Catalyst Treatment To Remove Metal Contaminants Patents (Class 208/52CT)
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Patent number: 6106695Abstract: A process to provide a multiplicity of hydrocracking reaction zones containing hydrocracking catalyst wherein the catalyst is rejuvenated or reactivated while the process unit remains on-stream by the periodic exposure of partially spent catalyst to hot recycle gas containing hydrogen. The hydrocracking catalyst always operates at "near" fresh activity and selectivity thereby resulting in more stable temperature, yield and product quality performance.Type: GrantFiled: March 22, 1999Date of Patent: August 22, 2000Assignee: UOP LLCInventors: Tom N. Kalnes, Vasant P. Thakkar
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Patent number: 5985134Abstract: A startup method for a fluidized catalytic cracking (FCC) unit operating with a magnetic catalyst separation means is disclosed. Magnetic strength, or separation severity, is maintained or increased until most of the catalyst has passed through the magnetic separation unit. After this point, magnetic flux and/or centrifugal forces, are decreased for lined-out operation. Preferably a MagnaCat.RTM. catalyst separation unit is used for magnetic fractionation of catalyst.Type: GrantFiled: February 12, 1998Date of Patent: November 16, 1999Assignee: M.W. Kellogg CompanyInventors: Terry L. Goolsby, Howard F. Moore
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Patent number: 5972201Abstract: Magnetic separation of fluid cracking catalyst and magnetic hooks can be improved by adding antimony, in the feed or during catalyst manufacture, to enhance the magnetic susceptibility, thus increasing the separation efficiency of the older less active fluid cracking catalyst from the more desirable fraction for recycle. Antimony can also be used as a tag for determination of age distribution of said catalyst. Concentration levels of 0.005-15 wt. % antimony (Sb) on the catalyst or sorbent are preferred. The invention is particularly preferred on catalyst and sorbents which comprise at least about 0.001 wt. %, more preferably above about 0.01 wt. % iron, because the antimony has been found to enhance the magnetic susceptibility of iron-containing particulates.Type: GrantFiled: February 24, 1997Date of Patent: October 26, 1999Assignee: Marathon Ashland Petroleum LLCInventors: Terry L. Goolsby, Maurice M. Mitchell
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Patent number: 5919352Abstract: A process wherein a residuum feedstock is upgraded in a short vapor contact time thermal process unit comprised of a horizontal moving bed of fluidized hot particles, then fed to a fluid catalytic cracking process unit. Hot flue gases from the fluid catalytic cracking unit is used to circulate solid particles and to provide process heat to the thermal process unit.Type: GrantFiled: July 17, 1997Date of Patent: July 6, 1999Assignee: Exxon Research and Engineering Co.Inventors: Willibald Serrand, David G. Hammond, Mitchell Jacobson, John F. Pagel, Martin C. Poole
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Patent number: 5618406Abstract: Bastnaesite and magnesium-containing materials can be chemically reacted by use of reactions wherein alumina is made into a sol by use of a mono-protonic acid and then reacted with a magnesium-containing ingredient (e.g., magnesium acetate) and a bastnaesite ingredient such that, upon spray drying and calcination of the resulting composition, the bastnaesite is chemically reacted with magnesia to form a bastnaesite/magnesia/alumina compound having SO.sub.x activity.Type: GrantFiled: December 28, 1995Date of Patent: April 8, 1997Assignee: Intercat, Inc.Inventor: Edward J. Demmel
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Patent number: 5565087Abstract: The rate of formation of carbon on the surfaces of thermal cracking tubes and the production of carbon monoxide during thermal cracking of hydrocarbons are inhibited by the use of cracking tubes treated with an antifoulant, including tin compound, silicon compound and sulfur compounds in the presence of a reducing gas such as hydrogen. Additionally, the concentration of carbon monoxide in a pyrolytic cracking process product stream is reduced by the treatment of the thermal cracking tubes of such process with a reducing gas having a concentration of a sulfur compound.Type: GrantFiled: March 23, 1995Date of Patent: October 15, 1996Assignee: Phillips Petroleum CompanyInventors: Ronald E. Brown, Larry E. Reed, Gil J. Greenwood, Timothy P. Harper, Mark D. Scharre
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Patent number: 5466363Abstract: Use of a carbon-based catalyst composition, particularly activated-carbon, optionally containing at least one metal selected from Ni, Co, Mo, W, Fe, or mixtures thereof, for heavy oil hydroprocessing. Recovery and partial gasification of the catalyst to produce a synthesis gas and a partially gasified catalyst residue. Use of the synthesis gas in a process to produce synthetic hydrocarbons and use of the catalyst residue in steel or alloy production. Catalysts used for heavy oil hydrocarbon hydroprocessing frequently become contaminated with metals which increase the cost of disposal of the spent catalysts, e.g. landfills. This invention uses a specific catalyst for hydroprocessing which can then be partially gasified to produce a catalyst residue which can be further used in steel or alloy production, thereby reducing the need for expensive disposal.Type: GrantFiled: February 10, 1994Date of Patent: November 14, 1995Assignee: Mobil Oil CorporationInventors: Costandi A. Audeh, Lillian A. Rankel
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Patent number: 5446229Abstract: A process for the production of olefins in an olefin plant, which includes an olefin pyrolysis furnace having pyrolysis tubes in which hydrocarbon feedstock is cracked, comprises introducing hydrocarbon feed substantially free of phosphorous-containing compounds into the pyrolysis furnace and operating the furnace under pyrolysis conditions producing olefin-containing effluent therefrom wherein the pyrolysis tubes have an effective passivator of metal catalytic sites bonded to the exposed metal surface by injecting an effective passivator into the furnace at a point above the dew point of water.Type: GrantFiled: December 9, 1993Date of Patent: August 29, 1995Assignee: Amoco CorporationInventors: Don M. Taylor, Lynn M. Allen, Myron E. Schroeder
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Patent number: 5445728Abstract: Spent or inactive alumina-supported catalysts removed from a catalytic hydrotreating process and having carbonaceous and metallic deposits thereon are reactivated. After a solvent wash to remove process oils, the spent catalyst is contacted with steam at a temperature of 1000.degree. to about 1250.degree. F. for a period of about 2 to about 5 hours to form a reactivated catalyst suitable for reuse in a catalytic hydrotreating process. Optionally, the steam-treated catalyst can be regenerated by contact with an oxygen-containing gas at a temperature of about 700.degree. to about 900.degree. F. to remove carbon deposits from the catalyst, or, alternatively, the steam-treated catalyst can be acid-leached to remove undesired metals and then contacted with an oxygen-containing gas at an elevated temperature to remove carbon deposits.Type: GrantFiled: July 18, 1994Date of Patent: August 29, 1995Assignee: Texaco Inc.Inventors: David E. Sherwood, Jr., Johnnie R. Hardee, Jr.
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Patent number: 5401384Abstract: An antimony and tin containing compound for passivating contaminant metals to which a catalyst is exposed during fluid catalytic cracking of hydrocarbons containing said contaminant metals, said compound having a composition as follows (R*).sub.x Sb(OSn(R**).sub.3).sub.n wherein R* and R** are aryl compounds having between 6 to 13 carbon atoms, wherein n=1, 2 or 3 and x=4 when n=1, x=3 when n=2, and x=0 when n=3.Type: GrantFiled: December 17, 1993Date of Patent: March 28, 1995Assignees: Inteven, S.A., Universidad Simon BolivarInventors: Nelson Martinez, Juan Lujano, Nieves Alvarez, Jacek Lubinkowski, William McEwen
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Patent number: 5384041Abstract: Disclosed is a vanadium trap for use in FCC which comprises a major amount of calcined kaolin clay, free magnesium oxide and an in situ formed magnesium silicate cement binder. Also disclosed are procedures for the preparation of the trap by forming a slurry in water of hydrous kaolin clay, magnesium oxide or magnesium hydroxide and sodium silicate, aging the slurry to form magnesium silicate in situ, optionally adding additional kaolin, colloidal silica or both, spray drying, and calcining the resulting spray dried microspheres without forming appreciable amounts of crystalline magnesium silicates or crystalline magnesium aluminates.Type: GrantFiled: March 4, 1994Date of Patent: January 24, 1995Assignee: Engelhard CorporationInventors: Michel Deeba, John M. Macaoay, Paul R. Suitch, Roland von Ballmoos
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Patent number: 5378349Abstract: A zeolite-containing cracking catalyst is passivated with compounds of (a) antimony and (b) zirconium and/or tungsten. The thus-passivated cracking catalyst is employed in a process for catalytically cracking a hydrocarbon-containing oil feed. In another embodiment, compounds of (a) antimony and (b) zirconium and/or tungsten are added to a hydrocarbon-containing oil feed which is catalytically cracked in the presence of a zeolite-containing cracking catalyst.Type: GrantFiled: May 26, 1993Date of Patent: January 3, 1995Assignee: Phillips Petroleum CompanyInventor: Dwayne R. Senn
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Patent number: 5358630Abstract: A method for countering the adverse effect of contaminating metals on a crystalline aluminosilicate catalyst comprising contacting the catalyst with a reducing gas under suitable conditions. In a preferred embodiment, the catalyst contains antimony.Type: GrantFiled: November 17, 1980Date of Patent: October 25, 1994Assignee: Phillips Petroleum CompanyInventors: Brent J. Bertus, Harold W. Mark, John S. Roberts, Arnold M. Schaffer
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Patent number: 5328594Abstract: This invention relates to an improved catalytic process for carrying out heavy hydrocarbon conversion, usually, but not necessarily, in the presence of nickel and vanadium on the catalyst and in the feedstock, by catalytic cracking gas oils and heavy carbometallic oils to lighter molecular weight fractions. The process is facilitated by the continuous addition of one or more heavy rare earth additives, including gadolinum, terbium, dysprosium, holmium, erbium, and thulium, all having exceptionally high paramagnetic properties, which as they accumulate on aged catalyst, are used to achieve enhanced magnetic separation of aged catalyst. These additives are unusual in that they not only act dramatically as magnetic hooks to assist in removing old, nickel and vanadium poisoned catalyst, but also act to achieve increased activity and improve selectivity of the remaining catalyst, and of equal importance, tend to resist catalyst deactivation.Type: GrantFiled: December 7, 1992Date of Patent: July 12, 1994Assignee: Ashland Oil, Inc.Inventor: William P. Hettinger
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Patent number: 5298153Abstract: An attrition resistant catalytic cracking catalyst is prepared by spray drying an aqueous slurry containing a molecular sieve having cracking activity, a clay such as kaolin, a silica sol and aluminum chlorhydroxide. The resultant catalyst has a high attrition resistance as compared to commercially available cracking catalysts.Type: GrantFiled: October 31, 1990Date of Patent: March 29, 1994Assignee: Union Oil Company of CaliforniaInventor: Julius Scherzer
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Patent number: 5286691Abstract: A process for demetallizing metals contaminated FCC catalyst in an FCC regenerator. A metals getter additive, with higher settling velocity, is added to the regenerator, to remove metals from FCC catalyst by solid-solid interaction. The FCC catalyst forms a light, discrete, dense phase fluidized bed on top of a fluidized bed of additive. FCC catalyst is recycled to the cracking reactor from the top fluidized bed, while additive can be withdrawn from the lower fluidized bed for disposal or for metals recovery and recycle. Additive can be optimized for metals removal and will not dilute the cracking catalyst in the FCC reactor.Type: GrantFiled: October 26, 1992Date of Patent: February 15, 1994Assignee: Mobil Oil CoprorationInventors: Mohsen N. Harandi, Joseph A. Herbst, Hartley Owen, Paul H. Schipper, Robert T. Thomson
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Patent number: 5260240Abstract: A process is disclosed for passivating the reactivity of contaminant metals, such as nickel and vanadium, which have been deposited on a catalytic cracking catalyst, by adding to the cracking catalyst a mixture of a calcium-containing material and a magnesium-containing material in a separate reactor in the presence of steam. The preferred calcium-containing material is dolomite and the preferred magnesium-containing material is sepiolite. It is also preferred to include antimony and/or bismuth compounds in the additive mixture.Type: GrantFiled: December 9, 1991Date of Patent: November 9, 1993Assignee: Chevron Research and Technology CompanyInventors: Charles F. Guthrie, Lawrence W. Jossens, James V. Kennedy, John A. Paraskos
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Patent number: 5254513Abstract: Spent or inactive alumina-supported catalysts removed from a catalytic hydrotreating process and having carbonaceous and metallic deposits thereon are reactivated. After a solvent wash to remove process oils, the spent catalyst is contacted with steam at a temperature of 1000.degree. to about 1250.degree. F. for a period of about 2 to about 5 hours to form a reactivated catalyst suitable for reuse in a catalytic hydrotreating process. Optionally, the steam-treated catalyst can be regenerated by contact with an oxygen-containing gas at a temperature of about 700.degree. to about 900.degree. F. to remove carbon deposits from the catalyst, or, alternatively, the steam-treated catalyst can be acid-leached to remove undesired metals and then contacted with an oxygen-containing gas at an elevated temperature to remove carbon deposits.Type: GrantFiled: May 20, 1991Date of Patent: October 19, 1993Assignee: Texaco, Inc.Inventors: David E. Sherwood, Jr., Johnnie R. Hardee, Jr.
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Patent number: 5250482Abstract: A process for beneficiating a particulate zeolite petroleum cracking catalyst having metal values in excess of 1000 ppm nickel equivalents. The particulate catalyst is passed through a magnetic field in the range of from about 2 Tesla to about 5 Tesla generated by a superconducting quadrupole open-gradient magnetic system for a time sufficient to effect separation of said catalyst into a plurality of zones having different nickel equivalent concentrations. A first zone has nickel equivalents of about 6,000 ppm and greater, a second zone has nickel equivalents in the range of from about 2000 ppm to about 6000 ppm, and a third zone has nickel equivalents of about 2000 ppm and less. The zones of catalyst are separated and the second zone material is recycled to a fluidized bed of zeolite petroleum cracking catalyst. The low nickel equivalent zone is treated while the high nickel equivalent zone is discarded.Type: GrantFiled: August 20, 1992Date of Patent: October 5, 1993Assignee: University of ChicagoInventor: Richard D. Doctor
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Patent number: 5232885Abstract: A method of regenerating a contaminant metal-containing, coke deactivated, molecular sieve-free catalyst having at least one hydrogenation metal and at least one Group IV metal deposited on an inorganic oxide support comprising contacting the catalyst with an oxygen-containing gas under conditions sufficient to remove a substantial amount of the coke from the catalyst.Type: GrantFiled: December 18, 1991Date of Patent: August 3, 1993Assignee: Amoco CorporationInventors: Frederick T. Clark, Mary C. Springman
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Patent number: 5230869Abstract: By continuously or intermittently adding amounts of magnetically active moieties, e.g. iron compounds, over time so that the moiety deposits on a catalyst or sorbent in a fluid catalytic cracker or similar circulating hydrocarbon conversion unit, older catalyst, being more magnetic, can be readily separated from catalyst which has been in the system a shorter time. Separation is readily accomplished by passing the catalyst and/or sorbent through a magnetic field and discarding the more magnetic 50% by wt. or more preferably 20% by wt., while recycling the remainder back to the hydrocarbon conversion unit.Type: GrantFiled: October 4, 1991Date of Patent: July 27, 1993Assignee: Ashland Oil, Inc.Inventors: William P. Hettinger, Roger M. Benslay
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Patent number: 5228978Abstract: The inventive solvent extraction process uses hydrotreated (HTR) and low sulfur (LSR) resids feedstreams in a single deasphalter unit and in a way that optimizes the disposition of the oils, resins, and asphaltene fractions of each resid for downstream processing. After the refractory asphaltenes are separated from the HTR feedstream, the LSR resid is introduced into the deasphalter so that its resin and asphaltene fractions are combined with the HTR resins. The oils fractions from the two resids are combined and then used as a feedstock for catalytic cracking.Type: GrantFiled: January 23, 1992Date of Patent: July 20, 1993Assignee: Amoco CorporationInventors: James L. Taylor, William I. Beaton, Jeffrey J. Kolstad
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Patent number: 5209840Abstract: Spent hydrotreating catalyst having carbonaceous and metallic deposits and of regular geometric shape after being stripped of process oil is fluidized by flowing air upwardly through the catalyst at a velocity sufficient to expand the bed thereby segregating the catalyst particles into a high activity, upper, less-contaminated fraction and a lower, more-contaminated fraction and recycling the high activity fraction to a hydrotreating process. Optionally, the high activity fraction can be regenerated with carbon burnoff or rejuvenated by acid leaching followed by regeneration with carbon burnoff to further improve catalyst activity.Type: GrantFiled: October 2, 1991Date of Patent: May 11, 1993Assignee: Texaco Inc.Inventors: David E. Sherwood, Jr., Johnnie R. Hardee, Jr., John A. Lemen
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Patent number: 5198098Abstract: An improved catalytic process for heavy hydrocarbon conversion, (usually, but not necessarily, in the presence of nickel and vanadium on the catalyst and in the feedstock.) to produce lighter molecular weight fractions. Manganese, which has paramagnetic properties, is added so it progressively accumulates on aged catalyst, and enhances magnetic separation of aged catalyst, to increase activity and improve selectivity of remaining catalyst which is recycled. Manganese acts as a "magnetic hook" to separate more magnetic, older, less catalytically active and less selective, higher-metals-containing catalyst particulates from less-magnetically-active, lower-metal-containing, more catalytically active and selective catalysts fractions, which are then recycled back to the unit.Type: GrantFiled: October 19, 1990Date of Patent: March 30, 1993Assignee: Ashland Oil, Inc.Inventor: William P. Hettinger
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Patent number: 5192724Abstract: A spent metal contaminated zeolite-containing catalytic cracking catalyst composition is reactivated by a process which comprises contacting with (a) dissolved lactic acid and either (b1) at least one dissolved calcium compound or, alternatively, (b2) at least one dissolved tin compound and at least one dissolved phosphorus compound.Type: GrantFiled: March 17, 1992Date of Patent: March 9, 1993Assignee: Phillips Petroleum CompanyInventors: Chia-Min Fu, Michael K. Maholland
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Patent number: 5188995Abstract: A spent metal-contaminated zeolite-containing catalytic cracking catalyst is reactivated by a process which comprises contacting the spent catalyst with at least one dissolved carboxylic acid and at least one antimony compound.Type: GrantFiled: March 24, 1992Date of Patent: February 23, 1993Assignee: Phillips Petroleum CompanyInventors: Michael K. Maholland, Chia-Min Fu, Richard E. Lowery
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Patent number: 5174890Abstract: A metals scavenging composition comprising a rare earth component and a layered magnesium silicate, such as sepiolite or attapulgite, is mixed with separate particles of a cracking catalyst and the mixture used to crack hydrocarbon feedstocks containing relatively high concentrations of vanadium and other contaminant metals. The use of the metals scavenger prolongs the life of the catalyst while maintaining (1) relatively high conversions and gasoline yields, and (2) relatively low hydrogen and coke makes.Type: GrantFiled: July 31, 1989Date of Patent: December 29, 1992Assignee: Union Oil Company of CaliforniaInventor: Mario L. Occelli
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Patent number: 5171424Abstract: This invention relates to an improved catalytic process for carrying out heavy hydrocarbon conversion, usually, but not necessarily, in the presence of nickel and vanadium on the catalyst and in the feedstock, by catalytic cracking gas oils and heavy carbometallic oils to lighter molecular weight fractions. The process is facilitated by the continuous addition of one or more heavy rare earth additives, including gadolinum, terbium, dysprosium, holmium, erbium, and thulium, all having exceptionally high paramagnetic properties, which as they accumulate on aged catalyst, are used to achieve enhanced magnetic separation of aged catalyst. These additives are unusual in that they not only act dramatically as magnetic hooks to assist in removing old, nickel and vanadium poisoned catalyst, but also act to achieve increased activity and improve selectivity of the remaining catalyst, and of equal importance, tend to resist catalyst deactivation.Type: GrantFiled: October 22, 1990Date of Patent: December 15, 1992Assignee: Ashland Oil, Inc.Inventor: William P. Hettinger
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Patent number: 5169517Abstract: Process for the treatment of a hydrocarbon fraction containing metals and comprising the following stages: (a) the said hydrocarbon fraction is treated in the presence of mean density particles (d.sub.o) under conditions for eliminating at least partly the metals contained therein and deposits of said metals on at least one fraction of said solid particles; (b) at least part of the solid particles from stage (a), whose mean density is (d.sub.i) is drawn off; (c) said solid particles from stage (b) are magnetohydrostatically separated by introducing said solid particles into a ferrofluid placed in a non-uniform magnetic field and creating a vertical magnetic field, whose intensity is adjusted in such a way that the apparent mean density (d.sub.af) of the ferrofluid permits the separation of said solid particles into at least one mean density fraction (d.sub.i) below said apparent mean density (d.sub.af) of the ferrofluid and into at least one mean density fraction (d.sub.s) above said mean apparent density (d.Type: GrantFiled: August 2, 1990Date of Patent: December 8, 1992Assignee: Institut Francais du PetroleInventors: Andre Buisson, Jean-Paul Euzen, Frederic Morel
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Patent number: 5155073Abstract: A demetallization process for catalysts used for chemical conversion of hydrocarbons, the catalysts containing at least vanadium as a metal poison, wherein the poisoned catalyst is contacted in a sulfiding zone with a sulfiding agent and a hydrocarbon having a minimum boiling point of about 300.degree. F., the hydrocarbon being at least partially vaporizable at the temperature in the sulfiding zone.Type: GrantFiled: April 24, 1991Date of Patent: October 13, 1992Assignee: Coastal Catalyst Technology, Inc.Inventor: Frank J. Elvin
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Patent number: 5151391Abstract: A spent metal contaminated zeolite-containing catalytic cracking catalyst composition is reactivated by a process which comprises contacting with an aqueous solution of HC1 and/or HNO.sub.3 and/or H.sub.2 SO.sub.4. The thus reactivated catalyst composition can be employed in a catalytic cracking process.Type: GrantFiled: February 15, 1991Date of Patent: September 29, 1992Assignee: Phillips Petroleum CompanyInventors: Chia-Min Fu, Michael K. Maholland, Richard E. Lowery
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Patent number: 5141624Abstract: A catalytic process for cracking vanadium-containing oils employs a physical mixture of (a) zeolite embedded in an inorganic matrix material and (b) magnesium oxide on alumina support.Type: GrantFiled: March 30, 1989Date of Patent: August 25, 1992Assignee: Phillips Petroleum CompanyInventors: Ping-Chau Liao, Douglas D. Klendworth, Fu M. Lee
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Patent number: 5141904Abstract: A spent metal contaminated zeolite-containing catalytic cracking catalyst composition is reactivated by a process which comprises contacting with an aqueous solution of at least one carboxylic acid (preferably at least one of formic acid, acetic acid, citric acid and lactic acid). The thus reactivated catalyst composition can be employed in a catalytic cracking process.Type: GrantFiled: February 15, 1991Date of Patent: August 25, 1992Assignee: Phillips Petroleum CompanyInventors: Donald H. Kubicek, Chia-Min Fu, Richard E. Lowery, Michael K. Maholland
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Patent number: 5124024Abstract: A method for prolonging a hydroconversion catalyst life-time is provided. An additive functional to partially redirect the deposition of catalytic poisoning agents on the catalyst is utilized. The additive may comprise a chemically inert, porous carbonaceous material or ferruginous clay.Type: GrantFiled: November 9, 1990Date of Patent: June 23, 1992Assignees: Nova Husky Research Corporation, Alberta Research CouncilInventors: Andrzej Krzywicki, Leszek Lewkowicz, Michael C. Oballa
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Patent number: 5096568Abstract: A zeolite-containing catalytic cracking catalyst having been passivated by treatment with an aqueous solution which has been prepared by mixing an antimony oxide, ammonium bifluoride and water, at an atomic ratio of F:Sb in excess of about 6:1, is used in a process for catalytically cracking a hydrocarbon-containing feed, in particular one which contains metal impurities. In one embodiment, the above-described aqueous solution is injected into the feed. In other embodiments, the solution is injected into the cracking zone or into a catalyst regeneration zone.Type: GrantFiled: April 8, 1991Date of Patent: March 17, 1992Assignee: Phillips Petroleum CompanyInventors: Ted H. Cymbaluk, Chia-Min Fu
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Patent number: 5064524Abstract: The present invention is directed to a method of using cerium and/or cerium containing compounds to passivate nickel contaminants in hydrocarbon feedstocks which are used in catalytic cracking processes.Type: GrantFiled: March 28, 1990Date of Patent: November 12, 1991Assignee: Betz Laboratories, Inc.Inventor: David R. Forester
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Patent number: 5059302Abstract: The present invention features the use of a particulate sorbent and a particulate FCC catalyst, which are physically separable, sequentially in the same FCC riser, followed by separation of commingled spent catalyst and sorbent particles from vapors, and the subsequent primary partial regeneration and heat up of spent sorbent particles and catalysts particles in an oxygen deficient burning zone, followed by physical separation of partially regenerated catalyst and sorbent particles, preferably using a cyclonic classifier to effect the separation. This is followed by secondary regeneration of the resulting segregated partially regenerated sorbent and catalyst streams in oxygen rich combustion zones to fully regenerate sorbent and catalyst particles.Type: GrantFiled: April 26, 1990Date of Patent: October 22, 1991Assignee: Engelhard CorporationInventors: Harold N. Weinberg, W. Benedict Johnson, Michael F. Raterman, Barry K. Speronello, William J. Reagan, Larry G. Sherman
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Patent number: 5057205Abstract: A catalytic cracking process especially useful for the catalytic cracking of high metals content feeds including resids in which the feed is cracked in the presence of a catalyst additive comprising an alkaline earth metal oxide and an alkaline earth metal spinel, preferably a magnesium aluminate spinel which acts as a trap for vanadium as well as an agent for reducing the content of sulfur oxides in the regenerator flue gas. The additive is used in the form of a separate additive from the cracking catalyst particles in order to keep the vanadium away from the cracking catalyst and so preserve the activity of the catalyst; in addition, use of separate additive particles permits the makeup rate for the additive to be varied relative to that of the cracking catalyst in order to deal with variations in the metals and sulfur content of the cracking feed.Type: GrantFiled: June 10, 1988Date of Patent: October 15, 1991Assignee: Mobil Oil CorporationInventors: Arthur A. Chin, Ajit V. Sapre, Michael S. Sarli
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Patent number: 5021146Abstract: A process for regeneration of cracking catalyst while minimizing NO.sub.x emissions is disclosed. A Group IIIB based DeNO.sub.x additive is present in an amount and in a form which reduces NO.sub.x emissions. Relatively small amounts of lanthanum or yttrium oxides, or lanthanum titanate, preferably impregnated on a separate support are effective to reduce NO.sub.x produced in the regenerator. The additive converts NO.sub.x to nitrogen even when Pt CO combustion promoter and some excess oxygen are present in the regenerator.Type: GrantFiled: December 28, 1989Date of Patent: June 4, 1991Assignee: Mobil Oil CorporationInventor: Arthur A. Chin
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Patent number: 5021145Abstract: The invention provides a catalyst composition useful in treating hydrocarbons contaminated with vanadium residues, the catalyst comprising a zeolite, a matrix and certain heavier alkaline earth metal oxides.Type: GrantFiled: June 5, 1990Date of Patent: June 4, 1991Assignee: Unilever Patent Holdings B.V.Inventor: Andrew P. Chapple
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Patent number: 5021377Abstract: A process for reactivating a spent, metal-contaminated zeolite-containing catalytic cracking catalyst composition comprises partially demetallizing (preferably by chlorinating and washing) the spent catalytic cracking catalyst composition, and thereafter contacting it with at least one fluorine compound (preferably NH.sub.4 F) and at least one antimony compound. The thus reactivated catalytic cracking catalyst composition is employed in a catalytic cracking process.Type: GrantFiled: June 5, 1990Date of Patent: June 4, 1991Assignee: Phillips Petroleum CompanyInventors: Michael K. Maholland, Chia-Min Fu, Richard E. Lowery, Donald H. Kubicek, Brent J. Bertus
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Patent number: 5019241Abstract: In a hydrocarbon fluid catalytic cracking process, high concentrations of sodium in the hydrocarbon entering the reactor will poison the reaction sites on the FCC catalysts, thereby reducing the efficiency of the cracking process. The addition of an aluminum compound to the hydrocarbon significantly reduces the poisoning effect of the sodium on the catalyst. The aluminum compound may be selected from the group consisting of aluminum nitrate, aluminum isopropoxide, aluminum oxide and sulfate salts of aluminum.Type: GrantFiled: April 27, 1990Date of Patent: May 28, 1991Assignee: Betz Laboratories, Inc.Inventor: David R. Forester
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Patent number: 5015362Abstract: Oxides of nitrogen (NO.sub.x) emissions are catalytically reduced by contacting a flue gas contain NO.sub.x with a carbonaceous substance, preferably sponge coke or coal, in the presence of a catalyst effective for promoting the reduction of NO.sub.x in the presence of such carbonaceous substances.Type: GrantFiled: December 28, 1989Date of Patent: May 14, 1991Assignee: Mobil Oil CorporationInventor: Arthur A. Chin
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Patent number: 5007999Abstract: A process for reducing sulfur oxides production during an FCC cracking operation comprises the steps of:(a) passivating metal contaminants on an FCC catalyst by contacting the FCC catalyst with a sulfur-containing compound under conditions that enable association of the sulfur with the metal contaminants;(b) cracking hydrocarbons with the passivated FCC catalyst in an FCC cracking zone;(c) oxidatively regenerating the catalyst in a regeneration zone whereby the carbonaceous material deposited on the catalyst in step (b) is burned off and the sulfur deposited on the FCC catalyst in step (a) is converted to sulfur oxides;(d) reacting the sulfur oxides with a sulfur oxide adsorption additive capable of adsorbing the sulfur oxides under sulfur oxide adsorbing conditions;(e) converting the adsorbed sulfur oxides from step (d) to hydrogen sulfide by contacting the adsorbed sulfur oxides in a separate treatment vessel with a reducing gas before the regenerated FCC catalyst and sulfur oxides adsorption additive enterType: GrantFiled: April 13, 1989Date of Patent: April 16, 1991Assignee: Mobil Oil CorporationInventor: Arthur A. Chin
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Patent number: 4986896Abstract: A known method for passivating contaminant metals on an FCC catalyst comprises treating the catalyst with a sufficient amount of a sulfur-containing compound capable of associating with the contaminant metals when in contact therewith. An improvement comprises contacting the catalyst with the sulfur-containing compound for at least 3 seconds. In another embodiment of the invention, the improvement comprises contacting the catalyst with the sulfur-containing compound in a separate treatment vessel.Type: GrantFiled: April 13, 1989Date of Patent: January 22, 1991Assignee: Mobil Oil Corp.Inventors: Amos A. Avidan, Arthur A. Chin
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Patent number: 4980052Abstract: Emission of noxious nitrogen oxides with the flue gas from the regenerator of a fluid catalytic cracking plant are reduced by incorporating into the circulating inventory of cracking catalyst separate additive particles that contain a copper-loaded zeolite. A particularly effective additive is provided by ion-exchanging ZSM-5 zeolite with cupric ion. With such preferred additive, CO emissions also are reduced, and the recovered gasoline has enhanced octane number.Type: GrantFiled: November 3, 1989Date of Patent: December 25, 1990Assignee: Mobil Oil CorporationInventors: Gary J. Green, David S. Shihabi, Tsoung Y. Yan
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Patent number: 4956075Abstract: The use of a catalyst containing Mn, a large pore crystalline molecular sieve, and optionally rare earths in catalytic cracking is disclosed. This catalyst gives high gasoline selectivity with low coke yields and is suitable for either gas oil or resid cracking applications.Type: GrantFiled: December 22, 1988Date of Patent: September 11, 1990Assignee: Mobil Oil CorporationInventors: Philip J. Angevine, Robert G. Bundens, Joseph A. Herbst, Albin Huss, Jr., Sadi Mizrahi
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Patent number: 4954467Abstract: This invention comprises improvements to processes for the catalytic cracking of hydrocarbon feedstocks. One such improvement to catalytic cracking processes provides compositions comprising metals passivating agents having an increased degree of stability. These compositions comprise aqueous suspensions of antimony by vinyl copolymers, aqueous suspensions of antimony oxide by diesters of phosphoric acid, or aqueous suspensions of antimony oxide by cellulose derivatives. Another improvement to catalytic cracking processes provides a process for reducing the viscosity of liquid suspensions of metals passivating agents without substantially reducing the stability of the liquid suspension by the utilization of at least two different particle ranges of metals passivating agents. A further improvement to catalytic cracking processes provides an efficient utilization of metals passivating agents by introducing the selected agent into the catalyst regeneration cycle of a catalytic cracking unit.Type: GrantFiled: October 28, 1988Date of Patent: September 4, 1990Assignee: Phillips Petroleum CompanyInventors: Marvin M. Johnson, Donald C. Tabler
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Patent number: 4954244Abstract: A process for reactivating a spent, metal-contaminated zeolite-containing cracking catalyst composition comprises the sequential steps of contacting the catalyst composition with dissolved ammonium compound (preferably NH.sub.4 NO.sub.3), contacting with a fluorine compound (preferably NH.sub.4 F), and treatment with a passivating agent (preferably Mg, Ca, B, A, P and/or Sb). The reactivated cracking catalyst obtained by this reactivation process is employed in a catalytic cracking process.Type: GrantFiled: June 22, 1989Date of Patent: September 4, 1990Assignee: Phillips Petroleum CompanyInventors: Chia-Min Fu, Michael K. Maholland
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Patent number: RE35166Abstract: The invention provides a catalyst composition useful in treating hydrocarbons contaminated with vanadium residues, the catalyst comprising a zeolite, a matrix and certain heavier alkaline earth metal oxides.Type: GrantFiled: May 10, 1994Date of Patent: March 5, 1996Assignee: Unilever Patent Holdings B.V.Inventor: Paul Chapple