Sulfur Removal (free Or Combined Sulfur) Patents (Class 208/208R)
  • Patent number: 6160193
    Abstract: A method for the removal of sulfur and nitrogen containing compounds from petroleum distillates. Sulfur- and nitrogen-containing compounds are oxidized using a selective oxidant to create compounds that can be preferentially extracted from a petroleum distillate due to their increased relative polarity. Oxidation is accomplished by contacting an oxidant with a distillate under optimum conditions for that distillate and continuing the reaction until oxidized sulfur- and nitrogen-containing compounds are confirmed. Extraction is accomplished by contacting oxidized distillate with a non-miscible solvent that is selective for the relatively polar oxidized sulfur- and nitrogen-containing compounds. The oxidized compounds and solvent are separated from the distillate by gravity separation or centrifugation. The distillate is water washed and polished using clay filtration. The extraction solvent is separated from the solvent/oxidized compound mixture by a simple distillation for recycling.
    Type: Grant
    Filed: November 23, 1998
    Date of Patent: December 12, 2000
    Inventor: Walter Gore
  • Patent number: 6149799
    Abstract: 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: Grant
    Filed: January 14, 1998
    Date of Patent: November 21, 2000
    Assignee: Institut Francais du Petrole
    Inventors: Pascal Raybaud, Herve Toulhoat, Slavik Kasztelan
  • Patent number: 6129835
    Abstract: A fuel processing system is operable to remove substantially all of the sulfur present in gasoline or diesel fuel used for operating an internal combustion engine. The fuel supply is passed through a nickel reactant desulfurizer bed wherein essentially all of the sulfur in organic sulfur compounds in the fuel combine with the nickel reactant in the desulfurizer bed, and are converted to nickel sulfide. The desulfurizing system can operate at ambient or elevated pressures. The fuel can be treated either in a liquid phase or in a vapor phase. The sulfur scrubbing operation can be performed either in a vehicle while the latter is being operated, or at the fueling station (gas station) prior to sale to the end user. The amount of sulfur in the fuel can be lowered to less than about 0.05 ppm. This extends the life of the catalytic converters in vehicles, reduces corrosion of parts of the internal combustion engine, and provides an environmentally compatible system.
    Type: Grant
    Filed: December 28, 1998
    Date of Patent: October 10, 2000
    Assignee: International Fuel Cells, LLC
    Inventors: Roger R. Lesieur, Leonard J. Bonville, Jr.
  • Patent number: 6107535
    Abstract: A process for selectively removing nitrogenated and/or sulfurated contaminants from streams prevalently containing hydrocarbons with from 3 to 8 crbon atoms characterized in that it comprises an adsorption step wherein said contaminants are adsorbed by an adsorbent essentially consisting of silica gel at a temperature of between 0 and 150.degree. C. and at a pressure of between 1 and 20 atm and a regeneration step to remove the adsorbed substances by thermal treatment in a stream of insert gas carried out at a temperature of between 100 and 200.degree. C.
    Type: Grant
    Filed: October 21, 1998
    Date of Patent: August 22, 2000
    Assignee: Snamprogette S.p.A.
    Inventors: Stefano Rossini, Valerio Piccoli
  • Patent number: 6099815
    Abstract: A method is provided for removing carbonyl sulfide out of a H.sub.2 O-containing fluid stream, such as petrochemical vent gas, air, carbon dioxide, nitrogen and hydrocarbons, by determining how much carbon monoxide is present in the fluid stream; adding carbon monoxide to the fluid stream to obtain a carbon monoxide to carbonyl sulfide volume ratio of at least 1:1 and to also convert the carbonyl sulfide into hydrogen sulfide and carbon dioxide, and passing the hydrogen sulfide containing fluid through a hydrogen sulfide removal system, so as to obtain a fluid substantially free from carbonyl sulfide and hydrogen sulfide.
    Type: Grant
    Filed: March 23, 1999
    Date of Patent: August 8, 2000
    Assignee: The Sulfatreat Company
    Inventors: Delbert C. Scranton, Brian R. Kay
  • Patent number: 6096194
    Abstract: An adsorbent for organic sulfur compound removal from mineral, vegetable or animal oils useful to protect a hydrogenation catalyst against poisoning, wherein the adsorbent is a zinc-exchanged form of low silica faujasite with a silica to alumina ratio from about 1.8 to about 2.1, wherein the adsorbent contains an inequivalent excess of zinc cations from about 8 to about 20% (equiv.) and a process for manufacture and use of the adsorbent.
    Type: Grant
    Filed: December 2, 1999
    Date of Patent: August 1, 2000
    Assignee: Zeochem
    Inventors: Albert M. Tsybulevskiy, Edward J. Rode, Eric J. Weston, Kerry C. Weston
  • Patent number: 6063346
    Abstract: A process for scavenging hydrogen sulfide and mercaptan contaminants from a fluid, including the steps of: providing a fluid containing hydrogen sulfide and mercaptan contaminants; mixing the fluid with a benign contaminant scavenger so as to provide a fluid mixture; and subjecting the fluid mixture to scavenging conditions so as to provide a fluid product containing benign contaminant transformants.
    Type: Grant
    Filed: June 5, 1998
    Date of Patent: May 16, 2000
    Assignee: Intevep, S. A.
    Inventor: German A. Luna
  • Patent number: 6059962
    Abstract: A product of reduced sulfur content is produced in a multiple stage process from a feedstock which is comprised of a mixture of hydrocarbons and includes sulfur-containing aromatic compounds as unwanted impurities. The first stage involves: (1) subjecting the feedstock to alkylation conditions which are effective to convert a portion of the impurities to higher boiling sulfur-containing products, and (2) separating the resulting products by fractional distillation into a lower boiling fraction and a higher boiling fraction. The lower boiling fraction is comprised of hydrocarbons and is of reduced sulfur content relative to the feedstock. The higher boiling fraction is comprised of hydrocarbons and contains unconverted sulfur-containing aromatic impurities and also the higher boiling sulfur-containing products.
    Type: Grant
    Filed: September 9, 1998
    Date of Patent: May 9, 2000
    Assignee: BP Amoco Corporation
    Inventors: Bruce D. Alexander, George A. Huff, Vivek R. Pradhan, William J. Reagan, Roger H. Cayton
  • Patent number: 6056871
    Abstract: A novel circulatable sorbent material suitable for use in a transport desulfurization system for removing sulfur from a fluid stream containing sulfur and the use thereof in such a transport desulfurization system. The transport desulfurization process utilizes a circulatable particulate material containing alumina, silica zinc oxide and a metal oxide which is contacted with a fluid stream and thereafter separated and reused with a portion being regenerated.
    Type: Grant
    Filed: January 12, 1999
    Date of Patent: May 2, 2000
    Assignee: Phillips Petroleum Company
    Inventors: Gyanesh P. Khare, Donald R. Engelbert, Bryan W. Cass
  • Patent number: 6048451
    Abstract: A product of reduced sulfur content is produced from a feedstock which is comprised of a mixture of hydrocarbons and contains organic sulfur compounds as unwanted impurities. The process comprises converting at least a portion of the sulfur-containing impurities to sulfur-containing products of higher boiling point by treatment with an alkylating agent in the presence of an acid catalyst and removing at least a portion of these higher boiling products by fractional distillation. Suitable alkylating agents include alcohols and olefins. In a preferred embodiment, catalytic cracking products which contain aromatic sulfur compounds as impurities are used as a feedstock for the process.
    Type: Grant
    Filed: January 14, 1997
    Date of Patent: April 11, 2000
    Assignee: BP Amoco Corporation
    Inventors: George A. Huff, Jr., Bruce D. Alexander, Douglas N. Rundell, William J. Reagan, Ozie S. Owen, Jin S. Yoo
  • Patent number: 6042798
    Abstract: A method for the desulfurization of hydrocarbons by desulfurizing unsaturated hydrocarbons or hydrocarbon materials containing unsaturated hydrocarbons, in the presence or absence of hydrogen, using a copper-zinc desulfurizing agent prepared by the co-precipitation method. By this method, the sulfur content of the hydrocarbons can be reduced while suppressing hydrogenation of the unsaturated hydrocarbons.
    Type: Grant
    Filed: January 21, 1997
    Date of Patent: March 28, 2000
    Assignee: Osaka Gas Company Limited
    Inventors: Masataka Masuda, Osamu Okada, Takeshi Tabata, Yasuhiro Hirai, Hiroki Fujita
  • Patent number: 6024865
    Abstract: A product of reduced sulfur content is produced from a feedstock which is comprised of a mixture of hydrocarbons and includes sulfur-containing aromatic compounds as unwanted impurities. The process involves separating the feedstock by fractional distillation into a lower boiling fraction which contains the more volatile sulfur-containing aromatic impurities and at least one higher boiling fraction which contains the less volatile sulfur-containing aromatic impurities. Each fraction is then separately subjected to reaction conditions which are effective to convert at least a portion of its content of sulfur-containing aromatic impurities to higher boiling sulfur-containing products by alkylation with an alkylating agent in the presence of an acidic catalyst. The higher boiling sulfur-containing products are removed by fractional distillation.
    Type: Grant
    Filed: September 9, 1998
    Date of Patent: February 15, 2000
    Assignee: BP Amoco Corporation
    Inventors: Bruce D. Alexander, George A. Huff, Vivek R. Pradhan, William J. Reagan, Roger H. Cayton
  • Patent number: 6013175
    Abstract: A method for scavenging mercaptans in a hydrocarbon fluid is disclosed. According to the method, an effective mercaptan-scavenging amount of an aqueous scavenging composition is added to the fluid. The composition comprises a quaternary ammonium hydroxide of the formula R.sup.1 R.sup.2 R.sup.3 R.sup.4 NOH. R.sup.1 and R.sup.2 are, independently, alkyl groups of from one to about eighteen carbon atoms, aryl groups of from six to about eighteen carbon atoms or alkylaryl groups of from seven to about eighteen carbon atoms. R.sup.3 is an alkyl group of from two to about eighteen carbon atoms, an aryl group of from two to about eighteen carbon atoms or an alkylaryl group of from four to about eighteen carbon atoms. R.sup.2 and R.sup.3 may be joined to form a heterocyclic ring including the N and optionally an oxygen atom. R.sup.4 is --(CH.sub.2 CH.sub.2 O).sub.n H, wherein n is an integer from one to about eighteen, or --CHR.sup.5 CHR.sup.6 Y, wherein R.sup.5 and R.sup.
    Type: Grant
    Filed: September 14, 1998
    Date of Patent: January 11, 2000
    Assignee: Baker Hughes, Inc.
    Inventors: Jerry J. Weers, David R. Gentry
  • Patent number: 5961820
    Abstract: Sulfur-containing carbonaceous materials are desulfurized by reaction with a mixture of an oxidizing agent and a carbonyl compound under alkaline conditions at a temperature ranging from ambient temperature to about 250.degree. F. and a pressure of about 1 atmosphere to 2 atmospheres. The products of the reaction are a desulfurized carbonaceous material in which the sulfur content is less than about 1%, and gaseous sulfur compounds. The carbonyl compound can be recovered and reused.
    Type: Grant
    Filed: May 27, 1998
    Date of Patent: October 5, 1999
    Assignee: DS2 Tech, Inc.
    Inventors: James K. Jeanblanc, William E. Wismann
  • Patent number: 5958224
    Abstract: The instant invention is directed to a process for removing hard sulfurs from hydrocarbon streams by selectively oxidizing hard sulfurs in a hydrotreated stream, under oxidizing conditions in the presence of an effective amount of an oxidizing agent, wherein the oxidizing agent is a peroxometal complex and wherein the hard sulfurs are oxidized into the corresponding sulfoxides and sulfones.
    Type: Grant
    Filed: August 14, 1998
    Date of Patent: September 28, 1999
    Assignee: Exxon Research and Engineering Co
    Inventors: Teh Chung Ho, Chang Samuel Hsu, Gerald Dennis Dupre, Ronald Liotta, Viktor Buchholz
  • Patent number: 5910242
    Abstract: A process for reducing the total acid number of an acidic crude by treating the crude with hydrogen treat gas in the presence of a hydrotreating catalyst wherein the treat gas also contains hydrogen sulfide.
    Type: Grant
    Filed: August 29, 1997
    Date of Patent: June 8, 1999
    Assignee: Exxon Research and Engineering Company
    Inventors: Thomas R. Halbert, Kenneth L. Riley, Kenneth L. Trachte, David L. Vannauker
  • Patent number: 5897768
    Abstract: Hydrocarbon feeds are upgraded by contact of the stream under hydrodesulfurization (HDS) conditions with a catalyst system comprising a sulfided, transition metal promoted tungsten/molybdenum HDS catalyst, e.g., Ni/Co--Mo/Al.sub.2 O.sub.3 and a solid acid catalyst which is effective for the isomerization/disproportionation/transalkylation of alkyl substituted, condensed ring heterocyclic sulfur compounds present in the feedstream, e.g. zeolite or a heteropolyacid compound. Isomerization, disproportionation and transalkylation reactions convert refractory sulfur compounds such as 4- or 4,6-alkyl dibenzothiophenes into corresponding isomers or disproportionated isomers which can be more readily desulfurized by conventional HDS catalysts to H.sub.2 S and other products.
    Type: Grant
    Filed: February 28, 1997
    Date of Patent: April 27, 1999
    Assignee: Exxon Research and Engineering Co.
    Inventors: Gary B. McVicker, Teh C. Ho, Stuart Soled, Michel Daage, Roman Krycak, Sabato Miseo, Viktor Buchholz, William E. Lewis
  • Patent number: 5871636
    Abstract: A process for reducing the acidity of acidic crude oils by contacting the crude oil with a hydrotreating catalyst in the absence of hydrogen.
    Type: Grant
    Filed: August 29, 1997
    Date of Patent: February 16, 1999
    Assignee: Exxon Research and Engineering Company
    Inventors: Kenneth L. Trachte, Jacob B. Angelo, Keith K. Aldous
  • Patent number: 5863419
    Abstract: A product of reduced sulfur content is produced from a feedstock which is comprised of a mixture of hydrocarbons and contains organic sulfur compounds as unwanted impurities. The process comprises converting at least a portion of the sulfur-containing impurities to sulfur-containing products of higher boiling point by treatment with an alkylating agent in the presence of an acid catalyst and removing at least a portion of these higher boiling products by fractional distillation. The process can be carried out in a distillation column reactor wherein the acid catalyzed reaction and fractional distillation are carried out simultaneously. Suitable alkylating agents include alcohols and olefins.
    Type: Grant
    Filed: August 18, 1997
    Date of Patent: January 26, 1999
    Assignee: Amoco Corporation
    Inventors: George A. Huff, Jr., Ozie S. Owen, Bruce D. Alexander, Douglas N. Rundell, William J. Reagan, Jin S. Yoo
  • Patent number: 5858212
    Abstract: A hydrocarbon stream containing sulfur and sulfur compounds is contacted with a water suspension of dolomitic lime and dibasic acid catalyst in a reaction vessel in order to transfer the sulfur and sulfur compounds from the petroleum vapor to the water phase. During sulfur removal, naphthenic acid present in the hot petroleum vapor is converted to a high quality naphtha fraction. In the water phase, the sulfur compounds react with the available alkalinity from the dolomitic lime and dibasic acid. The insoluble calcium or magnesium based reaction products can then be removed from the water phase through conventional solids concentrating and separating equipment.
    Type: Grant
    Filed: July 3, 1996
    Date of Patent: January 12, 1999
    Assignee: InterGlobal Desulfuruzations Systems, Inc.
    Inventor: John J. Darcy
  • Patent number: 5851383
    Abstract: A light hydrocarbon stream, such as a C.sub.3 -C.sub.5 stream recovered from an FCC unit, is catalytically treated for the selective hydrogenation of dienes and for the removal of mercaptans by thioetherification. The effluent of the reaction zone is fractionated to remove light ends and thioethers in a dual section fractionation zone, with the interconnection of the sections facilitating a reduction in capital and operating costs.
    Type: Grant
    Filed: December 15, 1997
    Date of Patent: December 22, 1998
    Assignee: UOP LLC
    Inventor: Stanley J. Frey
  • Patent number: 5843300
    Abstract: Removal of organic sulfur compounds, especially aromatic sulfur compounds from an FCC feedstock with minimal adsorption of aromatic hydrocarbons is achieved using a zeolite X exchanged with alkali or alkaline earth cations. KX is an especially effective adsorbent. Where the KX is loaded with a group VIII metal, particular palladium or platinum, the adsorbent is effectively regenerated by treatment with hydrogen at elevated temperatures.
    Type: Grant
    Filed: December 29, 1997
    Date of Patent: December 1, 1998
    Assignee: UOP LLC
    Inventors: Herman A. Zinnen, Laszlo T. Nemeth, Jennifer R. Holmgren, Blaise J. Arena
  • Patent number: 5840177
    Abstract: A method for scavenging mercaptans in a hydrocarbon fluid is disclosed. According to the method, an effective mercaptan-scavenging amount of an aqueous scavenging composition is added to the fluid. The composition comprises a quaternary ammonium hydroxide of the formula R.sup.1 R.sup.2 R.sup.3 R.sup.4 NOH. R.sup.1 and R.sup.2 are, independently, alkyl groups of from one to about eighteen carbon atoms, aryl groups of from six to about eighteen carbon atoms or alkylaryl groups of from seven to about eighteen carbon atoms. R.sup.3 is an alkyl group of from two to about eighteen carbon atoms, an aryl group of from two to about eighteen carbon atoms or an alkylaryl group of from four to about eighteen carbon atoms. R.sup.2 and R.sup.3 may be joined to form a heterocyclic ring including the N and optionally an oxygen atom. R.sup.4 is --(CH.sub.2 CH.sub.2 O).sub.n H, wherein n is an integer from one to about eighteen, or --CHR.sup.5 CHR.sup.6 Y, wherein R.sup.5 and R.sup.
    Type: Grant
    Filed: September 16, 1997
    Date of Patent: November 24, 1998
    Assignee: Baker Hughes Incorporated
    Inventors: Jerry J. Weers, David R. Gentry
  • Patent number: 5837130
    Abstract: A process for hydrotreating petroleum fractions early in the refining process by employing catalyst prepared as components of distillation structures or as contained beds of catalyst in atmospheric distillation columns and or side draw columns. For example, a crude petroleum is hydrotreated by taking side streams from an atmospheric distillation column and the vacuum gas oil from a vacuum distillation column which are individually fed to separate desulfurizations, preferably in distillation column reactors containing a hydrodesulfurization catalyst. The overheads from each of the distillation column reactors is returned to the atmospheric column and the bottoms from each distillation column reactor is withdrawn as hydrotreated product. The process may also be used for upgrading the effluent from a fluid catalytic cracking unit, preferably operated as a catalytic distillation reactor.
    Type: Grant
    Filed: October 22, 1996
    Date of Patent: November 17, 1998
    Assignee: Catalytic Distillation Technologies
    Inventor: Clifford S. Crossland
  • Patent number: 5837131
    Abstract: A method for desulfurizing a light sour oil by contacting the hydrocarbon fluid with a mesoporous catalyst at temperatures in the range of 20.degree.-500.degree. C. in the absence of molecular hydrogen to promote carbon--carbon and carbon-sulfur bond formation and increase the boiling point of sulfur containing hydrocarbons. The mesoporous catalyst is selected from the group consisting of alumina-silicate, alumina and silica, and is impregnated with an oxide of a metal that forms coordinate bonds with hydrocarbons in the hydrocarbon fluid. Suitable metals are aluminium, scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper and zinc. The hydrocarbon fluid may be contacted with the mesoporous catalyst in the presence of up to about 1 mole oxygen for each mole of sulfur in the sulfur containing hydrocarbons, or in the presence of an unsaturated hydrocarbon.
    Type: Grant
    Filed: April 5, 1996
    Date of Patent: November 17, 1998
    Assignee: University Technologies International Inc.
    Inventor: Peter David Clark
  • Patent number: 5827421
    Abstract: A process for hydrotreating a charge hydrocarbon feed containing components boiling above 1000.degree. F. and sulfur, metals, and carbon residue, to provide product containing decreased levels of components having a boiling point greater than 1000.degree. F., decreased levels of sulfur, particularly decreased sulfur contents in the unconverted 1000.degree. F.+ boiling point products, and reduced sediment, which comprises:contacting said hydrocarbon feed with hydrogen at isothermal hydroprocessing conditions in the presence of, as catalyst, a porous alumina support containing .ltoreq.0.5 wt % of silica, wherein no silicon containing components, particularly silicon oxide, are intentionally added to the alumina, alumina support, impregnating solution or impregnating solutions, and bearing 2.2-6 wt % of a Group VIII metal oxide, 7-24 wt % of a Group VIB metal oxide and 0.0-2.0 wt % of a phosphorus oxide,said catalyst having a Total Surface Area of 195-230 m.sup.2 /g, a Total Pore Volume of 0.
    Type: Grant
    Filed: August 24, 1995
    Date of Patent: October 27, 1998
    Assignee: Texaco Inc
    Inventor: David Edward Sherwood, Jr.
  • Patent number: 5817229
    Abstract: 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: Grant
    Filed: November 6, 1996
    Date of Patent: October 6, 1998
    Assignee: Texaco Inc
    Inventors: Chakka Sudhakar, Regis J. Pellet, Mahendra Somabhai Patel
  • Patent number: 5807475
    Abstract: A process for removing sulfur containing compounds from various hydrocarbon streams is disclosed and claimed. The process involves contacting the feedstream with an adsorbent such as nickel exchanged zeolite X or Y, or a smectite layered clay having a surface area of at least 150 m.sup.2 /g, thereby adsorbing the sulfur compounds onto the adsorbent.
    Type: Grant
    Filed: November 18, 1996
    Date of Patent: September 15, 1998
    Assignee: UOP LLC
    Inventors: Santi Kulprathipanja, Laszlo T. Nemeth, Jennifer S. Holmgren
  • Patent number: 5770047
    Abstract: A process for upgrading a nitrogen and sulfur rich heavy naphtha feedstock includes the steps of providing a naphtha feedstock having an initial nitrogen content, an initial sulfur content and an initial octane number; contacting the naphtha feedstock with an acid source so as to provide a reduced nitrogen feedstock having a reduced nitrogen content which is less than the initial nitrogen content; contacting the reduced nitrogen feedstock with a hydroconversion catalyst system under a hydrogen atmosphere, temperature and pressure so as to provide a final product having a final nitrogen content which is less than the initial nitrogen content, a final sulfur content which is less than the initial sulfur content, and having a final octane number which is substantially equal to or greater than the initial octane number of the feedstock, and wherein the final product has an increased isomerized component and substantially no increase in aromatic content with respect to the feedstock.
    Type: Grant
    Filed: June 11, 1996
    Date of Patent: June 23, 1998
    Assignee: Intevep, S.A.
    Inventors: Jose Armando Salazar, Luis M. Cabrera, Eusebio Palmisano, Wolfgang J. Garcia, Rodolfo Bruno Solari
  • Patent number: 5759386
    Abstract: A light hydrocarbon stream, such as a C.sub.3 -C.sub.5 stream recovered from an FCC unit, is catalytically treated for the selective hydrogenation of dienes and for the removal of mercaptans by thioetherification. The effluent of the reaction zone is fractionated to remove light ends and thioethers in a dual section fractionation zone, with the interconnection of the sections facilitating a reduction in capital and operating costs.
    Type: Grant
    Filed: January 9, 1997
    Date of Patent: June 2, 1998
    Assignee: UOP
    Inventor: Stanley J. Frey
  • Patent number: 5753102
    Abstract: The present invention provides a process and equipment for efficiently and economically recovering organic sulfur compounds in a fuel oil while maintaining the original chemical structures thereof. The fuel oil is admixed with a solvent low in solubility therein of hydrocarbons and high in solubility therein of organic sulfur compounds to effect migration of the organic sulfur compounds in the fuel oil into the solvent by making much of the nucleophilic properties of a lone pair of electrons on a bivalent sulfur atom of a sulfur-containing functional group, followed by fuel oil-solvent separation by settling out or with a centrifugal force.
    Type: Grant
    Filed: October 3, 1995
    Date of Patent: May 19, 1998
    Assignee: Izumi Funakoshi
    Inventors: Izumi Funakoshi, Tetsuo Aida
  • Patent number: 5689033
    Abstract: A process is directed to the removal of impurities such as sulfur compounds, oxygenates, and/or olefins from a light paraffin hydrocarbon feedstock such as a C.sub.4 -C.sub.6 fraction, which may be used subsequently in an isomerization process in an integrated complex for the production of ethers such as MTBE and TAME. The hydrocarbon feedstream is passed to a removal zone wherein the hydrocarbon feedstream is contacted with a selective solvent for the removal of the impurities comprising at least one of sulfur compounds, oxygenates and olefins to provide a rich solvent stream and a treated hydrocarbon stream. The rich solvent comprising the trace impurities is contacted with a stripping medium stream to regenerate the selective solvent in a stripping zone. The removal zone may be a liquid-liquid extraction zone or a gas absorption zone.
    Type: Grant
    Filed: May 2, 1996
    Date of Patent: November 18, 1997
    Assignee: UOP
    Inventors: Paulino Forte, Stanley J. Frey
  • Patent number: 5674379
    Abstract: The present invention relates to a process for removing carbonyl sulfide from a liquid hydrocarbon feedstock, said process comprising the steps of (a) passing said hydrocarbon feedstock over an absorbent material comprising nickel deposited on a support material wherein nickel is present as both nickel oxide and metallic nickel and wherein the absorbent material has been conditioned by passing an inert gas flow containing a minor amount of propylene; and (b) recovering a liquid hydrocarbon stream having substantially reduced carbonyl sulfide content.
    Type: Grant
    Filed: June 7, 1995
    Date of Patent: October 7, 1997
    Assignee: Fina Research, S.A.
    Inventors: Guy L. G. Debras, Georges E. M. J. De Clippeleir, Raymond M. Cahen
  • Patent number: 5674378
    Abstract: The present invention is directed to a process for the removal of elemental sulfur from fluids such as fuels, e.g. gasoline, kerosene, diesel or jet, by contacting said fluids with an immiscible treatment solution comprising water or immiscible alcohol, caustic, sulfide or hydrosulfide and optionally mercaptan, in a staged co-current mixer under conditions such that the immiscible treatment solution constitutes the continuous phase.
    Type: Grant
    Filed: June 11, 1996
    Date of Patent: October 7, 1997
    Assignee: Exxon Research & Engineering Company
    Inventors: Daniel William Kraemer, Ramesh Relumal Hemrajani
  • Patent number: 5674377
    Abstract: Gaseous or liquid hydrocarbon is treated with a scavenging compound comprising an oil soluble 1,3,5-trihexahydro-1,3,5-tert.-butyltriazine. The compound is an effective nonregenerated scavenger for oil field produced fluids, particularly sour hydrocarbon liquids.
    Type: Grant
    Filed: June 19, 1995
    Date of Patent: October 7, 1997
    Assignee: Nalco/Exxon Energy Chemicals, L.P.
    Inventors: Daniel S. Sullivan, III, Allan R. Thomas, Mark A. Edwards, Grahame N. Taylor, Paul Yon-Hin, Juan M. Garcia, III
  • Patent number: 5659109
    Abstract: A process for liquefying natural gas containing mercaptans. Mercaptans are concentrated into a distillate stream by distilling the feed gas stream without specific pretreatment for mercaptans removal. Thus, the mercaptans removal equipment is much smaller since mercaptans treatment can take place at a point in the process where the flowrate is much lower. A portion of the treated distillate stream can be reinjected to the upstream distilling stage to facilitate mercaptan absorption.
    Type: Grant
    Filed: June 4, 1996
    Date of Patent: August 19, 1997
    Assignee: The M. W. Kellogg Company
    Inventors: Felix J. Fernandez de la Vega, Charles A. Durr
  • Patent number: 5659106
    Abstract: Mercaptans and olefins are removed from paraffin-rich feed streams through the use of dual zone catalytic distillation in the substantial absence of hydrogen. The mercaptans are reacted with the olefins using a first catalyst such as a sulphonated resin to form less volatile thioethers removed as part of a net bottoms stream. The remaining olefins are oligomerized in a higher catalyst zone preferably employing a catalyst, such as a dealuminated Y zeolite, having a higher oligomerization activity at the imposed conditions.
    Type: Grant
    Filed: June 22, 1995
    Date of Patent: August 19, 1997
    Assignee: UOP
    Inventors: Stanley J. Frey, Masami Kojima
  • Patent number: 5656152
    Abstract: A continuous water washing process for removing salts from refinery process streams is disclosed. The salt and salt precursor content of a process stream is determined, and iterative calculations made to ensure an aqueous phase forms downstream of the water injection point with a salt and ion concentration within acceptable limits. Preferably chemical speciation calculations are used to check for corrosive, transient aqueous phases intermediate the point of water injection and the process outlet.
    Type: Grant
    Filed: December 5, 1994
    Date of Patent: August 12, 1997
    Assignee: Mobil Oil Coporation
    Inventors: Bruce D. McLaughlin, Yiing-Mei Wu
  • Patent number: 5656151
    Abstract: A process for determining if intermittent water injection is the best way to remove deposits such as salts from refinery process streams. A water vapor pressure, P1, at stream conditions and a water vapor pressure, Ps, at saturation conditions in the stream, are used to calculate a ratio P1/Ps. If the ratio is less than 0.1 intermittent water washing is preferred. An optimized intermittent injection procedure, frequency, duration, and constraints, is disclosed. Chemical speciation calculations ensure that all accumulated salts are removed, and that an aqueous phase forms downstream of the water injection point having a salt concentration within acceptable limits.
    Type: Grant
    Filed: December 5, 1994
    Date of Patent: August 12, 1997
    Assignee: Mobil Oil Corporation
    Inventors: Bruce D. McLaughlin, Yiing-Mei Wu
  • Patent number: 5626742
    Abstract: 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: Grant
    Filed: May 2, 1995
    Date of Patent: May 6, 1997
    Assignee: Exxon Reseach & Engineering Company
    Inventors: Glen Brons, Ronald D. Myers
  • Patent number: 5605619
    Abstract: A manganese derivative preferably with a zinc derivative and/or a promoter is used to reduce the content of the sulphur content in a hydrocarbon stream especially at low temperature.
    Type: Grant
    Filed: March 22, 1994
    Date of Patent: February 25, 1997
    Assignee: Dytech Corporation
    Inventor: Andrew Holt
  • Patent number: 5603824
    Abstract: The instant invention discloses a process of upgrading a waxy hydrocarbon feed mixture containing sulfur compounds which boils in the distillate range, in order to reduce sulfur content and 85% point while preserving the high octane of naphtha by-products and maximizing distillate yield. The process employs a single, downflow reactor having at least two catalyst beds and an inter-bed redistributor between the beds. The top bed contains a hydrocracking catalyst, preferably zeolite beta, and the bottom bed contains a dewaxing catalyst, preferably ZSM-5. A desulfurization catalyst may be added to either bed depending on sulfur distribution in the feed. The feed is separated into a lighter, lower boiling stream and a heavier, higher boiling stream. The effluent of the top bed cascades without interbed separation to the inter-bed redistributor, where it is recombined with the lighter stream. The recombined stream then enters the bottom bed for dewaxing.
    Type: Grant
    Filed: August 3, 1994
    Date of Patent: February 18, 1997
    Assignee: Mobil Oil Corporation
    Inventors: Chwan P. Kyan, Paul J. Oswald
  • Patent number: 5601700
    Abstract: A method for the removal of hydrogen sulphide from a hydrocarbon-water mixture. The method utilizes a sulphite or a bisulphite, preferably ammonium bisulphite. It may be added as a salt or in solution. It is used in amounts by weight of from 2:1 salt: hydrogen sulphide.
    Type: Grant
    Filed: December 23, 1994
    Date of Patent: February 11, 1997
    Assignees: William Blythe Limited, Blacksmith Chemical Services
    Inventors: Norman Bridge, Robert McGowan
  • Patent number: 5599441
    Abstract: Sulfur species present in cracked naphthas are converted and removed by first passing the naphtha over an acid catalyst to alkylate the thiophenic compounds in the naphtha using the olefins, i.e., monoolefins and diolefins, present in the naphtha as alkylating agent. Alkylated thiophenes are concentrated in the heavy portion of the naphtha by distillation, reducing the amount of naphtha that needs to be hydrodesulfurized. Olefins in cracked naphthas are concentrated in the light portion of the naphtha which is not subsequently hydrotreated. Thus, octane and hydrogen consumption penalties associated with hydrotreating are minimized.
    Type: Grant
    Filed: May 31, 1995
    Date of Patent: February 4, 1997
    Assignee: Mobil Oil Corporation
    Inventors: Nick A. Collins, Jeffrey C. Trewella
  • Patent number: 5597476
    Abstract: A catalytic cracked naphtha is desulfurized with minimum loss of olefins and octane. The naphtha is fed to a first distillation column reactor which acts as a depentanizer or dehexanizer with the lighter material containing most of the olefins and mercaptans being boiled up into a first distillation reaction zone where the mercaptans are reacted with diolefins to form sulfides which are removed in the bottoms along with any higher boiling sulfur compounds. The bottoms are subjected to hydrodesulfurization in a second distillation column reactor where the sulfur compounds are converted to H.sub.2 S and removed. The lighter fraction containing most of the olefins is thus not subjected to the more harsh hydrogenation conditions of the second reactor.
    Type: Grant
    Filed: August 28, 1995
    Date of Patent: January 28, 1997
    Assignee: Chemical Research & Licensing Company
    Inventors: Dennis Hearn, Thomas P. Hickey
  • Patent number: 5552036
    Abstract: This invention relates to a process for reducing the sulfur in a refinery process stream and/or crude oil, which comprises treating said refinery process stream and/or crude oil with an effective sulfur reducing amount of a reducing agent selected from the group consisting of hydrazine, oximes, hydroxylamines, carbohydrazide, erythorbic acid, and mixtures thereof wherein the reducing agent or the hydrocarbon treated has a temperature of at least 50.degree. C.
    Type: Grant
    Filed: June 1, 1994
    Date of Patent: September 3, 1996
    Inventors: Todd L. Foret, William D. Mansfield, Hubert P. Vidrine
  • Patent number: 5543036
    Abstract: 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: Grant
    Filed: December 16, 1993
    Date of Patent: August 6, 1996
    Assignee: Mobil Oil Corporation
    Inventors: Clarence D. Chang, Scott Han, Daniel J. Martenak, Jose G. Santiesteban, Dennis E. Walsh
  • Patent number: 5516421
    Abstract: A process for reducing the amount of down time or yield loss associated with a sulfur upset when using a sulfur-sensitive catalyst. The process comprises applying a metallic coat, cladding, plating or paint to a reactor system which comprises a base metal, so as to form an adherent metallic layer on the base metal and thereby produce a metal-coated reactor system; loading a sulfur-sensitive catalyst into the system; and, after a sulfur upset, using a process comprising sulfur stripping to remove sulfur contaminants from the metal-coated reactor system.
    Type: Grant
    Filed: August 17, 1994
    Date of Patent: May 14, 1996
    Inventors: Warren E. Brown, Dennis L. Holtermann, John V. Heyse
  • Patent number: 5482617
    Abstract: A process for desulfurizing a hydrocarbon stream which includes at least 50 ppmw sulfur in the form of organic sulfur compounds, and C.sub.5 + hydrocarbons including benzene. The hydrocarbon stream is contacted in the absence of added hydrogen with a fluidized bed of an acidic catalyst having a structure of ZSM-5, ZSM-11, ZSM-22, ZSM-23, ZSM-35, ZSM-48, MCM-22, MCM-36, MCM-49, zeolite Y, zeolite beta or mixtures thereof to convert the organic sulfur compounds to hydrogen sulfide. The catalyst contacts the hydrocarbon stream at a pressure of from 0.0 psig to about 400 psig, a temperature of from about 400.degree. F. to about 900.degree. F., and a weight hourly space velocity of from about 0.1 hr..sup.-1 to about 10.0 hr..sup.-1. Thereafter, the hydrogen sulfide is removed from the hydrocarbon stream.
    Type: Grant
    Filed: August 8, 1994
    Date of Patent: January 9, 1996
    Assignee: Mobil Oil Corporation
    Inventors: Nick A. Collins, Mohsen N. Harandi
  • Patent number: 5474670
    Abstract: The present invention relates to a method of removing sulfur from a hydrotreating process stream comprising contacting a sulfur containing feedstock with a stacked bed catalyst system comprising a first catalyst bed comprising hydrodesulfurization catalysts followed by a second catalyst bed comprising ruthenium sulfide having a surface area of at least about 30 m.sup.2 /g and wherein said hydrodesulfurization process is conducted at a temperature of about 150.degree. C. to about 400.degree. C. and a pressure of about 50 psig (344.74 kPa) to about 2500 psig (17236.89 kPa).
    Type: Grant
    Filed: May 17, 1994
    Date of Patent: December 12, 1995
    Assignee: Exxon Research and Engineering Company
    Inventors: Michel Daage, Teh C. Ho, Kenneth L. Riley