times faster than oxygen. Porous polymeric or ceramic membranes for ultrafiltration serve the purpose. Note, in case the pores are larger than the limit then viscous flow occurs, hence no separation. Ultrafiltration (UF) Ultrafiltration is most commonly used to separate a solution that has a mixture of some desirable components and some that are not desirable. UF is somewhat dependent on charge of the particle, and is much more concerned with the size of the particle. Typical rejected species include sugars, bio-molecules, polymers and colloidal particles. The driving force for transport across the membrane is a pressure differential. UF processes operate at 2-10 bars though in some cases up to 25-30 bars have been used. UF processes perform feed clarification, concentration of rejected solutes and fractionation of solutes. UF is typically not effective at separating organic streams. UF membranes are capable of retaining species in the range of 300-500,000 daltons of molecular weight, with pore sizes ranging from 10-1000 Angstroms (103-0.1 microns). These are mostly described by their nominal molecular weight cut-off (1000-100,000 MWCO), which means, the smallest molecular weight species for which the membranes have more than 90% rejection. UF usually implies separation of macromolecules such as protein from low molecular weight solvents. Pores in the support layer of the membrane are relatively larger than those of the surface layer. Material passing into fine pores can readily be transported through the open-celled, sponge-like structure of the support layer. For example, in electrodeposition paint recovery, the paint, composed of resin, a pigment and water are separated into two streams that can he reused. The first stream includes the water and a small amount of paint resin, which can be used to rinse the parts later in the process. The paint pigment is separated from that stream and can be re-used in the paint bath, allowing the bath to be concentrated to a useable level. Schematic diagrams of tubular membrane module and capillary membrane module It is found that, whenever the solvent of a mixture flows through the membrane, retained species are locally concentrated at the membrane surface, thereby resisting the flow. In the case of processing solution, this localized concentration of solute normally results in precipitation of a solute gel over the membrane. When processing a suspension, the solids collect as a porous layer over the membrane surface. In view of the above, it is clear that the permeate rate can be effectively controlled by the rate of transport through the polarization layer rather than by membrane properties. Hence, UF throughput depends on physical properties of the membrane, such as permeability, thickness, process and system variables like feed

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consumption, feed concentration, system pressure, velocity and temperature. UF has a wide range of applications as shown below: • Oil emulsion waste treatment Treatment of whey in dairy industries • Concentration of biological macromolecules • Electrocoat paint recovery Concentration of textile sizing • Concentration of heat sensitive proteins for food additives ' • Concentration of gelatine Enzyme & pharmaceutical preparations • Pulp mill waste treatment • Production of ultrapure water for electronics industry • Macromolecular separations replacing the conventional change of phase methods. The important characteristics for membrane materials are  porosity, morphology, surface properties, mechanical strength and chemical resistance. Polymeric materials, viz., polysulfone, polypropylene, nylon 6, Polytetrafluoroethylene (PTFE), PVC, acrylic copolymer etc. have been used successfully as UF membranes. Inorganic materials such as ceramics, carbon based membranes, zirconia etc. have been commercialized by several vendors. UF may find wide range of applications in the near future and some of those processes important from the separation and energy savings point of view are mentioned below: