Microporous support

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. 

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. 

Most solution-cast composite membranes are prepared by a technique pioneered at UOP (35). In this technique, a polymer solution is cast directly onto the microporous support film. The support film must be clean, defect-free, and very finely microporous, to prevent penetration of the coating solution into the pores. If these conditions are met, the support can be coated with a Hquid layer 50—100 p.m thick, which after evaporation leaves a thin permselective film, 0.5—2 pm thick. This technique was used to form the Monsanto Prism gas separation membranes (6) and at Membrane Technology and Research to form pervaporation and organic vapor—air separation membranes (36,37) (Fig. 16). 

Reverse Osmosis Asymmetric with homogeneous skin and microporous support Pressure, 10 -100 atm Solution diffusion... 

The microwave technique has also been found to be a potential method for the preparation of the catalysts containing highly dispersed metal compounds on high-porosity materials. The process is based on thermal dispersion of active species, facilitated by microwave energy, into the internal pore surface of a microporous support. Dealuminated Y zeolite-supported CuO and CuCl sorbents were prepared by this method and used for S02 removal and industrial gas separation, respectively [5], The results demonstrated the effective preparation of supported sorbents by micro-wave heating. The method was simple, fast, and energy-efficient, because the synthesis of both sorbents required a much lower temperature and much less time compared with conventional thermal dispersion. 

A common method to slip-cast ceramic membranes is to start with a colloidal suspension or polymeric solution as described in the previous section. This is called a slip . The porous support system is dipped in the slip and the dispersion medium (in most cases water or alcohol-water mixtures) is forced into the pores of the support by a pressure drop (APJ created by capillary action of the microporous support. At the interface the solid particles are retained and concentrated at the entrance of pores to form a gel layer as in the case of sol-gel processes. It is important that formation of the gel layer starts... 

Frcilich, D. and G. B. Tanny. 1978. The formation mechanism of dynamic hydrous Zr (IV) oxide membranes on microporous supports. J. Coll. Interface Sci. 64(2) 362-70. 

Interfacial polymerization membranes. This type of anisotropic membrane is made by polymerizing an extremely thin layer of polymer at the surface of a microporous support polymer. 

Solution-coated, composite membranes. To prepare these membranes, one or more thin, dense polymer layers are solution coated onto the surface of a microporous support. 

Membranes made by interfacial polymerization have a dense, highly crosslinked polymer layer formed on the surface of the support membrane at the interface of the two solutions. A less crosslinked, more permeable hydrogel layer forms under this surface layer and fills the pores of the support membrane. The dense, crosslinked polymer layer, which can only form at the interface, is extremely thin, on the order of 0.1. im or less, so the membrane permeability is high. Because the polymer is highly crosslinked, its selectivity is also high. Although the crosslinked interfacial polymer layer determines membrane selectivity, the nature of the microporous support film affects membrane flux... 

Another important group of anisotropic composite membranes is formed by solution-coating a thin (0.5-2.0 xm) selective layer on a suitable microporous support. Membranes of this type were first prepared by Ward, Browall, and others at General Electric [52] and by Forester and Francis at North Star Research [17,53] using a type of Langmuir trough system. In this system, a dilute polymer solution in a volatile water-insoluble solvent is spread over the surface of a water-filled trough. 

The apparatus used to make small sections of water-cast composite membranes is shown in Figure 3.23. The dilute polymer solution is cast on the surface between two Teflon rods. The rods are then moved apart to spread the film. The thin polymer film formed on the water surface is picked up on a microporous support. The main problem with this method is the transfer of the fragile, ultrathin film onto the microporous support. This is usually done by sliding the support... 

Figure 3.26 Schematic and scanning electron micrograph of a multilayer composite membrane on a microporous support. (Courtesy of Membrane Technology and Research, Inc.)...

In the particulate-sol method a metal alkoxide dissolved in alcohol is hydrolyzed by addition of excess water or acid. The precipitate that results is maintained as a hot solution for an extended period during which the precipitate forms a stable colloidal solution. This process is called peptization from the Greek pep—to cook (not a misnomer many descriptions of the sol-gel process have a strong culinary flavor). The colloidal solution is then cooled and coated onto the microporous support membrane. The layer formed must be dried carefully to avoid cracking the coating. In the final step the film is sintered at 500-800 °C. The overall process can be represented as ... 

An interesting group of composite membranes with very good properties is produced by condensation of furfuryl alcohol with sulfuric acid. The first membrane of this type was made by Cadotte at North Star Research and was known as the NS200 membrane [32], These membranes are not made by the interfacial composite process rather a polysulfone microporous support membrane is contacted first with an aqueous solution of furfuryl alcohol and then with sulfuric acid. The coated support is then heated to 140 °C. The furfuryl alcohol forms a polymerized, crosslinked layer on the polysulfone support the membrane is completely black. The chemistry of condensation and reaction is complex, but a possible polymerization scheme is shown in Figure 5.10. 

Recently, some membrane manufacturers have attempted to produce anisotropic microfiltration membranes in which the open microporous support is a built-in prefilter. Unlike most other applications of anisotropic membranes, these membranes are oriented with the coarse, relatively open pores facing the feed solution, and the most finely microporous layer is at the bottom of the membrane. The goal is to increase filter life by distributing the particle load more evenly across the filter than would be the case with an isotropic porous membrane. 

Another type of gas separation membrane is the multilayer composite structure shown in Figure 8.9. In this membrane, a finely microporous support membrane is overcoated with a thin layer of the selective polymer, which is a different material from the support. Additional layers of very permeable materials such as silicone rubber may also be applied to protect the selective layer and to seal any defects. In general it has been difficult to make composite membranes with... 

Figure 8.9 Two-layer composite membrane formed by coating a thin layer of a selective polymer on a microporous support that provides mechanical strength...

During the last few years, ceramic- and zeolite-based membranes have begun to be used for a few commercial separations. These membranes are all multilayer composite structures formed by coating a thin selective ceramic or zeolite layer onto a microporous ceramic support. Ceramic membranes are prepared by the sol-gel technique described in Chapter 3 zeolite membranes are prepared by direct crystallization, in which the thin zeolite layer is crystallized at high pressure and temperature directly onto the microporous support [24,25],... 

J. Brinker, C.-Y. Tsai and Y. Lu, Inorganic Dual-Layer Microporous Supported Membranes, US Patent 6,536,604 (March 2003). 

Membranes comprising silicone rubber coated onto polyimides, polyacrylonitrile or other microporous supports membranes are widely used [12,27]. Other rubbers such as ethylene-propylene terpolymers have been reported to have good properties also [28]. Polyamide-polyether block copolymers have also been used for pervaporation of some polar VOCs [29,30]... 

In supported liquid membranes, a microporous support impregnated with the liquid complexing agent separates the feed and product solutions. In coupled... 

Examples of the best results obtained are shown in Figure 11.21 [33,61], The composite membranes with which these data were obtained were formed by casting a solution of 80 wt% silver tetrafluoroborate in a propylene oxide copolymer matrix onto a microporous support. When subjected to a 40-day test with a gas... 

All gas-separation membranes have an anisotropic structure with a thin, dense selective layer facing the high-pressure feed gas. The selective layer is supported on a much thicker microporous support layer that provides mechanical strength. The chemical structure determines the permeability of the selective layer.1 The selective-... 

---