With Subsequent Treatment Of Product Patents (Class 208/229)
  • Patent number: 9441170
    Abstract: A reactor has two chambers, namely an oil feedstock chamber and a source chamber. An ion separator separates the oil feedstock chamber from the source chamber, wherein the ion separator allows alkali metal ions to pass from the source chamber, through the ion separator, and into the oil feedstock chamber. A cathode is at least partially housed within the oil feedstock chamber and an anode is at least partially housed within the source chamber. A quantity of an oil feedstock is within the oil feedstock chamber, the oil feedstock comprising at least one carbon atom and a heteroatom and/or one or more heavy metals, the oil feedstock further comprising naphthenic acid. When the alkali metal ion enters the oil feedstock chamber, the alkali metal reacts with the heteroatom, the heavy metals and/or the naphthenic acid, wherein the reaction with the alkali metal forms inorganic products.
    Type: Grant
    Filed: November 16, 2012
    Date of Patent: September 13, 2016
    Assignee: FIELD UPGRADING LIMITED
    Inventors: John Howard Gordon, Javier Alvare
  • Patent number: 8894845
    Abstract: Hydrocarbon feedstreams are desulfurized using an alkali metal reagent, optionally in the presence of hydrogen. Improved control over reaction conditions can be achieved in part by controlling the particle size of the alkali metal salt and by using multiple desulfurization reactors. The processes herein allow a simple and effective method for removing the majority of coke formed in the alkali metal reagent reactions with the hydrocarbon feedstreams. This makes it cost effective to run such processes at higher severities (which result in higher coke production) thereby resulting in increased amounts of valuable converted hydrocarbon product yields. The process improvements herein may also be used to increase total throughput through a unit due to the ability to effectively manage higher coke content in the reaction products.
    Type: Grant
    Filed: December 4, 2012
    Date of Patent: November 25, 2014
    Assignee: ExxonMobil Research and Engineering Company
    Inventors: Walter David Vann, Daniel Paul Leta, Jonathan Martin McConnachie, Richard Alan Demmin, Douglas Wayne Hissong, William C. Baird, Jr., Roby Bearden, Jr., James Ronald Bielenberg, Howard Freund, Chris Aaron Wright, Michael Francis Raterman, James Ronald Rigby, Brandon Thomas Stone
  • Patent number: 8658028
    Abstract: A process for removing elemental sulfur from liquid hydrocarbon steams such as transportation fuel streams, e.g. gasoline, diesel, kerosene, and jet, by contacting such streams with an immiscible aqueous solution under static mixing conditions. The aqueous solution contains a caustic and an effective amount of a Group I or Group II metal sulfide or polysulfide. The elemental sulfur in the stream is converted to a polysulfide that is not soluble in the hydrocarbon stream but is soluble in the aqueous solution, thus resulting in a hydrocarbon product stream having a substantially lower level of elemental sulfur.
    Type: Grant
    Filed: January 17, 2008
    Date of Patent: February 25, 2014
    Assignee: ExxonMobil Research and Engineering Company
    Inventors: Ashok Uppal, Ramesh R. Hemrajani, Robert J. Falkiner, Lawrence J. Lawlor, Joseph L. Feimer
  • Patent number: 8613852
    Abstract: Self-compatible heavy oil streams are produced from converted and/or desulfurized fractions. In a preferred embodiment, an incompatibility stream is added to the converted and/or desulfurized stream to reduce the solubility number of the stream. After using a water wash to remove incompatible material, a lighter fraction is removed from the stream to increase the solubility number.
    Type: Grant
    Filed: December 14, 2010
    Date of Patent: December 24, 2013
    Assignee: ExxonMobil Research and Engineering Company
    Inventors: Daniel P. Leta, Walter D. Vann, David T. Ferrughelli, Eric B. Sirota, Howard Freund
  • Publication number: 20130161234
    Abstract: Hydrocarbon feedstreams are desulfurized using an alkali metal reagent, optionally in the presence of hydrogen. Improved control over reaction conditions can be achieved in part by controlling the particle size of the alkali metal salt and by using multiple desulfurization reactors. The processes herein allow a simple and effective method for removing the majority of coke formed in the alkali metal reagent reactions with the hydrocarbon feedstreams. This makes it cost effective to run such processes at higher severities (which result in higher coke production) thereby resulting in increased amounts of valuable converted hydrocarbon product yields. The process improvements herein may also be used to increase total throughput through a unit due to the ability to effectively manage higher coke content in the reaction products.
    Type: Application
    Filed: December 4, 2012
    Publication date: June 27, 2013
    Applicant: EXXONMOBIL RESEARCH & ENGINEERING COMPANY
    Inventor: ExxonMobil Research & Engineering Company
  • Patent number: 7862708
    Abstract: The present invention relates to a process for desulfurizing bitumen and other heavy oils such as low API gravity, high viscosity crudes, tar sands bitumen, or shale oils with alkali metal compounds under conditions to promote in-situ regeneration of the alkali metal compounds. The present invention employs the use of superheated water and hydrogen under conditions to improve the desulfurization and alkali metal hydroxide regeneration kinetics at sub-critical temperatures.
    Type: Grant
    Filed: October 14, 2008
    Date of Patent: January 4, 2011
    Assignee: ExxonMobil Research and Engineering Company
    Inventors: Michael Siskin, Rustom M. Billimoria, David W. Savage, Roby Bearden, Jr.
  • Publication number: 20090152168
    Abstract: The present invention relates to a process for desulfurizing bitumen and other heavy oils such as low API gravity, high viscosity crudes, tar sands bitumen, or shale oils with alkali metal compounds under conditions to promote in-situ regeneration of the alkali metal compounds. The present invention employs the use of superheated water and hydrogen under conditions to improve the desulfurization and alkali metal hydroxide regeneration kinetics at sub-critical temperatures.
    Type: Application
    Filed: October 14, 2008
    Publication date: June 18, 2009
    Inventors: Michael Siskin, Rustom M. Billimoria, David W. Savage, Roby Bearden, JR.
  • Publication number: 20090065399
    Abstract: An improved method for desulfurizing a fuel stream such as a diesel stream is disclosed which includes generation of a sulfone oil, the desulfurization of the sulfone oil and the recycling of the resulting biphenyl-rich stream and ultra-low sulfur diesel streams. The method includes combining a thiophene-rich diesel stream with an oxidant to oxidize the thiophenes to sulfones to provide a sulfone-rich diesel stream. Sulfone oil is extracted from the sulfone-rich diesel stream to provide sulfone oil and a first low-sulfur diesel stream The low-sulfur diesel stream is recycled.
    Type: Application
    Filed: September 7, 2007
    Publication date: March 12, 2009
    Inventors: Joseph A. Kocal, Jeffrey C. Bricker, Gavin P. Towler
  • Patent number: 7342145
    Abstract: The present invention relates to a novel process for refining the liquefied petroleum gas (LPG) in a commercial scale. The process comprises: sequentially performing fine desulfurization and mercaptan conversion of the LPG after alcohol amine treatment through desulfurizer and catalyst set in fixed bed reactor in the absence of alkali, wherein, during the fine desulfurization, the resultants of reaction between hydrogen sulfide in the LPG and Fe—Ca oxides or their hydrates adhered on the desulfurizer, and during the mercaptan conversion, the mercaptan in the LPG reacts with the residual trace amount of air in the LPG under the action of the catalyst to produce the disulfides; letting the formed disulfides along with the LPG flow out of the fixed bed reactor; rectifying the LPG after the mercaptan conversion to obtain the refined LPG products, with further rectification to obtain the valuable disulfide products.
    Type: Grant
    Filed: November 12, 2002
    Date of Patent: March 11, 2008
    Assignee: Beijing SJ Environmental Protection and New Material Co., Ltd.
    Inventors: Qing Wu, Zhenyi Liu
  • Patent number: 7128828
    Abstract: A process for producing food grade wax which contains exceedingly low levels of nitrogen, sulfur and aromatic compounds. A waxy feedstock is firstly hydrotreated in a first hydrogenation zone to reduce the level of contaminants such as sulfur, nitrogen and aromatic compounds, and the resulting effluent from the first hydrogenation zone is introduced into a hot, high pressure stripper and contacted with a hot, hydrogen-rich stripping gas to remove ammonia and hydrogen sulfide. The stripped, hot liquid hydrocarbons are removed from the bottom of the hot, high-pressure stripper to further reduce the concentration of aromatic compounds by being hydrogenated in a second hydrogenation zone containing a platinum or palladium catalyst.
    Type: Grant
    Filed: February 28, 2003
    Date of Patent: October 31, 2006
    Assignee: UOP LLC
    Inventor: Tom N. Kalnes
  • Patent number: 7081196
    Abstract: In crude oil fractions, fossil fuels, and organic liquids in general in which it is desirable to reduce the levels of sulfur-containing and nitrogen-containing components, the process reduces the level of these compounds via the application of sonic energy. The process can be performed both with and without the added presence of an oxidizing agent, and with or without elevated temperature and/or pressure. The invention is performed either as a continuous process or a batch process.
    Type: Grant
    Filed: May 8, 2003
    Date of Patent: July 25, 2006
    Inventor: Mark Cullen
  • Patent number: 7029573
    Abstract: The invention relates to a composition and method for treating liquid hydrocarbons in order to remove acidic impurities, such as mercaptans, particularly mercaptans having a molecular weight of about C4 (C4H10S=90 g/mole) and higher, such as recombinant mercaptans.
    Type: Grant
    Filed: June 4, 2002
    Date of Patent: April 18, 2006
    Assignees: ExxonMobil Research and Engineering Company, Merichem Company
    Inventors: Mark A. Greaney, Binh N. Le, Daniel P. Leta, John N. Begasse, Charles T. Huang, Verlin Keith Turner
  • Patent number: 7014751
    Abstract: The invention relates to a method for treating and upgrading a hydrocarbon containing acidic species such as mercaptans, comprising: (a) contacting the hydrocarbon, in the essential absence of oxygen, with a first phase of a treatment composition containing water, dissolved alkali metal hydroxide, cobalt phthalocyanine sulfonate, and dissolved alkylphenylates and having at least two phases, (i) the first phase containing water, alkali metal alkylphenylate, dissolved alkali metal hydroxide, and dissolved sulfonated cobalt phthalocyanine, and (ii) the second phase containing water and dissolved alkali metal hydroxide; and then (b) separating an upgraded hydrocarbon.
    Type: Grant
    Filed: June 4, 2002
    Date of Patent: March 21, 2006
    Assignees: Exxonmobil Research and Engineering Co., Merichem Company
    Inventors: Mark A. Greaney, Binh N. Le, Daniel P. Leta, John N. Begasse, Charles T. Huang, Verlin Keith Turner
  • Patent number: 6960291
    Abstract: The invention relates to a method for desulfurizing naphtha boiling-range hydrocarbons such as cracked naphtha. More particularly, the invention relates to hydrotreating the naphtha under selective hydrotreating conditions, and then removing mercaptans from the hydrotreater effluent using a caustic extractant.
    Type: Grant
    Filed: June 4, 2002
    Date of Patent: November 1, 2005
    Assignees: ExxonMobil Research and Engineering Company, Merichem Company
    Inventors: Mark A. Greaney, Binh N. Le, Daniel P. Leta, John N. Begasse, Charles T. Huang, Verlin Keith Turner
  • Patent number: 6638418
    Abstract: A dual recycle catalytic hydrocracking process for the production of ultra low sulfur diesel while simultaneously processing two feedstocks. One preferred feedstock boils in the temperature range of diesel and the second preferred feedstock boils in the temperature range above that of diesel.
    Type: Grant
    Filed: November 7, 2001
    Date of Patent: October 28, 2003
    Assignee: UOP LLC
    Inventors: Tom N. Kalnes, Vasant P. Thakkar, Richard K. Hoehn
  • Publication number: 20030052044
    Abstract: The invention relates to a method for desulfurizing naphtha boiling-range hydrocarbons such as cracked naphtha. More particularly, the invention relates to hydrotreating the naphtha under selective hydrotreating conditions, and then removing mercaptans from the hydrotreater effluent using a caustic extractant.
    Type: Application
    Filed: June 4, 2002
    Publication date: March 20, 2003
    Inventors: Mark A. Greaney, Binh N. Le, Daniel P. Leta, John N. Begasse, Charles T. Huang, Verlin Keith Turner
  • Publication number: 20030052046
    Abstract: The invention relates to a method for treating and upgrading a hydrocarbon containing acidic species such as mercaptans, comprising:
    Type: Application
    Filed: June 4, 2002
    Publication date: March 20, 2003
    Inventors: Mark A. Greaney, Binh N. Le, Daniel P. Leta, John N. Begasse, Charles T. Huang, Verlin Keith Turner
  • Publication number: 20030052045
    Abstract: The invention relates to a composition and method for treating liquid hydrocarbons in order to remove acidic impurities, such as mercaptans, particularly mercaptans having a molecular weight of about C4 (C4H10S=90 g/mole) and higher, such as recombinant mercaptans.
    Type: Application
    Filed: June 4, 2002
    Publication date: March 20, 2003
    Inventors: Mark A. Greaney, Binh N. Le, Daniel P. Leta, John N. Begasse, Charles T. Huang, Verlin Keith Turner
  • Patent number: 6306288
    Abstract: A process for removing H2S and mercaptans from a hydrocarbon stream is disclosed. A hydrocarbon stream such as a LPG stream is contacted with a weakly basic stream, e.g., a sodium bicarbonate stream in order to extract the H2S and mercaptans from the hydrocarbon stream into the basic stream. The basic stream is now treated in a reactor containing a sulfide oxidizing microorganism in order to convert the H2S to sulfur and the mercaptans to disulfides. Finally, the sulfur and disulfides are separated from the basic aqueous stream which can be recycled and used to treat a fresh hydrocarbon stream. The treated hydrocarbon stream is purified to the point that it passes the copper strip test, while the purified basic stream contains less than 0.08 g/l of elemental sulfur.
    Type: Grant
    Filed: October 22, 1999
    Date of Patent: October 23, 2001
    Assignee: UOP LLC
    Inventors: Rusty Pittman, Blaise J. Arena, Albert J. Janssen
  • Patent number: 5985137
    Abstract: A method for upgrading an oil stream containing naphthenic acid and sulfur contaminants is described. In this method, an oil stream with naphthenic acid and sulfur contaminants is upgraded by the following steps. First, the oil stream is mixed with an alkaline earth metal oxide in an amount effective to convert substantially all of the naphthenic acid contaminants to non-acidic compounds and alkaline earth metal carbonate and also to convert substantially all of the sulfur contaminants to alkaline earth metal sulfide. Then, the mixture is heated under a pressure sufficient to prevent vaporization of the mixture to a temperature sufficient and for a time sufficient to react the naphthenic acid contaminants with the alkaline earth oxide to form the corresponding non-acidic compounds and alkaline earth carbonates. In the meantime, substantially all of the sulfur contaminants react with the alkaline earth oxide to form the alkaline earth sulfide.
    Type: Grant
    Filed: February 26, 1998
    Date of Patent: November 16, 1999
    Assignee: Unipure Corporation
    Inventors: Ernest O. Ohsol, Thomas E. Gillespie, John W. Pinkerton
  • Patent number: 5865989
    Abstract: A process for sweetening high mercaptan content gasoline or other liquid hydrocarbons is disclosed which utilizes aqueous caustic solution. A recycle stream is used to increase the conversion potential by reducing the relative mercaptan concentration of the untreated gasoline. Part of the treated gasoline effluent is recycled to the untreated feed. The treated gasoline has a low mercaptan concentration while the untreated gasoline is high in mercaptans. As the two streams combine, the feed to the unit becomes less concentrated in mercaptan compounds. In effect, the mercaptan concentration of the untreated gasoline has been diluted by the treated gasoline. Nitrogen inhibits the solubility of oxygen into gasoline. Nitrogen present in the recycle stream would create a system high in nitrogen and low in oxygen. By increasing the level of nitrogen, oxygen is limited in its ability to complete the sweetening reaction.
    Type: Grant
    Filed: September 20, 1995
    Date of Patent: February 2, 1999
    Assignee: Star Enterprise
    Inventors: John Clifton Cooper, Marc Daniel McConnell, Adam Richard Pawloski
  • Patent number: 5695632
    Abstract: The invention relates to an integrated, continuous process for the removal of organically bound sulfur (e.g., mercaptans, sulfides and thiophenes) comprising the steps of contacting a heavy oil, sodium hydroxide, hydrogen and water at a temperature of from about 380.degree. C. to 450.degree. C. to partially desulfurize the heavy oil and to form sodium sulfide, contacting said sodium sulfide with a transition metal in water to form a transition metal sulfide, sodium hydroxide and hydrogen. The sodium hydroxide is recirculated and the transition metal sulfide is removed. The partially desulfurized, dewatered heavy oil is treated with sodium metal under desulfurizing conditions, typically at a temperature of from about 340.degree. C. to about 450.degree. C., under a hydrogen pressure of at least about 50 psi to essentially desulfurize the oil, and form sodium sulfide. Optionally, the sodium salt generated can be regenerated to sodium metal using regeneration technology.
    Type: Grant
    Filed: May 2, 1995
    Date of Patent: December 9, 1997
    Assignee: Exxon Research and Engineering Company
    Inventors: Glen B. Brons, Ronald Myers, Roby Bearden, Jr.
  • Patent number: 5635056
    Abstract: The present invention relates to a continuous in-situ process for the removal from heavy oils, of organically bound sulfur in the form of mercaptans, sulfides and thiophenes, heteroatoms selected from the group consisting of nitrogen and oxygen and metals selected from the group consisting of nickel, vanadium and iron, comprising the steps of (a) contacting a heavy oil with aqueous sodium hydroxide at a temperature of about 380.degree. to about 450.degree. C. for a time sufficient to form sodium sulfide; (b) contacting said sodium sulfide of step (a) with water and a transition metal for a time and at a temperature sufficient to form transition metal sulfide, sodium hydroxide, hydrogen and impurities; and (c) recirculating said sodium hydroxide from step (b) to step (a) and removing said transition metal sulfide and said impurities, wherein said impurities are iron, vanadium and nickel. Optionally, molecular hydrogen may be added in the first step.
    Type: Grant
    Filed: May 2, 1995
    Date of Patent: June 3, 1997
    Assignee: Exxon Research and Engineering Company
    Inventors: Glen Brons, Ronald D. Myers
  • Patent number: 5389240
    Abstract: Naphthenic acids may be efficiently and conveniently removed from liquid hydrocarbon feedstocks by passing such feedstocks through a bed of certain metal oxide solid solutions related to hydrotalcites. The removal of naphthenic acids is an important adjunct to sweetening sour feedstocks and is particularly applicable to kerosines whose acid numbers may range as high as about 0.8. The metal oxide solid solutions of our invention show high adsorption capacity and can readily remove at least 95% of the naphthenic acids present in a liquid hydrocarbon feedstock.
    Type: Grant
    Filed: August 2, 1993
    Date of Patent: February 14, 1995
    Assignee: UOP
    Inventors: Ralph D. Gillespie, Blaise J. Arena
  • Patent number: 5271835
    Abstract: A process is disclosed for improving catalyst performance and yields in the manufacture of motor gasoline components. More particularly the process is directed to the removal of H.sub.2 S, sulfur compounds, trace amounts of acetonitrile or acetone or propionitrile from a hydrocarbon feedstock, comprising a C.sub.3 -C.sub.5 product fraction from a fluid catalytic cracking unit which may be used subsequently in an etherification process for the production of ethers such as MTBE and TAME and/or an alkylation process for the production of alkylate. The hydrocarbon feedstock is passed to an amine treating zone, a mercaptan sulfur removal zone and an adsorption zone for the removal of sulfur compounds, water and trace amounts of acetonitrile or acetone or propionitrile. The regeneration of the adsorption zone includes the contacting of the sorbent with a heated regenerant vapor stream. The spent regenerant vapor stream is condensed to provide a hydrocarbon phase and an aqueous phase.
    Type: Grant
    Filed: May 15, 1992
    Date of Patent: December 21, 1993
  • Patent number: 5124027
    Abstract: The invention reduces cracking catalyst fines in decanted oil by mixing the decanted oil (DCO) containing cracking catalyst fines with a resid oil and then treating the DCO-resid mixture with a non-aromatic hydrocarbon solvent in an extraction unit or in a multi-stage deasphalting unit.
    Type: Grant
    Filed: November 20, 1990
    Date of Patent: June 23, 1992
    Assignee: Amoco Corporation
    Inventors: William I. Beaton, James L. Taylor, Jeffrey J. Kolstad, Brian S. Kennedy, Robert D. Hughes
  • Patent number: 5114562
    Abstract: Middle distillate petroleum streams are hydrotreated to produce a low sulfur and low aromatic product in a process employing two reaction zones in series. The effluent of the first reaction zone is purged of hydrogen sulfide by hydrogen stripping and then reheated by indirect heat exchange. The second reaction zone employs a sulfur-sensitive noble metal hydrogenation catalyst. Operating pressure and space velocity increase and temperature decreases from the first to second reaction zones.
    Type: Grant
    Filed: August 3, 1990
    Date of Patent: May 19, 1992
  • Patent number: 5087350
    Abstract: A process for removing S and Fe and to reclaim V, Ni and Co from coal or oil and their derivatives or from minerals. The process is based upon an oxidative extraction performed with hypochlorous acid (HClO) whose oxidizing power is generated and regulated "in situ". The process is particularly applicable to the recovery of V from residual flexi-coke and to the recovery of Ni from coal.
    Type: Grant
    Filed: December 19, 1990
    Date of Patent: February 11, 1992
    Assignee: Laboratorios Paris, C.A.
    Inventor: Lucinda C. Paris-Marcano
  • Patent number: 4786405
    Abstract: Sulfur-bearing liquid hydrocarbon feedstocks such as kerosene undergo desulfurization and deodorization by contacting such feedstocks with sodium hydride at normal atmospheric pressure and at elevated temperatures. The resulting liquid is further contacted with a mineral acid such as sulfuric acid and an alkaline neutralizing agent such as caustic soda. The liquid may also be contacted with an oxidizying agent such as sodium hyprochlorite prior to being contacted with the neutralizing agent and with a dehydrating agent such as soda ash after being contacted with the neutralizing agent.
    Type: Grant
    Filed: March 4, 1986
    Date of Patent: November 22, 1988
    Assignee: Al Sanea Chemical Products
    Inventors: Keloth K. Kutty, Velamkalam A. James
  • Patent number: 4477337
    Abstract: Petroleum crudes, particularly heavy oil crudes produced by thermal or other enhanced recovery procedures, are treated to break the water-in-oil emulsion and reduce the BS&W content by use of additives, advantageously ammonium bisulfite, which act upon inorganic sulfur contained in the crude.
    Type: Grant
    Filed: August 12, 1983
    Date of Patent: October 16, 1984
    Assignee: Husky Oil Operations Ltd.
    Inventors: Clifford P. Ronden, Donald C. Boylance
  • Patent number: 4392947
    Abstract: An integrated method for refining a hydrocarbon distillate fraction such as kerosene which has sulfur-containing compounds by washing the fraction with an alkaline solution and then sweetening the resulting distillate by treating it with a phthalocyanine catalyst in the presence of a second alkaline solution and oxygen while simultaneously disposing of the spent caustic from the washing by incinerating same in the presence of a sulfur-containing fuel and oxygen to yield harmless sulfates.
    Type: Grant
    Filed: September 30, 1981
    Date of Patent: July 12, 1983
    Assignee: Mobil Oil Corporation
    Inventors: Costandi A. Audeh, Saverio G. Greco
  • Patent number: 4314902
    Abstract: A process for eliminating and removing impurities including sulfur compounds and microorganisms as well as preventing further microbial contamination is accomplished by treating petroleum products or other hydrocarbon fluids with an aqueous solution of an oxidizing agent such as hydrogen peroxide or ozone together with a metallic ion catalyst, such as a mixture of ferric chloride and cupric chloride, where the metal ion is capable of forming activated oxygen complexes in the presence of such oxidizing agent, or by treatment with an aqueous solution of metallic ion catalyst and activated oxygen complexes formed from permanganate, peroxyborate or chromate ions.
    Type: Grant
    Filed: January 3, 1974
    Date of Patent: February 9, 1982
    Inventors: Raymond S. Bouk, deceased, by Barbara Bouk, heir
  • Patent number: 4092240
    Abstract: A refrigeration oil processing sequence is disclosed which produces a superior oil without the use of sulfuric acid treating and the resultant sludge problems. The process comprises contacting a naphthenic based oil with an oxygen-containing gas in the presence of a permanganate under mild oxidation conditions of temperature and pressure followed by adsorbent fractionation.
    Type: Grant
    Filed: June 29, 1977
    Date of Patent: May 30, 1978
    Assignee: Texaco Inc.
    Inventors: Theodore C. Mead, Avilino Sequeira, Jr., Norman R. Odell