Method for converting coal to upgraded liquid product
IPC분류정보
국가/구분 |
United States(US) Patent
등록
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국제특허분류(IPC7판) |
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출원번호 |
US-0507864
(1983-06-27)
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발명자
/ 주소 |
- Hettinger, Jr., William P.
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출원인 / 주소 |
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대리인 / 주소 |
Willson, Jr., Richard C.Welsh, Stanley M.
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인용정보 |
피인용 횟수 :
5 인용 특허 :
5 |
초록
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An H-Coal Process hydrogenation operation and catalyst life is substantially improved when using colloidal particles of catalyst comprising a colloidal matrix of silica, alumina, titania and combinations thereof coated with hydrogenating components selected from cobalt, molybdenum, nickel, tungsten
An H-Coal Process hydrogenation operation and catalyst life is substantially improved when using colloidal particles of catalyst comprising a colloidal matrix of silica, alumina, titania and combinations thereof coated with hydrogenating components selected from cobalt, molybdenum, nickel, tungsten and combinations thereof. The colloidal catalyst activity may be altered by alkaline promoters, other metals and acidic promoters.
대표청구항
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1. A process for achieving hydrogenation of a coal liquefaction product which comprises dispersing coal particles in a heavy oil liquefaction solvent material at a temperature in the range of 399° C.-471° C. (750°-880° F.) in the presence of hydrogen at a pressure in the range 2000-4000 psig and uti
1. A process for achieving hydrogenation of a coal liquefaction product which comprises dispersing coal particles in a heavy oil liquefaction solvent material at a temperature in the range of 399° C.-471° C. (750°-880° F.) in the presence of hydrogen at a pressure in the range 2000-4000 psig and utilizing a colloidal matrix material coated with one or more hydrogenating metals as a catalyst composition dispersed in said liquefaction solvent for accelerating coal liquefaction, hydrogenation and removal of sulfur, nitrogen and oxygen therefrom. 2. The process of claim 1 in which the catalyst consists of a colloidal matrix material of silica, alumina, titania and silica coated with alumina and said matrix is coated with one or more hydrogenating metal components. 3. The process of claim 2 in which the catalyst consists of a colloidal matrix material coated with one of cobalt-molybdena, nickel-molybdena or nickel-tungstate. 4. The process of claim 1 in which the colloidal particles are 27-75 .ANG. in diameter. 5. The process of claim 1 in which the colloidal particles are in the range of 25-225 .ANG. in diameter. 6. The process of claim 1 in which the colloidal particles contain 2-8% cobalt oxide and 5-20% MoO 3 . 7. The process of claim 1 in which the colloidal catalyst is added to a coal oil slurry in a concentration of 5-100 ppm. 8. The process of claim 1 in which the colloidal catalyst is added in a concentration of 100-10,000 ppm. 9. The process of claim 1 in which the colloidal catalyst is recovered with a heavy distillate product of the coal oil and/or the slurry bottoms of coal liquefaction and recycled with freshly ground coal to the process. 10. The process of claim 1 in which the ratio of colloidal catalyst comprising recycled colloidal catalyst to fresh addition thereof is in the ratio of ten to one or less. 11. The process of claim 9 in which the ratio of recycled colloidal catalyst to fresh colloidal catalyst is at least one hundred to one. 12. A process for converting comminuted coal into a liquified hydrogenated product which comprises, slurrying comminuted coal with an oil liquifaction solvent, adding a colloidal catalyst to a comminuted coal-oil solvent slurry and passing said slurry with added colloidal catalyst in contact with an ebullating bed of fluidizable hydrogenation catalyst particles of larger particle size at a velocity in the range of 0.1 to 10 weight hourly space velocity, a temperature in the range of 399° C.-482° C. (750°-900° F.), a pressure in the range of 2000-4000 psig, and maintaining a hydrogen addition rate in the range of 500-3000 standard cubic feed of hydrogen per barrel of comminuted coal in slurry oil during said conversion. 13. The process of claim 12 in which the catalyst is a colloidal catalyst consisting of cobalt molybdate distributed on a colloidal material selected from alumina and silica. 14. The process of claim 12 in which the colloidal catalyst consists of cobalt molybdate distributed on alumina coated colloidal silica. 15. The process of claim 12 in which the colloidal catalyst is nickel molybdate distributed on colloidal material selected from alumina and silica. 16. The process of claim 12 in which the colloidal catalyst is a mixture of nickel and cobalt molybdate distributed on alumina coated colloidal silica. 17. The process of claim 12 in which the ebullating bed of fluidizable hydrogenation catalyst particles is selected from cobalt molybdate, nickel molybdate, nickel tungstate distributed in a matrix material selected from alumina, silica and silica-alumina. 18. The process of claim 12 in which a heavy oil product and a slurry oil product of said catalytic conversion containing colloidal catalyst are recycled to the conversion operation. 19. The process of claim 12 in which the ratio of recycled catalyst particles to fresh catalyst particles charged to the conversion operation is at least ten to one. 20. The process of claim 12 in which the ratio of recycled colloidal catalyst to fresh colloidal catalyst charged to the conversion operation is at least one hundred to one. 21. A process for hydrogenating a liquid product of coal liquefaction comprising preasphaltenes and asphaltenes at an elevated temperature and pressure to form hydrogenated oil product, which comprises, hydrogenating a liquefaction product of coal below 900° F. at a pressure in the range of 1550 to 4000 psig in the presence of a suspension of colloidal hydrogenation catalyst particles comprising layered components of hydrogenation metal components on a colloidal particle matrix material initially suspended in a liquid miscible with said coal liquefaction product, and recovering a hydrogenated liquid product of coal liquefaction. 22. The process of claim 21 wherein the hydrogenation catalyst comprises colloidal silicon oxide coated with one or more layers of alumina thereafter coated with layered hydrogenation metal catalyst components in an amount providing hydrogenation activity to said colloidal silica coated with alumina. 23. The process of claim 21 wherein the hydrogenation metal catalyst components are selected from cobalt-molybdenum, nickel-tungsten, and nickel-molybdenum. 24. The process of claim 21 wherein the colloidal matrix is selected from colloidal silica, colloidal alumina and alumina coated colloidal silica. 25. The process of claim 21 wherein the hydrogenation operation is accomplished at a temperature in the range of 371° C. (700° F.) to 482° C. (900° F.) and a pressure in the range of 2000 to 3500 psig. 26. The process of claim 21 wherein the hydrogenation process comprises a mixture of fluidizable hydrogenation catalyst particles in combination with said colloidal hydrogenation catalyst and the combination thereof is suspended in a liquid phase comprising said coal liquefaction product to be hydrogenated. 27. The process of claim 21 wherein hydrogenation of said coal liquefaction product is accomplished in a liquid phase operation supporting an ebullating bed of fluidizable hydrogenation catalyst particles in combination with suspended colloidal hydrogenation catalyst particles added to said ebullating bed of catalyst particles to improve the hydrogenating activity thereof. 28. The process of claim 21 wherein the colloidal hydrogenation catalyst is prepared from an aqueous suspension of silica-alumina colloid thereafter suspended in cellusolve to displace water, the cellusolve mixture is mixed with a solution comprising a suspension of cobalt cations and complex isopolymolybdic anions whereby the silica-alumina colloid particles are coated with cobalt and molybdenum colloidal components, and thereafter replacing the cellusolve with tetralin in a sequence of evaporation steps effected at a temperature permitting the complete substitution of tetralin for cellusolve. 29. The process of claim 21 wherein the colloidal hydrogenation catalyst is prepared by mixing molybdenum oxide with deionized water to which is added CoCo 3 with mixing, thereafter a mixture of colloidal silica coated with alumina and dispersed in ethyl cellusolve is added to the Co/Mo mixture at a temperature of about (180° F.), water is then flash evaporated from the mixture and replaced with cellusolve to produce particles deep blue in color, and thereafter gradually raising the temperature of the cellusolve mixture in sequential evaporation during addition of tetralin so that the cellusolve is replaced by the added tetralin to provide a tetralin solution comprising colloidal particles of silica-alumina coated with cobalt and molybdenum. 30. The process of claim 21 wherein the conversion of asphaltenes in the coal liquefaction product is substantially improved by employing the colloidal hydrogenation catalyst particles distributed in an ebullating bed of hydrogenation catalyst particles of larger particle size dispersed in said coal liquefaction product being hydrogenated. 31. A method for liquefying coal which comprises: (a) dispersing comminuted coal in a heavy oil material selected from petroleum resid and shale oil to form a mixture thereof with a colloidal suspension of silica coated with alumina and hydrogenating metal components; (b) maintaining the mixture of (a) under liquid phase elevated temperature and pressure conditions and hydrogen sufficient to form a hydrogenated coal liquid product in a hydrogenation zone; (c) recovering a liquid product from said hydrogenation zone comprising colloidal catalyst particles, and (d) recycling a portion of said liquid product phase comprising colloidal particles to said hydrogenation operation. 32. A method for liquefying coal which comprises: (a) dispersing comminuted coal particles in a heavy oil solvent selected from one or a combination of a coal liquefaction product, petroleum resid and shale oil to form a suspension of coal particles therein; (b) adding a miscible liquid suspension of colloidal hydrogenation metal components distributed on a colloidal matrix to said coal particle-heavy oil solvent suspension to form a mixed suspension thereof; (c) passing said mixed suspension downwardly through a fixed bed of hydrogenation catalyst particles in contact with hydrogen under conditions of temperature and pressure sufficient to form a hydrogenated coal oil product; (d) recovering said coal oil product from a hydrocarbon phase rich in colloidal particles; and (e) recycling said hydrocarbon phase rich in colloidal particles for admixture with said coal particle-heavy oil suspension.
이 특허에 인용된 특허 (5)
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Gatsis John G. (Des Plaines IL), Coal liquefaction process.
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Aldridge Clyde L. (Baton Rouge LA) Bearden ; Jr. Roby (Baton Rouge LA), Hydroconversion of an oil-coal mixture.
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Aldridge ; Clyde L. ; Bearden ; Jr. ; Roby, Hydroconversion of coal in a hydrogen donor solvent with an oil-soluble catalyst.
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Fu Yuan C. (Bethel Park PA), Liquefaction and desulfurization of coal using synthesis gas.
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Gatsis John G. (Des Plaines IL), Method of solvent extraction of coal by a heavy oil.
이 특허를 인용한 특허 (5)
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Parrott Stephen L. (Bartlesville OK), Hydrocracking catalyst for middle distillates.
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Parrott Stephen L. (Bartlesville OK), Hydrocracking catalyst for middle distillates.
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Hettinger ; Jr. William P. (Russell KY), Method for converting coal to upgraded liquid product.
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MacArthur James B. (Denville NJ) McLean Joseph B. (S. Somerville NJ) Comolli Alfred G. (Yardley PA), Two-stage co-processing of coal/oil feedstocks.
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Simmons John J. (P.O. Box 1971 Bismarck ND 58502), Utilization of low rank coal and peat.
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