Group Viii Metal Containing Catalyst Utilized Patents (Class 562/522)
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Patent number: 12054454Abstract: The present invention discloses a method for catalyzing olefin carbonylation, including the following steps: using cyclic alkylcarbene iridium as a catalyst and an olefin as a raw material to carry out carbonylation reaction to generate aldehydes, wherein a structural formula of the cyclic alkylcarbene iridium is as follows: wherein Dipp is 2,6-diisopropylbenzene; R1 and R2 are methyl or ethyl; X is Cl, Br, CH3CO2, NO3, BF4, PF6 or SbF6; wherein the olefin comprises one or more of ethylene, propylene, butylene and higher carbon olefins. According to the method for catalyzing olefin carbonylation of the present invention, by adopting an iridium catalyst, the catalytic activity is good, reaction energy consumption is reduced, and reaction temperature is fully lowered.Type: GrantFiled: November 16, 2021Date of Patent: August 6, 2024Assignee: NANJING INSTITUTE OF MICROINTERFACE TECHNOLOGY CO., LTDInventors: Xingbang Hu, Zhibing Zhang, Chenfei Yao, Lei Li, Zheng Zhou
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Patent number: 10584088Abstract: Processes for producing an ?,?-unsaturated carboxylic acid, such as acrylic acid, or a salt thereof, using treated solid oxides are disclosed. The treated solid oxides can be calcined solid oxides, metal-treated solid oxides, or metal-treated chemically-modified solid oxides, illustrative examples of which can include sodium-treated alumina, calcium-treated alumina, zinc-treated alumina, sodium-treated sulfated alumina, sodium-treated fluorided silica-coated alumina, and similar materials.Type: GrantFiled: October 29, 2018Date of Patent: March 10, 2020Assignee: Chevron Phillips Chemical Company LPInventors: Mark L. Hlavinka, Max P. McDaniel, Pasquale Iacono
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Patent number: 9416087Abstract: Processes for producing an ?,?-unsaturated carboxylic acid, such as acrylic acid, or a salt thereof, using solid promoters are disclosed. The solid promoters can be certain solid oxides, mixed oxides, and clays, illustrative examples of which can include alumina, zirconia, magnesia, magnesium aluminate, sepiolite, and similar materials.Type: GrantFiled: October 8, 2014Date of Patent: August 16, 2016Assignee: Chevron Phillips Chemical Company LPInventors: Mark L. Hlavinka, Max P. McDaniel
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Patent number: 9273020Abstract: Process for the production of a chemical compound from a carbon dioxide starting material, comprising the steps of a) providing a feed stream consisting mainly of carbon dioxide; b) electrolyzing in an electrolysis stage the carbon dioxide in the feed stream to a first gas stream containing carbon monoxide and a second gas stream containing oxygen, wherein the molar ratio between carbon monoxide and oxygen is about 1:0.5 in an electrolysis stage; c) adjusting the composition of the first gas stream or the second gas stream or both gas streams to include carbon dioxide, either by operating at less than full conversion of CO2 or by sweeping one or both gas streams with a gas containing CO2 or by at some stage between the electrolysis cell and the oxidative carbonylation reactor diluting one or both gas streams with a gas containing CO2; all while maintaining an overall molar ratio of carbon monoxide to oxygen of about 1:0.Type: GrantFiled: April 11, 2013Date of Patent: March 1, 2016Assignee: Haldor Topsoe A/SInventors: Niels Christian Schjødt, John Bøgild Hansen, Claus Friis Pedersen
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Publication number: 20140296570Abstract: The invention relates to a process for converting hydrocarbons into products containing aldehydes and/or alcohols. The invention also relates to producing olefins from the aldehyde and alcohol, to polymerizing the olefins, and to equipment useful for these processes.Type: ApplicationFiled: December 20, 2011Publication date: October 2, 2014Applicant: Exxonmobile Chemical Patents Inc.Inventors: Paul F. Keusenkothen, Frank Hershkowitz
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Patent number: 8642803Abstract: A process for preparing an alkali metal or alkaline earth metal salt of an ?,?-ethylenically unsaturated carboxylic acid, wherein a) an alkene, carbon dioxide and a carboxylation catalyst are converted to an alkene/carbon dioxide/carboxylation catalyst adduct, b) the adduct is decomposed to release the carboxylation catalyst with an auxiliary base to give the auxiliary base salt of the ?,?-ethylenically unsaturated carboxylic acid, c) the auxiliary base salt of the ?,?-ethylenically unsaturated carboxylic acid is reacted to release the auxiliary base with an alkali metal or alkaline earth metal base to give the alkali metal or alkaline earth metal salt of the ?,?-ethylenically unsaturated carboxylic acid. Salts of ?,?-ethylenically unsaturated carboxylic acids, such as sodium acrylate in particular, are required in large amounts, for example, for production of water-absorbing resins.Type: GrantFiled: March 3, 2011Date of Patent: February 4, 2014Assignee: BASF SEInventors: Michael Limbach, Jeremie Miller, Stephan Schunk
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Patent number: 8389760Abstract: Disclosed is a palladium-containing catalyst which enables to produce an ?,?-unsaturated carboxylic acid in high selectivity from an olefin or an ?,?-unsaturated aldehyde. Also disclosed are a method for producing such a catalyst and a method for producing an ?,?-unsaturated carboxylic acid using such a catalyst. Specifically disclosed is a palladium-containing catalyst containing 0.001 to 0.25 mole of antimony element to 1 mole of palladium element or a palladium-containing catalyst containing palladium element which composes a metal, tellurium element, and bismuth element.Type: GrantFiled: November 8, 2011Date of Patent: March 5, 2013Assignee: Mitsubishi Rayon Co., Ltd.Inventors: Toshiya Yasukawa, Toshiki Matsui, Ken Ooyachi, Yoshiyuki Himeno, Wataru Ninomiya
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Patent number: 8088947Abstract: The present invention relates to a method for producing methacrolein and/or methacrylic acid characterized in that the catalyst filling length of a dehydration catalyst layer is 3 to 20% of the catalyst filling length of an oxidation catalyst layer in a method where raw material gas containing gaseous t-butanol is supplied to a fixed-bed multitubular reactor having a dehydration catalyst layer and an oxidation catalyst layer in this order, from the entrance for raw material gas toward the exit, to produce methacrolein and/or methacrylic acid by dehydration reaction and catalytic gas phase oxidation reaction, and the present invention can increase the conventional yield of approximately 80% to 81 to 82% even when a reaction bath temperature is relatively low (approximately 355° C.).Type: GrantFiled: March 30, 2007Date of Patent: January 3, 2012Assignee: Nippon Kayaku Kabushiki KaishaInventors: Tatsuhiko Kurakami, Toshitake Kojima, Yoshimasa Seo
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Patent number: 8088945Abstract: Disclosed is a palladium-containing catalyst which enables to produce an ?,?-unsaturated carboxylic acid in high selectivity from an olefin or an ?,?-unsaturated aldehyde. Also disclosed are a method for producing such a catalyst and a method for producing an ?,?-unsaturated carboxylic acid using such a catalyst. Specifically disclosed is a palladium-containing catalyst containing 0.001 to 0.25 mole of antimony element to 1 mole of palladium element or a palladium-containing catalyst containing palladium element which composes a metal, tellurium element, and bismuth element.Type: GrantFiled: December 10, 2010Date of Patent: January 3, 2012Assignee: Mitsubishi Rayon Co., Ltd.Inventors: Toshiya Yasukawa, Toshiki Matsui, Ken Ooyachi, Yoshiyuki Himeno, Wataru Ninomiya
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Patent number: 8058472Abstract: The present invention concerns a new efficient method for the selective transformation, under mild conditions and in aqueous medium, of gaseous (ethane, propane and n-butane) and liquid (n-pentane, n-hexane, cyclopentane and cyclohexane) alkanes into carboxylic acids bearing one more carbon atom, characterized by a single-pot low-temperature (25-60° C.) reaction of the alkane with carbon monoxide in water/acetonitrile liquid medium, either in the absence or in the presence of a metal catalyst, in systems containing also an oxidant (a peroxodisulphate salt).Type: GrantFiled: January 17, 2008Date of Patent: November 15, 2011Assignee: Instituto Superior TecnicoInventors: Armando Pombeiro, Marina Kirillova, Alexander Kirillov, Jose Armando Silva, Joao Frausto Da Silva
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Publication number: 20110218359Abstract: A process for preparing an alkali metal or alkaline earth metal salt of an ?,?-ethylenically unsaturated carboxylic acid, wherein a) an alkene, carbon dioxide and a carboxylation catalyst are converted to an alkene/carbon dioxide/carboxylation catalyst adduct, b) the adduct is decomposed to release the carboxylation catalyst with an auxiliary base to give the auxiliary base salt of the ?,?-ethylenically unsaturated carboxylic acid, c) the auxiliary base salt of the ?,?-ethylenically unsaturated carboxylic acid is reacted to release the auxiliary base with an alkali metal or alkaline earth metal base to give the alkali metal or alkaline earth metal salt of the ?,?-ethylenically unsaturated carboxylic acid. Salts of ?,?-ethylenically unsaturated carboxylic acids, such as sodium acrylate in particular, are required in large amounts, for example, for production of water-absorbing resins.Type: ApplicationFiled: March 3, 2011Publication date: September 8, 2011Applicant: BASF SEInventors: Michael LIMBACH, Jeremie MILLER, Stephan SCHUNK
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Patent number: 7820849Abstract: A process is provided, in particular a continuous process for the carbonylation of butadiene by reacting the butadiene with carbon monoxide and a hydroxyl group-containing compound in the presence of a palladium catalyst system in a reaction zone to form a reaction mixture, said catalyst system comprising (a) a source of palladium cations, (b) a mono-, bi- or multidentate phosphine ligand, containing at least one phosphorus atom which is directly bound to two or three aliphatic carbon atoms, as process ligand to produce a palladium-phosphine ligand complex catalyst, and (c) a source of anions, said process ligand (b) containing the moiety shown in formula (I), wherein A1 and A2 each represent an aliphatic carbon atom which can be connected to one or more aliphatic or aromatic carbon atoms or both A1 and A2 are part of an at least 5-membered ring including the phosphorus atom, and X represents an aliphatic or aromatic carbon atom which can be connected to one or more aliphatic or aromatic carbon atoms or XType: GrantFiled: June 28, 2004Date of Patent: October 26, 2010Assignee: DSM IP Assets B.V.Inventors: Otto Erik Sielcken, Imre Toth, Henricus Anna Christiaan Baur
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Patent number: 7772419Abstract: A vinyl ester alkoxycarbonylation process comprising reacting a vinyl ester with carbon monoxide in the presence of an alkanol and a catalyst system. The catalyst system used is obtainable by combining: a) a metal of Group VIII B or a compound thereof, and b) a bidentate ligand of general formula (I) R is a covalent bridging group; R1 together with Q2 to which form an optionally substituted 2-Q2-tricyclo[3.3.1.1{3,7}]decyl group or derivative thereof (2-PA); R2 and R3 independently represent univalent radicals up to 20 atoms or jointly form a bivalent radical of up to 20 atoms; and Q1 and Q2 each independently represent phosphorous, arsenic or antimony. The process is carried out for the production of a 3-hydroxy propanoate ester or acid of formula (II) CH2(OH)CH2C(O)OR28??(II). or for the production of a lactate ester or acid of formula III.Type: GrantFiled: May 18, 2005Date of Patent: August 10, 2010Assignee: Lucite International UK Ltd.Inventor: Graham Eastham
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Patent number: 7629491Abstract: Disclosed is a hydrocarboxylation process for the production of carboxylic acid from olefins wherein an olefin, water, a Group VIII metal hydrocarboxylation catalyst, an onium salt compound are combined in a reaction zone and contacted with carbon monoxide under hydrocarboxylation conditions of pressure and temperature The process does not require or utilize the addition of a hydrogen halide or an alkyl halide exogenous or extraneous to the hydrocarboxylation process.Type: GrantFiled: June 26, 2006Date of Patent: December 8, 2009Assignee: Eastman Chemical CompanyInventors: Joseph Robert Zoeller, Mary Kathleen Moore
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Patent number: 7449597Abstract: A catalyst useful for carbonylation of olefins has been developed. The catalyst comprises a palladium compound, e.g. PdIm4Cl2, where Im is imidazole and HCl dissolved in water or an alcohol. Carbonylation using this catalyst involves contacting an olefin stream preferably in a solvent such as o-xylene with the catalyst and carbon monoxide at carbonylation conditions to provide a carboxylic acid or an ester. When the catalyst solvent is water one can obtain an acid as the product, but when the catalyst solvent is an alcohol one obtains an ester as the product.Type: GrantFiled: October 19, 2004Date of Patent: November 11, 2008Assignee: UOP LLCInventors: Irina Galperin, legal representative, Paul T. Barger, Robert H. Jensen, Albert L. Lapidus, Oleg L. Eliseev, Leonid B. Galperin
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Patent number: 7446223Abstract: The present invention provides: a palladium-containing catalyst which is used for highly selectively or highly productively producing an ?,?-unsaturated aldehyde and an ?,?-unsaturated carboxylic acid from an olefin or in that way producing an ?,?-unsaturated carboxylic acid from an ?,?-unsaturated aldehyde; a method for producing the catalyst; and a method for highly selectively or highly productively producing an ?,?-unsaturated aldehyde and an ?,?-unsaturated carboxylic acid from an olefin or in that way producing an ?,?-unsaturated carboxylic acid from an ?,?-unsaturated aldehyde. In particular, the present invention resides in a palladium-containing catalyst comprising 0.001 to 0.40 mole of tellurium metal to 1.0 mole of palladium metal. This catalyst can be preferably produced by a method having a step of reducing a compound containing palladium atom in its oxidized state and tellurium atom in its oxidized state by a reducing agent.Type: GrantFiled: June 2, 2005Date of Patent: November 4, 2008Assignee: Mitsubishi Rayon Co., Ltd.Inventors: Wataru Ninomiya, Yoshiyuki Himeno, Yuji Fujimori
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Publication number: 20080269520Abstract: A process for the carbonylation of a conjugated diene to a dicarboxylic acid, comprising the steps of (a) contacting a conjugated diene with carbon monoxide and water in the presence of a catalyst system including a source of palladium, a source of an anion and a bidentate phosphine ligand, to obtain a mixture comprising an ethylenically unsaturated acid and reversible diene adducts; (b) separating the obtained reaction mixture into a gaseous stream comprising unreacted conjugated diene and carbon monoxide, a first normally liquid stream comprising at least part of the ethylenically unsaturated acid and the reversible diene adducts, and a second normally liquid stream comprising the catalyst system in admixture with the ethylenically unsaturated acid; (c) recycling the second liquid stream obtained in step (b) to step (a); (d) separating the first liquid product stream obtained in step (b) into a stream comprising the ethylenically unsaturated acid and a stream comprising the reversible diene adducts; and (e)Type: ApplicationFiled: February 10, 2006Publication date: October 30, 2008Inventors: Eit Drent, Rene Ernst, Willem Wabe Jager, Cornelia Alida Krom, Timothy Michael Nisbet
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Publication number: 20070299280Abstract: Disclosed is a hydrocarboxylation process for the production of carboxylic acid from olefins wherein an olefin, water, a Group VIII metal hydrocarboxylation catalyst, an onium salt compound are combined in a reaction zone and contacted with carbon monoxide under hydrocarboxylation conditions of pressure and temperature The process does not require or utilize the addition of a hydrogen halide or an alkyl halide exogenous or extraneous to the hydrocarboxylation process.Type: ApplicationFiled: June 26, 2006Publication date: December 27, 2007Applicant: EASTMAN CHEMICAL COMPANYInventors: Joseph Robert Zoeller, Mary Kathleen Moore
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Patent number: 7265240Abstract: A process for the carbonylation of ethylenically unsaturated compounds is described. The process comprises reacting an ethylenically unsaturated compound with carbon monoxide in the presence of a source of hydroxyl groups and a catalyst system. The catalyst system is obtained by combining: (a) metal of Group VIII or a compound thereof; and (b) a bidentate phosphine of general formula (I) The carbonylation reaction is carried out at a temperature of between ?30° C. to 49° C. and under a CO partial pressure of less than 30×105 N.Type: GrantFiled: August 4, 2003Date of Patent: September 4, 2007Assignee: Lucite International UK LimitedInventors: Graham R. Eastham, Cristina Jimenez, David Cole-Hamilton
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Patent number: 7202382Abstract: A process for the production of acetic acid which comprises carbonylating methanol and/or a reactive derivative thereof in one or more reactors in a liquid reaction composition comprising iridium carbonylation catalyst, ruthenium promoter, methyl iodide co-catalyst, methyl acetate, acetic acid and water. The liquid reaction composition from the one or more reactors is passed to one or more flash separation stages to form (i) a vapor fraction comprising condensable components and a low pressure off-gas comprising carbon monoxide and (ii) a liquid fraction comprising iridium carbonylation catalyst, ruthenium promoter and acetic acid solvent. The condensable components are separated from the low pressure off-gas. The concentration of carbon monoxide in the low pressure off-gas is maintained according to the formula: Y>mX+C wherein Y is the molar concentration of carbon monoxide in the low pressure off-gas, X is the concentration in ppm by weight of ruthenium in the liquid reaction composition, m is about 0.Type: GrantFiled: April 9, 2003Date of Patent: April 10, 2007Assignee: BP Chemicals LimitedInventor: Michael James Muskett
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Patent number: 7009074Abstract: Acetic acid is produced by oxidation of methane with an oxygen-containing gas in the presence of an acid selected from concentrated sulfuric acid and fuming sulfuric acid, a palladium-containing catalyst and a promoter, preferably a copper or iron salt. The addition of a promoter and O2 to a system that includes a palladium-containing catalyst such as PdCl2 increases the rate of acetic acid formation from methane by more than an order of magnitude as compared with prior art and, in addition, inhibits the precipitation of Pd black.Type: GrantFiled: July 28, 2004Date of Patent: March 7, 2006Assignees: The Regents of the University of California, BP Chemicals LimitedInventors: Mark Zerella, Sudip Mukhopadhyay, Alexis T. Bell, John Glenn Sunley, Sander Gaemers, Philip Howard, Brian Ellis, Andrew Richard Lucy
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Patent number: 6984668Abstract: A liquid-phase chemical reaction medium comprises one or more reactants, optionally in the presence of a reaction product(s) and one or more solvents, diluents or other form of liquid carrier, a catalyst system comprising at least a metal or metal compound and optionally further compounds such as ligands or complexing agents; characterized in that the reaction medium further comprises a polymeric dispersant dissolved in said liquid carrier, said polymeric dispersant being capable of stabilizing a colloidal suspension of particles of said metal or metal compound within the liquid carrier. The presence of the polymeric dispersant enables metal formed by catalyst deactivation to be more easily recovered and recycled. Preferably, the polymeric dispersant has sufficiently acidic or basic functionality to stabilize the colloidal suspension of said metal or metal compound.Type: GrantFiled: August 2, 2000Date of Patent: January 10, 2006Assignee: Lucite International UK LimitedInventors: Graham Ronald Eastham, Raymond Anthony Hadden, David William Johnson
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Patent number: 6946574Abstract: The present invention relates to a process for the preparation of ?- or ?-unsaturated or saturated carboxylic acids. It relates more particularly to the hydroxycarbonylation of an organic compound comprising a conjugated unsaturation, such as butadiene, by the action of carbon monoxide and water in the presence of a palladium-based catalyst. The carboxylic acids thus obtained are preferably pentenoic acids. According to the invention, the reaction medium after the end of the hydroxycarbonylation stage is treated with hydrogen to reduce the palladium present in the 2+ oxidation state to palladium in the zero oxidation state and the precipitated palladium is recovered.Type: GrantFiled: December 21, 2001Date of Patent: September 20, 2005Assignee: Rhodia Polyamide IntermediatesInventors: Jean-Pierre Simonato, Pascal Metivier
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Patent number: 6916954Abstract: The invention relates to a catalyst system for carbonylating olefinically or acetylenically unsaturated compounds with carbon monoxide and a nucleophile compound, containing (a) palladium; (b) a phosphine and (c) a polymer containing nitrogen which is soluble in the reaction mixture, with the exception of polyvinyl polymers with aromatic radicals containing nitrogen on the polymer chain. The invention also relates to a method for carbonylation in the presence of one such catalyst system.Type: GrantFiled: September 25, 2001Date of Patent: July 12, 2005Assignee: BASF AktiengesellschaftInventors: Martin Schäfer, Michael Slany, Edgar Zeller, Michael Röper, Michael Schulz, Günther Grimm
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Patent number: 6906221Abstract: The invention relates to a method for producing acetic acid by oxidizing ethane in fluid bed reactors with high selectivity and high yields.Type: GrantFiled: October 17, 2001Date of Patent: June 14, 2005Assignee: Celanese International CorporationInventors: Sabine Zeyss, Uwe Dingerdissen, Manfred Baerns, Dorit Wolf, David Linke
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Patent number: 6835850Abstract: Process for the carbonylation of a conjugated diene by reacting the conjugated diene with carbon monoxide and an hydroxyl group containing compound in the presence of a catalyst system based on: (a) a source of palladium cations, (b) a diphosphine ligand, and (c) a source of anions, wherein the diphosphine ligand is a ligand having the general formula I wherein x1 and x2 represent a cyclic group with at least 5 ring atoms, of which one is a phosphorus atom, and R represents a bivalent aliphatic bridging group, connecting both phosphorus atoms, containing from 2 to 4 atoms in the bridge, which is substituted with at least one substituent or R represents a phenyl group with both phosphorus groups bound to the 1,2-position.Type: GrantFiled: August 25, 2003Date of Patent: December 28, 2004Assignee: DSW IP Assets B.V.Inventors: Eit Drent, Willem Wabe Jager, Otto Erik Sielcken, Imre Toth
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Patent number: 6812366Abstract: A catalyst useful for oxidation reactions is disclosed. The catalyst is useful for the gas phase oxidation of alkanes, propylene, acrolein, or isopropanol to unsaturated aldehydes or carboxylic acids.Type: GrantFiled: September 2, 2003Date of Patent: November 2, 2004Assignee: Rohm and Haas CompanyInventor: Manhua Lin
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Publication number: 20040068142Abstract: The present invention relates to a process for the preparation of &bgr;- or &ggr;-unsaturated or saturated carboxylic acids.Type: ApplicationFiled: November 6, 2003Publication date: April 8, 2004Inventors: Jean-Pierre Simonato, Pascal Metivier
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Patent number: 6706912Abstract: Process for the carbonylation of ethylenically unsaturated compounds having 3 or more carbon atoms by reaction with carbon monoxide and an hydroxyl group containing compound in the presence of a catalyst system. The catalyst system includes (a) a source of palladium cations; (b) a bidentate diphosphine of formula I, R1R2>P—R3—R—R4—P<R5R6 (I) wherein P represents a phosphorus atom; R1, R2, R5 and R6 independently represent the same or different optionally substituted organic groups containing a tertiary carbon atom through which the group is linked to the phosphorus atom; R3 and R4 independently represent optionally substituted alkylene groups and R represents an optionally substituted aromatic group; (c) a source of anions derived from an acid having a pKa less than 3, as measured at 18° C. in an aqueous solution. The process is carried out in the presence of an aprotic solvent.Type: GrantFiled: March 13, 2001Date of Patent: March 16, 2004Assignee: Shell Oil CompanyInventors: Eit Drent, Willem Wabe Jager
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Patent number: 6646159Abstract: Long chain alcohols and acids or other similar oxygenates such as esters are produced from paraffins of similar carbon number by a process comprising paraffin dehydrogenation, carbonylation, and separation. Preferably a mixture of paraffins extending over several carbon numbers and recovered from a kerosene fraction is processed, and unconverted paraffins are recycled to a dehydrogenation zone. Alternative reaction zone configurations, catalyst systems and product recovery methods are disclosed.Type: GrantFiled: December 21, 2000Date of Patent: November 11, 2003Assignee: UOP LLCInventors: Lance A. Baird, Leonid B. Galperin, R. Joe Lawson, Robert H. Jensen, Oleg L. Eliseev, Albert L. Lapidus, Aduard G. Ostapenco
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Patent number: 6613938Abstract: A vapor-phase carbonylation method for producing esters and carboxylic acids from reactants comprising lower alkyl alcohols, lower alkyl alcohol generating compositions and mixtures thereof. The method includes contacting the reactants and carbon monoxide in a carbonylation zone of a carbonylation reactor under vapor-phase conditions with a catalyst having a catalytically effective amount of platinum and tin associated with a solid carrier material.Type: GrantFiled: June 19, 2001Date of Patent: September 2, 2003Assignee: Eastman Chemical CompanyInventors: Joseph Robert Zoeller, Andy Hugh Singleton, Gerald Charles Tustin, Donald Lee Carver
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Patent number: 6596781Abstract: An integrated process for carrying out the production of Fischer-Tropsch products and acetic acid made using the methanol and carbonylation route which utilizes the hydrogen recovered from the methanol production to upgrade the Fischer-Tropsch products.Type: GrantFiled: May 2, 2002Date of Patent: July 22, 2003Assignee: Chevron U.S.A. Inc.Inventor: William L. Schinski
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Publication number: 20030092935Abstract: In a process for the hydroformylation of ethylenically unsaturated compounds, at least one ethylenically unsaturated compound is reacted with carbon monoxide and hydrogen in the presence of a ligand-metal complex of ruthenium, rhodium, palladium, iridium and/or platinum, where the ligand-metal complex comprises a monophosphine, monophosphinite or monophosphinamidite ligand of the formula I 1Type: ApplicationFiled: November 7, 2002Publication date: May 15, 2003Inventor: Wolfgang Ahlers
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Patent number: 6489506Abstract: A process for the liquid-phase carbonylation of ethylene, according to the equation C2H4+CO+ROH→C2H5CO2R, in the presence of a catalyst system comprising a Group VIII metal or compound thereof, a phosphine ligand and a source of anions, and in the presence of water or a source of organic hydroxyl groups, is carried out in conditions in which the molar ratio of ethylene to carbon monoxide in the gaseous phase of the reactor is greater than 1:1. The higher ratios of ethylene to carbon monoxide are beneficial in increasing the turnover number of the catalyst system.Type: GrantFiled: June 21, 2001Date of Patent: December 3, 2002Assignee: Lucite International UK LimitedInventors: Jean Margaret Pearson, Raymond Anthony Hadden
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Patent number: 6452043Abstract: A method for producing esters, carboxylic acids and mixtures thereof includes contacting, under carbonylation conditions, lower alkyl alcohols, ethers, lower alkyl alcohol derivatives and mixtures thereof and carbon monoxide with a catalyst having a catalytically effective amount a metal selected from iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium, platinum, tin and mixtures thereof associated with a carbonized polysulfonated divinylbenzene-styrene copolymer matrix. In a preferred aspect of the invention the method is called out under vapor-phase conditions.Type: GrantFiled: April 5, 2000Date of Patent: September 17, 2002Assignee: Eastman Chemical CompanyInventors: Joseph Robert Zoeller, Andy Hugh Singleton, Gerald Charles Tustin, Donald Lee Carver
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Patent number: 6388141Abstract: The present invention relates to processes for the preparation of oxo products by the hydroformylation of substrates having C═C double bonds using unmodified rhodium catalysts in a reaction mixture essentially consisting of the substrates, the catalyst and carbon dioxide in a supercritical state (scCO2). In particular, the invention relates to such processes for the preparation of products which contain substantial proportions of branched i-oxo products. Further, the invention relates to such processes for the hydroformylation of substrates which do not correspond to the general formula CnH2n. The invention further relates to such processes in which the separation of product and catalyst is effected using the special solvent properties of scCO2.Type: GrantFiled: January 13, 2000Date of Patent: May 14, 2002Assignee: Studiengesellschaft Kohle mbHInventors: Walter Leitner, Daniel Koch
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Patent number: 6326455Abstract: This invention relates to methods and reactor devices for controlling the oxidation of hydrocarbons to dibasic acids, in the presence of a cobalt catalyst and a monobasic acid, such as acetic acid, by treating the catalyst from the reaction mixture, outside the oxidation zone, after the oxidation has taken place at least partially. In one preferred embodiment, the catalyst is reduced to contain, preferably predominantly and more preferably substantially, cobalt ions in valence II, and at least partially precipitated by de-watering and/or thermal treatment. In a different preferred embodiment, the catalyst in the reaction mixture is first oxidized or maintained, preferably predominantly and more preferably substantially, at valence III, the reaction mixture is de-watered, the catalyst is reduced preferably predominantly and more preferably substantially, to valence II, causing precipitation either spontaneously at a predetermined temperature or after further thermal treatment.Type: GrantFiled: April 5, 2001Date of Patent: December 4, 2001Assignee: RPC Inc.Inventors: Eustathios Vassiliou, Mark W. Dassel, Ader M. Rostami, Douglas J. Dudgeon, David C. DeCoster
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Publication number: 20010043895Abstract: A method for generating a solution containing rhodium at a concentration of at least 0.01 M and preferably at least 0.20 M, comprising treating solid rhodium iodide or other solid source of rhodium with a reducing agent selected from a source of hydrazine, hydrazine hydrate, hydrazinium salts, organic derivatives of hydrazine, hypophosphorous acid and salts of hypophosphorous acid.Type: ApplicationFiled: May 11, 2001Publication date: November 22, 2001Applicant: Haldor Topsoe A/SInventor: Niels C. Schiodt
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Publication number: 20010023285Abstract: This invention relates to methods and reactor devices for controlling the oxidation of hydrocarbons to dibasic acids, in the presence of a cobalt catalyst and a monobasic acid, such as acetic acid, by treating the catalyst from the reaction mixture, outside the oxidation zone, after the oxidation has taken place at least partially. In one preferred embodiment, the catalyst is reduced to contain, preferably predominantly and more preferably substantially, cobalt ions in valence II, and at least partially precipitated by de-watering and/or thermal treatment. In a different preferred embodiment, the catalyst in the reaction mixture is first oxidized or maintained, preferably predominantly and more preferably substantially, at valence III, the reaction mixture is de-watered, the catalyst is reduced preferably predominantly and more preferably substantially, to valence II, causing precipitation either spontaneously at a predetermined temperature or after further thermal treatment.Type: ApplicationFiled: April 5, 2001Publication date: September 20, 2001Inventors: Eustathios Vassiliou, Mark W. Dassel, Ader M. Rostami, Douglas J. Dudgeon, David C. DeCoster
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Patent number: 6284919Abstract: A process for the liquid-phase carbonylation of ethylene, according to the equation C2H4+CO+ROH→C2H5CO2R, in the presence of a catalyst system comprising a Group VIII metal or compound thereof, a phosphine ligand and a source of anions, and in the presence of water or a source of organic hydroxyl groups, is carried out in conditions in which the molar ratio of ethylene to carbon monoxide in the gaseous phase of the reactor is greater than 1:1. The higher ratios of ethylene to carbon monoxide are beneficial in increasing the turnover number of the catalyst system.Type: GrantFiled: September 15, 1999Date of Patent: September 4, 2001Assignee: Imperial Chemical Industries PLCInventors: Jean Margaret Pearson, Raymond Anthony Hadden
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Patent number: 6239325Abstract: The invention provides process for oxidative dehydrogenation of lower alkanes, by vapor phase oxidative dehydrogenation of C2-C5 lower alkanes in the presence of a catalyst and molecular oxygen to produce the corresponding olefins, in which the catalyst has a composition expressed by a general formula (1) below: A&agr;Sb&bgr;W&ggr;D&dgr;Ox (1) in which A is at least one metal selected from the group consisting of molybdenum and chromium; Sb is antimony; W is tungsten; O is oxygen; and D is at least one metal selected from the group consisting of V, Nb, Ta, Fe, Co, Ni, Cu, Ag, Zn, B, Tl, Sn, Pb, Te, Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, La, Ce and Sm; &agr;, &bgr;, &ggr;, &dgr; and x denote atomic numbers of A, Sb, W, D and O, respectively, where when &agr;=1, &bgr;=0.5-10, &ggr;=0.1-10 and &dgr;=0-3; and x is a numerical value determined by the state of oxidation of those elements other than oxygen.Type: GrantFiled: May 18, 1999Date of Patent: May 29, 2001Assignee: Nippon Shokubai Co LtdInventors: Nobuji Kishimoto, Etsushige Matsunami
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Patent number: 6222069Abstract: The invention discloses a method for purifying adipic acid in water. More precisely it discloses an improvement in adipic acid crystallization or recrystallization in water, characterised in that the said crystallization or recrystallization is effected in presence of a strong proton acid and/or in the presence of carbon monoxide. This crystallization or recrystallization particularly enables the content of metal catalyst traces in the adipic acid to be reduced.Type: GrantFiled: March 17, 1999Date of Patent: April 24, 2001Assignee: Rhodia Fiber and Resin IntermediatesInventors: Eric B. Henriet, Philippe Leconte, Carl Patois, Robert Perron
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Patent number: 6133477Abstract: An improved process for the preparation of 3-pentenoic acid by reaction of butadiene with carbon monoxide and water in the presence of a rhodium-containing catalyst and an iodide promoter where carbon monoxide stripping is employed to separate and recover the 3-pentenoic acid product.Type: GrantFiled: July 23, 1998Date of Patent: October 17, 2000Assignees: E. I. du Pont de Nemours and Company, DSM N.V.Inventor: Harold Stanley Bruner
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Patent number: 6011171Abstract: The present invention provides a process for synthesizing tertiary carboxylic acids or the esters thereof having one or two more carbon atoms than the raw material has, comprising reacting in a strong acid (e.g., sulfuric acid, sulfuric acid-phosphoric acid, hydrogen fluoride, fluorosulfuric acid, boron trifluoride.water complex and trifluoromethanesulfonic acid) a raw material compound (i.e., olefin, alcohol, diene, diol or saturated hydrocarbon) with carbon monoxide in the presence of a specific metal carbonyl catalyst (i.e., platinum carbonyl catalyst, palladium carbonyl catalyst and gold dicarbonyl catalyst).The metal carbonyl catalyst is formed by reacting in a strong acid at least one specific metal compounds (e.g., platinum compound such as platinum (II, IV) oxide, platinum (II, IV) hydroxide, a platinum powder, etc.; palladium compound such as palladium (II, III, IV) oxide, palladium (II) hydroxide, palladium (II) sulfate, palladium (II) carboxylate, a palladium powder, etc.Type: GrantFiled: November 4, 1997Date of Patent: January 4, 2000Assignee: Jiro Hiraishi, Director-General, Agency of Industrial Science and TechnologyInventors: Qiang Xu, Yoshie Souma
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Patent number: 5977407Abstract: Disclosed is a process for the preparation of an aliphatic carbonyl derivative compound having a normal:iso ratio of at least 3, and preferably 4, selected from aliphatic carboxylic acids, alkylesters of aliphatic carboxylic acids and anhydrides of aliphatic carboxylic acids by the hydrocarboxylation of terminal linear olefins in the presence of a catalyst system comprising (1) a rhodium containing compound, (2) a halide promoter selected from iodine, bromine and compounds thereof and (3) a trisubstituted organic compound of a group-15 element, preferably a phosphine or arsine. This process constitutes an improvement over known processes since it provides a one-step, lower pressure, higher reaction rate method of producing carboxylic acid derivatives having an increased normal:iso ratio in the absence of potentially hazardous chlorinated hydrocarbons and aromatic hydrocarbons.Type: GrantFiled: August 10, 1998Date of Patent: November 2, 1999Assignee: Eastman Chemical CompanyInventor: Joseph Robert Zoeller
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Patent number: 5962732Abstract: Process for making 3-pentenoic acid by reacting butadiene with carbon monoxide in the presence of nickel and an iodide source.Type: GrantFiled: December 17, 1998Date of Patent: October 5, 1999Assignees: E. I. du Pont de Nemours and Company, DSM N.V.Inventor: Patrick Michael Burke
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Patent number: 5952522Abstract: A process is disclosed for the carbonylation of acetylenically unsaturated compounds by reaction with carbon monoxide and a co-reactant in the presence of a catalyst system based on: (a) a source of platinum; (b) a bidentate ligand of the formula R.sup.1 R.sup.2 M.sup.1 -R-M.sup.2 R.sup.3 R.sup.4, wherein M.sup.1 and M.sup.2 independently are P, As or Sb, R represents a bivalent substituted or non-substituted bridging group containing from 1 to 5 atoms in the bridge, R.sup.1 and R.sup.2 together are a substituted or non-substituted bivalent group whereby the two free valencies are linked to M.sup.1, and R.sup.3 and R.sup.4 together are a substituted or non-substituted bivalent group whereby the two free valencies are linked to M.sup.2 or R.sup.3 and R.sup.4 independently are substituted or non-substituted hydrocarbyl groups; and (c) a source of anions.Type: GrantFiled: December 18, 1996Date of Patent: September 14, 1999Assignee: Shell Oil CompanyInventors: Eit Drent, Willem Wabe Jager
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Patent number: 5919978Abstract: This invention relates in part to processes for producing one or more substituted or unsubstituted aldehyde acids or salts, e.g., 5-formylvaleric acid or salt, which comprises subjecting one or more substituted or unsubstituted alkadienes, e.g., butadiene, to hydroxycarbonylation in the presence of a hydroxycarbonylation catalyst, e.g., a metal-organophosphorus ligand complex catalyst, and optionally neutralization with a base to produce one or more substituted or unsubstituted unsaturated acids or salts, e.g., pentenoic acid or salt, and subjecting said one or more substituted or unsubstituted unsaturated acids or salts to hydroformylation in the presence of a hydroformylation catalyst, e.g., a metal-organophosphorus ligand complex catalyst, to produce said one or more substituted or unsubstituted aldehyde acids or salts and/or one or more substituted or unsubstituted epsilon caprolactam precursors.Type: GrantFiled: April 15, 1997Date of Patent: July 6, 1999Assignee: Union Carbide Chemicals & Plastics Technology CorporationInventors: Diane Lee Packett, Thomas Carl Eisenschmid, Michael Allen Brammer, John Michael Maher
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Patent number: 5908803Abstract: The present invention relates to the isolation of a palladium-based catalyst from a mixture in which it is dissolved. More specifically, the invention relates to the isolation of a palladium-based catalyst from a mixture originating from the reaction of hydroxycarbonylation of butadiene to pentenoic acids. It therefore consists of a process for the isolation of at least a portion of the palladium dissolved in a solution also containing at least 3-pentenoic acid, characterized in that the said solution is acidified and stirred with an aqueous solution of hydrochloric acid, so as to obtain two liquid phases including an aqueous phase containing at least a portion of the palladium.Type: GrantFiled: April 9, 1997Date of Patent: June 1, 1999Assignee: Rhone-Poulenc Fiber & Resin IntermediatesInventors: Philippe Leconte, Carl Patois
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Patent number: 5866716Abstract: A process for selectively preparing a carboxylic acid by reacting an olefin with carbon monoxide in the presence of at least an equimolar amount of water with respect to the olefin at a temperature of from 50.degree. to 150.degree. C.Type: GrantFiled: August 23, 1996Date of Patent: February 2, 1999Assignee: BASF AktiengesellschaftInventors: Martin Schafer, Arthur Hohn, Ferdinand Lippert