Patent GB-1252771-A (GB)
IPC: B01J37/20
Filed: 1968-10-09
Abstract: 1,252,771. Preparation of catalysts. ESSO RESEARCH & ENG. CO. 9 Oct., 1968 [10 Oct., 1967; 23 Sept., 1968 (2)], No. 47953/68. Heading B1E. [Also in Division C5] A catalyst is prepared by a method which comprises contacting a base material, which comprises a support material and at least one metal of Group VB, VIB, VIIB or VIII or compound thereof and which has been heated sufficiently to form a complex of the metal, sequentially with (a) a solution of an organometallic compound the metal constituent of which is a metal of Group I, II or III and (b) hydrogen sulphide, the contactings being effected in either order and volatile material being removed from the base material after contact with the solution of the organometallic compound. The contacting with hydrogen sulphide is effected at a temperature preferably of from -100‹F to 250‹F when contact with the organometallic compound precedes contact with hydrogen sulphide and preferably of from 400‹F to 1000‹F when contact with hydrogen sulphide. .precedes contact with the organometallic compound. The contact with hydrogen sulphide may be effected by use of either pure hydrogen sulphide or a gas mixture containing hydrogen sulphide in a concentration preferably of from 0.1 to 20 per cent by volume; the gas mixture may contain hydrogen or nitrogen as diluent. The support material may be an oxide of an element of Group II, III, IV, V or VIB, for example magnesium oxide, calcium oxide, strontium oxide, barium oxide, zinc oxide, boria, alumina, silica, titanium oxide, zirconium oxide or vanadium oxide, a combination of such oxides, for example silica-alumina or a material having a spiral structure, a diatomaceous earth, for example kieselguhr, a natural clay, activated carbon or coke. The metal of Group VB, VIB, VIIB or VIII may be vanadium, chromium, molybdenum, tungsten, manganese, rhenium, iron, cobalt, nickel or platinum; the base material may comprise a combination of such metals, for example Co-Mo, Ni-Mo or Ni-W. The base material may be formed from the support material and the metal or metals of Group VB, VIB, VIIB or VIII or compound or compounds thereof by impregnation, precipitation or co-precipitation techniques. The organometallic compound may have the general formula MR n  where M is boron or a metal of Group I, II or III, for example lithium, magnesium, calcium, strontium, zinc, cadmium or aluminium, of valency n and the or each R is a monovalent hydrocarbon radical which preferably contains from 1 to 20 carbon atoms; preferred organometallic compounds are trialkylaluminiums, especially those having up to 12 carbon atoms per hydrocarbon radical and up to 36 carbon atoms per molecule; compounds exemplified are trimethyl aluminium, triethyl aluminium; tri-n-butyl aluminium, tri-n-hexyl aluminium and tridodecyl aluminium. Examples (including comparative examples) relate to catalysts comprising rhenium (Examples 1 to 3), tunsten (Examples 4 to 8), molybdenum (Examples 9 to 16), chromium (Example 17), manganese (Example 18), vanadium (Example 19), nickel (Examples 20 to 26, 32 and 33), nickel and tungsten in combination (Examples 27, 28 and 39 to 42), platinum (Examples 29 and 30), cobalt (Example 31), cobalt and molybdenum in combination (Example 34) and nickel and molybdenum in combination (Examples 35 to 38), alumina constituting the support material of the catalysts of Examples 1 to 34, 39 and 40; triethyl aluminium in n-heptane or toluene is used as the organometallic compound. Contact with hydrogen sulphide precedes contact with triethyl aluminium in the preparation of the catalysts of Examples 1 to 31 and contact with triethyl aluminium precedes contact with hydrogen sulphide in the preparation of the catalysts of Examples 32 to 42. The catalysts of Examples 41 and 42 are prepared by subjecting a mixture of tungstic acid and nickel carbonate to ball milling, heating at 700‹F and thereafter either sulphiding with a 20/80 per cent volume mixture of hydrogen sulphide and nitrogen initially at 500‹F and thereafter at 700‹F (comparative Example 41) or heating in dry nitrogen at 600‹F, activating with triethyl aluminium at up to 175‹F, stripping with dry nitrogen at 400‹F and sulphiding at up to 73‹F (Example 42). The catalysts may be used in conversion reactions of organic compounds, in particular compounds containing olefinic or aromatic linkages, involving hydrogenation, dehydrogenation, isomerization, hydrodesulphurization, hydrodenitrogenation, hydrocracking and hydrogen transfer; examples relate to the hydrogenation of benzene or octene-1 or steam cracked naphtha and to the selective hydrogenation of octene-1 in a mixture of benzene and octene-1.