Proton-conducting dense ceramic membranes

Lin, J.Y.S., Proton conducting dense ceramic membranes for hydrogen separation, Annual Progress Report, U.S. DOE Contract DE-FG26-00NT40818, December 2002. 

Ceramic electrochemical reactors are currently undergoing intense investigation, the aim being not only to generate electricity but also to produce chemicals. Typically, ceramic dense membranes are either pure ionic (solid electrolyte SE) conductors or mixed ionic-electronic conductors (MIECs). In this chapter we review the developments of cells that involve a dense solid electrolyte (oxide-ion or proton conductor), where the electrical transfer of matter requires an external circuitry. When a dense ceramic membrane exhibits a mixed ionic-electronic conduction, the driving force for mass transport is a differential partial pressure applied across the membrane (this point is not considered in this chapter, although relevant information is available in specific reviews). 

Abstract Dense ceramic membrane reactors are made from composite oxides, usually having perovskite or fluorite structure with appreciable mixed ionic (oxygen ion and/or proton) and electronic conductivity. They combine the oxygen or hydrogen separation process with the catalytic reactions into a single step at elevated temperatures (>700°C), leading to significantly improved yields, simplified production processes and reduced capital costs. This chapter mainly describes the principles of various types of dense ceramic membrane reactors, and the fabrication of the membranes and membrane reactors. 

In Chapter 10, the use of membranes for different applications are described. One of the possible membranes for hydrogen cleaning is an asymmetric membrane comprised of the dense end of a proton conduction perovskite such as BaCe0 95 Yb0 05O3 5 and a porous end to bring mechanical stability to the membrane. In this case, it is possible to take from the slurry, obtained by the acetate procedure, several drops to be released over a porous ceramic membrane, located in the spinning bar of a spin-coating machine. Thereafter, the assembly powder, thin film porous membrane is heated from room temperature up to 1573 K at a rate of 2K/min, kept at this temperature for 12 h, and then cooled at the same rate in order to get the perovskite end film over the porous membrane [50],... 

Hydrogen-permselective silica membranes [8,10] can be, as well, synthesized by a particular application of solgel techniques [142,143], Additionally, hydrogen permselective asymmetric membranes composed of a dense ceramic of a proton-conducting perovskite over a porous support have been developed [40], However, some difficulties with respect to their stability is possible in certain reactive environments [121],... 

One category of dense proton conducting membranes that has received considerable attention in the preceding decade is proton conducting perovskite type oxide ceramics [4-6]. The stoichiometric chemical composition of perovskites is represented as ABO3, where A is a divalent ion (A +) such as calcium, magnesium, barium or strontium and B is a tetravalent ion (B +) such as cerium or zirconium. Although simple perovskites such as barium cerate (BaCeOs) and strontium cerate... 

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],... 

As discussed elsewhere in this text, there are two types of dense, hydrogen-permeable metal membranes to consider from the perspective of module scale-up and design thin metal foils and permselective metal layers formed on a porous support. Another class of hydrogen-permeable inorganic membranes - dense proton-conducting ceramic membranes - are still under development and are addressed in Chapter 2. 

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