Microporous metal membranes

Micropore diffusion, 1 596, 597-599 Microporous catalysts, in bisphenol A manufacture, 14 420 Microporous metal membranes, 15 813t Microporous particles, apparent effective diffusivity and, 15 729-730 Microporous range, pore diameters within, 16 812... 

From 1943 to 1945, Graham s law of diffusion was exploited for the first time, to separate U235F6 from U238F6 as part of the Manhattan project. Finely microporous metal membranes were used. The separation plant, constructed in Knoxville, Tennessee, represented the first large-scale use of gas separation membranes and remained the world s largest membrane separation plant for the next 40 years. However, this application was unique and so secret that it had essentially no impact on the long-term development of gas separation. 

Figure 3.15. A two-step molding process for fabricating a microporous metal membrane by using polymethylmethacrylate (PMMA) as an intermediate template [Masuda et al., 1993]...

H. Masuda, K. Nishio, and N. Babe, Preparation of microporous metal membrane using two-step replication of interconnected structure of porous glass, J. Mater, Sci Lett, 7i 338 (1994). 

Microporous metal membranes by electrochemical etching Aluminum metal, for example, is electrochemical ly etched to form a porous aluminum oxide film. Membranes are brittle but uniform, with small pore size 0.02-2.0 fim 49,50... 

Ceramic, Metal, and Liquid Membranes. The discussion so far implies that membrane materials are organic polymers and, in fact, the vast majority of membranes used commercially are polymer based. However, interest in membranes formed from less conventional materials has increased. Ceramic membranes, a special class of microporous membranes, are being used in ultrafHtration and microfiltration appHcations, for which solvent resistance and thermal stabHity are required. Dense metal membranes, particularly palladium membranes, are being considered for the separation of hydrogen from gas mixtures, and supported or emulsified Hquid films are being developed for coupled and facHitated transport processes. 

Because membranes appHcable to diverse separation problems are often made by the same general techniques, classification by end use appHcation or preparation method is difficult. The first part of this section is, therefore, organized by membrane stmcture preparation methods are described for symmetrical membranes, asymmetric membranes, ceramic and metal membranes, and Hquid membranes. The production of hollow-fine fiber membranes and membrane modules is then covered. Symmetrical membranes have a uniform stmcture throughout such membranes can be either dense films or microporous. 

Space available in porous glass [487], ultrafine Nafion [488, 489], and metallic membranes [490, 491] has also been utilized for the development of smal particles. Cylindrical micropores in alumina membranes have been used, for example, as templates for the electrodeposition of parallel arrays of gold particles (0.26 pm in diameter, 0.3 pm to 3 pm in length) which were infrared transparent [491] and could be used as chemical sensors [490],... 

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 ... 

Recently, attempts have been made to reduce the cost of palladium metal membranes by preparing composite membranes. In these membranes a thin selective palladium layer is deposited onto a microporous ceramic, polymer or base metal layer [19-21], The palladium layer is applied by electrolysis coating, vacuum sputtering or chemical vapor deposition. This work is still at the bench scale. 

Figure 21.4 Porous membranes developed for emulsification processes, (a) Shirasu porous glassy membrane (from SPG Technology Co., LTD, Japan), (b) metallic membrane (From Micropore Technologies, United Kingdom).

Figure 21.12 Marketed equipments for membrane emulsification, (a) Plant for crossflow membrane emulsification produced by SPG Technologies Co. Ltd (http //www.spg-techno. co.jp/) (b) spiral-wound metallic membrane module produced by Micropore Technologies (http //www.micropore.co.uk/).

Silver membranes are permeable to oxygen. Metal membranes have been extensively studied in the countries of the former Soviet Union (Gryaznov and co-workers are world pioneers in the field of dense-membrane reactors), the United States, and Japan, but, except in the former Soviet countries, they have not been widely used in industry (although fine chemistry processes were reported). This is due to their low permeability, as compared to microporous metal or ceramic membranes, and their easy clogging. Bend Research, Inc. reported the use of Pd-composite membranes for the water-gas shift reaction. Those membranes are resistant to H2S poisoning. The properties and performance characteristics of metal membranes are presented in Chapter 16 of this book. 

Hydrogen selective inorganic membranes can be mesoporous (2 nm < pore diameter < 50 nm ceramic, glass or carbon) microporous (pore diameter < 2 nm ceramic, carbon or zeolite) or dense (ceramic or metal). These membranes can be used from ambient temperatures up to about 600°C for mesoporous materials, up to about 500°C for microporous inorganic membranes and up to about 800°C for dense inorganic membranes [14-16]. These temperatures are only a rough indication, because of the different materials which can be used and the test conditions at which the membranes have to operate. 

Inorganic membrane development is still in progress [57] (see also Section 14.2.2). Microporous silica membranes have been developed at several universities and research institutes. Membrane selectivities of 15 and 20 for the separation of H2 from CO2 have been reported. Even higher selectivities for H2 arid CO, CH4 and N2 have been measured [20,57]. Most measurements reported in the literature have been performed on a laboratory scale. However, it has been shown that it is possible to upscale these microporous ceramic membranes to, at least, bench scale [31,57]. With other membranes such as noble (Pd) metal membranes and dense ceramic membranes very high and almost infinite selectivities for hydrogen are possible [58]. The permeation of these membranes is generally smaller than the permeation of microporous membranes. 

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