Preparing Esters By Carbonylation Patents (Class 560/206)
  • Publication number: 20150126766
    Abstract: A process for preparing 4-hydroxybutyl acrylate by transesterifying an alkyl acrylate with 1,4-butanediol in the presence of a dialkyltin oxide such that each of the alkyl groups has 4 to 8 carbon atoms, characterized in that the amount of the dialkyltin oxide is adjusted to 0.00001 to 0.01 moles per one mole of the alkyl acrylate.
    Type: Application
    Filed: October 17, 2014
    Publication date: May 7, 2015
    Applicant: OSAKA ORGANIC CHEMICAL INDUSTRY LTD.
    Inventors: Yukio Tanaka, Kohei Okamura, Toyoyuki Sugiura, Keisuke Ito, Naohiko Kawakami, Shigeaki Matsumoto, Masayoshi Matsuno
  • Publication number: 20150011749
    Abstract: Metal-accumulating plants for preparing compositions including a metal catalyst derived from the plants. The composition is substantially devoid of organic matter. Also, carrying out chemical reactions with the compositions prepared from metal-accumulating plants.
    Type: Application
    Filed: March 5, 2013
    Publication date: January 8, 2015
    Applicants: UNIVERSITE MONTPELLIER 2 SCIENCES ET TECHNIQUES, CENTRE NATIONAL DE LA RECHERCHE SCIENTIFIQUE
    Inventors: Claude Grison, Vincent Escande
  • Publication number: 20140309399
    Abstract: The methods of the present invention comprise the steps of: providing a feedstock stream comprising an epoxide and carbon monoxide; contacting the feedstock stream with a metal carbonyl in a first reaction zone to effect conversion of at least a portion of the provided epoxide to a beta lactone; directing the effluent from the first reaction zone to a second reaction zone where the beta lactone is subjected to conditions that convert it to a compound selected from the group consisting of: an alpha beta unsaturated acid, an alpha beta unsaturated ester, an alpha beta unsaturated amide, and an optionally substituted polypropiolactone polymer; and isolating a final product comprising the alpha-beta unsaturated carboxylic acid, the alpha-beta unsaturated ester, the alpha-beta unsaturated amide or the polypropiolactone.
    Type: Application
    Filed: October 25, 2012
    Publication date: October 16, 2014
    Applicant: Novomer, Inc.
    Inventors: Richard V. Porcelli, Jay J. Farmer, Robert E. Lapointe
  • Patent number: 8586778
    Abstract: A process for the production of acetic acid and/or methyl acetate by carbonylating methanol and/or reactive derivatives thereof with carbon monoxide in the presence of a catalyst which is a mordenite which has been treated with an aqueous basic solution containing at least one of aluminate ions and gallate ions and has a silica:X2O3 molar ratio (wherein X is A1 and/or Ga) of at least 12:1.
    Type: Grant
    Filed: May 6, 2010
    Date of Patent: November 19, 2013
    Assignee: BP Chemicals Limited
    Inventors: Evert Jan Ditzel, Bogdan Costin Gagea
  • Publication number: 20120214999
    Abstract: A metal complex having a pyridylphosphine compound represented by the formula (1) and a Group 10 metal atom of the periodic table.
    Type: Application
    Filed: October 5, 2010
    Publication date: August 23, 2012
    Applicant: SUMITOMO CHEMICAL COMPANY, LIMITED
    Inventor: Masato Kawamura
  • Publication number: 20120101298
    Abstract: A process for the production of acetic acid and/or methyl acetate by carbonylating methanol and/or reactive derivatives thereof with carbon monoxide in the presence of a catalyst which is a mordenite which has been treated with an aqueous basic solution containing at least one of aluminate ions and gallate ions and has a silica:X2O3 molar ratio (wherein X is A1 and/or Ga) of at least 12:1.
    Type: Application
    Filed: May 6, 2010
    Publication date: April 26, 2012
    Inventors: Evert Jan Ditzel, Bogdan Costin Gagea
  • Publication number: 20090216041
    Abstract: A continuous carbonylation process for high turnover carbonylation, and a carbonylation reaction medium and product stream thereof. The process comprises carbonylating an ethlenically unsaturated compound with carbon monoxide in the presence of a source of hydroxyl groups and a catalyst system. The catalyst system comprising: (a) a bidentate phosphine, arsine or stibine ligand; and (b) a catalytic metal selected from a group VIB or group VIIIB metal or a compound thereof. The catalytically active concentration of said catalytic metal, measured as the ACCF (product Kg·hr?1·Dm?3), is maintained at less than 0.5.
    Type: Application
    Filed: August 4, 2006
    Publication date: August 27, 2009
    Applicant: LUCITE INTERNATIONAL UK LIMITED
    Inventors: Graham Ronald Eastham, Neil Tindale
  • Publication number: 20090048411
    Abstract: A method for producing a mixture of ethylene and carbon monoxide by contacting ethane and an oxygen source at a temperature of at least 500° C. to produce ethylene and carbon monoxide. A method for producing an alkyl propionate by steps of: (a) contacting ethane and an oxygen source at a temperature of at least 500° C. to produce ethylene; (b) contacting an alcohol, ethylene and carbon monoxide with an ethylene carbonylation catalyst to produce the alkyl propionate; and (c) separating the alkyl propionate from byproducts and starting materials. The method further comprises condensing the alkyl propionate with formaldehyde to produce an alkyl methacrylate.
    Type: Application
    Filed: August 5, 2008
    Publication date: February 19, 2009
    Inventors: Abraham Benderly, Scott Han, Mark Anthony Silvano, Donald Lee Zolotorofe
  • Publication number: 20080281122
    Abstract: A method for preparing supported palladium-gold catalysts is disclosed. The method comprises increasing the porosity of a titanium dioxide support, impregnating the support with a palladium salt, a gold salt, and an optional alkali metal or ammonium compound, and reducing the calcined support. The resultant supported palladium-gold catalysts have increased activity in the acetoxylation.
    Type: Application
    Filed: May 11, 2007
    Publication date: November 13, 2008
    Inventor: Steven M. Augustine
  • Patent number: 7345192
    Abstract: Compositions including a conjugate of ?-difluoromethylornithine can be applied topically to reduce hair growth.
    Type: Grant
    Filed: November 10, 2005
    Date of Patent: March 18, 2008
    Assignee: The Gillette Company
    Inventors: Anwar Jardien, Roman Rariy, Gurpreet S. Ahluwalia, Douglas Shander
  • Patent number: 7297811
    Abstract: The invention provides alkene fluoroalkanol and fluorinated polyol precursors to fluoroalkanol-substituted ?,?-unsaturated esters. The fluoroalkanol-substituted ?,?-unsaturated esters are olefins that can be readily polymerized to provide fluoroalkanol-substituted polymers useful in lithographic photoresist compositions. Also provided are methods for synthesizing the alkene fluoroalkanol and fluorinated polyol precursors.
    Type: Grant
    Filed: December 4, 2003
    Date of Patent: November 20, 2007
    Assignee: International Business Machines Corporation
    Inventors: Gregory Breyta, Richard Anthony DiPietro, Daniel Joseph Dawson
  • Publication number: 20070191629
    Abstract: The invention disclosed a method for producing 3-hydroxy-propionate and 1,3-propylene glycol by using epoxide as raw material. In the method, a transitional metal cobalt catalyst and a cocatalyst for the hydroesterification reaction among epoxide, carbon monoxide, and alcohol were chosen, and a hydrogenation catalyst for hydrogenating 3-hydroxy-propionate as well as the corresponding process conditions were selected for producing 3-hydroxy-propionate and 1,3-propylene glycol.
    Type: Application
    Filed: September 6, 2006
    Publication date: August 16, 2007
    Inventors: Jing Chen, Fang Cui, Jianhua Liu, Chungu Xia, Jin Tong
  • Patent number: 7205443
    Abstract: A process for producing a fluorine-containing 2,4-diol represented by the formula [4], wherein R1 represents a hydrogen atom or an acyclic or cyclic alkyl group having a carbon atom number of 1 to 7; R2 represents an acyclic or cyclic alkyl group having a carbon atom number of 1 to 7; and R1 and R2 are optionally bonded to each other to form a ring, includes reducing a hydroxy ketone represented by the formula [3], wherein R1 and R2 are defined as above, by hydrogen in the presence of a ruthenium catalyst.
    Type: Grant
    Filed: January 26, 2005
    Date of Patent: April 17, 2007
    Assignee: Central Glass Company, Limited
    Inventors: Takeo Komata, Kei Matsunaga, Yoshiki Hirotsu, Shinya Akiba
  • Patent number: 6903231
    Abstract: Processes and apparatus for producing esters are described. The processes include: (a) providing a liquid reaction mixture comprising (i) an unsaturated carboxylic acid having a boiling point greater than water, (ii) a polyhydric alcohol, and (iii) a first polymerization inhibitor, in a reaction zone having an inner surface; (b) reacting the acid and the polyhydric alcohol to form an ester, such that a gas/vapor phase is formed comprising water of reaction; (c) removing at least a portion of the gas/vapor phase from the reaction zone to a dephlegmation zone having an inner surface; (d) partially condensing the portion of the gas/vapor phase in the dephlegmation zone such that a condensate is formed; and (e) returning the condensate to the reaction zone; wherein a second polymerization inhibitor is introduced into the dephlegmation zone such that the portion of the gas/vapor phase and/or the condensate are contacted with the second polymerization inhibitor.
    Type: Grant
    Filed: August 3, 2000
    Date of Patent: June 7, 2005
    Assignee: Cognis Deutschland GmbH & Co. KG
    Inventors: Harald Roessler, Matthias Fies, Bernhard Gutsche, Theo Stalberg
  • Patent number: 6790983
    Abstract: An integrated process for the production of vinyl acetate comprising the steps of: (a) containing in a first reaction zone a gaseous feedstock comprising essentially ethane with a molecular oxygen-containing gas in the presence of a catalyst to produce a first product stream comprising acetic acid and ethylene; (b) containing in a second reaction zone the first gaseous product stream with a molecular oxygen-containing gas in the presence of a catalyst to produce a second product stream comprising vinyl acetate; (c) separating the product stream from step (b) recovering vinyl acetate from the product stream from step (b).
    Type: Grant
    Filed: November 19, 2002
    Date of Patent: September 14, 2004
    Assignee: Celanese International Corporation
    Inventors: Sabine Zeyss, Uwe Dingerdissen, John Fritch
  • Patent number: 6531630
    Abstract: The converting of an existing methanol plant to make acetic acid is disclosed. The converted plant utilizes the steam reformer (10) to which (a) a hydrocarbon ,e.g., natural gas, or a lower alkanol, e.g., methanol, and (b) steam (water) are fed. Syngas is formed in the reformer (10). All or part of the syngas is processed to separate out carbon dioxide (24), carbon monoxide (30) and hydrogen (32), and the separated carbon dioxide (24) is fed either to the existing methanol synthesis loop (12) for methanol synthesis, or back into the feed to the reformer (10) to enhance carbon monoxide formation in the syngas (18). When a lower alkanol is fed to the reformer (10), the methanol synthesis loop (12) is shutdown and isolated from the rest of the plant.
    Type: Grant
    Filed: December 29, 2000
    Date of Patent: March 11, 2003
    Inventor: Kenneth Ebenes Vidalin
  • Patent number: 6521783
    Abstract: This invention relates in part to a processes for the conversion of a feedstock stream comprising carbon monoxide and hydrogen to a product stream comprising at least one of an ester, acid, acid anhydride and mixtures thereof. This invention also relates in part to processes for converting an alcohol and/or ether feedstock to oxygenated products, e.g., esters, acids, acid anhydrides and mixtures thereof. The processes and catalysts are especially suitable for the production of acetic acid and methyl acetate from a synthesis gas feedstock or from an alcohol and/or ether feedstock.
    Type: Grant
    Filed: July 10, 2000
    Date of Patent: February 18, 2003
    Assignee: Union Carbide Chemicals & Plastics Technology Corporation
    Inventors: Richard William Wegman, David McNeill Somerville, Barry Brent Fish, Raymond Edwin Rooks, Chinsoo Stephen Lee, Paul Frank Bryan, William J. Bartley, David Michael Anthony Minahan, Fungau Ho
  • Patent number: 6452043
    Abstract: 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: Grant
    Filed: April 5, 2000
    Date of Patent: September 17, 2002
    Assignee: Eastman Chemical Company
    Inventors: Joseph Robert Zoeller, Andy Hugh Singleton, Gerald Charles Tustin, Donald Lee Carver
  • Publication number: 20020103397
    Abstract: Methanol is reacted in presence of catalyst system comprising of an iron containing compound and a tin containing compound with or without an organic compound containing C, N, O, P, S, diamine, diketone, and or diphosphines as a ligand to produce acetic acid or methyl acetate. The reaction is effected in a solvent containing nitro or nitrile group.
    Type: Application
    Filed: January 30, 2001
    Publication date: August 1, 2002
    Applicant: Council of Scientific and Industrial Research
    Inventors: Ashutosh Anant Kelkar, Sunil Sopana Tonde, Sunil Sadashiv Divekar, Raghunath Vitthal Chaudhari
  • Patent number: 6353133
    Abstract: The retrofitting of an existing methanol or methanol/ammonia plant to make acetic acid is disclosed. The plant is retrofitted to feed carbon dioxide into a reformer to which natural gas and steam (water) are fed. Syngas is formed in the reformer wherein both the natural gas and the carbon dioxide are reformed to produce syngas with a large proportion of carbon monoxide relative to reforming without added carbon dioxide. The syngas is split into a first part and a second part. The first syngas part is converted to methanol in a conventional methanol synthesis loop that is operated at about half of the design capacity of the original plant. The second syngas part is processed to separate out carbon dioxide and carbon monoxide, and the separated carbon dioxide is fed back into the feed to the reformer to enhance carbon monoxide formation. The separated carbon monoxide is then reacted with the methanol to produce acetic acid or an acetic acid precursor by a conventional process.
    Type: Grant
    Filed: May 9, 2001
    Date of Patent: March 5, 2002
    Assignee: Acetex (Cyprus) Limited
    Inventors: Daniel Marcel Thiebaut, Kenneth Ebenes Vidalin
  • Patent number: 6274096
    Abstract: The retrofitting of an existing methanol or methanol/ammonia plant to make acetic acid is disclosed. The plant is retrofitted to feed carbon dioxide into a reformer to which natural gas and steam (water) are fed. Syngas is formed in the reformer wherein both the natural gas and the carbon dioxide are reformed to produce syngas with a large proportion of carbon monoxide relative to reforming without added carbon dioxide. The syngas is split into a first part and a second part. The first syngas part is converted to methanol in a conventional methanol synthesis loop that is operated at about half of the design capacity of the original plant. The second syngas part is processed to separate out carbon dioxide and carbon monoxide, and the separated carbon dioxide is fed back into the feed to the reformer to enhance carbon monoxide formation. The separated carbon monoxide is then reacted with the methanol to produce acetic acid or an acetic acid precursor by a conventional process.
    Type: Grant
    Filed: November 1, 1999
    Date of Patent: August 14, 2001
    Assignee: Acetex (Cyprus) Limited
    Inventors: Daniel Marcel Thiebaut, Kenneth Ebenes Vidalin
  • Patent number: 6228800
    Abstract: A noble metal-supported article which comprises a carrier and a palladium-containing metal component supported on the carrier, which article has (A) a layer in which substantially no palladium is supported in the interior of the carrier and (B) a layer in which palladium is supported in the region from the outer surface to a depth of less than 100 &mgr;m of the carrier.
    Type: Grant
    Filed: May 26, 1999
    Date of Patent: May 8, 2001
    Assignee: Asahi Kasei Kogyo Kabushiki Kaisha
    Inventors: Tatsuo Yamaguchi, Setsuo Yamamatsu, Hiroshige Okamoto
  • Patent number: 5869738
    Abstract: A carbonylation catalytic system comprises (A) a combination of (A1) a Group VIII metal source of Periodic Table of the Elements (e.g., palladium, palladium chloride) supported on a carrier, (A2) a ligand such as triphenylphosphine and (A3) an acid such as an alkylsulfonic acid, or (B) a combination of (B1) the Group VIII metal source except for palladium (e.g., a platinum compound), (B2) a ligand such as triphenylphosphine and (B3) an electron donative compound having an electron donability .DELTA..nu.D of not less than 2 (for instance, an amine such as a heterocyclic tertiary amine). The catalytic system (B) may further comprise (B4) an acid such as methanesulfonic acid.
    Type: Grant
    Filed: November 6, 1997
    Date of Patent: February 9, 1999
    Assignee: Daicel Chemical Industries, Ltd.
    Inventors: Li Rui Pan, Tomohide Ina, Kazuyuki Matsuoka
  • Patent number: 5693851
    Abstract: Process for the preparation of a mixture of alkyl pentenoates by carbonylation of butadiene in the liquid phase in the presence of an alkanol, carbon monoxide, palladium and a bidentate organic phosphorus, antimony or arsenic ligand, the bidentate ligand having as bridging group a bis(.eta.-cyclopentadienyl) coordination group of a transition metal. Preferably the transition metal is iron.
    Type: Grant
    Filed: February 2, 1996
    Date of Patent: December 2, 1997
    Assignees: DSM N.V., E. I. Du Pont de Nemours and Company
    Inventors: Otto E. Sielcken, Hans Hovenkamp
  • Patent number: 5527950
    Abstract: The invention relates to a process for the preparation of a 5-formylvalerate ester by hydroformylating a mixture of pentenoate esters in the presence of a catalyst system which catalyst system comprises a metal from group 8-10 of the Periodic Table of Elements and a mono- or multidentate organic phosphorous ligand, wherein the mixture of pentenoate esters contains less than 500 ppm hydroperoxide compounds.
    Type: Grant
    Filed: December 28, 1994
    Date of Patent: June 18, 1996
    Assignees: DSM N.V., E.I. Du Pont de Nemours & Co.
    Inventors: Carolina B. Hansen, Antonius J. J. M. Teunissen
  • Patent number: 5463095
    Abstract: A process for the production of esters, comprising allowing an olefin, carbon monoxide and an alcohol to react in the presence of hydrogen fluoride, in which the esters can be produced at high yields at a low temperature for a short period of time, the esters can be easily separated from a reaction solution, hydrogen fluoride can be recycled, the esters can be produced at a low cost, a mixture of esters can be easily produced, the kinetic viscosity of the mixture of the esters can be easily adjusted and the coloring of, and an increase in the viscosity of, the esters can be prevented.
    Type: Grant
    Filed: June 14, 1994
    Date of Patent: October 31, 1995
    Assignee: Mitsubishi Gas Chemical Company, Inc.
    Inventors: Yoshihiro Shiokawa, Tadayoshi Takefumi, Shunichi Matsumoto, Yoshifumi Sato
  • Patent number: 5240625
    Abstract: A lubricating oil additive suitable as an extreme pressure/anti-wear additive comprises the product obtainable by reacting at elevated temperature a mixture comprising (i) sulphur, (ii) at least one C.sub.10 to C.sub.100 unsaturated carboxylic acid, and (iii) at least one hydrocarbyl-substituted phenol, the amount of (iii) in the mixture being 15 to 65% w/w based on the combined weight of (i) (ii) and (iii). The reaction mixture can further comprise an olefin and/or, a mercaptan and/or a lubricating oil as a diluent. The additive is also useful as an anti-oxidant. Additive concentrates and lubricating oil compositions comprise a lubricating oil and the additives of the present invention.
    Type: Grant
    Filed: March 20, 1990
    Date of Patent: August 31, 1993
    Assignee: BP Chemicals (Additives) Limited
    Inventor: Sean P. O'Connor
  • Patent number: 5159107
    Abstract: A process for the continuous preparation of alkyl pentenoates comprises the following steps:a) reaction of a butadiene-containing C.sub.4 cut with an alkanol and carbon monoxide in the presence of a cobalt carbonyl catalyst and heterocyclic aromatic tertiary nitrogen base at from 100.degree. to 160.degree. C. and under from 100 to 1,200 bar andb) treatment of the resulting reaction mixture, at the rate at which it is obtained, in a treatment zone, at from 100.degree. to 160.degree. C. under from 250 to 1,200 bar with a residence time of from 5 to 60 minutes, substantially without back-mixing.
    Type: Grant
    Filed: October 29, 1991
    Date of Patent: October 27, 1992
    Assignee: BASF Aktiengesellschaft
    Inventors: Paul Panitz, Heinrich Reitz, Gunter Schuch, Wilfried Seyfert
  • Patent number: 5081286
    Abstract: A process for the preparation of an alkyl methacrylate, which process comprises:a) selectively removing propadiene from a C.sub.3 -mixture comprising a mixture of propyne and propadiene that has been obtained from an ethene cracker, a catalytic cracker or an LPG-dehydrogenation process, to provide a propyne feed in which the ratio of propyne to propadiene is at least about 6:1, ndb) contacting the propyene feed with carbon monoxide and an alkanol in the presence of a carboxylation catalyst.
    Type: Grant
    Filed: April 9, 1990
    Date of Patent: January 14, 1992
    Assignee: Shell Oil Company
    Inventors: Michael J. Doyle, Johan Van Gogh, Johan C. Van Ravenswaay Claasen
  • Patent number: 5003104
    Abstract: This invention involves a process for the carbonylation of a carbonylatable reactant, e.g., an alkyl ester, a dialkyl ether or mixtures thereof by reacting the same with carbon monoxide. The process comprises effecting the carbonylation in the presence of a solution of a catalyst system containing a rhodium compound, an iodide and a lithium component at a temperature of from 50.degree. C. to 400.degree. C. at a carbon monoxide partial pressure of 1 psig to 15,000 psig. Hydrogen may also be present. The invention also concerns a carbonylation catalyst system effective for the addition of carbon monoxide to a carbonylatable reactant which comprises a solution containing as essential components a rhodium containing active component, an iodide and a lithium component.
    Type: Grant
    Filed: October 31, 1988
    Date of Patent: March 26, 1991
    Assignee: BP Chemicals Limited
    Inventors: Frank E. Paulik, Arnold Hershman, Walter R. Knox, Robert G. Schultz, James F. Roth
  • Patent number: 4933467
    Abstract: Cyclic imides are prepared by reacting carbon monoxide with an ortho dihalide aromatic compound or a cis-1,2-vinyl dihalide and an amide in the presence of palladium catalyst and a base. The process is preferably conducted in the presence of a dipolar aprotic solvent as a liquid reaction medium.
    Type: Grant
    Filed: September 11, 1989
    Date of Patent: June 12, 1990
    Assignee: Eastman Kodak Company
    Inventors: Robert J. Perry, S. R. Turner
  • Patent number: 4933468
    Abstract: Amide-imides are prepared by reacting carbon monoxide with an ortho dihalide aromatic compound or a cis-1,2-vinyl dihalide having an isolated halogen function, and with an amine, in the presence of palladium catalyst and a base. The process is preferably conducted in the presence of a dipolar aprotic solvent as a liquid reaction medium.
    Type: Grant
    Filed: September 11, 1989
    Date of Patent: June 12, 1990
    Assignee: Eastman Kodak Company
    Inventors: Robert J. Perry, S. Richard Turner
  • Patent number: 4933466
    Abstract: Cyclic imides are prepared by reacting carbon monoxide with an ortho dihalide aromatic compound or a cis-1,2-vinyl dihalide and an amine in the presence of palladium catalyst and a base. The process is preferably conducted in the presence of a dipolar aprotic solvent as a liquid reaction medium.Acyclic imides are prepared by reacting CO with an activated halide and an amide (primary or secondary) in the presence of a Pd catalyst and a base.
    Type: Grant
    Filed: January 17, 1989
    Date of Patent: June 12, 1990
    Assignee: Eastman Kodak Company
    Inventors: Robert J. Perry, Sam R. Turner
  • Patent number: 4925972
    Abstract: Alkyl pentenoates are prepared by(a) reacting butadiene or a butadiene-containing hydrocarbon mixture with carbon monoxide and an alkanol in the presence of a tertiary aromatic heterocyclic nitrogen base and a cobalt carbonyl catalyst at from 80.degree. to 160.degree. C. under from 100 to 1,000 bar to obtain a reaction mixture which contains alkyl pentenoate, C.sub.6 -diester, tertiary nitrogen base, alkanol, butadiene, hydrocarbon and by-product,(b) substantially removing from the reaction mixture obtained any excess hydrocarbon, nitrogen base, alkanol and alkyl pentenoate by distillation to obtain a residue which contains cobalt carbonyl catalyst,(c) bringing the residue which contains cobalt carbonyl catalyst into contact with a mixture of carbon monoxide and hydrogen at elevated temperature and elevated pressure, and(d) recycling the residue which contains cobalt carbonyl catalyst into alkyl pentenoate synthesis stage (a).
    Type: Grant
    Filed: July 12, 1989
    Date of Patent: May 15, 1990
    Assignee: BASF Aktiengesellschaft
    Inventors: Robert Maerkl, Wolfgang Harder
  • Patent number: 4894474
    Abstract: Alkyl pentenoates are prepared by reacting butadiene with carbon monoxide and an alkanol in the presence of a cobalt carbonyl complex and a tertiary, aromatic heterocyclic nitrogen base at from 80.degree. to 160.degree. C. under from 100 to 1,000 bar in the presence of from 0.1 to 10% by volume of hydrogen, based on the amount of carbon monoxide used.
    Type: Grant
    Filed: July 29, 1988
    Date of Patent: January 16, 1990
    Assignee: BASF Aktiengesellschaft
    Inventors: Robert Maerkl, Werner Bertleff, Hans J. Wilfinger, Gunter Schuch, Wolfgang Harder, Gebhard Kuehn, Paul Panitz
  • Patent number: 4891346
    Abstract: Included is a process for redispersing catalysts wherein the catalyst metal is selected from the group consisting of ruthenium, osmium, rhodium and palladium comprising contacting the catalyst serially with (1) a reducing agent; (2) a halogen redispersing agent; and (3) a reducing agent, under conditions sufficient to redisperse the sintered catalyst. A preliminary oxygen treatment is optional. Also included are the novel catalysts such as redispersed by the foregoing process and processes in which sintered catalysts are redispersed and in which the redispersed catalysts are employed.The redispersed catalysts can have very high activity and can even have activity higher than originally found. A preferred metal is palladium and a preferred support is alumina.A preferred process for employing the redispersed catalyst is the production of .alpha.-substituted acrylate esters.
    Type: Grant
    Filed: February 25, 1986
    Date of Patent: January 2, 1990
    Assignee: The Dow Chemical Company
    Inventor: Dennis A. Hucul
  • Patent number: 4814492
    Abstract: A method for producing alkyl acrylates by reacting ethylene, CO, O.sub.2 and an alkanol in the presence of a PdCl.sub.2 /CuCl.sub.2 catalyst to produce an alkyl propionate which is passed over a base-treated zeolite catalyst to produce the alkyl acrylate.
    Type: Grant
    Filed: September 28, 1987
    Date of Patent: March 21, 1989
    Assignee: Texaco Inc.
    Inventor: Edward C. Nelson
  • Patent number: 4743705
    Abstract: The invention is a vapor phase process for the preparation of an a-substituted acrylate ester which comprises contacting a haloalkene, wherein the halogen is substituted on an olefinic carbon atom which is further substituted with a C.sub.1-10 alkyl, C.sub.3-10 cycloalkyl, C.sub.6-10 aryl, C.sub.7-10 alkaryl, C.sub.7-10 aralkyl, cyano, trihalomethyl group, with an alcohol or an ether, and carbon monoxide in the presence of a heterogeneous catalyst which comprises palladium, platinum, nickel, ruthenium or rhodium, on a support, under conditions such that an a-substituted acrylate ester and a hydrocarbyl halide is prepared wherein the catalyst productivity is 0.06 g of product per gram of catalyst per hour or greater.
    Type: Grant
    Filed: March 13, 1986
    Date of Patent: May 10, 1988
    Assignee: The Dow Chemical Company
    Inventors: Dennis A. Hucul, Kathryn A. Eickholt
  • Patent number: 4681707
    Abstract: Carboxylic acid esters are produced by reacting an unsaturated hydrocarbon, for example an olefin or an alkyne, with carbon monoxide and an alcohol in the presence of a protonic acid and as catalyst (a) at least one of the metals palladium, rhodium, ruthenium, iridium and cobalt, and (b) copper. In a modification of the invention carboxylic acids are produced by omitting the alcohol reactant and replacing it with water in an amount up to 8 mole equivalents based on the unsaturated hydrocarbon and a solvent other than an alochol, for example tetrahydrofuran.
    Type: Grant
    Filed: April 23, 1984
    Date of Patent: July 21, 1987
    Assignee: The British Petroleum Company p.l.c.
    Inventors: Howard Alper, Bertrand Despeyroux, David J. H. Smith, James B. Woell
  • Patent number: 4668816
    Abstract: High yields of aromatic, aromatic acetic and olefinic acids, esters, amides and the like are derived from a process wherein a halo-hydrocarbon is carbonylated in the presence of a palladium catalyst, a hindered amine base and phosphine in excess. The hindered amine base can comprise C.sub.3 -C.sub.10 branched alkyls, cyclic compounds, or mixtures of the above. The preferred amine is N,N-diisopropylethyl amine. The preferred catalyst is PdCl.sub.2 (PPH.sub.3).sub.2 with the excess phosphine generally supplied by a compound of the formula PR.sup.1 R.sup.2 R.sup.3 where R.sup.1, R.sup.2 and R.sup.3 are preferably phenyl.
    Type: Grant
    Filed: November 12, 1985
    Date of Patent: May 26, 1987
    Assignee: Stauffer Chemical Company
    Inventor: Ronald A. Epstein
  • Patent number: 4625049
    Abstract: A process for the preparation of carboxylic acids, alcohols, aldehydes or the secondary products thereof which comprises reacting an alcohol having from one to about twenty carbon atoms with hydrogen and carbon monoxide in the presence of a heterogeneous sulfided catalyst comprising nickel in admixture with a co-catalyst selected from the elements of Groups V-B, VI-B and the Actinide series of the Periodic Table.
    Type: Grant
    Filed: June 30, 1982
    Date of Patent: November 25, 1986
    Assignee: Chevron Research Company
    Inventor: Steven P. Current
  • Patent number: 4622416
    Abstract: A method is disclosed for the production of esters by reaction of an alkyl acyclic allylic ether such as 8-methoxy-1,6-octadiene with carbon monoxide in the presence of a halide of nickel, cobalt or iron as a catalyst and especially nickel iodide for the production of esters. Carbonylation of 8-methoxy-1,6-octadiene results in the production of methyl-3,8-nonadienoate; 2-(carbomethoxymethyl)-vinylcyclopentane; 2-(carbomethoxymethyl)-6-vinylcyclohexanone and 2-carbomethoxymethylbicyclo(3.3.0)-octan-3-one.
    Type: Grant
    Filed: April 19, 1985
    Date of Patent: November 11, 1986
    Assignee: National Distillers and Chemical Corporation
    Inventors: Ronnie M. Hanes, William D. Baugh
  • Patent number: 4613684
    Abstract: A commercially economical process for preparing a carboxylic acid ester from a carboxylic acid amide is disclosed. The process is very meritorious, since it produces neither ammonia nor ammonium sulfates. Rather, the process by-produces formamides which are very useful compounds as solvents. Further, formamide can easily be converted to hydrogen cyanide by dehydration. The process comprises reacting a carboxylic acid amide with a formic acid ester and/or methanol and carbon monoxide in the presence of a bicyclic amidine or tertiary amine catalyst and optionally in the co-existence of a metal carbonyl. An industrial process for preparing methyl methacrylate which is a materialization of the process shown above is described in detail referring to a figure.
    Type: Grant
    Filed: September 27, 1984
    Date of Patent: September 23, 1986
    Assignee: Mitsubishi Gas Chemical Company, Inc.
    Inventors: Tetsuo Aoyama, Koichi Kida, Takako Uchiyama
  • Patent number: 4586987
    Abstract: C.sub.1 -C.sub.4 -alkyl pentenoates are obtained from reaction mixtures which contain this and which are obtained by reacting butadiene, or a butadiene-containing hydrocarbon mixture, with carbon monoxide and a C.sub.1 -C.sub.4 -alkanol, in the presence of a cobalt carbonyl catalyst and a tertiary nitrogen base at elevated temperatures and under superatmospheric pressure by a process in which(a) the liquid reaction mixture freed from excess carbon monoxide is treated with hydrogen at elevated temperatures and under from 5 to 80 bar,(b) hydrocarbons are distilled off from the resulting liquid reaction mixture,(c) the C.sub.1 -C.sub.4 -alkyl pentenoate, the alkanol and the nitrogen base are then distilled off under reduced pressure, and(d) the C.sub.1 -C.sub.4 -alkyl pentenoate is obtained by fractional distillation from the distillate containing this compound, the alkanol and the tertiary nitrogen base.
    Type: Grant
    Filed: April 10, 1985
    Date of Patent: May 6, 1986
    Assignee: BASF Aktiengesellschaft
    Inventors: Heinz-Walter Schneider, Rudolf Kummer, Otto Leman, Paul Panitz
  • Patent number: 4582929
    Abstract: This invention is a process for the carbonylation of an organic halide to prepare a carbonyl-containing compound, and recovery of halogen values in a useful form which comprises(a) contacting an organic halide with carbon monoxide and an esterifying agent, a primary or secondary amine, or hydrogen gas, in an inert organic solvent in the presence of a water-insoluble tertiary amine or pyridine ring-containing compound, and a catalytic amount of a Group VIII metal catalyst, under conditions such that an organic ester, amide or aldehyde is prepared and the halide generated in the process forms a salt with tertiary amine or pyridine compound wherein the halide is bromine or iodine;(b) separating the organic ester, amide or aldehyde from the reaction mixture which contains the tertiary amine or pyridine compound-halide salt;(c) contacting the reaction mixture containing the tertiary amine or pyridine compound-halide salt mixture with a concentrated aqueous solution of an alkali metal base or alkaline earth metal b
    Type: Grant
    Filed: December 24, 1984
    Date of Patent: April 15, 1986
    Assignee: The Dow Chemical Company
    Inventor: Robert A. DeVries
  • Patent number: 4561942
    Abstract: Methyl 4-pentenoate is isolated from mixtures containing this and methyl 3-pentenoate by a process in which from 0.25 to 0.4 part by weight of water is added per part by weight of methyl 4-pentenoate, and the azeotrope of methyl 4-pentenoate and water is distilled off.
    Type: Grant
    Filed: March 28, 1985
    Date of Patent: December 31, 1985
    Assignee: BASF Aktiengesellschaft
    Inventors: Heinz-Walter Schneider, Rudolf Kummer, Dieter Zimmerling
  • Patent number: 4550195
    Abstract: A process for the manufacture of pent-3-enoic acid and its alkyl esters, of the general formulaCH.sub.3 --CH.dbd.CH--CH.sub.2 --CO--ORwhere R is hydrogen or alkyl of 1 to 4 carbon atoms, comprising carbonylating butadiene with carbon monoxide and a compound ROH at from 300 to 1,000 bars CO pressure and from 100.degree. to 160.degree. C. in the presence of cobalt catalysts and nitrogen bases, wherein C.sub.4 cuts are used as starting materials and a tertiary amine having a pK.sub.A of from 3 to 11 is used as the nitrogen base. The pent-3-enoic acid or alkyl esters produced may be used for the manufacture of adipic acid or its alkyl esters, which compounds are starting materials for the manufacture of nylons.
    Type: Grant
    Filed: August 21, 1981
    Date of Patent: October 29, 1985
    Assignee: BASF Aktiengesellschaft
    Inventors: Rolf Platz, Rudolf Kummer, Heinz-Walter Schneider, Kurt Schwirten
  • Patent number: 4540811
    Abstract: A carboxylic acid esters, such as methyl propionate, is prepared by carbonylation of an olefin, such as ethylene, in the presence of an alcohol by the use of a molybdenum-nickel-alkali metal, a tungsten-nickel-alkali metal or a chromium nickel-alkali metal co-catalyst and in the presence of a halide.
    Type: Grant
    Filed: September 30, 1982
    Date of Patent: September 10, 1985
    Assignee: The Halcon SD Group, Inc.
    Inventor: Nabil Rizkalla
  • Patent number: 4480121
    Abstract: The invention is a process for preparing a 2-halo-1-alkene comprising contacting a hydrocarbon stream with a hydrogen halide, in the presence of water and an effective amount of a catalyst, at a temperature between about 20.degree. C. and about 400.degree. C., wherein; the hydrocarbon stream comprises a 1,2-diene, a terminal acetylene or mixtures thereof, represented by the formulas CH.sub.2 .dbd.C.dbd.CH--R or CH.tbd.C--CH.sub.2 --R wherein R is hydrogen, alkyl, cycloalkyl or aryl and may be substituted or unsubstituted; the water is present in an amount capable of maintaining the selectivity of the catalyst for the insertion of the halide on the 2 carbon of the 1,2-diene or terminal acetylene; and the catalyst comprises carbon, silica alumina, aluminosilicates, silica gel, silica, silica magnesia, silicalite, group IIIA, IIIB, IVA, IVB or V metal oxides or rare earth oxides.
    Type: Grant
    Filed: August 26, 1982
    Date of Patent: October 30, 1984
    Assignee: The Dow Chemical Company
    Inventors: Robert T. Klun, Craig B. Murchison, Dennis A. Hucul
  • Patent number: 4451667
    Abstract: This invention is a process for the preparation of acrylate esters comprising contacting a vinyl halide with carbon monoxide and an organic carbonate in the presence of an effective amount of a group VIII metal catalyst.
    Type: Grant
    Filed: August 26, 1982
    Date of Patent: May 29, 1984
    Assignee: The Dow Chemical Company
    Inventors: Robert T. Klun, Thomas W. Regulski