Dense ceramic metal composite membranes

BalachandrianU.,LeeT. H.,Chen L.,Song S. J. and Dorris S.E.,Dense Ceramic-Metal Composite Membranes for Hydrogen Separation, Proc. 9 Int. Conf. on Inorganic membranes, LiUehammer (Norway), June 25-29,2006. 

Dense Cermet (Ceramic Metal) Composite Membranes... 

In this chapter membrane preparation techniques are organized by membrane structure isotropic membranes, anisotropic membranes, ceramic and metal membranes, and liquid membranes. Isotropic membranes have a uniform composition and structure throughout such membranes can be porous or dense. Anisotropic (or asymmetric) membranes, on the other hand, consist of a number of layers each with different structures and permeabilities. A typical anisotropic membrane has a relatively dense, thin surface layer supported on an open, much thicker micro-porous substrate. The surface layer performs the separation and is the principal barrier to flow through the membrane. The open support layer provides mechanical strength. Ceramic and metal membranes can be either isotropic or anisotropic. 

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. 

Supported, multilayered (as5onmetric) - dense oxide or metal - porous ceramic membranes alumina, zirconia, titania, carbon - composite ceramic-metal, ceramic-ceramic layers on porous support tube, disk multilayers on porous support plate, disk, tube, monolith... 

The complex phase diagrams and rich crystal chemistry of the transition metal-containing oxide systems, and great diversity in the defect chemistry and transport properties of mixed-conducting materials known in these systems, make it impossible to systematize all promising compositions in a brief survey. The primary attention here is therefore centered on the comparison of major families of the oxide mixed conductors used for dense ceramic membranes and porous electrodes of SOFCs and other high-temperature electrochemical devices. 

Composite membranes also employ dense cermets fabricated by sintering together mixed powders of metal and ceramic [10-12], Examples include powders of Pd and its alloys sintered with powders of perovskites [11,12], niobium sintered together with AI2O3 [12], and nickel sintered with proton-conducting perovskites. Layers of dense cermets, 25-100 xm thick, are supported by porous ceramic tubes. Cermets employing chemically reactive metals, Nb, Ta, U, V, Zr, and their alloys, are typically coated with Pd and alloys thereof [11,12],... 

Electroplating. Basically in electroplating, a substrate is coated with a metal or its alloy in a plating bath where the substrate is the cathode and the temperature is maintained constant Membranes from a few microns to a few millimeters thick can be deposited by carefully controlling the plating time, temperature, current density and the bath composition. Dense membranes made of palladium and its various alloys such as Pd-Cu have been prepared. Porous palladium-based membranes have also been made by deposition on porous support materials such as glass, ceramics, etc. 

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... 

In contrast, if the membrane is an inorganic composition (e.g., a dense metal membrane or a nanoporous ceramic membrane), the membrane module may be operated at the elevated temperature of 450 °C. In this case, there is no need for optional HEX 2 as the fuel gas stream will exit the membrane module at 450 °C and pass to the burner without further cooling. In addition to a net increase in overall process energy efficiency, the elimination of HEX 2 also represents a reduction in capital cost for the system. 

Membrane separators offer the possibility of compact systems that can achieve fuel conversions in excess of equilibrium values by continuously removing the product hydrogen. Many different types of membrane material are available and a choice between them has to be made on the basis of their compatibility with the operational environment, their performance and their cost. Separators may be classified as (i) non-porous membranes, e.g., membranes based on metals, alloys, metal oxides or metal—ceramic composites, and (ii) ordered microporous membranes, e.g., dense silica, zeolites and polymers. For the separation of hot gases, the most promising are ceramic membranes. 

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