With Alkali Metal Hydroxide Or Carbonate Patents (Class 208/203)
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Patent number: 9523047Abstract: Embodiments of apparatuses and methods for treating mercaptans are provided. In one example, an apparatus comprises a vessel capable of receiving a feed stream that comprises liquid hydrocarbons and the mercaptans. The vessel comprises an extraction section that is capable of extracting a portion of the mercaptans from the feed stream to form a mercaptan-reduced, liquid hydrocarbon-containing stream. A catalyst bed section is capable of contacting the mercaptan-reduced, liquid hydrocarbon-containing stream with a catalyst in the presence of oxygen (O2) and caustic at reaction conditions effective to oxidize a remaining portion of the mercaptans and form a sweetened liquid hydrocarbon-containing stream.Type: GrantFiled: June 12, 2014Date of Patent: December 20, 2016Assignee: UOP LLCInventors: Jonathan Andrew Tertel, Luigi Laricchia, Jasna Karagic
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Patent number: 9393538Abstract: The process and apparatus of the present invention selectively hydrogenates a heavier olefinic naphtha stream in an upstream catalyst bed and the hydrogenated effluent and a lighter olefinic naphtha stream in a downstream catalyst bed. The heavier di-alkenes are less re-active and are contacted with more hydrogenation catalyst than the lighter di-alkenes which are more re-active.Type: GrantFiled: October 10, 2014Date of Patent: July 19, 2016Assignee: UOP LLCInventors: Avnish Kumar, Steven F. Zink, Soumendra M. Banerjee
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Publication number: 20150114883Abstract: Disclosed is a method for treating hydrocarbon streams containing mercaptan compounds including contacting a first, relatively light hydrocarbon stream including mercaptan compounds with a first alkaline caustic solution to remove the mercaptan compounds from the first hydrocarbon stream and generate a second alkaline caustic solution including mercaptan compounds and oxidizing the mercaptan compounds in the second alkaline caustic solution to generate a third alkaline solution including a first concentration of disulfide compounds. The method further includes separating a portion of the disulfide compounds in the third alkaline solution to form a fourth alkaline solution including a second concentration of disulfide compounds.Type: ApplicationFiled: October 29, 2013Publication date: April 30, 2015Applicant: UOP LLCInventors: Jonathan Andrew Tertel, Luigi Laricchia
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Patent number: 8999149Abstract: A process for removing gases from a sweetened hydrocarbon stream. The process can include passing the sweetened hydrocarbon stream to a gas removal zone, contacting the sweetened hydrocarbon stream with an aqueous stream, passing the aqueous stream to the degassing drum, and removing gases including at least one of oxygen and nitrogen from the aqueous stream. Often, the gas removal zone includes a degassing drum.Type: GrantFiled: June 28, 2013Date of Patent: April 7, 2015Assignee: UOP LLCInventor: Jonathan Andrew Tertel
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Publication number: 20150034529Abstract: Processes and apparatuses for removing mercaptans from feed streams are provided. In one embodiment, a process for removing mercaptans from a feed stream includes extracting mercaptans and a polymeric precursor from the feed stream with a caustic solvent to form a polymeric precursor rich spent caustic solvent. The polymeric precursor rich spent caustic solvent is contacted with a polymeric precursor-deficient hydrocarbon stream in a multistage vessel and the polymeric precursor is extracted from the polymeric precursor rich spent caustic solvent to form a treated spent caustic solvent. The process contacts the treated spent caustic solvent with oxygen and oxidizes the mercaptans to disulfides to form an oxidized caustic solvent stream. The process includes separating the oxidized caustic solvent stream into an offgas stream, a disulfide stream, and a caustic solvent stream.Type: ApplicationFiled: July 31, 2013Publication date: February 5, 2015Applicant: UOP LLCInventors: Jessy E. Trucko, Luigi Laricchia, Jonathan A. Tertel
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Publication number: 20150001133Abstract: One exemplary embodiment can be a process for removing gases from a sweetened hydrocarbon stream. The process can include passing the sweetened hydrocarbon stream to a gas removal zone, contacting the sweetened hydrocarbon stream with an aqueous stream, passing the aqueous stream to the degassing drum, and removing gases including at least one of oxygen and nitrogen from the aqueous stream. Often, the gas removal zone includes a degassing drum.Type: ApplicationFiled: June 28, 2013Publication date: January 1, 2015Inventor: Jonathan Andrew Tertel
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Patent number: 8900446Abstract: In a catalytic treatment process, mercaptans in sour hydrocarbon are oxidized to disulfide oils using an aqueous treatment solution containing a chelated polyvalent metal catalyst, alkali metal hydroxide, and the alkali metal salt of at least one alcohol in a non-dispersive mixing apparatus wherein an upgraded hydrocarbon containing the disulfide oils is produced.Type: GrantFiled: January 31, 2011Date of Patent: December 2, 2014Assignee: Merichem CompanyInventors: Tiejun Zhang, K. Michael Hardy, V. Keith Turner, Ignacio C. Bincaz, Tom Varadi
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Patent number: 8894845Abstract: 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: GrantFiled: December 4, 2012Date of Patent: November 25, 2014Assignee: ExxonMobil Research and Engineering CompanyInventors: 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
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Publication number: 20130056391Abstract: A process for selective removal of mercaptan from aviation turbine fuel feed includes mixing aviation turbine fuel feed with hydrogen, at a pressure in a range from 3 bar to 20 bar to obtain a reaction mixture. The reaction mixture is heated at a temperature range of 150° C. to 350° C. to obtain a heated mixture. The heated mixture is reacted with a hydrotreating catalyst in a rector to obtain a reactor effluent, and H2S gas is stripped from the reactor effluent to obtain a stripper bottom product. Moisture is removed from the stripper bottom product to obtain aviation turbine fuel product having less than 10 ppm mercaptan. The aviation fuel product has improved properties such as color and acidity. Embodiments also relate to an aviation turbine fuel product having less than 10 ppm mercaptan prepared by the described process of the present invention.Type: ApplicationFiled: March 16, 2011Publication date: March 7, 2013Applicant: INDIAN OIL CORPORATION LIMITEDInventors: Rajesh Muralidhar Badhe, Alok Sharma, Brijesh Kumar, Santanam Rajagopal, Ravinder Kumar Malhotra, Anand Kumar
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Publication number: 20120111769Abstract: A method of removing sulfur from sour oil by subjecting sour oil having a first sulfur content to high shear in the presence of at least one desulfurizing agent to produce a high shear treated stream, wherein the at least one desulfurizing agent is selected from the group consisting of bases and inorganic salts, and separating both a sulfur-rich product and a sweetened oil product from the high shear-treated stream, wherein the sulfur-rich product comprises elemental sulfur and wherein the sweetened oil product has a second sulfur content that is less than the first sulfur content. A system for reducing the sulfur content of sour oil via at least one high shear device comprising at least one rotor and at least one complementarily-shaped stator, and at least one separation device configured to separate a sulfur-rich product and sweetened oil from the high shear-treated stream.Type: ApplicationFiled: August 2, 2011Publication date: May 10, 2012Applicant: H R D CorporationInventors: Abbas HASSAN, Aziz Hassan, Rayford G. Anthony, Gregory G. Borsinger
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Publication number: 20120103871Abstract: A method for reducing mercaptan concentration in a liquid hydrocarbon, comprising: contacting a mercaptan-rich liquid hydrocarbon having a first concentration of mercaptan sulfur with a composition comprising an oxidizing agent and water wherein the molar ratio of the oxidizing agent to mercaptan sulfur in the mercaptan-rich liquid hydrocarbon is from 3:1 to 10:1; and separating the water from the liquid hydrocarbon to yield a mercaptan-depleted liquid hydrocarbon having a second concentration of mercaptan sulfur, the second concentration being less than the first concentration; wherein a major amount of mercaptan compounds in the mercaptan-rich liquid hydrocarbon are converted to at least one sulfur oxoacid or salt thereof, having the formula: [RSOx]nY wherein R is a hydrocarbyl group; x is an integer from 1 to 3; n is 1 or 2; and Y is hydrogen, an alkaline metal, or alkaline earth metal.Type: ApplicationFiled: October 28, 2010Publication date: May 3, 2012Inventors: Zunqing He, Zhen Zhou, Lin Li
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Patent number: 7244352Abstract: A process for producing a naphtha having a decreased amount of sulfur by selective hydroprocessing a petroleum feedstream comprising cracked naphtha to reduce its sulfur content with minimum loss of octane. The reduced sulfur naphtha stream contains mercaptan sulfur reversion products that are removed preferably by use of an aqueous base solution containing a catalytically effective amount of a phase transfer catalyst.Type: GrantFiled: February 7, 2003Date of Patent: July 17, 2007Assignee: ExxonMobil Research and Engineering CompanyInventors: Thomas R. Halbert, Craig A. McKnight, John P. Greeley, Bruce R. Cook, Garland B. Brignac, Mark A. Greaney, Robert C. Welch
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Patent number: 7223332Abstract: The present invention is an apparatus and process for oxidizing mercaptans in a preferably kerosene stream. By using a catalyst promoter, sufficient separation of hydrocarbon and aqueous alkali occurs in the reactor vessel to obviate the need for a settling tank. Hence, the sweetened kerosene can be withdrawn from the reactor vessel and sent directly to a residual alkali removal unit such as a sand filter vessel or to a water wash vessel if jet grade fuel is desired. In an embodiment, the reactor vessel used for this purpose includes a reaction section and a separation section in the same reactor vessel and an aqueous alkali outlet and a sweetened hydrocarbon outlet in the separation section.Type: GrantFiled: October 21, 2003Date of Patent: May 29, 2007Assignee: UOP LLCInventor: Jonathan A. Tertel
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Patent number: 7207445Abstract: An apparatus for separating impurities from a liquid by a non-dispersive contacting of a liquid—liquid reactive systems, the liquids being immiscible with each other, having a cylindrical column separated into a first stage and a second stage, a plurality of modules of packed metallic fibers mounted in the first stage of the column on a support, a first distributor provided in the first stage of the column for distributing a first liquid located above the support such that the first liquid completely wets the fibers by capillary action and forms a film thereon, a second distributor fitted at a bottom portion of the second stage for distributing a second liquid containing impurities on to the metallic fibers, wherein the second liquid flows concurrently with said first liquid so that the impurities present in the second liquid react with the first liquid and dissolve therein and a separator connected to a bottom of said column separates the first liquid and purified second liquid.Type: GrantFiled: March 31, 2004Date of Patent: April 24, 2007Assignees: Engineers India Limited, Indian Oil Corporation, LimitedInventors: Ujjwal Manna, Ram Prakash Verma, Sarvesh Kumar, Sukumar Banik, Arpita Dasgupta, Shankar Khatua
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Patent number: 7029573Abstract: 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: GrantFiled: June 4, 2002Date of Patent: April 18, 2006Assignees: ExxonMobil Research and Engineering Company, Merichem CompanyInventors: Mark A. Greaney, Binh N. Le, Daniel P. Leta, John N. Begasse, Charles T. Huang, Verlin Keith Turner
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Patent number: 7014751Abstract: 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: GrantFiled: June 4, 2002Date of Patent: March 21, 2006Assignees: Exxonmobil Research and Engineering Co., Merichem CompanyInventors: Mark A. Greaney, Binh N. Le, Daniel P. Leta, John N. Begasse, Charles T. Huang, Verlin Keith Turner
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Patent number: 6960291Abstract: 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: GrantFiled: June 4, 2002Date of Patent: November 1, 2005Assignees: ExxonMobil Research and Engineering Company, Merichem CompanyInventors: Mark A. Greaney, Binh N. Le, Daniel P. Leta, John N. Begasse, Charles T. Huang, Verlin Keith Turner
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Patent number: 6860999Abstract: 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: GrantFiled: June 4, 2002Date of Patent: March 1, 2005Assignees: ExxonMobil Research and Engineering Company, Merichem CompanyInventors: Mark A. Greaney, Bihn N. Le, Daniel P. Leta, John N. Begasse, Charles T. Huang, Verlin Keith Turner
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Patent number: 6755964Abstract: A process for fixed bed sweetening of petroleum distillates using halogenating metal phthalocyanine as a catalyst comprising impregnating the catalyst on activated charcoal bed by circulating alcoholic alkaline solution of the catalyst through charcoal bed till colorless bed solution is obtained in the effluent, passing the petroleum distillate through the said catalyst loaded charcoal bed along with air or oxygen at a temperature and pressure with liquid hourly space velocity with continuous or intermittent injection of alkali solution such as sodium hydroxide of concentration to obtain the desired low mercaptan level petroleum distillates. The alkaline solution used is selected from methanolic and ethanolic solution of sodium hydroxide. The halogenated metal phthalocyanine catalyst used is selected from dichloro cobalt phthalocyanine and dibromo cobalt phthalocyanine. The petroleum fraction used is selected from diesel, kerosene and FCC gasoline.Type: GrantFiled: March 13, 2001Date of Patent: June 29, 2004Assignee: Council of Scientific & Industrial ResearchInventors: Brij Bahadur Agrawal, Som Nath Puri, Gautam Das, Bir Sain, Bhagwati Prasad Balodi, Sunil Kumar, Anil Kumar, Pushpa Gupta, Jai Prakash, Onkar Singh Tyagi, Turuga Sundara Rama Prasada Rao, Gur Pratap Rai
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Patent number: 6740619Abstract: The present invention relates to a process for the preparation of metal phthalocyanine sulphonamide [MPc(SO2NHR)x] catalyst useful for sweetening of LPG and light petroleum distillates which comprises reacting a metal phthalocyanine with chlorosulphonic acid at 90-150° C. for 1-5 hrs. cooling the reaction mixture adding 1-7 parts of a chloride reagent heating the said mixture at 60-80° C. from 0.5-3 hrs. to obtain the metal phthalocyanine sulphonyl chloride, isolating it by adding the reaction mixture in ice cold water, reacting the isolated metal phthalocyanine sulphonyl chloride with an amine of general formula H2NR where R is selected from hydrogen, aryl, alkyl and cycloalkyl in an aqueous or non-aqueous medium or a mixture thereof at a temperature in the range −4 to 15° C.Type: GrantFiled: March 13, 2001Date of Patent: May 25, 2004Assignee: Council of Scientific and Industrial ResearchInventors: Bir Sain, Som Nath Puri, Gautam Das, Bhagwati Prasad Balodi, Sunil Kumar, Anil Kumar, Virendra Kumar Kapoor, Virendra Kumar Bhatia, Turuga Sundara Rama Prasada Rao, Gur Pratap Rai
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Patent number: 6709639Abstract: An apparatus for the purification of catalytic cracking gasolines containing dienic and/or acetylenic impurities, and mercaptans, said apparatus comprising at least one selective hydrogenation reactor 3 containing at least one fixed catalyst bed, and having at least one line 1 for introducing a feed, at least one effluent outlet line, and a line supplying hydrogen to the reactor, said reactor being followed by at least one stabilization drum 4 connected to said effluent outlet line, the drum having at least one gas outlet line 5 and at least one stabilized effluent outlet line, and said effluent passing into at least one sweetening reactor 8 comprising at least one effluent inlet line 6 and at least one effluent outlet line, said reactor having close thereto at least one oxidizing agent supply line, said apparatus also comprising at least one drum 9 for degassing the effluent from the sweetening reactor 8, said drum 9 having at least one gas outlet line and at least one outlet line 11 for dedienized, stabilizType: GrantFiled: March 9, 2000Date of Patent: March 23, 2004Assignee: Institut Francais du PetroleInventors: Thierry Chapus, Blaise Didillon, Christian Marcilly, Charles Cameron
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Publication number: 20030188992Abstract: A process for decreasing the amount of sulfur in a petroleum stream.Type: ApplicationFiled: February 7, 2003Publication date: October 9, 2003Inventors: Thomas R. Halbert, Craig A. McKnight, John P. Greeley, Bruce R. Cook, Garland B. Brignac, Mark A. Greaney, Robert C. Welch
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Patent number: 6565740Abstract: The present invention related to a process for sweetening of LPG light petroleum distillates by liquid liquid extraction using metal phtalocyanine sulphonamide catalyst which comprises extracting the mercaptanes contain in LPG, light petroleum distillate like pentanes, light straight run naphtha by liquid-liquid extraction using an aqueous or alcoholic solution of alkali metal hydroxide of concentration ranging between 1 wt % to 50 wt % in the presence of a metal phthalocyanine sulphonamide catalyst in the concentration ranging from 5-4000 ppmw, at a temperature ranging from 10° C. to 80° C. at a pressure ranging from 1 kg/cm2-50 kg/cm2 in a continuous or batch manner, converting the mercaptanes present in above said extract into corresponding disulphides by passing air, oxygen or any oxygen containing gas at the above same temperature and pressure, regenerating the alkali solution containing catalyst for recycling by separating the upper layer of disulphides from said alkali solution of catalyst.Type: GrantFiled: March 26, 2001Date of Patent: May 20, 2003Assignee: Council of Scientific and Industrial ResearchInventors: Bir Sain, Som Nath Puri, Gautam Das, Bhagwati Prasad Balodi, Sunil Kumar, Anil Kumar, Virendra Kumar Kapoor, Virendra Kumar Bhatia, Turuga Sundara Rama Prasada Rao, Gur Pratap Rai
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Patent number: 6547959Abstract: A method for treating compounds which contain reactive sulfur is disclosed, wherein the treatment produces compounds which contain sulfur in a non reactive form. The method is based on the use of an oxidizing compound selected from the group consisting of water soluble inorganic persulfates, water soluble inorganic and organic adducts of hydrogen peroxide and mixtures thereof. The method is particularly useful in preventing stress corrosion cracking of stainless steel and in preventing auto-ignition of pyrophoric iron sulfide.Type: GrantFiled: September 19, 2000Date of Patent: April 15, 2003Assignee: United Laboratories International, LLCInventor: Jack G. Frost
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Publication number: 20030019793Abstract: This invention relates to reducing the amount of thiols (mercaptans) in petroleum streams, specifically, mercaptans above the five carbon molecular weight range.Type: ApplicationFiled: September 20, 2002Publication date: January 30, 2003Inventors: Mark Alan Greaney, Michael Charles Kerby, Roby Bearden
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Patent number: 6488840Abstract: This invention relates to reducing the amount of thiols (mercaptans) in petroleum streams, specifically, mercaptans above the five carbon molecular weight range.Type: GrantFiled: April 18, 2000Date of Patent: December 3, 2002Assignee: ExxonMobil Research and Engineering CompanyInventors: Mark Alan Greaney, Michael Charles Kerby, Roby Bearden, Jr.
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Publication number: 20020166799Abstract: The present invention relate to a process for sweetening of LPG, light petroleum distillates by liquid-liquid extraction using metal phthalocyanine sulphonamide catalyst which comprises extracting the mercaptanes contained in LPG, light petroleum distillate like pentanes, light straight run naphtha by liquid-liquid extraction using an aqueous or alcoholic solution of alkali metal hydroxide of concentration ranging between 1 wt % to 50 wt % in the presence of a metal phthalocyanine sulphonamide catalyst in the concentration ranging from 5-4000 ppmw, at a temperature ranging from 10° C. to 80° C., at a pressure ranging from 1 kg/cm2-50 kg/cm2 in a continuous or batch manner, converting the mercaptanes present in above said extract into corresponding disulphides by passing air, oxygen or any oxygen containing gas at the above same temperature and pressure, regenerating the alkali solution containing catalyst for recycling by separating the upper layer of disulphides from said alkali solution of catalyst.Type: ApplicationFiled: March 26, 2001Publication date: November 14, 2002Applicant: COUNCIL OF SCIENTIFIC & INDUSTRIAL RESEARCHInventors: Bir Sain, Som Nath Puri, Gautam Das, Bhagwati Prasad Balodi, Sunil Kumar, Anil Kumar, Virendra Kumar Kapoor, Virendra Kumar Bhatia, Turuga Sundara Rama Prasada Rao, Gur Pratap Rai
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Publication number: 20020139714Abstract: A method for reducing the level of elemental sulfur from sulfur-containing hydrocarbon streams as well as reducing the level of total sulfur in such streams. Preferred hydrocarbon streams include fuel streams such as naphtha streams that are transported through a pipeline. The sulfur-containing hydrocarbon stream is contacted with a mixture of water, a caustic, at least one metal sulfide, and an aromatic mercaptan. This results in an aqueous phase and a hydrocarbon phase containing reduced levels of both elemental sulfur and total sulfur.Type: ApplicationFiled: December 17, 2001Publication date: October 3, 2002Inventors: Joseph L. Feimer, Robert J. Falkiner
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Patent number: 6372124Abstract: The invention provides a method of purifying hydrocarbon streams from metallic impurities which comprises passing the stream through media comprising alumina with relatively minor amounts of calcia and magnesia.Type: GrantFiled: February 13, 2001Date of Patent: April 16, 2002Assignee: Saint-Gobain Norpro CorporationInventors: John S. Reid, Thomas Szymanski, Shaun A. Mesher
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Patent number: 6187173Abstract: A process and apparatus for treating raw gasoline from catalytic cracking to obtain gasoline with the qualities required for use as motor fuel comprises selective hydrogenation followed by stabilization and optional cooling of the effluent, then sweetening followed by degassing to obtain a dedienized, stabilized and sweetened gasoline. The hydrogenation catalyst preferably comprises 0.1-1% of palladium deposited on a support, sweetening is preferably carried out on a solid catalyst containing an aluminosilicate of an alkali metal (for example sodalite), a metal chelate and activated charcoal. The product from this process can be placed directly in the gasoline pool or, advantageously, fractionated to obtain one or more cuts which can be used as feeds for etherification.Type: GrantFiled: September 23, 1997Date of Patent: February 13, 2001Assignee: Institut Francais du PetroleInventors: Thierry Chapus, Blaise Didillon, Christian Marcilly, Charles Cameron
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Patent number: 6013175Abstract: 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: GrantFiled: September 14, 1998Date of Patent: January 11, 2000Assignee: Baker Hughes, Inc.Inventors: Jerry J. Weers, David R. Gentry
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Patent number: 5997731Abstract: An alkaline solution containing dissolved sodium sulfides, mercaptides and phenolates is treated with a carbon dioxide-containing solvent in a reaction zone under mass transfer conditions to neutralize effluent alkaline solution and recover processable hydrocarbon values.Type: GrantFiled: March 27, 1998Date of Patent: December 7, 1999Assignee: Merichem CompanyInventor: Felipe J. Suarez
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Patent number: 5961820Abstract: 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: GrantFiled: May 27, 1998Date of Patent: October 5, 1999Assignee: DS2 Tech, Inc.Inventors: James K. Jeanblanc, William E. Wismann
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Patent number: 5961819Abstract: An improved process is described for removing mercaptan sulfur from sour hydrocarbon distillate streams comprising of treating a sour hydrocarbon distillate stream in two oxidation zones within a reaction vessel. The first treatment occurs in the presence of a fiber bundle and the subsequent treatment over a bed of supported oxidation catalyst. The improvement comprises continuously keeping the bed in contact with an aqueous alkali metal hydroxide to maintain the catalyst in a caustic-wetted state, without interrupting the operation of the process.Type: GrantFiled: February 9, 1998Date of Patent: October 5, 1999Assignee: Merichem CompanyInventors: Binh N. Lee, Michael W. Walther
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Patent number: 5871637Abstract: The present invention relates to a continuous in-situ process for reducing the viscosity, corrosivity and density of heavy oils comprising the steps of (a) contacting a heavy oil with an aqueous alkaline earth, Group IIA metal hydroxide at a temperature of about 380.degree. to about 450.degree. C. for a time sufficient to form the corresponding alkaline earth metal sulfide, recovering the reduced sulfur feed and regenerating the alkaline metal hydroxide for recycle to treat additional feed. Beneficially, the process removes heteroatoms (sulfur and nitrogen).Type: GrantFiled: September 22, 1997Date of Patent: February 16, 1999Assignee: Exxon Research and Engineering CompanyInventor: Glen Brons
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Patent number: 5865989Abstract: 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: GrantFiled: September 20, 1995Date of Patent: February 2, 1999Assignee: Star EnterpriseInventors: John Clifton Cooper, Marc Daniel McConnell, Adam Richard Pawloski
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Patent number: 5840177Abstract: 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: GrantFiled: September 16, 1997Date of Patent: November 24, 1998Assignee: Baker Hughes IncorporatedInventors: Jerry J. Weers, David R. Gentry
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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: 5601702Abstract: Acidic halides, especially chlorides, are removed from gas by contact with particles of solid caustic covered by aqueous and hydrocarbon phases, respectively. Effective neutralization is achieved without swelling or plugging the bed of solid caustic. Halides are removed as brine. Efficient caustic utilization is achieved by controlling water vapor levels in the gas based on pH of brine product.Type: GrantFiled: December 30, 1994Date of Patent: February 11, 1997Assignee: Mobil Oil CorporationInventor: Tsoung Y. Yan
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Patent number: 5595648Abstract: Acidic halides, especially chlorides, are removed from dry liquid hydrocarbon streams such as catalytic reformate by contact with large particles of low surface area solid caustic such as a bed of NaOH pellets. Effective neutralization is achieved in a bed which is essentially free of any aqueous phase. Salt formed by the neutralization reaction deposit as solids on the surface of the solid caustic. A process for producing a low chloride, dry reformate product is also disclosed.Type: GrantFiled: December 30, 1994Date of Patent: January 21, 1997Assignee: Mobil Oil CorporationInventor: Tsoung Y. Yan
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Patent number: 5591323Abstract: A process for sweetening a petroleum cut containing mercaptans, wherein said petroleum cut is subjected to oxidation conditions by being contacted with a porous catalyst, in the presence of air said process being characterised in that said catalyst comprises 10 to 98% by weight of at least one mineral solid phase constituted of an alkaline aluminosilicate with a Si/Al atomic ratio less than or equal to 5, 1 to 60% by weight of active carbon, 0.02 to 2% by weight of at least one metal chelate and 0 to 20% by weight of at least one organic or mineral binding agent, has a basicity determined according to the 2896 ASTM standard with 20 milligrams of potash per gram and a total BET surface area of 10 m.sup.2 g.sup.-1, and contains inside its pore structure a permanent aqueous phase representing 0.1 to 40% by weight of dry catalyst.Type: GrantFiled: June 7, 1995Date of Patent: January 7, 1997Assignee: Institut Francais du PetroleInventors: Christian Marcilly, Serge Leporq, Philippe Courty
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Patent number: 5326456Abstract: A process for upgrading bitumen asphaltenes obtained from tar sands to hydrocarbons which comprises contacting the bitumen with a deasphalting solvent to yield a deasphalted oil and a residual solid asphaltene, separating the residual solid asphaltene from the deasphalted oil and treating the solid asphaltene fraction with superheated water containing a soluble carbonate salt at temperatures of from 300.degree. to 425.degree. C.Type: GrantFiled: April 2, 1993Date of Patent: July 5, 1994Assignee: Exxon Research and Engineering CompanyInventors: Glen B. Brons, Michael Siskin, Kazimierz O. Wrzeszczynski
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Patent number: 5273646Abstract: This invention relates to a process for improving the activity of a catalyst effective in sweetening a hydrocarbon fraction containing mercaptans. The process involves adding to the hydrocarbon fraction an effective amount of an aqueous solution comprising ammonium hydroxide, a metal chelate and an onium compound.Type: GrantFiled: October 19, 1992Date of Patent: December 28, 1993Assignee: UOPInventors: Robert R. Frame, Jeffery C. Bricker, Laurence O. Stine, Thomas A. Verachtert
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Patent number: 5271835Abstract: 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: GrantFiled: May 15, 1992Date of Patent: December 21, 1993
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Patent number: 5264187Abstract: Method and apparatus are described whereby a caustic-treated hydrocarbon feed mixture having a contaminating concentration of water and sulfur compounds is treated by separating the hydrocarbon feed into a first stream and a second stream. The first stream is contacted with an adsorbent material to produce a reactor feed stream having a significant reduction in the concentration of the contaminating water and sulfur compounds. The reactor feed stream is thereafter contacted in the presence of hydrogen under suitable isomerization conditions with an isomerization catalyst to produce an isomerate product.Type: GrantFiled: September 3, 1991Date of Patent: November 23, 1993Assignee: Phillips Petroleum CompanyInventors: Michael E. Olbrich, Rebecca L. Jones, Roger W. Fenstermaker
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Patent number: 5180484Abstract: This invention relates to a liquid-liquid process for treating a sour hydrocarbon fraction. The process comprises contacting the hydrocarbon fraction in the presence of an oxidizing agent with an aqueous solution containing ammonium hydroxide, a metal chelate and an onium compound selected from the group consisting of quaternary ammonium, phosphonium, arsonium, stibonium, oxonium and sulfonium compounds. A preferred onium compound is a quaternary ammonium compound with an especially preferred compound being a quaternary ammonium halide.Type: GrantFiled: November 29, 1991Date of Patent: January 19, 1993Assignee: UOPInventors: Robert R. Frame, Jeffery C. Bricker, Laurence O. Stine, Thomas A. Verachtert
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Patent number: 5169516Abstract: A process for removal of arsenic from a hydrocarbon stream containing arsenic together with mercaptan and non-mercaptan sulfur compounds. The hydrocarbon stream is passed through at least two mercaptan oxidizing reactors in series wherein the mercaptans are oxidized to disulfides to produce a low mercaptan liquid containing no more than 1.5 ppm sulfur as mercaptans. The low mercaptan liquid is passed over an arsenic sorbent catalyst containing less than 20 weight percent gamma alumina to selectively sorb arsenic substantially without sorbing non-mercaptan sulfur compounds.Type: GrantFiled: August 30, 1991Date of Patent: December 8, 1992Inventor: Norman L. Carr
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Patent number: 5039398Abstract: Although high naphthenic acid hydrocarbon feedstocks normally need to be washed with caustic prior to being sweetened in a fixed bed mercaptan-to-disulfide oxidation process to avoid bed plugging, the prewash can be eliminated if aqueous ammonia is used concurrent with and as a part of the sweetening process. Aqueous ammonia injected into a sour hydrocarbon stream prior to the sweetening zone not only eliminates bed plugging, but affords an aqueous phase from which naphthenic acids may be recovered easily and economically. The ammonia also can be recovered for reuse, affording a process with considerably enhanced economic return.Type: GrantFiled: March 19, 1990Date of Patent: August 13, 1991Assignee: UOPInventors: Laurence O. Stine, Jeffery C. Bricker, Gregory J. Thompson, Thomas A. Verachtert
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Patent number: 4956324Abstract: This invention relates to an improved catalyst for treating a sour hydrocarbon stream. The improvement comprises the use of a dipolar compound which has a positively charged atom and an electronegative group in the same structure. A particularly preferred dipolar compound is ephedrine. The dipolar compounds may be used in conjunction with a metal chelate and a basic solution either in a liquid-liquid process or a fixed bed process with substantially increased performance for oxidizing mercaptans which are found in the sour hydrocarbon stream.Type: GrantFiled: February 1, 1990Date of Patent: September 11, 1990Assignee: UOPInventors: Sheila Pollastrini, Jeffery C. Bricker, Robert R. Frame
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Patent number: 4929340Abstract: This invention relates to an improved process and catalyst for treating a sour hydrocarbon stream. The improvement comprises the use of a dipolar compound which has a positively charged atom and an electronegative group in the same structure. A particularly preferred dipolar compound is ephedrine. The dipolar compounds may be used in conjunction with a metal chelate and a basic solution either in a liquid-liquid process or a fixed bed process with substantially increased performance for oxidizing mercaptans which are found in the sour hydrocarbon stream.Type: GrantFiled: July 31, 1989Date of Patent: May 29, 1990Assignee: UOPInventors: Sheila Pollastrini, Jeffery C. Bricker, Robert R. Frame