Cobalt skeletal catalyst, preparation

Raney predicted that many other metal catalysts could be prepared with this technique, but he did not investigate them [8], Copper and cobalt catalysts were soon reported by others [4,5], These catalysts were not nearly as active as Raney s nickel catalyst and therefore have not been as popular industrially however they offer some advantages such as improved selectivity for some reactions. Skeletal iron, ruthenium and others have also been prepared [9-13], Wainwright [14,15] provides two brief overviews of skeletal catalysts, in particular skeletal copper, for heterogeneous reactions. Table 5.1 presents a list of different skeletal metal catalysts and some of the reactions that are catalyzed by them. 

Following the development of sponge-metal nickel catalysts by alkali leaching of Ni-Al alloys by Raney, other alloy systems were considered. These include iron [4], cobalt [5], copper [6], platinum [7], ruthenium [8], and palladium [9]. Small amounts of a third metal such as chromium [10], molybdenum [11], or zinc [12] have been added to the binary alloy to promote catalyst activity. The two most common skeletal metal catalysts currently in use are nickel and copper in unpromoted or promoted forms. Skeletal copper is less active and more selective than skeletal nickel in hydrogenation reactions. It also finds use in the selective hydrolysis of nitriles [13]. This chapter is therefore mainly concerned with the preparation, properties and applications of promoted and unpromoted skeletal nickel and skeletal copper catalysts which are produced by the selective leaching of aluminum from binary or ternary alloys. 

Alloys are prepared commercially and in the laboratory by melting the active metal and aluminum in a crucible and quenching the resultant melt which is then crushed and screened to the particle size range required for a particular application. The alloy composition is very important as different phases leach quite differently leading to markedly different porosities and crystallite sizes of the active metal. Mondolfo [14] provides an excellent compilation of the binary and ternary phase diagrams for aluminum alloys including those used for the preparation of skeletal metal catalysts. Alloys of a number of compositions are available commercially for activation in the laboratory or plant. They include alloys of aluminum with nickel, copper, cobalt, chromium-nickel, molybdenum-nickel, cobalt-nickel, and iron-nickel. 

A special type of catalyst which is typified by Raney Nickel is prepared by leaching out one component from a binary alloy leaving a skeletal structure of the desired catalyst. Raney Nickel itself is made by leaching out aluminium from an aluminium-nickel alloy with sodium hydroxide. Cobalt and iron catalysts have also been prepared in this manner. 

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