Including Regeneration Of Catalyst Patents (Class 518/709)
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Patent number: 6800579Abstract: There is provided a process for regenerating the activity of used metal catalysts for the hydrogenation of carbon monoxide comprising decreasing the hydrocarbon content thereof, calcining under an oxidant-containing atmosphere, impregnating with a solution of at least one of a metal compound, calcining under an oxidant-containing atmosphere and activating by contacting with a hydrogen-contacting gas at elevated temperatures to form an active catalyst. The process regenerates and enhances both supported and dispersed active metal (DAM) catalysts. Used catalysts enhanced by the process are initially treated to decrease their hydrocarbon content. The treatment may be carried out in a single reactor, or by carrying out up to all steps after catalyst may be withdrawn from a reactor and returned to at least one reactor, both preferably during operation thereof. Up to all steps may be effected in a subsequent reactor, or in specialized apparatus.Type: GrantFiled: January 29, 2002Date of Patent: October 5, 2004Assignee: ExxonMobil Research and Engineering CompanyInventors: Michel Daage, Russell John Koveal, Min Chang
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Patent number: 6777451Abstract: A process for enhancing metal catalysts for carbon monoxide hydrogenation comprising reducing the catalyst so that at least a portion is in the metallic state, impregnating under a non-oxidative atmosphere with a solution of a salt of at least one metal, optionally in combination with at least one of an ammonium salt, an alkyl ammonium salt, a weak organic acid and ammonia, oxidizing with a gaseous oxidant in the presence of the impregnating solution, and reducing to form an active catalyst. Used catalysts enhanced by the process are initially treated to decrease their hydrocarbon content. The treatment may be carried out in a single reactor, or by carrying out up to all steps after catalyst may be withdrawn from a reactor and returned to at least one reactor, both preferably during operations. Up to all steps may be effected in a subsequent reactor, or in specialized apparatus.Type: GrantFiled: January 29, 2002Date of Patent: August 17, 2004Assignee: ExxonMobil Research and Engineering CompanyInventors: Russell John Koveal, Michel Daage, Charles Harrison Mauldin, Janet Renee Clark
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Patent number: 6753351Abstract: A process for activating a supported metal catalyst or catalyst precursor useful for the hydrogenation of carbon monoxide to form a mixture of hydrocarbons, comprising reducing with a hydrogen-containing gas at elevated temperature so that at least a portion is in the metallic state, impregnating under a non-oxidizing atmosphere with a solution of at least one member selected from the group consisting of ammonium salts, alkyl ammonium salts and weak organic acids, optionally further including ammonia, to the point where it has absorbed a volume of solution equal to at least about 10% of its calculated pore volume, oxidizing with a gaseous oxidant in the presence of the impregnating solution and reducing with hydrogen-containing gas at elevated temperatures to form an active catalyst. The steps beginning with the impregnation may be repeated. Optionally, the catalyst may be calcined after the oxidation step and/or passivated after activation.Type: GrantFiled: January 29, 2002Date of Patent: June 22, 2004Assignee: ExxonMobil Research and Engineering CompanyInventors: Janet Renee Clark, Michel Daage, Russell John Koveal
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Patent number: 6753354Abstract: There is provided a process for hydrocarbon synthesis wherein a supported metal catalyst for hydrogenating carbon monoxide to form a mixture of hydrocarbons is regenerated by decreasing its hydrocarbon content, impregnating under a non-oxidative atmosphere with a solution of at least one member selected from the group consisting of ammonium salts, alkyl ammonium salts and weak organic acids, optionally including ammonia, oxidizing with a gaseous oxidant in the presence of the impregnating solution, activating the catalyst by reduction with hydrogen at elevated temperatures and reusing the catalyst. The treatment may be carried out in a single reactor, or by carrying out up to all steps after catalyst has been withdrawn therefrom and returned to at least one reactor. Up to all steps subsequent to decreasing the hydrocarbon content may be effected in a subsequent reactor, or in specialized apparatus.Type: GrantFiled: January 29, 2002Date of Patent: June 22, 2004Assignee: ExxonMobil Research and Engineering CompanyInventors: Russell John Koveal, Michel Daage, Eric Baochun Shen
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Patent number: 6730221Abstract: Catalyst particles are separated from the wax in a reactor slurry reactor by feeding a portion of the slurry to a dynamic settler. Heavier catalyst particles settle and are removed as the slurry at the bottom of the settler is recycled back to the reactor. Clarified wax is removed at the top of the settler. A multi-channel baffle prevents turbulence, improving retention of the desired heavier catalyst particles.Type: GrantFiled: May 29, 2001Date of Patent: May 4, 2004Assignee: Rentech, Inc.Inventors: Mark S. Bohn, James E. Siebarth
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Patent number: 6712982Abstract: Catalyst particles are separated from the wax in a reactor slurry reactor by feeding a portion of the slurry to a dynamic settler. Heavier catalyst particles settle and are removed as the slurry at the bottom of the settler is recycled back to the reactor. Clarified wax is removed at the top of the settler. A multi-channel baffle prevents turbulence, improving retention of the desired heavier catalyst particles.Type: GrantFiled: April 17, 2003Date of Patent: March 30, 2004Assignee: Rentech, Inc.Inventors: Mark S. Bohn, James E. Siebarth
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Patent number: 6703430Abstract: A process for rejuvenating reversibly deactivated catalyst particles in a three-phase slurry body of gas bubbles and catalyst particles in a slurry liquid, includes passing slurry from the top down to the bottom of the body through a slurry catalyst rejuvenating means. The slurry is sequentially passed through a first gas bubble reducing zone, a catalyst rejuvenating gas contacting zone, a second gas bubble reducing zone and then a downcomer transfer zone. The gas bubble reducing, contacting and at least a portion of transfer occur in slurry body. At least part of the means is in the slurry body.Type: GrantFiled: December 17, 2002Date of Patent: March 9, 2004Assignee: ExxonMobil Research and Engineering CompanyInventor: Claude Clarence Culross
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Patent number: 6696502Abstract: Fresh catalyst particles are added to a slurry hydrocarbon synthesis reactor and their activity increased by contact with hydrogen in-situ in the slurry in a catalyst activity increasing means, while the reactor is producing hydrocarbons. The means may be a simple, vertically oriented and hollow tube, open at the top and bottom, into which slurry and a hydrogen treat gas are passed. The treat gas acts as a lift gas which provides slurry circulation into and out of the means and back into the slurry body, while increasing the activity of the catalyst particles. During the activity increase of the fresh catalyst, partially and reversibly activated catalyst particles are rejuvenated. The activity increasing means may be inside the reactor and at least partially immersed in the slurry or external of the reactor, or both.Type: GrantFiled: June 2, 2000Date of Patent: February 24, 2004Assignee: ExxonMobil Research and Engineering CompanyInventors: Charles John Mart, Daniel Ray Neskora
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Patent number: 6642281Abstract: There is provided an improved system and process for the catalytic hydrogenation of carbon monoxide to form a mixture of hydrocarbons utilizing a plurality of reactors in series. Synthesis gas entering the system under pressure is partially converted in at least one initial stage reactor and the effluent therefrom introduced into a final stage reactor. In the at least one initial stage reactor, a portion of the catalyst is continuously or periodically removed with some hydrocarbons and treated to renew, or renew and enhance it, and returned. The treatment comprises reducing the hydrocarbon context of the withdrawn mixture, heating to a temperature above at least one of the metals in the catalyst thereby forming a melt, removing any slag forming on the melt, cooling the melt and reducing the particle size of the resulting solid to a fine powder of renewed catalyst.Type: GrantFiled: September 1, 2000Date of Patent: November 4, 2003Assignee: ExxonMobil Research and Engineering CompanyInventors: David Chester Long, Michel A. Daage, Russell John Koveal
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Patent number: 6624204Abstract: A method is disclosed for renewing the activity of a Dispersed Active Metal (DAM) catalyst during operation of a reactor wherein the hydrogenation of carbon monoxide to produce a mixture of hydrocarbons is being carried out comprising withdrawing a mixture of hydrocarbons and a portion of the DAM catalyst, reducing the hydrocarbon content thereof, heating the mixture above the melting temperature of at least one of the metals of the DAM to form a melt, removing any slag that forms on the melt, cooling the melt to form a solid, reducing the particle size thereof to form a renewed particulate DAM catalyst, which is then returned to the reactor. Wherein the DAM catalyst is a Raney catalyst, a leachable metal is added to the reduced hydrocarbon mixture or the melt under non-oxidizing conditions and, after the solid is reduced to a fine particle size, extracting the leachable metal with caustic.Type: GrantFiled: September 1, 2000Date of Patent: September 23, 2003Assignee: ExxonMobil Research and Engineering CompanyInventors: Michel A. Daage, Russell John Koveal, David Chester Long, Leroy Russell Clavenna, Trikur Anantharaman Ramanarayaman, James Dirickson Mumford, Claude Clarence Culross
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Patent number: 6602921Abstract: A Fischer-Tropsch process for producing hydrocarbons, comprising contacting a feed stream comprising hydrogen and carbon monoxide with a catalyst in a reaction zone maintained at conversion-promoting conditions effective to produce an effluent stream comprising hydrocarbons, wherein the catalyst comprises at least one catalytically active metal selected from the group consisting of cobalt, iron, nickel and ruthenium and combinations thereof, a catalyst support, and silver. The catalyst may include a promoter. A preferred catalyst comprises cobalt, platinum and/or ruthenium and/or rhenium, and silver supported on a support selected from the group consisting of Al2O3, ZrO2, sulfated ZrO2, WO3—ZrO2, MCM-41, H-Beta, Sylopol SiO2, AlF3, fluorided Al2O3, bentonite, zeolite, TiO2, and SiO2—Al2O3, molecular sieves, and combinations thereof.Type: GrantFiled: May 8, 2001Date of Patent: August 5, 2003Assignee: ConocoPhillips CompanyInventors: Leo E. Manzer, Stephan Schwarz, Sergej Maslov
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Patent number: 6590002Abstract: A hydrocarbon wax product from a HCS slurry comprising liquid synthesis product and catalyst particles is purified by circulating the slurry from a synthesis zone with a first temperature through a treatment zone with a second temperature in which a hydrogen-containing treatment gas contacts the slurry. The gas treatment removes impurities from the hydrocarbon wax product and also removes catalyst de-activating species which may be present in the slurry. Purified wax product is separated and removed from the treated slurry via wax withdrawal means. This avoids or minimizes the need for further treating the wax product. Remaining treated slurry may be returned to the synthesis zone.Type: GrantFiled: July 13, 2001Date of Patent: July 8, 2003Assignee: ExxonMobil Research and Engineering CompanyInventors: Robert Jay Wittenbrink, Louis Francis Burns, Gregg Johnston Howsmon, Geoffrey Rhys Say, Charles Harrison Mauldin
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Publication number: 20030092781Abstract: An in situ process for conducting regeneration of spent hydrocarbon synthesis catalyst. Regenerated, but not yet re-activated, catalyst (15) may be introduced into an operating HCS reactor (1) that has catalyst rejuvenation means (14). Any combination of a fresh, activated catalyst, a fresh, passivated catalyst or short-term or long-term deactivated catalysts may already be present in the HCS reactor (1). The regenerated, but not yet re-activated catalyst is activated in the HCS reactor (1) with rejuvenation means (14) at normal process conditions. The HCS reactor (1) receives syngas through the inlet line (3) and releases liquid hydrocarbons through outlet line (4) and gaseous hydrocarbon and unreacted syngas through the offgas line (2). Catalyst is removed from the HCS reactor (1) through the slipstream line (5) and into a filtration unit (6) which is fed with a stripping fluid (7). The filtered catalyst proceeds to the regeneration unit (9) which is fed a regenerative fluid (10).Type: ApplicationFiled: November 13, 2001Publication date: May 15, 2003Inventors: Stuart Leon Soled, Joseph Ernest Baumgartner, Gabor Kiss
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Patent number: 6559191Abstract: A method is disclosed for enhancing the activity of a particulate Dispersed Active Metal (DAM) catalyst during operation of a reactor wherein the hydrogenation of carbon monoxide to produce a mixture of hydrocarbons is being carried out comprising withdrawing a mixture of hydrocarbons and a portion of the DAM catalyst from the reactor, reducing the hydrocarbon content thereof with hydrogen at a temperature above the temperature of the reactor, oxidizing a slurry of the catalyst particles in a suitable fluid at low temperature to form an oxidized precursor, reducing the precursor at elevated temperature to reform the catalyst and returning it to the reactor. The catalyst may be passivated before returning to the reactor.Type: GrantFiled: September 1, 2000Date of Patent: May 6, 2003Assignee: ExxonMobil Research and Engineering CompanyInventors: Russell John Koveal, Michel A. Daage
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Patent number: 6541525Abstract: A process for rejuvenating reversibly deactivated catalyst particles in a three-phase slurry body of gas bubbles and catalyst particles in a slurry liquid, includes passing slurry from the top down to the bottom of the body through a slurry catalyst rejuvenating means. The slurry is sequentially passed through a first gas bubble reducing zone, a catalyst rejuvenating gas contacting zone, a second gas bubble reducing zone and then a downcomer transfer zone. The gas bubble reducing, contacting and at least a portion of transfer occur in slurry body. At least part of the means is in the slurry body.Type: GrantFiled: March 27, 2001Date of Patent: April 1, 2003Assignee: ExxonMobil Research and Engineering CompanyInventor: Claude Clarence Culross
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Patent number: 6531517Abstract: A process for increasing the hydrogenation activity, particularly the carbon monoxide hydrogenation activity, of a catalyst or catalyst precursor comprised of a particulate solids support component and a catalytic metal, or metals component, preferably cobalt; cobalt alone or cobalt and an additional metal, or metals added to promote or modify the reaction produced by the cobalt. Treatment of the catalyst, or catalyst precursor is conducted at low temperature ranging from ambient to about 275° C. sufficient to form on the surface of a catalyst precursor, e.g., a cobalt catalyst precursor, a cobalt metal hydroxide, low valence cobalt metal oxide, or mixture of cobalt metal hydroxide and low valence cobalt metal oxide. Sometimes also metallic metal, e.g., cobalt, is also formed, and dispersed on the surface of the support.Type: GrantFiled: August 1, 2000Date of Patent: March 11, 2003Assignee: ExxonMobil Research and Engineering CompanyInventors: William Augustine Wachter, Gregg Johnston Howsmon, Jeffrey Thomas Elks, Leroy Russell Clavenna, Hyung Suk Woo, Claude Clarence Culross, Charles Harrison Mauldin, Christine Esther Kliewer
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Patent number: 6531518Abstract: A process of enhancing both the activity and the methane selectivity of a particulate Dispersed Active Metal (“DAM”) hydrogenation catalyst is disclosed wherein the DAM undergoes low temperature oxidation in a slurry phase to form a stable, unique oxidized catalyst precursor that is subsequently reduced to form an enhanced catalyst by treatment with hydrogen-containing gas at elevated temperature, wherein one or more promoter metal oxides of chromium, lanthanum and manganese are added to the DAM. Precursors of the promoter metal oxides may be combined with the DAMs prior to or during formation of the initial slurry, during the oxidation step or between recovery of the oxidized catalyst precursor and treatment of it with hydrogen-containing gas to reactivate the catalyst. Conversion of the precursors to the promoter metal oxides is carried out prior to the treatment with hydrogen-containing gas unless said treatment itself produces the conversion.Type: GrantFiled: September 1, 2000Date of Patent: March 11, 2003Assignee: ExxonMobil Research and Engineering Co.Inventors: Albert L'Vovich Lapidus, Alla Jurievna Krylova, Lilia Vadimovna Sineva, Russell John Koveal, Michel A. Daage
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Patent number: 6509382Abstract: Process for activating a Fischer-Tropsch synthesis catalyst that comprises at least two stages: at least one stage for activation in the presence of hydrogen, or a mixture of hydrogen and an inert gas, and at least one stage for activation in the presence of carbon monoxide or a mixture of carbon monoxide and an inert gas, and optionally a third activation stage that is carried out either in the presence of hydrogen or a mixture of hydrogen and an inert gas, or in the presence of carbon monoxide or a mixture of carbon monoxide and an inert gas.Type: GrantFiled: November 22, 2000Date of Patent: January 21, 2003Assignees: Institut Français du Petrole, AGIP Petroli S.p.A., ENI S.p.A.Inventors: Olivier Ducreux, Marie Claire Marion, Magalie Roy-Auberger, John Lynch
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Publication number: 20020183403Abstract: A process for regenerating a slurry Fischer-Tropsch catalyst, which needs regeneration, involves de-waxing and drying the catalyst sufficiently to produce a free-flowing catalyst powder that is fluidizable; fluidizing the catalyst powder; treating the catalyst powder with an oxygen treatment; reducing the catalyst powder with a reducing gas to form a reduced catalyst powder; and mixing the reduced catalyst powder with hydrocarbons to form a regenerated, slurry catalyst. The oxidation and reduction steps may be repeated. An oxygen treatment includes using a fixed O2 level with ramped temperatures, fixed temperatures with increased O2 levels, or a combination.Type: ApplicationFiled: April 12, 2002Publication date: December 5, 2002Inventors: Jui-Hsin R. Huang, Kenneth L. Agee, Kym B. Arcuri, Paul F. Schubert
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Patent number: 6486220Abstract: A process is disclosed for regenerating catalyst used in a process for synthesizing hydrocarbons. The synthesis process involves contacting a feed stream comprising hydrogen and carbon monoxide with a catalyst in a reaction zone maintained at conversion-promoting conditions effective to produce an effluent stream comprising hydrocarbons. The regeneration. process comprises contacting a deactivated Fischer-Tropsch catalyst with a steam under regeneration-promoting conditions, for a period of time sufficient to reactivate the Fischer-Tropsch catalyst.Type: GrantFiled: November 15, 2000Date of Patent: November 26, 2002Assignee: Conoco Inc.Inventor: Harold A. Wright
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Patent number: 6475943Abstract: The present invention relates to a process for the activation of a catalyst in the presence of a hydrocarbon liquid, which catalyst comprises a Group Ib, VIIb or VIII metal compound, by contacting the catalyst with a hydrogen-containing gas at a hydrogen partial pressure of at least 15 bar abs. The present invention further relates to a hydrocarbon synthesis process which comprises activating a hydrocarbon synthesis catalyst in the presence of a hydrocarbon liquid by contacting the catalyst with a hydrogen-containing gas at a hydrogen partial pressure of at least 15 bar abs., and, subsequently, contacting the catalyst with a mixture of hydrogen and carbon monoxide at hydrocarbon synthesis reaction conditions.Type: GrantFiled: September 9, 1998Date of Patent: November 5, 2002Assignee: Shell Oil CompanyInventors: Arend Hoek, Jeroen Harrie Moors
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Patent number: 6465529Abstract: An aqueous low temperature oxidation (ALTO) process wherein a catalyst or catalyst precursor constituted of a solids support, or powder component, and a metal, or metals component, inclusive of cobalt, is oxidized, reduced and rendered catalytically active for conducting carbon monoxide hydrogenation reactions. The cobalt catalyst or cobalt catalyst precursor is thus contacted at low temperature with an oxidant in the presence of water (e.g., water to which an oxidant is added), sufficient to oxidize the cobalt metal, or metals component of the catalyst or catalyst precursor. On reduction, the hydrogenation activity of the cobalt catalyst is increased. All or a portion of the cobalt metal of the catalyst precursor is oxidized to form a Co2+ cationic or oxo-anionic species at least during the initial phase of the reaction.Type: GrantFiled: August 1, 2000Date of Patent: October 15, 2002Assignee: ExxonMobil Research and Engineering CompanyInventors: Michel Andre Daage, Russell John Koveal, Leroy Russell Clavenna
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Publication number: 20020137805Abstract: A process and apparatus for synthesizing hydrocarbons from synthesis gas is disclosed. The process useful for initial start-up of a Fischer-Tropsch reactor system in a slurry bubble column reactor. Synthesis gas comprising hydrogen and carbon dioxide is reacted to form hydrocarbons. A liquid slurry comprising a start-up composition may include polyalpha olefins, astor wax, waxes, and paraffins. The reaction employs a low superficial vapor velocity, a medium to high catalyst concentration, and relatively mild reactor temperatures as compared to conventional Fischer-Tropsch processes.Type: ApplicationFiled: January 26, 2001Publication date: September 26, 2002Inventors: Jui-Hsin Ray Huang, Kym B. Arcuri
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Patent number: 6455596Abstract: A process for the desulfurization, and reactivation of a sulfur deactivated catalyst constituted of cobalt composited with a titania support. The sulfur deactivated cobalt titania catalyst is first contacted with a gaseous stream of molecular oxygen at temperature sufficiently high to oxidize the sulfur component of the catalyst. The sulfur oxidized catalyst is next contacted with a liquid, preferably water, to remove the oxide, or oxides of the sulfur. The catalyst is then contacted with a reducing agent, suitably hydrogen, to restore the activity of the catalyst. During the treatment there is no substantial loss, if any, of cobalt from the catalyst.Type: GrantFiled: January 9, 2001Date of Patent: September 24, 2002Assignee: ExxonMobil Research and Engineering CompanyInventors: Albert L'Vovich Lapidus, Michel A. Daage, Russell J. Koveal, Alla Jurievna Krylova, Anatoliy B. Erofeev
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Patent number: 6331574Abstract: A process for the preparation of a catalyst useful for conducting carbon monoxide hydrogenation reactions, especially Fischer-Tropsch reactions. The steps of the process begin with the activation, or reactivation, of a deactivated catalyst, or with the preparation and activation of a fresh catalyst. In accordance with the latter, the steps of the process comprise, first contacting, in one or more steps, a powder or preformed, particulate refractory inorganic support with a liquid, or solution in which there is dispersed or dissolved a compound, or salt of a catalytically active metal, or metals, to impregnate and deposit the metal, or metals, upon the support, or powder. The metal, or metals, impregnated support is calcined following each impregnation step to form oxides of the deposited metal, or metals.Type: GrantFiled: October 8, 1999Date of Patent: December 18, 2001Assignee: ExxonMobil Research and Engineering CompanyInventors: Albert L'Vovoch Lapidus, Alla Jurievna Krylova, Michel A. Daage, Russell J. Koveal, Rocco A. Fiato
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Patent number: 6323248Abstract: Fresh catalyst particles are added to a slurry hydrocarbon synthesis reactor and their activity increased by contact with hydrogen in-situ in the slurry in a catalyst activity increasing means, while the reactor is producing hydrocarbons. The means may be a simple, vertically oriented and hollow tube, open at the top and bottom, into which slurry and a hydrogen treat gas are passed. The treat gas acts as a lift gas which provides slurry circulation into and out of the means and back into the slurry body, while increasing the activity of the catalyst particles. During the activity increase of the fresh catalyst, partially and reversibly activated catalyst particles are rejuvenated. The activity increasing means may be inside the reactor and at least partially immersed in the slurry or external of the reactor, or both.Type: GrantFiled: June 2, 2000Date of Patent: November 27, 2001Assignee: ExxonMobil Research and Engineering CompanyInventors: Charles John Mart, Daniel Ray Neskora
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Publication number: 20010006984Abstract: A process for the desulfurization, and reactivation of a sulfur deactivated catalyst constituted of cobalt composited with a titania support. The sulfur deactivated cobalt titania catalyst is first contacted with a gaseous stream of molecular oxygen at temperature sufficiently high to oxidize the sulfur component of the catalyst. The sulfur oxidized catalyst is next contacted with a liquid, preferably water, to remove the oxide, or oxides of the sulfur. The catalyst is then contacted with a reducing agent, suitably hydrogen, to restore the activity of the catalyst. During the treatment there is no substantial loss, if any, of cobalt from the catalyst.Type: ApplicationFiled: January 9, 2001Publication date: July 5, 2001Inventors: Albert L?apos;Vovich Lapidus, Michel A. Daage, Russell J. Koveal, Alla Jurievna Krylova, Anatoliy B. Erofeev
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Patent number: 6239184Abstract: A process for extending the life of a Fisher-Tropsch catalyst in a process for converting synthesis gas produced in an autothermal reactor by the substoichiometric oxidation of a light hydrocarbon gas by removing ammonia from the synthesis gas prior to passing the synthesis gas to a Fischer-Tropsch reactor.Type: GrantFiled: September 22, 1999Date of Patent: May 29, 2001Assignee: Syntroleum CorporationInventors: Gary L. Beer, James F. Leahy, Greg A. Lisewsky, Kernan J. McHugh, Michael D. Briscoe
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Patent number: 6201030Abstract: A method of regenerating a finely-divided particulate catalyst involves the use of an external regeneration system comprising first and second regeneration stations. The method is particularly adapted to regenerating supported catalysts used in Fischer-Tropsch slurry reactors. A slurry-containing partially spent catalyst is flowed from the reactor and alternately regenerated in one of the first and second regeneration stations. The alternate use of the stations for catalyst regeneration permits one station to receive partially deactivated slurry from the reactor while the other station returns regenerated slurry to the reactor. The operation of the reactor thus may be continuous.Type: GrantFiled: September 22, 1999Date of Patent: March 13, 2001Assignee: Syntroleum CorporationInventor: Gary L. Beer
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Patent number: 6162754Abstract: Continuous process for the production of prevalently heavy hydrocarbons starting from synthesis gas in the presence of a gas phase, a liquid and a solid catalyst, the above process being carried out using a bubble column, characterized in that the bubble column internally has: (a) at least one draft-tube; (b) at least one device for the inlet of the synthesis gas; (c) at least one device for the inlet of the regenerating gas; (d) at least one device for activating/interrupting the stream of regenerating gas; (e) optional devices suitable for minimizing the mixing of the synthesis gas with the regenerating gas.Type: GrantFiled: March 18, 1999Date of Patent: December 19, 2000Assignees: Agip Petroli S.p.A., ENI S.p.A., Institut Francais du PetroleInventors: Cristina Maretto, Vincenzo Piccolo, Dominique Casanave, Pierre Galtier
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Patent number: 6147126Abstract: A gas conversion process including catalytic hydrocarbon synthesis from a synthesis gas comprising a mixture of H.sub.2 and CO, produces hydrogen from the synthesis gas and upgrades synthesized hydrocarbons by one or more hydroconversion operations which utilize this hydrogen. The hydroconversion also produces a hydrogen rich tail gas which is used in the process for at least one of (i) hydrocarbon synthesis catalyst rejuvenation, (ii) the hydrocarbon synthesis, and (iii) hydrogen production. In one embodiment the tail gas is used to hydrodesulfurize sulfur-containing hydrocarbon liquids recovered from the natural gas used to form the synthesis gas. The hydrogen production is accomplished by physical separation, such as PSA, with or without chemical means such as a water gas shift reaction.Type: GrantFiled: February 10, 1998Date of Patent: November 14, 2000Assignee: Exxon Research and Engineering CompanyInventors: Charles W. DeGeorge, Robert J. Wittenbrink, Thomas M. Stark
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Patent number: 6136868Abstract: A process for the preparation of a catalyst useful for conducting carbon monoxide conversion reactions, especially a Fischer-Tropsch catalyst, use of the catalyst for conducting such reactions, especially Fischer-Tropsch reactions, and the composition produced by said process. In the preparation of the catalyst, a solution of a carbohydrate, or sugar, notably a monosaccharide or disaccharide, particularly sucrose, is employed to impregnate and disperse a compound or salt of a catalytic metal, or metals, e.g., copper or an Iron Group metal such as iron, cobalt, or nickel, or in a preferred embodiment both a compound or salt of rhenium and a compound or salt of a catalytic metal, or metals, e.g., copper or an Iron Group metal such as iron, cobalt, or nickel, onto a refractory inorganic oxide support, e.g., titania. The rhenium, when present only in small amount permits full and complete reduction of the catalytic metal, or metals, dispersed by the carbohydrate.Type: GrantFiled: September 15, 1998Date of Patent: October 24, 2000Assignee: Exxon Research and Engineering CompanyInventors: Claude C. Culross, Charles H. Mauldin
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Patent number: 6103773Abstract: A gas conversion process comprising synthesis gas production, hydrocarbon synthesis and hydrogen production from the synthesis gas, also includes hydrodesulfurizing sulfur-containing hydrocarbon liquids separated from a mixture of natural gas and the liquids produced from a gas well. Hydrogen produced from the synthesis gas is used for the hydrodesulfurization, to remove at least a portion of the sulfur as H.sub.2 S and form desulfurized hydrocarbon liquid. The hydrogen is produced from the synthesis gas by one or more of (i) physical separation means such as pressure swing adsorption and (ii) chemical means such as a water gas shift reactor. The synthesized hydrocarbons are upgraded by hydroconversion. A portion of the hydrogen produced from the synthesis gas may also be used for at least one of (i) hydrocarbon synthesis catalyst rejuvenation and the hydroconversion.Type: GrantFiled: February 27, 1998Date of Patent: August 15, 2000Assignee: Exxon Research and Engineering CoInventors: Robert J. Wittenbrink, Charles W. DeGeorge
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Patent number: 6068760Abstract: Catalyst particles are separated from the wax in a Fischer-Tropsch reactor by feeding a portion of the reactor slurry to a dynamic settler which does not require any pump. As the slurry flows down a pipe in the center of the settler, the slurry flows into the surrounding annular region at the bottom of the settler. The heavier catalyst particles settle down and are removed as the slurry at the bottom of the settler is recycled back to the reactor. The wax rises up in the annular section and this clarified wax is removed by a wax outlet pipe. In an embodiment with an expanded diameter section above the Fischer-Tropsch reactor an additional dynamic settler can be placed inside this section. The Fischer-Tropsch catalyst can be regenerated by purging the catalyst with an inert gas for a period of time and by treating the catalyst with naphtha.Type: GrantFiled: August 7, 1998Date of Patent: May 30, 2000Assignee: Rentech, Inc.Inventors: Charles B. Benham, Dennis L. Yakobson, Mark S. Bohn
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Patent number: 6066679Abstract: Partially deactivated catalyst in a slurry hydrocarbon synthesis process is rejuvenated employing a cyclic rejuvenation process in which syngas or CO flow into the slurry is stopped to stop the hydrocarbon synthesis reaction, the CO purged out of the slurry with a purge gas in the presence of hydrogen, the catalyst rejuvenated with a hydrogen containing rejuvenating gas and the hydrocarbon synthesis reaction restarted by passing the synthesis gas feed back into the reactor. All or a portion of the purge gas and/or the rejuvenating gas may be recycled during the respective purge and/or rejuvenation. The hydrogen required during the purge is typically part of the purge gas.Type: GrantFiled: October 16, 1998Date of Patent: May 23, 2000Assignee: Exxon Research and Engineering CompanyInventors: Stephen C. Leviness, Willard N. Mitchell
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Patent number: 6060524Abstract: The invention concerns a process for optimal operation of a slurry bubble column containing a suspension of solid particles in a liquid, characterized in that a gas phase containing the reactant(s) required for the production of the desired products is injected in the form of bubbles close to the lower extremity of said reactor and at least a portion of the liquid fraction and optionally of the solid fraction of said suspension is recirculated, drawn off from close to one extremity of said reactor and reintroduced close to the other extremity of said reactor, with a liquid flow rate U.sub.1 in the reactor which is at least equal to and preferably greater than the sedimentation rate U.sub.s of the solid particles. The invention also concerns an apparatus for optimal operation of the process. Finally, the invention concerns the use of the process and apparatus in the Fischer-Tropsch synthesis.Type: GrantFiled: January 11, 1999Date of Patent: May 9, 2000Assignees: Institut Francais du Petrole,, Agip S.p.A., Agip Petroli S.p.A.Inventors: Dominique Casanave, Pierre Galtier, Jean-Charles Viltard
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Patent number: 6043288Abstract: A gas conversion process in which both hydrocarbons and hydrogen are produced from a synthesis gas feed which comprises a mixture of H.sub.2 and CO, uses hydrogen from a portion of the feed for one or more of (i) hydrocarbon synthesis catalyst rejuvenation and (ii) hydroconversion upgrading of at least a portion of the synthesized hydrocarbons. Hydrogen is produced from a slipstream of the synthesis gas fed into the hydrocarbon synthesis reactor by one or more of (i) physical separation means such as pressure swing adsorption and (ii) chemical means such as a water gas shift reactor. If a shift reactor is used due to insufficient capacity of the synthesis gas generator, physical separation means such as pressure swing adsorption will still be used to separate a pure stream of hydrogen from the shift reactor gas effluent.Type: GrantFiled: February 13, 1998Date of Patent: March 28, 2000Assignee: Exxon Research and Engineering Co.Inventors: Charles W. DeGeorge, Robert D. Denton
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Patent number: 5962537Abstract: A downcomer for producing at least two slurries having different solids and gas concentrations from a single three phase slurry of particulate solids and gas bubbles in a slurry liquid has two or more concentric gas and solids disengaging zones, each having an open fluid conduit depending from an orifice in the bottom. The dowwncomer is useful in a slurry hydrocarbon synthesis process for forming a catalyst and gas reduced slurry which is passed to a liquid filter to remove hydrocarbon liquid from the slurry reactor.Type: GrantFiled: May 6, 1997Date of Patent: October 5, 1999Assignee: Exxon Research and Engineering CoInventor: Stephen Claude Leviness
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Patent number: 5958986Abstract: A reversibly deactivated hydrocarbon synthesis catalyst in a hydrocarbon synthesis slurry is rejuvenated by passing the slurry into a lift pipe external of the reactor in which it contacts a hydrogen containing rejuvenating gas. The hydrogen rejuvenates the catalyst particles in the slurry and forms a mixture of a rejuvenation offgas which may contain catalyst deactivating species and a rejuvenated catalyst slurry. This mixture is passed into a gas separating and removal vessel in which the offgas is separated and removed from the slurry, which is then returned back into the reactor or elsewhere. The rejuvenating gas also acts as a lift gas to create slurry circulation up through the lift pipe and into the gas removal vessel.Type: GrantFiled: May 2, 1997Date of Patent: September 28, 1999Assignee: Exxon Research and Engineering Co.Inventors: Charles John Mart, Stephen Ju-Ming Hsia
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Patent number: 5929126Abstract: A gas conversion process includes producing a synthesis gas which contains ammonia and hydrogen cyanide and forms hydrocarbons by reacting the hydrogen and carbon monoxide in the gas in the presence of a hydrocarbon synthesis catalyst also reversibly deactivates the catalyst due to the presence of the ammonia and hydrogen cyanide in the gas. The catalyst is rejuvenated with a gas comprising hydrogen and produces an ammonia containing rejuvenation offgas. The ammonia is dissolved out of the offgas with water and then stripped out of the water with the hydrocarbon feed to the synthesis gas generator and into the generator where it is consumed.Type: GrantFiled: January 30, 1998Date of Patent: July 27, 1999Assignee: Exxon Research and Engineering Co.Inventors: Russel J. Koveal, Dennis G. Alexion
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Patent number: 5844006Abstract: A process for producing liquid and, optionally, gaseous products from gaseous reactants comprises feeding gaseous reactants into a slurry bed of solid particles suspended in a liquid; allowing the reactants to react as they pass upwardly through the slurry bed, thereby to form liquid and, optionally, gaseous products; and separating liquid product from the solid particles by passing, in a filtration zone within the slurry bed, liquid product through a filtration medium in a first direction, so that a cake of the solid particles forms on the filtration medium. The passage of liquid product through the filtering medium is interrupted. The filtering medium is then backflushed by passing a flushing fluid through the filtering medium in a second direction, opposite to the first direction, for at least portions of the periods that the liquid product passage is interrupted, thereby to dislodge the cake from the filtering medium.Type: GrantFiled: September 27, 1996Date of Patent: December 1, 1998Assignee: Sasol Chemical Industries (Proprietary) LimitedInventors: Berend Jager, Andre Peter Steynberg, Juan Ricardo Inga, Renus Constantyn Kelfkens, Michael Anthony Smith, Francois Erenst Johannes Malherbe
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Patent number: 5260239Abstract: Catalyst which has become deactivated during a hydrocarbon synthesis (HCS) process is reactivated - rejuvenated using an external reactivation - rejuvenation vessel resulting in a multiple HCS reaction - catalyst rejuvenation reactor vessel design. Flow of the catalyst is synthesis product slurry from the reactor vessel to the rejuvenation vessel and the flow of rejuvenated catalyst back to the reactor vessel are driven by gravity only.Type: GrantFiled: December 18, 1992Date of Patent: November 9, 1993Assignee: Exxon Research & Engineering CompanyInventor: Stephen J. Hsia
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Patent number: 5118891Abstract: A composition for use after reductive activation as a catalyst in the conversion of synthesis gas to hydrocarbons, the composition having formula: Ru.sub.z A.sub.b CeO.sub.Type: GrantFiled: July 30, 1991Date of Patent: June 2, 1992Assignee: The British Petroleum Company p.l.c.Inventors: Graham Butler, Malcolm P. Heyward
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Patent number: 5004717Abstract: A process is provided for regenerating aged copper-containing coprecipitated methanol synthesis catalyst. The process includes treating the aged catalyst in an oxidizing atmosphere according to a specified time-temperature ramp, then in a reducing atmosphere. The oxidation-reduction cycle may be repeated as needed. An advantage of the invention is that the catalyst may be regenerated in situ in the same vessel in which the catalyst is utilized to make alcohol.Type: GrantFiled: April 28, 1989Date of Patent: April 2, 1991Assignee: Electric Power Research Institute, Inc.Inventors: Sunggyu Lee, Sawant Ashok, Conrad J. Kulik
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Patent number: 4978689Abstract: The medium pressure Fischer-Tropsch synthesis of liquid hydrocarbons conducted with an iron catalyst is made more efficient by temporarily suspending conventional synthesis and treating the catalyst with a high partial pressure of water vapor, after which conventional synthesis is resumed. The treatment inparts a large increase in selectivity for liquids with reduction of methane formation. The treatment is very effective with alkali (e.g. potassium) promoted precipitated iron catalyst.Type: GrantFiled: March 17, 1989Date of Patent: December 18, 1990Assignee: Mobil Oil Corp.Inventors: Weldon K. Bell, Werner O. Haag
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Patent number: 4822824Abstract: A hydrogen regenerable hydrocarbon synthesis catalyst useful for preparing higher hydrocarbons from synthesis gas is prepared by depositing cobalt and ruthenium on a refractory carrier and oxidizing and reducing the catalytic metals to form a catalyst in which the cobalt and ruthenium are in intimate contact.Type: GrantFiled: December 7, 1987Date of Patent: April 18, 1989Assignee: Exxon Research and Engineering CompanyInventors: Enrique Iglesia, Stuart L. Soled, Rocco A. Fiato
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Patent number: 4801574Abstract: The present invention relates to a method of activation of a CuO/ZnO/Al.sub.2 O.sub.3 catalyst slurried in a chemically inert liquid. Successful activation of the catalyst requires the use of a process in which the temperature of the system at any time is not allowed to exceed a certain critical value, which is a function of the specific hydrogen uptake of the catalyst at that same time. This process is especially critical for activating highly concentrated catalyst slurries, typically 25 to 50 wt %. Activation of slurries of CuO/ZnO/Al.sub.2 O.sub.3 catalyst is useful in carrying out the liquid phase methanol or the liquid phase shift reactions.Type: GrantFiled: December 2, 1987Date of Patent: January 31, 1989Assignee: Air Products and Chemicals, Inc.Inventors: Dennis M. Brown, Thomas H. Hsiung, Pradip Rao, George W. Roberts
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Patent number: RE37515Abstract: A cobalt- or ruthenium-containing hydrocarbon synthesis catalyst, subjected to short term, reversible, partial deactivation in a slurry synthesis process can be rejuvenated, i.e., at least about 80+% catalyst activity recovery, by treating the catalyst in the presence of liquid hydrocarbons, preferably the slurry hydrocarbons, with hydrogen at elevated temperatures and pressures.Type: GrantFiled: August 13, 1998Date of Patent: January 15, 2002Assignee: Exxon Research and Engineering CompanyInventor: Willard N. Mitchell
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Patent number: RE37649Abstract: Catalyst in a slurry phase reactor is rejuvenated and uniformly distributed in said reactor using a substantially vertical draft tube fully immersed in the slurry which utilizes a rejuvenating gas injected substantially near the bottom of the substantially vertical draft tube whereby catalyst near the bottom of the slurry phase reactor is drawn up the draft tube and discharged from the top of the draft tube near the top of the slurry phase in said reactor.Type: GrantFiled: August 13, 1998Date of Patent: April 9, 2002Assignee: Exxon Research and Engineering CompanyInventors: Larry E. Pedrick, Charles H. Mauldin, William C. Behrmann
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Patent number: RE38170Abstract: A gas conversion process in which both hydrocarbons and hydrogen are produced from a synthesis gas feed which comprises a mixture of H2 and CO, uses hydrogen from a portion of the feed for one or more of (i) hydrocarbon synthesis catalyst rejuvenation and (ii) hydroconversion upgrading of at least a portion of the synthesized hydrocarbons. Hydrogen is produced from a slipstream of the synthesis gas fed into the hydrocarbon synthesis reactor by one or more of (i) physical separation means such as pressure swing adsorption and (ii) chemical means such as a water gas shift reactor. If a shift reactor is used due to insufficient capacity of the synthesis gas generator, physical separation means such as pressure swing adsorption will still be used to separate a pure stream of hydrogen from the shift reactor gas effluent.Type: GrantFiled: March 28, 2002Date of Patent: July 1, 2003Assignee: ExxonMobil Research and Engineering CompanyInventors: Charles William DeGeorge, Robert Dean Denton