SE448951B - HYDRATION CATALYST AND METHOD OF CATALYTIC HYDRATION - Google Patents

Description

According to the invention, it has been found that such a catalyst has improved hydrogenation activity and improved catalyst life, provided that the catalyst is calcined at such temperatures. According to the invention, it has been found that calcination of such a catalyst at temperatures normally used for calcination of supported nickel-containing catalysts (ca. 538-56500) does not provide a useful catalyst for hydrogenation of high-boiling starting materials, since strong coking of the catalyst occurs after only a short period of use.

The catalyst according to the invention contains a catalytically effective amount of nickel, molybdenum and optionally cobalt.

The catalyst according to the invention generally contains from 1 to 6%, preferably from 1 to 4% nickel, and from up to 16%, preferably from 6 to 10% molybdenum, and from 0 to 6% cobalt, all by weight. If cobalt is used, cobalt is generally present in an amount of from 1 to 6% by weight.

The particle size of the catalyst according to the invention is generally of the order of 0.127 to 3.18 mm, the catalyst, if present in extruded form, generally having the order of 0.38 to 3.18 mm and, if present in spherical form , a size of the order of 0.127 to 3.18 mm.

In general, the surface area of the catalyst is at least 125 m 2 / g and generally from 150 to 300 m 2 / g. The alumina of the catalyst is generally in the gamma form. In some cases, the alumina support may comprise up to 10% silica.

Nickel and molybdenum and possibly also cobalt are carried on the alumina by methods which are generally known to those skilled in the art. Thus, for example, a molybdenum compound, for example ammonium molybdate, may be added to an aqueous slurry of alumina having a porosity and pore size distribution, _......-................ ..- .._..._... ~ _-_- W »... i _ _ _...........___..._...._-, -. .-- ~ _.._. V «448 951 3 which gives a finished catalyst with the porosity defined above and the pore size distribution, followed by spray drying and shaping, for example into spheres. Optionally, the supported molybdenum can be calcined at this time, but this calcination is a complement to and not instead of the final calcination according to the invention. The molybdenum carried on the alumina is then impregnated with nickel, for example in the form of an aqueous solution of nickel nitrate, and optionally also a console, followed by drying.

The supported catalyst is then calcined according to the invention at a temperature of from 621 to 704 ° C, preferably a temperature of from 621 to 677 ° C, the calcination temperature in most cases being about 649 ° C. As stated above, the use of lower calcination temperatures, which are conventionally used for supported or supported catalysts containing nickel, does not provide an acceptable catalyst (excessive coke deposition) and temperatures above 70,500 would not be suitable due to of the volatility of molybdenum. When using the higher parts of the specified calcination temperatures, there may be some deactivation of the nickel component in the catalyst and as a result, in most cases the calcination temperature should not exceed 677 ° C.

According to another aspect of the invention, the above-described hydrogenation catalyst is used for the hydrogenation of hydrocarbonaceous feedstocks containing heavier (higher boiling) components, these feedstocks generally being characterized in that at least 50% of the components boil above 524 ° C. . Such feedstocks are generally derived from either petroleum or coal sources and as a representative example of such feedstocks may be mentioned: Heavy petroleum crude oils, petroleum residues from atmospheric distillation or vacuum distillation, shale oil, shale oil residues, tar sands, coal tar, bitumen, coal bitumen, bitumen , solvent deasphalted oils, etc.

Claims (8)

448 951 PATENT CLAIMS Hydrogenation catalyst with improved catalyst life comprising a catalytically effective amount of nickel, molybdenum and optionally cobalt, supported on an alumina support, characterized in that the catalyst is prepared by adding a compound of the metal to an aqueous suspension of alumina and spray drying of this and calcination at a temperature of from 621 to 704 ° C, the catalyst having a total porosity of at least 0.5 cma / g and a pore size distribution of from 0.25 to 0.40 cma / g pores with a diameter of less than 25 cma / g nm, 0.10-0.25 cm 2 / g pores with a diameter of from 25 to 50 nm, from 0.20 to 0.30 cm 3 / g pores with a diameter of from 50 to 150 nm, from 0.05 to 0.15 cma / g pores with a diameter of from 150 to 400 nm and from 0.03 to 1.0 cm 2 / g pores with a diameter greater than 400 nm. Catalyst according to Claim 1, characterized in that the surface area (specific surface area) of the catalyst is at least 125 m2 / g and preferably 150-300 m2 / g. Catalyst according to Claim 1 or 2, characterized in that it contains from 0.34 to 0.36 cm 3 / g of pores down to a diameter of less than 25 nm, from 0.4 to 0.15 cm 3 / g pores with a diameter of from 25 to 50 nm, from 0.22 to 0.23 cm 2 / g Pores with a diameter of from 50 to 150 nm, from 0.10 to 0.11 Cmg / g POs with a diameter of meters of from 150 to 400 nm and from 0.04 to 0.07 cma / g pores with a diameter exceeding 400 nm. Catalyst according to one of the preceding claims, characterized in that the catalyst contains f from 1 to 1 H z nickel] and from 5 to 16 Z molybdenum, by weight. Catalyst according to any one of the preceding claims, 448,951 characterized in that the calcination temperature is from 621 to 677 ° C. Catalyst according to any one of the preceding claims, characterized in that the total porosity is from 0.75 to 0.95 cma / g. ~ 1 Catalyst according to one of the preceding claims, characterized in that the alumina is gamma alumina. Process for the catalytic hydrogenation of a heavier hydrocarbonaceous feedstock in the presence of a hydrogenation catalyst, characterized in that the hydrogenation is carried out in the presence of a hydrogenation catalyst comprising a catalytically efficient amount of nickel, molybdenum and optionally cobalt, supported on an alumina support, the catalyst being prepared by adding a compound of the metal to an aqueous suspension of alumina and spray drying thereof and calcining at a temperature of from 621 to 704 ° C, the catalyst having a total porosity of at least 0.5 cm 2 / g and a pore size distribution of from 0.25 to 0.40 cm 2 / g pores with a diameter of less than 25 nm, 0.10 ~ 0.25 cm 2 / g pores with a diameter of from 25 to 50 nm, from 0.20 to 0.30 cma / g pores with a diameter of from 50 to 150 nm, from 0.05 to 0.15 cm 2 / g pores with a diameter of from 150 to 400 nm and from 0.03 to 0.10 cm ”/ G pores with a diameter greater than 400 nm. KO. Process according to Claim 8, characterized in that the hydrocarbon feedstock contains at least 50% of components with a boiling point above 524 ° C. l0. Process according to Claim 8 or 9, characterized in that the hydrogenation is carried out at a temperature of from 371 to 482 ° C. ll. Process according to one of Claims 8 to 10, characterized in that the hydrogenation is carried out with a degree of conversion of at least 50% based on components boiling above 524 ° C.