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The invention provides an unsupported catalyst composition which comprises one or more Group VIb metals, one or more Group VIII metals, one or more zeolites, and, optionally, a refractory oxide material. A (co)precipitation preparation process is described and also use of the composition in hydrocra

The invention provides an unsupported catalyst composition which comprises one or more Group VIb metals, one or more Group VIII metals, one or more zeolites, and, optionally, a refractory oxide material. A (co)precipitation preparation process is described and also use of the composition in hydrocracking.

대표청구항 ▼

That which is claimed is: 1. An unsupported hydrocracking catalyst composition having improved mono-aromatics hydrogenation activity and selectivity for middle distillates, which comprises: a Group VIb metal and a non-noble Group VIII metal, wherein the total amount of said Group VIb metal and said

That which is claimed is: 1. An unsupported hydrocracking catalyst composition having improved mono-aromatics hydrogenation activity and selectivity for middle distillates, which comprises: a Group VIb metal and a non-noble Group VIII metal, wherein the total amount of said Group VIb metal and said non-noble Group VIII metal present in said unsupported catalyst composition is in the range of from 15 to 99 wt % on an oxide basis and based on the total unsupported catalyst composition, and wherein the molar ratio of said non-noble Group VIII metal to Group VIb metal is in the range of from 0.5:1 to 3:1, and a zeolite that is present in said unsupported catalyst composition ranging from 20 to 85 wt % based on the total unsupported catalyst composition, wherein said unsupported catalyst composition is prepared by the co-precipitation of said Group VIb metal, said non-noble Group VIII metal, and said zeolite at one and the same time, and wherein from 4 to 25 wt % of said Group VIb metal is incorporated into said pores of said co-precipitated zeolite, said unsupported hydrocracking catalyst composition having improved mono-aromatics hydrogenation activity and selectivity for middle distillates compared to hydrocracking catalyst compositions containing similar amounts of Group VIb metal, non-noble Group VIII metal, and zeolite, but not prepared by co-precipitation of all three of these components at one and the same time. 2. A catalyst composition as claimed in claim 1, wherein the zeolite is an ultrastable or very ultrastable zeolite Y present in an amount in the range of from 20 to 80 wt %, based on the total composition. 3. A catalyst composition as claimed in claim 2, further comprising: a refractory oxide present in said unsupported catalyst composition in an amount in the range of from 0 to 40 wt %, basis total composition. 4. A catalyst composition as claimed in claim 3, wherein the refractory oxide is either silica or titania and is present in said unsupported catalyst composition in an amount in the range of from 5 to 40 wt %, basis total composition. 5. A catalyst composition as claimed in claim 4, wherein said non-noble Group VIII metal is nickel and said Group VIb metal is molybdenum, which are present in a molar ratio of nickel to molybdenum in the range of from 0.5:1 to 2.5:1. 6. A catalyst composition as claimed in claim 5, wherein the amount of molybdenum present in the zeolite pores is in the range of from 4, to 25 wt %, basis the composition in oxidic form. 7. A process for converting a hydrocarbonaceous feedstock into lower boiling materials, which comprises contacting the feedstock at elevated temperature in the presence of a catalyst composition as claimed in claim 1. 8. A process as claimed in claim 7, wherein the catalyst composition has been sulfided utilising a liquid phase sulfidation agent. 9. An unsupported hydrocracking catalyst composition as recited in claim 1, wherein: said non-noble Group VIII metal is selected from the group consisting of nickel, cobalt and a combination thereof; said Group VIB metal is selected from the group consisting of molybdenum, tungsten and a combination thereof; and said zeolite is selected from the group consisting of zeolite Y, ZSM-5, ZSM-12, and zeolite beta. 10. The unsupported hydrocracking catalyst composition as recited in claim 9, wherein the total amount of Group VIII metal and Group VIB metal in said unsupported mixture is in the range of from 20 to 80 wt. %, on an oxide basis. 11. The unsupported hydrocracking catalyst composition as recited in claim 10, wherein the molar ratio of said non-noble Group VIII metal to said Group VIB metal is in the range of from 0.5:1 to 3:1. 12. The unsupported hydrocracking catalyst composition as recited in claim 11, wherein the content of said zeolite in said unsupported mixture is in the range of from 20 to 85 wt %. 13. The unsupported hydrocracking catalyst composition as recited in claim 12, wherein said unsupported mixture further comprises a refractory oxide material selected from the group consisting of silica, titania, amorphous silica-alumina, and alumina. 14. The unsupported hydrocracking catalyst composition as recited in claim 13, wherein said refractory oxide material is present in said unsupported mixture in an amount upwardly to 70 wt. %. 15. The unsupported hydrocracking catalyst composition as recited in claim 12, wherein said unsupported mixture has an absence of alumina. 16. The unsupported hydrocracking catalyst composition as recited in claim 12, wherein said unsupported mixture has a substantial absence of a refractory oxide material. 17. A hydrocracking process comprising: contacting under suitable conversion reaction conditions a feedstock comprising hydrocarbons having a boiling point of at least 330° C. with the unsupported hydrocracking catalyst composition of claim 1 and providing a conversion product. 18. A method for the preparation of an unsupported hydrocracking catalyst composition having improved mono-aromatics hydrogenation activity and selectivity for middle distillates, wherein said method comprises: combining a Group VIb metal compound, a non-noble Group VIII metal compounds, and a zeolite, at one and the same time, in the presence of a protic liquid and an alkali compound to thereby provide a mixture; forming a precipitate; and recovering said precipitate that comprises said unsupported catalyst composition that comprises said Group VIb metal and said non-noble Group VIII metal that are present in a total amount in said unsupported catalyst composition in the range of from 15 to 99 wt %, on an oxide basis and based on the total unsupported catalyst composition and at a molar ratio of said non-noble Group VIII metal to said Group VIb metal in the range of from 0.5:1 to 3:1, and said zeolite that is present in the range of from 4 to 85 wt % based on said unsupported catalyst composition, and wherein from 4 to 25 wt % of said Group VIb metal is incorporated into said the pores of said precipitated zeolite, said unsupported hydrocracking catalyst composition having improved mono-aromatics hydrogenation activity and selectivity for middle distillates compared to hydrocracking catalyst compositions containing similar amounts of Group VIb metal, non-noble Group VIII metal and zeolite, but not prepared by coprecipitation of all three of these components at one and the same time. 19. A process as claimed in claim 18, wherein during precipitation the mixture of components has a pH of at least 6.0. 20. A process as claimed in claim 19, wherein at least one of the metals compounds is partly in the solid state and partly in dissolved state. 21. A process as claimed in claim 20, further comprising: aging said mixture at a temperature in the range of from 20 to 95° C. for a minimum of 10 minutes prior to recovering said precipitate. 22. A process as claimed in claim 21, wherein said precipitate is recovered by spray drying. 23. A method as recited in claim 18, further comprising: drying said recovered precipitate at a drying temperature in the range of from 20° C. to 200° C. to provide a dried precipitate. 24. A method as recited in claim 23, further comprising: calcining said dried precipitate at a calcination temperature in the range of from 100 to 600° C. 25. A method as recited in claim 24, wherein said non-noble Group VIII metal is selected from the group consisting of nickel, cobalt and a combination thereof; said Group VIB metal is selected from the group consisting of molybdenum, tungsten and a combination thereof; and said zeolite is selected from the group consisting of zeolite Y, ZSM-5, ZSM-12, and zeolite beta. 26. An unsupported hydrocracking catalyst composition having improved mono-aromatics hydrogenation activity and selectivity for middle distillates, which comprises: 13 to 26 wt % nickel, 25 to 50 wt % molybdenum, and from 20 to 73 wt % zeolite VUSY, wherein the total amount of molybdenum and nickel present in said unsupported hydrocracking catalyst composition is in the range of from 20 to 80 wt % on an oxide basis and based on the total composition, wherein the molar ratio of nickel to molybdenum is in the range of from 0.5:1 to 2.0:1, based on the total composition, and wherein said unsupported catalyst composition is prepared by the coprecipitation of a nickel compound, a molybdenum compound and said zeolite VUSY, at one and the same time, under conditions that from 10 to 25 wt % of molybdenum is incorporated into the pores of said coprecipitated zeolite VUSY, said unsupported hydrocracking catalyst composition having improved mono-aromatics hydrogenation activity and selectivity for middle distillates compared to hydrocracking catalyst compositions containing similar amounts of nickel, molybdenum and zeolite VUSY, but not prepared by coprecipitation of all three of these components at one and the same time.