Reverse Loeb-Sourirajan

The seminal discovery that transformed membrane separation from a laboratory to an industrial process was the development, in the early 1960s, of the Loeb-Sourirajan process for making defect-free, high flux, asymmetric reverse osmosis membranes (5). These membranes consist of an ultrathin, selective surface film on a microporous support, which provides the mechanical strength. The flux of the first Loeb-Sourirajan reverse osmosis membrane was 10 times higher than that of any membrane then avaUable and made reverse osmosis practical. The work of Loeb and Sourirajan, and the timely infusion of large sums of research doUars from the U.S. Department of Interior, Office of Saline Water (OSW), resulted in the commercialization of reverse osmosis (qv) and was a primary factor in the development of ultrafiltration (qv) and microfiltration. The development of electro dialysis was also aided by OSW funding. 

Fig. 11. Schematic of Loeb-Sourirajan membrane casting machine used to prepare reverse osmosis or ultrafiltration membranes. A knife and trough is used to coat the casting solution onto a moving fabric or polyester web which enters the water-filled gel tank. After the membrane has formed, it is washed...

Cellulose acetate Loeb-Sourirajan reverse osmosis membranes were introduced commercially in the 1960s. Since then, many other polymers have been made into asymmetric membranes in attempts to improve membrane properties. In the reverse osmosis area, these attempts have had limited success, the only significant example being Du Font s polyamide membrane. For gas separation and ultrafUtration, a number of membranes with useful properties have been made. However, the early work on asymmetric membranes has spawned numerous other techniques in which a microporous membrane is used as a support to carry another thin, dense separating layer. 

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. 

Reverse Osmosis. This was the first membrane-based separation process to be commercialized on a significant scale. The breakthrough discovery that made reverse osmosis (qv) possible was the development of the Loeb-Sourirajan asymmetric cellulose acetate membrane. This membrane made desalination by reverse osmosis practical within a few years commercial plants were installed. The total worldwide market for reverse osmosis membrane modules is about 200 million /yr, spHt approximately between 25% hoUow-ftber and 75% spiral-wound modules. The general trend of the industry is toward spiral-wound modules for this appHcation, and the market share of the hoUow-ftber products is gradually falling (72). 

The advent of the Loeb-Sourirajan asyimnetric membrane some twenty years ago gave birth to an industry now exceeding 200 million dollars in annual sales. Reverse osmosis (RO) and ultrafiltration (UP) were previously only laboratory curiosities. Today, there are many large membrane plants (up to 16 million gallons per day) in service for applications as diverse as desalinating seawater concentrating serum proteins, or the recovery of paint and other by-products from waste streams. 

During the 1960s and 1970s the Office of Saline Water sponsored development of noncellulosic reverse osmosis membranes. Many polymers were evaluated as Loeb-Sourirajan membranes but few matched the properties of cellulose acetate. Following the development of interfacial composite membranes by Cadotte, this line of research was abandoned by most commercial membrane producers. 

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. 

In 1969, I founded Osmonics, Inc. to carry the technology of reverse osmosis and ultrafiltration to the marketplace. We originally purchased membrane from Eastman Kodak Company and made our own spiral elements. We continued purchasing membrane until Kodak decided not to remain in the membrane business and we decided to begin the manufacture of membrane. By 1973, we were in full production manufacturing cellulose acetate membrane using the Loeb-Sourirajan approach. One year later, we were manufacturing polysulfone membrane for ultrafiltration. Last year, 1979, Osmonics manufactured over one million square feet of RO/UF membrane. 

The first composite reverse osmosis membrane to be developed and described consisted of an ultrathin film of secondary cellulose acetate deposited onto a porous Loeb-Sourirajan membrane.3 The ultrathin film of cellulose acetate was fabricated by a water surface float-casting technique. This has been described to some extent in the published technical literature,4 5 and in considerable detail in several reports on government-funded research projects.3 6 Figure 5.2 illustrates this process schematically. 

The seminal discovery that transformed membrane separation fi-om a laboratory to an industrial process was the development in the 1960s of the Loeb-Sourirajan process to make defect-free ultrathin cellulose acetate membranes [1]. Loeb and Sourirajan were trying to use membranes to desalt water by reverse osmosis (RO). The concept of using a membrane permeable to water and impermeable to salt to remove salt from water had been known for a long time, but the fluxes of aU the membranes then available were far too low for a practical process. The Loeb-Sourirajan breakthrough was the development of an anisotropic membrane. The membrane consisted of a thin, dense polymer skin 0.2-0.5 pm thick sup-... 

The adaptation of the principles used in the development of the membranes for the desalination of water via reverse osmosis was all that was needed to develop membranes for gas separation. It was realized that gas separation through dense polymer films was not practicable (due to the low gas flux) unless ultrathin dense films could be obtained. A thin film ensures a high flux even if the intrinsic permeability of the polymer is low. In 1970, using Loeb Sourirajan CA membranes which were dried, Merten and Gantzel obtained a separation factor of approximately 40 for He/N2, with high fluxes equivalent to those of a silicone rubber film 10 pm thick, but which would have a corresponding separation factor of only 1.5. 

On account of the relatively low water regain of cellulose acetate, the molal concentration of ionic groups in the swollen material exceeds Smmolal. This is comparable to the concentration of 300 ppm sodium chloride, a typical reverse osmosis product solution. Our homogeneous membranes are believed to be very similar to the active layer of an asymmetric membrane as developed by Loeb and Sourirajan. It is evident therefore that the concentration of fixed charges in the membrane is sufficient to exercise a significant Donnan exclusion of co-ions on the downstream side of the membranes in a reverse osmosis plant. 

The successful development of asymmetric cellulose acetate membranes by Loeb and Sourirajan in the early sixties, at the University of California, Los Angeles, has been primarily responsible for the rapid development of Reverse Osmosis (RO) technology for brack sh/sea water desalination. Reverse Osmosis approaches a reversible process when the pressure barely exceeds the osmotic pressure and hence the energy costs are quite low. Theenergy requirement to purify one litre of water by RO is only O.OO3 KW as against 0,7 KV required just to supply the vaporisation energy to change the phase of one litre of water from liquid to vapour by evaporation. Thus RO has an inherent capability to convert brackish water to potable water at economic cost and thus contribute effectively to the health and prosperity of all humanity. 

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