Loeb-Sourirajan method

Interfdci l Composite Membra.nes, A method of making asymmetric membranes involving interfacial polymerization was developed in the 1960s. This technique was used to produce reverse osmosis membranes with dramatically improved salt rejections and water fluxes compared to those prepared by the Loeb-Sourirajan process (28). In the interfacial polymerization method, an aqueous solution of a reactive prepolymer, such as polyamine, is first deposited in the pores of a microporous support membrane, typically a polysulfone ultrafUtration membrane. The amine-loaded support is then immersed in a water-immiscible solvent solution containing a reactant, for example, a diacid chloride in hexane. The amine and acid chloride then react at the interface of the two solutions to form a densely cross-linked, extremely thin membrane layer. This preparation method is shown schematically in Figure 15. The first membrane made was based on polyethylenimine cross-linked with toluene-2,4-diisocyanate (28). The process was later refined at FilmTec Corporation (29,30) and at UOP (31) in the United States, and at Nitto (32) in Japan. 

The technology to fabricate ultrathin high-performance membranes into high-surface-area membrane modules has steadily improved during the modem membrane era. As a result the inflation-adjusted cost of membrane separation processes has decreased dramatically over the years. The first anisotropic membranes made by Loeb-Sourirajan processes had an effective thickness of 0.2-0.4 xm. Currently, various techniques are used to produce commercial membranes with a thickness of 0.1 i m or less. The permeability and selectivity of membrane materials have also increased two to three fold during the same period. As a result, today s membranes have 5 to 10 times the flux and better selectivity than membranes available 30 years ago. These trends are continuing. Membranes with an effective thickness of less than 0.05 xm have been made in the laboratory using advanced composite membrane preparation techniques or surface treatment methods. 

Since the discovery by Cadotte and his co-workers that high-flux, high-rejection reverse osmosis membranes can be made by interfacial polymerization [7,9,10], this method has become the new industry standard. Interfacial composite membranes have significantly higher salt rejections and fluxes than cellulose acetate membranes. The first membranes made by Cadotte had salt rejections in tests with 3.5 % sodium chloride solutions (synthetic seawater) of greater than 99 % and fluxes of 18 gal/ft2 day at a pressure of 1500 psi. The membranes could also be operated at temperatures above 35 °C, the temperature ceiling for Loeb-Sourirajan cellulose acetate membranes. Today s interfacial composite membranes are significantly better. Typical membranes, tested with 3.5 % sodium chloride solutions,... 

Most gas separation processes require that the selective membrane layer be extremely thin to achieve economical fluxes. Typical membrane thicknesses are less than 0.5 xm and often less than 0.1 xm. Early gas separation membranes [22] were adapted from the cellulose acetate membranes produced for reverse osmosis by the Loeb-Sourirajan phase separation process. These membranes are produced by precipitation in water the water must be removed before the membranes can be used to separate gases. However, the capillary forces generated as the liquid evaporates cause collapse of the finely microporous substrate of the cellulose acetate membrane, destroying its usefulness. This problem has been overcome by a solvent exchange process in which the water is first exchanged for an alcohol, then for hexane. The surface tension forces generated as liquid hexane is evaporated are much reduced, and a dry membrane is produced. Membranes produced by this method have been widely used by Grace (now GMS, a division of Kvaemer) and Separex (now a division of UOP) to separate carbon dioxide from methane in natural gas. 

Particularly, the nonsolvent immersion, that is, the Loeb-Sourirajan preparation method is an important methodology. In this method, a polymer solution is cast into a film and the polymer precipitated by immersion into water [10,144], The nonsolvent (water) quickly precipitates the polymer on the surface of the cast film, producing an extremely thin, dense-skin layer of the membrane [10,144], The polymer under the skin layer precipitates gradually, ensuing in a more porous polymer sublayer [145], Following polymer precipitation, the membrane is usually annealed in order to improve solute rejection [10,144]. 

The first breakthrough came in 1959 when Sourirajan and Loeb discovered a method to make a very thin cellulose acetate (CA) membrane using the phase inversion method [4]. This technique produces homogenous membranes with an asymmetric (or anisotropic) structure. The membranes were subsequently found to be skinned when examined under an electron microscope by Riley in 1964 [3]. The membranes consisted of a very thin, porous salt-rejecting barrier of CA, integrally supported by a fine CA porous substrate. Pictures of asymmetric membranes are shown in Figures 1.2 and 1.3. These early Loeb-Sourirajan (L-S) membranes exhibited water fluxes that were lOtimes higher than those observed by Reid, and with comparable salt rejection [5]. The membrane flux was 8—18 1/m /h (knh) with 0.05% NaCl product water from a 5.25% NaCl feedwater... 

There are four main types of polymeric membranes (a) Loeb—Sourirajan phase separation RO, UF and MF membranes, (b) interfacial composite RO and NF membranes, (c) solution-coated composite GS membranes, and (d) other anisotropic membranes such as plasma polymerisation coated. Several methods of manufacturing synthetic membranes are given in Table 1.5. Each method produces different membrane morphology porosity, pore size distribution, and ultrastructure. Membrane formulation techniques are discussed in detail in several texts [8, 16—18]. 

Hollow-fiber fabrication methods can be divided into two classes (62,63). The most common is solution spinning, in which a 20-30% polymer solution is extruded and precipitated into a bath of a nonsolvent, generally water. Solution spinning allows fibers with the asymmetric Loeb-Sourirajan structure to be made. An alternative technique is melt spinning, in which a hot polymer melt is extruded from an appropriate die and is then cooled and solidified in air or a quench tank. Melt-spun fibers are usually relatively dense and have lower fluxes than solution-spim fibers, but, because the fiber can be stretched after it leaves the die, very fine fibers can be made. Melt spinning can also be used with polymers such as poly(trimethylpentene), which are not soluble in convenient solvents and are difficult to form by wet spinning. 

Phase inversion is a process in which a polymer is transformed from a liquid to a solid state. There are a number of methods to achieve phase inversion. Among others, the dry-wet phase inversion technique and the temperature induced phase separation (TIPS) are most commonly used in the industrial membrane manufacturing. The dry-wet phase inversion technique was applied by Loeb and Sourirajan in their development... 

For the investigations reported here polyvinyl alcohol (PVA) and its derivatives such as polyvinyl acetate, polyvinyl ether etc. were used as the basic polymeric materials. These compounds can easily be converted into polymeric analogues [1]. It was shown in an earlier work [2] that PVA-membranes with an asymmetrical structure can be obtained by phase-inverted precipitation similar to the method of Loeb and Sourirajan [3]. These membranes can also be rendered inso].uble in water by... 

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