Gas Phase Rearrangement Patents (Class 540/536)
  • Patent number: 9533944
    Abstract: Provided is a method for producing an oxime compound with satisfactory selectivity. Provide is a method for producing an oxime represented by the following formula (II): wherein R1 and R2 are respectively the same as defined below, the method including oxidizing an amine represented by the following formula (I): wherein R1 and R2 each independently represents a hydrogen atom, an optionally substituted hydrocarbon group, or an optionally substituted heterocyclic group (provided that R1 and R2 are not simultaneously hydrogen atoms), or R1 and R2, together with the carbon atom to which R1 and R2 are attached, form an optionally substituted alicyclic hydrocarbon group having 3 to 12 carbon atoms [hereinafter sometimes referred to as the amine compound (I)], with oxygen in the presence of a layered silicate.
    Type: Grant
    Filed: December 12, 2013
    Date of Patent: January 3, 2017
    Assignee: Sumitomo Chemical Company, Limited
    Inventors: Masahiro Hoshino, Yuta Kikuchi, Sho Tsujiuchi
  • Patent number: 9375678
    Abstract: The growth of continuous MOF membranes on porous polymeric supports is reported, wherein a dip-coating procedure is used to deposit a layer of seed MOF nanocrystals on the surfaces of porous polymers, preferably in the form of hollow fibers, and polycrystalline MOF membranes are subsequently grown at temperatures as low as 65° C. from precursor solutions. The present work opens the road to inexpensive and scalable fabrication of MOF membranes for large-scale separation applications.
    Type: Grant
    Filed: May 20, 2013
    Date of Patent: June 28, 2016
    Assignee: Georgia Tech Research Corporation
    Inventors: Sankar Nair, Andrew Brown, Christopher W. Jones
  • Patent number: 8779124
    Abstract: A redox ammoximation process in which a ketone or aldehyde is reacted with ammonia and oxygen in the presence of a catalyst, wherein: the catalyst is an aluminophosphate based redox catalyst having the qualitative general formula (I) M1M2AlPO-5 (I) in which M1 is at least one transition metal atom having redox catalytic capability; M2 is at least one metal atom in the (IV) oxidation state; M1 and M2 are different from each other; and a proportion of the phosphorous atoms in the M1M2AlPO-5 type structure are replaced by M2 atoms.
    Type: Grant
    Filed: May 8, 2013
    Date of Patent: July 15, 2014
    Assignee: University of Southampton
    Inventors: Robert Raja, Alexander James Patterson
  • Patent number: 8779125
    Abstract: A redox ammoximation process in which a ketone or aldehyde is reacted with ammonia and oxygen in the presence of a catalyst; wherein the catalyst is an aluminophosphate based redox catalyst having at least two different redox catalytic sites comprising different transition metal atoms.
    Type: Grant
    Filed: May 8, 2013
    Date of Patent: July 15, 2014
    Assignee: University of Southampton
    Inventors: Robert Raja, John Meurig Thomas
  • Patent number: 8772476
    Abstract: Methods for producing lactams from oximes by performing a Beckmann rearrangement using a silicoaluminophosphate catalyst are provided. These catalysts may be used in gas phase or liquid phase reactions to convert oximes into lactams. High conversion of oxime and high selectivity for the desired lactams are produced using the disclosed methods, including high conversion and selectivity for ?-caprolactam produced from cyclohexanone oxime and high conversion and selectivity for ?-laurolactam produced from cyclododecanone oxime.
    Type: Grant
    Filed: October 23, 2012
    Date of Patent: July 8, 2014
    Assignee: Honeywell International Inc.
    Inventors: Alan B. Levy, Robert Raja, Matthew E. Potter
  • Patent number: 8212028
    Abstract: The present invention provides a method which can produce ?-caprolactam with a good selectivity by reacting cyclohexanone oxime with a good conversion in a vapor phase Beckmann rearrangement reaction. Disclosed is a method for producing ?-caprolactam, which comprises performing a vapor phase Beckmann rearrangement reaction of cyclohexanone oxime in the presence of a pentasil type zeolite, wherein the pentasil type zeolite is a zeolite obtained by subjecting a mixture containing a silicon compound, water, and a compound represented by formula (I): [(R1)3N+—(CH2)m—N+(R1)2—(CH2)m—N+(R1)3]·3/n(A)??(I) wherein R1 represents an alkyl group having 1 to 4 carbon atoms, A represents an n-valent anion, m represents an integer of 5 to 7, and n represents an integer of 1 to 3, to a hydrothermal synthesis reaction.
    Type: Grant
    Filed: August 18, 2009
    Date of Patent: July 3, 2012
    Assignees: Sumitomo Chemical Company, Limited, The University of Tokyo
    Inventors: Tatsuya Okubo, Yuki Suzuki, Tsuyoshi Matsushita, Tatsuya Suzuki
  • Publication number: 20100105893
    Abstract: The present invention provides a method which can produce ?-caprolactam with a good selectivity by reacting cyclohexanone oxime with a good conversion in a vapor phase Beckmann rearrangement reaction. Disclosed is a method for producing ?-caprolactam, which comprises performing a vapor phase Beckmann rearrangement reaction of cyclohexanone oxime in the presence of a pentasil type zeolite, wherein the pentasil type zeolite is a zeolite obtained by subjecting a mixture containing a silicon compound, water, and a compound represented by formula (I): [(R1)3N+—(CH2)m—N+(R1)2—(CH2)m—N+(R1)3]·3/n (A) ??(I) wherein R1 represents an alkyl group having 1 to 4 carbon atoms, A represents an n-valent anion, m represents an integer of 5 to 7, and n represents an integer of 1 to 3, to a hydrothermal synthesis reaction.
    Type: Application
    Filed: August 18, 2009
    Publication date: April 29, 2010
    Applicants: SUMITOMO CHEMICAL COMPANY, LIMITED, THE UNIVERSITY OF TOKYO
    Inventors: Tatsuya OKUBO, Yuki SUZUKI, Tsuyoshi MATSUSHITA, Tatsuya SUZUKI
  • Patent number: 7687621
    Abstract: The present invention provides a process for regenerating a catalyst for producing e-caprolactam comprising the steps of adsorbing a silicon compound on a zeolite catalyst that had been used for a Beckmann rearrangement reaction of cyclohexanone oxime and contacting the catalyst with an aqueous solution containing a compound selected from a quaternary ammonium compound, lower alkylamines and ammonia. The present invention also provides a process for producing e-caprolactam comprising subjecting cyclohexanone oxime to the Beckmann rearrangement reaction in the presence of the catalyst thus regenerated.
    Type: Grant
    Filed: July 2, 2007
    Date of Patent: March 30, 2010
    Assignee: Sumitomo Chemical Company, Limited
    Inventors: Keisuke Sugita, Masaru Kitamura
  • Patent number: 7547778
    Abstract: The present invention relates to a process for the preparation of zeolitic catalysts of the MFI type in spheroidal form. The process consists in emulsifying and consolidating in paraffinic hydrocarbons, in the presence of a non-ionic surface-active agent or a suitable combination of a non-ionic surface-active agent and a cationic surface-active agent, a dispersion of particles of zeolitic material of the MFI type in a silica sol.
    Type: Grant
    Filed: March 29, 2007
    Date of Patent: June 16, 2009
    Assignee: Polimeri Europa S.p.A.
    Inventors: Luigi Balducci, Leonardo Dalloro, Alberto Cesana, Roberto Buzzoni
  • Patent number: 7238803
    Abstract: ?-Caprolactam is produced by the method comprising the step of introducing a gas comprising cyclohexanone oxime into a layer of solid catalyst particles through a plurality of holes of a gas diffusion plate so that the solid catalyst particles are brought into contact with the gas, while fluidizing the catalyst layer, wherein the holes have an average diameter of about 3 mm or smaller. In accordance with the production method, ?-caprolactam can be produced from a raw material gas comprising cyclohexanone oxime with a high conversion of cyclohexanone oxime and a high selectivity to ?-caprolactam.
    Type: Grant
    Filed: July 6, 2004
    Date of Patent: July 3, 2007
    Assignee: Sumitomo Chemical Company, Limited
    Inventors: Masashi Yokota, Yoshinori Kobayashi, Masaru Kitamura
  • Patent number: 7232784
    Abstract: Disclosed are a kenyaite catalyst containing a metal oxide between layers of a layered silicate having kenyaite structure, a method for preparing the same, and a method for preparing ?-caprolactam from cyclohexanone oxime by applying the catalyst to gas phase Beckmann rearrangement.
    Type: Grant
    Filed: December 23, 2004
    Date of Patent: June 19, 2007
    Assignee: Korea Institute of Science and Technology
    Inventors: Sun-Jin Kim, Oh-Shim Joo, Kwang-Deog Jung, Min-Jo Park
  • Patent number: 7189845
    Abstract: The invention provides a method for producing ?-caprolactam comprising the steps of: a reaction process which subjects cyclohexanone oxime to a Beckmann rearrangement reaction in the presence of a solid catalyst; and a catalyst regeneration process which regenerates the solid catalyst used in the reaction process by heat treatment under an atmosphere comprising an oxygen-containing gas, wherein the solid catalyst heat-treated in the catalyst regeneration process is used in the reaction process, the carbon contents in the solid catalyst in the reaction process and the catalyst regeneration process are maintained in a range of 0.5 to 2% by weight, and the nitrogen contents in the solid catalyst in the reaction process and the catalyst regeneration process are maintained in a range of 0.01 to 0.2% by weight. According to the invention, ?-caprolactam can be produced in a high production yield for a long period of time by enhancing persistence of the catalytic activity for producing ?-caprolactam.
    Type: Grant
    Filed: March 25, 2005
    Date of Patent: March 13, 2007
    Assignee: Sumitomo Chemical Company, Limited
    Inventors: Keisuke Sugita, Masaru Kitamura, Masahiro Hoshino
  • Patent number: 7084269
    Abstract: It is an object of the present invention to provide an efficient method of continuously producing a lactam in high-temperature high-pressure water, and the present invention relates to a method of producing a lactam characterized by efficiently synthesizing the lactam while suppressing oxime hydrolysis by introducing an oxime as a reaction substrate and an acid into a reaction zone through which high-temperature high-pressure water is flowing, or introducing an oxime into flowing high-temperature high-pressure water containing an acid, thus raising the temperature of the reaction substrate to put the reaction substrate into a prescribed high-temperature high-pressure state within a short time and subjecting the reaction substrate to reaction; through the method, the lactam can be efficiently and continuously synthesized at a high rate from the oxime using an acid catalyst in water at a high temperature of at least 250° C. and a high pressure of at least 15 MPa.
    Type: Grant
    Filed: March 5, 2002
    Date of Patent: August 1, 2006
    Assignee: National Institute of Advanced Industrial Science and Technology
    Inventors: Kiyotaka Hatakeda, Osamu Sato, Yutaka Ikushima, Kazuo Torii
  • Patent number: 7060645
    Abstract: The present invention provides a method for manufacturing a zeolite comprising following steps of: (1): calcining crystals obtained by hydrothermal synthesis reaction of a silicon compound; (2): contact treating a calcined product obtained by the step (1) with an aqueous solution including an amine and/or a quaternary ammonium compound; (3): calcining a treated product obtained by the step (2); and (4): contact treating the calcined product obtained by the step (3) with an aqueous solution including ammonia and/or an ammonium salt. According to the present invention, a method is also provided wherein ?-caprolactam is manufactured by Beckmann rearrangement reaction of cyclohexanone oxime in a gaseous phase in the presence of the zeolite manufactured by the above-described method.
    Type: Grant
    Filed: June 24, 2005
    Date of Patent: June 13, 2006
    Assignee: Sumitomo Chemical Company, Limited
    Inventors: Masahiro Hoshino, Masaru Kitamura, Keisuke Sugita
  • Patent number: 7045622
    Abstract: It is an object of the present invention to provide a method of continuously producing a lactam in high-temperature high-pressure water, and the present invention relates to a method for producing a lactam characterized by selectively synthesizing the lactam without bringing about hydrolysis by introducing an oxime into flowing high-temperature high-pressure water, wherein the lactam is continuously synthesized at a high rate from the oxime in water at a high temperature of at least 250° C. and a high pressure of at least 12 MPa.
    Type: Grant
    Filed: March 23, 2001
    Date of Patent: May 16, 2006
    Assignee: National Institute of Advanced Industrial Science and Technology
    Inventors: Kiyotaka Hatakeda, Osamu Sato, Yutaka Ikushima, Kazuo Torii
  • Patent number: 7026474
    Abstract: A method for producing ?-caprolactam and a method for reactivating a zeolite catalyst for the production are provided. In the reactivation step, a zeolite catalyst is allowed to contact a gas containing a carboxylic acid, water and a compound selected from ammonia and amines. In accordance with the present invention, the catalytic activities of a zeolite catalyst used for the Beckmann rearrangement reaction of cyclohexanone oxime can be effectively restored. Consequently, ?-caprolactam may be produced with a high production yield for a long period of time by reusing the catalyst by the method described above.
    Type: Grant
    Filed: February 11, 2005
    Date of Patent: April 11, 2006
    Assignee: Sumitomo Chemical Company, Limited
    Inventors: Keisuke Sugita, Masaru Kitamura, Masahiro Hoshino
  • Patent number: 6946553
    Abstract: Improved processes for producing an ?-caprolactam using a solid catalyst and for producing a catalyst which can be used in the production of ?-caprolactam are provided. In the present invention, a solid catalyst such as a zeolite is treated with an aqueous solution containing an ammonia and at least one compound selected from the group consisting of quaternary ammonium compounds and lower alkylamines. In accordance with the present invention, a zeolite having a high catalyst activity and a long lifetime is produced, and a solid catalyst which has been used in the production of ?-caprolactam can be re-activated. In the present invention, by using the thus obtained zeolite and/or the thus activated solid catalyst, an ?-caprolactam is produced in a high yield over the long period of time.
    Type: Grant
    Filed: February 19, 2003
    Date of Patent: September 20, 2005
    Assignee: Sumitomo Chemical Company, Limited
    Inventors: Keisuke Sugita, Tsuyoshi Matsushita, Hiroshi Ichihashi
  • Patent number: 6894163
    Abstract: ?-Caprolactam is produced by contacting cyclohexanone oxime with a solid acid catalyst in the gaseous phase to effect a rearrangement reaction of the cyclohexanone oxime. The solid acid catalyst is produced by calcining a dried catalyst precursor that can be a zeolite, a crystalline clay mineral and at least one substance selected from an inorganic oxide and a compound which forms the inorganic oxide by calcination. The inorganic oxide includes at least one element selected Groups 4, 13 and 14 of the Periodic Table, and the inorganic oxide excludes oxides contained in a crystalline form in the zeolite and the crystalline clay mineral. Alternately, the rearrangement reaction occurs in the presence of a polyhydric alcohol compound R1—O—R2—OH (where R1 represents C1-C5 alkyl or phenyl, and R2 represents C2-C5 alkylene).
    Type: Grant
    Filed: February 14, 2002
    Date of Patent: May 17, 2005
    Assignee: Asahi Kasei Kabushiki Kaisha
    Inventors: Takashi Tsunoda, Kenji Akagishi, Mitsuhiro Sekiguchi
  • Patent number: 6768013
    Abstract: A novel process for the direct oxidation of hydrogen and hydrocarbons is disclosed, where the explosion risks inherent in gas phase oxidations are substantially eliminated. Gaseous oxidation reactants are soluble in a first reaction solvent phase such as a perfluorocarbon (e.g. C8F18) and the oxidation product is preferentially soluble in a second product solvent phase such as water or a dilute acid. A solid catalyst such as palladium on alumina is then contacted with the dissolved reactants. The oxidation product such as hydrogen peroxide may be separated from the reaction solvent phase by extraction into the immiscible product solvent phase and then separated from it by distillation, thereby allowing re-use of the aqueous phase. The present invention may be carried out using a two-phase reaction system whereby both the reaction solvent and product solvent are contained within a reaction vessel into which the solid catalyst is slurried and mechanically agitated to promote the reaction.
    Type: Grant
    Filed: June 15, 2001
    Date of Patent: July 27, 2004
    Assignee: UOP LLC
    Inventor: Peter R. Pujado
  • Patent number: 6750336
    Abstract: A method for producing a lactam by using an organic solvent as a substrate solution, which makes it possible to introduce a high-concentration oxime into flowing high-temperature and high-pressure water, thereby allowing the high-concentration lactam to be synthesized with a high efficiency. With this method, the lactam is continuously synthesized at a high rate from the oxime under high-temperature and high-pressure water mixture conditions within a temperature range of no less than 250° C. and a pressure range of no less than 15 MPa.
    Type: Grant
    Filed: November 1, 2002
    Date of Patent: June 15, 2004
    Assignee: National Institute of Advanced Industrial Science and Technology
    Inventors: Osamu Sato, Kiyotaka Hatakeda, Yutaka Ikushima, Kazuo Torii
  • Publication number: 20040054169
    Abstract: In the production of &egr;-caprolactam by contacting cyclohexanone oxime with a solid acid catalyst in the gaseous phase to effect a rearrangement reaction of the cyclohexanone oxime, wherein the solid acid catalyst is produced by calcining a dried catalyst precursor: in a first aspect, the catalyst precursor comprises a zeolite, a crystalline clay mineral and at least one substance selected from the group consisting of an inorganic oxide and a compound which forms the inorganic oxide by calcination, wherein the inorganic oxide comprises an oxide of at least one element selected from the group consisting of elements belonging to Groups 4, 13 and 14 of the Periodic Table and wherein the inorganic oxide is other than oxides contained in a crystalline form in the zeolite and the crystalline clay mineral; or in a second aspect, the rearrangement reaction is effected in the presence of a polyhydric alcohol derivative represented by the following formula: R1—O—R2—OH (wherein: R1 represents a C1-C5
    Type: Application
    Filed: July 22, 2003
    Publication date: March 18, 2004
    Inventors: Takashi Tsunoda, Kenji Akagishi, Mitsuhiro Sekiguchi
  • Patent number: 6703501
    Abstract: The present invention relates to porous catalysts comprising layered silicate and metal oxides, and a method of preparing &egr;-caprolactam from cyclohexanone oxime using the catalyst. This new catalyst can resolve the environmental and safety problems arising from conventional liquid acid process. Also the present catalyst solves the problem of short lifetime of current solid acid catalysts. Moreover, the present catalyst provides higher selectivity and yield.
    Type: Grant
    Filed: June 11, 2002
    Date of Patent: March 9, 2004
    Assignee: Korea Institute of Science and Technology
    Inventors: Myunghun Kim, Sunjin Kim, Youngsun Uh, Younghee Kim
  • Publication number: 20030125545
    Abstract: The present invention relates to a process for the preparation of zeolitic catalysts of the MFI type in spheroidal form.
    Type: Application
    Filed: November 18, 2002
    Publication date: July 3, 2003
    Applicant: POLIMERI EUROPA S.p.A.
    Inventors: Luigi Balducci, Leonardo Dalloro, Alberto Cesana, Roberto Buzzoni
  • Publication number: 20030088093
    Abstract: A method for producing a lactam by using an organic solvent as a substrate solution, which makes it possible to introduce a high-concentration oxime into flowing high-temperature and high-pressure water, thereby allowing the high-concentration lactam to be synthesized with a high efficiency. With this method, the lactam is continuously synthesized at a high rate from the oxime under high-temperature and high-pressure water mixture conditions within a temperature range of no less than 250° C. and a pressure range of no less than 15 MPa.
    Type: Application
    Filed: November 1, 2002
    Publication date: May 8, 2003
    Applicant: National Inst. of Advanced Ind. Science and Tech.
    Inventors: Osamu Sato, Kiyotaka Hatakeda, Yutaka Ikushima, Kazuo Torii
  • Patent number: 6531595
    Abstract: A method is provided for producing &egr;-caprolactam from cyclohexanone oxime by using a zeolite or non-zeolitic material as a catalyst under gas phase reaction conditions. The method comprises a reaction step converting cyclohexanone oxime into &egr;-caprolactam in the presence of the zeolite or non-zeolitic material; and a regeneration step of treating the zeolite or non-zeolitic material with a non-oxidizing gas at a temperature of from about 100°C. to about 600° C.
    Type: Grant
    Filed: September 27, 2001
    Date of Patent: March 11, 2003
    Assignee: Sumitomo Chemical Company, Limited
    Inventors: Wolfgang F. Hölderich, Gerd Dahlhoff, Hiroshi Ichihashi, Keisuke Sugita
  • Patent number: 6482945
    Abstract: A process is provided for producing &egr;-caprolactam from cyclohexanone oxime. The process comprises a evaporation step of a mixture of cyclohexanone oxime and a solvent by introducing the mixture into a fluidized bed in which inert particles is fluidized by an inert gas, the particles having heat enough to evaporate the mixture; and a rearrangement step of cyclohexanone oxime in the evaporated mixture into &egr;-caprolactam by a gas phase Beckmann rearrangement reaction using a solid catalyst, excluding a catalyst consisting of a boric acid or a boron oxide.
    Type: Grant
    Filed: September 28, 2001
    Date of Patent: November 19, 2002
    Assignee: Sumitomo Chemical Company, Limited
    Inventors: Wolfgang F. Hölderich, Gerd Dahlhoff, Andre Sbresny, Hiroshi Ichihashi
  • Patent number: 6469163
    Abstract: An improvement in the conventional process for the production of caprolactam. The process involves: (a) reacting air with ammonia gas in an ammonia conversion zone to produce nitric oxide; (b) oxidizing a portion of the nitric oxide to nitrogen dioxide to produce an NOx-rich process gas stream; (c) reacting the NOx-rich stream with ammonium carbonate in a nitriting zone to produce ammonium nitrite; (d) reducing the ammonium nitrite to hydroxylamine diammonium sulfate; (e) hydrolyzing the hydroxylamine diammonium sulfate to hydroxylamine sulfate; (f) oximating the hydroxylamine sulfate with cyclohexanone to produce cyclohexanone oxime; and (g) converting the cyclohexanone oxime to caprolactam. The process is improved by adding supplemental oxygen downstream of the ammonia conversion zone to increase the quantity and rate of formation of nitrogen dioxide in the NOx-rich process gas stream.
    Type: Grant
    Filed: December 24, 1998
    Date of Patent: October 22, 2002
    Assignee: Praxair Technology Inc.
    Inventors: Diego Fernandez Echegaray, Antonio Augusto M. Velloso, Matthew Lincoln Wagner
  • Patent number: 6432982
    Abstract: The invention provides novel benzothiophenes of the formula: wherein R1 is —H, —OH, —O(C1-C4 alkyl), —O—CO(C1-C6 alkyl), —OSO2(C4-C6 alkyl, or —OCOAr where Ar is optionally substituted phenyl; R2 is —H, —OH, —Cl, —Br, —O(C1-C4 alkyl), —OCO(C1-C6 alkyl), —OSO2(C4-C6 alkyl, or —OCOAr where Ar is optionally substituted phenyl; R3 is —H, —F, —Cl, —(C1-C4 alkyl), —CN, or —O(C1-C3 alkyl); R4 is —H, —F, —Cl, —(C1-C4 alkyl), —CN or —O(C1-C3 alkyl); R5 is —H, —F, —Cl, —(C1-C4 alkyl), or —O(C1-C3 alkyl); and R6 is —H, —F, —Cl, —(C1-C4 alkyl), or —O(C1-C3 alkyl); with the provisos that R3, R4, R5 and R6 can not all be hydrogen, and that when one of R3, R4, R5 or R6 is C1-C4 alkyl, no more than two of R3, R4, R5 and R6 can be hydrogen; Y is —CO—, —CHOH—, or &mda
    Type: Grant
    Filed: January 14, 1997
    Date of Patent: August 13, 2002
    Assignee: Eli Lilly and Company
    Inventors: George Joseph Cullinan, Kennan Joseph Fahey
  • Publication number: 20020042509
    Abstract: A method is provided for producing &egr;-caprolactam from cyclohexanone oxime by using a zeolite or non-zeolitic material as a catalyst under gas phase reaction conditions. The method comprises a reaction step converting cyclohexanone oxime into &egr;-caprolactam in the presence of the zeolite or non-zeolitic material; and a regeneration step of treating the zeolite or non-zeolitic material with a non-oxidizing gas at a temperature of from about 100° C. to about 600° C.
    Type: Application
    Filed: September 27, 2001
    Publication date: April 11, 2002
    Inventors: Wolfgang F. Holderich, Gerd Dahlhoff, Hiroshi Ichihashi, Keisuke Sugita
  • Publication number: 20020040137
    Abstract: A process is provided for producing &egr;-caprolactam from cyclohexanone oxime. The process comprises a evaporation step of a mixture of cyclohexanone oxime and a solvent by introducing the mixture into a fluidized bed in which inert particles is fluidized by an inert gas, the particles having heat enough to evaporate the mixture; and a rearrangement step of cyclohexanone oxime in the evaporated mixture into &egr;-caprolactam by a gas phase Beckmann rearrangement reaction using a solid catalyst, excluding a catalyst consisting of a boric acid or a boron oxide.
    Type: Application
    Filed: September 28, 2001
    Publication date: April 4, 2002
    Inventors: Wolfgang F. Holderich, Gerd Dahlhoff, Andre Sbresny, Hiroshi Ichihashi
  • Patent number: 6333411
    Abstract: A method for production of caprolactam. The method involves: (a) reacting air with ammonia gas in an ammonia conversion zone to produce nitric oxide; (b) oxidizing at least a portion of the nitric oxide to nitrogen dioxide to produce an NOx-rich process gas stream; (c) reactively absorbing the NOx-rich gas stream with phosphoric acid containing solution in an absorption zone to form nitrate ions; (d) contacting the nitrate ions with air in a degassing zone to produce a nitrate-rich aqueous process stream; (e) reducing the nitrate-rich aqueous stream with hydrogen in the presence of phosphoric acid to produce hydroxylammonium phosphate; (f) oximating the hydroxylammonium phosphate with cyclohexanone to produce cyclohexanone oxime; and (g) converting the cyclohexanone oxime to caprolactam. According to the invention, supplemental oxygen is added downstream of the ammonia conversion zone to increase the quantity and rate of formation of nitrogen dioxide in the NOx-rich process gas stream.
    Type: Grant
    Filed: December 24, 1998
    Date of Patent: December 25, 2001
    Assignee: Praxair Technology, Inc.
    Inventors: Diego Fernandez Echegaray, Antonio Augusto M. Velloso, Matthew Lincoln Wagner
  • Patent number: 6291484
    Abstract: This invention provides novel benzothiophene compounds of the formula I: which are useful for the treatment of the various medical conditions associated with postmenopausal syndrome, as well as estrogen dependent diseases including cancer of the breast, uterus, and cervix. The present invention further relates to pharmaceutical formulations of compounds of formula I.
    Type: Grant
    Filed: January 13, 2000
    Date of Patent: September 18, 2001
    Assignee: Eli Lilly and Company
    Inventors: Henry Uhlman Bryant, Jeffrey Alan Dodge
  • Patent number: 6265574
    Abstract: A process for producing &egr;-caprolactam is provided which comprises the steps of subjecting cyclohexanone oxime to a gaseous phase Beckmann rearrangement reaction in a fluidized bed system using a solid catalyst and re-generating the catalyst, wherein said process comprises a step of treating the catalyst with an oxygen-containing gas at an elevated temperature in a re-generation step so that the nitrogen content of the catalyst falls within a range of 10 ppm to 2,500 ppm on its way to the reaction step from the re-generating step. According to the present invention, &egr;-caprolactam is produced with a high conversion or a high selectivity without interrupting the rearrangement reaction or the re-generation step.
    Type: Grant
    Filed: February 9, 2000
    Date of Patent: July 24, 2001
    Assignee: Sumitomo Chemical Company, Limited
    Inventors: Masaru Kitamura, Yasumoto Shimazu, Makoto Yako
  • Patent number: 6258826
    Abstract: Formulations and applications thereof are described which are useful for the inhibition of various medical conditions associated with estrogen deprivation syndrome including osteoporosis and hyperlipidemia utilizing compounds of structure I represented by the following structure in combination with compounds of formula II represented by the following structure where X, Y, R, R′, R6, R7 and R8 are as defined herein.
    Type: Grant
    Filed: September 1, 1999
    Date of Patent: July 10, 2001
    Assignee: Eli Lilly and Company
    Inventors: George Joseph Cullinan, Brian Stephen Muehl, Kenneth Jeff Thrasher
  • Patent number: 6258949
    Abstract: An apparatus for the production of &egr;-caprolactam is provided which comprises (i) a fluidized bed reactor having a solid catalyst therein for subjecting cyclohexanone oxime to a rearrangement reaction to obtain a reaction product containing unreacted cyclohexanone oxime and (ii) a fixed bed reactor packed with a solid catalyst for subjecting the unreacted cyclohexanone oxime to a rearrangement reaction to obtain &egr;-caprolactam. Using the apparatus, &egr;-caprolactam is obtained with a high yield.
    Type: Grant
    Filed: March 16, 2000
    Date of Patent: July 10, 2001
    Assignee: Sumitomo Chemical Company, Limited
    Inventors: Masaru Kitamura, Yasumoto Shimazu
  • Patent number: 6252065
    Abstract: For the preparation of lactams comprising 6 to 12 carbon atoms from the corresponding cycloalkanone oximes by rearrangement according to the Beckmann reaction in the presence of acid, the process is characterized in that use is made of methanesulphonic acid.
    Type: Grant
    Filed: September 21, 1999
    Date of Patent: June 26, 2001
    Assignee: Elf Atochem, S.A.
    Inventor: Jean Ollivier
  • Patent number: 6251921
    Abstract: This application relates to the use as thrombin inhibitors, coagulation inhibitors and thromboembolic disorder agents of diamines of formula I as defined herein. It also provides novel compounds of formula I, processes and intermediates for their preparation, and pharmaceutical formulations comprising the novel compounds of formula I.
    Type: Grant
    Filed: May 14, 1999
    Date of Patent: June 26, 2001
    Assignee: Eli Lilly and Company
    Inventors: Jolie Anne Bastian, Nickolay Yuri Chirgadze, Michael Lyle Denney, Matthew Joseph Fisher, Robert James Foglesong, Richard Waltz Harper, Mary George Johnson, Valentine Joseph Klimkowski, Todd Jonathan Kohn, Ho-Shen Lin, Michael Patrick Lynch, Jefferson Ray McCowan, Alan David Palkowitz, Michael Enrico Richett, Daniel Jon Sall, Gerald Floyd Smith, Kumiko Takeuchi, Jennifer Marie Tinsley, Minsheng Zhang
  • Patent number: 6051706
    Abstract: A method is disclosed of producing .epsilon.-caprolactam by the Beckmann rearrangement of cyclohexanone oxime using (B) .beta. zeolites as catalyst.
    Type: Grant
    Filed: May 11, 1999
    Date of Patent: April 18, 2000
    Assignee: Degussa-Huls Aktiengesellschaft
    Inventors: Wolfgang Holderich, Georg Philip Heitmann, Dietrich Arntz
  • Patent number: 5994547
    Abstract: The preparation of benzo[b]thiophenes by the acylation of alkoxy protected starting materials followed by demethylation using essentially odorless thiol compounds are provided herewith. Demethylation may be carried out in the same reaction vessel without isolation of the acylated, protected material.
    Type: Grant
    Filed: April 29, 1998
    Date of Patent: November 30, 1999
    Assignee: Eli Lilly and Company
    Inventors: David Warren Hoard, Wayne Douglas Luke
  • Patent number: 5942613
    Abstract: Process for the preparation of amides via the catalytic rearrangement of oximes which comprises putting an oxime in vapor phase in contact with a catalyst selected from a mesoporous silica-alumina having a molar ratio SiO/Al.sub.2 O.sub.2 of between 20 and 1000, an average pore diameter of between 20 and 100 .ANG. and an X-ray diffraction pattern (XRD) from powders which, after calcination, has the deepest reflection at d-spacing of more than 18 .ANG. (2.theta.<4.9.degree., CuK.alpha. radiation).
    Type: Grant
    Filed: July 9, 1997
    Date of Patent: August 24, 1999
    Assignee: Enichem S.p.A.
    Inventors: Angela Carati, Carlo Perego, Leonardo Dalloro, Giordano De Alberti, Stefano Palmery
  • Patent number: 5914398
    Abstract: Process for the preparation of caprolactam by the catalytic rearrangement of cyclohexanone oxime in which a vapour phase oxime is contacting a catalyst selected from an essentially amorphous, micro-mesoporous silica-alumina having a molar ratio SiO.sub.2 /Al.sub.2 O.sub.3 of 30 to 5000, a surface area of at least 500 m.sup.2 /g and a total pore volume of 0.3 to 1.3 ml/g.
    Type: Grant
    Filed: July 3, 1997
    Date of Patent: June 22, 1999
    Assignee: Enichem S.p.A
    Inventors: Angela Carati, Carlo Perego, Leonardo Dalloro, Giordano De Alberti, Stefano Palmery
  • Patent number: 5900482
    Abstract: The present invention provides a method for producing .epsilon.-caprolactam, which comprises subjecting cyclohexene to a hydration reaction to obtain cyclohexanol, subjecting the cyclohexanol to a dehydrogenation reaction to obtain cyclohexanone, subjecting the cyclohexanone to an oxime-forming reaction to obtain cyclohexanone oxime, and subjecting the cyclohexanone oxime to a Beckmann rearrangement reaction to obtain .epsilon.-caprolactam, wherein methylcyclopentanones contained in the cyclohexanone subjected to the oxime-forming reaction are controlled to be not more than 400 ppm.According to the present invention, it is possible to produce .epsilon.-caprolactam having a quality not inferior to conventional quality at a low cost.
    Type: Grant
    Filed: March 19, 1997
    Date of Patent: May 4, 1999
    Assignee: Mitsubishi Chemical Corporation
    Inventors: Kouji Teramoto, Yu Kanda, Makoto Tezuka, Toshio Uchibori, Hidefumi Sano
  • Patent number: 5741904
    Abstract: A method of producing .epsilon.-caprolactam from cyclohexanone in the gaseous phase using MFI catalysts on whose surface symmetrically arranged OH groups are present.
    Type: Grant
    Filed: May 6, 1996
    Date of Patent: April 21, 1998
    Assignee: Degussa Aktiengesellschaft
    Inventors: Wolfgang Hoelderich, Joerg Roeseller, Dietrich Arntz
  • Patent number: 5525725
    Abstract: A process for producing a high purity caprolactam is disclosed in which a crude caprolactam obtained by a catalytic rearrangement of cyclohexanone oxime is subjected(1) to mixing, while stirring, with at least one hydrocarbon selected from the group consisting of aliphatic hydrocarbons and alicyclic hydrocarbons to form a liquid-liquid, two-layer liquid mixture, and then crystallizing caprolactam out of the liquid mixture;(2) to mixing with both at least one hydrocarbon selected from the group consisting of aliphatic hydrocarbons and alicyclic hydrocarbons, and water to form a liquid mixture, separating the liquid mixture into a hydrocarbon layer and a water layer, and then recovering caprolactam from the water layer; or(3) to distillation in the co-presence of at least one aliphatic saturated hydrocarbon of 10 to 18 carbon atoms.
    Type: Grant
    Filed: August 19, 1994
    Date of Patent: June 11, 1996
    Assignee: Sumitomo Chemical Company, Limited
    Inventors: Yasuhiko Higashio, Hiroshi Kajikuri, Keisuke Sugita, Hideki Doi, Masanobu Matsubara
  • Patent number: 5510357
    Abstract: The present invention provides pharmaceutically active compounds of formula I ##STR1## wherein R.sup.1 is --H, --OH, --O(C.sub.1 -C.sub.4 alkyl), --OCOC.sub.6 H.sub.5, --OCO (C.sub.1 -C.sub.6 alkyl), or --OSO.sub.2 (C.sub.2 -C.sub.6 alkyl);R.sup.2 is --H, --OH, --O(C.sub.1 -C.sub.4 alkyl), --OCOC.sub.6 H.sub.5, --OCO(C.sub.1 -C.sub.6 alkyl), --OSO.sub.2 (C.sub.2 -C.sub.6 alkyl), or halo, providing when Z is --S--, R.sup.2 is not halo;R.sup.3 is 1-piperidinyl, 1-pyrrolidinyl, methyl-1-pyrrolidinyl, dimethyl-1-pyrrolidinyl, 4-morpholino, dimethylamino, diethylamino, diisopropylamino, or 1-hexamethyleneimino;n is 2 or 3; andz is --O-- or --S--;or a pharmaceutically acceptable salt thereof for, inter alia, alleviating the symptoms of post menopausal syndrome and hormonally-dependent cancer, particularly breast cancer.
    Type: Grant
    Filed: February 28, 1995
    Date of Patent: April 23, 1996
    Assignee: Eli Lilly and Company
    Inventor: Alan D. Palkowitz
  • Patent number: 5502184
    Abstract: The invention provides a process for producing high quality .epsilon.-caprolactam which comprises allowing crude .epsilon.-caprolactam obtained by gas phase Beckmann rearrangement of cyclohexanone oxime to contact with hydrogen at 100.degree.-200.degree. C. in the presence of a hydrogenation catalyst.
    Type: Grant
    Filed: August 19, 1994
    Date of Patent: March 26, 1996
    Assignee: Sumitomo Chemical Company, Limited
    Inventors: Hiroshi Kajikuri, Hideto Tojima, Tomokazu Nakamura, Masaru Kitamura
  • Patent number: 5459261
    Abstract: A process for producing a high purity caprolactam is disclosed in which a crude caprolactam obtained by a catalytic rearrangement of cyclohexanone oxime is subjected(1) to mixing, while stirring, with at least one hydrocarbon selected from the group consisting of aliphatic hydrocarbons and alicyclic hydrocarbons to form a liquid-liquid, two-layer liquid mixture, and then crystallizing caprolactam out of the liquid mixture;(2) to mixing with both at least one hydrocarbon selected from the group consisting of aliphatic hydrocarbons and alicyclic hydrocarbons, and water to form a liquid mixture, separating the liquid mixture into a hydrocarbon layer and a water layer, and then recovering caprolactam from the water layer; or(3) to distillation in the co-presence of at least one aliphatic saturated hydrocarbon of 10 to 18 carbon atoms.
    Type: Grant
    Filed: August 15, 1994
    Date of Patent: October 17, 1995
    Assignee: Sumitomo Chemical Company, Limited
    Inventors: Yasuhiko Higashio, Hiroshi Kajikuri, Keisuke Sugita, Hideki Doi, Masanobu Matsubara
  • Patent number: 5362870
    Abstract: A process for producing a high purity caprolactam is disclosed in which a crude caprolactam obtained by a catalytic rearrangement of cyclohexanone oxime is subjected(1) to mixing, while stirring, with at least one hydrocarbon selected from the group consisting of aliphatic hydrocarbons and alicyclic hydrocarbons to form a liquid-liquid, two-layer liquid mixture, and then crystallizing caprolactam out of the liquid mixture;(2) to mixing with both at least one hydrocarbon selected from the group consisting of aliphatic hydrocarbons and alicyclic hydrocarbons, and water to form a liquid mixture, separating the liquid mixture into a hydrocarbon layer and a water layer, and then recovering caprolactam from the water layer; or(3) to distillation in the co-presence of at least one aliphatic saturated hydrocarbon of 10 to 18 carbon atoms.
    Type: Grant
    Filed: April 15, 1993
    Date of Patent: November 8, 1994
    Assignee: Sumitomo Chemical Company, Ltd.
    Inventors: Yasuhiko Higashio, Hiroshi Kajikuri, Keisuke Sugita, Hideki Doi, Masanobu Matsubara
  • Patent number: 5354859
    Abstract: .epsilon.-Caprolactam is prepared by bringing cyclohexanone oxime into contact in gas phase with solid catalysts such as a zeolite catalyst in the presence of at least one nitrogen-containing compound selected from the group consisting of ammonia, methylamines and .epsilon.-caprolactam.
    Type: Grant
    Filed: November 25, 1992
    Date of Patent: October 11, 1994
    Assignee: Sumitomo Chemical Company Limited
    Inventors: Hiroshi Ichihashi, Masaru Kitamura, Hiroshi Kajikuri, Eiji Tasaka
  • Patent number: 5312915
    Abstract: .epsilon.-Caprolactam is produced efficiently with high selectivity by contacting cyclohexanone oxime in gas phase with a solid catalyst which is a crystalline zeolite having a pore size smaller than molecular size of cyclohexanone oxime or a crystalline zeolite having closed pores.
    Type: Grant
    Filed: September 10, 1993
    Date of Patent: May 17, 1994
    Assignee: Sumitomo Chemical Company, Limited
    Inventors: Tatsuaki Yashima, Takayuki Komatsu