Employing Hydrogen Patents (Class 208/251H)
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Patent number: 4681869Abstract: A composition of matter consisting essentially of alumina and at least one compound (preferably oxide) of yttrium and/or zirconium is provided and is employed as a catalyst in the hydrotreating of a substantially liquid hydrocarbon containing feed stream (particularly a heavy oil) which also contains compounds of nickel, vanadium and sulfur. The preferred preparation of the catalyst compositions of this invention comprises at least one impregnating step using a solution containing at least one aluminum compound, which is at least partially converted to aluminum oxide in a subsequent calcining step.Type: GrantFiled: September 27, 1985Date of Patent: July 21, 1987Assignee: Phillips Petroleum CompanyInventors: Simon G. Kukes, Stephen L. Parrott
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Patent number: 4680105Abstract: A new composition of matter comprises nickel phosphate and titanium phosphate, preferably prepared by coprecipitation. A process for removing metals from a hydrocarbon-containing feed stream, in particular a heavy oil, comprises hydrotreatment in the presence of a solid catalyst composition comprising nickel phosphate and titanium phosphate (preferably coprecipitated).Type: GrantFiled: May 5, 1986Date of Patent: July 14, 1987Assignee: Phillips Petroleum CompanyInventors: Daniel M. Coombs, Ted H. Cymbaluk, Brent J. Bertus, Simon G. Kukes
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Patent number: 4677093Abstract: The invention relates to a hydrodemetallization process and catalyst, of a sulfur and organometallic containing hydrocarbon feedstock which consists in contacting the feedstock under the usual hydrotreating conditions with a catalyst comprising a refractory mineral carrier composed essentially of a mesoporous alumina with defined characteristics, said catalyst having previously been sulfurized. The process is characterized in that the catalyst contains, in addition to the carrier, in free or combined form, from 0.01 to 0.7 weight percent, based on the total weight of the catalyst, and calculated as if in elemental form, of at least one metal selected from groups Vb, VIb, VIIb and VIII of the periodic table of the elements, so as to give optimum initial demetallizing activity.Type: GrantFiled: August 29, 1986Date of Patent: June 30, 1987Assignee: Compagnie Francaise de RaffinageInventors: Jacques Devanneaux, Jean-Paul Gallez, Laurent Mariette
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Patent number: 4671866Abstract: A process for removing metals from a hydrocarbon-containing feed stream comprises hydrotreatment in the presence of a solid catalyst composition comprising aluminum phosphate, zirconium phosphate and copper phosphate (preferably coprecipitated).Type: GrantFiled: February 26, 1986Date of Patent: June 9, 1987Assignee: Phillips Petroleum CompanyInventors: Daniel M. Coombs, Gerhard P. Nowack, Brent J. Bertus, Simon G. Kukes
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Patent number: 4670134Abstract: Hydrocarbon-containing feed streams, which contain at least about 5 ppmw nickel and at least about 10 ppmw vanadium, are hydrodemetallized either (I) in the presence of a catalyst composition consisting essentially of (a) a support material (preferably alumina), and (b) at least one lanthanide metal compound (preferably CeO.sub.2 and/or Ce.sub.2 O.sub.3); or (II) in the presence of a catalyst composition comprising (a) a support material (preferably alumina), (b) at least one lanthanide metal compound (preferably La.sub.2 O.sub.3) and (c) at least one manganese compound (preferably at least one manganese oxide).Type: GrantFiled: May 2, 1986Date of Patent: June 2, 1987Assignee: Phillips Petroleum CompanyInventors: John H. Kolts, Brent J. Bertus, Daniel M. Coombs
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Patent number: 4666588Abstract: The present invention provides for an improved three-phase reactor design and method of operation. A liquid feed/catalyst slurry is mixed with a hydrogen-containing gas stream in an external mixing loop in fluid communication with a vertically oriented reaction vessel. The hydrogen-enriched slurry is subsequently passed downwardly through the reaction vessel where the liquid feed is reacted with the hydrogen to form a usable product.Type: GrantFiled: June 19, 1985Date of Patent: May 19, 1987Assignee: Air Products and Chemicals, Inc.Inventor: James R. Murphy
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Patent number: 4659454Abstract: Catalytic hydroconversion of a relatively heavy hydrocarbon residual fraction is effected in the presence of a lighter oil fraction by adding a thermally decomposable metal compound to the oil, along with an acidic catalyst solid to the oil, and passing the mixture to a hydroconversion zone containing hydrogen at an elevated temperature. Preferred metals are cobalt and molybdenum. Preferred solids are large pore zeolites, silica/alumina, clays and surface activated metal oxides.Type: GrantFiled: September 30, 1985Date of Patent: April 21, 1987Assignee: Mobil Oil CorporationInventors: Philip Varghese, Darrell D. Whitehurst
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Patent number: 4659452Abstract: A two-stage hydrotreating process comprises the steps of (1) contacting a liquid hydrocarbon-containing feed stream, which contains nickel, vanadium and Ramsbottom carbon residue, with hydrogen and a solid inorganic refractory material (preferably alumina) for at least partial removal of Ni and V, and then (2) hydrovisbreaking the intermediate product stream from step (1). Preferably, step (2) is carried out in the presence of at least one decomposable compound of a metal, preferably a molybdenum dithiophosphate.Type: GrantFiled: May 23, 1986Date of Patent: April 21, 1987Assignee: Phillips PetroleumInventor: Jerald A. Howell
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Patent number: 4657665Abstract: Disclosed is an improved ebullated bed process for the hydroconversion of heavy hydrocarbon feedstocks containing asphaltenes, metals, and sulfur compounds. The disclosed process is characterized by the use of a catalyst comprising a relatively small amount of cobalt, i.e., 0.4 to 0.8 wt. % incorporated with a high macropore volume Group VIB metal containing catalyst.Type: GrantFiled: December 20, 1985Date of Patent: April 14, 1987Assignee: Amoco CorporationInventors: William I. Beaton, Albert L. Hensley, April J. Evans
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Patent number: 4657663Abstract: The catalytic hydrotreating of a residual oil-containing feedstream is carried out in a multi-catalyst bed in which the feedstream is first contacted with a catalyst bed which comprises of alumina, cobalt, molybdenum and nickel. The feedstream is then contacted with a second catalyst bed which contains a catalyst comprising alumina to which molybdenum, titanium and nickel have been added, followed by a third catalyst bed which contains a catalyst comprising alumina to which molybdenum and nickel have been added.Type: GrantFiled: April 24, 1985Date of Patent: April 14, 1987Assignee: Phillips Petroleum CompanyInventors: Lloyd E. Gardner, Robert J. Hogan, Edward L. Sughrue, II, John W. Myers
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Patent number: 4657664Abstract: Disclosed is an improved multi-stage process for the hydroconversion of heavy hydrocarbon feedstocks containing asphaltenes, metals and sulfur compounds. The process is characterized by the use of a relatively inexpensive demetallation catalyst in a first reaction zone comprising a Group VIB and/or a Group VIII metal deposed on a high macropore volume inorganic support followed by the use of a desulfurization catalyst in a second reaction zone comprising a Group VIB and a Group VIII metal on a high macropore volume inorganic oxide support.Type: GrantFiled: December 20, 1985Date of Patent: April 14, 1987Assignee: Amoco CorporationInventors: April J. Evans, Albert L. Hensley
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Patent number: 4655905Abstract: The invention relates to a process for catalytic treatment of heavy hydrocarbons, in a fixed or moving bed, over a catalyst containing an alumina carrier and at least one catalytic metal or compound of metal from groups VB, VI B and VIII of the periodic classification of elements, characterized by the direct injection into the charge, continuously or periodically, of at least one metal compound selected from the group consisting of halides, oxyhalides, oxides, polyacids and polyacid salts of metals from groups VI B, VII B and VIII, before introducing the charge into the hydrotreatment zone.Type: GrantFiled: October 24, 1985Date of Patent: April 7, 1987Assignee: Institut Francais Du PetroleInventors: Jean-Claude Plumail, Jean-Francois Le Page, Pierre Giuliani
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Patent number: 4652361Abstract: A composition of matter consisting essentially of alumina and at least one compound (preferably oxide) of yttrium and/or zirconium is provided and is employed as a catalyst in the hydrotreating of a substantially liquid hydrocarbon containing feed stream (particularly a heavy oil) which also contains compounds of nickel, vanadium and sulfur. The preferred preparation of the catalyst compositions of this invention comprises at least one impregnating step using a solution containing at least one aluminum compound, which is at least partially converted to aluminum oxide in a subsequent calcining step.Type: GrantFiled: June 26, 1986Date of Patent: March 24, 1987Assignee: Phillips Petroleum CompanyInventors: Simon G. Kukes, Stephen L. Parrott
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Patent number: 4648963Abstract: A catalyst composition is prepared by dissolving a suitable oxygen containing compound of a Group VIB metal (preferably Mo), a suitable compound of a Group VIII metal (preferably Ni) and phosphorous acid in water, mixing this solution with an alumina containing support material, and calcining this mixture. This catalyst composition is used primarily for hydrotreating of hydrocarbon feed stream, which contain nitrogen and sulfur impurities, particularly heavy cycle oils.Type: GrantFiled: January 29, 1986Date of Patent: March 10, 1987Assignee: Phillips Petroleum CompanyInventors: Simon G. Kutes, Stephen L. Parrott
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Patent number: 4642179Abstract: A catalyst for the hydrotreatment of heavy crudes and their residues, and a method of preparing same, is disclosed, which has significant simultaneous hydrodemetallizing and hydrodesulfurizing activity. The catalyst is prepared by successively impregnating an extruded refractory support with a Group VIb and a Group VIII metal, calcining the pellet thus produced, and presulfurizing same. Pore volume of the catalyst ranges between 0.50 and 1.2 ml/g, total surface area ranges between 120 and 140 m.sup.2 /g, at least 60% of said pore volume consists of pores having diameters greater than 100 .ANG., and x-ray photoelectron spectroscopy signal band strength ratios are as follows: I(Me VIb)/I(refractory metal) is between 5 and 8, and I(Me VIII)/I(refractory metal) is between 1 and 5.Type: GrantFiled: February 28, 1986Date of Patent: February 10, 1987Assignee: Intevep, S.A.Inventors: Alfredo L. Morales, Roberto Galiasso, Angel R. Carrasquel, Jose A. Salazar
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Patent number: 4640765Abstract: A method for cracking a heavy fraction oil is provided in which is solved a problem as to an increase in pressure loss due to coking in a cracking tower during the treatment of heavy fraction oils containing at least 1.0 wt. % of asphaltene. The cracking tower is vertically divided into at least two portions with a partition for housing a solid catalyst having a hydrogenation function, and the divided portions are communicated with each other at the upper and lower parts of the tower. A starting heavy fraction oil, a hydrogen donative solvent, and a hydrogen-containing gas are introduced into at least one of the divided portions at the lower part thereof, and further the fluid is circulated between the divided portions. Another method for cracking heavy fraction oils is provided in which a heavy hydrocarbon oil containing at least 1.0 wt.Type: GrantFiled: August 29, 1985Date of Patent: February 3, 1987Assignee: Nippon Oil Co., Ltd.Inventor: Junichi Kubo
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Patent number: 4627910Abstract: A hydrocarbon conversion catalyst containing cobalt and a Group VIB metal and having a substantially uniform cross-sectional phosphorus distribution is prepared by impregnating support particles with a solution containing dissolved cobalt, phosphorus, and at least 17 weight percent of Group VIB metal components, calculated as the trioxides, having a pH of less than 1.2, and characterized by an extinction coefficient in the ultraviolet spectrum of about 0.7.times.10.sup.4 to about 1.8.times.10.sup.4 liters/cm.multidot.moles of Group VIB metal, followed by aging, drying and calcining. The catalyst is useful for promoting a number of hydrocarbon conversion reactions, particularly those involving hydrogenative desulfurization.Type: GrantFiled: October 19, 1983Date of Patent: December 9, 1986Assignee: Union Oil Company of CaliforniaInventor: William S. Millman
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Patent number: 4626340Abstract: A process for the conversion of heavy hydrocarbon feedstocks which are characterized by high molecular weight, low reactivity and high metal contents comprising feeding the feedstock to a hydrodemetallization zone where the feedstock is contacted with hydrogen and a catalyst capable of demetallizing organometallic complexes of high molecular weight and cracking resistance, thereafter removing the effluent from the demetallization zone and feeding same to the thermal cracking zone where the effluent is contacted with hydrogen and thereafter feeding the product from the cracking zone to a hydrocarbon conversion zone where the product is contacted with hydrogen and a catalyst capable of cracking molecules of high cracking resistance.Type: GrantFiled: September 26, 1985Date of Patent: December 2, 1986Assignee: Intevep, S.A.Inventors: Roberto E. Galiasso, Beatriz R. Arias, Lino Caprioli, Juan Garcia, Humberto Kum
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Patent number: 4619759Abstract: The catalytic hydrotreatment of a mixture comprising a resid and a light cycle oil is carried out in a multiple catalyst bed in which the portion of the catalyst bed with which the feedstock is first contacted contains a catalyst which comprises of alumina, cobalt and molybdenum and the second portion of the catalyst bed through which the feedstock is passed after passing through the first portion contains a catalyst comprising alumina to which molybdenum and nickel have been added.Type: GrantFiled: April 24, 1985Date of Patent: October 28, 1986Assignee: Phillips Petroleum CompanyInventors: John W. Myers, Stephen L. Parrott, Edward L. Sughrue
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Patent number: 4617110Abstract: In a two-stage hydrofining process, hydrogen is utilized as a quench fluid to reduce the temperature of the effluent withdrawn from the hydrodemetallization stage prior to providing such effluent to the hydrodesulfurization stage and the flow of such hydrogen is controlled so as to maintain a desired temperature for the feed to the hydrodesulfurization stage. Also, the flow of fuel to a furnace is controlled so as to maintain a desired temperature for the feed to the hydrodemetallization stage and hydrogen flow rates are manipulated throughout the process so as to maintain desired hydrogen concentrations throughout the hydrofining process.Type: GrantFiled: June 11, 1984Date of Patent: October 14, 1986Assignee: Phillips Petroleum CompanyInventors: Antonio R. Hinojos, Bertram T. Bone, Jr.
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Patent number: 4613425Abstract: A two-stage process for hydrotreating asphaltenes and metallic contaminants-containing heavy hydrocarbon oils which comprises a demetallization step using a catalyst composition which is smaller in pore size and less in active metal amount than the conventional demetallization catalysts, and a hydrotreating step using a catalyst composition which is larger in pore size and more in active metal amount than the conventional hydrodesulfurization catalysts or hydrocracking catalysts, said hydrotreating step being located downstream of said demetallization step.Type: GrantFiled: January 19, 1984Date of Patent: September 23, 1986Assignee: Catalysts & Chemicals Industries Co., Ltd.Inventors: Hidehiro Higashi, Katsuhiro Shirono, Yuusaku Arima, Yoichi Nishimura, Shinichi Yoshida
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Patent number: 4613427Abstract: A natural active stable catalyst for use in the hydrodemetallization (HDM) and the hydroconversion (HC) of heavy crudes and residues and, in particular, a method for the preparation of the catalyst from natural clay and a process for the treatment of heavy crudes and residues with the catalyst. The catalyst is free of hydrogenating metals of Groups VIB and VIII of the Periodic Table and comprises primarily iron, silica and alumina derived from the composition of the natural clay. The catalyst possesses a surface area of between 20 to 100 m.sup.2 /g, a total pore volume of between 0.20 to 0.90 cc/g, where 50 to 100% of the total pore volume contains pores of diameter greater than 400 .ANG.. The catalyst has a ratio I(Fe)/I(Si+Al) of between 0.2 to 0.9 as determined by XPS.Type: GrantFiled: August 28, 1985Date of Patent: September 23, 1986Assignees: Intevep, S.A., Universidad Central de VenezuelaInventors: Gonzalo Sepulveda, Marcos Rosa-Brussin, Nereida Carrion, Pedro Roa, Alfredo Morales Ruiz, Jose Guitian, Otto Rodriguez, Carlos Zerpa
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Patent number: 4612110Abstract: At least one decomposable molybdenum dithiocarbamate compound is mixed with a hydrocarbon-containing feed stream. The hydrocarbon-containing feed stream containing such decomposable molybdenum dithiocarbamate compound is then contacted in a hydrofining process with a catalyst composition comprising a support selected from the group consisting of alumina, silica and silica-alumina and a promoter comprising at least one metal selected from Group VIB, Group VIIB and Group VIII of the Periodic Table. The introduction of the decomposable molybdenum dithiocarbamate compound may be commenced when the catalyst is new, partially deactivated or spent with a beneficial result occurring in each case.Type: GrantFiled: March 14, 1984Date of Patent: September 16, 1986Assignee: Phillips Petroleum CompanyInventors: Simon G. Kukes, Thomas Davis, Howard F. Efner, Robert J. Hogan, Daniel M. Coombs
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Patent number: 4608152Abstract: At least one decomposable molybdenum additive selected from the group consisting of a mixture of a molybdenum dithiophosphate and a molybdenum carboxylate and a mixture of a molybdenum dithiocarbamate and a molybdenum carboxylate is mixed with a hydrocarbon-containing feed stream. The hydrocarbon-containing feed stream containing such decomposable molybdenum additive is then contacted in a hydrovisbreaking process with hydrogen under suitable hydrovisbreaking conditions.Type: GrantFiled: November 30, 1984Date of Patent: August 26, 1986Assignee: Phillips Petroleum CompanyInventors: Jerald A. Howell, Simon G. Kukes
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Patent number: 4606812Abstract: A process for hydrotreating carbonaceous materials is disclosed. The carbonaceous material is contacted with steam and with empirical hydrates of alkali metal hydrosulfides, monosulfides, or polysulfides. The process hydrocracks, hydrogenates, denitrogenates, demetallizes, and desulfurizes. In a preferred embodiment, hydrogen sulfide is co-fed to the reaction zone.Type: GrantFiled: November 7, 1983Date of Patent: August 19, 1986Assignee: Chemroll Enterprises, Inc.Inventor: Rollan Swanson
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Patent number: 4606815Abstract: A process for hydrotreating hydrocarbon feedstocks using shaped catalysts is disclosed. When the catalyst is used for diffusion limited reactions, and particularly when it is used for demetalation, shaped catalysts give longer catalyst lifetimes. Preferred shaped include oval and elliptical shapes, with and without bumps.Type: GrantFiled: September 28, 1984Date of Patent: August 19, 1986Assignee: Chevron Research CompanyInventor: Kirk R. Gibson
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Patent number: 4604189Abstract: Catalytic hydroconversion of a relatively heavy hydrocarbon residual fraction is effected by adding a thermally decomposable metal compound to the oil, along with an acidic catalyst solid to the oil, and passing the mixture to a hydroconversion zone containing hydrogen at an elevated temperature. Preferred metals are cobalt and molybdenum. Preferred solids are large pore zeolites, silica/alumina, clays and surface activated metal oxides.Type: GrantFiled: December 24, 1984Date of Patent: August 5, 1986Assignee: Mobil Oil CorporationInventors: Francis J. Derbyshire, Philip Varghese
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Patent number: 4600504Abstract: At least one decomposable compound selected from the group consisting of compounds of the metals of Group IIB and Group IIIB of the Periodic Table is mixed with a hydrocarbon-containing feed stream. The hydrocarbon-containing feed stream containing such decomposable compound is then contacted in a hydrofining process with a catalyst composition comprising a support selected from the group consisting of alumina, silica and silica-alumina and a promoter comprising at least one metal selected from Group VIB, Group VIIB and Group VIII of the Periodic Table. The introduction of the decomposable compound may be commenced when the catalyst is new, partially deactivated or spent with a beneficial result occurring in each case.Type: GrantFiled: January 28, 1985Date of Patent: July 15, 1986Assignee: Phillips Petroleum CompanyInventors: Simon G. Kukes, Robert J. Hogan, Daniel M. Coombs, Jerald A. Howell
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Patent number: 4600503Abstract: A method for hydrotreating residual oil which comprises utilizing a hydrotreating catalyst which contains a thermally stable composition comprising a layered metal oxide containing an interspathic polymeric oxide having a d-spacing of at least about 10 angstroms at hydrotreating conditions. Said conditions include temperature ranging from about 357.degree. C. to 454.degree. C. (675.degree. F. to 850.degree. F.), a hydrogen partial pressure of at least about 2860 kPa (400 psig) and a liquid hourly space velocity ranging between about 0.1 and 10 hr.sup.-1.Type: GrantFiled: September 10, 1985Date of Patent: July 15, 1986Assignee: Mobil Oil CorporationInventors: Philip J. Angevine, Thomas F. Degnan, Jr., Michael E. Landis
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Patent number: 4597855Abstract: A hydrocarbon containing feed stream, e.g., a heavy oil or residuum, is contacted under suitable reaction conditions with a free hydrogen containing gas and a selenium compound, preferably selenium dioxide, so as to produce a hydrocarbon stream having an increased API.sup.60 gravity. Generally the amounts of impurities (sulfur, coke precursors, metals) contained in the feed stream are reduced in this hydrotreating process.Type: GrantFiled: June 21, 1985Date of Patent: July 1, 1986Assignee: Phillips Petroleum CompanyInventor: Paul R. Stapp
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Patent number: 4596654Abstract: A catalyst composition is prepared by dissolving a suitable vanadium and oxygen containing compound, a suitable nickel (II) compound and ammonia in water, mixing this solution with an alumina containing support material, and calcining this mixture. This catalyst composition is used primarily for hydrotreating of hydrocarbon feed stream, which contain nickel, vanadium and sulfur impurities, particularly heavy oils.Type: GrantFiled: September 30, 1985Date of Patent: June 24, 1986Assignee: Phillips Petroleum CompanyInventors: Simon G. Kukes, Stephen L. Parrott, Karlheinz K. Brandes
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Patent number: 4592827Abstract: Heavy crudes or vacuum residues are treated in a thermal hydroconversion process in the presence of a metal catalyst from Groups IVb, Vb, VIb, VIIb and VIII of the Periodic Table of Elements and water. Fresh catalyst is introduced into the process as a soluble, metallic catalyst precursor which is then decomposed while feedstock admixed with water is preheated to a temperature of at least about 230.degree. C. but no more than about 420.degree. C.Type: GrantFiled: June 25, 1985Date of Patent: June 3, 1986Assignee: Intevep, S.A.Inventors: Roberto Galiasso, Jose A. Salazar, Alfredo Morales, Angel R. Carrasquel
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Patent number: 4591429Abstract: Supported, hydroprocessing catalysts comprising a sulfide of (i) trivalent chromium, (ii) Mo, W or mixture thereof and (iii) at least one metal selected from the group consisting of Ni, Co, Mn, Cu, Zn and mixture thereof and mixture thereof with Fe. These catalysts are made by compositing a preselected quantity of support material with a precursor comprising a mixture of (i) hydrated oxide of trivalent chromium and (ii) a salt containing a thiometallate anion of Mo or W and a cation comprising at least one divalent promoter metal chelated by at least one, neutral, nitrogen-containing polydentate ligand and heating the composite in the presence of sulfur and hydrogen in an oxygen-free atmosphere. These catalysts have been found to be useful hydrotreating catalysts having nitrogen removal activity superior to that of commercial catalysts such as sulfided cobalt-molybdate on alumina.Type: GrantFiled: September 28, 1984Date of Patent: May 27, 1986Assignee: Exxon Research and Engineering Co.Inventors: Teh C. Ho, Archie R. Young, II, Russell R. Chianelli, Allan J. Jacobson
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Patent number: 4591426Abstract: A process for upgrading feedstocks containing not less than about 200 ppm metals, an API gravity of less than about 20.degree., a Conradson Carbon of more than about 8%, by hydroconversion with hydrogen in the presence of a naturally occurring inorganic material as a catalyst. The invention further provides, inter alia, subsequently fractionating the hydroconverted product and solvent deasphalting the distillation bottoms and optionally hydrodesulfurizing atmospheric distillates and the mix of vacuum gas oils and deasphalted oils separately. When a heavy crude of 12.degree. API, 10% Conradson Carbon, 3.2% sulfur and 350 ppm metals is fed to this process, more than 90% (v/v) of a synthetic crude of 25.degree.API, 0.17% sulfur and only 13.8% (v/v) 950.degree. F.+ fraction may be obtained.Type: GrantFiled: March 28, 1983Date of Patent: May 27, 1986Assignee: Intevep, S.A.Inventors: Julio H. Krasuk, Fernando J. Silva, Roberto E. Galiasso, Alfredo Souto
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Patent number: 4588709Abstract: A catalyst for the hydrotreatment of heavy crudes and their residues, and a method of preparing same, is disclosed, which has significant simultaneous hydrodemetallizing and hydrodesulfurizing activity. The catalyst is prepared by successively impregnating an extruded refractory support with a Group VIb and a Group VIII metal, calcining the pellet thus produced, and presulfurizing same. Pore volume of the catalyst ranges between 0.50 and 1.2 ml/g, total surface area ranges between 120 and 400 m.sup.2 /g, at least 60% of said pore volume consists of pores having diameters greater than 100 .ANG., and X-ray photoelectron spectroscopy signal band strength ratios are as follows: I(Me VIb)/I(refractory metal) is between 5 and 8, and I(Me VIII)/I(refractory metal) is between 1 and 5.Type: GrantFiled: April 19, 1985Date of Patent: May 13, 1986Assignee: Intevep, S.A.Inventors: Alfredo L. Morales, Roberto Galiasso, Angel R. Carrasquel, Jose A. Salazar
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Patent number: 4587012Abstract: A process for upgrading a hydrocarbonaceous feedstock employing an alumina-based catalyst at least a portion of which is in the alpha phase. The catalyst has at least 25% of its pore volume in pores from 300-1,000 .ANG. in diameter, has no more than 10% macropores, and has a surface area of less that 100 m.sup.2 /g.Type: GrantFiled: October 31, 1983Date of Patent: May 6, 1986Assignee: Chevron Research CompanyInventor: Richard J. Quann
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Patent number: 4584093Abstract: Supported catalysts which are made by shaping catalyst carrier, with or without catalyst precursors, into balls, calcining the balls at 300.degree.-1000.degree. C., and crushing the calcined balls to particles whose average size is 0.2-0.8 times the average diameter of the balls. When the precursors are not present during the manufacture, they are added thereafter.Type: GrantFiled: January 22, 1985Date of Patent: April 22, 1986Assignee: Ste Francaise des Produits pour Catalyse Pro-Catalyse chez Institut Francais du PetroleInventors: Herve Toulhoat, Jean-Claude Plumail, Marc Mercier, Yves Jacquin
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Patent number: 4582594Abstract: The reaction product of a mercaptoalcohol and a molybdenum compound selected from the group consisting of molybdic acids, alkali metal salts of molybdic acids and ammonium salts of molybdic acids is mixed with a hydrocarbon-containing feed stream. The hydrocarbon-containing feed stream containing such reaction product is then contacted in a hydrofining process with a catalyst composition comprising a support selected from the group consisting of Al.sub.2 O.sub.3, SiO.sub.2, Al.sub.2 O.sub.3 --SiO.sub.2, Al.sub.2 O.sub.3 --TiO.sub.2, Al.sub.2 O.sub.3 --P.sub.2 O.sub.5, Al.sub.2 O.sub.3 --BPO.sub.4, Al.sub.2 O.sub.3 --AlPO.sub.4, Al.sub.2 O.sub.3 --Zr.sub.3 (PO.sub.4).sub.4, Al.sub.2 O.sub.3 --SnO.sub.2 and Al.sub.2 O.sub.3 --ZnO and a promoter comprising at least one metal selected from Group VIB, Group VIIB and Group VIII of the Periodic Table. The introduction of the reaction product may be commenced when the catalyst is new, partially deactivated or spent with a beneficial result occuring in each case.Type: GrantFiled: September 4, 1984Date of Patent: April 15, 1986Assignee: Phillips Petroleum CompanyInventors: Simon G. Kukes, Robert J. Hogan, Daniel M. Coombs, Howard F. Efner
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Patent number: 4582595Abstract: Disclosed is a catalyst and process for making same wherein sepiolite is ion exchanged with a Group Ib, IIb, IIb, IVb, Vb, or VIIa metal, impregnated with a VIa metal and exchanged with a magnesium salt with intervening processing steps of calcining. The catalyst composition is useful in removing metals and hydroprocessing of hydrocarbon feedstocks. The catalyst can also be mixed with a high silica/alumina ratio zeolite such as sodium ZSM-5 zeolite.Type: GrantFiled: February 23, 1984Date of Patent: April 15, 1986Assignee: Mobil Oil CorporationInventors: Costandi A. Audeh, Tsoung-Yuan Yan
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Patent number: 4581129Abstract: Deactivated hydrorefining catalysts are regenerated by incorporation of a phosphorus component followed by combustive coke-removal from the catalyst. The regenerated catalyst is useful for promoting hydrodesulfurization reactions, particularly those involving demetallation of hydrocarbons.Type: GrantFiled: September 17, 1984Date of Patent: April 8, 1986Assignee: Union Oil Company of CaliforniaInventors: Richard B. Miller, Ryden L. Richardson
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Patent number: 4579649Abstract: A new active stable catalyst for use in the removal of sulphur, nitrogen, contaminating metals, asphaltenes and Conradson carbon from heavy crudes and residues and, in particular, a method for the preparation of the catalyst and a process for the treatment of heavy crudes and residues with the catalyst. The catalyst comprises a hydrogenation component selected from Group VIB of the Periodic Table, a hydrogenation component selected from Group VIII of the Periodic Table and a phosphorus oxide component as active components all supported on an alumina carrier. The catalyst is made up of a dispersion of the above metals on the surface of the alumina carrier such that, when the catalyst is sulphided under specific conditions, catalytic activities such as hydrodesulphurization (HDS), hydrodenitrogenation (HDN) and hydrodemetallization (HDM) and the conversion of asphaltenes and Conradson carbon are improved.Type: GrantFiled: April 1, 1985Date of Patent: April 1, 1986Assignee: Intevep, S.A.Inventors: Alfredo L. Morales, Roberto E. Galiasso, Maria M. Agudelu, Jose A. Salazar, Angel R. Carrasquel
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Patent number: 4578180Abstract: At least one decomposable compound selected from the group consisting of dimanganese decacarbonyl and chromium hexacarbonyl is mixed with a hydrocarbon-containing feed stream. The hydrocarbon containing feed stream containing such decomposable compound is then contacted in a hydrofining process with a catalyst composition comprising a support selected from the group consisting of alumina, silica and silica-alumina and a promoter comprising at least one metal selected from Group VIB, Group VIIB and Group VIII of the Periodic Table. The introduction of the decomposable compound may be commenced when the catalyst is new, partially deactivated or spent with a beneficial result occurring in each case.Type: GrantFiled: April 5, 1984Date of Patent: March 25, 1986Assignee: Phillips Petroleum CompanyInventors: Simon G. Kukes, Robert J. Hogan, Daniel M. Coombs, Daniel J. Strope
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Patent number: 4578179Abstract: A treated decomposable compound of molybdenum, which has been prepared by the catalytic hydrogenation of a decomposable compound of molybdenum, wherein the molybdenum has a valence state greater than zero, or by the treating of the decomposable compound of molybdenum with a reducing agent, is mixed with a hydrocarbon-containing feed stream. The hydrocarbon-containing feed stream containing such treated decomposable compound of molybdenum is then contacted with a catalyst composition comprising a support selected from the group consisting of alumina, silica and silica alumina and a promoter comprising at least one metal selected from the group consisting of Group VIB, Group VIIB, and Group VIII of the Periodic Table to reduce the concentration of metals, sulfur, nitrogen, Ramsbottom carbon residue and/or heavies contained in the hydrocarbon-containing feed stream.Type: GrantFiled: November 18, 1983Date of Patent: March 25, 1986Assignee: Phillips Petroleum CompanyInventors: Simon G. Kukes, Marvin M. Johnson, Daniel J. Strope, Robert J. Hogan
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Patent number: 4572778Abstract: Hydroprocessing of hydrocarbon oils is carried out utilizing a catalyst containing nickel and tungsten active metal components on a porous support material and having a narrow pore size distribution, with essentially all pores being of diameter greater than about 100 angstroms, with less than about 10 percent of the total pore volume being in pores of diameter greater than 300 angstroms, and with at least about 60 percent of the total pore volume being in pores of diameter from about 180 to about 240 angstroms. The catalyst is useful for promoting the conversion of asphaltenes contained in hydrocarbon oils, especially in the second reaction zone of a multiple-stage hydrodesulfurization process wherein demetallization catalysts are employed in upstream reaction zones.Type: GrantFiled: January 19, 1984Date of Patent: February 25, 1986Assignee: Union Oil Company of CaliforniaInventor: John W. Ward
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Patent number: 4568655Abstract: A single catalyst system capable of demetalizing, hydrotreating and hydrodewaxing petroleum residue in a single stage process is described. The catalyst system utilized includes one or more metal oxides or sulfides of Group VIA and Group VIII of the periodic Table impregnated on a base of refractory oxide material and Zeolite Beta. The catalyst also has about 75% of its pore volume in pores no greater than 100 Angstrom units in diameter and about 20% of its pore volume in pore greater than about 300 Angstrom units in diameter.Type: GrantFiled: October 29, 1984Date of Patent: February 4, 1986Assignee: Mobil Oil CorporationInventors: Stephen M. Oleck, Robert C. Wilson, Jr.
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Patent number: 4568450Abstract: A hydrocarbon conversion catalyst containing a Group VIB metal on a porous refractory oxide is prepared by impregnating support particles with a solution containing Group VIB metal components and citric acid, followed by drying and calcining. The catalyst is useful for promoting a number of hydrocarbon conversion reactions, particularly those involving hydrogenative desulfurization, demetallization and denitrogenation.Type: GrantFiled: March 30, 1984Date of Patent: February 4, 1986Assignee: Union Oil Company of CaliforniaInventors: Pauline B. Ting, Howard D. Simpson
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Patent number: 4565800Abstract: A catalyst composition is prepared by dissolving a suitable vanadium and oxygen containing compound, a suitable nickel (II) compound and ammonia in water, mixing this solution with an alumina containing support material, and calcining this mixture. This catalyst composition is used primarily for hydrotreating of hydrocarbon feed stream, which contain nickel, vanadium and sulfur impurities, particularly heavy oils.Type: GrantFiled: June 24, 1985Date of Patent: January 21, 1986Assignee: Philips Petroleum CompanyInventors: Simon G. Kukes, Stephen L. Parrott, Karlheinz K. Brandes
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Patent number: 4564439Abstract: A process for the production of transportation fuels from heavy hydrocarbonaceous feedstock is provided comprising a two-stage, close-coupled process, wherein the first stage comprises a hydrothermal zone into which is introduced a mixture comprising the feedstock, dispersed demetalizing contact particles having coke-suppressing activity, and hydrogen; and the second, close-coupled stage comprises a hydrocatalytic zone into which substantially all the effluent from the first stage is directly passed and processed under hydrocatalytic conditions.Type: GrantFiled: June 29, 1984Date of Patent: January 14, 1986Assignee: Chevron Research CompanyInventors: Christopher W. Kuehler, Arthur J. Dahlberg
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Patent number: 4564441Abstract: At least one decomposable compound of a metal selected from the group consisting of copper, zinc and the metals of Group III-B, Group IV-B, Group VB, Group VIB, Group VIIB and Group VIII of the Periodic Table is mixed with a hydrocarbon-containing feed stream. The hydrocarbon-containing feed stream containing such decomposable compound is then contacted with a suitable refractory inorganic material to reduce the concentration of metals, sulfur and Ramsbottom carbon residue contained in the hydrocarbon-containing feed stream. The suitable refractory inorganic material may also be slurried with the hydrocarbon-containing feed stream.Type: GrantFiled: May 21, 1984Date of Patent: January 14, 1986Assignee: Phillips Petroleum CompanyInventors: Simon G. Kukes, Edward L. Sughrue, II, Robert J. Hogan
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Patent number: 4560467Abstract: A hydrocarbon containing feed stream, e.g., a heavy oil or residuum, is contacted under suitable reaction conditions with a carbon monoxide containing gas, so as to produce a hydrocarbon stream having a reduced level of metal impurities, especially nickel and vanadium compounds, and an increased API.sup.60 gravity, essentially in the absence of a catalyst or extractant.Type: GrantFiled: April 12, 1985Date of Patent: December 24, 1985Assignee: Phillips Petroleum CompanyInventor: Paul R. Stapp