Oxidation Of Organic Compound Utilizing Gaseous Oxygen Patents (Class 568/320)
  • Patent number: 5426237
    Abstract: The present invention provides a process for the oxidation of straight-chain, branched-chain or cyclic alkanes of 1-20 carbon atoms and benzene derivatives represented by the following formulas (1)-(2). The alcohols and ketones obtained by the oxidation of the alkanes mentioned above and those by the oxidation of the benzene derivatives mentioned above represented by the following formulas (3)-(6) are important as basic starting materials in producing various chemical products including resins, such as nylon and polyester, pharmaceuticals, agricultural chemicals, perfumes, dyes, etc.
    Type: Grant
    Filed: March 24, 1994
    Date of Patent: June 20, 1995
    Assignee: Sumitomo Chemical Co., Ltd.
    Inventors: Shun-Ichi Murahashi, Yoshiaki Oda
  • Patent number: 5254326
    Abstract: Hydrogen peroxide is produced by liquid phase molecular oxidation of methyl benzyl alcohol in an oxidation zone, product hydrogen peroxide being recovered as vapor from the oxidation zone.
    Type: Grant
    Filed: March 22, 1993
    Date of Patent: October 19, 1993
    Assignee: ARCO Chemical Technology, L.P.
    Inventors: David W. Leyshon, Robert J. Jones, Robert N. Cochran
  • Patent number: 5233092
    Abstract: The invention relates to a new compound of the formular (1): ##STR1## wherein m.sub.1 =0, 1 or 2, m.sub.2 =0, 1 or 2, m.sub.1 and m.sub.2 are not to be simultaneously 0 or simultaneously 2; n.sub.1 =2-m.sub.1, n.sub.2 =2-m.sub.2 ; R=either H or alkyl with 1 to 8 carbon atoms, R'=alkyl with 1 through 18 carbon atoms, and X=H or OH.The invention also relates to the preparation thereof, the compositions containing them and the application in catalysis of oxidation of hydrocarbons, particularly in catalysis of oxidation of cyclohexane.
    Type: Grant
    Filed: January 17, 1992
    Date of Patent: August 3, 1993
    Inventor: Xiao Zaosheng
  • Patent number: 5214168
    Abstract: Epoxides are produced by an integrated process involving air oxidation of an aryl-substituted secondary alcohol, epoxidation of an olefin by the secondary alcohol oxidation product in the presence of a titanium silicalite catalyst, and generation of the secondary alcohol by hydrogenation.
    Type: Grant
    Filed: April 30, 1992
    Date of Patent: May 25, 1993
    Assignee: Arco Chemical Technology, L.P.
    Inventors: John G. Zajacek, Guy L. Crocco
  • Patent number: 5194067
    Abstract: A process is provided whereby the hydrogen peroxide-containing oxidate from methyl benzyl alcohol oxidation is extracted with water and with ethyl benzene extractive solvent and an aqueous hydrogen peroxide phase is separated from an ethyl benzene solvent phase which also contains methyl benzyl alcohol and acetophenone, the improvement being that ethyl benzene is introduced into the extraction zone below the point of introduction of the oxidate, thus avoiding the possibility of formation of an aqueous hydrogen peroxide phase concentrated to a hazardous degree in hydrogen peroxide in the extraction zone.
    Type: Grant
    Filed: June 29, 1992
    Date of Patent: March 16, 1993
    Assignee: Arco Chemical Technology, L.P.
    Inventors: Rajendra S. Albal, Robert N. Cochran, David W. Leyshon, Lawrence M. Candela
  • Patent number: 5149884
    Abstract: In a tube bundle reactor for carrying out catalytic organic reactions in the gas phase, comprising reaction tubes (A) arranged between tubesheets (B), the reaction tubes have an inside diameter ranging from 0.5 to 3 cm, the ratio of reaction tube length to inside diameter ranges from 2 to 10, and the reaction tubes (A) are surrounded by a fluid heat transport medium flowing in the crosswise direction; said tube bundle reactor is useful in particular in exothermic organic reactions.
    Type: Grant
    Filed: April 1, 1991
    Date of Patent: September 22, 1992
    Assignee: BASF Aktiengesellschaft
    Inventors: Karl Brenner, Wilhelm Ruppel, Otto Woerz, Klaus Halbritter, Hans-Juergen Scheiper, Werner Aquila, Hartwig Fuchs
  • Patent number: 5149880
    Abstract: Nitrogen-containing aromatic heterocyclic ligand-metal complexes and their use for the activation of hydrogen peroxide and dioxgen are disclosed. Processes whereby activated hydrogen peroxide or dioxygen are used to transform various organic substrates are also disclosed. In particular, processes for the conversion of methylenic carbons to carbonyls, for the dioxygenation of aryl olefins, acetylenes and aryl-.alpha.-diols, for the oxidation of alcohols and aldehydes and for the removal of mercaptans from gaseous streams and for the removal of hydrogen sulfide and/or mercaptans from liquid streams are disclosed.
    Type: Grant
    Filed: August 24, 1990
    Date of Patent: September 22, 1992
    Assignee: The Texas A & M University System
    Inventors: Donald T. Sawyer, Ceshing Sheu, Andrzej Sobkowiak, Hui-Chan Tung
  • Patent number: 5126490
    Abstract: A process is disclosed for the catalytic oxydation of olefins to carbonyl compounds with molecular oxygen at elevated temperatures in the presence of rhodium oxide on a support. The process is applicable to a broad variety of olefins and is not limited to special olefins and forms especially ketones in a high selectivity.
    Type: Grant
    Filed: November 28, 1990
    Date of Patent: June 30, 1992
    Assignee: Princeton University
    Inventors: Jeffrey Schwartz, H. Eric Fischer, Jeffrey W. McMillan
  • Patent number: 5118862
    Abstract: Disclosed is a process for producing an .alpha.,.beta.-unsaturated carbonyl compound represented by the formula [II]: ##STR1## wherein R.sub.1, R.sub.2, R.sub.3 and R.sub.4 each represents a hydrogen atom or a hydrocarbon residue and may be linear or may form a ring in optional combination thereof and total carbon atom number of R.sub.1, R.sub.2, R.sub.3 and R.sub.4 is 12 or less, which comprises contacting oxygen with an alkenyl compound represented by the formula [I]: ##STR2## wherein R.sub.1, R.sub.2, R.sub.3 and R.sub.4 are as defined above and X represents a trihydrocarbylsilyl group or an acyl group in the presence of a platinum group metal-supporting catalyst.
    Type: Grant
    Filed: August 27, 1990
    Date of Patent: June 2, 1992
    Assignee: Nippon Zeon Co., Ltd.
    Inventors: Toshihide Baba, Mitsuo Masai
  • Patent number: 5095143
    Abstract: A method to oxidize an oxidizable component in a liquid phase with an oxygen-containing gas is disclosed. The method comprises mixing the liquid phase and gas phase in a reactor with a rotating agitator element operated at constant power.
    Type: Grant
    Filed: June 13, 1990
    Date of Patent: March 10, 1992
    Assignee: Amoco Corporation
    Inventors: Daniel L. Heberer, Paul R. Schiller, Virginia R. Seemann, Michael J. Yerkes
  • Patent number: 5039508
    Abstract: Hydrogen peroxide is produced by liquid phase molecular oxygen oxidation of methyl benzyl alcohol, the reaction being carried out such that the oxygen absorption rate is 90% or more of the maximum at the reaction conditions and the exit gas oxygen partial pressure is not greater than 3.0, the minimum necessary to establish the maximum oxygen absorption rate.
    Type: Grant
    Filed: July 19, 1990
    Date of Patent: August 13, 1991
    Assignee: ARCO Chemical Technology, Inc.
    Inventors: Robert N. Cochran, Lawrence M. Candela
  • Patent number: 4975266
    Abstract: Hydrogen peroxide is produced by liquid phase molecular oxygen oxidation of methyl benzyl alcohol. Inhibiting impurities are removed prior to oxidation.
    Type: Grant
    Filed: December 27, 1989
    Date of Patent: December 4, 1990
    Assignee: Arco Chemical Technology, Inc.
    Inventors: Rajendra S. Albal, Robert N. Cochran, Lawrence M. Candela
  • Patent number: 4959494
    Abstract: A method for oxidizing organic compounds by contacting organic compounds with molecular oxygen in the presence of a noble metal pyrochlore having the formula:A.sub.2+x B.sub.2-x O.sub.7-ywherein A is a pyrochlore structure metal cation, and B is one or more of Ru, Rh, Ir, Os, and Pt; x and y are greater than or equal to 0 and less than or equal to 1.0, at a temperature up to about 200.degree. C.
    Type: Grant
    Filed: July 6, 1987
    Date of Patent: September 25, 1990
    Assignee: Monsanto Company
    Inventor: Timothy R. Felthouse
  • Patent number: 4950794
    Abstract: The oxidation of ethylbenzene to products comprised of ethylbenzene hydroperoxide and acetophenone is modified in order to enhance acetophenone production by reducing the alkali content of the oxidation mixture below 0.1 ppm and by incorporation of 0.05 to 2 wt. % water in the oxidation mixture.
    Type: Grant
    Filed: May 24, 1989
    Date of Patent: August 21, 1990
    Assignee: Arco Chemical Technology, Inc.
    Inventors: Lawrence M. Candela, Robert N. Cochran, Scott H. Sandler
  • Patent number: 4897252
    Abstract: Hydrogen peroxide is produced by liquid phase molecular oxygen oxidation of methyl benzyl alcohol, water concentration in the reaction mixture being maintained below 4% by weight, more preferably below 2% by weight, and most preferably below 1% by weight.
    Type: Grant
    Filed: January 10, 1989
    Date of Patent: January 30, 1990
    Assignee: Arco Chemical Technology, Inc.
    Inventors: Robert N. Cochran, Lawrence M. Candela
  • Patent number: 4897085
    Abstract: A process is provided whereby the hydrogen peroxide-containing oxidate from methyl benzyl alcohol oxidation is contacted with ethyl benzene extractive solvent and a hydrogen peroxide phase is separated from a solvent phase which also contains methyl benzyl alcohol and acetophenone.
    Type: Grant
    Filed: January 10, 1989
    Date of Patent: January 30, 1990
    Assignee: Arco Chemical Technology, Inc.
    Inventors: Robert N. Cochran, Lawrence M. Candela
  • Patent number: 4847421
    Abstract: A substantially chloride-free palladium oxidation system, comprising a palladium component, a copper component, and a ligand is described. The Wacker system, consisting of palladium and copper chlorides is also improved by the addition of a ligand. The palladium and copper counterion are independently selected from BF.sub.4.sup.--, CF.sub.3 COO.sup.--, CH.sub.3 COO.sup.--, SO.sub.4.sup..dbd., and NO.sub.3.sup.--. The ligand is preferably a nitrile-containing compound.
    Type: Grant
    Filed: January 29, 1988
    Date of Patent: July 11, 1989
    Assignee: Catalytica, Associates
    Inventors: Janis Vasilevskis, Paul L. Ridgway, Eric R. Evitt
  • Patent number: 4839323
    Abstract: Insoluble complex oxidation catalysts comprising chromium salts bound on an insoluble polymer supports having pendant pyridine groups, that are useful in oxidation reactions such as Tetralin.RTM. to .alpha.-tetralone, ethylbenzene to acetophenone, and 2-methyl-5-ethylpyridine to 2-methyl-5-acetylpyridine. Also disclosed are processes for accomplishing such oxidations utilizing such catalysts.
    Type: Grant
    Filed: November 2, 1987
    Date of Patent: June 13, 1989
    Assignee: Reilly Tar & Chemical Corporation
    Inventors: Gerald L. Goe, Thomas D. Bailey, James R. Beadle
  • Patent number: 4822527
    Abstract: A process is disclosed for producing cyclized aromatic compounds by the liquid-phase air oxidation of 2-methyl-substituted biphenyls and diphenylmethanes in an acetic acid medium in the presence of a cobalt-manganese-bromine catalyst or a zirconium-cobalt-manganese-bromine catalyst wherein the mole ratio of cobalt-to-manganese is about 1.0:0.1 to about 1.0:10.0 and the ratio of zirconium-to-cobalt is about 0.005:1.0 to about 0.20:1.0, and mole ratio of bromine to total metals of said cobalt-manganese-bromine catalyst or zirconium-cobalt-manganese-bromine catalyst is from about 0.2:1.0 to about 20.0:1.0, which process comprises conducting the reaction in a batch process at a temperature of from 75.degree. C. to about 250.degree. C. at a pressure of from 1 to 100 atmospheres, or continuously in two stages comprising a first-stage reaction at a temperature of about 75.degree. C. to about 200.degree. C. and a second-stage reaction at a temperature of about 150.degree. C. to about 250.degree. C.
    Type: Grant
    Filed: December 14, 1987
    Date of Patent: April 18, 1989
    Assignee: Amoco Corporation
    Inventors: David E. James, Neal R. Nowicki
  • Patent number: 4816606
    Abstract: Aldehydes and ketones of the general formula I ##STR1## where R.sup.1 is hydrogen or an organic radical of 1 to n carbon atoms and R.sup.2 is a non-aromatic organic radical of 1 to m carbon atoms, (m+n) ranging from 2 to 24 and R.sup.1 and R.sup.2 being combinable to form a 4- to 12-membered ring, are prepared in a continuous manner by oxidizing an alcohol of the general formula II ##STR2## with oxygen or an oxygen-containing gas at elevated temperatures in the gas phase in the presence of a catalyst, by effecting the oxidation by means of a supported catalyst composed of an inert carrier having a smooth surface and from 0.1 to 20% by weight, based on the amount of carrier, of an active layer of copper, silver and/or gold in a tubular reactor or tube bundle reactor where the internal diameter D of the tube or tubes ranges from 10 to 50 mm and the largest diameter d of the coated supported catalysts is subject to the relationship d=from 0.1 to 0.2 D.
    Type: Grant
    Filed: September 30, 1987
    Date of Patent: March 28, 1989
    Assignee: Basf Aktiengesellschaft
    Inventors: Karl Brenner, Manfred Eggersdorfer, Wilhelm Ruppel, Harald Schultheiss, Hans-Ulrich Scholz
  • Patent number: 4806671
    Abstract: Substituted acenaphthenes and their use as inhibitors of phospholipase A.sub.2 are provided. The acenaphthenes have the formula ##STR1## wherein R.sup.1 is H or alkyl;R.sup.2 is alkyl, cycloalkyl, or aryl; andR.sup.1 and R.sup.2 taken together are various aryl groups optionally substituted; andA is .dbd.O, .dbd.CH.sub.2 and derivatives thereof, ##STR2## and derivatives thereof, or .dbd.NOH and derivatives thereof.
    Type: Grant
    Filed: May 7, 1986
    Date of Patent: February 21, 1989
    Assignee: E. I. Du Pont de Nemours and Company
    Inventors: William C. Ripka, William J. Sipio
  • Patent number: 4804501
    Abstract: A process is disclosed for producing cyclized aromatic compounds by the liquid-phase air oxidation of 2-methyl-substituted biphenyls and diphenylmethanes in an acetic acid medium in the presence of a cobalt-manganese-bromine catalyst or a zirconium-cobalt-manganese-bromine catalyst wherein the mole ratio of cobalt-to-manganese is about 1.0:0.1 to about 1.0:10.0 and the ratio of zirconium-to-cobalt is about 0.005:1.0 to about 0.20:1.0, and mole ratio of bromine to total metals of said cobalt-manganese-bromine catalyst or zirconium-cobalt-manganese-bromine catalyst is from about 0.2:1.0 to about 20.0:1.0, which process comprises conducting the reaction in a batch process at a temperature of from 75.degree. C. to about 250.degree. C. at a pressure of from 1 to 100 atmospheres, or continuously in two stages comprising a first-stage reaction at a temperature of about 75.degree. C. to about 200.degree. C. and a second-stage reaction at a temperature of about 150.degree. C. to about 250.degree. C.
    Type: Grant
    Filed: April 25, 1988
    Date of Patent: February 14, 1989
    Assignee: Amoco Corporation
    Inventors: David E. James, Neal R. Nowicki
  • Patent number: 4769464
    Abstract: The invention relates to a process for the preparation of monocarbonyl or biscarbonyl compounds by reacting organic carbon compounds having one or more olefinic or aromatic double bonds in the molecule with the equivalent amount of ozone and by subsequently catalytically hydrogenating the ozonization products, wherein the peroxide-containing ozonization solution is fed continuously into a suspension of the hydrogenation catalyst in a lower aliphatic alcohol, while a peroxide content of not more than 0.1 mole/l is maintained, and the ozonization products are continuously cleaved reductively to give the corresponding carbonyl compounds.
    Type: Grant
    Filed: December 17, 1984
    Date of Patent: September 6, 1988
    Assignee: Chemie Linz Gesellschaft m.b.H.
    Inventor: Alexander Sajtos
  • Patent number: 4753911
    Abstract: Insoluble complex oxidation catalysts comprising chromium salts bound on an insoluble polymer supports having pendant pyridine groups, that are useful in oxidation reactions such as Tetralino.RTM. to .alpha.-tetralone, ethylbenzene to acetophenone, and 2-methyl-5-ethylpyridine to 2-methyl-5-acetylpyridine. Also disclosed are processes for accomplishing such oxidations utilizing such catalysts.
    Type: Grant
    Filed: November 24, 1986
    Date of Patent: June 28, 1988
    Assignee: Reilly Tar and Chemical Corp.
    Inventors: Gerald L. Goe, Thomas D. Bailey, James R. Beadle
  • Patent number: 4560804
    Abstract: An improved process is provided for forming ketones from the corresponding olefins by vapor phase oxidation of the olefin in the presence of water vapor, and optionally in the additional presence of molecular oxygen employing a heterogeneous catalyst comprising at least one member selected from the group consisting of Ce, Nd and La and compounds and complexes thereof, optionally containing at least one metal compound or complex selected from the group consisting of Group VIB metals and Group VIII noble metals, and mixtures thereof. It has been surprisingly found that these catalysts effect the formation of ketones in high selectivities with minimal selectivities to the undesirable carbon dioxide and carbon monoxide by-products.
    Type: Grant
    Filed: July 25, 1983
    Date of Patent: December 24, 1985
    Assignee: Exxon Research & Engineering Co.
    Inventors: Chuen Y. Yeh, Charles Savini
  • Patent number: 4560803
    Abstract: An improved process is provided for forming ketones from the corresponding olefins by vapor phase oxidation of the olefin in the presence of molecular oxygen and water vapor employing a heterogeneous catalyst comprising rhenium compounds and complexes, optionally containing at least one metal compound or complex selected from the group consisting of Group VIB metals and Group VIII noble metals, and mixtures thereof. It has been surprisingly found that these catalysts effect the formation of ketones in high selectivities with minimal selectivities to the undesirable carbon dioxide and carbon monoxide by-products.
    Type: Grant
    Filed: July 25, 1983
    Date of Patent: December 24, 1985
    Assignee: Exxon Research & Engineering Co.
    Inventors: Chuen Y. Yeh, Charles Savini
  • Patent number: 4400558
    Abstract: The present invention provides a novel method for recovering 2-phenylethanol which is produced as a by-product of non-catalytic air oxidation of ethylbenzene, and as a by-product, in the ethylbenzene hydroperoxide epoxidation of an olefinically unsaturated compound, e.g., propylene, to the corresponding alkylene oxide, e.g., propylene oxide. In such processes, 2-phenylethanol accumulates in a process stream typically comprising major proportions of methylbenzyl alcohol, ethylbenzene, alkylene oxide and acetophenone. Conventional distillation-separation procedures may remove most of the alkylene oxide and ethylbenzene, leaving a process stream which is eventually used for styrene monomer production which contains minor amounts, i.e., less than about 20 weight percent, of 2-phenylethanol.
    Type: Grant
    Filed: April 17, 1981
    Date of Patent: August 23, 1983
    Assignee: Atlantic Richfield Company
    Inventors: Margaret I. Nemet-Mavrodin, John F. White
  • Patent number: 4322562
    Abstract: An oxidation process in which a metal nitro complex transfers an oxygen atom from the nitro ligand to a substrate; especially such process conducted cyclically or catalytically using molecular oxygen as the oxygen source. Metal nitrosyl complex is formed as a coproduct together with an oxidation product of the substrate. In a cyclic process, nitrosyl ligand of the metal nitrosyl coproduct is reoxidized by molecular oxygen in presence of a monodentate base such as pyridine to nitro ligand; and the nitro complex, thus regenerated, can be used again to oxidize the substrate. In a catalytic process, using an activator such as a Lewis acid with alcohols or divalent palladium with olefins, elemental oxygen maintains a concentration of nitro ligand in the reaction mixture. In particular the metal is a Group VIII metal, especially cobalt and the ligand is saloph or tetraphenylporphyrin.
    Type: Grant
    Filed: December 19, 1980
    Date of Patent: March 30, 1982
    Assignee: Allied Corporation
    Inventors: Benjamin S. Tovrog, S. Elliot Diamond, Frank Mares
  • Patent number: 4271320
    Abstract: An industrially suitable process for producing a higher carbonyl compound by the oxidation of an olefinic compound having at least six carbon atoms is provided. Said improved process comprises oxidizing the olefinic compound in aqueous medium containing palladium or salt thereof and a copper salt in the presence of a specific water-soluble polyoxyalkylene compound in an amount of from about 1/4 to about 3 parts by weight per 1 part by weight of water contained in the reaction mixture. The improvement is demonstrated in terms of yield, selectivity, separation of the product, and recycle of the catalyst.
    Type: Grant
    Filed: August 31, 1979
    Date of Patent: June 2, 1981
    Assignee: Kuraray Co., Ltd.
    Inventors: Yasuo Tokitoh, Noriaki Yoshimura, Masuhiko Tamura
  • Patent number: 4269788
    Abstract: Cyclohexadiene derivatives of the formula ##STR1## wherein R.sup.1,R.sup.2,R.sup.3 and R.sup.4 are as hereinafter set forth, are described. The compounds of formula I are useful as analgesic agents.
    Type: Grant
    Filed: October 4, 1979
    Date of Patent: May 26, 1981
    Assignee: Hoffmann-La Roche Inc.
    Inventors: Peter M. Muller, Rudolf Pfister, Rene Urban
  • Patent number: 4225728
    Abstract: Equimolar amounts of vinyl acetate and phenol may be prepared by oxidation of ethyl benzene. The catalytic oxidation, of ethyl benzene, when carried out in the presence of acetic anhydride, forms phenyl acetate and ethylidene diacetate. Pyrolysis of these two intermediates yields vinyl acetate and phenol.In a further embodiment of this invention it has been found that persulfate promoters such as potassium persulfate, persulfuric acid, or Caro's dry acid are particularly effective promoters for this oxidation reaction.
    Type: Grant
    Filed: November 3, 1978
    Date of Patent: September 30, 1980
    Assignee: Suntech, Inc.
    Inventors: James E. Lyons, George Suld, Robert W. Shinn
  • Patent number: 4218401
    Abstract: Primary and secondary alcohols are oxidized to aldehydes and ketones, respectively, by passing a gaseous mixture of the alcohol and oxygen (air) over a supported catalyst of Ru, Rh, Pd, Pt, Ir or Os. The catalyst is improved by admixture with a tin compound. The support for the catalyst is preferably alumina, silicon carbide or other inert material having a low surface to weight ratio. Preferred conditions are atmospheric pressure, about 250.degree.-500.degree. C. and a space velocity of 1000-4000/hr. Preferred alcohols are isopropanol, 1-methoxy-2-propanol and ethanol.
    Type: Grant
    Filed: January 11, 1974
    Date of Patent: August 19, 1980
    Assignee: The Dow Chemical Company
    Inventor: C. Elmer Wymore