Employing Hydrogen Patents (Class 208/251H)
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Patent number: 6149799Abstract: The invention concerns a catalyst for hydrorefining and hydroconverting hydrocarbon feeds, comprising a mixed sulphide comprising at least two elements selected from elements with an atomic number selected from the group formed by the following numbers: 3, 11, 12, 19 to 33, 37, to 51, 55 to 83, 87 to 103, characterized in that the mixed sulphide results from a combination of at least one element the sulphide of which has a bond energy between the metal and sulphur of less than 50.+-.3 kcal/mol (209.+-.12 kJ/mol) and at least one element the sulphide of which has a bond energy between the metal and sulphur of more than 50.+-.3 kcal/mol (209.+-.12 kJ/mol), the mixed sulphide thus having a mean bond energy between the metal and sulphur which is in the range 30 to 70 kcal/mol (125 to 293 kJ/mol).Type: GrantFiled: January 14, 1998Date of Patent: November 21, 2000Assignee: Institut Francais du PetroleInventors: Pascal Raybaud, Herve Toulhoat, Slavik Kasztelan
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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: 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: 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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Patent number: 6007705Abstract: The present invention relates to a process for demetallating a petroleum stream by contacting a metals-containing petroleum feed in the presence of an aqueous base selected from Group IA and IIA hydroxides and carbonates and ammonium hydroxide and carbonate and mixtures thereof, an oxygen containing gas and a phase transfer agent at a temperature of up to 180.degree. C. for a time sufficient to produce a treated petroleum feed having a decreased metals content. The invention provides a method for enhancing the value of petroleum feeds that traditionally have limited use in refineries due to their metals, e.g., Ni and V content.Type: GrantFiled: December 18, 1998Date of Patent: December 28, 1999Assignee: Exxon Research and Engineering CoInventors: Mark Alan Greaney, Paul James Polini
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Patent number: 5989412Abstract: A hydrodemetallizing catalyst for a hydrocarbon oil comprising a support and a catalytic component carried on the support, this catalyst having a surface, part of which has a coating layer composed of an inert substance having substantially no demetallizing activity, this coating layer allowing substantially no reaction fluid to permeate therethrough. This catalyst preferably has a reaction flow path through which a reaction fluid flows thereinside and is preferred to be, for example, in the form of a honeycomb structure or cylinder having one or a plurality of through holes.In the hydrodemetallization of heavy oils using the above hydrodemetallizing catalyst for a hydrocarbon oil, the sticking of the catalyst can be prevented and the spacing between catalyst particles can be maintained to thereby prevent a rapid increase of differential pressure, so that a continuous operation can be performed for a prolonged period of time.Type: GrantFiled: December 5, 1997Date of Patent: November 23, 1999Assignee: Catalysts & Chemicals Industries Co., Ltd.Inventors: Akio Okagami, Akio Furuta, Fujio Tsuchiya, Shinichiro Suhara
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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: 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: 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: 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: 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: 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: 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: 5928499Abstract: A process for hydrotreating a hydrocarbon feed containing components boiling above 1000.degree. F. and sulfur, metals and carbon residue utilizing a heterogeneous catalyst having a specified pore size distribution, median pore diameter by surface area and pore mode by volume, to give a product containing a decreased content of components boiling above 1000.degree. F. and decreased sulfur, metals and carbon residue is disclosed. The process includes contacting the hydrocarbon feed with hydrogen in the presence of the catalyst at isothermal hydroconversion conditions. The catalyst includes an porous alumina support containing less than or equal to 2.5 wt % silica on the finished catalyst basis, and bearing 2.2 to 6 wt % of a Group VIII metal oxide, 7 to 24 wt % of a Group VIB metal oxide and preferably less than 0.2 wt % of a phosphorous oxide. The catalyst may be characterized as having a Total Surface Area of 215 to 245 m.sup.2 /g, a Total Pore Volume of 0.82 to 0.Type: GrantFiled: December 29, 1995Date of Patent: July 27, 1999Assignee: Texaco IncInventors: David Edward Sherwood, Jr., Pei-Shing Eugene Dai
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Patent number: 5925238Abstract: A process for catalytic two-stage hydrodesulfurization of metal-containing petroleum residua feedstocks to achieve at least about 75% desulfurization of the liquid product while also providing at least about 40% reduction in catalyst consumption. In the process, used catalyst having a catalyst equilibrium age of 0.3-5.0 bbl oil feed/lb catalyst is withdrawn from the second stage reactor, rejuvenated so as to remove 10-50 wt. % of the contaminant metals and at least 80 wt. % of carbon deposited on the catalyst, and then cascaded forward and added to the first stage reactor. Sufficient fresh make-up catalyst is added to the second stage reactor to replace the used catalyst withdrawn there, and only sufficient fresh catalyst is added to the first stage reactor to replace any catalyst transfer losses. Used catalyst having a catalyst equilibrium age of 0.6 to 10.0 bbl. oil per lb. catalyst is withdrawn from the first stage reactor for discard.Type: GrantFiled: May 9, 1997Date of Patent: July 20, 1999Assignee: IFP North AmericaInventors: John E. Duddy, Lawrence M. Abrams, Steven J. Hildebrandt
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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: 5906731Abstract: A hydroprocess catalyzed by a catalyst composition comprising a porous refractory oxide, a molybdenum component, a phosphorus component and an underbedded nickel component, the composition characterized by a Raman spectrum comprising at least one Raman band in each of the regions of (1) about 240 cm.sup.-1 to about 250 cm.sup.-1, and (2) about 595 cm.sup.-1 to about 605 cm.sup.-1. The catalyst is prepared by sequential incorporation of the nickel metal followed by the additional catalytic promoters including a molybdenum component and a phosphorus component.Type: GrantFiled: July 28, 1997Date of Patent: May 25, 1999Assignee: UOPInventors: Suheil F. Abdo, Howard D. Simpson, Pradeep S. Iyer
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Patent number: 5888380Abstract: A catalyst composition suitable for effecting simultaneous hydrodesulphurisation and hydrodemetallisation of sulphur and metals containing feedstocks which shows a high hydrodesulphurisation activity, a high hydrodemetallisation activity, and a long life is disclosed.The catalyst includes: a) a support, at least 90 wt. % of which includes alumina, which alumina has an R value of from 0.08 to 0.30, the R value being defined as the ratio between the integrated intensity of the X-ray diffraction peak at 2 .theta.=32.degree. and the integrated intensity of the X-ray diffraction peak at 2 .theta.=46.degree., b) from 2 to 8 wt. % of a Group VIB metal component, calculated as metal, c) from 0.5 to 2.5 wt. % of a Group VIII metal component, calculated as metal; and d) a pore size distribution as determined by nitrogen adsorption satisfying the following requirements: (i) a pore volume of from 0.5 to 1.Type: GrantFiled: September 19, 1995Date of Patent: March 30, 1999Assignee: Nippon Ketjen Co., Ltd.Inventors: Katsuhisa Fujita, Tetsuro Kamo, Masafumi Shimowake, Yoshimasa Inoue
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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: 5868923Abstract: An improved ebullated bed hydroconversion process is disclosed that utilizes a bimodal heterogeneous catalyst and a metal containing oil-miscible-catalysts compound to achieve a reduction in sediment, an increase in conversion, a reduction in the energy utilized to maintain reaction conditions and increases the stability of the ebullated catalyst bed. The oil-miscible compound may be provided in a concentration so as to provide about 1 to about 60 wppm metal based on the charge hydrocarbon oil.Type: GrantFiled: April 23, 1997Date of Patent: February 9, 1999Assignee: Texaco IncInventors: Michael K. Porter, Glenn A. Clausen, Jeffery B. Harrison, Ajit K. Bhattacharya
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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: 5746907Abstract: A method is provided to remove metals from a residual oil containing an initial amount of a selected metal, the method comprising the steps of:providing a vessel for exposing the residual oil to a DC electric field having a strength of about one kV/inch or greater,passing the residual oils through the vessel whereby at least ten percent by weight of the initial amount of the selected metal is removed by attraction to an electrode; andpassing the residual oil that has been passed through the vessel over a hydrodemetalization catalyst in the presence of hydrogen. Metal containing particles and other toluene insoluble organic and inorganic solids are effectively removed from residual oil streams by treatment with a DC electrical field prior to hydrodemetalization resulting in significant increases in useful lives for downstream hydrodemetalization catalyst.Type: GrantFiled: February 20, 1996Date of Patent: May 5, 1998Assignee: Shell Oil CompanyInventors: Antonius Franziskus Heinrich Wielers, Vitold Raimond Kruka
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Patent number: 5744025Abstract: The present invention provides a process for hydrotreating a metal-contaminated hydrocarbonaceous feedstock of which at least 60% wt. boils at a temperature 370.degree. C., the process comprising contacting the feedstock at elevated temperature and elevated pressure in the presence of hydrogen with one or more catalyst beds each of a first catalyst, a second catalyst and a third catalyst, wherein(i) the first catalyst comprises a Group VI and/or a Group VIII hydrogenation metal component on an inorganic oxide support having at least 40% of its pore volume in pores with diameters in the range from 17 nm to 25 nm and a surface area in the range from 100 m.sup.2 /g to 160 m.sup.2 /g;(ii) the second catalyst comprises a Group VI and/or a Group VIII hydrogenation metal component on an inorganic oxide support having at least 40% of its pore volume in pores with diameters in the range from 3 nm to 17 nm and a surface area in the range from 160 m.sup.2 /g to 350 m.sup.Type: GrantFiled: February 28, 1997Date of Patent: April 28, 1998Assignee: Shell Oil CompanyInventors: Andries Qirin Maria Boon, Constantinus Johannes Jacobus Den Ouden, Opinder Kishen Bhan
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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: 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: 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: 5601701Abstract: The invention concerns a process for the elimination of mercury from hydrocarbons by passage of the feedstock with hydrogen over a catalyst then bringing the product obtained into contact with a mercury retention bed, the catalyst comprising at least one element selected from the group constituted by iron, nickel, cobalt, molybdenum, tungsten, palladium, wherein at least 5% is in the sulphide state. Any arsenic present in the feedstock is also eliminated.In accordance with the invention, the catalyst is simultaneously presulphurated and reduced.The invention results in a considerable reduction in operation period and high retention efficiency at temperatures between 120.degree. C. and 250.degree. C. and in the presence of 0-1000 mg of sulphur/kg of feed.Type: GrantFiled: February 8, 1994Date of Patent: February 11, 1997Assignee: Institut Francais du PetroleInventors: Charles Cameron, Jean Cosyns, Patrick Sarrazin, Jean Paul Boitiaux, Philippe Courty
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Patent number: 5591326Abstract: A catalytic desalting process for processing whole crude oils. The desalting process uses an M41S catalyst to remove salts from the whole crude. Solids may also be removed from the whole crude using a porous material having a pore size greater than about 10 microns. The catalytic desalting process does not generate waste water.Type: GrantFiled: December 1, 1994Date of Patent: January 7, 1997Assignee: Mobil Oil CorporationInventor: Stuart S. Shih
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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: 5565092Abstract: A process has been developed for decolorizing (and/or hydrogenating, and/or dehalogenating) a halogen containing unsaturated feedstock and/or polymeric resins. The process has the advantage of being substantially less affected by prolonged exposure to halogen contaminants and impurities than typical hydrogenation catalysts. A novel catalyst comprising (a) one or more metals selected from the group consisting of the metals in Group 8, Group 9 Group 10 and mixtures thereof; (b) one or more promoters selected from the group consisting of oxides of the elements in Group 1, Group 2, the Lanthanides group, the Actinides group and mixtures thereof; and (c) a support has also been developed.Type: GrantFiled: March 16, 1994Date of Patent: October 15, 1996Assignee: Exxon Chemical Patents Inc.Inventors: Richard B. Pannell, Serge M. J. P. Maroie
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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: 5531886Abstract: A process for the elimination of arsenic from hydrocarbons with a retention mass wherein the retention mass is pretreated before being brought into contact with the feedstock to be purified. The retention mass contains at least one element selected from the group formed by iron, nickel, cobalt, molybdenum, tungsten, palladium and chromium. At least 5% by weight of these element(s) are in the sulfide form. The pretreatment involves impregnation with a sulfur compound carried out simultaneously with reduction. The arsenic elimination process is carried out between 120.degree. C. and 250.degree. C.Type: GrantFiled: February 8, 1994Date of Patent: July 2, 1996Assignee: Institut Francals du PetroleInventors: Charles Cameron, Jean Cosyns, Patrick Sarrazin, Jean Paul Boitiau, Philippe Courty
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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: 5468709Abstract: Catalysts for hydrodesulfurization and hydrodenitrogenation of hydrocarbon oils are provided which have high catalytic activity, excellent productivity and low pollution. The catalysts are made from an alumina carrier substance, at least one active metal element selected from the Group VI metals in the periodic table, at least one active metal element chosen from the Group VIII metals in the periodic table, phosphoric acid, and an additive agent. The additive agent is at least one substance selected from dihydric or trihydric alcohols having 2-10 carbon atoms per one molecule, ethers of the alcohols, monosaccharides, disaccharides, and polysaccharides. A method for preparing the catalysts is also provided and includes impregnating the alumina carrier substance with a solution mixed with a certain amount of the active metal elements, phosphoric acid and the additive agent, and drying the impregnated carrier substance at a temperature of less than 200.degree. C.Type: GrantFiled: November 18, 1993Date of Patent: November 21, 1995Assignee: Sumitomo Metal Mining Co., Ltd.Inventors: Eiji Yamaguchi, Yuji Uragami, Hideharu Yokozuka, Kikoo Uekusa, Toshio Yamaguchi, Satoshi Abe, Tetsuro Kamo, Takao Suzuki
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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
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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: 5449450Abstract: Hydrocarbon conversion processes are described which use novel microporous compositions. These compositions have a three-dimensional microporous framework structure of ZnO.sub.2, PO.sub.2 and M'O.sub.2 tetrahedral units, and an intracrystalline pore system. The M' metal is selected from the group consisting of magnesium, copper, gallium, aluminum, germanium, cobalt, chromium, iron, manganese, titanium and mixtures thereof. Examples of the hydrocarbon conversion processes include hydrocracking, hydrotreating and hydrogenation.Type: GrantFiled: December 15, 1993Date of Patent: September 12, 1995Assignee: UOPInventor: Robert L. Bedard
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Patent number: 5435908Abstract: 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 VI-B metal oxide on alumina having a Total Surface Area of 150-240 m.sup.2 /g, a Total Pore Volume, (TPV) of 0.7-0.98, and a Pore Diameter Distribution whereby .ltoreq.20% of the TPV is present as primary micropores of diameter .ltoreq.100 .ANG., at least about 34% of TPV is present as secondary micropores of diameter of about 100 .ANG.-200 .ANG., and about 26%-46% of the TPV is present as mesopores of diameter >200 .ANG..Type: GrantFiled: May 16, 1994Date of Patent: July 25, 1995Assignee: Texaco Inc.Inventors: Gerald V. Nelson, Govanon Nongbri, Roy E. Pratt, David E. Sherwood, Jr., Pei-Shing E. Dai
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Patent number: 5423975Abstract: Naphtha is selectively hydrodesulfurized using spent resid upgrading catalyst to remove sulfur while minimizing loss in octane level due to olefin saturation.Type: GrantFiled: July 8, 1992Date of Patent: June 13, 1995Assignee: Texaco Inc.Inventors: Chakka Sudhakar, Gerald G. Sandford, Ajit K. Bhattacharya
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Patent number: 5417846Abstract: The invention concerns a hydro treatment method in at least two stages, for a heavy hydrocarbon fraction containing asphaltenes, sulphur impurities and metallic impurities, wherein:a) in at least one first stage described as hydrodemetallization, the hydrocarbon charge and hydrogen are passed over a hydrodemetallization catalyst,b) in at least one subsequent stage described as hydrodesulphurization, the product of stage a) and hydrogen are passed over a hydrodesulphurization catalyst.The invention, in which the hydrodemetallization stage comprises one or more zones each containing hydrodemetallization catalyst operating in a fixed bed, is characterised in that this zone or these zones are preceded by two protective zones arranged in parallel, each containing a fixed bed of a hydrodemetallization catalyst, the two protective zones operating alternately.Type: GrantFiled: April 14, 1993Date of Patent: May 23, 1995Assignee: Institut Francais du PetroleInventor: Pierre Renard
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Patent number: 5403471Abstract: A process is disclosed for refining distillation residual fractions of a crude petroleum oil. The process employs a high gradient magnetic separator for magnetically depositing iron impurities from such distillation residual oil onto a ferromagnetic filler in the separator. The ferromagnetic filler is cleaned at predetermined intervals by a selected class of washing liquids so that the refining operation can be carried out continually.Type: GrantFiled: December 28, 1992Date of Patent: April 4, 1995Assignee: Nippon Oil Co., Ltd.Inventors: Masaru Ushio, Kozo Kamiya, Toru Morita
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Patent number: 5401392Abstract: For removing mercury and any arsenic in hydrocarbon charges containing mercury and sulfur, the charge is contacted with an arsenic collecting material having catalytic properties ("catalyst") in hydrogen, the material containing at least one metal selected from the group consisting of nickel, cobalt, iron, palladium, and platinum; at least one metal selected from the group consisting of chromium, molybdenum, tungsten, and uranium; and an active phase carrier. Downstream of the catalyst or mixed therewith is a mercury collecting material containing a sulfide of at least one metal selected from the group consisting of copper, iron, and silver or sulfur, and an active phase carrier.Type: GrantFiled: November 8, 1993Date of Patent: March 28, 1995Assignee: Institut Francais du PetroleInventors: Philippe Courty, Pierre Dufresne, Jean P. Boitiaux, Germain Martino