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An ebullated bed hydroprocessing system, and also a method for upgrading a pre-existing ebullated bed hydroprocessing system, involves introducing a colloidal or molecular catalyst, or a precursor composition capable of forming the colloidal or molecular catalyst, into an ebullated bed reactor. The

An ebullated bed hydroprocessing system, and also a method for upgrading a pre-existing ebullated bed hydroprocessing system, involves introducing a colloidal or molecular catalyst, or a precursor composition capable of forming the colloidal or molecular catalyst, into an ebullated bed reactor. The colloidal or molecular catalyst is formed by intimately mixing a catalyst precursor composition into a heavy oil feedstock and raising the temperature of the feedstock to above the decomposition temperature of the precursor composition to form the colloidal or molecular catalyst in situ. The improved ebullated bed hydroprocessing system includes at least one ebullated bed reactor that employs both a porous supported catalyst and the colloidal or molecular catalyst to catalyze hydroprocessing reactions involving the feedstock and hydrogen. The colloidal or molecular catalyst provides catalyst in what would otherwise constitute catalyst free zones within the ebullated bed hydroprocessing system. Asphaltene or other hydrocarbon molecules too large to diffuse into the pores of the supported catalyst can be upgraded by the colloidal or molecular catalyst. A slurry phase reactor may be positioned upstream from one or more ebullated bed reactors or converted from a pre-existing ebullated bed reactor.

대표청구항 ▼

What is claimed is: 1. A method of upgrading a pre-existing ebullated bed hydroprocessing system in order to reduce formation of coke and/or sediment, comprising: (a) operating a pre-existing ebullated bed hydroprocessing system comprising one or more ebullated bed reactors, each of which comprises

What is claimed is: 1. A method of upgrading a pre-existing ebullated bed hydroprocessing system in order to reduce formation of coke and/or sediment, comprising: (a) operating a pre-existing ebullated bed hydroprocessing system comprising one or more ebullated bed reactors, each of which comprises a liquid hydrocarbon phase, a solid phase comprised of an expanded bed of a porous supported catalyst, a gaseous phase comprised of hydrogen gas, and catalyst free zones above and below the expanded bed of the porous supported catalyst; (b) mixing an oil-soluble catalyst precursor composition with a hydrocarbon oil diluent at a temperature below which a substantial portion of the catalyst precursor composition begins to decompose to form a diluted catalyst precursor mixture; (c) after forming the diluted catalyst precursor mixture and prior to heating the catalyst precursor composition to a temperature at which a substantial portion of the catalyst precursor composition decomposes, mixing the diluted catalyst precursor mixture with a heavy oil feedstock to form a conditioned feedstock comprised of a mixture of the heavy oil feedstock and diluted catalyst precursor mixture, wherein the conditioned feedstock contains from about 10 ppm to about 500 ppm catalyst metal by weight of the heavy oil feedstock prior to substantial decomposition of the catalyst precursor composition in order to dilute the catalyst precursor composition with the heavy oil feedstock prior to substantial decomposition of the catalyst precursor composition and in situ formation of a colloidal or molecular catalyst within the heavy oil feedstock upon further heating and decomposition of the catalyst precursor composition; (d) heating the catalyst precursor composition within the heavy oil feedstock in order to decompose the catalyst precursor composition and form a colloidal or molecular catalyst having a particle size less than 100 nm in situ within the heavy oil feedstock; (e) introducing the heavy oil feedstock from (c), optionally after (d), into at least one ebullated bed reactor of the pre-existing ebullated bed hydroprocessing system to form an upgraded ebullated bed hydroprocessing system comprising the one or more ebullated bed reactors and in which the colloidal or molecular catalyst is dispersed throughout the liquid hydrocarbon phase including what were previously catalyst free zones in the at least one ebullated bed reactor of the pre-existing ebullated bed hydroprocessing system; and (f) operating the upgraded ebullated bed hydroprocessing system to form a hydroprocessed material, the colloidal or molecular catalyst catalyzing beneficial hydroprocessing reactions throughout the liquid hydrocarbon phase, including what were previously catalyst free zones in the pre-existing ebullated bed hydroprocessing system, thereby reducing formation of coke or sediment in the upgraded ebullated bed hydroprocessing system compared to the pre-existing ebullated bed hydroprocessing system. 2. A method as defined in claim 1, the pre-existing ebullated bed hydroprocessing system being an LC-Fining or an H-Oil ebullated bed hydroprocessing system. 3. A method as defined in claim 1, wherein the catalyst precursor composition comprises an organo-metallic compound or complex. 4. A method as defined in claim 1, the catalyst precursor composition comprising at least one transition metal and at least one organic moiety comprising or derived from octanoic acid, 2-ethylhexanoic acid, naphthanic acid, pentacarbonyl, or hexacarbonyl. 5. A method as defined in claim 4, the catalyst precursor composition comprising at least one of molybdenum 2-ethylhexanoate, molybdenum naphthanate, molybdenum hexacarbonyl, vanadium octoate, vanadium naphthanate, or iron pentacarbonyl. 6. A method as defined in claim 1, wherein the heavy oil feedstock comprises at least one of heavy crude oil, oil sand bitumen, atmospheric tower bottoms, vacuum tower bottoms, resid, visbreaker bottoms, coal tar, heavy oil from oil shale, or liquefied coal. 7. A method as defined in claim 1, the heavy oil feedstock comprising at least about 5% by weight of asphaltenes. 8. A method as defined in claim 7, at least a portion of the colloidal or molecular catalyst being associated with at least a portion of the asphaltenes in the heavy oil feedstock, the colloidal or molecular catalyst associated with the asphaltenes in the heavy oil feedstock promoting reactions between free radicals formed from the asphaltenes and hydrogen within the ebullated bed reactor during (f), the reactions between the free radicals formed from the asphaltenes and hydrogen reducing or eliminating formation of coke precursors and sediment. 9. A method as defined in claim 1, wherein the hydrocarbon oil diluent comprises at least one of vacuum gas oil, decant oil, cycle oil, or light gas oil. 10. A method as defined in claim 1, the ratio of catalyst precursor composition to hydrocarbon oil diluent being in a range of about 1:500 to about 1:1. 11. A method as defined in claim 1, the ratio of catalyst precursor composition to hydrocarbon oil diluent being in a range of about 1:150 to about 1:2. 12. A method as defined in claim 1, the ratio of catalyst precursor composition to hydrocarbon oil diluent being in a range of about 1:100 to about 1:5. 13. A method as defined in claim 1, the hydrocarbon oil diluent and catalyst precursor composition being mixed at temperature in a range of about 25�� C. to about 250�� C., the diluted catalyst precursor mixture and heavy oil feedstock being mixed at a temperature in a range of about 25�� C. to about 350�� C., the conditioned feedstock being heated to a temperature in a range of about 275�� C. to about 450�� C. in order to form the colloidal or molecular catalyst in (d). 14. A method as defined in claim 1, the hydrocarbon oil diluent and catalyst precursor composition being mixed at temperature in a range of about 50�� C. to about 200�� C., the diluted catalyst precursor mixture and heavy oil feedstock being mixed at a temperature in a range of about 50�� C. to about 300�� C., the conditioned feedstock being heated to a temperature in a range of about 350�� C. to about 440�� C. in order to form the colloidal or molecular catalyst in (d). 15. A method as defined in claim 1, the hydrocarbon oil diluent and catalyst precursor composition being mixed at temperature in a range of about 75�� C. to about 150�� C., the diluted catalyst precursor mixture and heavy oil feedstock being mixed at a temperature in a range of about 75�� C. to about 250�� C., the conditioned feedstock being heated to a temperature in a range of about 375�� C. to about 420�� C. in order to form the colloidal or molecular catalyst in (d). 16. A method as defined in claim 1, the hydrocarbon oil diluent and catalyst precursor composition being mixed for a time period in a range of about 1 second to about 20 minutes, and the diluted catalyst precursor mixture and heavy oil feedstock being mixed for a time period in a range of about 1 second to about 20 minutes prior to substantial decomposition of the catalyst precursor composition and formation of the molecular or colloidal catalyst. 17. A method as defined in claim 1, the hydrocarbon oil diluent and catalyst precursor composition being mixed for a time period in a range of about 5 seconds to about 10 minutes, and the diluted catalyst precursor mixture and heavy oil feedstock being mixed for a time period in a range of about 5 seconds to about 10 minutes prior to substantial decomposition of the catalyst precursor composition and formation of the molecular or colloidal catalyst. 18. A method as defined in claim 1, the hydrocarbon oil diluent and catalyst precursor composition being mixed for a time period in a range of about 20 seconds to about 3 minutes, and the diluted catalyst precursor mixture and heavy oil feedstock being mixed for a time period in a range of about 20 seconds to about 5 minutes prior to substantial decomposition of the catalyst precursor composition and formation of the molecular or colloidal catalyst. 19. A method as defined in claim 1, wherein (d) occurs before (e). 20. A method as defined in claim 1, wherein (d) occurs during or after (e). 21. A method as defined in claim 1, the catalyst metal in the colloidal or molecular catalyst having a concentration in a range of about 10 ppm to about 500 ppm by weight of the heavy oil feedstock in (e). 22. A method as defined in claim 1, the catalyst metal in the colloidal or molecular catalyst having a concentration in a range of about 25 ppm to about 300 ppm by weight of the heavy oil feedstock in (e). 23. A method as defined in claim 1, the catalyst metal in the colloidal or molecular catalyst having a concentration in a range of about 50 ppm to about 175 ppm by weight of the heavy oil feedstock in (e). 24. A method as defined in claim 1, wherein the colloidal or molecular catalyst comprises molybdenum disulfide. 25. A method as defined in claim 1, further comprising reducing the concentration of the porous supported catalyst within one or more of the ebullated bed reactors of the upgraded ebullated bed hydroprocessing system. 26. A method as defined in claim 1, further comprising beginning to operate a slurry phase reactor upstream from at least one ebullated bed reactor of the pre-existing ebullated bed hydroprocessing system, the slurry phase reactor comprising the heavy oil feedstock and the colloidal or molecular catalyst as a liquid phase and hydrogen gas as a gaseous phase. 27. A method as defined in claim 26, the slurry phase reactor comprising a new reactor that is constructed upstream from the at least one ebullated bed reactor of the pre-existing ebullated bed hydroprocessing system. 28. A method as defined in claim 26, the slurry phase reactor comprising a former ebullated bed reactor of the pre-existing ebullated bed hydroprocessing system that has been converted into the slurry phase reactor of the upgraded ebullated bed hydroprocessing system by eliminating the porous supported catalyst from the former ebullated bed reactor. 29. A method as defined in claim 26, the slurry phase reactor comprising a recycle channel, recycling pump, and a distributor grid plate. 30. A method as defined in claim 1, further comprising introducing the hydroprocessed feedstock from (f) into a guard bed reactor in order to remove at least a portion of the colloidal or molecular catalyst and metal impurities from the hydroprocessed feedstock and thereby form a cleaned material, the guard bed reactor being added as part of the method of upgrading the pre-existing ebullated bed hydroprocessing system. 31. A method as defined in claim 1, further comprising introducing supplemental colloidal or molecular catalyst into an upgraded feedstock removed from an upstream ebullated bed reactor prior to introducing the upgraded feedstock into a downstream ebullated bed reactor. 32. An upgraded ebullated bed hydroprocessing system resulting from the method of claim 1. 33. A method of upgrading a pre-existing ebullated bed hydroprocessing system in order to reduce formation of coke and/or sediment, comprising: (a) operating a pre-existing ebullated bed hydroprocessing system comprising one or more ebullated bed reactors, each of which comprises a liquid hydrocarbon phase, a solid phase comprised of an expanded bed of a porous supported catalyst, a gaseous phase comprised of hydrogen gas, and catalyst free zones above and below the expanded bed of the porous supported catalyst; and (b) following (a), constructing and operating one or more slurry phase reactors upstream from at least one ebullated bed reactor of the pre-existing ebullated bed hydroprocessing system in order to form an upgraded feedstock from a heavy oil feedstock, the one or more slurry phase reactors comprising a liquid phase comprised of the heavy oil feedstock and a colloidal or molecular catalyst having a particle size less than 100 nm and a gaseous phase comprised of hydrogen gas, the colloidal or molecular catalyst being prepared by: (1) intimately mixing a catalyst precursor composition into the heavy oil feedstock prior to heating the catalyst precursor composition to a temperature at which a substantial portion of the catalyst precursor composition decomposes so as to form a conditioned feedstock comprised of the heavy oil feedstock and intimately mixed catalyst precursor composition, wherein the conditioned feedstock contains from about 10 ppm to about 500 ppm catalyst metal by weight of the heavy oil feedstock prior to substantial decomposition of the catalyst precursor composition in order to dilute the catalyst precursor composition with the heavy oil feedstock prior to substantial decomposition of the catalyst precursor composition and in situ formation of the colloidal or molecular catalyst upon heating the heavy oil feedstock to above the decomposition temperature of the catalyst precursor composition; and (2) heating the catalyst precursor composition in order to decompose the catalyst precursor composition and form the colloidal or molecular catalyst in situ within the heavy oil feedstock; and (c) introducing the upgraded feedstock and colloidal or molecular catalyst from the slurry phase reactor into at least one ebullated bed reactor of the pre-existing ebullated bed hydroprocessing system to form an upgraded ebullated bed hydroprocessing system comprising the one or more slurry phase reactors in combination with the one or more ebullated bed reactors, the colloidal or molecular catalyst catalyzing beneficial hydroprocessing reactions throughout the liquid hydrocarbon phase, including what were previously catalyst free zones in the pre-existing ebullated bed hydroprocessing system, thereby reducing formation of coke or sediment in the upgraded ebullated bed hydroprocessing system compared to the pre-existing ebullated bed hydroprocessing system. 34. A method of upgrading a pre-existing ebullated bed hydroprocessing system, comprising: (a) operating a pre-existing ebullated bed hydroprocessing system comprising one or more ebullated bed reactors, each of which comprises a liquid hydrocarbon phase, a solid phase comprised of an expanded bed of a porous supported catalyst, a gaseous phase comprised of hydrogen gas, and catalyst free zones above and below the expanded bed of the porous supported catalyst; and (b) following (a), converting at least one of the one or more ebullated bed reactors of the pre-existing ebullated bed hydroprocessing system into a slurry phase reactor by replacing the porous supported catalyst with a molecular or colloidal catalyst having a particle size less than 100 nm to form an upgraded ebullated bed hydroprocessing system comprising one or more slurry phase reactors in combination with one or more ebullated bed reactors, the one or more slurry phase reactors comprising a liquid phase comprised of a heavy oil feedstock and the colloidal or molecular catalyst and a gaseous phase comprised of hydrogen gas, the colloidal or molecular catalyst catalyzing beneficial hydroprocessing reactions throughout the liquid hydrocarbon phase, including what were previously catalyst free zones in the pre-existing ebullated bed hydroprocessing system, thereby reducing formation of coke or sediment in the upgraded ebullated bed hydroprocessing system compared to the pre-existing ebullated bed hydroprocessing system, the colloidal or molecular catalyst being prepared by: (1) intimately mixing a catalyst precursor composition into the heavy oil feedstock prior to heating the catalyst precursor composition to a temperature at which a substantial portion of the catalyst precursor composition decomposes so as to form a conditioned feedstock comprised of the heavy oil feedstock and intimately mixed catalyst precursor composition, wherein the conditioned feedstock contains from about 10 ppm to about 500 ppm catalyst metal by weight of the heavy oil feedstock prior to substantial decomposition of the catalyst precursor composition in order to dilute the catalyst precursor composition with the heavy oil feedstock prior to substantial decomposition of the catalyst precursor composition and in situ formation of the colloidal or molecular catalyst upon heating the heavy oil feedstock to above the decomposition temperature of the catalyst precursor composition; and (2) heating the catalyst precursor composition in order to decompose the catalyst precursor composition and form the colloidal or molecular catalyst in situ within the heavy oil feedstock. 35. A method of hydroprocessing a heavy oil feedstock, comprising: preparing a heavy oil feedstock comprised of a substantial quantity of liquid hydrocarbons having a boiling point greater than about 650�� F. and a colloidal or molecular catalyst having a particle size less than 100 nm dispersed throughout the feedstock, the colloidal or molecular catalyst being prepared by: intimately mixing a catalyst precursor composition into the heavy oil feedstock prior to heating the catalyst precursor composition to a temperature at which a substantial portion of the catalyst precursor composition decomposes so as to form a conditioned feedstock comprised of the heavy oil feedstock and intimately mixed catalyst precursor composition, wherein the conditioned feedstock contains from about 10 ppm to about 500 ppm catalyst metal by weight of the heavy oil feedstock prior to substantial decomposition of the catalyst precursor composition in order to dilute the catalyst precursor composition with the heavy oil feedstock prior to substantial decomposition of the catalyst precursor composition and in situ formation of the colloidal or molecular catalyst upon heating the heavy oil feedstock to above the decomposition temperature of the catalyst precursor composition; and heating the catalyst precursor composition in order to decompose the catalyst precursor composition and form the colloidal or molecular catalyst in situ within the heavy oil feedstock; and heating or maintaining the heavy oil feedstock at a hydrocracking temperature within an ebullated bed reactor to yield an upgraded material, the ebullated bed reactor comprising: a liquid phase comprised of the liquid hydrocarbons and the colloidal or molecular catalyst; a solid phase comprised of a porous supported catalyst within an expanded catalyst bed; a gaseous phase comprised of hydrogen; and supported catalyst free zones above and below the expanded catalyst bed that are devoid of the porous supported catalyst, the colloidal or molecular catalyst being dispersed throughout the liquid phase, including the supported catalyst free zones, and catalyzing reactions between the hydrogen and free radicals formed from the heavy oil feedstock throughout the liquid phase, including the supported catalyst free zones, to yield an upgraded material while reducing or eliminating formation of coke precursors and sediment within the ebullated bed reactor compared to an ebullated bed reactor in the absence of the molecular or colloidal catalyst. 36. A method as defined in claim 35, the method achieving at least about 50% conversion of the heavy oil feedstock, including at least about 50% conversion of any asphaltenes contained therein. 37. A method as defined in claim 35, the method achieving at least about 65% conversion of the heavy oil feedstock, including at least about 65% conversion of any asphaltenes contained therein. 38. A method as defined in claim 35, the method achieving at least about 80% conversion of the heavy oil feedstock, including at least about 80% conversion of any asphaltenes contained therein. 39. A method as defined in claim 1, the colloidal or molecular catalyst having a particle size less than about 10 nm. 40. A method as defined in claim 1, the colloidal or molecular catalyst having a particle size less than about 5 nm. 41. A method as defined in claim 1, the colloidal or molecular catalyst having a particle size less than about 1 nm.