Patent EP-0568303-A2 (EP)
Inventor: DURANTE VINCENT A
IPC: B01J27/049
Filed: 1993-04-27
Abstract: Alkanes are dehydrogenated in one embodiment by passage through alternating dehydrogenation zones and selective oxidation zone(s) , in which latter zone(s) hydrogen produced in the preceding endothermic dehydrogenation reaction is selectively oxidized to generate heat for the succeeding dehydrogenation reaction. In one embodiment, dehydrogenation is carried out without limitation to particular flow sequence, using a catalyst comprising an alloy or combination of nickel with copper, tin, lead or indium on non-acidic supports. In another embodiment, new catalyst compositions, active for dehydrogenation of alkanes, are prepared comprising reduced and sulfided nickel crystallites on siliceous supports which have been treated with chromium compounds and oxidized to provide surface-anchored chromyl species. In another embodiment, new catalyst compositions, active for dehydrogenation of alkanes, are prepared comprising nickel supported on a non-acidic form of zeolite L. In another embodiment, new catalyst compositions are prepared by sulfiding nickel-containing compositions with carbonaceous sulfur compounds such as dialkylsulfoxides. Another embodiment of the invention is catalyst and dehydrogenation therewith, in which pores having radius of 50 to 200 Angstroms occupy pore volume from 0.30 to 1.50 ml per gram of the support, and pores having radius of 20 to 50 Angstroms occupy pore volume less than 0.1 ml per gram of the support. In another embodiment, alkanes are dehydrogenated using as catalyst a metal or metal compound having dehydrogenating activity supported on alkali-treated alumina. In other embodiments, reaction of dehydrogenating metal, nickel for example, with a Group III oxide or hydroxide, alumina for example, support during catalyst preparation by forming a layer of a Group IV metal oxide or hydroxide, zirconia or titania for example, on the support prior to applying the dehydrogenating metal to the support, or by reacting another metal, for example copper, prior to applying the dehydrogenating metal, for example nickel, to the support. Another embodiment of the invention is catalyst preparation wherein a dehydrogenating metal, for example nickel, is selectively deposited in the larger pores of a catalyst support by previously contacting the support with a liquid organic compound, a glycol for example, whereby said compound selectively enters or remains in the smaller pores of the support, and the catalyst thereby obtained. In another embodiment, catalyst is prepared by impregnating a porous support, alumina for example, with a dehydrogenating metal, for example nickel, calcining the support at a first temperature sufficiently high to react metal with the support, reimpregnating the support with the same, or a different, metal and calcining the support at a second temperature, 200°C. for example, lower than the temperature of the first calcining, 500°C. for example. In another embodiment, dehydrogenation catalyst is prepared by forming a carbonaceous layer on a noncarbonaceous porous support, alumina for example, the carbonaceous layer being formed by precoking of the support, prior to depositing a dehydrogenating metal, nickel for example, on the support; the resulting catalyst containing carbon filaments between dehydrogenating metal particles and the support.