초록

A novel method is disclosed for the hydroconversion of a heavy hydrocarbon feedstock wherein the feed is partially hydroconverted and demetalized in the presence of a catalytic additive and then the hydroconversion is completed in an ebullent bed reactor system.

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1. A method for the hydroconversion of a heavy hydrocarbon feedstock comprising: (a) demetallizing and partially converting a heavy hydrocarbon feedstock comprising a fraction having a boiling point higher than 520° C. by a process comprising: (i) admixing with said heavy hydrocarbon feedstock

1. A method for the hydroconversion of a heavy hydrocarbon feedstock comprising: (a) demetallizing and partially converting a heavy hydrocarbon feedstock comprising a fraction having a boiling point higher than 520° C. by a process comprising: (i) admixing with said heavy hydrocarbon feedstock an additive comprising (1) a water or oil soluble transition metal compound and (2) an ultra fine powder selected from fine ceramics and carbonaceous substances having an average particle size of from about 5 to 1000 mμ; (ii) hydroconverting the admixture in a reactor int he presence of a hydrogen-containing gas at a temperature ranging from about 300° to about 550° C., a pressure ranging from about 30 Kg/cm 2 to about 300 Kg/cm 2, and a residence time ranging from about 1 minute to about 2 hours such that the percentage conversion is less than about 60%; (iii) removing a partially converted effluent at a conversion of less than about 60% from the reactor; (b) feeding said partially converted effluent to a hydrogenation zone wherein effluent is introduced into a catalyst containing reaction vessel; and (c) recovering a converted hydrocarbon oil. 2. A method as defined in clam 1 wherein said heavy hydrocarbon feedstock is selected from crude oil, atmospheric residue of a crude oil, vacuum residue of a crude oil, shale oil, tar sand oil, liquefied coal oil and mixtures of any of the foregoing. 3. A method as defined in claim 1 wherein said additive comprises a suspension in a hydrocarbon oil of (1) a solution comprising at least one molybdenum compound selected from the group consisting of a heteropolyacid containing a molybdenum atom as a polyatom and a transition metal salt thereof, dissolved in an oxygen-containing polar solvent; and (2) a carbon black having an average particle size of from about 1 to 200 nm; wherein in said suspension the weight mount of said molybdenum compound calculated as weight of molybdenum is smaller than the weight amount of said carbon black. 4. A method as define in claim 3 wherein said oxygen-containing polar solvent is water. 5. A method as define in claim 1 wherein said percentage conversion in said step (a)(ii) is from about 40 to about 60%. 6. A method as define in claim 5 wherein said percentage conversion in said step (a)(ii) is from about 50 to about 60%. 7. A method as define in claim 1 further comprising quenching the partially converted effluent in step (a)(iii). 8. A method as defined in claim 1 wherein said catalyst contained in the reaction vessel of step (b) is selected from oxides or sulfides of Group VIB or Group VIII metals. 9. A method as define in claim 8 wherein said catalyst is selected from the group consisting of cobalt-molybdate, nickel-molybdate, cobalt-nickel-molybdate, tungsten-nickel sulfide, tungsten-sulfide and mixtures of any of the foregoing. 10. A method as defined in claim 1 wherein said hydrogenation zone (b) operates at a temperature ranging from about 650° to about 900 F., a pressure ranging from about 500 psig to about 4000 psig, and a hydrogen partial pressure of from about 500 to about 3000 psia. 11. A method as define in claim 1 wherein said water soluble transition metal compound comprises a compound selected from the group consisting of carbonates, carboxylates, sulfates, nitrates, hydroxides, halogenides and ammonium or alkali metal salts of transition metals and mixture of any of the foregoing. 12. A method as define in claim 11 wherein said transition metal is selected from the group consistent of vanadium, chromium, iron, cobalt, nickel, copper, molybdenum, tungsten and mixtures thereof. 13. A method as define in claim 12 wherein said water soluble transition metal compound comprises ammonium heptamolybdenate. 14. A method as define in claim 1 wherein said oil soluble transition metal compound comprises a transition metal compound selected form the group consisting of organic carboxylic acid compounds, organic alkoxy compounds, diketone compounds, carbonyl compounds, organic sulfonic acid or organic sulfinic compounds, xanthinic acid compounds, amine compounds, nitrile or isonitrile compounds, phosphine compounds and mixtures of any of the foregoing. 15. A method as define in claim 14 wherein said transition metal is selected from the group consisting of vanadium, chromium, iron, cobalt, nickel, copper, molybdenum, tungsten and mixtures thereof. 16. A method as define in claim 15 wherein said oil-soluble transition metal compounds are transition metal compounds of salts of aliphatic carboxylic acids. 17. A method as define in claim 1 wherein said carbonaceous ultra fine powder comprises carbon black. 18. A method as define in claim 1 wherein said ultra fine ceramics comprises ultra fine particulate silicic acid, silicate, alumina, titania and mixtures of any of the foregoing. 19. A method for the hydroconversion of a heavy hydrocarbon feedstock comprising: (a) demetallizing and partially converting a heavy hydrocarbon feedstock comprising a fraction having a boiling point higher than 520° C. by a process comprising (i) admixing with said heavy hydrocarbon feedstock an additive comprising a suspension in a hydrocarbon oil of (1) a solution comprising at least one molybdenum compound selected from the group consisting of a heteropolyacid containing a molybdenum atom as a polyatom and a transition metal salt thereof, dissolved in an oxygen-containing polar solvent; (2) a carbon black having an average particle size of from about 1 to 200 nm; and further comprising adding sulfur or a sulfur compound to said suspension in an amount of two gram atoms or more of sulfur per gram atom of molybdenum, and dispersing said sulfur or sulfur compound in said suspension; (ii) hydroconverting the admixture in a reactor in the presence of a hydrogen-containing gas at a temperature ranging from about 300° to about 550° C., a pressure ranging from about 30 Kg/cm 2 to about 300 Kg/cm 2, and a residence time ranging from about 1 minute to about 2 hours such that the percentage conversion is less than about 60°; (iii) removing a partially converted effluent from the reactor; (b) feeding said partially converted effluent to a hydrogenation zone wherein the partially converted effluent is introduced into a catalyst containing reaction vessel; and (c) recovering a converted hydrocarbon oil. 20. A method for the hydroconversion of a heavy hydrocarbon feedstock comprising (a) demetalizing and partially converting a heavy hydrocarbon feedstock comprising a fraction having a boiling point higher than 520° C. by a process comprising: (i) admixing with said heavy hydrocarbon feedstock an additive comprising (1) a water or oil soluble transition metal compound and (2) an ultra fine powder selected from fine ceramics and carbonaceous substances having an average particle size of from about 5 to 1000 mμ; (ii) hydroconverting the admixture in a reactor int he presence of a hydrogen-containing gas at a temperature ranging from about 300° to about 550° C., a pressure ranging from about 30 kg/cm 2 to about 300 kg/cm 2, and a residence time ranging from about 1 minute to about 2 hours wherein the percentage conversion is less than about 60%; (iii) removing a partially converted effluent at a conversion of less than about 60% from the reactor; (b) feeding said partially converted effluent to a hydrogenation zone wherein effluent is introduced into a catalyst containing reaction vessel and hydroconverting at a temperature ranging form about 750° to about 850° F. 21. A method for the hydroconversion of a heavy hydrocarbon feedstock comprising: (a) demetallizing and partially converting a heavy hydrocarbon feedstock comprising a fraction having a boiling point higher than 520° C. by a process comprising: (i) admixing with said heavy hydrocarbon feedstock an additive comprising (1) a water or oil soluble transition metal compound and (2) an ultra fine powder selected from fine ceramics and carbonaceous substances having an average particle size of from about 5 to 1000 mμ; (ii) hydroconverting the admixture in a reactor int he presence of a hydrogen-containing gas at a temperature ranging from about 300° to about 550° C., a pressure ranging from about 30 kg/cm 2 to about 300 kg/cm 2, and a residence time ranging from about 1 mixture to about 2 hours such that the percentage conversion is less than about 60%; (iii) removing a partially converted effluent at a conversion of less than about 60% from the reactor; (b) feeding said partially converted effluent to a hydrogenation zone wherein the effluent is introduced into the lower end of a generally vertical reaction vessel having a static volume catalyst bed wherein said catalyst bed is placed in random motion within the fluid hydrocarbon and whereby the catalyst bed is expanded to a volume greater than the static volume of the catalyst bed; and (c) recovering a converted hydrocarbon oil. 22. In a method for the hydroconversion of a heavy hydrocarbon feedstock comprising a conversion step of adding to the heavy hydrocarbon an additive comprising a water or oil soluble transition metal compound and an ultra fine powder selected from fine ceramics and carbonaceous substances having an average particle side of from about 5 to about 1000 mμ and converting the admixture in a reactor int he presence of a hydrogen-containing gas at a temperature ranging from about 300° to about 550° C. and a pressure ranging from about 30 kg/cm 2 to about 300 kg/cm 2 ; the improvement comprising: carrying out said conversion step to a conversion of less than about 60% an removing the partially converted effluent at a conversion of less than about 60% from said reactor; and completing the conversion said hydroconversion by hydrogenating said partially converted effluent in a hydrogenation zone comprising introducing said partially converted effluent into a catalyst containing vessel and hydrogenating said partially converted effluent.