Bismuth Containing Material Utilized Patents (Class 558/324)
  • Patent number: 10328418
    Abstract: A method for producing a catalyst according to the present invention includes: a preparation step of preparing a precursor slurry comprising molybdenum, bismuth, iron, silica, and a carboxylic acid; a drying step of spray-drying the precursor slurry and thereby obtaining a dried particle; and a calcination step of calcining the dried particle, wherein the preparation step comprises: a step (I) of mixing a starting material for silica with the carboxylic acid and thereby preparing a silica-carboxylic acid mixed liquid; and a step (II) of mixing the silica-carboxylic acid mixed liquid, molybdenum, bismuth, and iron.
    Type: Grant
    Filed: August 1, 2017
    Date of Patent: June 25, 2019
    Assignee: ASAHI KASEI KABUSHIKI KAISHA
    Inventors: Shota Aiki, Akiyoshi Fukuzawa
  • Patent number: 9815045
    Abstract: The present disclosure relates to metal oxide catalyst materials useful, for example, in the ammoxidation of propylene or isobutylene, processes for making them, and processes for making acrylonitrile and methacrylonitrile using such catalyst materials. In certain aspects, a catalyst material is a fused composite of a metal oxide catalyst and nanoparticulate silica, the nanoparticulate silica comprising in the range of about 40 wt % to about 80 wt % of silica having a particle size in the range of 10 nm to 35 nm, and in the range of about 20 wt % to about 60 wt % of silica having a particle size in the range of 36 nm to 80 nm. The metal oxide catalyst can be, for example, a molybdenum-containing mixed metal oxide catalyst.
    Type: Grant
    Filed: March 4, 2016
    Date of Patent: November 14, 2017
    Assignee: Clariant Corporation
    Inventors: Claus G. Lugmair, Hailian Li
  • Patent number: 9000207
    Abstract: A method for producing a silica-supported catalyst comprising Mo, V. Nb, and a component X (Sb and/or Te) to be used in a vapor phase catalytic oxidation or ammoxidation of proprane, comprising the steps of: (I) preparing a raw material mixture solution by mixing Mo, V, Nb, component X, a silica sol, and water; (II) obtaining a dry powder by drying the raw material mixture solution; and (III) obtaining a silica-supported catalyst by calcining the dry powder, wherein the silica sol contains 10 to 270 wt ppm of nitrate ions based on SiO2.
    Type: Grant
    Filed: May 22, 2014
    Date of Patent: April 7, 2015
    Assignee: Asahi Kasei Chemicals Corporation
    Inventors: Yusuke Ishii, Takaaki Kato
  • Publication number: 20150065744
    Abstract: The invention relates to a method for producing acrylonitrile which includes a vapor phase catalytic ammoxidation process of performing vapor phase catalytic ammoxidation by bringing a source gas containing propylene, molecular oxygen, and ammonia into contact with a fluidized bed catalyst to obtain acrylonitrile. The method is characterized in that the fluidized bed catalyst is a catalyst containing molybdenum and bismuth and the vapor phase catalytic ammoxidation process is performed while maintaining an adsorbed amount of ammonia per specific surface area (m2/g) of the fluidized bed catalyst in the range of 0.05 to 0.6 ?mol/m2. According to the method for producing acrylonitrile of the invention, it is possible to stably maintain a high acrylonitrile yield over a long period of time.
    Type: Application
    Filed: February 26, 2013
    Publication date: March 5, 2015
    Applicant: Mitsubishi Rayon Co., Ltd.
    Inventors: Hirokazu Watanabe, Motoo Yanagita, Takashi Karasuda, Kazufumi Nishida, Kenichi Miyaki
  • Publication number: 20140296558
    Abstract: A process for producing geometric shaped catalyst bodies K whose active material is a multielement oxide of stoichiometry [Bi1WbOx]a[Mo12Z1cZ2dFeeZ3fZ4gZ5hOy]1, in which a finely divided oxide Bi1WbOx with the particle size d50A1 and, formed from element sources, a finely divided intimate mixture of stoichiometry Mo12Z1cZ2dFeeZ3fZ4gZ5h with the particle size d90A2 are mixed in a ratio of a:1, this mixture is used to form shaped bodies and these are treated thermally, where (d50A1)0.7·(d90A2)1.5·(a)?1?820. A shaped catalyst body obtained by the process. A catalyst obtained by grinding the shaped catalyst body. A process for heterogeneously catalyzing the partial gas phase oxidation of an alkane, alkanol, alkanal and/or an alkenal of 3 to 6 carbon atoms using the catalyst.
    Type: Application
    Filed: June 16, 2014
    Publication date: October 2, 2014
    Applicant: BASF SE
    Inventors: Andreas RAICHLE, Catharina Horstmann, Frank Rosowski, Klaus Joachim Mueller-Engel, Holger Borchert, Gerhard Cox, Ulrich Cremer
  • Patent number: 8835666
    Abstract: A process for preparation of catalysts for the production of acrylonitrile, acetonitrile and hydrogen cyanide comprising contacting at an elevated temperature, propylene, ammonia and oxygen in the vapor phase in the presence of a catalyst, said catalyst comprising a complex of metal oxides wherein a heat-decomposable nitrogen containing compound is added during the process for the preparation of the catalyst.
    Type: Grant
    Filed: November 26, 2012
    Date of Patent: September 16, 2014
    Assignee: Ineos USA LLC
    Inventors: James Frank Brazdil, Jr., Charles James Besecker, Michael J. Seely, Muin S. Haddad, Mark A. Toft
  • Publication number: 20140148610
    Abstract: A process for preparation of catalysts for the production of acrylonitrile, acetonitrile and hydrogen cyanide comprising contacting at an elevated temperature, propylene, ammonia and oxygen in the vapor phase in the presence of a catalyst, said catalyst comprising a complex of metal oxides wherein a heat-decomposable nitrogen containing compound is added during the process for the preparation of the catalyst.
    Type: Application
    Filed: November 26, 2012
    Publication date: May 29, 2014
    Applicant: INEOS USA LLC
    Inventors: James Frank Brazdil, JR., Charles James Besecker, Michael J. Seely, Muin S. Haddad, Mark A. Toft
  • Publication number: 20140039213
    Abstract: A process for producing geometric shaped catalyst bodies K whose active material is a multielement oxide of stoichiometry [Bi1WbOx]a[Mo12Z1cZ2dFeeZ3fZ4gZ5hOy]1, in which a finely divided oxide Bi1WbOx with the particle size d50A1 and, formed from element sources, a finely divided intimate mixture of stoichiometry Mo12Z1cZ2dFeeZ3fZ4gZ5h with the particle size d90A2 are mixed in a ratio of a:1, this mixture is used to form shaped bodies and these are treated thermally, where (d50A1)0.7·(d90A2)1.5·(a)?1?820. A shaped catalyst body obtained by the process. A catalyst obtained by grinding the shaped catalyst body. A process for heterogeneously catalyzing the partial gas phase oxidation of an alkane, alkanol, alkanal and/or an alkenal of 3 to 6 carbon atoms using the catalyst.
    Type: Application
    Filed: August 5, 2013
    Publication date: February 6, 2014
    Applicant: BASF SE
    Inventors: Andreas RAICHLE, Catharina Horstmann, Frank Rosowski, Klaus Joachim Mueller-Engel, Holger Borchert, Gerhard Cox, Ulrich Cremer
  • Publication number: 20130204030
    Abstract: Disclosed is a method for producing a catalyst, in which physical properties of a dried material or a calcined material in a production process of the catalyst are stable and a change in at least one of a catalyst activity and a selectivity to a target product is small and hence reproducibility of the catalyst is excellent. The present invention is a method for producing a catalyst containing molybdenum, bismuth, and iron, which contains the steps of washing a surface of at least one device equipped in an apparatus for the production of catalyst, to which a solid matter adheres, with a basic solution, and producing the catalyst with the apparatus for the production of catalyst thus washed.
    Type: Application
    Filed: March 15, 2013
    Publication date: August 8, 2013
    Applicant: Mitsubishi Rayon Co., LTD.
    Inventor: Mitsubishi Rayon Co., LTD.
  • Patent number: 8455388
    Abstract: A catalytic composition useful for the conversion of an olefin selected from the group consisting of propylene, isobutylene or mixtures thereof, to acrylonitrile, methacrylonitrile, and mixtures thereof. The catalytic composition comprising a complex of metal oxides comprising bismuth, molybdenum, iron, cerium and other promoters, wherein the ratio of cerium to iron in the composition is greater than or equal to 0.8 and less than or equal to 5.
    Type: Grant
    Filed: March 23, 2010
    Date of Patent: June 4, 2013
    Assignee: INEOS USA LLC
    Inventors: James F. Brazdil, Mark A. Toft, Michael J. Seely, Charles J. Besecker, Robert A. Gustaferro
  • Patent number: 8420566
    Abstract: A process and novel catalyst for the production of acrylonitrile, acetonitrile and hydrogen cyanide characterized by the relative yields of acrylonitrile, acetonitrile and hydrogen cyanide produced in the process and by the catalyst, which are defined by the following: ?=[(% AN+(3×% HCN)+(1.5×% ACN))÷% PC]×100 wherein % AN is the Acrylonitrile Yield and % AN?81, % HCN is the Hydrogen Cyanide Yield, % ACN is the Acetonitrile Yield, % PC is the Propylene Conversion, and ? is greater than 100.
    Type: Grant
    Filed: March 15, 2011
    Date of Patent: April 16, 2013
    Assignee: Ineos USA LLC
    Inventors: James F. Brazdil, Mark A. Toft, Charles J. Besecker, Michael J. Seely
  • Patent number: 8350075
    Abstract: Olefins selected from the group consisting of propylene, isobutylene or mixtures thereof, are converted to acrylonitrile, methacrylonitrile, and mixtures thereof in a process comprising reacting in the vapor phase at an elevated temperature and pressure said olefin with a molecular oxygen containing gas and ammonia in the presence of a catalytic composition comprising a complex of metal oxides comprising bismuth, molybdenum, iron, cerium and other promoter elements, wherein the X-ray diffraction pattern of the catalytic composition has X-ray diffraction peaks at 2? angle 28±0.3 degrees and 2? angle 26.5±0.3 degrees, and wherein the ratio of the intensity of the most intense x-ray diffraction peak within 2? angle 28±0.3 degrees to the intensity of most intense x-ray diffraction peak within 2? angle 26.5±0.3 degrees is defined as X/Y, and wherein X/Y is greater than or equal to 0.7.
    Type: Grant
    Filed: January 17, 2012
    Date of Patent: January 8, 2013
    Assignee: Ineos USA LLC
    Inventors: James F. Brazdil, Mark A. Toft, Michael J. Seely, Charles J. Besecker, Robert A. Gustaferro
  • Publication number: 20120296108
    Abstract: A process for producing geometric shaped catalyst bodies K whose active material is a multielement oxide of stoichiometry [BiaZ1bOx]p[BicMo12FedZ2eZ3fZ4gZ5hZ6iOy]1, in which a finely divided oxide BiaZ1bOx and, formed from element sources, a finely divided mixture of stoichiometry BicMo12FedZ2eZ3fZ4gZ5hZ6i are mixed in a ratio of p:1, this mixture is used to form shaped bodies and these are treated thermally, where 0<c?0.8.
    Type: Application
    Filed: July 31, 2012
    Publication date: November 22, 2012
    Applicant: BASF SE
    Inventors: Andreas Raichle, Catharina Horstmann, Frank Rosowski, Klaus Joachim Mueller-Engel, Jochen Petzoldt, Ulrich Cremer
  • Patent number: 8258073
    Abstract: A process for the preparation of a catalyst comprising bismuth, molybdenum, iron, cerium and other promoter elements, wherein the elements in said catalyst are combined together in an aqueous catalyst precursor slurry, the aqueous precursor slurry so obtained is dried to form a catalyst precursor, and the catalyst precursor is calcined to form said catalyst, the process comprising: (i) combining, in an aqueous solution, source compounds of Bi and Ce, and optionally one or more of Na, K, Rb, Cs, Ca, a rare earth element, Pb, W and Y, to form a mixture, (ii) adding a source compound of molybdenum to the mixture to react with the mixture and form a precipitate slurry, and (iii) combining the precipitate slurry with source compounds of the remaining elements and of the remaining molybdenum in the catalyst to form the aqueous catalyst precursor slurry.
    Type: Grant
    Filed: March 23, 2010
    Date of Patent: September 4, 2012
    Assignee: iNEOS USA LLC
    Inventors: Charles J. Besecker, James Frank Brazdil, Jr., Mark A. Toft, Michael J. Seely, Robert A. Gustaferro
  • Publication number: 20120130112
    Abstract: Olefins selected from the group consisting of propylene, isobutylene or mixtures thereof, are converted to acrylonitrile, methacrylonitrile, and mixtures thereof in a process comprising reacting in the vapor phase at an elevated temperature and pressure said olefin with a molecular oxygen containing gas and ammonia in the presence of a catalytic composition comprising a complex of metal oxides comprising bismuth, molybdenum, iron, cerium and other promoter elements, wherein the X-ray diffraction pattern of the catalytic composition has X-ray diffraction peaks at 2? angle 28±0.3 degrees and 2? angle 26.5±0.3 degrees, and wherein the ratio of the intensity of the most intense x-ray diffraction peak within 2? angle 28±0.3 degrees to the intensity of most intense x-ray diffraction peak within 2? angle 26.5±0.3 degrees is defined as X/Y, and wherein X/Y is greater than or equal to 0.7.
    Type: Application
    Filed: January 17, 2012
    Publication date: May 24, 2012
    Applicant: INEOS USA LLC
    Inventors: James F. Brazdil, Mark A. Toft, Michael J. Seely, Charles J. Besecker, Robert A. Gustaferro
  • Publication number: 20110237820
    Abstract: A process for the preparation of a catalyst comprising bismuth, molybdenum, iron, cerium and other promoter elements, wherein the elements in said catalyst are combined together in an aqueous catalyst precursor slurry, the aqueous precursor slurry so obtained is dried to form a catalyst precursor, and the catalyst precursor is calcined to form said catalyst, the process comprising: (i) combining, in an aqueous solution, source compounds of Bi and Ce, and optionally one or more of Na, K, Rb, Cs, Ca, a rare earth element, Pb, W and Y, to form a mixture, (ii) adding a source compound of molybdenum to the mixture to react with the mixture and form a precipitate slurry, and (iii) combining the precipitate slurry with source compounds of the remaining elements and of the remaining molybdenum in the catalyst to form the aqueous catalyst precursor slurry.
    Type: Application
    Filed: March 23, 2010
    Publication date: September 29, 2011
    Inventors: Charles J. Besecker, James Frank Brazdil, JR., Mark A. Toft, Michael J. Seely, Robert A. Gustaferro
  • Publication number: 20110237821
    Abstract: A catalytic composition useful for the conversion of an olefin selected from the group consisting of propylene, isobutylene or mixtures thereof, to acrylonitrile, methacrylonitrile, and mixtures thereof. The catalytic composition comprising a complex of metal oxides comprising bismuth, molybdenum, iron, cerium and other promoters, wherein the ratio of cerium to iron in the composition is greater than or equal to 0.8 and less than or equal to 5.
    Type: Application
    Filed: March 23, 2010
    Publication date: September 29, 2011
    Inventors: James F. Brazdil, Mark A. Toft, Michael J. Seely, Charles J. Besecker, Robert A. Gustaferro
  • Publication number: 20100069659
    Abstract: A process for producing geometric shaped catalyst bodies K whose active material is a multielement oxide of stoichiometry [Bi1WbOx]a[Mo12Z1cZ2dFeeZ3fZ4gZ5nOy]1, in which a finely divided oxide Bi1WbOx with the particle size d50A1 and, formed from element sources, a finely divided intimate mixture of stoichiometry Mo12Z1cZ2dFeeZ3fZ4gZ5h with the particle size d50A2 are mixed in a ratio of a:1, this mixture is used to form shaped bodies and these are treated thermally, where (d50A1)0.7•(d90A1)1.5•(a)?1?820.
    Type: Application
    Filed: August 25, 2009
    Publication date: March 18, 2010
    Applicant: BASF SE
    Inventors: Andreas RAICHLE, Catharina Horstmann, Frank Rosowski, Klaus Joachim Muller-Engel, Holger Borchert, Gerhard Cox, Ulrich Cremer
  • Publication number: 20090221843
    Abstract: A catalyst for producing acrylonitrile capable of maintaining a high yield of acrylonitrile for a long time is provided. The catalyst has a composition represented by MoaBibFecWdRbeAfBgChDiOj(SiO2)k, wherein A is Ni, Mg, Ca, Sr, Ba, Mn, Co, Cu, Zn, Cd or mixture thereof; B is Al, Cr, Ga, Y, In, La, Ce, Pr, Nd, Sm or mixture thereof; C is Ti, Zr, V, Nb, Ta, Ge, Sn, Pb, Sb, P, B, Te or mixture thereof; D is Ru, Rh, Pd, Re, Os, Ir, Pt, Ag or mixture thereof; SiO2 is silica, when a is 10, b is 0.1 to 1.5, c is 0.5 to 3.0, d is 0.01 to 2.0, e is 0.02 to 1.0, fis 2.0 to 9.0, g isO to 5, his 0 to 3, i isO to 2, k is 10 to 200; and j is the atomic ratio of oxygen determined by the valence of other elements (excluding silicon); and (a×2+d×2)/(b×3+c×3+e×1+f×2+g×3) is 0.90 to 1.00.
    Type: Application
    Filed: February 26, 2009
    Publication date: September 3, 2009
    Applicant: DIA-NITRIX CO., LTD.
    Inventors: Hirokazu Watanabe, Motoo Yanagita, Kenichi Miyaki
  • Patent number: 6984750
    Abstract: A supported catalyst comprising a mixed metal oxide is useful for the vapor phase oxidation of an alkane or a mixture of an alkane and an alkene to an unsaturated carboxylic acid and for the vapor phase ammoxidation of an alkane or a mixture of an alkane and an alkene to an unsaturated nitrile.
    Type: Grant
    Filed: June 12, 2003
    Date of Patent: January 10, 2006
    Assignee: Rohm and Haas Company
    Inventors: Sanjay Chaturvedi, Jingguang Chen, Michael Bruce Clark, Jr., Anne Mae Gaffney
  • Patent number: 6965046
    Abstract: A catalyst composition comprising a complex of catalytic oxides of iron, bismuth, molybdenum, cobalt, cerium, antimony, at least one of nickel or magnesium, and at least one of lithium, sodium, potassium, rubidium, or thallium, and characterized by the following empirical formula: AaBbCcFedBieCofCegSbhMomOx wherein A is at least one of Cr, P, Sn, Te, B, Ge, Zn, In, Mn, Ca, W, or mixtures thereof B is at least one of Li, Na, K, Rb, Cs, Tl, or mixtures thereof C is least one of Ni, Mg or mixtures thereof a is 0 to 4.0 b is 0.01 to 1.5 c is 1.0 to 10.0 d is 0.1 to 5.0 e is 0.1 to 2.0 f is 0.1 to 10.0 g is 0.1 to 2.0 h is 0.1 to 2.0 m is 12.0 to 18.0 and x is a number determined by the valence requirements of the other elements present. The catalyst is useful in processes for the ammoxidation of an olefin selected from the group consisting of propylene, isobutylene or mixtures thereof, to acrylonitrile, methacrylonitrile and mixtures thereof, respectively.
    Type: Grant
    Filed: August 6, 2002
    Date of Patent: November 15, 2005
    Assignee: The Standard Oil Co.
    Inventors: Christos Paparizos, Michael J. Seely, Maria S. Friedrich, Dev D. Suresh
  • Patent number: 6924387
    Abstract: The present invention relates to a sold catalyst for manufacturing of a nitrile compound and a method of preparation thereof. More particularly, this invention relates to the solid catalyst expressed by the following formula (1): BiaAaBbQqOx][(100-z) % DdEeFefNigMomOy+z % SiO2] comprising a core catalytic phase expressed by [(100-z) %=DdEeFefNigMomOy+z % SiO2] and a shell catalytic phase expressed by [BinAaBbQqOx], which increases a yield in the manufacturing of a nitrile compound via ammoxidation of olefin, and the method of preparation thereof.
    Type: Grant
    Filed: February 12, 1999
    Date of Patent: August 2, 2005
    Assignee: Korea Research Institute of Chemical Technology
    Inventors: Tae-Sun Chang, Deug-Hee Cho, Dong-Koo Lee, Guijia Li, Young Kil Lee
  • Patent number: 6740769
    Abstract: A process for producing a molybdenum-bismuth-iron-containing metal oxide fluidized bed catalyst which has a controlled particle diameter and has satisfactory activity and physical properties. In a process for producing a fluidized bed catalyst containing molybdenum-bismuth-iron and silica as a carrier component, dried products formed in a spray drying step and having a particle diameter outside a desired range are pulverized, then the pulverized one is mixed into a slurry before spray drying, the resulting mixture is spray-dried, and the spray-dried particles are subjected to a classification operation to obtain particles having a diameter within the desired range, which are then calcined. The catalyst produced according to the present invention is suitable for producing acrylonitrile by ammoxidation of propylene.
    Type: Grant
    Filed: January 4, 2002
    Date of Patent: May 25, 2004
    Assignee: Mitsubishi Rayon Co., Ltd.
    Inventors: Kouichi Mizutani, Yoshimi Nakamura, Yutaka Sasaki, Kunio Mori
  • Patent number: 6723869
    Abstract: For the production of acrylonitrile by ammoxidation of propylene, there is provided a catalyst capable of giving a high yield for a long period of time. In producing acrylonitrile by ammoxidation of propylene, there is used a metal oxide as a catalyst, which metal oxide contains iron, antimony, molybdenum, bismuth, potassium, an F element, a G element, an H element and silica as essential components in a specific composition ratio, and in which metal oxide iron antimonate exists as a crystal phase, provided that the F element is at least one element selected from the group consisting of magnesium, calcium, strontium, barium, manganese, cobalt, nickel, copper, silver, zinc and cadmium, the G element is at least one element selected from the group consisting of chromium, aluminum, gallium and indium, and the H element is at least one element selected from the group consisting of yttrium, lanthanum, cerium, praseodymium, neodymium and samarium.
    Type: Grant
    Filed: April 9, 2002
    Date of Patent: April 20, 2004
    Assignee: Mitsubishi Rayon Co., Ltd.
    Inventors: Kunio Mori, Yutaka Sasaki, Kenichi Miyaki, Hirokazu Watanabe
  • Patent number: 6667020
    Abstract: A process increasing the yield of both HCN and acetonitrile produced during the manufacture of acrylonitrile comprising introducing a hydrocarbon selected from the group consisting of propylene and propane, a crude ketone and/or a mixture of at least two ketones, ammonia and air, into a reaction zone containing an ammoxidation catalyst, reacting the. hydrocarbon, the ketone, ammonia and oxygen over said catalyst at an elevated temperature to produce acrylonitrile, hydrogen cyanide and acetonitrile, and recovering the acrylonitrile, hydrogen cyanide and acetonitrile from the reactor.
    Type: Grant
    Filed: December 10, 2001
    Date of Patent: December 23, 2003
    Assignee: The Standard Oil Company
    Inventors: Michael J. Seely, Sanjay Purushottam Godbole, Dev Dhanaraj Suresh
  • Patent number: 6596897
    Abstract: A fluidized-bed catalyst for producing acrylonitrile by the ammoxidation of propylene, which comprises a silica carrier and a composite having the following formula: AaCcDdNafFegBihMiMo12Ox wherein A selected from the group consisting of potassium, rubidium, cesium, samarium, thallium and mixtures thereof; C is selected from the group consisting of phosphorus, arsenic, boron, antimony, chromium and mixtures thereof; D is selected from nickel, cobalt or mixtures thereof; M is selected from tungsten, vanadium or mixtures thereof. The catalyst of the present invention particularly suits the use under higher pressure and higher duties, and still maintains very high single-pass yield of acrylonitrile and a high ammonia conversion. This catalyst particularly suits the requirement for existing acrylonitrile plants to raise capacity. For new plants it can also reduce the investment on the catalyst and the pollution.
    Type: Grant
    Filed: June 30, 2000
    Date of Patent: July 22, 2003
    Assignees: China Petro-Chemical Corporation, Research Institute of Petroleum Processing
    Inventors: Xingya Guan, Xin Chen, Lianghua Wu
  • Patent number: 6479691
    Abstract: A catalyst composition represented by the following empirical formula which is useful in production of unsaturated nitrites by ammoxidation: Mo10BiaFebSbcNidCreFfGgHhKkXxYyOi(SiO2)j wherein F represents at least one element selected from the group consisting of zirconium, lanthanum and cerium, G represents at least one element selected from the group consisting of magnesium, cobalt, manganese and zinc, H represents at least one element selected from the group consisting of vanadium, niobium, tantalum and tungsten, x represents at least one element selected from the group consisting of phosphorus, boron, and tellurium, Y represents at least one element selected from the group consisting of lithium, sodium, rubidium and cesium, the suffixes a-k, x and y represent a ratio of atoms or atomic groups, and a=0.1-3, b=0.3-15, c=0-20, d=3-8, e=0.2-2, f=0.05-1, e/f>1, g=0-5, h=0-3, k=0.
    Type: Grant
    Filed: October 18, 2000
    Date of Patent: November 12, 2002
    Assignee: Mitsubishi Rayon Co., Ltd.
    Inventors: Yutaka Sasaki, Kunio Mori, Yoshimi Nakamura, Takao Shimizu, Yuichi Tagawa, Kenichi Miyaki, Seiichi Kawato
  • Patent number: 6413485
    Abstract: A process increasing the yield of both HCN and acetonitrile produced during the manufacture of acrylonitrile comprising introducing a hydrocarbon selected from the group consisting of propylene and propane, a crude ketone and/or a mixture of at least two ketones, ammonia and air, into a reaction zone containing an ammoxidation catalyst, reacting the hydrocarbon, the ketone, ammonia and oxygen over said catalyst at an elevated temperature to produce acrylonitrile, hydrogen cyanide and acetonitrile, and recovering the acrylonitrile, hydrogen cyanide and acetonitrile from the reactor.
    Type: Grant
    Filed: May 27, 1999
    Date of Patent: July 2, 2002
    Assignee: The Standard Oil Company
    Inventors: Michael J. Seely, Sanjay Purushottam Godbole, Dev Dhanaraj Suresh
  • Patent number: 6245931
    Abstract: Disclosed is a process for producing acrylonitrile from propylene, or methacrylonitrile from isobutylene by ammoxidation using an improved catalyst composition comprising an oxide catalyst represented by the formula: MomBibFefNinQqAaEeOx, wherein Q is a mixture of chromium and indium, A is at least one element selected from potassium, rubidium and cesium, E is at least one element selected from manganese magnesium, zinc, cerium, sodium and phosphorus, and m is a number of from 10 to 14, b is a number of from 0.1 to 3, f is a number of from 0.1 to 3, n is a number of from 4 to 10, q is a number of from 0.1 to 2, a is a number of from 0.01 to 0.5, e is a number of from 0 to 3, and x is a number determined by the valence requirements of the other elements present, and a silica carrier having the oxide catalyst supported thereon, wherein the silica carrier is present in an amount of from 40 to 60% by weight, based on the total weight of the oxide catalyst and the silica carrier.
    Type: Grant
    Filed: February 21, 1996
    Date of Patent: June 12, 2001
    Assignee: Asahi Kasei Kabushiki Kaisha
    Inventors: Kunitoshi Aoki, Satoru Komada
  • Patent number: 6238574
    Abstract: A process for upgrading aqueous acrylonitrile waste streams containing organic material comprising atomizing an acrylonitrile waste water stream containing organic material, introducing the atomized acrylonitrile waste water stream at a temperature below the decomposition temperature of the organics present in the waste water stream, into a reaction zone containing a catalyst and at least one reactant gas, reacting the atomized waste water stream and reactant gas in the presence of the catalyst to convert at least some of the organics in the waste water stream into at least one compound selected from the group consisting of acetonitrile, hydrogen cyanide and acrylonitrile.
    Type: Grant
    Filed: October 30, 1998
    Date of Patent: May 29, 2001
    Assignee: The Standard Oil Company
    Inventors: Mark Clark Cesa, Anne Marie Graham, Albert Richard Shuki
  • Patent number: 6136998
    Abstract: In the gas phase oxidation of an organic compound, using a metallic oxide fluidized-bed catalyst that contains molybdenum in an amount of 10% by weight or more, bismuth, and at least an element selected from the group consisting of iron and cerium, when tellurium is incorporated into this catalyst in such an amount that the atomic ratio of the tellurium to the molybdenum is (0.05-1.5):10, the catalytic activity can be retained for a prolonged period of time, and, at the same time, the loss of molybdenum and tellurium can be prevented during the oxidation reaction.
    Type: Grant
    Filed: October 10, 1997
    Date of Patent: October 24, 2000
    Assignee: Mitsubishi Rayon Co., Ltd.
    Inventors: Yutaka Sasaki, Kunio Mori, Yoshimi Nakamura, Kazuo Morishita, Ken Ohyachi
  • Patent number: 6124233
    Abstract: An improved catalyst for the production of unsaturated nitriles from their corresponding olefins, the catalyst having the atomic ratios described by the empirical formula Bi.sub.a Mo.sub.b V.sub.c Sb.sub.d Nb.sub.e A.sub.f B.sub.g O.sub.x and methods of using the same.
    Type: Grant
    Filed: November 1, 1999
    Date of Patent: September 26, 2000
    Assignee: Saudi Basic Industries Corporation
    Inventors: Mazhar Abdulwahed, Khalid El Yahyaoui
  • Patent number: 6087525
    Abstract: An improved catalyst for the production of unsaturated nitrites from their corresponding olefins, the catalyst composition having the atomic ratios described by the empirical formula Bi.sub.a Mo.sub.b V.sub.c Sb.sub.d Nb.sub.e Ag.sub.f A.sub.g B.sub.h O.sub.x and methods of using the same.
    Type: Grant
    Filed: November 2, 1999
    Date of Patent: July 11, 2000
    Assignee: Saudia Basic Industries Corporation
    Inventors: Mazhar Abdulwahed, Khalid El Yahyaoui
  • Patent number: 6087524
    Abstract: A method of preparing a catalyst having the elements and the proportions indicated by the following empirical formula:VSb.sub.m A.sub.a D.sub.d O.sub.xwhereA is one or more Ti, Sn, where Sn is always presentD is one or more Li, Mg, Ca, Sr, Ba, Co, Fe, Cr, Ga, Ni, Zn, Ge, Nb, Zr, Mo, W, Cu, Te, Ta, Se, Bi, Ce, In, As, B, Al and Mn whereinm is 0.5 to 10a is greater than zero to 10d is zero to 10x is determined by the oxidation state of the cations present,comprising making an aqueous slurry of a mixture of source batch materials comprising compounds of said elements to be included in the final catalyst, followed by drying and heat calcining the mixture to an active catalyst, wherein the source batch material for the tin is a solution which comprises SnO.sub.2 .multidot.xH.sub.2 O wherein x.gtoreq.0 dispersed in tetraalkyl ammonium hydroxide wherein the tetraalkyl ammonium hydroxide is defined by the following formula:C.sub.n H.sub.2n+1 NOHwherein 5.gtoreq.n.gtoreq.
    Type: Grant
    Filed: April 16, 1999
    Date of Patent: July 11, 2000
    Assignee: The Standard Oil Company
    Inventors: James Frank Brazdil, Jr., Joseph Peter Bartek
  • Patent number: 6084119
    Abstract: A process for producing acrylonitrile or methacrylonitrile, wherein a molybdenum compound, which is convertible to molybdenum oxide and not supported on a carrier is added to a fluidized bed reactor as an activator, in such a way that the ratio y of molybdenum atoms in the oxide catalyst represented by the formula:Mo.sub.y Bi.sub.p Fe.sub.q A.sub.a B.sub.b C.sub.c D.sub.d E.sub.e O.sub.fwill be maintained in the range of 1.02x to 1.12x (x=1.5p+q+a+c+1.5d+1.5e) during an ammoxydation reaction.
    Type: Grant
    Filed: September 8, 1998
    Date of Patent: July 4, 2000
    Assignee: Asahi Kasei Kogyo Kabushiki Kaisha
    Inventors: Hideo Midorikawa, Ken Someya
  • Patent number: 6072070
    Abstract: Mixed oxide vanadium/antimony/titanium ammoxidation catalysts, particularly suited for the ammoxidation of alkanes and exhibiting X-ray diffraction spectra which are characteristic of a crystallographic phase of rutile TiO.sub.2, are prepared by (a) dissolving respective soluble compounds of vanadium, of antimony and of titanium in at least one saturated alcohol, (b) contacting the alcoholic solution thus obtained with water and precipitating the mixed oxide therefrom, and (c) separating and calcining the mixed oxide thus precipitated.
    Type: Grant
    Filed: May 8, 1997
    Date of Patent: June 6, 2000
    Assignee: R.P. Fiber & Resin Intermediates
    Inventors: Stefania Albonetti, Gilbert Blanchard, Paolo Burattin, Fabrizio Cavani, Ferruccio Trifiro
  • Patent number: 6063728
    Abstract: An ammoxidation catalyst comprising a compound oxide of Mo, V, Nb, and at least one element selected from the group consisting of Te and Sb, wherein the compound catalyst exhibits an X-ray diffraction pattern satisfying the following relationship:0.40.ltoreq.R.ltoreq.0.75wherein R represents the intensity ratio defined by the following formula:R=P.sub.1 /(P.sub.1 +P.sub.2)wherein P.sub.1 and P.sub.2 represent the intensities of peak 1 and peak 2 appearing at diffraction angles (2.theta.) of 27.3.+-.0.3.degree. and 28.2.+-.0.3.degree., respectively.By the use of the ammoxidation catalyst of the present invention, not only can acrylonitrile or methacrylonitrile be produced in high yield, but also oxidative decomposition of ammonia feedstock into nitrogen can be effectively suppressed, thereby enabling an improved utilization of ammonia as a feedstock.
    Type: Grant
    Filed: August 5, 1998
    Date of Patent: May 16, 2000
    Assignee: Asahi Kasei Kogyo Kabushiki Kaisha
    Inventors: Hidenori Hinago, Satoru Komada
  • Patent number: 6057471
    Abstract: An ammoxidation method in a fluidized-bed reactor, in which, when a starting material to be ammoxidized is ammoxidized by means of vapor-phase catalytic fluidized-bed reaction, the reaction is carried out in a fluidized-bed reactor to which an oxygen-containing gas is fed through feed openings provided at the bottom thereof, and a starting material to be ammoxidized is fed through feed openings provided above the feed openings for the oxygen-containing gas, the distance between the feed openings for the oxygen-containing gas and those for the starting material being from 30 to 250% of the height of a fluidized solid matter in a static state so as to form such a fluidized bed that the density of the fluidized solid matter at the feed openings for the starting material to be ammoxidized is in the range of 50 to 300 kg/m.sup.3 and that the gas velocity is 1 m/s or lower.
    Type: Grant
    Filed: September 25, 1997
    Date of Patent: May 2, 2000
    Assignee: Mitsubishi Rayon Co., Ltd.
    Inventors: Toshio Nakamura, Hiroshi Murata, Katsumasa Nishijima, Masanori Yamaguchi, Yoshikazu Sawada
  • Patent number: 6013825
    Abstract: The present invention is a process for producing an unsaturated nitrile such as acrylonitrile or methacrylonitrile by ammoxidation of an organic compound such as propylene, isobutene or tertiary butanol. The process comprises carrying out the ammoxidation such that the organic acid/unreacted ammonia ratio in an ammoxidation product gas is controlled to remain within the range from 0.8 to 3.0 inclusive in a reactor, introducing the ammoxidation product gas into a quench tower, and reacting in the tower the unreacted ammonia with the organic acid produced in a reactor, to fix the unreacted ammonia as an ammonium salt of the organic acid.
    Type: Grant
    Filed: September 30, 1997
    Date of Patent: January 11, 2000
    Assignee: Asahi Kasei Kogyo Kabushiki Kaisha
    Inventors: Ken Someya, Hideo Midorikawa
  • Patent number: 5840955
    Abstract: A process for the enhanced recovery of hydrogen cyanide (HCN) obtained from the reactor effluent of an ammoxidation reaction of propylene or isobutylene comprising passing the reactor effluent through a quench column, an absorber column, a first distillation column, a second distillation column, a cooler and a knock-out pot, wherein the improvement comprises contacting the vapor phase containing hydrogen cyanide with an aqueous stream.
    Type: Grant
    Filed: November 25, 1997
    Date of Patent: November 24, 1998
    Inventors: Edward J. Sockell, Joseph C. Sarna, Ali Kerr, Sanjay P. Godbole
  • Patent number: 5686373
    Abstract: Polymetal oxide materials of the general formula I?A!.sub.p ?B!.sub.q (I),where ##STR1## X.sup.1 is W, Nb, Ta, Cr and/or Ce, X.sup.2 is Cu, Ni, Co, Fe, Mn and/or Zn,X.sup.3 is Sb and/or Bi,X.sup.4 is Li, Na, K, Rb, Cs and/or H,X.sup.5 is Mg, Ca, Sr and/or Ba,X.sup.6 is Si, Al, Ti and/or Zr,X.sup.7 is Mo, W, V, Nb and/or Ta,a is from 1 to 8,b is from 0.2 to 5,c is from 0 to 23,d is from 0 to 50,e is from 0 to 2,f is from 0 to 5,g is from 0 to 50,h is from 4 to 30,i is from 0 to 20,x and y are each a number which is determined by the valency and frequency of the elements other than oxygen in I and p and q are non-zero numbers whose ratio p/q is from 160:1 to 1:1,and their use as catalysts.
    Type: Grant
    Filed: February 22, 1995
    Date of Patent: November 11, 1997
    Assignee: BASF Aktiengesellschaft
    Inventors: Andreas Tenten, Friedrich-Georg Martin, Hartmut Hibst, Laszlo Marosi, Veronika Kohl
  • Patent number: 5663113
    Abstract: Disclosed is an ammoxidation catalyst composition for use in producing acrylonitrile from propylene, or methacrylonitrile from isobutene or tert-butanol, by ammoxidation of the propylene or of the isobutene or tert-butanol, comprising an oxide catalyst composition represented by the formula:Mo.sub.12 (Bi.sub.1-a A.sub.a).sub.b Fe.sub.c Co.sub.d X.sub.e Y.sub.f O.sub.g,wherein A is at least one rare earth element, X is at least one element selected from the group consisting of nickel, magnesium, zinc and manganese, Y is at least one element selected from the group consisting of potassium, rubidium and cesium, a is a number of from 0.6 to 0.8, b is a number of from 0.5 to 2, c is a number of from 0.1 to 3, d is a number of from more than 0 to 10, e is a number of from 0 to 8, f is a number of from 0.01 to 2, and g is a number determined by the valence requirements of the other elements present.
    Type: Grant
    Filed: February 16, 1996
    Date of Patent: September 2, 1997
    Assignee: Asahi Kasei Kogyo Kabushiki Kaisha
    Inventors: Hideo Midorikawa, Ken Someya
  • Patent number: 5658842
    Abstract: Disclosed is an ammoxidation catalyst composition for use in producing acrylonitrile from propylene, or methacrylonitrile from isobutene or tert-butanol, by ammoxidation of the propylene or of the isobutene or tert-butanol, comprising an oxide catalyst composition represented by the formula:Mo.sub.12 (Bi.sub.1-a A.sub.a).sub.b Fe.sub.c Ni.sub.d X.sub.e Y.sub.f O.sub.g,whereinA is at least one rare earth element,X is at least one element selected from magnesium and zinc,Y is at least one element selected from potassium, rubidium and cesium,a is a number of from 0.6 to 0.8,b is a number of from 0.5 to 2,c is a number of from 0.1 to 3,d is a number of from 4 to 10,e is a number of from 0 to 3,f is a number of from 0.01 to 2, andg is a number determined by the valence requirements of the other elements present.
    Type: Grant
    Filed: December 27, 1995
    Date of Patent: August 19, 1997
    Assignee: Asahi Kasei Kogyo Kabushiki Kaisha
    Inventors: Hideo Midorikawa, Ken Someya, Kunitoshi Aoki, Osamu Nagano
  • Patent number: 5576469
    Abstract: The process for the ammoxidation of a C.sub.3 to C.sub.5 paraffinic hydrocarbon to its corresponding .alpha.,.beta.-unsaturated hydrocarbon comprising reacting the C.sub.3 to C.sub.5 paraffinic hydrocarbon with ammonia and oxygen in a fluid bed reactor at a temperature of between 250.degree. C. to 600.degree. C. in the presence of a catalyst having the empirical formula as follows:V.sub.v Sb.sub.m A.sub.a D.sub.d O.sub.xwherein A when present is Sn and/or Ti;D when present is one or more of Li, Mg, Na, Ca, Sr, Ba, Co, Fe, Cr, Ga, Ni, Zn, Ge, Nb, Zr, Mo, W, Cu, Te, Ta, Se, Bi, Ce, In, As, B, Al, P and Mn; andwherein v is 1, m is 0.5-75, a is 0 to 25, d is 0 to 25, and x is determined by the oxidation state of the cations present,and a minor quantity of an halogen-containing component, preferably characterized by the following formula:R--X or X.sub.2where R=Hydrogen, C.sub.1 -C.sub.20 alkyland X=F, Cl, Br, I or mixtures thereof.
    Type: Grant
    Filed: June 5, 1995
    Date of Patent: November 19, 1996
    Assignee: The Standard Oil Co.
    Inventors: James F. Brazdil, Jr., Fernando A. P. Cavalcanti
  • Patent number: 5466837
    Abstract: An ethylene stream which contains ethane as an impurity or a propylene stream which contains propane as an impurity is subjected to adsorption at a temperature of 50.degree. to 200.degree. C. in a bed of adsorbent which selectively adsorbs ethylene or propylene, thereby adsorbing substantially all of the ethylene or propylene. The purified ethylene or propylene stream is then subjected to partial oxidation in the presence of oxygen and, optionally ammonia to produce various partial oxidation products. The process is operated on a low per pass conversion with recycle of unreacted ethylene or propylene. In the system of the invention the adsorption unit may be upstream or downstream of the partial oxidation reactor.
    Type: Grant
    Filed: April 22, 1994
    Date of Patent: November 14, 1995
    Assignee: The BOC Group, Inc.
    Inventors: Ramakrishnan Ramachandran, Loc H. Dao
  • Patent number: 5466857
    Abstract: A process for the reduction in the amount of waste material generated during the manufacture of acrylonitrile comprising introducing an additional amount of oxygen containing gas, preferably air, in the substantial absence of any oxygenate compounds, into the upper portion of the fluid bed reactor to react with at least some of the unreacted ammonia to reduce the amount of unreacted ammonia present in the reactor effluent.
    Type: Grant
    Filed: August 10, 1994
    Date of Patent: November 14, 1995
    Assignee: The Standard Oil Company
    Inventors: Vincent G. Reiling, Jeffrey E. Rinker, Timothy R. McDonel, Joseph C. Sarna
  • Patent number: 5378668
    Abstract: Molybdenum/bismuth-based fluid-bed catalysts which are used for the ammoxidation of olefins can be reactivated by addition of a mixed oxide of formulaMo.sub.20 (P, Cr).sub.0.3-2.0 (Bi, Ni, Fe, Co).sub.1.33-4.0 O.sub.xwherein, besides Mo, one element from component group (P, Cr) and one or more metals from component group (Bi, Ni, Fe, Co) are present, andx results from the valency requirements,the mixed oxide being applied to SiO.sub.2 as support.
    Type: Grant
    Filed: April 12, 1993
    Date of Patent: January 3, 1995
    Assignee: EC Erdolchemie GmbH
    Inventors: Brigitte Beuke, Jens Herwig, Ernst-Friedrich Neeb, Nikolaus Paris
  • Patent number: 5268497
    Abstract: A process for the production of an ethylenically unsaturated nitrile from a hydrocarbon feed stream comprised of a mixture of an alkene and an alkane by reaction with an oxygen-containing gas and ammonia. The alkene is converted to unsaturated nitrile by reaction with the oxygen and ammonia in the presence of a suitable catalyst in an ammoxidation reactor; the nitrile product is recovered from the product stream; some of the byproduct carbon oxides and some of the inert gas introduced into the system with the reactants are removed from product stream and the remainder of this stream, now rich in unreacted alkene and alkane, and containing the rest of the byproduct gases and inert gases is introduced into a reactor which contains a catalyst that causes alkane contained in the gas stream to convert to the corresponding alkene. The effluent from the dehydrogenation reactor is recycled to the ammoxidation reactor.
    Type: Grant
    Filed: February 24, 1992
    Date of Patent: December 7, 1993
    Assignee: The BOC Group, Inc.
    Inventor: Ramakrishnan Ramachandran
  • Patent number: 5264608
    Abstract: A process for the production of an ethylenically unsaturated nitrile from a hydrocarbon feed stream comprised of a mixture of an alkene and an alkane by reaction with an oxygen-containing gas and ammonia. The alkene is converted to unsaturated nitrile by reaction with the oxygen and ammonia in the presence of a suitable catalyst in a first ammoxidation reactor; the nitrile product is recovered from the product stream; some of the byproduct carbon oxides and some of the inert gas introduced into the system with the reactants are removed from product stream and the remainder of this stream, now rich in unreacted alkene and alkane, and containing the rest of the byproduct gases and inert gases is introduced with additional oxygen-containing gas and ammonia into a second ammoxidation reactor which contains a catalyst that catalyzes reaction between the alkane, oxygen and ammonia to produce additional unsaturated nitrile.
    Type: Grant
    Filed: February 24, 1992
    Date of Patent: November 23, 1993
    Assignee: The BOC Group, Inc.
    Inventor: Ramakrishnan Ramachandran
  • Patent number: 5258543
    Abstract: Disclosed is a method for ammoxidizing C.sub.3 to C.sub.5 mono-olefins to .alpha.,.beta.-mono-unsaturated acyclic nitriles having 3 to 5 carbon atoms and HCN by introducing such mono-olefins molecular oxygen and ammonia into a reaction zone into vapor phase contact with a solid ammoxidation catalyst, wherein the mol ratio of introduced molecular oxygen and ammonia to said introduced mono-olefin is at least 1.5 and 1.0, respectively, wherein said catalyst contains the elements and proportions indicated by the empirical formula:V1Sb.sub.a M.sub.m N.sub.n O.sub.xwherea=0.5 to 2M=one or more of: Sn, Ti, Fe, and Gam=0.05 to 3, usually at least 0.1 and at most 1N=one or more of: W, Bi, Mo, Li, Mg, P, Zn, Mn, Te, Ge, Nb, Zr, Cr, Al, Cu, Ce, Bn=0.0 to 0.5,and wherein the preparation of the catalyst includes contacting in an aqueous dispersion a vanadium compound and an antimony compound while said vanadium is in solution.
    Type: Grant
    Filed: June 26, 1992
    Date of Patent: November 2, 1993
    Assignee: The Standard Oil Company
    Inventors: Dev D. Suresh, Michael J. Seely, Maria S. Friedrich, Christos Paparizos