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Kafe 바로가기국가/구분 | United States(US) Patent 등록 |
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국제특허분류(IPC7판) |
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출원번호 | US-0116195 (2011-05-26) |
등록번호 | US-8303802 (2012-11-06) |
발명자 / 주소 |
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출원인 / 주소 |
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대리인 / 주소 |
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인용정보 | 피인용 횟수 : 1 인용 특허 : 179 |
An ebullated bed hydroprocessing system, and also a method for upgrading an existing ebullated bed hydroprocessing system, involves introducing a colloidal or molecular catalyst, or a catalyst precursor capable of forming the colloidal or molecular catalyst, into an ebullated bed reactor. The colloi
An ebullated bed hydroprocessing system, and also a method for upgrading an existing ebullated bed hydroprocessing system, involves introducing a colloidal or molecular catalyst, or a catalyst precursor 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 into a heavy oil feedstock and raising the temperature of the feedstock to above the decomposition temperature of the catalyst precursor 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 an existing ebullated bed reactor.
1. 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 dispersed throughout the feedstock, the colloidal or mo
1. 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 dispersed throughout the feedstock, the colloidal or molecular catalyst being prepared by: intimately mixing a catalyst precursor into the heavy oil feedstock prior to heating the catalyst precursor to effect decomposition of the catalyst precursor and in situ formation of active colloidal or molecular catalyst so as to form a conditioned feedstock comprised of the heavy oil feedstock and catalyst precursor in order to dilute the catalyst precursor composition with the heavy oil feedstock prior to substantial decomposition of the catalyst precursor 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; andheating 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; andheating 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; andsupported 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 increasing asphaltene conversion and/or 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. 2. A method of upgrading an existing ebullated bed hydroprocessing system in order to reduce formation of coke and/or sediment, comprising: (a) providing an existing ebullated bed hydroprocessing system comprising one or more ebullated bed reactors, each comprising 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 with a hydrocarbon oil diluent at a temperature below which a substantial portion of the catalyst precursor 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 to effect decomposition of the catalyst precursor and in situ formation of active colloidal or molecular catalyst, 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 in order to further dilute the catalyst precursor with the heavy oil feedstock prior to decomposition of the catalyst precursor and in situ formation of a colloidal or molecular catalyst within the heavy oil feedstock;(d) heating the catalyst precursor within the heavy oil feedstock in order to decompose the catalyst precursor and form a colloidal or molecular catalyst 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 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 existing ebullated bed hydroprocessing system; and(f) operating the upgraded ebullated bed hydroprocessing system to form a hydroprocessed material, the upgraded ebullated bed hydroprocessing system operating with higher asphaltene conversion and/or increased longevity of porous supported catalyst compared to the existing ebullated bed hydroproces sing system, the colloidal or molecular catalyst catalyzing beneficial hydroproces sing reactions throughout the liquid hydrocarbon phase. 3. A method as defined in claim 2, the existing ebullated bed hydroprocessing system comprising an LC-Fining or an H-Oil ebullated bed hydroprocessing system. 4. A method as defined in claim 1 or 2, the catalyst precursor comprising an organometallic compound or complex. 5. A method as defined in claim 1, the method achieving at least about 50% conversion of the heavy oil feedstock, including at least about 50% conversion of asphaltenes contained therein. 6. A method as defined in claim 1, the method achieving at least about 65% conversion of the heavy oil feedstock, including at least about 65% conversion of asphaltenes contained therein. 7. A method as defined in claim 1, the method achieving at least about 80% conversion of the heavy oil feedstock, including at least about 80% conversion of asphaltenes contained therein. 8. A method as defined in claim 1 or 2, the catalyst precursor 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. 9. A method as defined in claim 1 or 2, the catalyst precursor comprising at least one of molybdenum 2-ethylhexanoate, molybdenum naphthanate, molybdenum hexacarbonyl, vanadium octoate, vanadium naphthanate, or iron pentacarbonyl. 10. A method as defined in claim 1 or 2, 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. 11. A method as defined in claim 1 or 2, the heavy oil feedstock comprising at least about 5% by weight of asphaltenes. 12. A method as defined in claim 11, 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 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. 13. A method as defined in claim 2, the hydrocarbon oil diluent comprising at least one of vacuum gas oil, decant oil, cycle oil, or light gas oil. 14. A method as defined in claim 2, the ratio of catalyst precursor to hydrocarbon oil diluent being in a range of about 1:500 to about 1:1. 15. A method as defined in claim 2, the ratio of catalyst precursor to hydrocarbon oil diluent being in a range of about 1:150 to about 1:2. 16. A method as defined in claim 2, the ratio of catalyst precursor to hydrocarbon oil diluent being in a range of about 1:100 to about 1:5. 17. A method as defined in claim 2, the hydrocarbon oil diluent and catalyst precursor 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). 18. A method as defined in claim 2, the hydrocarbon oil diluent and catalyst precursor 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). 19. A method as defined in claim 2, the hydrocarbon oil diluent and catalyst precursor 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). 20. A method as defined in claim 2, the hydrocarbon oil diluent and catalyst precursor 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 and formation of the molecular or colloidal catalyst. 21. A method as defined in claim 2, the hydrocarbon oil diluent and catalyst precursor 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 and formation of the molecular or colloidal catalyst. 22. A method as defined in claim 2, the hydrocarbon oil diluent and catalyst precursor 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 and formation of the molecular or colloidal catalyst. 23. A method as defined in claim 2, wherein (d) occurs before (e). 24. A method as defined in claim 2, wherein (d) occurs during or after (e). 25. A method as defined in claim 1 or 2, the colloidal or molecular catalyst providing catalyst metal having a concentration in a range of about 5 ppm to about 500 ppm by weight of the heavy oil feedstock in. 26. A method as defined in claim 1 or 2, the colloidal or molecular catalyst providing catalyst metal having a concentration in a range of about 15 ppm to about 300 ppm by weight of the heavy oil feedstock in. 27. A method as defined in claim 1 or 2, the colloidal or molecular catalyst providing catalyst metal having a concentration in a range of about 25 ppm to about 175 ppm by weight of the heavy oil feedstock in. 28. A method as defined in claim 1 or 2, wherein the colloidal or molecular catalyst comprises molybdenum disulfide. 29. A method as defined in claim 2, 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 as compared to the existing ebullated bed hydroprocessing system. 30. A method as defined in claim 2, wherein (a) through (d) comprise operating a hydroprocessing reactor upstream from at least one ebullated bed reactor of the existing ebullated bed hydroprocessing system, the hydroprocessing reactor comprising the heavy oil feedstock and the colloidal or molecular catalyst as primary or sole hydroprocessing catalyst within the hydroproces sing reactor. 31. A method as defined in claim 30, the hydroprocessing reactor comprising a new reactor that is constructed upstream from the at least one ebullated bed reactor of the existing ebullated bed hydroproces sing system. 32. A method as defined in claim 30, the hydroprocessing reactor comprising a former ebullated bed reactor of the existing ebullated bed hydroprocessing system that has been converted into the hydroprocessing reactor of the upgraded ebullated bed hydroprocessing system by eliminating the porous supported catalyst from the former ebullated bed reactor and replacing it with the colloidal or molecular catalyst. 33. A method as defined in claim 1 or 2, 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. 34. A method as defined in claim 1 or 2, the colloidal or molecular catalyst having a particle size less than about 100 nm. 35. A method as defined in claim 1 or 2, the colloidal or molecular catalyst having a particle size less than about 10 nm. 36. A method as defined in claim 1 or 2, the colloidal or molecular catalyst having a particle size less than about 5 nm. 37. An upgraded ebullated bed hydroprocessing system resulting from the method of claim 2. 38. An ebullated bed hydroprocessing system for performing the method of claim 1, the ebullated bed hydroprocessing system comprising: means for 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 dispersed throughout the feedstock, the means for preparing comprising: pre-mixing apparatus configured to intimate mix a catalyst precursor into the heavy oil feedstock prior to heating the catalyst precursor to effect decomposition of the catalyst precursor and in situ formation of active colloidal or molecular catalyst so as to form a conditioned feedstock comprised of the heavy oil feedstock and catalyst precursor in order to dilute the catalyst precursor composition with the heavy oil feedstock prior to substantial decomposition of the catalyst precursor 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; andheating means for 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; andan ebullated bed reactor that heats or maintains the heavy oil feedstock at a hydrocracking temperature 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; andsupported 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 increasing asphaltene conversion and/or 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. 39. A method of upgrading an existing ebullated bed hydroprocessing system in order to reduce formation of coke and/or sediment, comprising: (a) operating an 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 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 heavy oil feedstock and a colloidal or molecular catalyst a sole or primary hydroprocessing catalyst, the colloidal or molecular catalyst being prepared by: (1) mixing a catalyst precursor with the heavy oil feedstock prior to heating the catalyst precursor to effect decomposition of the catalyst precursor and in situ formation of active colloidal or molecular catalyst so as to form a conditioned feedstock comprised of the heavy oil feedstock and diluted catalyst precursor; and(2) heating the conditioned feedstock in order to decompose the catalyst precursor 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 one or more slurry phase reactors into at least one ebullated bed reactor of the 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 existing ebullated bed hydroprocessing system, thereby increasing asphaltene conversion and/or increasing longevity of the porous supported catalyst compared to the existing ebullated bed hydroprocessing system. 40. A method of upgrading an existing ebullated bed hydroprocessing system, comprising: (a) operating an existing ebullated bed hydroproces sing 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 existing ebullated bed hydroproces sing system into a slurry phase reactor by replacing the porous supported catalyst with a molecular or colloidal catalyst as sole hydroprocessing catalyst 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 existing ebullated bed hydroprocessing system, thereby increasing asphaltene conversion and/or reducing formation of coke or sediment in the upgraded ebullated bed hydroprocessing system compared to the existing ebullated bed hydroprocessing system, the colloidal or molecular catalyst being prepared by: (1) mixing a catalyst precursor with the heavy oil feedstock prior to heating the catalyst precursor to effect decomposition of the catalyst precursor and in situ formation of active colloidal or molecular catalyst so as to form a conditioned feedstock comprised of the heavy oil feedstock and diluted catalyst precursor; and(2) heating the conditioned feedstock in order to decompose the catalyst precursor and form the colloidal or molecular catalyst in situ within the heavy oil feedstock. 41. An upgraded ebullated bed hydroprocessing system resulting from the method of claim 39 or 40. 42. A method of hydroprocessing a heavy oil feedstock, comprising: operating an ebullated bed hydroproces sing system operating at hydrocracking conditions and comprising a plurality of ebullated bed reactors, each ebullated bed reactor comprising: a solid phase comprised of a porous supported catalyst within an expanded catalyst bed;a gaseous phase comprised of hydrogen;supported catalyst free zones above and below the expanded catalyst bed that are devoid of the porous supported catalyst;a liquid phase circulating throughout the expanded catalyst bed and the supported catalyst free zones, the liquid phase comprising liquid hydrocarbons provided by a heavy oil feedstock and having a boiling point greater than about 650° F.;a colloidal or molecular catalyst dispersed throughout the liquid phase 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 hydrocarbon material while increasing asphaltene conversion and/or 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;prior to introducing a heavy oil feedstock into a first ebullated bed reactor, blending a catalyst precursor with the heavy oil feedstock so as to form a conditioned feedstock comprised of the heavy oil feedstock and catalyst precursor in order to dilute the catalyst precursor with the heavy oil feedstock prior to heating the catalyst precursor to effect substantial decomposition of the catalyst precursor and in situ formation of active colloidal or molecular catalyst within the heavy oil feedstock;heating the conditioned feedstock upstream from or within the first ebullated bed reactor in order to decompose the catalyst precursor and form the colloidal or molecular catalyst in situ within the heavy oil feedstock;introducing at least a portion of a liquid hydrocarbon product from the first ebullated bed reactor into a second ebullated bed reactor downstream from the first ebullated bed reactor, the liquid hydrocarbon product including residual colloidal or molecular catalyst from the first ebullated bed reactor; andproviding supplemental colloidal or molecular catalyst to the second ebullated bed reactor in addition to the residual colloidal or molecular catalyst from the first ebullated bed reactor. 43. A method as defined in claim 42, further comprising: introducing at least a portion of a second liquid hydrocarbon product from the second ebullated bed reactor into a third ebullated bed reactor downstream from the second ebullated bed reactor, the liquid hydrocarbon product including residual colloidal or molecular catalyst from the second ebullated bed reactor; andproviding supplemental colloidal or molecular catalyst to the third ebullated bed reactor in addition to the residual colloidal or molecular catalyst from the second ebullated bed reactor. 44. An ebullated bed hydroprocessing system for performing the method of claim 42, the ebullated bed hydroprocessing system comprising: an ebullated bed hydroprocessing system operating at hydrocracking conditions and comprising first and second ebullated bed reactors, each ebullated bed reactor comprising: a solid phase comprised of a porous supported catalyst within an expanded catalyst bed;a gaseous phase comprised of hydrogen;supported catalyst free zones above and below the expanded catalyst bed that are devoid of the porous supported catalyst;a liquid phase circulating throughout the expanded catalyst bed and the supported catalyst free zones, the liquid phase comprising liquid hydrocarbons provided by a heavy oil feedstock and having a boiling point greater than about 650° F.;a colloidal or molecular catalyst dispersed throughout the liquid phase 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 hydrocarbon material while increasing asphaltene conversion and/or 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;a mixing apparatus positioned upstream from a first ebullated bed reactor and configured to blend a catalyst precursor with the heavy oil feedstock so as to form a conditioned feedstock comprised of the heavy oil feedstock and catalyst precursor in order to dilute the catalyst precursor with the heavy oil feedstock prior to heating the catalyst precursor to effect substantial decomposition of the catalyst precursor and in situ formation of active colloidal or molecular catalyst within the heavy oil feedstock;heating means for heating the conditioned feedstock upstream from or within the first ebullated bed reactor in order to decompose the catalyst precursor and form the colloidal or molecular catalyst in situ within the heavy oil feedstock;means for introducing at least a portion of a liquid hydrocarbon product from the first ebullated bed reactor into the second ebullated bed reactor downstream from the first ebullated bed reactor, the liquid hydrocarbon product including residual colloidal or molecular catalyst from the first ebullated bed reactor; andmeans for providing supplemental colloidal or molecular catalyst to the second ebullated bed reactor in addition to the residual colloidal or molecular catalyst from the first ebullated bed reactor.
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