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AssigneeUnion Oil Company of California
InventorJohn W. Ward
Estimating the term…
A novel process for the demetallization of petroleum feedstocks comprising contacting a petroleum feedstock at elevated pressures and temperatures, and preferably in the presence of hydrogen, with a catalyst comprising a manganese component composited with alumina, said catalyst having a surface area in excess of 175 m.sup.2 /gm and having at least 60% of its pore volume in pores having diameters between 50 and 200 A. Preferred catalysts comprise between about 2 and 15 weight-percent manganese. Removal of more than 25%, usually more than 50%, of the organometallic impurities can be achieved.
In a process for the demetallization and desulfurization of a liquid hydrocarbon feedstock wherein said feedstock is contacted with a demetallization and desulfurization catalyst at a hydrogen partial pressure between about 100 and 3000 psia and at a temperature between about 600.degree. and 850.degree. F and at a space velocity between about 0.1 and 10.0 L.H.S.V. to obtain therefrom a substantially demetallized product oil, the improvement which comprises utilizing as said demetallization catalyst a composition comprising one or more active manganese components composited with alumina, said catalyst composition having at least 60% of its total pore volume distributed in pores having diameters between about 50 and 200 A, having a surface area in excess of 250 m.sup.2 /gm, and containing between about 0.1 and 30 wt.% (calculated as manganese) of said one or more manganese components.
A catalyst composition consisting essentially of between about 0.1 and 30 wt.% (calculated as manganese) of one or more active manganese components selected from the class consisting of manganese metal and the oxides and sulfides thereof, supported on alumina, said catalyst composition having at least 60% of its total pore volume in pores having diameters between 50 and 200 A and having a surface area in excess of 250 m.sup.2 /gm.
Dependencies are inferred from the claim text.
Catalysts, in general, characterised by their form or physical properties: characterised by their surface properties or porosity
Manganese, technetium or rhenium: manganese
Surface area: 100-500 m2/g
Pore volume: less than 0.5 ml/g
Term ended 30 Aug 1994 (estimated)
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This invention relates to the demetallization of hydrocarbon charge stocks. More particularly, it relates to the removal of metallic contaminants, especially those of nickel and vanadium, from residual oils.
Various petroleum feedstocks, such as crude petroleum oils, heavy vacuum gas oils, shale oils, oils from bituminous sands, topped crudes and atmospheric or vacuum residual fractions contain varying amounts of non-metallic and metallic impurities. The non-metallic impurities usually include nitrogen, sulfur and oxygen; the metallic impurities usually include nickel, vanadium, iron, sodium, copper, zinc and arsenic. In addition, it is known that most of the metallic contaminants are present as inorganic sulfides, oxides and water soluble constituents, while the remainder is usually in the form of relatively thermally stable organometallic complexes such as metal porphyrins and derivatives thereof. It is generally conceded by the art that for purposes of demetallization the removal of the organometallics is more difficult than that for the inorganics.
The presence of these contaminants in petroleum feedstocks presents assorted difficulties in the refining process. In most petroleum refineries today, however, the problems associated with the inorganic metallics and non-metallic impurities have largely been resolved. Catalytic hydrotreating or hydrofining operations effectively remove sulfur, nitrogen and oxygen from petroleum stocks by hydrodecomposition. Inorganic metallics, on the other hand, are generally removed at least in part, by filtration, water washing or electric desalting operations performed prior to hydrofining. But removal of the organometallics, especially those of vanadium and nickel, is especially troublesome. These components are readily adsorbed by conventional hydrofining catalysts and other catalysts used in cracking and reforming operations, resulting in rapid deactivation thereof.
The following two examples describe the preparation of catalysts useful for demetallization of petroleum feedstocks by the process of this invention. (Note: All the examples herein are illustrative only, and not limiting.)
100 gm (dry basis) of cylindrical gamma alumina 1/16 inch diameter extrudate (precalcined at 1200.degree. F.) having 60% of its total pore volume distributed in pores having diameters between 50 and 200 A is impregnated by pore saturation with a solution of 90 gm of analytical reagent grade manganese chloride dissolved in 90 ml of deionized water. After contacting the alumina extrudate for 30 minutes, the excess solution is filtered off. The catalyst is then dried at 230.degree. F. overnight and calcined in air at 900.degree. F. for 2 hours. The catalyst so formed will contain between 11 and 13 weight-percent manganese (see Examples III, IV and VI hereinafter).
100 gm (dry basis) of granular, uncalcined gamma alumina having 60% of its total pore volume in pores having diameters between 50 and 175 A is mulled with a solution of Mn(NO.sub.3).sub.2. The solution is made by dissolving 202 gm of analytical reagent grade Mn(NO.sub.3).sub.2 in deionized water and then diluting the solution formed with more deionized water until the final solution has a volume of 1000 ml. The paste so produced is extruded through a 1/16 inch die. The extrudates are then calcined at 1200.degree. F. This catalyst will contain about 6 to 7 weight-percent manganese.