Dense metallic membrane applications

The discussion so far implies that membrane materials are organic polymers, and in fact most membranes used commercially are polymer-based. However, in recent years, interest in membranes made of less conventional materials has increased. Ceramic membranes, a special class of microporous membranes, are being used in ultrafiltration and microfiltration applications for which solvent resistance and thermal stability are required. Dense, metal membranes, particularly palladium membranes, are being considered for the separation of hydrogen from gas mixtures, and supported liquid films are being developed for carrier-facilitated transport processes. 

To conclude this section, it is necessary to state that Pd and Pd-based membranes are currently the membranes with the highest hydrogen permeability and selectivity. However, the cost, availability, their mechanical and thermal stabilities, poisoning, and carbon deposition problems have made the large-scale industrial application of these dense metal membranes difficult, even when prepared in a composite configuration [26,29,33-37],... 

The inorganic membranes had until the late nineties received fairly little attention for applications in gas separation. This has mainly been due to their porous stmcmre, and therefore lack of ability to separate gas molecules. Within the group of inorganic membranes there are however the dense metallic membranes and the solid oxide electrolytes these are discussed separately in Section 4.3.5. With reference to Section 4.2, the possible transport mechanisms taking place in a porous membrane may be summarized as in Table 4.4 below, as well as the ability to separate gases (+) or not (—). Recent findings [29] have however documented that activated Knudsen diffusion may take place also in smaller pores than indicated in the table. 

There are essentially four different types of membranes, or semipermeable barriers, which have either been commercialized for hydrogen separations or are being proposed for development and commercialization. They are polymeric membranes, porous (ceramic, carbon, metal) membranes, dense metal membranes, and ion-conductive membranes (see Table 8.1). Of these, only the polymeric membranes have seen significant commercialization, although dense metal membranes have been used for commercial applications in selected niche markets. Commercial polymeric membranes may be further classified as either asymmetric (a single polymer composition in which the thin, dense permselective layer covers a porous, but thick, layer) or composite (a thick, porous layer covered by a thin, dense permselective layer composed of a different polymer composition).2... 

Multi-phase catalytic reactions have attracted some attention but the area has not in our opinion been fully exploited. Previous studies have demonstrated that the yields obtained with the catalytic membrane reactors are often better than the yields obtained with more conventional reactors. Future research in this area must involve reactions with more immediate industrial applications. Examples of such reactions could be the hydrogenation reactions studied by Gryaznov and co-workers with dense metallic membranes which we discussed earlier. New materials like zeolite membrane could offer some advantages here with their enhanced regio- or chemioselectivity. 

As with any engineering exercise, when the objective is to successfully scale-up and develop a product for commercial and industrial applications, the focus must be on achieving acceptable economics. Of course, economics involves the upfront capital expenditure, as well as any ongoing maintenance costs and fuel or other utiUty costs. One of the potential advantages of dense metal membranes for hydrogen purification is that the membranes are preferably operated at signifi-... 

This chapter focuses mainly on Pd-based MRs with respect to the gas permeation mechanism, membrane preparation, MR construction and operation, as well as applications in a variety of chemical reactions. In addition to a general description of Pd membranes and MRs, recent progress and critical issues in the dense metal membrane area will also be presented at the end of this chapter. 

Technologies must be developed to produce membranes for high-temperature separation and reaction applications. Composite dense metallic membranes, such as Pd and its alloys. 

In contrast to dense inorganic membranes, the rate of advances toward industrial-scale applications of porous inorganic membranes has been rapid in recent years. In the early periods of this century, microporous porcelain and sintered metals have been tested for microfiltration applications and, in the 1940s, microporous Vycor-type glass membranes became available. Then in the mid-1960s porous silver membranes were commercialized. These membranes, however, have not seen large scale applications in... 

---