Reverse-osmosis membranes preparation

Yasuda, H. "Composite Reverse Osmosis Membranes Prepared by Plasma Polymerization," in "Reverse Osmosis and Synthetic Membranes," Sourirajan, S., Ed., National Research Council, Canada, Ottawa, 1977, p.263. 

Reverse osmosis membranes prepared by LCVD on porous membrane showed unique but very peculiar reverse osmosis membrane performance [10,13]. In general, the reverse osmosis membrane performance declines with time, i.e., salt rejection and particularly water flux decline with time, which is recognized as membrane fouling. 

Vasuda, H "Composite Reverse Osmosis Membranes Prepared by Plasma... 

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 membrane separations are governed by the properties of the membrane used in the process. These properties depend on the chemical nature of the membrane material, which is almost always a polymer, as well as its physical stmcture. Properties for the ideal RO membrane include low cost, resistance to chemical and microbial attack, mechanical and stmctural stabiHty over long operating periods and wide temperature ranges, and the desired separation characteristics for each particular system. However, few membranes satisfy all these criteria and so compromises must be made to select the best RO membrane available for each appHcation. Excellent discussions of RO membrane materials, preparation methods, and stmctures are available (8,13,16-21). 

UF Membranes as a Substrate for RO An important use of UF membranes is as a substrate for composite reverse-osmosis membranes. After the UF membrane (usually polysulfone) is prepared, it is coated with an aqueous solution of an amine, then dipped in an organic solution of an acid chloride to produce an interfacially polymerized membrane coating. 

Mitrovic and Knezic (1979) also prepared ultrafiltration and reverse osmosis membranes by this technique. Their membranes were etched in 5% oxalic acid. The membranes had pores of the order of 100 nm, but only about 1.5 nm in the residual barrier layer (layer AB in Figure 2.15). The pores in the barrier layer were unstable in water and the permeability decreased during the experiments. Complete dehydration of alumina or phase transformation to a-alumina was necessary to stabilize the pore structure. The resulting membranes were found unsuitable for reverse osmosis but suitable for ultrafiltration after removing the barrier layer. Beside reverse osmosis and ultrafiltration measurements, some gas permeability data have also been reported on this type of membranes (Itaya et al. 1984). The water flux through a 50/im thick membrane is about 0.2mL/cm -h with a N2 flow about 6cmVcm -min-bar. The gas transport through the membrane was due to Knudsen diffusion mechanism, which is inversely proportional to the square root of molecular mass. 

The aim of this study is to investigate the ability of ortho-phosphoric acid to function as the pore-producing additive for the preparation of CA reverse osmosis membranes. Ortho-phosphoric acid (PA) is known to be a strongly hydrogen bonded liquid, and it has been claimed ( ) to be a promising additive for the asymmetric CA membrane formation. To our knowledge, there has not been a thorough study on the problem. 

Method D in Table 1 represents a case where dry support films were always used because of the need to employ a vacuum and because of the very nature of plasma deposition processes. Yasuda (12) showed that a wide variety of gas phase reactants could be used in this technique. Not only conventional vinyl monomers were used but also any organic compounds with adequate vapor pressure. Further, copolymers could be prepared by introduction of a second reactant such as nitrogen. Wydeven and coworkers (13,14) showed the utility of this method in preparing reverse osmosis membranes from an allylamine plasma. 

Considerable activity has been generated on composite reverse osmosis membranes by Japanese researchers. Patent applications were recently published, for example, covering research at Teijin Ltd. on interfacially formed membranes prepared from polydiallylamines (17) and from amine adducts of trls-(glycidyl) isocyanurate (18). Both types of membranes were formed on micro-porous polysulfone supports. Kurihara and coworkers have developed a composite membrane, designated PEC-1000, which is formed by an... 

Cadotte, J.E. King, R.S. Majerle, R.J. Petersen, R.J. "Interfacial Synthesis in the Preparation of Reverse Osmosis Membranes," paper presented at 179th Ann. Amer. Chem. Soc. Meeting, Houston, TX, March 23-28, 1980 Marcel Dekker, in press. 

Albany International Research Co. has developed an advanced hollow fiber composite reverse osmosis membrane and module under the name of Quantro II . This composite membrane is comprised of a porous hollow fiber substrate on which has been deposited a rejection barrier capable of fluxes of commercial importance at high rejection of dissolved salts at elevated temperatures. Resistance to active chlorine has been demonstrated. Proprietary processes have been developed for spinning of the fiber, establishment of the rejection barrier and processing of the fiber to prepare modules of commercial size. Prototype modules are currently in field trials against brackish and seawater feed solutions. Applications under consideration for this membrane include brackish and seawater desalination as well as selected industrial concentration processes. 

Poly(ethersulfone) (PES) is widely used for the preparation of membranes, including ultrafiltration, nanofiltration, and reverse osmosis membranes (88). However, PES lacks hydrophilic groups and the membrane material must be therefore modified. 

Polybenzimidazols developed for heat-resistant resins were also applied to reverse osmosis membranes, first by Cellanese Corporation 67 68). The asymmetric poly-2,2 -(m-phenylene)-5,5 -dibenzimidazole membrane 18 was prepared from 3,3 -diamino-benzidine (79) and diphenyl isophthalate (20) and had a high water flux permeability,... 

Another copolyamide containing carboxyl groups was prepared from 3,3 -methy-lenebis (anthranilic acid) 32, m-phenylenediamine, isophthaloyl chloride and terephth-aloyl chloride 89 K The reverse osmosis membrane from this copolyamide was made by treatment with transition metals (such as NiS04), Al, or Pb and shaping. 

Reverse osmosis membranes were also prepared from polyamides with pendant carboxamide groups 90). For example, 4,4 -diaminodiphenylmethane-3,3 -dicarbox-amide-isophthaloyl chloride copolymer 33 was dissolved in DMF containing LiCl, cast to 250 p thickness, dried at 100 °C for 15 min, and gelled in ice water to give a membrane with the water flux permeability of 900 1/m2 day and salt rejection of 80% (0.5% NaCl aqueous solution, 30 kg/cm2). After heating the membrane in... 

Bacterial cells for the laboratory studies were prepared by growing V. alginolyticus in a M9 minimal salts bacterial growth medium with 8mM glucose as the carbon and energy source (70). The standard M9 medium was modified by addition of 21 g/L of NaCl (SWM9). Water used for all studies was deionized and passed through a reverse osmosis membrane (Milli-Q). 

The temperature of the water used to precipitate the casting solution is important this temperature is controlled in commercial membrane plants. Generally low-temperature precipitation produces lower flux, more retentive membranes. For this reason chilled water is frequently used to prepare cellulose acetate reverse osmosis membranes. 

R.L. Riley, H.K. Lonsdale, C.R. Lyons and U. Merten, Preparation of Ultrathin Reverse Osmosis Membranes and the Attainment of Theoretical Salt Rejection, J. Appl. Polym. Sci. 11, 2143 (1967). 

A number of membrane materials and membrane preparation techniques have been used to make reverse osmosis membranes. The target of much of the early work was seawater desalination (approximately 3.5 wt% salt), which requires membranes with salt rejections of greater than 99.3 % to produce an acceptable permeate containing less than 500 ppm salt. Early membranes could only meet... 

Cadotte JE, King RS, Majerle RJ, and Merten U. Interfacial synthesis in the preparation of reverse osmosis membranes. J. Macromol. Sci. Chem. A. 1981 A15(5) 727-755. 

A variety of reverse osmosis membrane systems based on cellulose acetate, aromatic polyamides, and other polymers have been tested for their potential applications. Reverse osmosis membrane equipment is available for large-scale operation since the process is widely used for the production of potable water from sea or brackish waters and upstream of ion exchange in the preparation of ultrapure water for steam-generating boilers. In these applications, the feed concentrations may vary from 500 to 40,000 mg/L of dissolved solids. The RO technique can be used at pH values between 3 and 12 and up to 45°C. 

---