Patent GB-1327783-A (GB)
Title: Regeneration of a coke-deactivated catalyst containing platinum and rhenium
IPC: C10G49/06
Filed: 1970-10-12
Abstract: 1327783 Regeneration of hydrocarbon conversion catalysts UNIVERSAL OIL PRODUCTS CO 12 Oct 1970 48367/70 Heading B1E [Also in Division C5] Hydrocarbon conversion catalyst comprising a Group VIII noble metal component, a rhenium component and halogen component supported on alumina carrier material, which catalyst has a Group VIII noble metal: rhenium atomic ratio greater than 1:1 and contains sulphur in free and/or combined form and has been deactivated by deposition thereon of carbonaceous material during contact with hydrocarbon charge, is regenerated by sequential contact with (a) a sulphur-free hydrogen stream at a temperature of from 350 to 600C and a pressure of from 1 to 50 atmospheres until the effluent gas stream is substantially free from hydrogen sulphide, (b) a sulphurfree gaseous mixture containing from 0.3 to 2 mole per cent oxygen at a temperature of from 375 to 500C and a pressure of from 1 to 7 atmospheres until combustion of carbonaceous material is substantially complete, (c) a sulphur-free gaseous mixture containing from 0.5 to 10 mole per cent oxygen at a temperature of from 500 to 550C and a pressure of from 1 to 7 atmospheres for a period of from 0.5 to 10 hours and (d) a water-free and sulphur-free hydrogen stream at a temperature of from 400 to 600C for a period of from 0.5 to 5 hours. After step (a) and prior to step (b), the catalyst is purged from hydrogen, for example by contact with an inert gas, for example nitrogen, and/or by application of vacuum. After step (c) and prior to step (d), the catalyst is purged from oxygen and water by contact with a stream of water-free inert gas, for example nitrogen, until the effluent gas stream contains less than 100 mole parts per million water; after step (c) and prior to such purge, the catalyst may be contacted with a sulphur-free gaseous mixture comprising water, halogen or a compound thereof, for example hydrogen chloride, and air or an inert gas, for example nitrogen, in order to adjust the halogen content of the catalyst. The hydrogen stream used in step (a) may contain hydrocarbon charge, the contact being effected under conditions selected both to strip sulphur from the catalyst and to convert the charge. The hydrogen stream used in step(d) may contain an inert gas, for example nitrogen; step (d) preferably is effected at a hydrogen pressure initially of from 0.1 to 3 atmospheres and thereafter of from 4 to 10 atmospheres. The metal of the Group VIII noble metal component may be selected from ruthenium, rhodium, palladium, osmium, iridium and platinum. The halogen of the halogen component may be selected from fluorine, chlorine, bromine and iodine. The alumina support material, which may contain a minor proportion of refractory oxide material selected from magnesia, silica and zirconia, preferably is selected from gamma-, eta- and theha-aluminas and preferably has an apparent bulk density of from 0.30 to 0.70 g/cm<SP>3</SP>, an average pore diameter of from 20 to 300 Angstrons, a pore volume of from 0.10 to 1.0 cm<SP>3</SP>/g and a surface area of from 25 to 500 m<SP>2</SP>/g. The catalyst may contain, on a carbon-free elemental basis, from 0.01 to 1 weight per cent rhenium, from 0.1 to 1.5 weight per cent halogen, from 0.05 to 1 weight per cent sulphur and Group VIII noble metal in an amount to provide a Group VIII noble metal: rhenium atomic ratio of from 1.5:1 to 10:1. An example relates to the regeneration of a deactivated sulphur-containing catalyst comprising platinum, rhenium and chlorine supported on gammaalumina in the form of spheres having a diameter of 1.6 mm.