Hydroprocessing method and system for upgrading heavy oil using a colloidal or molecular catalyst
IPC분류정보
국가/구분
United States(US) Patent
등록
국제특허분류(IPC7판)
C10G-047/00
B01J-008/00
출원번호
UP-0117262
(2005-04-28)
등록번호
US-7578928
(2009-09-08)
발명자
/ 주소
Lott, Roger K.
Lee, Lap Keung
출원인 / 주소
Headwaters Heavy Oil, LLC
대리인 / 주소
Workman Nydegger
인용정보
피인용 횟수 :
20인용 특허 :
115
초록▼
Methods and systems for hydroprocessing heavy oil feedstocks to form an upgraded material involve the use of a colloidal or molecular catalyst dispersed within a heavy oil feedstock, a hydrocracking reactor, and a hot separator. The colloidal or molecular catalyst promotes hydrocracking and other hy
Methods and systems for hydroprocessing heavy oil feedstocks to form an upgraded material involve the use of a colloidal or molecular catalyst dispersed within a heavy oil feedstock, a hydrocracking reactor, and a hot separator. The colloidal or molecular catalyst promotes hydrocracking and other hydroprocessing reactions within the hydrocracking reactor. The catalyst is preferentially associated with asphaltenes within the heavy oil feedstock, which promotes upgrading reactions involving the asphaltenes rather than formation of coke precursors and sediment. The colloidal or molecular catalyst overcomes problems associated with porous supported catalysts in upgrading heavy oil feedstocks, particularly the inability of such catalysts to effectively process asphaltene molecules. The result is one or more of reduced equipment fouling, increased conversion level, and more efficient use of the supported catalyst if used in combination with the colloidal or molecular catalyst.
대표청구항▼
What is claimed is: 1. A method of hydroprocessing a heavy oil feedstock, comprising: preparing a heavy oil feedstock comprised of a substantial quantity of hydrocarbons having a boiling point greater than about 650° F. and a colloidal or molecular catalyst dispersed throughout the feedstock; heati
What is claimed is: 1. A method of hydroprocessing a heavy oil feedstock, comprising: preparing a heavy oil feedstock comprised of a substantial quantity of hydrocarbons having a boiling point greater than about 650° F. and a colloidal or molecular catalyst dispersed throughout the feedstock; heating or maintaining the heavy oil feedstock at a hydrocracking temperature within a hydrocracking reactor to form hydrocarbon free radicals from the heavy oil feedstock, the colloidal or molecular catalyst catalyzing reactions between hydrogen and the free radicals in the hydrocracking reactor to yield an upgraded material and reducing or eliminating formation of coke precursors and sediment in the hydrocracking reactor; transferring the upgraded material, together with residual colloidal or molecular catalyst and hydrogen, to a hot separator so as to separate gaseous and volatile fractions from a liquid fraction; withdrawing the liquid fraction from the hot separator and introducing the liquid fraction together with residual colloidal or molecular catalyst into a guard bed containing a solid supported catalyst for hydroprocessing of the liquid fraction, the solid supported catalyst removing at least a portion of the residual colloidal or molecular catalyst and metal contaminants from the liquid fraction to yield an upgraded liquid fraction; and introducing the upgraded liquid fraction into a fixed bed hydroprocessing reactor containing a solid supported catalyst in order to further upgrade the upgraded liquid fraction. 2. 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. 3. A method as defined in claim 1, wherein the heavy oil feedstock comprises at least about 5% by weight of asphaltenes. 4. A method as defined in claim 3, at least a portion of the colloidal or molecular catalyst being associated with at least a portion of the asphaltenes. 5. A method as defined in claim 4, the colloidal or molecular catalyst promoting reactions between free radicals formed from the asphaltenes and hydrogen within the hydrocracking reactor, the reactions between the free radicals formed from the asphaltenes and hydrogen preventing or inhibiting formation of coke precursors and sediment within the hydrocracking reactor. 6. A method as defined in claim 1, wherein the upgraded material within the hot separator comprises asphaltenes and wherein at least a portion of the residual colloidal or molecular catalyst in the upgraded material is associated with at least a portion of the asphaltenes, the residual colloidal or molecular catalyst associated with the asphaltenes promoting reactions between asphaltene free radicals and hydrogen, the reactions between the asphaltene free radicals and hydrogen preventing or inhibiting formation of coke precursors and sediment within the hot separator. 7. A method as defined in claim 1, the heavy oil feedstock initially comprising at least about 30% by weight of hydrocarbons having a boiling point of at least about 975° F. 8. A method as defined in claim 1, the heavy oil feedstock initially comprising at least about 50% by weight of hydrocarbons having a boiling point of at least about 975° F. 9. A method as defined in claim 1, the heavy oil feedstock initially comprising at least about 95% by weight of hydrocarbons having a boiling point of at least about 975° F. 10. A method as defined in claim 1, the catalyst metal in the colloidal or molecular catalyst at least initially having a concentration in a range of about 5 ppm to about 500 ppm by weight of the heavy oil feedstock. 11. A method as defined in claim 1, the catalyst metal in the colloidal or molecular catalyst at least initially having a concentration in a range of about 15 ppm to about 300 ppm by weight of the heavy oil feedstock. 12. A method as defined in claim 1, the catalyst metal in the colloidal or molecular catalyst at least initially having a concentration in a range of about 25 ppm to about 175 ppm by weight of the heavy oil feedstock. 13. A method as defined in claim 1, the colloidal or molecular catalyst in the heavy oil feedstock being formed by: mixing a hydrocarbon oil diluent and an oil soluble catalyst precursor composition at a temperature below which a significant portion of the catalyst precursor composition staffs to decompose to form a diluted precursor mixture; mixing the diluted precursor mixture with a heavy oil feedstock in a manner so as to yield a conditioned feedstock that forms the colloidal or molecular catalyst upon decomposing the precursor composition and allowing metal liberated therefrom to react with sulfur liberated from the feedstock; and heating the conditioned feedstock so as to decompose the catalyst precursor composition and allow metal liberated from the decomposed catalyst precursor composition to react with sulfur liberated from the heavy oil feedstock so as to form the colloidal or molecular catalyst. 14. A method as defined in claim 13, the hydrocarbon oil diluent comprising at least one of vacuum gas oil, decant oil, cycle oil, or light gas oil. 15. A method as defined in claim 13, 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. 16. A method as defined in claim 13, the catalyst precursor composition comprising at least one of molybdenum 2-ethyihexanoate, molybdenum naphthanate, molybdenum hexacarbonyl, vanadium octoate, vanadium naphthanate, or iron pentacarbonyl. 17. A method as defined in claim 13, the ratio of catalyst precursor composition to hydrocarbon oil diluent being in a range of about 1:500 to about 1:1. 18. A method as defined in claim 13, the ratio of catalyst precursor composition to hydrocarbon oil diluent being in a range of about 1:150 to about 1:2. 19. A method as defined in claim 13. the ratio of catalyst precursor composition to hydrocarbon oil diluent being in a range of about 1:100 to about 1:5. 20. A method as defined in claim 13, 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 precursor mixture and heavy oil feedstock being mixed at a temperature in a range of about 25° C. to about 350° C., and the conditioned feedstock being heated to a temperature in a range of about 275° C. to about 450° C. 21. A method as defined in claim 13, 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 precursor mixture and heavy oil feedstock being mixed at a temperature in a range of about 50° C. to about 300° C., and the conditioned feedstock being heated to a temperature in a range of about 350° C. to about 440° C. 22. A method as defined in claim 13, 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 precursor mixture and heavy oil feedstock being mixed at a temperature in a range of about 75° C. to about 250° C., and the conditioned feedstock being heated to a temperature in a range of about 375° C. to about 420° C. 23. A method as defined in claim 13, 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 precursor mixture and heavy oil feedstock being mixed for a time period in a range of about 1 second to about 20 minutes. 24. A method as defined in claim 13, 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 precursor mixture and heavy oil feedstock being mixed for a time period in a range of about 5 seconds to about 10 minutes. 25. A method as defined in claim 13, 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 precursor mixture and heavy oil feedstock being mixed for a time period in a range of about 20 seconds to about 5 minutes. 26. A method as defined in claim 13, at least a portion of the colloidal or molecular catalyst being formed prior to introducing the feedstock into the hydrocracking reactor. 27. A method as defined in claim 13, at least a portion of the colloidal or molecular catalyst being formed after introducing the feedstock into the hydrocracking reactor. 28. A method as defined in claim 1, the upgraded material within the hot separator being maintained at a temperature within about 10° F. of the hydrocracking temperature within the hydrocracking reactor. 29. A method as defined in claim 1, the upgraded material within the hot separator being maintained at a temperature within about 20° F. of the hydrocracking temperature within the hydrocracking reactor. 30. A method as defined in claim 1, the hydrocracking reactor comprising at least one of a slurry phase reactor or an ebullated bed reactor. 31. A method as defined in claim 30, prior to introducing the liquid fraction and residual colloidal or molecular catalyst from the hot separator into the guard bed, the method further comprising: introducing the liquid fraction and residual colloidal or molecular catalyst from the hot separator into a second hydrocracking reactor to form a preliminary upgraded liquid fraction, the second hydrocracking reactor comprising at least one of a slurry phase reactor, an ebullated bed reactor, or a fixed bed reactor; and introducing the preliminary upgraded liquid fraction from the second hydrocracking reactor into a second hot separator. 32. A method of hydroprocessing a heavy oil feedstock, comprising: preparing a heavy oil feedstock comprised of higher boiling hydrocarbons having a boiling point greater than about 650° F. and a colloidal or molecular catalyst dispersed throughout the feedstock; heating or maintaining the heavy oil feedstock at a hydrocracking temperature within a slurry phase hydrocracking reactor together with hydrogen in order to convert at least a portion of the higher boiling hydrocarbons to lower boiling hydrocarbons and thereby form an upgraded material, the slurry phase reactor including (i) an inlet port at a bottom of the slurry phase reactor into which the heavy oil feedstock and hydrogen are introduced and (ii) an outlet port at a top of the slurry phase reactor from which the upgraded material, colloidal or molecular catalyst, and hydrogen are withdrawn; transferring the upgraded material, colloidal or molecular catalyst, and hydrogen to a hot separator while maintaining the upgraded material at a hot separation temperature within about 20° F. of the hydrocracking temperature so as to separate gaseous and volatile fractions from a liquid fraction in the upgraded material and form or maintain hydrocarbon free radicals in the liquid fraction; the colloidal or molecular catalyst catalyzing reactions between hydrogen and hydrocarbon free radicals within the slurry phase reactor and also the hot separator, the colloidal or molecular catalyst reducing or eliminating formation of coke precursors and sediment within the slurry phase reactor and also the hot separator; and withdrawing the liquid fraction from the hot separator and introducing the liquid fraction together with residual colloidal or molecular catalyst into a guard bed containing a solid supported catalyst for hydroprocessing of the liquid fraction, the solid supported catalyst removing at least a portion of the residual colloidal or molecular catalyst and metal contaminants from the liquid fraction to yield an upgraded liquid fraction. 33. A method as defined in claim 32, the slurry phase reactor further comprising a recycle channel, a recycling pump, and a distributor grid plate. 34. A method as defined in claim 32, further comprising: introducing a preliminary feedstock into an ebullated bed reactor for preliminary upgrading in the presence of a solid supported catalyst and the colloidal or molecular catalyst to form a preliminary upgraded product, the solid supported catalyst removing at least a portion of sulfur, nitrogen and metals from the preliminary feedstock, the colloidal or molecular catalyst catalyzing reactions between hydrogen and hydrocarbon free radicals within the ebullated bed reactor, thereby reducing or eliminating formation of coke precursors or sediments and extending the useful life of the solid supported catalyst compared to a solid supported catalyst within an ebullated bed reactor in the absence of the colloidal or molecular catalyst; and withdrawing the preliminary upgraded product and colloidal or molecular catalyst from the ebullated bed reactor and introducing it as the heavy oil feedstock into the slurry phase reactor. 35. A method as defined in claim 32, further comprising introducing the upgraded material and colloidal or molecular catalyst from the slurry phase reactor into at least one ebullated bed reactor containing a solid supported catalyst for further hydroprocessing prior to transferring the upgraded material into the hot separator, the solid supported catalyst removing at least a portion of sulfur, nitrogen and metals from the upgraded material, the colloidal or molecular catalyst catalyzing reactions between hydrogen and hydrocarbon free radicals within the ebullated bed reactor, thereby reducing or eliminating formation of coke precursors or sediments and extending the useful life of the solid supported catalyst compared to a solid supported catalyst within an ebullated bed reactor in the absence of the colloidal or molecular catalyst. 36. A method as defined in claim 32, further comprising withdrawing the liquid fraction from the hot separator and introducing the liquid fraction together with residual colloidal or molecular catalyst and additional hydrogen into at least one ebullated bed reactor containing a solid supported catalyst for hydroprocessing of the liquid fraction, the liquid fraction within the ebullated bed reactor being heated or maintained at a hydroprocessing temperature so as to form hydrocarbon free radicals, the residual colloidal or molecular catalyst catalyzing reactions between hydrogen and hydrocarbon free radicals within the ebullated bed reactor, the solid supported catalyst removing at least a portion of sulfur, nitrogen and metals from the liquid fraction. 37. A method as defined in claim 36, further comprising transferring the upgraded liquid fraction and residual colloidal or molecular catalyst from the ebullated bed reactor to a second hot separator in order to separate gaseous and volatile liquid fractions from a second liquid fraction in the upgraded liquid fraction, the residual colloidal or molecular catalyst in the upgraded liquid fraction promoting reactions between at least a portion of hydrogen and hydrocarbon free radicals within the second hot separator, thereby reducing or eliminating formation of coke precursors and sediment within the second hot separator. 38. A method as defined in claim 32, further comprising withdrawing the liquid fraction from the hot separator and introducing the liquid fraction together with residual colloidal or molecular catalyst into a fixed bed reactor containing a solid supported catalyst for hydroprocessing of the liquid fraction, the residual colloidal or molecular catalyst reducing or eliminating formation of coke precursors or sediments within at least a portion of the fixed bed reactor, at least one of the solid supported catalyst or residual colloidal or molecular catalyst promoting reactions between hydrogen and hydrocarbon free radicals within the fixed bed reactor in order to yield an upgraded liquid fraction. 39. A method as defined in claim 32, further comprising introducing the upgraded liquid fraction from the guard bed into at least one hydrotreating fixed bed reactor in order to remove at least one of nitrogen, sulfur, oxygen, or halides and yield a hydrotreated material having increased hydrogen content. 40. A method as defined in claim 39, further comprising introducing the hydrotreated material into a second hot separator. 41. A method as defined in claim 32, further comprising introducing the upgraded material and residual colloidal or molecular catalyst from the slurry phase reactor into at least one fixed bed reactor containing a solid supported catalyst for further hydroprocessing prior to transferring the upgraded feedstock into the hot separator. 42. A method of hydroprocessing a heavy oil feedstock, comprising: (a) mixing a hydrocarbon oil diluent and an oil soluble catalyst precursor composition at a temperature below which a significant portion of the catalyst precursor composition starts to decompose to form a diluted precursor mixture; (b) mixing the diluted precursor mixture with a heavy oil feedstock comprised of a substantial quantity of hydrocarbons having a boiling point greater than about 650° F. in a manner so as to yield a conditioned feedstock; (c) heating the conditioned feedstock so as to decompose the catalyst precursor composition, liberate sulfur from the heavy oil feedstock, and allow metal liberated from the decomposed catalyst precursor composition to react with sulfur liberated from the heavy oil feedstock so as to form a colloidal or molecular catalyst; (d) prior to, during, or after (c), introducing the heavy oil feedstock into an ebullated bed reactor for preliminary upgrading in the presence of a solid supported catalyst and the colloidal or molecular catalyst to form a preliminary upgraded product, the solid supported catalyst removing at least a portion of sulfur, nitrogen and metals from the preliminary feedstock, the colloidal or molecular catalyst catalyzing reactions between hydrogen and hydrocarbon free radicals within the ebullated bed reactor, thereby reducing or eliminating formation of coke precursors or sediments and extending the useful life of the solid supported catalyst compared to a solid supported catalyst within an ebullated bed reactor in the absence of the colloidal or molecular catalyst; (e) withdrawing the preliminary upgraded product and colloidal or molecular catalyst from the ebullated bed reactor and introducing it as the heavy oil feedstock into a slurry phase reactor; (f) heating or maintaining the heavy oil feedstock at a hydrocracking temperature within the slurry phase reactor to form hydrocarbon free radicals from the heavy oil feedstock, the colloidal or molecular catalyst catalyzing reactions between hydrogen and the free radicals in the slurry phase reactor to yield an upgraded material and reducing or eliminating formation of coke precursors and sediment in the hydrocracking reactor; and (g) transferring the upgraded material, together with residual colloidal or molecular catalyst and hydrogen, to a hot separator so as to separate gaseous and volatile fractions from a liquid fraction in the upgraded material and form or maintain hydrocarbon free radicals in the liquid fraction, the residual colloidal or molecular catalyst catalyzing reactions between the hydrocarbon free radicals and residual hydrogen within the hot separator and reducing or eliminating formation of coke precursors and sediment within the hot separator. 43. A method as defined in claim 1, the colloidal or molecular catalyst in the hydrocracking reactor having a particle size less than about 100 nm. 44. A hydroprocessing system for hydroprocessing a heavy oil feedstock, comprising: a heavy oil feedstock comprised of a substantial quantity of hydrocarbons having a boiling point greater than about 650° F. and a colloidal or molecular catalyst dispersed throughout the feedstock; a hydrocracking reactor that heats or maintains the heavy oil feedstock at a hydrocracking temperature together with hydrogen during use in order to convert at least a portion of the higher boiling hydrocarbons to lower boiling hydrocarbons and thereby form an upgraded material, the hydrocracking reactor comprised of (i) an inlet port at a bottom of the reactor into which the heavy oil feedstock and hydrogen are introduced and (ii) an outlet port at a top of the reactor from which the upgraded material, colloidal or molecular catalyst, and hydrogen are withdrawn; a hot separator that separates gaseous and volatile fractions from a liquid fraction in the upgraded material, the hot separator comprised of (i) an inlet through which the upgraded material is introduced into the hot separator, (ii) a first outlet through which the gaseous and volatile fractions are withdrawn, and (iii) a second outlet through which the liquid fraction is withdrawn; a guard bed containing a solid supported catalyst for hydroprocessing the liquid fraction, wherein the solid supported catalyst removes at least a portion of the residual colloidal or molecular catalyst and metal contaminants from the liquid fraction to yield an upgraded liquid fraction; and a fixed bed hydroprocessing reactor containing a solid supported catalyst that further upgrades the upgraded liquid fraction.
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이 특허에 인용된 특허 (115)
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