Employing Hydrogen Patents (Class 208/254H)
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Patent number: 6162351Abstract: A naphtha or a middle distillate hydrocarbon is hydrodenitrogenized by hydrotreating in the presence of a catalyst containing a carbon support bearing (i) molybdenum or tungsten, (ii) a metal of non-noble Group VIII, and (iii) chromium.Type: GrantFiled: May 24, 1994Date of Patent: December 19, 2000Assignee: Texaco Inc.Inventors: Chakka Sudhakar, Frank Dolfinger, Jr., Max Raphael Cesar
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Patent number: 6132597Abstract: The present invention relates to the use of a catalyst comprising an extruded essentially alumina-based support, constituted by a plurality of juxtaposed agglomerates and partially in the form of packs of flakes and partially in the form of needles, and optionally comprising at least one catalytic metal or a compound of a catalytic metal from group VIB, and/or optionally at least one catalytic metal or compound of a catalytic metal from group VIII, in an ebullating bed process and for hydrorefining and hydroconverting hydrocarbon feeds.Type: GrantFiled: June 10, 1998Date of Patent: October 17, 2000Assignee: Institut Francais du PetroleInventors: Virginie Harle, Slavik Kazstelan, Frederic Morel, Stephane Kressmann, Philippe Courty
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Patent number: 6110358Abstract: A method for producing a process oil in which a naphthenic rich distillate is processed through a single hydrotreating stage, the hydrotreated distillate is then solvent extracted to yield a process oil which passes IP-346 and AMES screening test.Type: GrantFiled: May 21, 1999Date of Patent: August 29, 2000Assignee: Exxon Research and Engineering CompanyInventors: Keith K. Aldous, Jacob B. Angelo, Joseph P. Boyle
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Patent number: 6103104Abstract: A process for hydroprocessing middle distillate petroleum streams in two temperature stages. The feedstream is hydroprocessed in two or more first temperature stages operated at a temperature from about 360.degree. C. to about 450.degree. C. The reaction product of the first temperature stage(s) is quenched to a temperature from about 260.degree. C. to about 350, stripped of H.sub.2 S, NH.sub.3 and other dissolved gases, then sent to the second temperature stage which is operated at said quenched temperature range. The product from the second temperature stage is also stripped of dissolved gases. Color bodies produced in the higher temperature first stage are hydrogenated in the last stage.Type: GrantFiled: May 7, 1998Date of Patent: August 15, 2000Assignee: Exxon Research and Engineering CompanyInventor: Ramesh Gupta
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Patent number: 6090274Abstract: A nitrided calcined modified zeolite composition having incorporated therein a molybdenum promoter and a co-promoter. A carburized nitrided calcined modified zeolite composition having incorporated therein a molybdenum promoter and a co-promoter. Producing the composition by incorporating a molybdenum promoter compound and a co-promoter compound into the zeolite followed by thermal treatment of the resulting zeolite with a nitriding agent and, optionally, further thermally treating the resulting zeolite with a hydrocarbon, preferably in the presence of hydrogen. A hydrotreating process that contacts a hydrocarbon-containing fluid with the nitrided, optionally carburized, calcined modified zeolite composition under a condition sufficient to effect the reduction of sulfur content in the hydrocarbon-containing fluid.Type: GrantFiled: December 29, 1998Date of Patent: July 18, 2000Assignee: Phillips Petroleum CompanyInventors: An-hsiang Wu, Charles A. Drake
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Patent number: 6086749Abstract: A method and catalyst mixture for hydroprocessing a hydrocarbon feed stream through a moving catalyst bed having a catalyst mixture and contained within a single onstream reactor vessel. The reactor vessel contains the catalyst mixture which includes two or more different and distinct catalyst for any hydroprocessing application. The different and distinct catalyst have different catalyst density and are designed for a different function, such as HDM and HDN. The different and distinct catalysts can also have different average residence times if their densities and physical properties are properly selected.Type: GrantFiled: December 19, 1997Date of Patent: July 11, 2000Assignee: Chevron U.S.A. Inc.Inventors: David C. Kramer, Bruce E. Stangeland
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Patent number: 6071402Abstract: The present invention concerns a hydrorefining and/or hydrocracking catalyst for hydrocarbon feeds, comprising at least one mixed sulphide comprising sulphur, at least one group VB element, preferably niobium, and at least one group VIB element, preferably molybdenum or tungsten, more preferably molybdenum, optionally combined with a support and/or at least one group VIIA metal and/or at least one group VIII metal and/or an element selected from the group formed by S, P, B, Si.Type: GrantFiled: December 29, 1997Date of Patent: June 6, 2000Assignee: Institut Francais du PetroleInventors: Michel Danot, Nabil Allali, Valerie Gaborit, Christophe Geantet, Pavel Afanassiev, Samuel Mignard, Slavik Kasztelan
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Patent number: 6059961Abstract: A process and arrangement for contacting a moving bed of compact particulate material, usually catalyst, with a radial flow of fluid maintains an unconfined surface of catalyst particles in place by passing fluid axially into the upper surface of the bed and maintaining radial gas flow across an inlet screen at an elevation that is above the upper most elevation of perforations for withdrawing gas flow from the particulate bed. Two vertical screens confine the bed of catalyst. Perforations cover substantially the entire length of the inlet screen. The outlet portion of the screen has perforations that end below the top of the free surface of the catalyst bed and define an upper bed portion therebetween. The inlet screen directs gas flow radially across the inlet screen into an upper portion of the bed and cause at least partial axial flow of gas through the upper portion of the particle bed.Type: GrantFiled: April 27, 1998Date of Patent: May 9, 2000Assignee: UOP LLCInventors: William John Koves, Gary Alan Schulz, Robert John Sanger
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Patent number: 6031146Abstract: A thermowell assembly and method which allows for arresting leakage in the case a thermowell begins to leak in a hydroprocessing process without having to shut down a flow of a hydrocarbon feed stream through a hydroconversion reaction zone in the hydroprocessing process. The thermowell assembly comprises a first hollow sleeve section which supports a thermowell member, a ferrule sealing member which engages the first hollow sleeve section, a second generally cup-shaped second sleeve section wherethrough a thermocouple member slidably passes, and an outer sleeve member for maintaining the union of the first sleeve section, the ferrule sealing member, and the second sleeve section. The method comprises severing and/or removing the thermocouple member from the commenced-leaking thermowell member and placing a high pressure cap over an aperture left vacant by the thermocouple member to seal-off the leaking thermowell member from the atmosphere.Type: GrantFiled: October 2, 1998Date of Patent: February 29, 2000Assignee: Chevron U.S.A. IncInventor: Robert W. Bachtel
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Patent number: 6024864Abstract: A method for producing a process oil is provided in which an aromatic extract oil is added to a paraffinic rich feed to provide a blended feed. The blended feed is then hydrotreated in a first hydrotreating stage to convert at least a portion of sulfur and nitrogen in the feed to hydrogen sulfide and ammonia. After stripping, the feed is subjected to a second hydrotreating stage to provide a process oil.Type: GrantFiled: December 17, 1998Date of Patent: February 15, 2000Assignee: Exxon Research and Engineering CoInventors: Keith Kaluna Aldous, Jacob Ben Angelo, Joseph Philip Boyle, Bruce M. Jarnot, Wayne E. Hanson
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Patent number: 6015485Abstract: Provided are high activity catalysts based upon gamma alumina containing substrates impregnated with one or more catalytically active metals, which catalysts in addition contain a nanocrystalline phase of alumina of a crystallite size at the surface of less than 25 .ANG.. Also provided are processes for preparing such high activity catalysts and various uses thereof.Type: GrantFiled: September 25, 1995Date of Patent: January 18, 2000Assignee: Cytec Technology CorporationInventors: Peter Joseph Shukis, James Donald Carruthers, Vincent Joseph Lostaglio
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Staged upflow hydroprocessing with noncatalytic impurity removal from the first stage vapor effluent
Patent number: 5989411Abstract: A hydroprocessing process for removing impurities from a feed comprising a hydrocarbonaceous liquid comprises at least two cocurrent, upflow hydroprocessing reaction stages and a non-catalytic, vapor-liquid contacting stage. The reaction and contacting stages may all be in the same reactor vessel. The feed and a hydrogen treat gas are passed up into a catalyst bed which comprises the first reaction stage, which produces a partially hydroprocessed liquid and vapor effluent. This first stage vapor is passed up into the contacting stage in which it contacts a hydrocarbonaceous liquid which reduces the vapor impurity content. The impurity-enriched contacting liquid passes down and mixes with the first stage liquid effluent. The combined effluents and hydrogen are passed up into the second reaction stage to form a processed product liquid and hydrogen-containing vapor effluent.Type: GrantFiled: October 23, 1998Date of Patent: November 23, 1999Assignee: Exxon Research and Engineering CompanyInventor: Ramesh Gupta -
Patent number: 5985131Abstract: A process for upgrading a liquid petroleum or chemical stream wherein said stream flows countercurrent to the flow of a treat gas, such as a hydrogen-containing gas, in at least one reaction zone. The reaction vessel used in the practice of the present invention contains vapor and optionally liquid passageway means to bypass one or more catalyst beds. This permits more stable and efficient reaction vessel operation.Type: GrantFiled: August 23, 1996Date of Patent: November 16, 1999Assignee: Exxon Research and Engineering CompanyInventors: Ramesh Gupta, David C. Dankworth, Dennis D. Fleming, Edward S. Ellis, James J. Schorfheide
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Patent number: 5985135Abstract: A hydroprocessing process for removing impurities from a feed comprising a hydrocarbonaceous liquid comprises at least one cocurrent, upflow hydroprocessing reaction stage, a vapor-liquid contacting stage and a downflow hydroprocessing reaction stage. The feed and hydrogen react in the upflow stage to produce a partially hydroprocessed liquid and vapor effluent. The vapor contacts a hydrocarbonaceous liquid in the contacting stage, which transfers impurities from the vapor into the liquid. The impurity-enriched contacting liquid mixes with the upflow stage liquid effluent and the combined liquid effluents react with hydrogen in the downflow reaction stage, to form a hydroprocessed product liquid and vapor effluent. Additional product liquid is recovered by cooling and condensing either or both the contacting and downflow stage vapor effluents.Type: GrantFiled: October 23, 1998Date of Patent: November 16, 1999Assignee: Exxon Research and Engineering Co.Inventor: Ramesh Gupta
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Patent number: 5968348Abstract: A process for converting a charge of heavy hydrocarbons containing components boiling above 1000.degree. F. to a product containing a decreased content of components boiling above 1000.degree. F. and decreased sediment content employing a NiMo catalyst having a specified pore distribution under hydroconversion conditions is disclosed. The process includes contacting the charge of heavy hydrocarbon with hydrogen in the presence of a heterogeneous catalyst supported on alumina and containing .ltoreq.2.5 wt % of silica and bearing 2.2 to 6 wt % of a Group VIII metal oxide, 7 to 24 wt % of a Group VIB metal oxide and 0.3 to 2 wt % of a loaded phosphorus oxide, the phosphorous being loaded onto the catalyst as aqueous phosphoric acid. The catalyst also may be characterized by having a Total Surface Area of 175 to 205 m.sup.2 /g, a Total Pore Volume of 0.82 to 0.98 cc/g, and a Pore Diameter Distribution wherein 29.6 to 33.0% of the Total Pore Volume is present as macropores of diameter greater than 250 .ANG., 67.Type: GrantFiled: August 24, 1995Date of Patent: October 19, 1999Assignee: Texaco Inc.Inventor: David Edward Sherwood, Jr.
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Patent number: 5968346Abstract: A hydroprocessing process includes two hydroprocessing reaction stages, both of which produce a liquid and a vapor effluent, and a liquid-vapor contacting stage. The first stage vapor effluent contains impurities, such as heteroatom compounds, which are removed from the vapor by contact with processed liquid effluent derived from one or both reaction stages and, optionally, also liquid recovered from processed vapor. The first and contact stage liquid effluents are passed into the second stage to finish the hydoprocessing. The contact and second stage vapor effluents are cooled to recover additional hydroprocessed product liquid.Type: GrantFiled: September 16, 1998Date of Patent: October 19, 1999Assignee: Exxon Research and Engineering Co.Inventors: Henry Jung, Ramesh Gupta, Edward S. Ellis, William E. Lewis
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Patent number: 5958220Abstract: A distributor assembly for hydroprocessing a hydrocarbon mixture of hydrogen-containing gas and liquid hydrocarbon is presented. The distributor assembly has a circular plate with a plurality of hollow risers bound thereto for distributing hydrogen-containing gas and liquid hydrocarbon through openings in the circular plate member. Each of the hollow risers has a tubular opening In its associated side. The distributor assembly is connected to an internal wall of a reactor. A method is also presented for hydroprocessing a hydrocarbon feed stream comprising flowing a mixture of hydrogen-containing gas and liquid hydrocarbon into a reactor zone to produce evolved hydrogen-containing gas; and flowing the mixture of hydrogen-containing gas and liquid hydrocarbon through a plurality of tubular zones while admixing simultaneously therewith the evolved hydrogen-containing gas.Type: GrantFiled: November 23, 1998Date of Patent: September 28, 1999Assignee: Chevron U.S.A. Inc.Inventors: Bruce E. Reynolds, Bruce E. Stangeland, Krishniah Parimi, Robert W. Bachtel
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Patent number: 5958223Abstract: A catalyst system for selective hydrogenation of sulfur-containing and nitrogen-containing compounds of a heteroaromatic organic phase includes a mixture of a noble metal selected from Group VIII of the Periodic Table of Elements and a water-soluble ligand. A process for preparing the catalyst system and hydrogenation process using the catalyst system are also provided.Type: GrantFiled: January 7, 1998Date of Patent: September 28, 1999Assignee: Intevep. S.A.Inventors: Daniel E. Paez, Antida Andriollo, Roberto A. Sanchez-Delgado, Norma del V. Valencia, Roberto E. Galiasso, Francisco A. Lopez
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Patent number: 5954944Abstract: A process for producing middle distillates by hydrocracking a heavy distillate oil under middle pressure uses a hydrofining catalyst and a hydrocracking catalyst in series and once-through operation. The once-through volume conversion to 350.degree. C.--products is up to 80 vol. %. The yield and selectivity of middle distillates are greater than 40 wt % and less than 50 wt %, respectively. The process is particularly suited to treat heavy distillate oil having the nitrogen content of up to 1500 ppmw, the sulfur content of up to 3.5 wt % and dry point in the boiling range of higher than 500.degree. C. to produce the feed for reforming process, jet fuel, the low sulfur content diesel, the feed for catalytic cracker and the feed for producing ethylene.Type: GrantFiled: June 30, 1997Date of Patent: September 21, 1999Assignees: China Petrochemical Corp., Research Institute of Petroleum Processing SinopecInventors: Yanping Zhang, Yulin Shi, Zhenlin Xiong, Jianwen Shi, Hong Nie, Yahua Shi, Yigin Zhu, Zhihai Hu
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Patent number: 5948239Abstract: Disclosed herein is a highly efficient process for producing distillate fuels using a multi-bed hydrogenation reactor. The temperature of the feed to the second and subsequent reactor beds is controlled by removing effluent from the prior bed, cooling the effluent in an external heat exchanger, injecting hydrogen gas into the effluent mixture, and inserting the cooled mixture containing hydrogen gas into the inlet of the next reaction zone.Type: GrantFiled: March 12, 1997Date of Patent: September 7, 1999Assignee: ABB Lummus Global Inc.Inventors: Harjeet S. Virdi, Benjamin Klein, R. John McNab
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Patent number: 5948243Abstract: A composition comprises a hydrodesulfurization or hydrodenitrogenation, or both, catalyst component and a support component which comprises aluminum, zirconium, and a borate. A process for making the composition comprises the steps of (1) contacting an aluminum salt, a zirconium salt, and an acidic boron compound under a condition sufficient to effect the production of a support component comprising aluminum, zirconium, and borate and (2) combining a hydrodesulfurization or hydrodenitrogenation, or both, catalyst component with the support component. Also disclosed are processes for removing organic sulfur compounds or organic nitrogen compounds, or both, from hydrocarbon-containing fluids which comprise contacting a hydrocarbon-containing fluid, with a hydrogen-containing fluid, in the presence of a catalyst composition.Type: GrantFiled: February 24, 1998Date of Patent: September 7, 1999Assignee: Phillips Petroleum CompanyInventor: Lyle R. Kallenbach
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Patent number: 5944983Abstract: This invention relates to a hydrotreating catalyst for a hydrocarbon oil and also to a process for hydrotreating the hydrocarbon oil by using the catalyst. More specifically, the present invention is concerned with a hydrotreating catalyst formed by having a hydrogenation-active component supported on a silica-alumina carrier and having a specific pore distribution and also with a hydrotreating process making use of the catalyst for the removal of sulfur compounds and nitrogen compounds from a hydrocarbon oil.Type: GrantFiled: April 28, 1998Date of Patent: August 31, 1999Assignee: Tonen CorporationInventors: Fumitaka Hayashi, Akira Kamo, Hiroshi Toshima, Akira Saiai
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Patent number: 5935418Abstract: A reactor system is provided which is particularly suitable for hydroprocessing a heavy hydrocarbon under catalytic slurry hydroprocessing conditions. This reactor system includes a single reaction zone containing at least one filter element for the separation of liquid product from catalyst particles in the reaction zone. Means are provided for backwashing the filter element. Preferably, at least two filter elements are provided one of which is used for separation of product and the other for introduction of hydrogen into the reactor. Additionally, means are provided for switching the flow between the two filter elements thereby permitting continuous operation of the system.Type: GrantFiled: August 29, 1997Date of Patent: August 10, 1999Assignee: Exxon Research and Engineering Co.Inventors: Tapantosh Chakrabarty, Ghosh Mainak
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Patent number: 5916433Abstract: A catalyst system for treating sulfur and nitrogen contaminated hydrocarbon feedstock includes a matrix, at least one support medium substantially uniformly distributed through said matrix and comprising a silica alumina molecular sieve material having a composition xSiO.sub.2 :Al.sub.2 O.sub.3 :yP.sub.2 O.sub.5, wherein x is at least about 0.1, a first catalytically active metal phase supported on said support medium, said first catalytically active metal phase comprising a first metal and a second metal each selected from group VIII of the Periodic Table of Elements, said first metal being different from said second metal, a second catalytically active metal phase supported on said matrix, said second catalytically active metal phase comprising a third metal and a fourth metal each selected from group VIII of the Periodic Table of Elements and a fifth metal selected from group VIb of the Periodic Table of Elements, said third metal being different from said fourth metal.Type: GrantFiled: October 21, 1997Date of Patent: June 29, 1999Assignee: Intevep, S.A.Inventors: Jorge Alejandro Tejada, Yilda Margot Romero, Edito Jose Reyes
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Patent number: 5910241Abstract: Catalyst comprising a porous inorganic refractory oxide wherein the catalyst has:(a) a total pore volume in the range of from 0.2 to 0.5 ml/g,(b) a macroporosity of at least 0.1 ml/g,(c) a microporosity of at least 0.05 ml/g, and(d) a surface area of at least 5 m.sup.2 /g.Process for reducing the amount of solid contaminants and the amount or dissolved metallic contaminants, wherein a hydrocarbon oil containing such contaminants is contacted with hydrogen under hydrotreating conditions in the presence of the above catalyst.Type: GrantFiled: December 9, 1997Date of Patent: June 8, 1999Assignee: Shell Oil CompanyInventors: David John McNamara, Willem Hartman Jurriaan Stork
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Patent number: 5871635Abstract: Hydrocarbonaceous feedstocks admixed with a flow-through catalyst and hydrogen are hydroprocessed in a hydroprocessing reactor containing a captive hydroprocessing catalyst. The flow-through catalyst is continually withdrawn with the hydroprocessed feed from the hydroprocessing reactor. The flow-through catalyst may be an FCC, hydrocracking, isomerization or ring-opening catalyst. In a preferred embodiment, the captive hydroprocessing catalyst contains Co, Ni and/or Mo on an alumina base and the flow-through catalyst is an FCC zeolitic catalyst which is withdrawn with the hydroprocessed feed from the hydroprocessing reactor and then sent to an FCC unit.Type: GrantFiled: December 3, 1996Date of Patent: February 16, 1999Assignee: Exxon Research and Engineering CompanyInventors: Ramesh Gupta, Edward S. Ellis, William Ernest Lewis
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Patent number: 5837128Abstract: A method is disclosed for optimizing the pressure drop in the catalytic conversion of a feed in a bed of catalyst particles in a vertically arranged reactor by grading the catalyst particles within the bed by pressure drop.Type: GrantFiled: May 24, 1996Date of Patent: November 17, 1998Assignee: Amoco CorporationInventors: George A. Huff, Jr., Frederick T. Clark, James L. Taylor
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Patent number: 5820749Abstract: The invention relates to catalytic hydrogenation processes for hydrocarbon molecules of number-average molecular weight greater than about 180, and to use therein of an inert catalyst support comprising porous refractory substrate particles having: a) a pore volume distribution wherein i) pores having diameters >150,000 .ANG. constitute greater than about 2% of the total volume, ii) pores having diameters >20,000 .ANG. and <150,000 .ANG. constitute greater than about 1% of the total volume, iii) pores having diameters >2,000 .ANG. and <20,000 .ANG. constitute greater than about 12% of the total volume; and, b) a total pore volume of from about 45% to 86% of the total volume of the substrate particles. Using the invention increased resin productivity of 150% or more can be achieved in industrial operations.Type: GrantFiled: November 22, 1996Date of Patent: October 13, 1998Assignee: Exxon Chemical Patents, Inc.Inventors: Jerry L. Haluska, Richard B. Pannell
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Patent number: 5817229Abstract: A hydrocarbon feedstock is brought into contact with activated carbon at a temperature of about 300.degree. to about 650.degree. C. and a pressure of about 0-1000 psig in the absence of added hydrogen to reduce the content of aromatic, sulfur and nitrogen compounds contained therein and to simultaneously lower the specific gravity thereof.Type: GrantFiled: November 6, 1996Date of Patent: October 6, 1998Assignee: Texaco IncInventors: Chakka Sudhakar, Regis J. Pellet, Mahendra Somabhai Patel
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Patent number: 5800698Abstract: A catalyst system for treating sulfur and nitrogen contaminated hydrocarbon feedstock includes a matrix, at least one support medium substantially uniformly distributed through said matrix and comprising a silica alumina molecular sieve material having a silica/alumina ratio of at least about 20, a first catalytically active metal phase supported on said support medium, said first catalytically active metal phase comprising a first metal and a second metal each selected from group VIII of the Periodic Table of Elements, said first metal being different from said second metal, a second catalytically active metal phase supported on said matrix, said second catalytically active metal phase comprising a third metal and a fourth metal each selected from group VIII of the Periodic Table of Elements and a fifth metal selected from group VIb of the Periodic Table of Elements, said third metal being different from said fourth metal.Type: GrantFiled: June 3, 1996Date of Patent: September 1, 1998Assignee: Intevep, S.A.Inventors: Jorge Tejada, Yilda Romero, Edito Reyes, Ricardo Prada, Mariana Torrealba
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Patent number: 5767332Abstract: In the production of aromatic hydrocarbon from coking crude by-product benzene after a vaporization stage in which the crude benzene is evaporated to leave a residue, the crude benzene is subjected to pressure refining in the presence of hydrogen. The residue is distilled to form high and low boiling fractions and at least the gas pressure and temperature of the distillation stage is controlled so that the sump product apart from styrene is substantially free from aromatic hydrocarbons with less than 9 carbon atoms. The rate of withdrawal of the vaporization residue from the vaporizing column is controlled, depending upon the concentration of polymer formers in the crude benzene to be in the range of 6 to 40% of the rate of feed of the coking by-product benzene to the vaporizing column.Type: GrantFiled: August 29, 1995Date of Patent: June 16, 1998Assignee: Krupp Koppers GmbHInventors: Hans-Jurgen Vollmer, Uwe Ranke, Reiner Wieczorkowski, Thottakudi Ramanuja Narasimhan
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Patent number: 5738779Abstract: In a hydrotreating process a two phase flow splitter is used in combination with parallel heat exchanger trains for heat transfer stability. Flow maldistribution of liquid and vapor between heat exchanger trains is thereby avoided without more complex feedback control. The two phase flow splitter is inherently phase volume ratio stable. Prior methods of flow splitting were only phase volume ratio metastable. Improved heat recovery at lower equipment cost is thereby achieved.Type: GrantFiled: July 18, 1996Date of Patent: April 14, 1998Assignee: Texaco Inc.Inventors: Michael Markel Dach, Rich Walter Barkley, Jon Andrew Branson, James Raymond Stoy, James Lindsey Gilbert Schrodt
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Patent number: 5733440Abstract: This invention makes possible substantially continuous flow of uniformly distributed hydrogen and hydrocarbon liquid across a densely packed catalyst bed to fill substantially the entire volume of a reactor vessel by introducing the fluids as alternate annular rings of gas and liquid (i.e. a mixture of liquid hydrocarbon and a hydrogen-containing gas) at a rate insufficient to levitate or ebullate the catalyst bed. Catalyst are selected by density, shape and size at a design feed rate of liquids and gas to prevent ebullation of the packed bed at the design feed rates. Catalysts are selected by measuring bed expansion, such as in a large pilot plant run, with hydrocarbon, hydrogen, and catalyst at the design pressures and flow velocities. The liquid and gas components of the feed flow into the bed in alternate annular rings across the full area of the bed.Type: GrantFiled: November 14, 1996Date of Patent: March 31, 1998Assignee: Chevron U.S.A. Inc.Inventors: Bruce E. Stangeland, David C. Kramer, David S. Smith, James T. McCall, Georgieanna L. Scheuerman, Robert W. Bachtel, David R. Johnson
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Patent number: 5730860Abstract: An apparatus and method for treating a liquid hydrocarbon stream useful as a precursor for transportation fuel and which contains an unacceptably high level of heteroatom compounds is provided for the removal of a significant portion of the heteroatom compounds from the hydrocarbon stream. The method and apparatus employ an adsorbent which is brought into countercurrent contact with a hydrocarbon stream in an adsorption zone to form a product hydrocarbon stream and a spent adsorbent stream. The adsorbent is recirculated to a desorption zone and is thereafter brought into cross-current contact with a reactivating medium, such as hydrocarbon gas, at elevated temperatures to form a reactivated adsorbent stream and a hydrogen/heteroatom stream. The regenerated adsorbent is recirculated back to the adsorption zone to form the adsorbent stream.Type: GrantFiled: August 14, 1995Date of Patent: March 24, 1998Assignee: The Pritchard CorporationInventor: Robert L. Irvine
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Patent number: 5720872Abstract: A process for hydroprocessing liquid petroleum and chemical streams in two or more hydroprocessing stages, which stages are in separate reaction vessels and wherein each reaction stage contains a bed of hydroprocessing catalyst. The liquid product from the first reaction stage is sent to a stripping stage and stripped of H.sub.2 S, NH.sub.3 and other dissolved gases. The stripped product stream is then sent to the next downstream reaction stage, the product from which is also stripped of dissolved gases and sent to the next downstream reaction stage until the last reaction stage, the liquid product of which is stripped of dissolved gases and collected or passed on for further processing. The flow of treat gas is in a direction opposite the direction in which the reaction stages are staged for the flow of liquid. Each stripping stage is a separate stage, but all stages are contained in the same stripper vessel.Type: GrantFiled: December 31, 1996Date of Patent: February 24, 1998Assignee: Exxon Research and Engineering CompanyInventor: Ramesh Gupta
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Patent number: 5705052Abstract: A process for hydroprocessing liquid petroleum and chemical streams in a single reaction vessel containing two or more hydroprocessing reaction stages. The liquid product from the first reaction stage is stripped of H.sub.2 S, NH.sub.3 and other dissolved gases, then sent to the next downstream reaction stage. The product from the downstream reaction stage is also stripped of dissolved gases and sent to the next downstream reaction stage until the last reaction stage, the liquid product of which is stripped of dissolved gases and collected or passed on for further processing. The flow of treat gas is in a direction opposite the direction in which the reaction stages are staged for the flow of liquid.Type: GrantFiled: December 31, 1996Date of Patent: January 6, 1998Assignee: Exxon Research and Engineering CompanyInventor: Ramesh Gupta
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Patent number: 5676822Abstract: A process for treating a charge hydrocarbon oil containing undesired aromatic components, sulfur and nitrogen compounds, which comprises maintaining a bed of a sulfided catalyst comprising 0.1 to 15% by weight of one or more non-noble Group VIII metals; and from 1 to 50% by weight of tungsten and/or from 1 to 20% by weight or molybdenum or chromium, and 0.01 to 10% by weight of zinc, on an activated carbon support, passing a charge hydrocarbon feed in the presence of hydrogen into contact with said catalyst at hydrotreating conditions, thereby effecting hydrogenation, hydrodearomatization, hydrodesulfurization and hydrodenitrogenation of said charge hydrocarbon feed containing undesired aromatic components, sulfur and nitrogen, and forming a product stream of hydrocarbon containing a lesser concentration of undesired aromatic components, sulfur and nitrogen; and recovering said product stream of hydrocarbon containing a lesser concentration of undesired aromatic components, sulfur and nitrogen.Type: GrantFiled: March 9, 1995Date of Patent: October 14, 1997Assignee: Texaco Inc.Inventor: Chakka Sudhakar
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Patent number: 5651878Abstract: A naphtha or a middle distillate hydrocarbon is hydrodearomatized by hydrotreating in the presence of a catalyst containing a carbon support bearing (i) molybdenum or tungsten, (ii) a metal or non-noble Group VIII, and (iii) chromium.Type: GrantFiled: April 4, 1996Date of Patent: July 29, 1997Assignee: Texaco Inc.Inventors: Chakka Sudhakar, Frank Dolfinger, Jr., Max Raphael Cesar
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Patent number: 5626742Abstract: The present invention relates to a continuous in-situ process for the removal of organically bound sulfur existing as mercaptans, sulfides and thiophenes comprising the steps of (a) contacting a heavy oil with aqueous sodium hydroxide at a temperature of about 380.degree. C. to about 450.degree. C. for a time sufficient to form sodium sulfide, and (b) steam stripping the sodium sulfide of step (a) at a temperature sufficient to convert said sodium sulfide to sodium hydroxide and recirculating the sodium hydroxide from step (b) back to step (a) and removing hydrogen sulfide and the metals from the organically bound metal complex of the sodium sulfide to convert it back to sodium hydroxide, in which case the sulfur may be recovered as H.sub.2 S rather than the metal sulfide. Optionally, molecular hydrogen may be added in the first step. The present invention is useful in removing organically bound sulfur that has been recognized to be difficult to remove, such as thiophenes.Type: GrantFiled: May 2, 1995Date of Patent: May 6, 1997Assignee: Exxon Reseach & Engineering CompanyInventors: Glen Brons, Ronald D. Myers
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Patent number: 5591325Abstract: The present invention provides a process for hydrotreating a heavy oil, comprising the steps of (a) feeding a heavy oil into a fixed-bed reactor packed with a hydrotreating catalyst to thereby effect hydrotreating of the heavy oil, and (b) feeding the heavy oil hydrotreated in the step (a) into a suspended-bed reactor packed with a hydrotreating catalyst for hydrotreating the heavy oil to thereby effect further hydrotreating of the heavy oil, and also provides a hydrotreating apparatus comprising (a') a fixed-bed reactor packed with a catalyst for hydrotreating a feed heavy oil and (b') a suspended-bed reactor packed with a hydrotreating catalyst for hydrotreating the heavy oil hydrotreated in the fixed-bed reactor. The hydrotreating of the heavy oil can be conducted for a prolonged period of time.Type: GrantFiled: November 15, 1994Date of Patent: January 7, 1997Assignee: Catalysts & Chemicals Industries Co., Ltd.Inventor: Hidehiro Higashi
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Patent number: 5543036Abstract: A process for hydrotreating a hydrocarbon feedstock, such as light cycle oil, using a catalyst composition containing a hydrogenation/dehydrogenation component and an acidic solid component including a Group IVB metal oxide modified with an oxyanion of a Group VIB metal. The hydrotreating process removes contaminants, such as sulfur and/or nitrogen, from the feedstock.Type: GrantFiled: December 16, 1993Date of Patent: August 6, 1996Assignee: Mobil Oil CorporationInventors: Clarence D. Chang, Scott Han, Daniel J. Martenak, Jose G. Santiesteban, Dennis E. Walsh
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Patent number: 5534135Abstract: A novel zeolite characterized by a large number of secondary pores, a substantially decreased Lattice Constant of below about 24.19 .ANG., and a substantially decreased Acid Site Density is attained by hydrothermal and acid-treating of an ultrastable Y-zeolite.Type: GrantFiled: March 7, 1994Date of Patent: July 9, 1996Assignee: ABB Lummus Global Inc.Inventors: Pei-Shing E. Dai, David E. Sherwood, Jr., Burton H. Bartley
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Patent number: 5522983Abstract: A process is provided for converting a hydrocarbon feedstock comprising the steps of introducing the hydrocarbon feedstock to a first hydroconversion zone at superatmospheric pressure and at a temperature between about 450.degree. F. and about 850.degree. F. in the presence of hydrogen, the hydrogen flowing in a countercurrent relationship to the hydrocarbon feedstock, to form a hydrogen-rich vapor effluent and a hydrocarbon-rich liquid effluent; reacting the hydrogen-rich vapor effluent in a second hydroconversion zone to form a converted vapor effluent; and introducing a portion of the hydrocarbon-rich liquid effluent to the second hydroconversion zone in countercurrent relationship to the hydrogen-rich vapor effluent. By recycling to the second hydroconversion zone a stream having sufficiently high boiling range that it remains a liquid, a greater range of operating conditions are possible in the second hydroconversion zone, thus allowing for higher conversions and product yields.Type: GrantFiled: February 6, 1992Date of Patent: June 4, 1996Assignee: Chevron Research and Technology CompanyInventors: Dennis R. Cash, Robert W. Bachtel
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Patent number: 5520799Abstract: This invention is a process for the upgrading of distillate feeds. A batch of supported hydroprocessing catalyst is placed in a reaction zone, which is usually a fixed bed reactor. The hydroprocessing catalyst comprises an effective amount of a noble metal or metals and has a specific activity. Both low aromatic diesel and jet fuel may be produced in separate blocks over the same catalyst batch, using different feeds and often different conditions. The activity of the catalyst is restored each time the feed is switched. When production is switched from jet fuel to low aromatics diesel, activity may be regained more quickly by holding the catalyst at a higher temperature than the reaction temperature for a specific period of time prior to dropping the temperature to the reaction temperature. Switching from one feed to the other may continue for about one year before the catalyst batch is changed. A dual catalyst system may alternatively be employed.Type: GrantFiled: September 20, 1994Date of Patent: May 28, 1996Assignee: Mobil Oil CorporationInventors: Stephen H. Brown, Paul P. Durand, Timothy L. Hilbert, Thomas R. Kiliany, Chang-Kuei Lee, Jeffrey C. Trewella
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Patent number: 5514274Abstract: A process for the simultaneous hydrodenitrogenation and hydrodesulfurization of a gas oil utilizing a novel catalyst. The novel hydroprocessing catalyst comprises an overlayer of at least one Group VIB metal component, at least one Group VIII metal component and at least one phosphorous component on a support comprising at least one underbedded phosphorus component combined with a porous refractory oxide, said catalyst having a median pore diameter from about 60 to about 120 .ANG..Type: GrantFiled: April 3, 1995Date of Patent: May 7, 1996Assignee: UOPInventor: Howard D. Simpson
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Patent number: 5514273Abstract: Heavy oils may be hydrotreated in the presence of a porous alumina support bearing metals of Group VIII, excluding cobalt, and VI-B and optionally phosphorus, the catalyst having a Total Surface Area of 240-320 m.sup.2 /g, a Total Pore Volume of 0.65-0.9 cc/g, and a Pore Diameter Distribution whereby 50-62.8% of the Total Pore Volume is present as micropores of diameter 55-115 .ANG. and 20-30.5% of the Total Pore Volume is present as macropores of diameter greater than 250 .ANG..The heavy oils and hydrogen are contacted with the catalyst such that the catalyst is maintained at isothermal conditions and is exposed to a uniform quality of feed. The process is particularly effective in achieving desired levels of hydroconversion of feedstock components having a boiling point greater than 1000.degree. F. to products having a boiling point less than 1000.degree. F.Type: GrantFiled: October 1, 1993Date of Patent: May 7, 1996Assignee: Texaco Inc.Inventors: David E. Sherwood, Jr., Pei-Shing E. Dai, Charles N. Campbell, II
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Patent number: 5507940Abstract: The instant invention relates to a method for preparing a hydrotreating catalyst having improved hydrodenitrification activity by impregnating an alumina supported Group VIB/Group VIII hydrogenating catalyst with a liquid form of a silicon compound having the general formula ##STR1## wherein U, V, W, X, Y, and Z can individually be --R, --OR, --Cl, --Br, --SiH.sub.3, --COOR, --SiH.sub.n Cl.sub.m, R being either hydrogen, or an alkyl, cycloalkyl, aromatic, alkyl aromatic, alkylcycloalkyl radical having from 1 to 30 carbon atoms, "n" and "m" being whole numbers in the range of from 1 to 3 and "a" being a whole number in the range of from 0 to 80, in an amount sufficient to deposit from about 2 to about 8 percent by weight of the total catalyst of Si, and subsequently calcining said impregnated catalyst at a temperature ranging from about 300.degree. C. to about 600.degree. C. in an oxidizing atmosphere.Type: GrantFiled: November 17, 1994Date of Patent: April 16, 1996Assignee: Shell Oil CompanyInventor: Robert C. Ryan
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Patent number: 5494572Abstract: This process for the desulfurization and denitration of light oil is effected by extraction with an organic solvent containing nitrogen. The invention also relates to light oil desulfurized and denitrated by said process as well as an organic solvent containing nitrogen for the extraction. The solvent is selected from among, for example, hetrocyclic compounds containing nitrogen, such as pyrrolidones, imidazolidinones, pyrimidinones and pyridinium salts, and acid amides. The combination of the process of this invention with any ordinary process for hydrodesulfurization enables the production of light oil having a sulfur content not exceeding 0.01% by weight. Light oil still containing benzothiophenone and dibenzothiophenone derivatives after hydrodesulfurization can be easily desulfurized to yield a desulfurized product not having any undesirable color, or any offensive smell. Also, the extraction of nitrogen compounds and aromatic compound from light oil is effected by the same process.Type: GrantFiled: June 2, 1995Date of Patent: February 27, 1996Assignee: General Sekiyu KabushikikaishaInventors: Yuji Horii, Hitoshi Onuki, Sadaaki Doi, Toshiatsu Mori, Takeo Takatori, Hideaki Sato, Tsuyoshi Ookuro, Toru Sugawara
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Patent number: 5472595Abstract: A process for treating a charge hydrocarbon oil containing undesired aromatic components, sulfur and nitrogen compounds, which comprisesmaintaining a bed of a sulfided catalyst comprising 0.1 to 15% by weight of nickel; and from 1 to 50% by weight of tungsten and 0.01 to 10% by weight of phosphorus, on an activated carbon support, andpassing a charge hydrocarbon feed in the presence of hydrogen into contact with said catalyst at hydrotreating conditions, thereby effecting hydrodearomatization, hydrodesulfurization and hydrodenitrogenation of said charge hydrocarbon feed containing undesired aromatic components, sulfur and nitrogen, and forming a product stream of hydrocarbon containing a lesser quantity of undesired aromatic components, sulfur and nitrogen; andrecovering said product stream of hydrocarbon containing a lesser quantity of undesired aromatic components, sulfur and nitrogen.Type: GrantFiled: August 9, 1994Date of Patent: December 5, 1995Assignee: Texaco Inc.Inventors: Chakka Sudhakar, Frank Dolfinger, Jr., Max R. Cesar, Mahendra S. Patel
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Patent number: 5468371Abstract: Heavy hydrocarbons are hydrotreated to increase content of components boiling below 1000.degree. F. by contact with Group VIII non-noble metal oxide and Group VIB metal oxide on alumina having a Total Surface Area of 175-220 m.sup.2 /g, a Total Pore Volume (TPV) of 0.6-0.8, and a Pore Diameter Distribution whereby .ltoreq.33% of the TPV is present as primary micropores of diameter .ltoreq.100 .ANG., at least about 41% of TPV is present as secondary micropores of diameter of about 100 .ANG.-200 .ANG., and about 16%-26% of the TPV is present as mesopores of diameter .gtoreq.200 .ANG.. Phosphorus containing compounds are avoided during catalyst preparation.Type: GrantFiled: April 11, 1994Date of Patent: November 21, 1995Assignee: Texaco Inc.Inventors: Gerald V. Nelson, Govanon Nongbri, Roy E. Pratt