Preparing By Oxidation Patents (Class 568/836)
  • Patent number: 6160183
    Abstract: A catalytic process is disclosed for oxidizing cycloalkanes directly to form, in a single step, a mixture containing the corresponding alcohol and ketone. In particular, the invention relates to oxidizing a cycloalkane by contacting it with a source of oxygen and a catalytic amount of a heterogeneous catalyst. The catalysts of the invention include gold (including gold sol-gel compounds) and sol-gel compounds containing particular combinations of Cr, Co, Zr, Ta, Si, Mg, Nb, Al and Ti, wherein certain of those metals have been combined with an oxide, such as an inorganic matrix of hydroxides or oxides, or combinations thereof. The catalysts may also optionally be supported on a suitable support member.
    Type: Grant
    Filed: February 8, 1999
    Date of Patent: December 12, 2000
    Assignee: E. I. du Pont de Nemours and Company
    Inventors: Joe Douglas Druliner, Norman Herron, Kostantinos Kourtakis
  • Patent number: 6143927
    Abstract: This invention relates to methods for controlling the oxidation of hydrocarbons to intermediate oxidation products, such as adipic acid for example, by removing the catalyst from the reaction mixture, outside the reaction zone, after the oxidation has taken place at least partially. The catalyst is at least partially precipitated by reducing the water level in the reaction mixture and subjecting the reaction mixture to a temperature, at which or over which catalyst precipitates.
    Type: Grant
    Filed: March 12, 1999
    Date of Patent: November 7, 2000
    Assignee: RPC Inc.
    Inventors: Mark W. Dassel, Ader M. Rostami, David C. DeCoster, Eustathios Vassiliou
  • Patent number: 6075169
    Abstract: In a process for preparing oxidation products of cyclohexane by catalytic oxidation with oxygen-containing gases in the liquid phase, where the gases are brought into contact essentially uniformly with the liquid cyclohexane in a reaction zone, liquid cyclohexane and the oxygen-containing gases are passed in countercurrent through the reaction zone.
    Type: Grant
    Filed: April 14, 1999
    Date of Patent: June 13, 2000
    Assignee: BASF Aktiengesellshcaft
    Inventors: Alwin Rehfinger, Martin Gann, Robert Markl, Rudiger Schmitt
  • Patent number: 6075170
    Abstract: This invention relates to a process for preparing cyclohexanol and cyclohexanone, in particular, to a process for preparing cyclohexanol and cyclohexanone by selectively oxidizing cyclohexane with Fe/Pd catalyst in a flow of hydrogen and oxygen gases in the mixture of acetone and acetic acid.
    Type: Grant
    Filed: September 1, 1998
    Date of Patent: June 13, 2000
    Assignee: Korea Research Institute of Chemical Technology
    Inventors: Ki Won Jun, Sang Bum Kim, Seong Bo Kim, Kyu Wan Lee
  • Patent number: 6037491
    Abstract: This invention relates to methods and devices of preparing acids, such as adipic acid for example, by oxidizing a hydrocarbon, such as cyclohexane for example, with a gas containing an oxidant, preferably oxygen. A respective hydrocarbon is reacted, preferably at a steady state, with a gaseous oxidant to form an acid in a liquid mixture which preferably contains a solvent, a catalyst, water, and an initiator. The ratio of solvent to hydrocarbon may be controlled in a manner to maintain in the reaction zone maximum reaction rate and/or reactivity, or reaction rate and/or reactivity within a desired range, or reaction rate and/or reactivity directed toward a desired range. In addition, the ratio of solvent to hydrocarbon is controlled in a manner to maintain in the reaction zone substantially maximum selectivity and/or yield, or selectivity and/or yield within a desired range, or selectivity and/or yield directed toward a desired range.
    Type: Grant
    Filed: July 25, 1997
    Date of Patent: March 14, 2000
    Assignee: RPC Inc.
    Inventors: Eustathios Vassiliou, Mark W. Dassel, Sharon M. Aldrich, Ader M. Rostami, David C. DeCoster
  • Patent number: 6008415
    Abstract: Cyclohexane is catalytically oxidized to produce cyclohexanol and cyclohexanone and precursors of these products. The oxidation is carried out in a liquid oxidation reactor at high oxygen concentrations (greater than 30% and preferably greater than 90% oxygen concentration) and at relatively low temperatures (less than 160.degree. C.). The use of the liquid oxidation reactor permits the use of these high oxygen concentrations without forming dangerously high levels of oxygen in the overhead gas phase. The result is an increased yield and selectivity of the desired products.
    Type: Grant
    Filed: July 10, 1998
    Date of Patent: December 28, 1999
    Assignee: ABB Lummus Global Inc.
    Inventors: Marvin I. Greene, Charles Summer, Robert J. Gartside
  • Patent number: 6002026
    Abstract: The present invention relates to novel oxidative processes for substrates such as olefins, alkanes, aromatics and alcohols using metallic porphyrin or salen catalytic complexes which have been specifically designed to maximize catalytic activity, thereby enhancing efficiency, selectively and speed of oxidation of these substrates. The choice of the substituents in the metallic complexes may be varied, but must be chosen to prevent specific ligand set arrangements known to be stable and therefore less catalytically efficient. Coordination complexes, particularly porphyrins and salens having nitrosyl axial ligands and electron-withdrawing peripheral substituents are preferred. Ruthenium coordination metals are the preferred metal center, with the highly reactive catalytic species found to be Ru.sup.III.
    Type: Grant
    Filed: December 5, 1996
    Date of Patent: December 14, 1999
    Assignee: The Trustees of Princeton University
    Inventors: John T. Groves, Tommaso Carofiglio, Marcella Bonchio, Anthony Sauve
  • Patent number: 5981420
    Abstract: A substrate (e.g., a cycloalkane, a polycyclic hydrocarbon, an aromatic compound having a methyl group) is oxidized with oxygen in the presence of an oxidation catalytic system comprising an imide compound of the following formula (1) (e.g., N-hydroxyphthalimide) and a co-catalyst containing a element selected from Group 3 to 12 elements (in particular, Group 4 to 11 elements) of the Periodic Table of Elements. The co-catalyst comprises a compound containing plural elements (except heteropolyacid and a combination of Group 7 and 8 elements of the Periodic Table of Elements), and is useful for the formation of an oxide (e.g., a ketone, an alcohol, a carboxylic acid): ##STR1## wherein R.sup.1 and R.sup.2 represent a substituent such as a hydrogen atom or a halogen atom, or R.sup.1 and R.sup.2 may together form a double bond or an aromatic or nonaromatic 5- to 12-membered ring, X is O or OH, and n is 1 to 3.
    Type: Grant
    Filed: February 17, 1998
    Date of Patent: November 9, 1999
    Assignees: Daicel Chemical Industries, Ltd., Yasutaka Ishii
    Inventors: Tatsuya Nakano, Yasutaka Ishii
  • Patent number: 5892122
    Abstract: An improved method for making cyclohexanone and cyclohexanol from oxidation of cyclohexane in which a polyprotic acid is used to neutralize caustic to prevent oligomerization of cyclohexanone during fractional distillation.
    Type: Grant
    Filed: August 25, 1997
    Date of Patent: April 6, 1999
    Assignee: E. I. du Pont de Nemours and Company
    Inventors: John Joseph Ostermaier, George Crumbaugh Russell, III
  • Patent number: 5817868
    Abstract: Methods and devices for controlling the oxidation of a hydrocarbon to an acid by regulating the temperature, hold-up time, and conversion in consecutive reaction zones. The temperature in the consecutive reaction zones progressively decreases, while the hold-up time increases. Preferably, the conversion also increases. One of the major advantages of the methods and devices of the present invention is that an outstanding balance between productivity and selectivity/yield of the desired acid may be achieved. In this respect high yields and selectivities may be obtained without sacrificing productivity.
    Type: Grant
    Filed: May 21, 1997
    Date of Patent: October 6, 1998
    Assignee: Twenty-First Century Research Corporation
    Inventors: Ader M. Rostami, Mark W. Dassel, Eustathios Vassiliou, David C. DeCoster
  • Patent number: 5811599
    Abstract: A process for the oxidation of hydrocarbons and their derivatives having the general formula RX, wherein R is from n-alkyl, iso-alkyl, benzyl, cyclohexyl, mono, di or tricyclic aryl, or alkenic groups and X is selected from H, OH or Cl to compounds having formula R.sup.1 XY wherein R.sup.1 =(R--H), X has the meaning defined as above and Y=OH; which comprises of reacting the appropriate hydrocarbon or it's derivative of the formula RX where R and X have the meaning given above, with a solution of aqueous hydrogen peroxide at a temperature in the range of 10.degree.-100.degree. C. in the presence of an amorphous titanium-silicate catalyst having molar chemical composition in terms of the anhydrous oxides of TiO.sub.2 : (5-400) SiO.sub.2, having an average micropore radius between 10 and 40 .ANG., an absorption band around 220 nm in the ultraviolet region, a band around 960 cm.sup.-1 in the infrared region, interatomic vectors around 1.6-1.7, 2.7-2.8, 4.1-4.2 and 5.0-5.2 .ANG.
    Type: Grant
    Filed: August 2, 1995
    Date of Patent: September 22, 1998
    Inventors: Keshavaraja Alive, Ramaswamy Arumugamangalam Venkataraman, Ratnasamy Paul
  • Patent number: 5801282
    Abstract: Methods of making intermediate oxidation products by atomizing a first liquid (in the form of droplets) containing a reactant into a gas containing an oxidant in a manner to form an intermediate oxidation product different than carbon monoxide and/or carbon dioxide. The oxidation is controlled by monitoring the pre-coalescing temperature (temperature of the droplets just before they coalesce into a mass of liquid), or transient temperature difference (difference between the pre-coalescing temperature and the temperature of the droplets just before atomized), or transient conversion (conversion taking place in the time interval between the formation of the droplets and their coalescence into a mass of liquid) or a combination thereof.
    Type: Grant
    Filed: June 7, 1995
    Date of Patent: September 1, 1998
    Assignee: Twenty-First Century Research Corporation
    Inventors: Mark William Dassel, Eustathios Vassiliou
  • Patent number: 5801273
    Abstract: Methods and devices for controlling the reaction rate of a hydrocarbon to an acid or other intermediate oxidation product by pressure drop rate adjustments. The pressure drop rate measurements are conducted at predetermined time intervals, after stopping the feeding and exiting of gases. The pressure drop at a predetermined time interval is measured or the time it takes for the pressure to drop by a certain degree. Adjustments are then made in one or more temperature, feeding rates of hydrocarbon, solvent, catalyst, promoter, and the like until the pressure drop rate and the reaction rate fall within desirable predetermined limits.
    Type: Grant
    Filed: May 21, 1997
    Date of Patent: September 1, 1998
    Assignee: Twenty-First Century Research Corporation
    Inventors: Eustathios Vassiliou, Mark W. Dassel, David C. DeCoster, Ader M. Rostami, Sharon M. Aldrich
  • Patent number: 5780683
    Abstract: Cyclohexane is catalytically oxidized to produce cyclohexanol and cyclohexanone and precursors of these products. The product is then catalytically hydrogenated while the product is still at reaction temperature to produce additional cyclohexanol and cyclohexanone from the precursors. The oxidation is carried out in a liquid oxidation reactor at high oxygen concentrations (greater than 30% and preferably greater than 90% oxygen concentration) and at relatively low temperatures (less than 160.degree. C.). The use of the liquid oxidation reactor permits the use of these high oxygen concentrations without forming dangerously high levels of oxygen in the overhead gas phase. The result is an increased yield and selectivity of the desired products. The hydrogenation is carried out in a reactor using a catalyst of palladium supported on carbon.
    Type: Grant
    Filed: September 11, 1996
    Date of Patent: July 14, 1998
    Assignee: ABB Lummus Global Inc.
    Inventors: Marvin I. Greene, Charles Sumner, Robert J. Gartside
  • Patent number: 5767320
    Abstract: Cyclohexane is oxidized to a mixture of cyclohexanone and cyclohexanol by reaction with oxygen in the presence of a metal complex of phthalocyanine or porphyrin wherein some or all of the hydrogen atoms of the phthalocyanine or porphyrin have been replace by electron withdrawing groups.
    Type: Grant
    Filed: July 26, 1996
    Date of Patent: June 16, 1998
    Assignee: Council of Scientific & Industrial Research
    Inventors: Robert Raja, Paul Ratnasamy
  • Patent number: 5654475
    Abstract: Methods of making intermediate oxidation products by atomizing a first liquid (in the form of droplets) containing a reactant into a gas containing an oxidant in a manner to form an intermediate oxidation product different than carbon monoxide and/or carbon dioxide. The oxidation rate is controlled by monitoring and adjusting the temperatures and/or conversions at critical points of the process.
    Type: Grant
    Filed: March 25, 1996
    Date of Patent: August 5, 1997
    Assignee: Twenty-First Century Research Corporation
    Inventors: Eustathios Vassiliou, Mark William Dassel
  • Patent number: 5512543
    Abstract: The chiral isomers of 3,3-dimethyl-5-(2,2,3-trimethyl-3-cyclopenten-1-yl)-4-penten-2-ol and, more particularly, the (-)-(1'R,2S,E)-3,3-dimethyl-5-(2',2',3'-trimethyl-3'-cyclopenten-1'-yl)-4- penten-2-ol and (+)-(1'S,2S,E)-3,3-dimethyl-5-(2',2',3'-trimethyl-3'-cyclopenten-1'-yl)-4- penten-2-ol, are useful as perfuming ingredients to impart sandalwood type odor notes to the perfuming compositions and perfumed articles into which they are incorporated.
    Type: Grant
    Filed: August 2, 1994
    Date of Patent: April 30, 1996
    Assignee: Firmenich S.A.
    Inventors: Christian Chapuis, Antoine Gautier, Pierre-Alain Blanc
  • Patent number: 5502245
    Abstract: Methods of making intermediate oxidation products by atomizing a first liquid containing a reactant into a gas containing an oxidant in a manner to form an intermediate oxidation product different than carbon monoxide and/or carbon dioxide. The oxidation is controlled by monitoring the transient conversion (conversion taking place in the time interval between the formation of the droplets and their coalescence into a mass of liquid) of first reactant to oxidation product just before the droplets coalesce into a mass of a second liquid.
    Type: Grant
    Filed: June 7, 1995
    Date of Patent: March 26, 1996
    Assignee: Twenty-First Century Research Corporation
    Inventors: Mark W. Dassel, Eustathios Vassiliou
  • Patent number: 5489716
    Abstract: The invention provides novel methods for the oxidation of hydrocarbons with oxygen-containing gas to form hydroxy-group containing compounds and for the decomposition of hydroperoxides to form hydroxygroup containing compounds. The catalysts used in the methods of the invention comprise transition metal complexes of a porphyrin ring having 1 to 12 halogen substituents on the porphyrin ring, at least one of said halogens being in a meso position and/or the catalyst containing no aryl group in a meso position. The catalyst compositions are prepared by halogenating a transition metal complex of a porphyrin.
    Type: Grant
    Filed: September 7, 1994
    Date of Patent: February 6, 1996
    Assignee: Sun Company, Inc. (R&M)
    Inventors: Paul E. Ellis, Jr., James E. Lyons
  • Patent number: 5463082
    Abstract: Stoichiometric and catalytic chemical transformations may be carried out in solution using novel fluorous multiphase systems (FMS). The term "fluorous" is defined as a carbon-fluorine bond rich organic molecule. The FMS consists of a fluorous phase containing a fluorous solvent, typically a fluorocarbon or a fluorohydrocarbon and a reagent or a catalyst containing a sufficient number of fluorous moieties to render it preferentially soluble in the fluorous solvent without impairing the ability of the catalyst or reagent to be effective in the reaction and while maintaining the reaction in a liquid or fluid phase. The nonfluorous solvent may be any suitable organic or nonorganic solvent(s) with limited or no solubility in the fluorous solvent that is effective for dissolving the reactant(s) and most desirably, for separating the resulting product(s). Typically, such solvents have a Hildebrand solubility parameter of at least about 18.0 MPa1/2.
    Type: Grant
    Filed: July 8, 1993
    Date of Patent: October 31, 1995
    Assignee: Exxon Research and Engineering Company
    Inventors: Istvan T. Horvath, Jozsef Rabai
  • 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: 5414157
    Abstract: Process and apparatus are provided for oxidation of oxidation of organic compounds in which a reaction zone is provided, containing an open space and a bed of solid granular catalyst, an organic feedstock and oxygen are passed in gas phase through the open space and then into contact with the catalyst bed, and reaction products are removed from the open space after relatively less contact with the catalyst, and from at least one other location after relatively greater contact with the catalyst. Greater yield of desired product may be obtained in such operation than in operation where all of the reaction products are removed after the greater contact with the catalyst.
    Type: Grant
    Filed: July 20, 1992
    Date of Patent: May 9, 1995
    Assignee: Sun Company, Inc. (R&M)
    Inventors: Vincent A. Durante, Darrell W. Walker, Steven M. Gussow, James E. Lyons, Robert C. Hayes
  • Patent number: 5406002
    Abstract: An organophosphine-treated titanium-containing zeolite is a catalyst for hydrocarbon oxidation.
    Type: Grant
    Filed: February 25, 1994
    Date of Patent: April 11, 1995
    Assignee: Exxon-Chemical Patents Inc.
    Inventors: Luc R. M. Martens, Georges M. K. Mathys
  • Patent number: 5406001
    Abstract: The present invention relates to a method for the continuous preparation of a mixture of a cycloalkanone, a cycloalkanol and a cycloalkylhydroperoxide. In the method, a cycloalkane, corresponding to the cycloalkenone, cycloalkenol and cycloalkylhydroperoxide, is oxidized in a continuous process, with the aid of an oxygen-containing gas, in the absence of a metal catalyst, at a temperature of between 130.degree. C. and 200.degree. C. The oxidation is at least partly carried out in the presence of between 0.002 and 2 mmol of a phenolic compound per kg of reaction mixture (mmol/kg).
    Type: Grant
    Filed: December 15, 1993
    Date of Patent: April 11, 1995
    Assignee: DSM N.V.
    Inventors: Johannes G. H. M. Housmans, Ubaldus F. Kragten
  • Patent number: 5233099
    Abstract: A process for producing an alcohol by continuously passing a fatty acid ester, a fatty acid triglyceride or a fatty acid through a hydrogenation catalyst to thereby produce the aimed alcohol through catalytic reduction is disclosed, wherein the employed reactor is a fixed bed reactor in which the liquid phase and the gas phase are continuously passed together in descending parallel flows through the hydrogenation catalyst fixed in the reactor; and at least one cooling mean for cooling the reaction system is provided at a position in the vertical direction of the reactor. According to the process of the present invention with the use of a fixed bed reactor, an alcohol, which has extremely high qualities and a high purity and is contaminated with little hydrocarbon and aldehyde by-products, can be produced. The process of the present invention further makes it possible to omit the post-treatment for eliminating the by-products.
    Type: Grant
    Filed: December 24, 1991
    Date of Patent: August 3, 1993
    Assignee: Kao Corporation
    Inventors: Osamu Tabata, Kunizo Hashiba, Takahiro Kawakami
  • Patent number: 5233100
    Abstract: A process for producing an alcohol from a fatty acid ester, a fatty acid triglyceride or a fatty acid by continuously catalytically reducing the starting material in the presence of a hydrogenation catalyst is disclosed. In the process of the present invention, two reactors (i.e., the main reactor located upstream and the after reactor located downstream) being located in series are employed. In the process of the present invention, two reactors are employed and the temperatures thereof are individually controlled, whereby the conversion ratio is elevated while suppressing the formation of hydrocarbon and aldehyde by-products. Thus, an alcohol of extremely high quality and high purity can be produced. Further, the process of the present invention makes it possible to omit any post-treatment for eliminating the by-products. Furthermore, the active life of the hydrogenation catalyst can be remarkably prolonged by using three reactors (i.e., the guard reactor, the main reactor and the after reactor).
    Type: Grant
    Filed: December 27, 1991
    Date of Patent: August 3, 1993
    Assignee: Kao Corporation
    Inventors: Osamu Tabata, Atsuhito Mori, Takahiro Kawakami, Kunizo Hashiba, Kiyoshi Tsukada
  • 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: 5208392
    Abstract: The present invention provides a novel Fe-Pd catalyst prepared by impregnating, either together or respectively, an iron source compound and a palladium source compound onto a carrier selected from the group consisting of silica, alumina and silica-alumina, and drying and calcining said Fe-Pd impregnated carrier in a flow of air or H.sub.2 /N.sub.2 ; and a method for preparing a mixture of cyclohexanol and cyclohexanone by selectively oxidizing cyclohexane in a reaction medium provided with hydrogen and oxygen gases in the presence of said Fe-Pd catalyst.
    Type: Grant
    Filed: April 27, 1992
    Date of Patent: May 4, 1993
    Assignee: Korea Research Institute of Chemical Technology
    Inventors: Kyu-Wan Lee, Ki-Won Jun, Eun-Kyung Shim
  • Patent number: 5175316
    Abstract: The preparation of cyclohexene oxide, cyclohexanol and cyclohexanone involvesa) oxidizing cyclohexane using a gas containing molecular oxygen to form cyclohexyl hydroperoxide, cyclohexanol and cyclohexanone,b) jointly separating the mixture from a) and c) by distillation, andc) reaction of the cyclohexyl hydroperoxide fraction from b) with cyclohexene in the presence of a transition-metal compound from group 4 to 6, forming cyclohexene oxide, and separating the product mixture in b).
    Type: Grant
    Filed: February 10, 1992
    Date of Patent: December 29, 1992
    Assignee: BASF Aktiengesellschaft
    Inventors: David Agar, Paul-Michael Bever, Hans H. Schuster, Gerald Neubauer
  • Patent number: 5168983
    Abstract: A process for separating cyclohexanol and other impurities from a mixture containing cyclohexanone and cyclohexanol is disclosed.
    Type: Grant
    Filed: March 22, 1991
    Date of Patent: December 8, 1992
    Assignee: Mitsubishi Kasei Corporation
    Inventors: Kazuo Tan, Kazuhiro Fujii, Michio Nakamura, Kazunao Hanada
  • Patent number: 5132472
    Abstract: Process is provided for oxidation of organic compounds in which a reaction zone is provided, containing an open space and a bed of solid granular catalyst, an organic feedstock and oxygen are passed in gas phase through the open space and then into contact with the catalyst bed, and reaction products are removed from the open space after relatively less contact with the catalyst, and from at least one other location after relatively greater contact with the catalyst. Greater yield of desired product may be obtained in such operation than in operation where all of the reaction products are removed after the greater contact with the catalyst.
    Type: Grant
    Filed: October 17, 1990
    Date of Patent: July 21, 1992
    Assignee: Sun Refining and Marketing Company
    Inventors: Vincent A. Durante, Darrell W. Walker, Steven M. Gussow, James E. Lyons, Robert C. Hayes
  • Patent number: 5077394
    Abstract: Disclosed are tetraphenyl porphyrins which are beta-substituted by fluoro or chloro and/or bear electronegative substituents on the phenyl including one or two water solubilizing substituents. The new porphorins are particularly suitable as catalysts in a variety of oxidative reactions and methods.
    Type: Grant
    Filed: December 21, 1989
    Date of Patent: December 31, 1991
    Assignee: Sandoz Ltd.
    Inventors: David H. Dolphin, Taku Nakano, Thomas K. Kirk, Tilak P. Wijesekera, Roberta L. Farrell, Theodore E. Maione
  • Patent number: 5068464
    Abstract: A continuous process for the partial oxidation of hydrocarbons is disclosed wherein the oxidizing gas is partitioned into the hydrocarbon by means of countercurrent flow of an aqueous solution of oxygen prepared in a separate vessel, thus avoiding direct contact of hydrocarbon and oxidizing gas.
    Type: Grant
    Filed: May 26, 1988
    Date of Patent: November 26, 1991
    Assignee: BASF Corporation
    Inventor: David C. Hendrix
  • Patent number: 5021607
    Abstract: Saturated hydrocarbon chains are oxidized using a titanium containing silicalite catalyst having an infra red absorption band around 950 cm.sup.-1 preferably in solutions, the chains may be alkanes or alkyl groups of alkyl cyclic compounds.
    Type: Grant
    Filed: September 10, 1990
    Date of Patent: June 4, 1991
    Assignee: Exxon Chemical Patents Inc.
    Inventor: Diana R. Huybrechts
  • Patent number: 4943644
    Abstract: A method of oxidizing olefins or alkanes by contacting with oxygen and a catalyst composition of the formula:Ru.sub.3 O[OCO(CF.sub.2).sub.y CF.sub.3 ].sub.6 LWherein: Ru are reuthenium atoms having a formal oxidation state of +2 or +3,L is a neutral or anionic ligand,Y is an integer from 0 to 6, andx is an integer from 1 to 3; and an anion.
    Type: Grant
    Filed: November 23, 1988
    Date of Patent: July 24, 1990
    Assignee: The University of Florida
    Inventors: Russell S. Drago, Shannon Davis
  • Patent number: 4927974
    Abstract: The invention relates to a process for preparing cyclohexanol and/or cyclohexanone, in which cyclohexene in a feed stream containing cyclohexene, cyclohexane and benzene is hydrated into cyclohexanol and/or oxidized into cyclohexanone, the cyclohexanol and/or cyclohexanone formed is separated from the reaction mixture thus obtained and the remaining cyclohexane and benzene are recycled to a preconnected cyclohexene preparation section, part of the stream that is recycled to the cyclohexene preparation section being subjected to a dehydrogenation reaction and the remaining part to a hydrogenation reaction, and the reaction streams thus obtained being combined to form the feed stream to the hydration and/or oxidation step.
    Type: Grant
    Filed: April 6, 1989
    Date of Patent: May 22, 1990
    Assignee: Stamicarbon B.V.
    Inventors: Paul C. van Geem, Franciscus T. B. van den Brink
  • Patent number: 4877903
    Abstract: Mixtures containing cyclohexanol and cyclohexanone are produced by oxidizing cyclohexane with air, and then decomposing the cyclohexyl hydroperoxide in such reaction mixture, in the presence of the cyclohexane, to form cyclohexanol and cyclohexanone, such oxidation and/or decomposition being carried out in the presence of a manganese source, a Bronsted acid and a pyridine ligand.
    Type: Grant
    Filed: November 14, 1988
    Date of Patent: October 31, 1989
    Assignee: Rhone-Poulenc Chimie
    Inventors: Michel Costantini, Francoise Igersheim
  • Patent number: 4735741
    Abstract: Solutions of molecular oxygen in liquid hydrocarbons are prepared by bringing a liquid hydrocarbon into contact with molecular oxygen under superatmospheric pressure in a vertical absorption zone, by a process in which(a) a layer of water is maintained at the lower end of the absorption zone,(b) molecular oxygen is passed into the layer of water,(c) a liquid hydrocarbon is fed in above the layer of water,(d) the finely divided molecular oxygen rising from the layer of water is passed upward together with the liquid hydrocarbon at from 0.degree. to 50.degree. C., with thorough mixing in the absorption zone, with the proviso that no cohesive gas phase is formed, and(e) the solution of molecular oxygen in the liquid hydrocarbon is discharged in the upper part of the absorption zone.
    Type: Grant
    Filed: April 23, 1986
    Date of Patent: April 5, 1988
    Assignee: BASF Aktiengesellschaft
    Inventors: Otto-Alfred Grosskinsky, Guenter Herrmann, Ulrich Loeffler, Rolf Schnabel, Dieter Stuetzer
  • Patent number: 4720592
    Abstract: The reaction mixture obtained by oxidation of cyclohexane using a cobalt catalyst is extracted with water to remove undesirable oxidation products such as diacids, hydroxy acids, and cobalt catalyst. The resulting mixture is then hydrogenated using a fixed bed hydrogenation catalyst to convert cyclohexyl hydroperoxide to cyclohexanol and cyclohexanone.
    Type: Grant
    Filed: September 5, 1986
    Date of Patent: January 19, 1988
    Assignee: E. I. Du Pont de Nemours and Company
    Inventors: Usamah N. Besmar, John B. Lyon, Francis J. Miller, Michael T. Musser
  • Patent number: 4691053
    Abstract: A novel process for producing oxygen-containing organic compounds with high selectivity and good yield by oxidizing organic compounds under mild conditions is provided, which process comprises using as a catalyst for the oxidation, a complex (M.sub.m X.sub.n.L.sub.l) consisting of a transition metal compound (M.sub.m X.sub.n) and an organic phosphorous compound (L) as a ligand, wherein M represents a transition metal belonging to group I, group IV.about.VII or iron group in group VIII of the periodic table; X represents an anion such as a halogen; ligand L represents an organic phosphorous compound; and m and n mean a number of the atomic valence of said transition metal (ion) M and said anion X, respectively, and l means a number of said ligand.
    Type: Grant
    Filed: June 4, 1984
    Date of Patent: September 1, 1987
    Assignee: Babcock-Hitachi Kabushiki Kaisha
    Inventors: Mutsuo Yamada, Yasuyuki Nishimura, Yoshijiro Arikawa, Takanori Kuwahara, Taiji Kamiguchi, Hirotoshi Tanimoto
  • Patent number: 4675450
    Abstract: Production of cyclohexyl hydroperoxide during the cobalt catalyzed oxidation of cyclohexane is enhanced by conducting the oxidation in the presence of a phosphate ester.
    Type: Grant
    Filed: November 12, 1985
    Date of Patent: June 23, 1987
    Assignee: E. I. Du Pont de Nemours and Company
    Inventors: John B. Lyon, Gerald T. Stowe
  • Patent number: 4659829
    Abstract: The invention concerns peroxide complexes of metals complying with the general formula LnMXpY, wherein M is a metal selected from groups VIII, IB and VIIB, particularly cobalt, X is an anionic group, for example carboxylate, R is an alkyl, cycloalkyl or arylalkyl group, n=1 or 2, p=0 or 1 and n+p=2.L is a tridentated ligand from the group of 1,3 bis (2-pyridylimino) isoindolines.These complexes are obtained by reaction of a hydroperoxide ROOH with a complex of formula LnMXp. They can be used in oxidizing hydrocarbons to a mixture of alcohols and ketones, either as reactants or as catalysts.They are particularly useful to prepare tert-butanol by oxidation of isobutane in liquid phase, by means of an oxygen-containing gas such as air.
    Type: Grant
    Filed: January 31, 1985
    Date of Patent: April 21, 1987
    Assignee: Institut Francais du Petrole
    Inventors: Lucien Saussine, Alain Robine, Hubert Mimoun
  • Patent number: 4658056
    Abstract: A process for the catalytic oxidation of liquid cycloparaffins to oxidation products thereof is disclosed. In the process, partial oxidation products are formed by oxidizing the cycloparaffin with molecular oxygen-containing gas in the presence of an oxidation catalyst comprising two heavy metal compounds. The first heavy metal compound is a cobalt compound having ligands selected from dialkyl phosphate, dicycloalkylphosphate and alkylcycloalkylphosphate, optionally additionally combined with pyridine. The second heavy metal compound is a chromium alkanoate. A preferred catalyst is cobalt bis[di(2-ethylhexyl)phosphate] combined with chromium naphthenate.
    Type: Grant
    Filed: April 22, 1982
    Date of Patent: April 14, 1987
    Assignee: Du Pont Canada Inc.
    Inventor: Peter A. Sipos
  • Patent number: 4609763
    Abstract: A process for the oxidation of alkanes or alkenes is described. The process uses a hydrocarbyl hydroperoxide as an oxidizing agent in combination with a ruthenium catalyst and optionally a hydrogen bromide or hydrobromide acid promoter. The products of the oxidation are alcohols, ketones or a mixture of both.
    Type: Grant
    Filed: September 3, 1985
    Date of Patent: September 2, 1986
    Assignee: The British Petroleum Company P.L.C.
    Inventors: Colin G. Griggs, Anthony R. Middleton
  • Patent number: 4587363
    Abstract: Oxygen-containing compounds are prepared by oxidizing a hydrocarbon in the liquid phase with a gas containing molecular oxygen, at elevated temperatures and under superatmospheric pressure, by a continuous process in which the said gas is fed into the liquid reaction mixture, in a downward direction, at several points along the reaction zone via nozzle apertures, so that it emerges at each nozzle aperture with a velocity of from 0.01 to 1 m/sec in an amount of from 0.001 to 10 liters per second per nozzle aperture, and the said reaction mixture is brought into substantially uniform contact with the gas containing molecular oxygen, over the volume of the reaction zone.
    Type: Grant
    Filed: August 10, 1984
    Date of Patent: May 6, 1986
    Assignee: BASF Aktiengesellschaft
    Inventors: Jurgen Hartig, Gunter Schuch, Armin Stoessel, Guenter Herrmann, Arthur Brunner, Peter Zehner, Otto-Alfred Grosskinsky
  • Patent number: 4568769
    Abstract: Disclosed in a method for producing a mixture containing cycloalkanone and/or cycloalkanol which comprises oxidizing a cycloalkane with molecular oxygen to a cycloalkyl hydroperoxide represented by the formula (1): ##STR1## (wherein m represents an integer of 4.ltoreq.m.ltoreq.11) and decomposing the cycloalkyl hydroperoxide to obtain a mixture containing cycloalkanone and/or cycloalkanol, wherein the oxidation of the cycloalkane with molecular oxygen and/or the decomposition of the cycloalkyl hydroperoxide are carried out in the presence of a catalyst composition comprising at least one metallic salt represented by the formula (2):MX.sub.n (2)(wherein M represent Co, Mn, Cr or Fe, X represents an anionic ligand and n represents 2 or 3) and at least one compound represented by the formula (3): ##STR2## (wherein R.sup.1, R.sup.2, R.sup.3 and R.sup.
    Type: Grant
    Filed: June 20, 1984
    Date of Patent: February 4, 1986
    Assignee: Sumitomo Chemical Company
    Inventors: Akira Yashima, Teruo Matsuda, Tadao Sato, Mitsuaki Takahashi, Kiyomi Sakai
  • Patent number: 4532347
    Abstract: The instant invention relates to a membrane solvent extraction and reaction system. More particularly it pertains to an improvement in the membrane solvent extraction system wherein a solute is extracted through a polymeric membrane from one solvent liquid phase to an extracting solvent liquid without direct contact between the liquid phases which are separated by the membrane and in which the extracting solvent has no greater solubility and usually substantially less solubility for the solute than the feed solvent. The impovement comprises converting the solute permeating across the membrane to a different chemical compound, whereby a high concentration gradient for the solute across the membrane is maintained to improve the separation of the solute from the feed solvent liquid phase.
    Type: Grant
    Filed: January 21, 1980
    Date of Patent: July 30, 1985
    Assignee: Varen Technology
    Inventor: Ronald J. Vaughan
  • Patent number: 4491674
    Abstract: A process for the safe supply of molecular oxygen or gas containing molecular oxygen to an oxidation of hydrocarbons in the liquid phase, wherein, immediately before the point of entry into the liquid hydrocarbon, the oxygen, or gas containing oxygen, to be supplied is at least 20.degree. C. colder than the hydrocarbon, and wherein, as soon as the oxygen, or gas containing oxygen, which is to be supplied exceeds the predetermined temperature at the supply orifice, the supply ceases.
    Type: Grant
    Filed: December 8, 1980
    Date of Patent: January 1, 1985
    Assignee: BASF Aktiengesellschaft
    Inventors: Norbert Rieber, Hans Hellbach, Gerhard Hunziker, Guenter Mueller
  • Patent number: 4459427
    Abstract: A mixture of the alcohol and ketone derivatives of alkanes is produced by reacting the alkane with a hydrocarbyl hydroperoxide, eg t-butyl hydroperoxide, at ambient or elevated temperature and pressure in the presence as catalyst of an iron or manganese square planar complex having heterocyclic nitrogen-donor ligands, e.g. a porphyrin or phthalocyanine complex, which complex has either no axial ligands, eg the lower valency or cationic complex, or an axial ligand which is non-coordinating or weakly-coordinating.
    Type: Grant
    Filed: October 26, 1982
    Date of Patent: July 10, 1984
    Assignee: The British Petroleum Company p.l.c.
    Inventors: Anthony R. Middleton, David J. H. Smith
  • Patent number: 4341907
    Abstract: A process is disclosed for the catalytic oxidation of a cycloparaffin, e.g., cyclohexane, to partial oxidation products thereof, especially for the production of mixtures of cycloalkanols and cycloalkanones. In the process, molecular oxygen, usually in the presence of an inert gas, is introduced into the cycloparaffin at elevated pressure and a temperature of 130.degree.-180.degree. C., in the presence of an oxidation catalyst comprising a heavy metal compound along with an N-heterocyclic compound. The heavy metal of the heavy metal compound may be cobalt, vanadium, manganese, copper, iron or nickel. The heavy metal compound may have ligands of alkanoate, dialkylphosphate, dicycloalkylphosphate or alkylcycloalkylphosphate. The N-heterocyclic compound may be dipyridyl, pyrimidine, pyrazine, pyridine and pyridine substituted with --CN, --R, and/or --OR where R is alkyl. A preferred catalyst is cobalt bis[di(2-ethylhexyl)phosphate] in combination with pyridine.
    Type: Grant
    Filed: January 30, 1981
    Date of Patent: July 27, 1982
    Assignee: Du Pont Canada Inc.
    Inventor: Ronald A. Zelonka