Preparing Esters By Carbonylation Patents (Class 560/232)
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Patent number: 12083504Abstract: Catalysts containing a support and a metal oxide, and reactors and methods of using the catalysts in a carbonylation reaction, such as alcohol carbonylation and ester carbonylation, are described herein. The support is typically chemically inert and has a high surface area. The metal oxide typically contains a transition metal or a mixture of metals, such as rhenium, aluminum, tungsten, molybdenum, or a combination thereof. Typically, the metal oxide is mainly atomically dispersed on the surface of the support, as indicated by STEM. For example, at least 10% of the metal oxide is atomically dispersed on the surface of the support. The method includes (i) exposing a mixture of one or more alcohols or one or more esters and carbon monoxide to the catalyst. Typically, the one or more alcohols or one or more esters and carbon monoxide are in a gas phase.Type: GrantFiled: November 16, 2020Date of Patent: September 10, 2024Assignee: The Regents of the University of CaliforniaInventors: Phillip Christopher, Ji Qi
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Patent number: 12006287Abstract: Process for alkoxycarbonylation of ethylenically unsaturated compounds using benzene-based diphosphine ligands and aluminium triflate.Type: GrantFiled: November 19, 2021Date of Patent: June 11, 2024Assignee: EVONIK OXENO GMBH & CO. KGInventors: Peter Kucmierczyk, Ricarda Dühren, Dirk Fridag, Johannes Knossalla, Anna Chiara Sale, Ana Markovic, Alexander Brächer, Matthias Beller, Robert Franke
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Patent number: 11779911Abstract: In one aspect, the invention provides a method for synthesizing a fatty olefin derivative. The method includes: a) contacting an olefin according to Formula I with a metathesis reaction partner according to Formula IIb in the presence of a metathesis catalyst under conditions sufficient to form a metathesis product according to Formula IIIb: and b) converting the metathesis product to the fatty olefin derivative. Each R1 is independently selected from H, C1-18 alkyl, and C2-18 alkenyl; R2b is C1-8 alkyl; subscript y is an integer ranging from 0 to 17; and subscript z is an integer ranging from 0 to 17. In certain embodiments, the metathesis catalyst is a tungsten catalyst or a molybdenum catalyst. In various embodiments, the fatty olefin derivative is a pheromone. Pheromone compositions and methods of using them are also described.Type: GrantFiled: July 30, 2021Date of Patent: October 10, 2023Assignee: PROVIVI, INC.Inventors: Keith M. Wampler, Peter Meinhold, Pedro Coelho, Vu Bui, Hasan Mehdi
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Patent number: 11453634Abstract: A process of preparation of carboxylic acids by oxidative cleavage of compounds having substituted or non-substituted, linear or branched, saturated or unsaturated alkyl chains containing at least one vicinal diol or an epoxide in the presence of an oxidant comprising molecular oxygen and a heterogeneous catalyst comprising a copper oxide.Type: GrantFiled: November 22, 2018Date of Patent: September 27, 2022Assignees: NOVAMONT S.P.A., MATRICA S.P.A., ALMA MATER STUDIORUM—Universita' di BolognaInventors: Fabrizio Cavani, Andrea Vassoi
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Patent number: 11225453Abstract: A method for producing tricyclo[5.2.1.02,6]decane-2-carboxylate according to the present invention is a method for producing tricyclo[5.2.1.02,6]decane-2-carboxylate, containing reacting tricyclo[5.2.1.02,6]deca-3-ene in a dilute solution containing the tricyclo[5.2.1.02,6]deca-3-ene with carbon monoxide in the presence of an acid catalyst, followed by reaction with an alcohol, wherein the dilute solution contains 100 parts by mass or more of a tricyclo[5.2.1.02,6]decane isomer mixture based on 100 parts by mass of the tricyclo[5.2.1.02,6]deca-3-ene, the tricyclo[5.2.1.02,6]decane isomer mixture contains endo-tricyclo[5.2.1.02,6]decane (Endo form of TCD) and exo-tricyclo[5.2.1.02,6]decane (Exo form of TCD), and a constituent ratio thereof (Endo form of TCD/Exo form of TCD) is greater than 1.0.Type: GrantFiled: February 12, 2019Date of Patent: January 18, 2022Assignee: Mitsubishi Gas Chemical Company, Inc.Inventors: Shiori Shinagawa, Mitsuharu Kitamura, Shinichi Nagao, Ken Sugito
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Patent number: 11167281Abstract: The present disclosure relates to a composition that includes a core in the shape of a particle having a characteristic length between about one micron and about one millimeter, an active material that includes a noble metal deposited on a surface of the core, and a coating that includes a first metal-oxide, where the active material is positioned between the core and the coating, the active material has a diameter between about one nanometer and about 20 nanometers, and the coating has a thickness between greater than zero nanometers and about 20 nanometers.Type: GrantFiled: August 8, 2019Date of Patent: November 9, 2021Assignees: Alliance for Sustainable Energy, LLC, Colorado School of MinesInventors: Derek Richard Vardon, Steven T. Christensen, Katherine E. Hurst, Amy Elizabeth Maurer, Michael Brandon Griffin
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Patent number: 11111190Abstract: Process (P) for the decarboxylative ketonization of fatty acids, fatty acid derivatives or mixtures thereof in the liquid phase with metal compounds as catalyst wherein the fatty acids, fatty acid derivatives or mixtures thereof are added sequentially. Downstream chemistry can be realized starting from internal ketones obtained by process (P), especially in order to design and develop new surfactants.Type: GrantFiled: November 8, 2017Date of Patent: September 7, 2021Assignee: RHODIA OPERATIONSInventors: Olivier Back, Rémy Leroy, Philippe Marion
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Patent number: 11111200Abstract: The present invention provides a method for preparing acrylic acid and methyl acrylate. The method comprises passing the feed gas containing dimethoxymethane and carbon monoxide through a solid acid catalyst to generate acrylic acid and methyl acrylate with a high conversion rate and selectivity at a reaction temperature in a range from 180 to 400 and a reaction pressure in a range from 0.1 MPa to 15.0 MPa, the mass space velocity of dimethoxymethane in the feed gas is in a range from 0.05 h?1 to 10.0 h?1, and the volume percentage of dimethoxymethane in the feed gas is in a range from 0.1% to 95%.Type: GrantFiled: November 25, 2016Date of Patent: September 7, 2021Assignee: Dalian Institute of Chemical Physics, Chinese Academy of SciencesInventors: Lei Shi, Zongmin Liu, Youming In, Wenliang Zhu, Yong Liu, Hongchao Liu
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Patent number: 11097243Abstract: Embodiments include a system that may include a reactor including a reaction zone and a gas release zone separated by a selectively permeable membrane, wherein the selectively permeable membrane permits hydrogen to pass through the membrane and substantially blocks a substrate and its dehydrogenative coupling product from passing through the membrane. Embodiments further include a method of producing a dehydrogenative coupling product, wherein the method may include exposing a substrate to a catalyst in a reaction zone of a reactor; coupling the substrate to form the dehydrogenative coupling product and hydrogen; and separating the hydrogen from the dehydrogenative coupling product using a selectively permeable membrane and passing the hydrogen to a gas release zone of the reactor.Type: GrantFiled: October 31, 2019Date of Patent: August 24, 2021Assignee: KING ABDULLAH UNIVERSITY OF SCIENCE AND TECHNOLOGYInventors: Kuo-Wei Huang, Zhiping Lai
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Patent number: 11053187Abstract: A process for the production of methyl acetate by carbonylating dimethyl ether with carbon monoxide at a temperature of 250 to 350° C. in the presence of a zeolite catalyst and hydrogen such that the molar ratio of hydrogen to carbon monoxide is at least 1, and one or more compounds containing a hydroxyl functional group and in the absence of any added methyl acetate.Type: GrantFiled: April 10, 2018Date of Patent: July 6, 2021Assignee: Ineos Acetyls UK LimitedInventor: Thomas Edward Clark
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Patent number: 11053275Abstract: Provided herein is a method of preparing a bile acid derivative using a continuous flow reaction. When bile acid derivatives are synthesized using a continuous flow reaction according to the present invention, the reaction is very safe compared to an existing batch-type reaction, the reaction time is significantly reduced, and high-quality bile acid derivatives may be synthesized with high efficiency. In particularly, according to the present invention, a hydrogenation reaction proceeds under substantially water-free reaction conditions, and thus the conversion rate (UDCA: CDCA) of a UDCA hydrogenation reaction may be significantly enhanced.Type: GrantFiled: April 20, 2018Date of Patent: July 6, 2021Assignee: DAEWOONG BIO INC.Inventors: Tae Seop Hwang, Phil Goo Kang, Joon Hwan Lee, Jin Yong Eo, Seung Jae Lee
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Patent number: 11046633Abstract: A process for the production of methyl acetate by carbonylating at a temperature of 250 to 350° C., in the presence of a zeolite catalyst, a feed comprising dimethyl ether, a gas comprising carbon monoxide and hydrogen at a molar ratio of hydrogen to carbon monoxide of at least 1, methyl acetate and one or more compounds containing a hydroxyl functional group.Type: GrantFiled: April 12, 2017Date of Patent: June 29, 2021Assignee: Ineos Acetyls UK LimitedInventors: Thomas Edward Clark, Nicholas John Hazel, John Glenn Sunley
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Patent number: 10988430Abstract: Disclosed is a continuous process for producing ?,?-unsaturated carboxylic acids or salts thereof, comprising: 1) in a first stage, contacting (a) a transition metal precursor compound comprising at least one first ligand, (b) optionally, at least one second ligand, (c) an olefin, (d) carbon dioxide (CO2), and (e) a diluent to form a first composition; 2) in a second stage, contacting a polyanionic solid with the first composition to form a second composition; and 3) in a third stage, (a) contacting the second composition with a polar solvent to release a metal salt of an ?,?-unsaturated carboxylic acid and form a reacted solid. Methods of regenerating the polyanionic solid are described.Type: GrantFiled: December 17, 2019Date of Patent: April 27, 2021Inventors: Mark L. Hlavinka, Gregory G. Hendrickson, Pasquale Iacono
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Patent number: 10941101Abstract: This disclosure provides routes of synthesis of acrylic acid and other ?,?-unsaturated carboxylic acids and their salts, including catalytic methods. In an aspect, there is provided a process for producing an ?,?-unsaturated carboxylic acid or a salt thereof, the process comprising: (1) contacting in any order a group 8-11 transition metal precursor compound comprising at least one first ligand, at least one second ligand, an olefin, carbon dioxide, a diluent, and an anionic polyaromatic resin with associated metal cations to provide a reaction mixture; and (2) applying conditions to the reaction mixture suitable to produce the ?,?-unsaturated carboxylic acid or a salt thereof. Methods of regenerating the polyaromatic resin with associated metal cations are described.Type: GrantFiled: July 23, 2019Date of Patent: March 9, 2021Assignee: Chevron Phillips Chemical Company, LPInventors: Pasquale Iacono, Mark L. Hlavinka
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Patent number: 10844088Abstract: The present invention relates to a process for the preparation of estra-1,3,5(10)-trien-3, 15a, 16a, 17?-tetraol (estetr-01), via a silyl enol ether derivative 17-B-oxy-3-A-oxy-estra-1,3,5(10), 16-tetraene, wherein A is a protecting group and B is —Si(R2)3. The invention further relates to a process for the synthesis of 3-A-oxy-estra-1,3,5(10), 15-tetraen-17-one, in which A is a protecting group, via silyl enol ether derivative 17-B-oxy-3-A-oxy-estra-1,3,5(10),16-tetraene, and B is —Si(R2)3.Type: GrantFiled: February 7, 2017Date of Patent: November 24, 2020Assignee: ESTETRA SPRLInventors: Johannes Jan Platteeuw, Herman Jan Tijmen Coelingh Bennink, Franciscus Wilhelmus Petrus Damen, Michiel Christian Alexander Van Vliet
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Patent number: 10828628Abstract: A method for separating a homogeneous catalyst from a solution includes forming a host-guest compound between a first isomer of the catalyst and inclusion compound in the solution and isolating the host-guest compound from the solution. The catalyst may be released from the inclusion compound by converting the first isomer of the catalyst to a second isomer of the catalyst.Type: GrantFiled: June 6, 2019Date of Patent: November 10, 2020Assignee: Florida State University Research Foundation, Inc.Inventor: Hoyong Chung
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Patent number: 10807963Abstract: A process is provided for converting mevalonic acid into various useful products and derivatives. More particularly, the process comprises reacting mevalonic acid, or a solution comprising mevalonic acid, in the presence of a solid catalyst at an elevated temperature and pressure to thereby form various biobased products. The process may also comprise: (a) providing a microbial organism that expresses a biosynthetic mevalonic acid pathway; (b) growing the microbial organism in fermentation medium comprising suitable carbon substrates, whereby biobased mevalonic acid is produced; and (c) reacting the biobased mevalonic acid in the presence of a solid catalyst at an elevated temperature and pressure to yield various biobased products.Type: GrantFiled: February 18, 2019Date of Patent: October 20, 2020Assignee: Visolis, Inc.Inventors: Deepak Dugar, Brian Neltner
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Patent number: 10774024Abstract: The present invention relates to a catalytic process for preparing an ?,?-ethylenically unsaturated carboxylic acid salt, comprising contacting an alkene and carbon dioxide with a carboxylation catalyst being a transition metal complex, an alkoxide, and an organic solvent, to obtain an ?,?-ethylenically unsaturated carboxylic acid salt, the organic solvent being incompletely miscible with water at a pressure of 1 bar at at least one temperature T and selected from amides and ureas, T being a temperature in the range from 10° C. to 90° C.Type: GrantFiled: April 4, 2017Date of Patent: September 15, 2020Assignee: BASF SEInventors: Thomas Schaub, Rocco Paciello, Nuria Huguet Subiela, Oliver Trapp, Simone Manzini
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Patent number: 10730821Abstract: Methods for preparing isotopically modified 1,4-diene systems from non-isotopically modified 1,4-dienes involve selective oxidation of one or more bis-allylic position(s), or the preparation of isotopically modified 1,4-diene systems via trapping pi-allylic complexes with a source of deuterium or tritium. Such methods are useful for preparing isotopically modified polyunsaturated lipid including polyunsaturated fatty acids and polyunsaturated fatty acid derivatives.Type: GrantFiled: September 9, 2016Date of Patent: August 4, 2020Assignee: Retrotope, Inc.Inventors: Dragoslav Vidovic, Mikhail Sergeevich Shchepinov
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Patent number: 10562836Abstract: A process for producing acetic acid while efficiently separating permanganate reducing compounds (PRC's) and methyl iodide is provided. PRC's are separated or removed from a mixed composition (3A) containing PRC's and methyl iodide by distilling the mixed composition in a distillation step (5) to form an overhead stream (5A), a side-cut stream (5B), and a lower stream (5C). In a distillation column of the distillation step (5), an extractant (e.g., water) extracting PRC's preferentially to methyl iodide is added to a concentration zone in which PRC's and methyl iodide are concentrated, and an extraction mixture falling from the concentration zone is withdrawn as the side-cut stream (5B).Type: GrantFiled: May 27, 2016Date of Patent: February 18, 2020Assignee: DAICEL CORPORATIONInventors: Masahiko Shimizu, Hiroyuki Miura, Yoshihisa Mizutani
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Patent number: 10512902Abstract: A carbonylation process in the presence of a pretreated zeolite catalyst which comprises the sequential steps (i) pretreating the catalyst and (ii) carbonylating dimethyl ether with a carbon monoxide-containing gas to produce methyl acetate in which the catalyst pretreatment step (i) comprises a step (a) contacting the catalyst with a first treatment mixture comprising water vapour; and a step (b) contacting the treated catalyst of step (a) with a second treatment mixture comprising an inert gas and at least one of dimethyl ether and methanol.Type: GrantFiled: November 25, 2016Date of Patent: December 24, 2019Assignee: BP Chemicals LimitedInventors: Nicholas John Hazel, David John Law
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Patent number: 10508073Abstract: The present application provides a method for preparing acetal carbonyl compound used as an intermediate for producing ethylene glycol, which comprises a step in which a raw material acetal and a raw gas carbon monoxide go through a reactor loaded with a catalyst containing an acidic microporous silicoaluminophosphate molecular sieve, for carrying out a carbonylation reaction. In the method of the present invention, the conversion rate of the raw material acetal is high, and the selectivity of acetal carbonylation is high, and the catalyst life is long, and no additional solvent is needed in the reaction process, and the reaction condition is relatively mild, and the process is continuous, showing the potential for industrial application. Moreover, the product of acetal carbonyl compound can be used for producing ethylene glycol by hydrogenation followed by hydrolysis.Type: GrantFiled: December 8, 2015Date of Patent: December 17, 2019Assignee: Dalian Institute of Chemical Physics, Chinese Academy of SciencesInventors: Youming Ni, Wenliang Zhu, Yong Liu, Hongchao Liu, Zhongmin Liu, Miao Yang, Peng Tian
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Patent number: 10501398Abstract: In processes for the hydrolysis of a methyl acetate with at least one of water and methanol in the presence of at least one Brønsted acid catalyst to produce acetic acid the performance of the catalyst is improved by using a methyl acetate feed in which the total amount of acetaldehyde and 1,1 dimethoxyethane impurities is maintained at 100 ppm wt or less calculated as mass equivalents of acetaldehyde.Type: GrantFiled: December 11, 2018Date of Patent: December 10, 2019Assignee: BP Chemicals LimitedInventors: Berian John Daniel, John Glenn Sunley, Russell Alan Taylor, Gareth Gerald Armitage
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Patent number: 10457624Abstract: Reactor systems and processes produce organic acids through thermolysis of polylactones. The reactor systems and processes introduce at least one epoxide reagent and carbon monoxide reagent to at least one reaction vessel through at least one feed stream inlet. The epoxide reagent and carbon monoxide reagent contact at least one carbonylation catalyst to produce at least one beta-lactone intermediate. The beta-lactone intermediate is polymerized with at least one initiator in the presence of a metal cation to produce at least one polylactone product. The polylactone product is heated under thermolysis conditions to produce at least one organic acid product. The processes control the presence of contaminates, impurities, catalytic materials, and/or reagents to provide for highly pure organic acid products.Type: GrantFiled: June 2, 2017Date of Patent: October 29, 2019Assignee: Novomer, Inc.Inventors: Sadesh H. Sookraj, Kyle Evan Sherry
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Patent number: 10435349Abstract: A process for preparing a variety of secondary and tertiary alkyl formate esters via the coupling of methanol and secondary (or tertiary) alcohols. Iron-based catalysts, supported by pincer ligands, are employed to produce these formate esters in high yields and unprecedentedly high selectivities (>99%). Remarkably, the coupling strategy is also applicable to bulkier tertiary alcohols, which afford corresponding tertiary formate esters in moderately high yields and high selectivities.Type: GrantFiled: July 24, 2018Date of Patent: October 8, 2019Assignee: Eastman Chemical CompanyInventors: Sumit Chakraborty, Steven J. Adams, Robert Thomas Hembre, Scott Donald Barnicki, Michael Richard Laningham, Gerarld Wayne Ollis, Randy Lynn Jennings
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Patent number: 10435347Abstract: The present invention relates to a method for preparing acrylic acid from glycerin. More specifically, the present invention provides a method which can improve the selectivity of acrolein by applying a specific catalyst composition and process conditions to minimize the generation of coke carbon of the catalyst, and can prepare acrylic acid with higher productivity for a longer duration of time because a dehydration reaction can be performed for a longer working period while maintaining catalyst activity at a high level during the reaction.Type: GrantFiled: December 15, 2016Date of Patent: October 8, 2019Assignee: LG CHEM, LTD.Inventors: Kyung Soo Kim, Jun Seon Choi, Ji Yeon Kim, Joo Young Cheon, Wang Rae Joe, Hye Jeong Ok
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Patent number: 10392336Abstract: This disclosure provides for routes of synthesis of acrylic acid and other ?,?-unsaturated carboxylic acids and their salts, including catalytic methods. For example, there is provided a process for producing an ?,?-unsaturated carboxylic acid or a salt thereof, the process comprising: (1) contacting in any order, a group 8-11 transition metal precursor, an olefin, carbon dioxide, a diluent, and a polyaromatic resin with associated metal cations to provide a reaction mixture; and (2) applying conditions to the reaction mixture suitable to produce the ?,?-unsaturated carboxylic acid or a salt thereof. Methods of regenerating the polyaromatic resin with associated metal cations are described.Type: GrantFiled: November 7, 2018Date of Patent: August 27, 2019Assignee: Chevron Phillips Chemical Company LPInventors: Pasquale Iacono, Mark L. Hlavinka
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Patent number: 10357763Abstract: A method for separating a homogeneous catalyst from a solution includes forming a host-guest compound between a first isomer of the catalyst and inclusion compound in the solution and isolating the host-guest compound from the solution. The catalyst may be released from the inclusion compound by converting the first isomer of the catalyst to a second isomer of the catalyst.Type: GrantFiled: August 22, 2017Date of Patent: July 23, 2019Assignee: Florida State University Research Foundation, Inc.Inventor: Hoyong Chung
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Patent number: 10315980Abstract: The present disclosure relates to a catalyst used in the preparation of acrylic acid and acrylic acid preparation method using the same, and more specifically, discloses a catalyst capable of enhancing selectivity of acrylic acid and a production yield of acrylic acid when preparing acrylic acid from allyl alcohol using a heterogeneous catalyst including bimetallic alloy catalyst particles of gold and another metal, and an acrylic acid preparation method using the same.Type: GrantFiled: August 24, 2016Date of Patent: June 11, 2019Assignee: LG CHEM, LTD.Inventors: Dongsu Song, Daesung Kim, Wonjae Lee, Yongjin Choe, Hyunjoo Lee, Minsu Kim
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Patent number: 10301250Abstract: A method of producing an ethylenically unsaturated carboxylic acid or ester, preferably an ?, ? ethylenically unsaturated carboxylic acid or ester. The method includes contacting formaldehyde or a suitable source thereof with a carboxylic acid or ester in the presence of a catalyst and optionally in the presence of an alcohol. The catalyst includes a nitrided metal oxide having at least two types of metal cations, M1 and M2, wherein M1 is selected from the metals of group 2, 3, 4, 13 (called also IIIA) or 14 (called also IVA) of the periodic table and M2 is selected from the metals of groups 5 or 15 (called also VA) of the periodic table.Type: GrantFiled: June 21, 2016Date of Patent: May 28, 2019Assignee: LUCITE INTERNATIONAL UK LIMITEDInventors: Ian Andrew York, Sabina Zieman
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Patent number: 10300463Abstract: Provided is a catalyst for manufacturing an unsaturated aldehyde and/or an unsaturated carboxylic acid, which is prepared by a method in which a molybdenum component raw material is composed of only an ammonium molybdate, the weight of water for dissolution is 8.5 times or less relative to the weight of molybdenum contained in the ammonium molybdate; and a bismuth component raw material is composed of only bismuth nitrate, the weight of a nitric acid aqueous solution for dissolution is 2.3 times or more relative to the weight of bismuth contained in the bismuth nitrate, and a nitric acid concentration in the nitric acid aqueous solution for dissolving the bismuth nitrate is 10% by weight or more.Type: GrantFiled: February 25, 2016Date of Patent: May 28, 2019Assignee: NIPPON KAYAKU KABUSHIKI KAISHAInventors: Tomoyuki Kawamura, Motohiko Sugiyama, Ryota Hiraoka
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Patent number: 10227283Abstract: The present disclosure provides for a method for measuring the concentration of one or more components in a feed stream or reactor mixture of a process for producing acetic acid by both infrared and Raman spectroscopic analyses. In some embodiments, at least one feed stream comprising water is adjusted in response to the measured concentration of one or more components.Type: GrantFiled: June 28, 2018Date of Patent: March 12, 2019Assignee: LyondellBasell Acetyls, LLCInventors: Noel C. Hallinan, John D. Hearn, Ryan J. Mathews, Brian A. Salisbury, Daniel F. White
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Patent number: 10208008Abstract: A process is provided for converting mevalonic acid into various useful products and derivatives. More particularly, the process comprises reacting mevalonic acid, or a solution comprising mevalonic acid, in the presence of a solid catalyst at an elevated temperature and pressure to thereby form various biobased products. The process may also comprise: (a) providing a microbial organism that expresses a biosynthetic mevalonic acid pathway; (b) growing the microbial organism in fermentation medium comprising suitable carbon substrates, whereby biobased mevalonic acid is produced; and (c) reacting the biobased mevalonic acid in the presence of a solid catalyst at an elevated temperature and pressure to yield various biobased products.Type: GrantFiled: November 24, 2015Date of Patent: February 19, 2019Assignee: Visolis, Inc.Inventors: Deepak Dugar, Brian Neltner
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Patent number: 10189768Abstract: The present invention relates to a method for hydrogenolysis of alpha-hydroxy esters or acids, comprising reacting the alpha-hydroxy ester or acid in the presence of a heterogeneous catalyst. The present invention also relates to a method for producing propionic acid ester, and the use of any of the methods for the production of propionic acid esters, such as alkyl propionate.Type: GrantFiled: June 23, 2016Date of Patent: January 29, 2019Assignee: Danmarks Tekniske UniversitetInventors: Shunmugavel Saravanamurugan, Santosh Govind Khokarale, Anders Riisager
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Patent number: 10183906Abstract: Process for the hydrolysis of a methyl acetate with at least one of water and methanol in the presence of at least one Brønsted acid catalyst to produce acetic acid. The process employs a methyl acetate feed in which the total amount of acetaldehyde and 1,1 dimethoxyethane impurities is maintained at 100 pm wt or less calculated as mass equivalents of acetaldehyde.Type: GrantFiled: June 12, 2015Date of Patent: January 22, 2019Assignee: BP CHEMICALS LIMITEDInventors: Berian John Daniel, John Glenn Sunley, Russell Alan Taylor, Gareth Gerald Armitage
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Patent number: 10160712Abstract: A method of catalytic oxidation of a lignite using oxygen as an oxidant at atmospheric pressure is provided. The method includes the following steps, pulverizing the lignite to 200-mesh or less; drying the pulverized lignite at a temperature of 80° C. in vacuum for 10 h; weighing 0.5 g of the dried lignite and sequentially adding 10 ml of acetic acid, 0.5 mmol of a catalyst and 0.15-0.25 mmol of a cocatalyst into a round-bottom flask filled with the oxygen, keeping oxygen pressure at 0.1 MPa, reacting at a temperature of 80-120° C. for 4-12 h; using oxygen as the oxidant to catalytically oxidize the reacted lignite at an atmospheric pressure of 0.1 MPa; filtering after the reaction is finished; decompressing the filtrate to remove the acetic acid, adding a small amount of ethyl acetate to dissolve, and using an excess CH2N2/ether solution to esterify for 10 h at room temperature; and analyzing the esterified product through a gas chromatography-mass spectrometer.Type: GrantFiled: December 7, 2016Date of Patent: December 25, 2018Assignee: CHINA UNIVERSITY OF MINING AND TECHNOLOGYInventors: Jing Liang, Huihui Yang, Xianyong Wei, Zhimin Zong
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Patent number: 10160711Abstract: This disclosure provides for routes of synthesis of acrylic acid and other ?,?-unsaturated carboxylic acids and their salts, including catalytic methods. For example, there is provided a process for producing an ?,?-unsaturated carboxylic acid or a salt thereof, the process comprising: (1) contacting in any order, a group 8-11 transition metal precursor, an olefin, carbon dioxide, a diluent, and a polyaromatic resin with associated metal cations to provide a reaction mixture; and (2) applying conditions to the reaction mixture suitable to produce the ?,?-unsaturated carboxylic acid or a salt thereof. Methods of regenerating the polyaromatic resin with associated metal cations are described.Type: GrantFiled: December 13, 2016Date of Patent: December 25, 2018Assignee: Chevron Phillips Chemical Company LPInventors: Pasquale Iacono, Mark L. Hlavinka
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Patent number: 10160830Abstract: An alkylene oxide mixture containing greater than 50% by weight ethylene oxide is continuously polymerized in the presence of a double metal cyanide polymerization catalyst and certain magnesium, Group 3-Group 15 metal or lanthanide series metal compounds. The presence of the magnesium, Group 3-Group 15 metal or lanthanide series metal compound permits the polymerization to be performed continuously without premature deactivation of the double metal cyanide catalyst.Type: GrantFiled: June 15, 2016Date of Patent: December 25, 2018Assignee: Dow Global Technologies LLCInventors: David A. Babb, Jean-Paul Masy, Mattias Schaefer, William A. Koonce, Donald Cameron
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Patent number: 10144693Abstract: Carboxylic acids are prepared by a one-step gas phase process comprising the step of contacting under halogen-free hydroxycarbonylation conditions an alkene, carbon monoxide, water, and a solid sulfide-containing catalyst.Type: GrantFiled: October 6, 2015Date of Patent: December 4, 2018Assignee: Dow Global Technologies LLCInventors: David G. Barton, Gerolamo Budroni, Steven L. F. Corthals
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Patent number: 10138197Abstract: This disclosure describes a new route to acrylate esters via direct catalytic partial oxidation of allyl ether using heterogeneous manganese oxide catalysts. The method involves forming allyl acrylate by contacting allyl ether, where the allyl ether is in solution with a solvent, with one or more oxidants in the presence of a mesoporous manganese oxide (MnOx) catalyst. Oxygen or peroxide can be used as the oxidant. The yield of and selectivity for acrylate ester can be very high, and process efficiency is improved over current processes.Type: GrantFiled: February 26, 2018Date of Patent: November 27, 2018Assignee: EXXONMOBIL RESEARCH AND ENGINEERING COMPANYInventors: Partha Nandi, Steven L. Suib, Timothy D. Shaffer
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Patent number: 10138196Abstract: A catalytic process for preparing an ?,?-ethylenically unsaturated carboxylic acid salt from an alkene, carbon dioxide and an alkoxide having a secondary or tertiary carbon atom directly bound to a [O?] group is described. The alcohol byproduct is distilled off after an intermediate phase separation. This provides pure ?,?-ethylenically unsaturated carboxylic acid salt at minimum effort.Type: GrantFiled: May 9, 2016Date of Patent: November 27, 2018Assignee: BASF SEInventors: Thomas Schaub, Nuria Huguet Subiela, Rocco Paciello, Donata Maria Fries, Simone Manzini
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Patent number: 10125081Abstract: Provided is a production method whereby corresponding carboxylic acid anhydrides and carboxylic acid esters can be obtained at high yield from various carboxylic acids even without a solvent and near room temperature. A method for producing a carboxylic acid anhydride represented by formula (II), the method comprising reacting a compound represented by formula (I) and a carboxylic acid in the presence of a Group II metal compound having an ionic ligand containing an oxygen atom. A method for producing a carboxylic acid ester, the method comprising reacting a carboxylic acid anhydride produced by the aforementioned method and an alcohol. In formula (I), R1 represents a C1-20 hydrocarbon group. In formula (II), R2 represents a C1-20 hydrocarbon group.Type: GrantFiled: June 4, 2015Date of Patent: November 13, 2018Assignee: Mitsubishi Chemical CorporationInventors: Akihiro Goto, Yoshihiro Kamon
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Patent number: 10124321Abstract: A carbon nitride heterogeneous catalyst containing rhodium, a method for preparing the catalyst, and a method for preparing acetic acid using the catalyst is disclosed. The heterogeneous catalyst is characterized in that the rhodium metal is contained in carbon nitride which is a support insoluble in a liquid solvent, such as water or alcohol. Thus, the catalyst can easily be separated from a resulting product even by a simple process such as filtration. Accordingly, the carbon nitride heterogeneous catalyst exhibits excellent long-term stability and activity by being capable of overcoming the disadvantages of the method using a conventional homogeneous catalyst and minimizing the phenomenon of rhodium leaching, compared to the results of the conventional homogeneous catalytic reactions. The catalyst can thus be effectively used for the preparation of acetic acid by a carbonylation reaction between methanol and carbon monoxide.Type: GrantFiled: January 26, 2018Date of Patent: November 13, 2018Assignee: Korea Research Institute of Chemical TechnologyInventors: Jong Wook Bae, Tae Sun Chang, Beom Sik Kim, Jae Hyun Park, Ji Soo Nam
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Patent number: 10106487Abstract: The present invention relates to a simple one step oxidative dehydrogenation process for the synthesis of alkyl pyruvate with 100% selectivity towards alkyl pyruvate comprising reacting an alkyl lactate in the presence of catalyst at the temperature ranging from 25-100° C. for the time period ranging from 5 to 40 hours in an organic solvent and hydrogen peroxide to afford alkyl pyruvate.Type: GrantFiled: June 10, 2016Date of Patent: October 23, 2018Assignee: COUNCIL OF SCIENTIFIC & INDUSTRIAL RESEARCHInventors: Shubhangi Bhalchandra Umbarkar, Mohan Keraba Dongare, Swati Laxmikantrao Pandhare, Sonali Balasaheb Khomane, Dhananjay Shahauraj Doke
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Patent number: 10100007Abstract: A continuous flow process for the preparation of one or more esters of lactic acid and 2-hydroxy-3-butenoic acid or ?-hydroxy methionine analogs from a sugar in the presence of a solid Lewis acid catalyst and a solvent comprising an organic solvent and water. The invention provides a means for stabilizing a Lewis acid catalyst for use in a continuous reaction process wherein the water is present in an amount of up to or equal to 10 vol. % of the organic solvent.Type: GrantFiled: November 12, 2015Date of Patent: October 16, 2018Assignee: Haldor Topsoe A/SInventors: Irantzu Sadaba Zubiri, Esben Taarning
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Patent number: 10067113Abstract: Processes for producing acetic acid and determining corrosion therein are described herein. The processes generally include contacting methanol and carbon monoxide in the presence of a liquid reaction medium under carbonylation conditions sufficient to form acetic acid, wherein the liquid reaction medium includes: a carbonylation catalyst selected from rhodium catalysts, iridium catalysts and palladium catalysts; from 1 wt. % to 14 wt. % water; and one or more, in-situ generated derivatives of the one or more additives and combinations thereof; wherein the one or more additives are independently selected from non-benzoyl containing pentavalent phosphine oxides, compound mixtures of at least four phosphine oxides and pentavalent aryl or alkaryl phosphine oxides including one or more benzoyl groups; and recovering acetic acid from the process.Type: GrantFiled: February 24, 2015Date of Patent: September 4, 2018Assignee: LyondellBasell Acetyis, LLCInventors: Noel C. Hallinan, Brian A. Salisbury, Daniel F. White, David L. Ramage
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Patent number: 10059594Abstract: In an embodiment, a method of producing phosgene in a tube reactor comprises introducing a feed comprising carbon monoxide and chlorine to a tube of the reactor, the tube having a particulate catalyst disposed therein, wherein a thermally conductive material separate from the tube contacts at least a portion of the particulate catalyst; to produce a product composition comprising phosgene, and carbon tetrachloride in an amount of 0 to 10 ppm by volume based on the volume of the phosgene.Type: GrantFiled: July 25, 2014Date of Patent: August 28, 2018Assignee: SABIC GLOBAL TECHNOLOGIES B.V.Inventors: Pankaj Singh Gautam, William E. Hollar, Jr.
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Patent number: 10011551Abstract: Catalytic process for preparing an ?,?-ethylenically unsaturated carboxylic acid salt, comprising reacting an alkene and carbon dioxide in the presence of a carboxylation catalyst and releasing the ?,?-ethylenically unsaturated carboxylic acid salt with a base, the carboxylation catalyst being a transition metal complex, which comprises a structurally constrained bidentate P,X ligand, wherein X is selected from the group consisting of P, N, O, and carbene, the P and X atom are separated by 2 to 4 bridging atoms, and wherein the bridging atoms are part of at least one 5- to 7-membered cyclic substructure. A further catalytic processes for preparing ?,?ethylenically unsaturated carboxylic acid derivatives from CO2 and an alkene is provided.Type: GrantFiled: May 13, 2015Date of Patent: July 3, 2018Assignee: BASF SEInventors: Michael Limbach, Ivana Jevtovikj, Nuria Huguet Subiela, Alvaro Gordillo, Sabine Chantal Eileen Stieber, Ronald Lindner, Miriam Bru Roig, Michael Lejkowski, Takeharu Kageyama, Stephan A. Schunk
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Patent number: 9988268Abstract: The present invention relates to novel anthraquinone derivatives, 2,6-diisohexylanthracene-9,10-dione and 2,7-diisohexyl-anthracene-9,10-dione, preferably to be used for the preparation of hydrogen peroxide, and to a process for the preparation of these anthraquinone derivatives.Type: GrantFiled: May 28, 2015Date of Patent: June 5, 2018Assignee: BASF SEInventors: Dominic Riedel, Joaquim Henrique Teles, Thomas Wurm
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Patent number: 9981903Abstract: The invention relates to a method for preparing di- or tricarboxylic esters by alkoxycarbonylation of dienes having conjugated double bonds. The method includes the steps of initially charging a diene having two conjugated double bonds, adding a phosphine ligand according to formula (I) and a catalyst precursor, adding an alcohol, feeding in CO, and heating the reaction mixture with conversion of the diene to a di- or tricarboxylic ester.Type: GrantFiled: July 17, 2017Date of Patent: May 29, 2018Assignee: EVONIK DEGUSSA GMBHInventors: Kaiwu Dong, Ralf Jackstell, Matthias Beller, Dirk Fridag, Dieter Hess, Katrin Marie Dyballa, Frank Geilen, Robert Franke