Metal Or Metal Oxide Containing Catalyst Patents (Class 208/121)
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Patent number: 4895638Abstract: A process for the catalytic cracking of heavy petroleum fractions into lower hydrocarbons, such as fuel products. The process comprises contacting the petroleum fractions at an elevated temperature with a cracking catalyst comprising (a) a layered metal oxide of the titanometallate type intercalated with an interspathic polymeric chalcogenide, e.g., polymeric silica and, optionally (b) a porous crystalline silicate component such as a large pore zeolite material.Type: GrantFiled: April 17, 1989Date of Patent: January 23, 1990Assignee: Mobil Oil CorporationInventors: Brent A. Aufdembrink, Thomas F. Degnan, Charles T. Kresge
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Patent number: 4895637Abstract: This application is directed to a process and apparatus for regenerating an elutriable mixture of fluidized catalytic cracking (FCC) catalyst and a demetallizing additive. Deactivated catalyst and coke containing additive are added to a single dense bed regenerator. Within the regenerator, differences in settling velocity segregate the elutriable mixture into a lower dense bed containing most of the additive and a contiguous upper dense bed containing most of the FCC catalyst. Some regeneration gas is added to the lower dense bed to at least partially decoke the additive, while additional regeneration gas is added to the upper dense bed. Decoked additive and regenerated FCC catalyst are preferably withdrawn separately and charged to a riser reactor for demetallizing and catalytic cracking of heavy feed. Flue gas is withdrawn from the regenerator from a dilute phase vapor space above the single dense bed.Type: GrantFiled: October 18, 1988Date of Patent: January 23, 1990Assignee: Mobil Oil CorporationInventor: Hartley Owen
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Patent number: 4894143Abstract: Catalytic compositions which comprise alumina bound spinel and/or spinel-mullite mixtures having an alkali metal content of below about 0.50 weight percent, preferably below about 0.10. The compositions are obtained by calcining and caustic leaching preformed particulate composites of clay and alumina sol, preferably chlorhydrol. The catalysts are particularly useful for the catalytic cracking of heavy hydrocarbon feedstocks to obtain gasoline and light cycle oil. When used for cracking feedstocks high in vanadium content these compositions may contain added alkaline earth oxide in order to passivate the vanadium.Type: GrantFiled: September 26, 1988Date of Patent: January 16, 1990Assignee: W. R. Grace & Co.-Conn.Inventor: Roger J. Lussier
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Patent number: 4889615Abstract: 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 a dehydrated magnesium-aluminum hydrotalcite 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.Type: GrantFiled: December 6, 1988Date of Patent: December 26, 1989Assignee: Mobil Oil CorporationInventors: Arthur A. Chin, Ivy D. Johnson, Charles T. Kresge, Michael S. Sarli
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Patent number: 4889618Abstract: A process for separating finely divided petroleum cracking catlyst from a mixture of the finely divided catalyst particles with a high boiling refractory hydrocarbon oil by intimately contracting said mixture with a concentrated aqueous solution of a basic alkali metal compound at a temperature above 170.degree. F., the quantity of aqueous solution employed being substantially greater than the quantity of said mixture with which it is contracted.Type: GrantFiled: November 28, 1988Date of Patent: December 26, 1989Inventors: William H. Tyson, Jr., Frank A. Stuart
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Patent number: 4889617Abstract: A process is disclosed for passivating sodium contaminants in FCC feed using tin or tin compounds.Type: GrantFiled: March 24, 1986Date of Patent: December 26, 1989Assignee: Chevron Research CompanyInventor: Alan R. English
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Patent number: 4880521Abstract: Hydrocarbon feedstocks containing relatively high levels of nitrogen contaminants are converted by catalytic cracking to products of lower average molecular weight by contacting the feedstock under cracking conditions with a cracking catalyst having a surface area of at least 150 m.sup.2 /gm and comprising greater than about 25 weight percent of a Y zeolite dispersed in a matrix containing a synthetic silica-alumina component in which the weight ratio of silica-to-alumina is preferably equal to or greater than about 0.10.Type: GrantFiled: February 17, 1989Date of Patent: November 14, 1989Assignee: Union Oil Company of CaliforniaInventor: Julius Scherzer
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Patent number: 4877514Abstract: Commercial catalysts are prepared combining the various ingredients into a catalytic binder system which has been freed of sodium so that the catalyst ingredients can be preferably spray dried and used in Fluid Catalytic Cracking or Reduced Crude Conversion hydrocarbon conversion operations without subsequent washing or drying. Catalysts can even be prepared on site, e.g., in spray drier operations performed in the FCC/RCC refenerator. Low-sodium slurries of any or all of the following ingredients can be employed in the manufacture: zeolites, clays, sols, carbon blacks, sacrificial sieves, acid matrix substances, and getters.Type: GrantFiled: November 10, 1988Date of Patent: October 31, 1989Assignee: Ashland Oil, Inc.Inventors: William P. Hettinger, H. Wayne Beck
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Patent number: 4859314Abstract: Catalytic cracking catalysts and their use in catalytic cracking processes are disclosed. The instant catalytic cracking catalysts are useful for cracking a hydrocarbon feedstock to produce lower boiling hydrocarbons. The catalysts comprise an effective amount of at least one non-zeolitic molecular sieve characterized in its calcined form by an adsorption of isobutane of at least 2 percent by weight at a partial pressure of 500 torr and a temperature of 20.degree. C. The non-zeolitic molecular sieve is characterized as containing framework tetrahedral components of aluminum and phosphorus and at least one additional framework tetrahedral component, e.g., the non-zeolitic molecular sieve may be a silicoaluminophosphate as described in U.S. Pat. No. 4,440,871.Type: GrantFiled: June 2, 1987Date of Patent: August 22, 1989Assignee: UOPInventors: Regis J. Pellet, Peter K. Coughlin, Mark T. Staniulis, Gary N. Long, Jule A. Rabo
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Patent number: 4851106Abstract: Molecular sieve compositions having three-dimensional microporous framework structures of CrO.sub.2, AlO.sub.2 and PO.sub.2 tetrahedral oxide units are disclosed. These molecular sieves have an empirical chemical composition on an anhydrous basis expressed by the formula:mR: (Cr.sub.x Al.sub.Y P.sub.z)O.sub.2wherein "R" represents at least one organic templating agent present in the intracrystalline pore system; "m" represents the molar amount of "R" present per mole of (Cr.sub.x Al.sub.y P.sub.z)O.sub.2 ; and "x", "y" and "z" represents the mole fractions of chromium, aluminum and phosphorus, respectively, present as tetrahedral oxides. Their use as adsorbents, catalysts, etc. is also disclosed.Type: GrantFiled: March 31, 1988Date of Patent: July 25, 1989Assignee: UOPInventors: Edith M. Flanigen, Brent M. T. Lok, Robert L. Patton, Stephen T. Wilson
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Patent number: 4844790Abstract: Delaminated clays whose X-ray diffraction patterns do not contain a distinct first order reflection are prepared from synthetic and natural swelling clays whose particles have a length-to-width ratio greater than about 2.0, a length-to-thickness ratio greater than about 5.0 and are comprised of randomly oriented platelets by reacting the clay with a pillaring agent selected from the group consisting of polyoxymetal cations, mixtures of polyoxymetal cations, colloidal particles comprising alumina, silica, titania, chromia, tin oxide, antimony oxide or mixtures thereof, and cationic metal clusters comprising nickel, molybdenum, cobalt or tungsten and then subjecting the resulting reaction products to drying in a gaseous medium, preferably spray drying. The resulting acidic delaminated clays, which contain the microporosity associated with zeolites and pollared clays and the macroporosity associated with amorphous aluminosilicates, may be used as the active component of cracking and hydroprocessing catalysts.Type: GrantFiled: May 2, 1988Date of Patent: July 4, 1989Assignee: Union Oil Company of CaliforniaInventor: Mario Occelli
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Patent number: 4840724Abstract: There is disclosed a process for cracking a hydrocarbon feed in the presence of a fluidizable cracking catalyst composition containing a sepiolite, an ultrastable Y-zeolite and a matrix material, characterized in that the hydrocarbon feed is metal-free.Type: GrantFiled: January 12, 1989Date of Patent: June 20, 1989Assignee: Akzo NVInventors: Cornelis J. Groenenboom, Peter A. Wieringa
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Patent number: 4836913Abstract: Catalysts which comprise or contain caustic leached spinel/mullite are found to possess a particularly high activity and stability for the catalytic conversion of hydrocarbons.Type: GrantFiled: March 24, 1988Date of Patent: June 6, 1989Assignee: W. R. Grace & Co.-Conn.Inventors: Roger J. Lussier, George J. Surland
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Patent number: 4810369Abstract: Hydrocarbon feedstocks containing relatively high levels of nitrogen contaminants are converted by catalytic cracking to products of lower average molecular weight by contacting the feedstock under cracking conditions with a cracking catalyst having a surface area of at least 150 m.sup.2 /gm and comprising greater than about 25 weight percent of a rare earth exchanged Y zeolite dispersed in a matrix containing a synthetic silica-alumina component in which the weight ratio of silica-to-alumina is equal to or greater than about 0.5.Type: GrantFiled: May 7, 1987Date of Patent: March 7, 1989Assignee: Union Oil Company of CaliforniaInventor: Julius Scherzer
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Patent number: 4810358Abstract: A cracking catalyst composition comprising a zeolitic, crystalline aluminosilicate, a matrix material and a barium titanium oxide. The catalyst composition is particularly suitable for cracking metal-containing hydrocarbon feedstocks.Type: GrantFiled: August 27, 1987Date of Patent: March 7, 1989Assignee: Akzo N.V.Inventor: Cornelis J. Groenenboom
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Patent number: 4784750Abstract: The invention concerns a hydrocarbon cracking catalyst containing a mixture of amorphous matrix with a zeolite, the zeolite having a SiO.sub.2 /Al.sub.2 O.sub.3 molar ratio ranging from about 8 to 70, a sodium content lower than 0.15% by weight, a parameter a.sub..degree. of elementary mesh from 24.55 to 24.24.times.10.sup.-10 m, a capacity C.sub.Na to retake sodium ions, expressed in grams of sodium per 100 grams of modified zeolite, higher than 0.85, a specific surface higher than 400 m.sup.2.g.sup.-1, a sodium ion uptake steam adsorption capacity at 25.degree. C. (with a P/Po ratio of 0.10) higher than 6% by weight, a pore distribution such that from 1 to 20% of the pore volume is pores of a diameter ranging from 20 to 80.10.sup.-10 m, the remaining pore volume being essentially pores of a diameter lower than 20.10.sup.-10 m, the matrix being characterized by the following textural properties:S .gtoreq.100 m.sup.2.g.sup.-1TPV .gtoreq.0.4 cm.sup.3.g.sup.-1PV.sub.75 .gtoreq.0.25 cm.sup.3.g.sup.-1PV.sub.Type: GrantFiled: June 4, 1986Date of Patent: November 15, 1988Assignee: Institut Francais du PetroleInventors: Pierre Dufresne, Christian Marcilly
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Patent number: 4775461Abstract: A process for catalytic cracking using a catalyst obtained by preparing pillared interlayered clay materials comprises the steps of contacting a smectite containing material, preferably bentonite, with a solution comprising at least one of ammonium and alkali metal carboxylates and alkali metal carbonates and bicarbonates, plus preferably also alkali metal dithionite; separating the thus-contacted material from the solution; treating the separated material with a solution comprising a polymeric cationic hydroxy metal complex, preferably of aluminum (more preferably, polymeric hydroxy aluminum chloride); separating and finally heating the thus-treated smectite material. The pillared interlayered clay material of this invention can be intimately admixed with zeolite. The pillared interlayered clay material of this invention, with or without zeolite, can be used as catalyst for cracking hydrocarbon-containing oils.Type: GrantFiled: January 21, 1988Date of Patent: October 4, 1988Assignee: Phillips Petroleum CompanyInventors: Jesse R. Harris, David R. Battiste, Brent J. Bertus
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Patent number: 4770765Abstract: In a catalytic cracking process which includes contacting a hydrocarbon feedstock in a contacting zone in the presence of solid composition containing molecular sieve-containing catalyst capable of promoting hydrocarbon cracking at conditions effective to crack the hydrocarbon feedstock to lower boiling components, the improvement comprising conducting the contacting in the presence of at least one metal component, other than the catalyst, containing calcium and tin. A composition of matter comprising such catalyst and metal component is also disclosed.Type: GrantFiled: July 14, 1987Date of Patent: September 13, 1988Assignee: Katalistiks International, Inc.Inventors: Robert Bartek, Gerald M. Woltermann
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Patent number: 4756819Abstract: This invention concerns a process for the thermal treatment of hydrocarbon charges having a high content of asphaltenes in the presence of additives which prevent coke formation. The additive according to the invention is a salt of a metal selected from V, Mo, Cr, W, Fe, Co and Ni at a concentration between 100 and 2500 ppm of metal relative to the charge either in the form of a suspension of solid particles, in solution or as an emulsion. These additives prevent the coke formation in all thermal treatments of which the temperature is above about 420.degree. C., such as viscoreduction or hydro viscoreduction.Type: GrantFiled: November 19, 1984Date of Patent: July 12, 1988Assignee: Elf FranceInventors: Jacques Bousquet, Thierry Barbou des Courieres, Jean Pierre Mermoz
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Patent number: 4747935Abstract: Hydrocarbon feedstocks containing relatively high levels of nitrogen contaminants are converted by catalytic cracking to products of lower average molecular weight by contacting the feedstock with a mixture of a cracking catalyst and separate particles of a nitrogen scavenger comprising microporous solids selected from the group consisting of acid clays; hydrogen or ammonium exchanged mordenite, clinoptilolite, chabazite and erionite; mineral acids or mineral acid precursors supported on an inorganic, refractory oxide; and Catapal alumina.Type: GrantFiled: March 26, 1986Date of Patent: May 31, 1988Assignee: Union Oil Company of CaliforniaInventor: Julius Scherzer
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Catalytic process for production of light hydrocarbons by treatment of heavy hydrocarbons with water
Patent number: 4743357Abstract: A process for converting heavy hydrocarbons into light hydrocarbons which comprises contacting, in a reaction zone, a heavy hydrocarbon having an API gravity at 25.degree. C. of less than about 20, such as Boscan heavy crude oil or tar sand bitumen, with a liquid comprising water and with an effective amount of selected catalyst materials such as iron (II and/or III) oxides, sulfides or sulfates, in the absence of externally added hydrogen, at a temperature between greater than about 340.degree. and about 480.degree. C. and at a pressure between about 1350 kPa (about 196 psig, about 13.2 atm) and about 15,000 kPa (about 2175 psig, about 148 atm), for a time sufficient to produce a residue and a vapor phase comprising light hydrocarbons, gaseous product and water, withdrawing the residue and said phase from the second zone; and recovering a light hydrocarbon product having an API gravity at 25.degree. C. of greater than about 20 and substantially free of vanadium and nickel values, i.e.Type: GrantFiled: December 26, 1985Date of Patent: May 10, 1988Assignee: Allied CorporationInventors: Kundanbhai M. Patel, Andiappan K. S. Murthy, Alex Y. Bekker -
Patent number: 4743358Abstract: A strontium colloid system is introduced into a hydrocarbon conversion process to suppress the harmful effects of one or more metal contaminants in the hydrocarbon feedstock on the active component(s) of the catalyst used in said process. The strontium compound in the colloid system reacts with or traps the metal contaminants before they contact the active component(s) of said catalyst, thereby reducing catalyst deactivation, coke make and hydrogen production relative to that obtained had said compound been introduced into the process in non-colloid form. In a preferred embodiment, the strontium colloid system is introduced into the reaction zone of said process and, preferably, with at least a portion of the hydrocarbon feedstock to said process.Type: GrantFiled: December 10, 1986Date of Patent: May 10, 1988Assignee: Exxon Research and Engineering CompanyInventors: Edwin L. Kugler, Richard P. Rhodes
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Patent number: 4708786Abstract: Hydrocarbon feedstocks containing relatively high levels of nitrogen contaminants are converted by catalytic cracking to products of lower average molecular weight by contacting the feedstock with a mixture of a cracking catalyst and separate particles of a nitrogen scavenger. The nitrogen scavenger is a particulate solid acid capable of sorbing pyridine at room temperature and retaining greater than about 5 weight percent of the sorbed pyridine after heating in a vacuum to about 300.degree. C. Examples of the nitrogen scavengers that can be used in the process include amorphous aluminosilicates, nonzeolitic molecular sieves such as pillared clays and delaminated clays, and zeolitic molecular sieves.Type: GrantFiled: March 26, 1986Date of Patent: November 24, 1987Assignee: Union Oil Company of CaliforniaInventor: Mario L. Occelli
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Patent number: 4686029Abstract: Dewaxing processes for hydrocarbon feedstocks are disclosed using novel catalysts comprising titanoaluminosilicates. The products of the instant dewaxing processes are characterized by lower pour points than the hydrocarbon feedstock.Type: GrantFiled: December 6, 1985Date of Patent: August 11, 1987Assignee: Union Carbide CorporationInventors: Regis J. Pellet, Frank P. Gortsema, Gary N. Long, Jule A. Rabo
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Process for the regeneration of spent catalyst used in the upgrading of heavy hydrocarbon feedstocks
Patent number: 4678557Abstract: A process for the regeneration of a spent catalyst used in the upgrading of heavy hydrocarbon feedstocks comprises roasting a spent natural iron base catalyst contaminated with carbon, sulfur and vanadium at a temperature of not more than 400.degree. C. in the presence of a carbonate selected from the group consisting of sodium, potassium, and mixtures thereof so as to eliminate carbon from the catalyst and obtain a roasted product containing iron oxide and water soluble salts of sulfur and vanadium. The roasted product is thereafter water leached so as to dissolve the soluble salts of sulfur and vanadium. The regenerated catalyst is thereafter separated from the leaching liquor so as to obtain a catalyst substantially free of carbon and sulfur.Type: GrantFiled: September 9, 1985Date of Patent: July 7, 1987Assignee: Intevep, S.A.Inventors: Domingo Rodriguez, Roberto Schemel -
Patent number: 4664777Abstract: A process for the conversion of fused two-ring aromatic and fused two-ring hydroaromatic hydrocarbons into lower boiling aromatics, particularly alkylbenzenes of higher octane values. Such feeds are contacted in the presence of hydrogen over an iron catalyst at temperature sufficient to selectively hydrogenate and hydrocrack said fused two-ring aromatic hydrocarbon compound, or fused two-ring hydroaromatic hydrocarbon compounds, or both, to produce lower molecular weight, higher octane components suitable for direct blending with gasoline.Type: GrantFiled: July 31, 1985Date of Patent: May 12, 1987Assignee: Exxon Research and Engineering CompanyInventors: Carl W. Hudson, Glen P. Hamner
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Patent number: 4608153Abstract: A process wherein a feed comprising an admixture of liquid hydrocarbon compounds which includes a polynuclear aromatic hydrocarbon compound, or compounds (PNA's) is contacted in the presence of hydrogen over an iron catalyst at temperature sufficient to selectively hydrogenate and hydrocrack, or destroy the PNA's of the admixture without excessively hydrogenating and hydrocracking the non-PNA's of said feed. The process is particularly applicable for the removal of PNA's from reformates, processed naphthas, and other hydroprocessed streams or the like to achieve a lower and more favorable distribution of PNA's in a motor gasoline pool, and further to remove PNA's from prime fuels and heavier hydrocarbon mixtures.Type: GrantFiled: July 31, 1985Date of Patent: August 26, 1986Assignee: Exxon Research and Engineering Co.Inventors: Carl W. Hudson, Glen P. Hamner
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Patent number: 4597856Abstract: A process for fluidized catalytic cracking of heavy oils and production of hydrogen is described, comprising contacting steam and heavy oils with fluidized catalyst particles containing reduced iron at high temperatures, wherein a fluidized bed is formed such that the catalyst particles are fed from the bottom and withdrawn from the top of the fluidized bed and the fluidized bed is provided with a means for retarding the mixing rate of the catalyst particles in the vertical direction, to thereby generate a temperature difference between zones of the fluidized bed above and below said means, and use the upper zone for cracking of heavy oils and the lower zone for production of hydrogen. Catalyst particles withdrawn from the fluidized bed may be regenerated and recycled. Thus, light oils and hydrogen can be produced in high yields.Type: GrantFiled: October 17, 1984Date of Patent: July 1, 1986Assignee: Processing Research Association of Residual OilInventors: Susumu Yoshioka, Nobuo Matsuo, Nobuyasu Meguri, Tadashi Murakami, Yasushi Ishibashi, Kenichi Matsuda, Teruo Suzuka, Satoshi Fukase, Hidetaka Ohse
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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: 4578181Abstract: A process of preparing a highly dispersed (colloidal or submicron size) heterogeneous catalyst for the hydrothermal conversion of heavy oils and residua is described. The process comprises preparing a reverse micellar dispersion by mixing water, an organic solvent, and an ionic or neutral surfactant to which is added an aqueous solution of a metal salt. The metal salt is reduced to a colloidal dispersion of the catalyst in a mixed water-organic liquid phase. The colloidal catalyst is then blended into resid or heavy oil fractions, and the blend is treated under hydrothermal conditions.Type: GrantFiled: June 25, 1984Date of Patent: March 25, 1986Assignee: Mobil Oil CorporationInventors: Eric G. Derouane, Philip Varghese
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Patent number: 4522706Abstract: Hydrocarbon treating processes such as catalytic cracking and fluid coking are provided in which a perovskite-containing catalytic composition is used as catalyst. The perovskite-containing catalytic composition is produced by interrupting the reaction of perovskite precursors after formation of at least 60 wt. % perovskite and before formation of more than 99 wt. % perovskite from the precursors.Type: GrantFiled: December 23, 1983Date of Patent: June 11, 1985Assignee: Exxon Research & Engineering Co.Inventors: Kenneth S. Wheelock, Robert C. Schucker
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Patent number: 4454025Abstract: A process for economically converting carbo-metallic oils to lighter products. The carbo-metallic oils contain 650.degree. F. plus material which is characterized by a carbon residue on pyrolysis of at least about 1 and a Nickel Equivalents of heavy metals content of at least about 4 parts per million. This process comprises flowing the carbo-metallic oil together with particulate cracking catalyst through a progressive flow type reactor having an elongated reaction chamber, which is at least in part vertical or inclined, for a predetermined vapor riser residence time in the range of about 0.5 to about 10 seconds, at a temperature of about 900.degree. to about 1400.degree. F., and under a pressure of about 10 to about 50 pounds per square inch absolute sufficient for causing a conversion per pass in the range of about 50% to about 90% while producing coke in amounts in the range of about 6 to about 14% by weight based on fresh feed, and laying down coke on the catalyst in amounts in the range of about 0.Type: GrantFiled: May 13, 1981Date of Patent: June 12, 1984Assignee: Ashland Oil, Inc.Inventor: William P. Hettinger, Jr.
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Patent number: 4452693Abstract: The activity of a fresh alkaline earth metal perovskite-containing catalyst can be increased by contacting the fresh catalyst with a reducing gas at reducing conditions prior to use. The activated catalyst is useful in hydrocarbon treating processes such as catalytic cracking and fluid coking.Type: GrantFiled: June 24, 1983Date of Patent: June 5, 1984Assignee: Exxon Research and Engineering Co.Inventors: Robert C. Schucker, Kenneth S. Wheelock
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Patent number: 4446011Abstract: A catalyst regeneration process is provided in which the rate of removal of carbon from the coked catalyst is increased at a relatively low temperature when the catalyst comprises a perovskite. Hydrocarbon treating processes utilizing the regenerated perovskite-containing catalysts are also provided. The regenerated catalyst is particularly suited for use in catalytic cracking of hydrocarbon residua.Type: GrantFiled: August 25, 1982Date of Patent: May 1, 1984Assignee: Exxon Research and Engineering Co.Inventors: Kenneth S. Wheelock, Robert C. Schucker
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Patent number: 4440632Abstract: Emissions of sulfur oxides from the regenerator of a fluidized catalytic cracking unit are reduced by selectively removing a portion of the sulfur from sulfur-containing coke deposits on deactivated cracking catalyst. This is accomplished by reaction of these deposits with limited amounts of molecular oxygen in a stripping zone at a temperature in the range from about 550.degree. to about 700.degree. C. Effluent gas from the striping zone is combined with the cracked hydrocarbon products.Type: GrantFiled: September 15, 1980Date of Patent: April 3, 1984Assignee: Standard Oil Company (Indiana)Inventors: Iacovos A. Vasalos, Eugene G. Wollaston
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Patent number: 4432863Abstract: A process is disclosed for economically converting carbo-metallic oils to liquid fuel products by bringing a converter feed containing 650.degree. F.+ material characterized by a carbon residue on pyrolysis of at least about 1 and by containing at least about 4 ppm of Nickel Equivalents of heavy metals, including nickel, into contact with a particulate cracking catalyst in a progressive flow type reactor having an elongated conversion zone. The suspension of catalyst and feed in the reactor has a vapor residence time in the range of about 0.5 to about 10 seconds, a temperature of about 900.degree. F. to about 1400.degree. F. and a pressure of about 10 to about 50 pounds per square inch absolute for causing a conversion per pass in the range of about 50 to about 90 percent while depositing nickel on the catalyst and coke on the catalyst in amounts in the range of about 0.3 to about 3 percent by weight.Type: GrantFiled: July 20, 1981Date of Patent: February 21, 1984Assignee: Ashland Oil, Inc.Inventors: George D. Myers, deceased, William P. Hettinger, Jr., Stephen M. Kovach, Oliver J. Zandona
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Patent number: 4431515Abstract: A process for the production of high octane gasoline and/or valuable lower molecular weight products from carbometallic oils comprising contacting hydrogen and a carbometallic feed in a progressive flow reaction zone with hot conversion catalysts capable of activating hydrogen. The hydrogen gas may be introduced into the feed prior to or simultaneous with contacting the feed with catalysts. Alternately, the hydrogen gas may be introduced to the catalysts prior to or simultaneously with its contact with the carbometallic feed.Type: GrantFiled: June 24, 1982Date of Patent: February 14, 1984Assignee: Ashland Oil, Inc.Inventors: George D. Myers, deceased, Lloyd E. Busch
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Patent number: 4421635Abstract: A process for simultaneously cracking a heavy hydrocarbons to form light oil and producing hydrogen is described, which comprises (1) a first step wherein steam and heavy hydrocarbons are simultaneously contacted with a catalyst in a reduced state, containing iron in the form of iron oxide, to produce hydrogen, cracked gases and cracked light oils, to convert the reduced-state catalyst into an oxidized-state catalyst, and to deposit coke on the catalyst, (2) a second step wherein the oxidized-state catalyst with coke deposited thereon is contacted with an oxygen-containing gas to partially combust the coke on the catalyst, to convert the oxidized-state catalyst into a reduced-state catalyst, and to fix a sulfur compound contained in the coke as iron sulfide with a part of the reduced-state catalyst; and (3) a third step wherein catalyst obtained from the second step, the major portion of the catalyst being recycled between the first step and second step, is contacted with an oxygen-containing gas at a temperaType: GrantFiled: February 12, 1982Date of Patent: December 20, 1983Assignee: Research Association for Residual Oil ProcessingInventors: Tadashi Murakami, Teruo Suzuka, Yukio Inoue, Shirou Aizawa
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Patent number: 4417974Abstract: Conversion of a hydrocarbon feed containing a catalyst-deactivating component in a riser FCC cracking system can be increased by employing a baffle in the lower part of the riser to exclude a portion of the upwardly flowing catalyst from initial contact with feed hydrocarbons containing the catalyst-deactivating component. Part of the catalyst flowing upwardly through the riser thereby is excluded from contact with the catalyst-deactivating component until the catalyst-deactivating component has been at least partially removed from the resulting hydrocarbonaceous vapor by deposition on another portion of the upwardly flowing catalyst.Type: GrantFiled: August 23, 1982Date of Patent: November 29, 1983Assignee: Chevron Research CompanyInventor: Willard M. Haunschild
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Patent number: 4414099Abstract: A fluid coking process is provided in which a catalyst comprising an alkaline earth metal ferrite is present in the fluid coking zone.Type: GrantFiled: September 13, 1982Date of Patent: November 8, 1983Assignee: Exxon Research and Engineering Co.Inventor: Robert C. Schucker
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Patent number: 4412911Abstract: A partially deactivated alkaline earth metal perovskite-containing catalyst is reactivated by contact with a reducing gas at reducing conditions. The reactivated catalyst is useful in hydrocarbon treating processes such as catalytic cracking and fluid coking.Type: GrantFiled: February 24, 1982Date of Patent: November 1, 1983Assignee: Exxon Research and Engineering Co.Inventors: Robert C. Schucker, Kenneth S. Wheelock
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Patent number: 4411777Abstract: A petroleum cracking catalyst having thereon metals usually found in petroleum, e.g., iron, nickel and vanadium, is modified by addition of potassium to increase significantly the rate of hydrogen production when employing the thus-modified catalyst for cracking of petroleum.Type: GrantFiled: February 4, 1982Date of Patent: October 25, 1983Assignee: Phillips Petroleum CompanyInventor: Dwight L. McKay
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Patent number: 4411772Abstract: A fluid coking process is provided in which a catalyst comprising a perovskite comprising at least one transition metal cation is present in the fluid coking zone.Type: GrantFiled: February 24, 1982Date of Patent: October 25, 1983Assignee: Exxon Research and Engineering Co.Inventors: Robert C. Schucker, Kenneth S. Wheelock
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Patent number: 4409094Abstract: A process for treating liquid hydrocarbons to remove toxic, mutagenic and/or carcinogenic aromatic hydrocarbons comprises feeding the hydrocarbons into a reactor where vapors are thermally treated in contact with a catalyst consisting essentially of calcium oxide or a calcium oxide containing mineral. Thermally treating liquid hydrocarbons in contact with calcium oxide preferentially increases the cracking of aromatics thus producing a product having a reduced amount of aromatic compounds.Type: GrantFiled: August 8, 1980Date of Patent: October 11, 1983Assignee: Massachusetts Institute of TechnologyInventors: John P. Longwell, William A. Peters
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Patent number: 4404090Abstract: A contaminating metal on a cracking catalyst used for the cracking of hydrocarbons is passivated by contacting the catalyst with a hydrocarbon gas or mixture of gases comprising molecules of three carbon atoms or less at passivation reaction conditions prior to the cycling of the catalyst to the cracking zone, which gas or mixture of gases is first saturated with water at specific conditions.Type: GrantFiled: July 16, 1982Date of Patent: September 13, 1983Assignee: UOP Inc.Inventors: Carmen Castillo, John C. Hayes
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Patent number: 4399023Abstract: A process for simultaneously cracking heavy hydrocarbons to form light oil and producing hydrogen is described, which comprises (1) a first step wherein steam and heavy hydrocarbons are simultaneously contacted with a catalyst in a reduced state, containing iron in the form of iron oxide, to produce hydrogen, cracked gases and cracked light oils, to convert the reduced-state catalyst into an oxidized-state catalyst, and to deposit coke on the catalyst, (2) a second step wherein the oxidized-state catalyst with coke deposited thereon is contacted with an oxygen-containing gas to partially combust the coke on the catalyst, to convert the oxidized-state catalyst into a reduced-state catalyst, and to fix a sulfur compound contained in the coke as iron sulfide with a part of the reduced-state catalyst; and (3) a third step wherein catalyst obtained from the first step, the major portion of the catalyst being recycled between the first step and second step, is contacted with an oxygen-containing gas at a temperaturType: GrantFiled: February 12, 1982Date of Patent: August 16, 1983Assignee: Research Association for Residual Oil ProcessingInventors: Teruo Suzuka, Yukio Inoue, Shirou Aizawa, Yasushi Ishibashi, Hidetaka Ohse
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Patent number: 4384948Abstract: A process for cracking a carbo-metallic oil feed having an initial boiling point of about 450.degree. F. or below comprising a naturally-occurring crude or a portion of such crude, including a portion boiling above 1000.degree. F. The 650.degree. F. portion is characterized by a carbon residue on pyrolysis of at least about 1 and containing at least about 4 ppm of Nickel Equivalents. The process comprises bringing the feed under cracking conditions in a progressive flow-type reactor into contact with a cracking catalyst bearing more than about 1500 parts per million of Nickel Equivalents of heavy metal(s). At least about 70% by weight of catalyst is abruptly separated from at least about 80% of the cracked products at the end of the reactor chamber.Type: GrantFiled: May 13, 1981Date of Patent: May 24, 1983Assignee: Ashland Oil, Inc.Inventor: Dwight F. Barger
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Patent number: 4376038Abstract: A process is disclosed for the production of high octane gasoline and/or other valuable lower molecular weight products from carbo-metallic oils. Examples include crude oil, topped crude, reduced crude, residua, the extract from solvent deasphalting and other heavy hydrocarbon fractions. These carbo-metallic oils contain quantities of coke precursors and heavy metal catalyst poisons substantially in excess of what is normally considered acceptable for Fluid Catalytic Cracking (FCC) and substantial amounts of sulfur, nitrogen and other troublesome components may also be present. Such carbo-metallic oils are converted to the desired products in a catalytic conversion process where the oil feed is mixed with naphtha and brought together with a high-metal content cracking catalyst.Type: GrantFiled: March 23, 1981Date of Patent: March 8, 1983Assignee: Ashland Oil, Inc.Inventor: George D. Myers, deceased
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Patent number: 4363720Abstract: A hydrocarbon cracking catalyst is treated with zinc to passivate contaminant metals, e.g., nickel, copper, vanadium, and iron, which are deposited on the catalyst during the catalytic cracking of hydrocarbon feedstocks.Type: GrantFiled: May 13, 1981Date of Patent: December 14, 1982Assignee: Standard Oil Company (Indiana)Inventors: Eugene H. Hirschberg, Ralph J. Bertolacini, Frank S. Modica
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Patent number: 4325812Abstract: A process is described for cracking a heavy hydrocarbon to form a light oil and for producing hydrogen by the use of a catalyst containing at least 30 wt % Fe which comprises a first step wherein steam and heavy hydrocarbon are simultaneously contacted with the catalyst in a reduced state to produce hydrogen, cracked gases, and a cracked light oil, to oxidize the reduced-state catalyst, and to deposit coke on the catalyst; and a second step wherein the oxidized-state catalyst on which said coke is deposited is contacted with an oxygen-containing gas insufficient for achieving complete combustion of the coke, to thereby partially combust the coke and regenerate the catalyst to a reduced state.Type: GrantFiled: September 29, 1980Date of Patent: April 20, 1982Assignee: Research Association for Residual Oil ProcessingInventors: Kuniaki Fujimori, Teruo Suzuka, Yukio Inoue, Shirou Aizawa