PROCESS FOR THE PREPARATION OF IMPROVED HYDROCONVERSION CATALYSTS AND CATALYSTS THUS PREPARED

Abstract: Process for preparing supported hydroconversion cata­ lysts having improved hydrodenitrification activity contain­ ing catalytically active amounts of Group VIII and/or Group VIB metals incorporated on a support, and particularly those containing nickel and molybdenum on alumina, which com­ prises adding from about 0.5 to 15 %wt of molybdenum and/­ or tungsten carbonyls to said catalysts by sublimation at el­ evated temperature and drying and calcining said metal car­ bony impregnated catalysts.

Description: This invention relates to a process for preparing supported hydroconversion catalysts, particularly with respect to improved hydrodenitrification (HDN) activity. Considerable research has been undertaken to develop and commercialize new, cost effective highly active hydroconversion catalysts for large volume first stage hydrocracking and catalytic cracking feed hydrotreater applications. The inclusion of significant amounts of 535 °C⁺ residual components, including cracked stocks, in the hydrocarbon feed to these processes has caused severe activity and stability problems for the catalysts currently used commercially in these applications. The growing demand for new catalysts for up-grading such poor quality feedstocks has led to the discovery of improved catalysts by a special technique for adding additional catalytically active metals onto supported catalysts. Methods for preparing supported hydrogenation metal catalysts which are suitable starting points for the instant invention are well-known. In U.S. patent specification 3,629,146, for example, a method is disclosed for preparing a supported catalyst containing high catalytic metal concentrations in a single aqueous impregnation from a stabilized solution. In U.S. patent specification 3,094,480 it is described that the denitrogenation activity of cobalt oxide-molybdenum oxide catalysts can be improved by raising the Mo-content from the conventional range to the 8.2-13.5 %wt range, which metals are deposited on the support by impregnation, coprecipitation or co-impregnation. It is also known to combine molybdenum carbonyls with alumina to prepare a catalyst for the metathesis of olefins(J. Mol. Catalysis, 1 ,(1975/76/)77-84). Surprisingly, it has now been found that the hydrodenitrification activity of commercial hydrotreating catalysts can be further improved by adding small amounts of molybdenum and/or tungsten carbonyls to said catalysts by sublimation. The present invention thus relates to a process for preparing supported hydroconversion catalysts having improved hydrodenitrification activity which catalysts contain catalytically active amounts of at least one Group VIII and at least one Group VIB metal incorporated into a suitable support, which comprises adding from 0.5 to 15 %wt of molybdenum and/or tungsten carbonyls to said catalysts by sublimation at elevated temperature and drying and calcining said metal carbonyl impregnated catalysts. The invention further relates to supported hydroconversion catalysts with improved hydrodenitrification activity prepared in this manner. This invention is applicable to supported hydroconversion catalysts which contain at least one Group VIII and at least one Group VIB metal of the Periodic Table incorporated into a support. Typically such catalysts will contain from 1 to 5 %wt nickel and/or cobalt as Group VIII metals and from 5 to 15 %wt molybdenum or tungsten as the Group VIB metal. Any of the usual catalyst supports are thought to be suitable for use in the process according to the invention. Suitable supports for the catalysts according to the invention include refractory oxides, such as alumina, silica and mixtures thereof. Crystalline synthetic zeolites such as aluminosilicates, iron silicates, gallium silicates and mixtures thereof may also be used as supports, preferably in combination with refractory oxide supports. A particularly preferred support is gamma-alumina which contains less than 1 %wt silica. Molybdenum and tungsten metal carbonyls are zero valent as far as the metals are concerned. Known metal carbonyls include to M(CO)₆, XM(CO)₃ where X can be benzene, toluene, cycloheptatriene, etc., and all of these carbonyls should be equally suitable for the invention. However, not all metal carbonyls appear to be equally effective. While molybdenum and tungsten carbonyls, added to a catalyst by the process according to the present invention, improve its HDN activity, chromium carbonyl, added by the same method, decreases the HDN activity. Therefore, the present invention is restricted to the use of molybdenum and tungsten carbonyls. It is preferred to dry the catalysts containing catalytically active amounts of at least one Group VIII and at least one Group VIB metal incorporated in a suitable support, before adding molybdenum and/or tungsten carbonyls onto said catalysts by sublimation. Suitably the molybdenum and/or tungsten carbonyls are sublimed onto the catalysts at reduced pressure. Previous efforts at improving the HDN activity of catalysts by incorporating additional molybdenum in the form of MoO₃ have been less successful. It was hoped that the interaction of a metal in a low oxidation state with a catalytic metal on a support might produce a unique metal-metal interaction and possibly high dispersion of the added metal. Although the interaction of metal carbonyls with alumina, silica, and zeolite supports has recently been discussed in the literature (A. Brenner and D.A. Hucul, J . Am . Chem . Soc ., 102, 2484 (1980)) the interaction of metals with metals on supports is believed to be novel. Initial exploratory studies showed that sublimation of Mo and W carbonyls onto a commercial hydrotreating catalyst produced and sold by Shell Chemical Co., U.S.A., had a profound effect on catalytic activity. By adding 1.5 %wt Mo to the catalyst, HDN activity was increased 16% relative to the base catalyst. From 0.5 %wt up to 15 %wt metal carbonyl added by the process according to the invention met with good results. However, it is preferred to add only from 1 %wt to 5 %wt by the process according to the invention. Suitably from 1 to 5 %wt molybdenum carbonyl compound (basis catalyst) is incorporated by sublimation, preferably at reduced pressure, on a catalyst comprising nickel and molybdenum compounds supported on alumina. A substantial increase in the hydrodenitrification (HDN) activity, relative to commercial catalysts, is required to commercialize a new hydroconversion catalyst. In an effort to develop such improved catalysts, many experimental catalysts were prepared and tested for HDN activity. The HDN activity test used in the testing program is designed to measure denitrification by using a standard set of conditions, including temperature, pressure, gas flow and liquid flow, for each catalyst. A standard commercial catalyst is tested under the same conditions as the experimental catalysts. The first order denitrification rate constant of the standard catalyst is defined as 1.00 and all experimental catalysts have activities measured relative to this standard. This method was used to determine the HDN improvement as shown in the Examples herein. Suitable hydroconversion conditions for processes using improved catalysts according to the present invention comprise a temperature of 350-420 °C; a total pressure of 75-200 bar; a partial hydrogen pressure of 60-200 bar; a space velocity of 0.4-1,5 kg oil/1 catalyst/hour; and a hydrogen feed rate of 250-2500 Nl/kg oil feed. The hydrodenitrification of heavy oil feeds according to the present process is preferably carried out under the following conditions: a temperature of 360-410 °C; a total pressure of 100-150 bar; a partial hydrogen pressure of 80-150 bar; a space velocity of 0.4-1.0 kg oil/1 catalyst/hour; and a hydrogen feed rate of 500-1500 Nl/kg oil feed. The hydrogen applied can be pure hydrogen or a hydrogen-containing gas, preferably one comprising more than 70% of hydrogen. The hydrogen-containing gas may also contain up to about 10% of hydrogen sulphide. It is preferred that the hydrocarbon oil feed streams contain less than 3 ppmw, and most preferably less than 1 ppmw of vanadium and nickel combined. In some cases it may be necessary to subject the hydrocarbon oil feed to a demetallization pre-treatment in order to reach these levels. The preferred catalysts used for a demetallization pre-treatment comprise 1-5 %wt of nickel and 5-15 %wt of molybdenum, both percentages based on total catalyst. The preferred molybdenum:nickel weight ratio lies between 3:1 and 6:1. These metals may be incorporated into the catalyst by any method known in the art, for example by impregnation of alumina in one or more stages with an aqueous solution containing one or more salts of the metals concerned. Suitable conditions for carrying out the demetallization pre-treatment comprise a temperature of 370-420 °C; a total pressure of 65-220 bar; a partial hydrogen pressure of 60-200 bar; a space velocity of 0.2-2 kg oil/1 catalyst/hour; and a hydrogen feed rate of 250-2500 Nl/kg oil feed. The gas streams separated from both the pre-treated and the converted hydrocarbon oils, as well as the residual fractions and the product obtained, can all be partially or completely recycled. The invention will now be illustrated by the following examples: Example 1 Six catalyst samples were prepared using a commercial Ni/Mo/Al₂O₃ hydrotreating catalyst, as a starting material. The starting material was prepared by first drying a sample of the catalyst, which was a 1.6 mm diameter extrudate, at 480 °C for two hours and then cooling it under nitrogen for 30 minutes. A weighed amount of extrudate was then placed in a round-bottom flask with an appropriate amount of molybdenum, tungsten or chromium carbonyls, whereby a desired additional catalytic metal content was impregnated onto the commercial catalyst by sublimation. The extrudates were placed on a rotovap under(2,6.10⁻³ bar) 2 mm Hg pressure and heated for 75 minutes at 80 °C. The finished catalyst samples were then obtained by drying and calcining in air at 480 °C for two hours. The percent weight increases in metal content of the catalyst samples after adding metals by sublimation are shown in Table 1. The metals added were assumed to be MoO₃, CrO₃ and WO₃ after calcining the respective catalysts. Catalysts A and E were prepared by subliming metal hexacarbonyls onto a dried catalyst by using 50 grams of a first sample of commercial hydrotreating catalyst. Catalyst B was prepared by using 300 grams of a second sample of commercial hydrotreating catalyst. Catalysts C, D and F were prepared by using 50 grams of the second sample of the commercial hydrotreating catalyst. These six "added metal" catalysts and the commercial hydrotreating catalyst were used to hydrotreat a sample of catalytically cracked heavy gas oil having feed properties shown in Table 1. All the catalysts were sulphided before the hydrotreating tests began by treatment with a H₂/H₂S (5 %v H₂S) gaseous mixture at elevated temperature (371 °C) for two hours. Catalyst A, which contained approximately 1.5 %wt additional Mo, showed an increase in HDN activity of 16% relative to the first sample of commercial catalyst. Catalyst B, which contained 3.3 %wt additional Mo, and was prepared from a larger batch of a second sample of commercial catalyst, was roughly equivalent in HDN activity to the first commercial catalyst. Catalyst C, which was prepared in the same manner as Catalyst A, but had the same 3.3 %wt Mo content as Catalyst B, showed about a 12% increase in HDN activity over the commercial catalyst. Catalyst D, which was prepared similar to Catalyst A, was not calcined prior to sulphiding and testing. This catalyst showed an 8% increase in HDN activity as compared to the commercial catalyst. Catalysts E and F were prepared starting with 50 gram samples of the second sample of commercial catalyst. Catalyst E, which contained chromium, was significantly less active for hydrogenation, hydrodenitrification and hydrodesulphurization than the commercial catalyst. Catalyst F, which contained tungsten, showed an increase of 9% in HDN activity over the commercial catalyst.

Claims: A process for preparing supported hydroconversion catalysts having improved hydrodenitrification activity which catalysts contain catalytically active amounts of at least one Group VIII and at least one Group VIB metal incorporated into a suitable support, which comprises adding from 0.5 to 15 %wt of molybdenum and/or tungsten carbonyls to said catalysts by sublimation at elevated temperature; drying and calcining said metal carbonyl impregnated catalysts. A process according to claim 1, wherein from 1 to 5 %wt metal carbonyl is added to said catalyst. A process according to claim 1 or 2, wherin the Group VIII metal incorporated into said support is nickel and/or cobalt and the Group VIB metal is molybdenum and/or tungsten. A process according to any one of claims 1-3, wherein a support is used selected from the group consisting of alumina, silica or mixtures thereof, which support may also include a crystalline silicate zeolite. A process according to any one of claims 1-4, wherein said hydroconversion catalyst is dried before adding said carbonyl and molybdenum and/or tungsten hexacarbonyl compound is sublimed onto said catalyst at reduced pressure. A process according to any one of claims 1-5, wherein said metal carbonyl impregnated catalyst is sulphided before use in said hydroconversion process. A process according to claim 1, wherein said hydroconversion catalyst comprises nickel and molybdenum compounds supported on alumina and from 1 to 5 %wt molybdenum carbonyl compound (basis catalyst) is incorporated thereon by sublimation at reduced pressure. A supported hydroconversion catalyst with improved hydrodenitrification activity prepared from a composite obtained by incorporating catalytically active amounts of at least one Group VIII and at least one Group VIB metal into a suitable support, drying and calcining the support after incorporating said metals thereinto, impregnating the composite with from 0.5 to 15 %wt of molybdenum and/or tungsten as metal carbonyls by sublimation at elevated temperature and reduced pressure; drying and calcining said metal carbonyl impregnated catalyst. A catalyst according to claim 8, wherein said catalytically active Group VIII metal is nickel and/or cobalt and said Group VIB metal is molybdenum and/or tungsten. A catalyst according to claim 8 or 9, having a support selected from the group consisting of alumina, silica and mixtures thereof. A catalyst according to any one of claims 8-10, wherein said composite is dried and then impregnated by sublimation of from 1 to 5 %wt of molybdenum and/or tungsten hexacarbonyl onto said catalyst at reduced pressure. A catalyst according to any one of claims 8-11, wherein said metal carbonyl is converted to a sulphide before said catalyst is used in a hydroconversion process. A catalyst according to claim 8, wherein said composite comprises nickel and molybdenum compounds supported on alumina and wherein the molybdenum content added to the catalyst by sublimation of a molybdenum hexacarbonyl compound at reduced pressure is from 1 to 5 %wt.

Inventors: RYAN, ROBERT CHARLES
Applicants: SHELL INTERNATIONALE RESEARCH MAATSCHAPPIJ B.V.
Application year: 1985
Main classification: B01J37
IPC codes: C10G45, B01J23, B01J37, B01J31