Antimony Containing Material Utilized Patents (Class 558/325)
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Patent number: 9000207Abstract: 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: GrantFiled: May 22, 2014Date of Patent: April 7, 2015Assignee: Asahi Kasei Chemicals CorporationInventors: Yusuke Ishii, Takaaki Kato
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Publication number: 20130072710Abstract: Catalytic compositions are provided that are effective for providing increased acrylonitrile product without a significant decrease in hydrogen cyanide and/or acetonitrile production and provide an overall increase in production of acrylonitrile, hydrogen cyanide and acetonitrile. The catalytic compositions include a complex of metal oxides and include at least about 15% m-phase plus t-phase by weight and have a weight ratio of m-phase to m-phase plus t-phase of 0.45 or greater.Type: ApplicationFiled: September 21, 2011Publication date: March 21, 2013Inventors: James F. Brazdil, Mark A. Toft, Stephen T. McKenna
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Patent number: 8299203Abstract: A melt phase process for making a polyester polymer melt phase product by adding an antimony containing catalyst to the melt phase, polycondensing the melt containing said catalyst in the melt phase until the It.V. of the melt reaches at least 0.75 dL/g. Polyester polymer melt phase pellets containing antimony residues and having an It.V. of at least 0.75 dL/g are obtained without solid state polymerization. The polyester polymer pellets containing antimony residues and having an It.V. of at least 0.70 dL/g obtained without increasing the molecular weight of the melt phase product by solid state polymerization are fed to an extruder, melted to produce a molten polyester polymer, and extruded through a die to form shaped articles. The melt phase products and articles made thereby have low b* color and/or high L* brightness, and the reaction time to make the melt phase products is short.Type: GrantFiled: December 22, 2011Date of Patent: October 30, 2012Assignee: Grupo Petrotemex, S.A. DE C.V.Inventors: Mary Therese Jernigan, Michael Paul Ekart, Richard Gill Bonner
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Patent number: 7786247Abstract: A melt phase process for making a polyester polymer melt phase product by adding an antimony containing catalyst to the melt phase, polycondensing the melt containing said catalyst in the melt phase until the It.V. of the melt reaches at least 0.75 dL/g. Polyester polymer melt phase pellets containing antimony residues and having an It.V. of at least 0.75 dL/g are obtained without solid state polymerization. The polyester polymer pellets containing antimony residues and having an It.V. of at least 0.70 dL/g obtained without increasing the molecular weight of the melt phase product by solid state polymerization are fed to an extruder, melted to produce a molten polyester polymer, and extruded through a die to form shaped articles. The melt phase products and articles made thereby have low b* color and/or high L* brightness, and the reaction time to make the melt phase products is short.Type: GrantFiled: February 24, 2006Date of Patent: August 31, 2010Assignee: Eastman Chemical CompanyInventors: Mary Therese Jernigan, Michael Paul Ekart, Richard Gill Bonner
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Patent number: 7473666Abstract: A particulate porous ammoxidation catalyst for use in producing acrylonitrile or methacrylonitrile by reacting propylene, isobutene or tert-butyl alcohol with molecular oxygen and ammonia in a fluidized-bed reactor, the catalyst comprising a metal oxide and a silica carrier having supported thereon the metal oxide, wherein the metal oxide contains at least two elements selected from the group consisting of molybdenum, bismuth, iron, vanadium, antimony, tellurium and niobium, and the catalyst having a particle diameter distribution wherein the amount of catalyst particles having a particle diameter of from 5 to 200 ?m is from 90 to 100% by weight, based on the weight of the catalyst, and having a pore distribution wherein the cumulative pore volume of pores having a pore diameter of 80 ? or less is not more than 20%, based on the total pore volume of the catalyst and wherein the cumulative pore volume of pores having a pore diameter of 1,000 ? or more is not more than 20%, based on the total pore volume of theType: GrantFiled: February 27, 2004Date of Patent: January 6, 2009Assignee: Asahi Kasei Chemicals CorporationInventors: Hiroyuki Yanagi, Hideo Midorikawa, Tutomu Ueda
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Patent number: 6984750Abstract: 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: GrantFiled: June 12, 2003Date of Patent: January 10, 2006Assignee: Rohm and Haas CompanyInventors: Sanjay Chaturvedi, Jingguang Chen, Michael Bruce Clark, Jr., Anne Mae Gaffney
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Patent number: 6864384Abstract: A process for the manufacture of an improved iron promoted vanadium antimony oxide catalyst useful in the ammoxidation of propane to acrylonitrile wherein the source of iron (i.e. an iron containing compound such as Fe2O3) employed in the catalyst preparation has a BET surface area greater than 120 m2/gram. Such catalysts are useful in processes for the ammoxidation of a C3-C5 paraffinic hydrocarbon to its corresponding ?-?-unsaturated nitrile, the ammoxidation of propylene with NH3 and oxygen to acrylonitrile, the ammoxidation of methylpyridine with NH3 and oxygen to make cyanopyridine, the ammoxidation of m-xylene with NH3 and oxygen to make isophthalonitrile, and the oxidation of o-xylene to make phthalic anhydride.Type: GrantFiled: November 27, 2002Date of Patent: March 8, 2005Assignee: The Standard Oil CompanyInventors: James F. Brazdil, Joseph P. Bartek, Steven S. Trail
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Publication number: 20040181072Abstract: A process for the manufacture of an improved vanadium antimony oxide oxidation or ammoxidation catalyst which comprises heat treating the catalyst at a temperature above 780° C. in the presence of an oxygen enriched environment. Such catalysts are useful in processes for the ammoxidation of a C3-C5 paraffinic hydrocarbon to its corresponding &agr;-&bgr;-unsaturated nitrile, the ammoxidation of propylene with NH3 and oxygen to acrylonitrile, the ammoxidation of methylpyridine with NH3 and oxygen to make cyanopyridine, the ammoxidation of m-xylene with NH3 and oxygen to make isophthalonitrile, and the oxidation of o-xylene to make phthalic anhydride.Type: ApplicationFiled: March 5, 2004Publication date: September 16, 2004Inventors: James F. Brazdil, Fernando Antonio Pessoa Cavalcanti
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Publication number: 20040171861Abstract: Vanadium antimony oxide catalysts useful for the selective oxidation and ammoxidation of paraffins, olefins, and aromatic compounds are manufactured in a process comprising (i) forming a catalyst precursor slurry comprising a vanadium containing compound and an antimony containing compound in a liquid solvent medium which comprises an organic solvent, and (ii) recovering a vanadium antimony oxide from the slurry by drying the slurry in order to remove water and organic solvent.Type: ApplicationFiled: March 5, 2004Publication date: September 2, 2004Inventor: James F. Brazdil
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Publication number: 20040110978Abstract: A catalyst comprising a complex of catalytic oxides comprising potassium, cesium, cerium, chromium, cobalt, nickel, iron, bismuth, molybdenum, wherein the relative ratios of these elements is represented by the following general formulaType: ApplicationFiled: November 19, 2003Publication date: June 10, 2004Inventors: Christos Paparizos, Stephen C. Jevne, Michael J. Seely
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Publication number: 20040102642Abstract: A process for the manufacture of an improved iron promoted vanadium antimony oxide catalyst useful in the ammoxidation of propane to acrylonitrile wherein the source of iron (i.e. an iron containing compound such as Fe2O3) employed in the catalyst preparation has a BET surface area greater than 120 m2/gram. Such catalysts are useful in processes for the ammoxidation of a C3-C5 paraffinic hydrocarbon to its corresponding &agr;-&bgr;-unsaturated nitrile, the ammoxidation of propylene with NH3 and oxygen to acrylonitrile, the ammoxidation of methylpyridine with NH3 and oxygen to make cyanopyridine, the ammoxidation of m-xylene with NH3 and oxygen to make isophthalonitrile, and the oxidation of o-xylene to make phthalic anhydride.Type: ApplicationFiled: November 27, 2002Publication date: May 27, 2004Inventors: James F. Brazdil, Joseph P. Bartek, Steven S. Trail
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Publication number: 20040102643Abstract: A process for preparing an antimonate-based mixed metal oxide catalyst in a catalytically active oxidized state, wherein the catalyst is represented by the empirical formula MeaSbbXcQdReOf, wherein Me, X, Q, R, a, b, c, d, e, and f are as defined herein, comprising (a) contacting an aqueous Sb2O3 slurry with HNO3 and one or more Me compounds, and, optionally, one or more compounds selected from X, Q, or R compounds to form a first mixture; (b) heating and drying the first mixture to form a solid product; and (c) calcining the solid product to form the catalyst, the catalysts prepared by the process, and the use of the catalysts in ammoxidation and oxidation processes. The catalysts of the invention are particularly useful for the production of acrylonitrile from propylene, ammonia, and an oxygen-containing gas.Type: ApplicationFiled: November 27, 2002Publication date: May 27, 2004Inventor: Cathy L. Tway
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Patent number: 6667020Abstract: 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: GrantFiled: December 10, 2001Date of Patent: December 23, 2003Assignee: The Standard Oil CompanyInventors: Michael J. Seely, Sanjay Purushottam Godbole, Dev Dhanaraj Suresh
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Publication number: 20030144539Abstract: A catalyst composition for the vapor phase ammoxidation of alkanes and olefins of the general empirical formulae:Type: ApplicationFiled: December 21, 2001Publication date: July 31, 2003Applicant: Saudi Basic Industries Corporation (SABIC)Inventors: Edouard A. Mamedov, Kathleen A. Bethke, Shahid N. Shaikh, Armando Araujo, Neeta K. Kulkarni, Andrei Khodakov
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Patent number: 6596897Abstract: 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: GrantFiled: June 30, 2000Date of Patent: July 22, 2003Assignees: China Petro-Chemical Corporation, Research Institute of Petroleum ProcessingInventors: Xingya Guan, Xin Chen, Lianghua Wu
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Patent number: 6413485Abstract: 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: GrantFiled: May 27, 1999Date of Patent: July 2, 2002Assignee: The Standard Oil CompanyInventors: Michael J. Seely, Sanjay Purushottam Godbole, Dev Dhanaraj Suresh
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Patent number: 6171571Abstract: A new family of crystalline metal oxide compositions have been synthesized. These compositions are described by the empirical formula: AnNbMxM′yM″mOp where A is an alkali metal cation, ammonium ion and mixtures thereof, M is tungsten, molybdenum, or mixtures thereof. M′ is vanadium, tantalum and mixtures thereof, and M″ is antimony, tellurium and mixtures thereof. M′ and M″ are optional metals. These compositions are characterized by having an x-ray diffraction pattern having at least one peak at a d spacing of about 3.9 Å. A hydrothermal synthesis procedure as well as processes using the composition, e.g., ammoxidation of propane, are also disclosed.Type: GrantFiled: May 10, 1999Date of Patent: January 9, 2001Assignee: UOP LLCInventors: Robert L. Bedard, Paula L. Bogdan, Lisa M. King, Susan C. Koster
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Patent number: 6143916Abstract: 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: GrantFiled: December 3, 1999Date of Patent: November 7, 2000Assignee: Asahi Kasei Kogyo Kabushiki KaishaInventors: Hidenori Hinago, Satoru Komada
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Patent number: 6087524Abstract: 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: GrantFiled: April 16, 1999Date of Patent: July 11, 2000Assignee: The Standard Oil CompanyInventors: James Frank Brazdil, Jr., Joseph Peter Bartek
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Patent number: 6087525Abstract: 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: GrantFiled: November 2, 1999Date of Patent: July 11, 2000Assignee: Saudia Basic Industries CorporationInventors: Mazhar Abdulwahed, Khalid El Yahyaoui
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Patent number: 6083869Abstract: The present invention relates to a process for the preparation of mixed vanadium, antimony and iron oxides and to their use as catalysts for the ammoxidation of alkanes. The process for the preparation of a mixed oxide defined above is characterized in that:respective vanadium, antimony and iron compounds are dissolved in at least one saturated alcohol or in water,the alcoholic .epsilon.olution or the aqueous solution thus obtained is brought into contact with an aqueous solution containing an ammonium salt, in order to precipitate the mixed oxide,the mixed oxide obtained is separated and calcined.Type: GrantFiled: June 11, 1998Date of Patent: July 4, 2000Assignee: Rhodia Fiber and Resin IntermediatesInventors: Stefania Albonetti, Gilbert Blanchard, Paolo Burattin, Fabrizio Cavani, Ferruccio Trifiro
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Patent number: 6072070Abstract: 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: GrantFiled: May 8, 1997Date of Patent: June 6, 2000Assignee: R.P. Fiber & Resin IntermediatesInventors: Stefania Albonetti, Gilbert Blanchard, Paolo Burattin, Fabrizio Cavani, Ferruccio Trifiro
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Patent number: 6063728Abstract: 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: GrantFiled: August 5, 1998Date of Patent: May 16, 2000Assignee: Asahi Kasei Kogyo Kabushiki KaishaInventors: Hidenori Hinago, Satoru Komada
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Patent number: 6043185Abstract: A catalyst useful in the manufacture of acrylonitrile or methacrylonitrile by the catalytic reaction in the vapor phase of a paraffin selected from propane and isobutane with molecular oxygen and ammonia by catalytic contact of the reactants in a reaction zone with a catalyst, the feed composition having a mole ratio of the paraffin to ammonia in the range of about 1.0 to 10 and a mole ratio of paraffin to oxygen in the range of about 1.0 to 10, wherein said catalyst has the elements in the proportions indicated by the empirical formula:MO.sub.a V.sub.b Sb.sub.c Ga.sub.d X.sub.e O.sub.xwhereX is one or more of As, Te, Se, Nb, Ta, W, Ti, Zr, Cr, Mn, Fe, Ru, Co, Rh, Ni, Pd, Pt, B, In, Ce, Re, Ir, Ge, Sn, Bi, Y, Pr, an alkali metal, and an alkaline earth metal, preferably Nb, Ce, Fe, Ge, Sn, In, As, Se, and B, especially preferred being Nb,a equals 1,b equals 0.0 to 0.99, preferably 0.1 to 0.5,c equals 0.01 to 0.9, preferably 0.05 to 0.5,d equals 0.01 to 0.5, preferably 0.01 to 0.4,e equals 0.0 to 1.Type: GrantFiled: April 2, 1999Date of Patent: March 28, 2000Assignee: The Standard Oil CompanyInventors: Larry M. Cirjak, Anne Venturelli, Timothy J. Cassidy, Marc A. Pepera, Tama L. Drenski
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Patent number: 6020533Abstract: Hydrocarbon conversion processes using a new family of crystalline manganese phosphate compositions is disclosed. These compositions have an extended network; which network can be a one-, two-, or three-dimensional network. The composition has an empirical formula of:(A.sup.a+).sub.v (Mn.sup.b+)(M.sup.c+).sub.x P.sub.y O.sub.zwhere A is a templating agent such as an alkali metal, M is a metal such as Al, Fe.sup.3+ and "b" is the average manganese oxidation state and varies from greater than 3.0 to about 4.0.Type: GrantFiled: July 10, 1998Date of Patent: February 1, 2000Assignee: UOP LLCInventors: Gregory J. Lewis, Paula L. Bogdan
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Patent number: 5985788Abstract: A process for the preparation of (meth)acrylonitriles following ammoxidation process comprising catalytically oxidizing at least one saturated hydrocarbon selected from the group consisting of propane and isobutane with a mixed gas containing molecular oxygen and ammonia in the presence of a catalyst, is provided, the process being characterized by the use of a catalyst composed of complex oxide which is expressed by the general formula (I) below:Mo.alpha.Sb.beta.W.gamma.Ox (I)(in which .alpha., .beta. and .gamma. denote the number of atoms of Mo, Sb and W, respectively, and when .alpha. is 1, .beta. is 0.5-10 and .gamma. is 0.5-10; and x is a value determined by valence of the existing elements)as supported on a refractory inorganic carrier.According to this process, the object nitrites can be prepared at high yields with industrial advantages.Type: GrantFiled: October 7, 1996Date of Patent: November 16, 1999Assignee: Nippon Shokubai Co LtdInventors: Nobuji Kishimoto, Taizou Matsueda
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Patent number: 5747411Abstract: Supported catalysts which are suitable for ammonoxidation, comprisinga) a spherical or approximately spherical support material which essentially comprises aluminum oxide, silicon dioxide, titanium dioxide and/or zirconium dioxide and whose bulk density is from 0.6 to 1.2 kg/l, andb) an active material which comprises, as essential components, vanadium and antimony in oxidic form.Type: GrantFiled: August 10, 1995Date of Patent: May 5, 1998Assignee: BASF AktiengesellschaftInventors: Lothar Karrer, Frank-Friedrich Pape, Ulrich Kohler, Rainer Becker, Peter Weidlich, Michael Hullmann, Heinz-Josef Kneuper
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Patent number: 5576469Abstract: 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: GrantFiled: June 5, 1995Date of Patent: November 19, 1996Assignee: The Standard Oil Co.Inventors: James F. Brazdil, Jr., Fernando A. P. Cavalcanti
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Patent number: 5466857Abstract: 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: GrantFiled: August 10, 1994Date of Patent: November 14, 1995Assignee: The Standard Oil CompanyInventors: Vincent G. Reiling, Jeffrey E. Rinker, Timothy R. McDonel, Joseph C. Sarna
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Patent number: 5466837Abstract: 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: GrantFiled: April 22, 1994Date of Patent: November 14, 1995Assignee: The BOC Group, Inc.Inventors: Ramakrishnan Ramachandran, Loc H. Dao
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Patent number: 5268497Abstract: 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: GrantFiled: February 24, 1992Date of Patent: December 7, 1993Assignee: The BOC Group, Inc.Inventor: Ramakrishnan Ramachandran
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Patent number: 5264608Abstract: 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: GrantFiled: February 24, 1992Date of Patent: November 23, 1993Assignee: The BOC Group, Inc.Inventor: Ramakrishnan Ramachandran
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Patent number: 5258543Abstract: 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: GrantFiled: June 26, 1992Date of Patent: November 2, 1993Assignee: The Standard Oil CompanyInventors: Dev D. Suresh, Michael J. Seely, Maria S. Friedrich, Christos Paparizos
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Patent number: 5256810Abstract: An improved process for substantially eliminating, preferably completely eliminating of nitride formation on feed conduits for fluid bed catalyst reactors used in the manufacture of unsaturated nitriles from corresponding olefins, NH.sub.3 and oxygen comprising maintaining the temperature of the ammonia inside the conduit below its dissociation temperature and/or maintaining the temperature of the inside surface of the conduit below the temperature at which any monoatomic nitrogen can react with the conduit to form a nitride.Type: GrantFiled: October 14, 1992Date of Patent: October 26, 1993Assignee: The Standard Oil CompanyInventors: Steven J. Rowe, John T. Shultz, Robert J. Mack, Susan L. Dio
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Patent number: 5214016Abstract: Disclosed is a method of making a catalyst containing vanadium antimony and tin in the oxide state which comprises making an aqueous slurry of a mixture of source batch materials comprising compounds of the elements to be included in the final catalyst followed by drying and heat calcining the mixture to an active catalyst, using as the source batch material for tin a stannous salt of a C.sub.1 to C.sub.18 acyclic, monocarboxylic acid containing no ethylenic or acetylenic carbon-to-carbon unsaturation.Type: GrantFiled: April 2, 1992Date of Patent: May 25, 1993Assignee: The Standard Oil CompanyInventors: James F. Brazdil, Ian R. Little, Joseph B. Hazen
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Patent number: 5079207Abstract: Disclosed is a process for making an .alpha., .beta.-unsaturated monoitrile by the catalytic reaction of a paraffin containing 3-5 carbon atoms with molecular oxygen and ammonia by catalytic contact of the foregoing reactants in a reaction zone with a metal oxide catalyst containing the elements indicated by the empirical formula,V.sub.v A.sub.a D.sub.d Sn.sub.m Sb.sub.n Cu.sub.c O.sub.x (formula 1)in the relative atomic proportions indicated by the subscripts, whereA is selected from Te and BiD is one or more optional elements selected from Mo, W, Ti, Ge, Ce, La, Cr, Mn, Mg, Ca, Co, Ni, Fe, Nb, Ta, Ag, Zn, Cd, B, P, Na, K and Cs, anda is 0.001 to 30d is zero to 30c is 0.001 to 30m is 0.1 to 60n is 0.1 to 60n/v is>12 and<100m+n is.gtoreq.v+a+c+d, andx is determined by the valence requirements of the elements present, andwherein the reactants fed to the reaction zone contain a mole ratio of said paraffin:NH.sub.3 in the range from 2 to 16 and a mole ratio of said paraffin:O.sub.Type: GrantFiled: December 3, 1990Date of Patent: January 7, 1992Assignee: The Standard Oil CompanyInventors: James F. Brazdil, Linda C. Glaeser, Mark A. Toft
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Patent number: 5015756Abstract: An improved process is provided for the production of nitriles from hydrocarbons by reaction with an oxygen-containing gas comprising oxygen, air or a gas enriched in oxygen relative to air and ammonia in the presence of a suitable catalyst. In the process, a selective separator provides recycle of a substantial portion of the unreacted hydrocarbon as well as for a controlled amount of a gaseous flame suppressor in the system. The gaseous flame suppressor comprises a substantially unreactive hydrocarbon containing 1 to 5 carbon atoms, carbon dioxide and nitrogen when present in the feed to the ammoxidation reactor. The use of air or oxygen-enriched air in the feed to the ammoxidation reactor is particularly advantageous from an economic view in combination with a pressure swing adsorption unit as the selective separator. The process is characterized by high selectivity to the formation of the product.Type: GrantFiled: May 1, 1989Date of Patent: May 14, 1991Assignee: The BOC Group, Inc.Inventors: Ramakrishnan Ramachandran, Yagya Shukla, Donald L. MacLean
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Patent number: 4960921Abstract: Certain novel multiply promoted Mn-Sb oxides are superior catalysts for the ammoxidation of olefins to the corresponding unsaturated nitriles, the selective oxidation of olefins to unsaturated aldehydes and acids, and the oxydehydrogenation of olefins to diolefins.Type: GrantFiled: February 12, 1990Date of Patent: October 2, 1990Assignee: The Standard Oil CompanyInventors: Dev. D. Suresh, Robert K. Grasselli, Frances I. Ratka, James F. Brazdil
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Patent number: 4877764Abstract: Disclosed is ammoxidation of C.sub.3 to C.sub.5 acyclic alkanes with NH.sub.3 and O.sub.2 using (1) a mole ratio of alkane:NH.sub.3 in the range from 2 to 16 and a mole ratio of alkane:O.sub.2 in the range 1 to 10 and (2) a mixture of particulate catalyst compositions, the first being especially effective to promote formation of an unsaturated nitrile and an olefin from the paraffin, and the second catalyst composition being especially effective to promote the conversion of the olefin to the unsaturated nitrile. Catalyst compositions useful in the process are also disclosed.Type: GrantFiled: July 22, 1988Date of Patent: October 31, 1989Assignee: The Standard Oil CompanyInventors: Linda C. Glaeser, James F. Brazdil, Jr., Mark A. Toft
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Patent number: 4871706Abstract: Disclosed is the reaction of C.sub.3 to C.sub.4 paraffins with O.sub.2 and NH.sub.3 to make .alpha.,.beta.-unsaturated nitriles and olefins, using certain complex metal oxide catalysts containing V, Sb, W and certain optional elements.Type: GrantFiled: December 16, 1987Date of Patent: October 3, 1989Assignee: The Standard Oil CompanyInventors: James F. Brazdil, Jr., Linda C. Glaeser, Mark A. Toft
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Patent number: 4868330Abstract: An improved process is provided for the production of nitriles from hydrocarbons by reaction with an oxygen-containing gas comprising oxygen, air or a gas enriched in oxygen relative to air and ammonia in the presence of a suitable catalyst. In the process, a selective separator provides recycle of a substantial portion of the unreacted hydrocarbon as well as for a controlled amount of a gaseous flame suppressor in the system. The gaseous flame suppressor comprises a substantially unreactive hydrocarbon containing 1 to 5 carbon atoms, carbon dioxide and nitrogen when present in the feed to the ammoxidation reactor. The use of air or oxygen-enriched air in the feed to the ammoxidation reactor is particularly advantageous from an economic view in combination with a pressure swing adsorption unit as the selective separator. The process is characterized by high selectivity to the formation of the product.Type: GrantFiled: July 7, 1988Date of Patent: September 19, 1989Assignee: The BOC Group, Inc.Inventors: Ramakrishnan Ramachandran, Yagya Shukla, Donald L. MacLean
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Patent number: 4855275Abstract: A process for improving the performance of an ammoxidation catalyst comprising contacting said catalyst with a boron containing or heat decomposable boron compound to deposit boron on the catalyst.Type: GrantFiled: February 18, 1988Date of Patent: August 8, 1989Assignee: The Standard Oil CompanyInventors: Dev D. Suresh, Michael J. Seely, James F. Brazdil, Robert K. Grasselli
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Patent number: 4801731Abstract: An improved process for the preparation of acrylonitrile by the reaction of propylene, ammonia and oxygen in a fluidized catalyst bed in which the propylene and ammonia are premixed and fed in downwardly streams that are directly aligned with upwardly directed streams of an oxygen containing gas under conditions such that there is complete mixing of the gas streams prior to the gases having significant contact with the catalyst.Type: GrantFiled: December 14, 1987Date of Patent: January 31, 1989Assignee: E. I. Du Pont de Nemours and CompanyInventor: Stephen P. Jordan
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Patent number: 4769355Abstract: Ammoxidation of C.sub.3 to C.sub.5 acyclic alkanes with NH.sub.3 and O.sub.2 using (1) a mole ratio of alkane:NH.sub.3 in the range from 2 to 16 and a mole ratio of alkane:O.sub.2 in the range 1 to 10 and (2) a mixture of particulate catalyst compositions, the first being especially effective to promote formation of an unsaturated nitrile and an olefin from the paraffin, and the second catalyst composition being especially effective to promote the conversion of the olefin to the unsaturated nitrile. Catalytic compositions useful in the process are disclosed.Type: GrantFiled: April 20, 1987Date of Patent: September 6, 1988Assignee: The Standard Oil CompanyInventors: Linda C. Glaeser, James F. Brazdil, Jr., Mark A. Toft
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Patent number: 4767739Abstract: Disclosed is ammoxidation of C.sub.3 to C.sub.5 acyclic alkanes with NH.sub.3 and O.sub.2 using (1) a mole ratio of alkane:NH.sub.3 in the range from 2 to 16 and a mole ratio of alkane:O.sub.2 in the range 1 to 10 and (2) a mixture of particulate catalyst compositions, the first being especially effective to promote formation of an unsaturated nitrile and an olefin from the paraffin, and the second catalyst composition being especially effective to promote the conversion of the olefin to the unsaturated nitrile. Catalyst compositions useful in the process are also disclosed.Type: GrantFiled: April 20, 1987Date of Patent: August 30, 1988Assignee: The Standard Oil CompanyInventors: Linda C. Glaeser, James F. Brazdil, Jr., Mark A. Toft
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Patent number: 4757038Abstract: Iron-antimony metallic oxide catalysts which have become deactivated after being used for the production of aldehydes, acids, nitriles, or dienes through oxidation, ammoxidation, or oxidative dehydrogenation of organic compounds in fluidized-bed reactors are regenerated by adding to the catalyst a molybdenum-enriched catalyst formed by supporting a molybdenum component which is volatile or capable of forming a volatile compound under reaction conditions on a metallic oxide catalyst. The metallic oxide catalysts contain as essential components (I) Fe, (II) Sb, (III) at least one element selected from the group consisting of V, Mo and W, and (IV) Te.Type: GrantFiled: May 15, 1987Date of Patent: July 12, 1988Assignee: Nitto Chemical Industry Co., Ltd.Inventors: Yutaka Sasaki, Yutaka Kiyomiya, Toshio Nakamura, Yoshimi Nakamura, Masanori Yamaguchi
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Patent number: 4599430Abstract: A process is provided for the nitrogenation of hydrocarbons, resulting in the production of cyclic imides and nitriles from hydrocarbons contacted with molecular oxygen and a nitrogenating agent, including ammonia or primary amines, in the presence of an oxidation catalyst containing variable valency metal oxides, in the vapor phase at elevated temperature.Type: GrantFiled: February 2, 1984Date of Patent: July 8, 1986Assignee: The Standard Oil CompanyInventors: Ernest C. Milberger, Eunice K. T. Wong