Chromium Patents (Class 502/256)
  • Patent number: 5834572
    Abstract: Process for the manufacture of a support containing silica and at least one constituent chosen from alumina and aluminium phosphate, according to which an alcohol, water, a silicon alkoxide and an acid are mixed under conditions such that gelling or precipitation of silica is prevented, an acidic solution of an aluminium compound and/or a solution of a source of phosphate ions are added thereto, a gelling agent is added thereto, a gel is recovered which is washed with water and then by means of an organic liquid, the gel is then dried by atomization until a powder is obtained, and the powder is calcined. Polymerization of olefins in the presence of a catalyst containing chromium on a support as described above.
    Type: Grant
    Filed: February 2, 1996
    Date of Patent: November 10, 1998
    Assignee: Solvay (Societe Anonyme)
    Inventors: Helmut Derleth, Benoit Koch, Andre Rulmont, Fabienne Wijzen
  • Patent number: 5733836
    Abstract: A composition comprises at least one inorganic oxide and an oxygen-containing metal compound selected from the group consisting of a metal hydroxide, a metal oxide, and combinations of any two or more thereof. The composition can be optionally supported on a support such as an alumina. A process for producing mercaptans comprises contacting an alcohol with hydrogen sulfide in the presence of the composition under a condition sufficient to produce a mercaptan.
    Type: Grant
    Filed: March 22, 1996
    Date of Patent: March 31, 1998
    Assignee: Phillips Petroleum Company
    Inventors: Dean E. Stinn, Harold J. Swindell, Donald H. Kubicek, Marvin M. Johnson
  • Patent number: 5670438
    Abstract: Catalyst compositions are provided that comprise (a) discrete silica particles; (b) chromium; and (c) a support comprising silica. These composition are useful in polymerizing ethylene or copolymerizing ethylene with a comonomer and provide better control over the molecular weight and the molecular weight distribution of a resulting polymer.
    Type: Grant
    Filed: May 25, 1995
    Date of Patent: September 23, 1997
    Assignee: Phillips Petroleum Company
    Inventor: Rickey D. Badley
  • Patent number: 5654249
    Abstract: Chromium catalyst compositions are provided. These chromium catalyst compositions comprise at least two chromium catalyst systems that have a certain amount of chromium and a support that comprises silica and titania. the supports have certain pore volumes and surface areas. These catalyst compositions are useful for homopolymerizing ethylene or copolymerizing ethylene with a comonomer. The resins produced are useful in film applications.
    Type: Grant
    Filed: May 25, 1995
    Date of Patent: August 5, 1997
    Assignee: Phillips Petroleum Company
    Inventors: Kent W. Rollmann, Elizabeth A. Benham, William M. Whitte, Max P. McDaniel, William R. Coutant, F. Wallace Bailey
  • Patent number: 5641842
    Abstract: A process is provided comprising copolymerizing, under copolymerizing conditions, ethylene with one or more alpha-olefins, using a catalyst system, where said catalyst system has been sized, to produce a lower-density-copolymer, where said lower-density-copolymer has a density lower than a similar copolymer produced by copolymerizing, under said copolymerizing conditions, ethylene with said one or more alpha-olefins, using said catalyst system, where said catalyst system has not been sized, where said catalyst system that has been sized has had substantially all particles removed that produce, under said copolymerizing conditions, a higher-density-copolymer, where said higher-density-copolymer has a density higher than said similar copolymer.
    Type: Grant
    Filed: June 7, 1995
    Date of Patent: June 24, 1997
    Assignee: Phillips Petroleum Company
    Inventors: Max P. McDaniel, Rickey D. Badley, Bruce E. Kreischer, Joseph S. Shveima
  • Patent number: 5624877
    Abstract: A process is provided to produce polyolefins having a multimodal molecular weight distribution at the molecular level by contacting at least one mono-1-olefin in a polymerization zone, under polymerization conditions, with two different types of supported chromium catalyst systems. The first catalyst system comprises a chromium oxide catalyst system which comprises chromium oxide supported on an inorganic oxide. The second catalyst system comprises a chromocene catalyst system which comprises chromocene supported on an inorganic oxide. The resultant, recovered polymer has a multimodal, or at least a bimodal, molecular weight distribution.
    Type: Grant
    Filed: June 2, 1995
    Date of Patent: April 29, 1997
    Assignee: Phillips Petroleum Company
    Inventors: Joseph J. Bergmeister, Scott E. Kufeld, Max P. McDaniel
  • Patent number: 5625013
    Abstract: A process for the preparation of a supported catalyst for the polymerization of .alpha.-olefins, in which(1) a silicon dioxide-containing support gel is prepared by(1.1) introducing a sodium water glass or potassium water glass solution into a swirling stream of an aqueous mineral acid longitudinally and tangentially to the stream, spraying the resultant silica hydrosol in drop form into a gaseous medium and allowing it to solidify to form a hydrogel, and freeing the resultant hydrogel from salts by washing without prior ageing,(1.2) drying the hydrogel resulting from (1.1) to form the support gel,(2) the support gel (1) is charged with chromium trioxide or a chromium compound which can be converted into chromium trioxide under the conditions of process step (3), giving a chromium-containing support gel, and(3) the chromium-containing support gel (2) is heated at from 400.degree. to 1100.degree. C.
    Type: Grant
    Filed: May 24, 1995
    Date of Patent: April 29, 1997
    Assignee: BASF Aktiengesellschaft
    Inventors: Hans-Joachim Mueller, Godofredo Follmer, Rainer Konrad, Roland Saive, Martin Lux, Hans-Helmut Goertz, Guido Funk
  • Patent number: 5616529
    Abstract: Branched low-pressure polyethylenes are prepared by oligomerization of ethylene on a nickel-containing catalyst and polymerization of the oligomers obtained, if appropriate in the presence of ethylene, on a chromium-containing catalyst.
    Type: Grant
    Filed: February 27, 1996
    Date of Patent: April 1, 1997
    Assignee: Bayer AG
    Inventors: Karl-Heinz A. Ostoja-Starzewski, Josef Witte, Herbert Bartl, Karl-Heinz Reichert, Georgios Vasiliou
  • Patent number: 5607890
    Abstract: A supported Lewis acid catalyst system for catalyzing hydrocarbon conversion reactions including cationic polymerization, alkylation, isomerization and cracking reactions is disclosed, wherein the catalyst system comprises an inorganic oxide support having immobilized thereon a least one strong Lewis acid comprising at least one metal salt of a strong Bronsted acid wherein the metal is selected from the group consisting of aluminum, boron gallium, antimony, tantalum, niobium, yttrium, cobalt, nickel, iron, tin, zinc, magnesium barium strontium, calcium, tungsten, molybdenum and the metals of the lanthanide series and wherein the strong Bronsted acid is selected from the group consisting of mineral and organic acids stronger than 100% sulfuric acid.
    Type: Grant
    Filed: July 15, 1996
    Date of Patent: March 4, 1997
    Assignee: Exxon Chemical Patents Inc.
    Inventors: Frank J. Chen, Alain Guyot, Thierry Hamaide, Christophe Le Deore
  • Patent number: 5599887
    Abstract: This invention provides a chromium catalyst system that comprises[a] a support that comprises silica, wherein said support has a surface area to pore volume relationship as follows0.5.ltoreq.Pore volume.ltoreq.f(SA)wherein said f(SA) is(1.14.times.10.sup.-7)(SA).sup.3 -(1.19.times.10.sup.-4)(SA).sup.2 +(3.19.times.10.sup.-2)(SA)+0.20;and[b] a hexavalent chromium compound;wherein the surface concentration of said hexavalent chromium on said support is from 0.25 to 1 hexavalent chromium atoms per square nanometer.Another embodiment of this invention provides a process to homopolymerize ethylene, or copolymerize ethylene with a comonomer, said process comprises polymerizing ethylene with the above chromium catalyst composition.
    Type: Grant
    Filed: May 25, 1995
    Date of Patent: February 4, 1997
    Assignee: Phillips Petroleum Company
    Inventors: Rickey D. Badley, Kent W. Rollmann, Max P. McDaniel
  • Patent number: 5595953
    Abstract: Chromium catalyst compositions are provided. Theses chromium catalyst compositions can be used to polymerized olefins. The resulting polymerization product can have improved properties.
    Type: Grant
    Filed: June 7, 1995
    Date of Patent: January 21, 1997
    Assignee: Phillips Petroleum Company
    Inventors: Max P. McDaniel, Elizabeth A. Benham, Rickey D. Badley
  • Patent number: 5576263
    Abstract: This invention provides a chromium catalyst system that comprises[a] a support that comprises silica, wherein said support has a surface area to pore volume relationship as follows0.5.ltoreq.Pore volume.ltoreq.f(SA)wherein said f(SA) is(1.14.times.10.sup.-7)(SA).sup.3 -(1.19.times.10.sup.-4)(SA).sup.2 +(3.19.times.10.sup.-2)(SA)+0.20;and[b] a hexavalent chromium compound;wherein the surface concentration of said hexavalent chromium on said support is from 0.25 to 1 hexavalent chromium atoms per square nanometer.Another embodiment of this invention provides a process to homopolymerize ethylene, or copolymerize ethylene with a comonomer, said process comprises polymerizing ethylene with the above chromium catalyst composition.
    Type: Grant
    Filed: December 28, 1993
    Date of Patent: November 19, 1996
    Assignee: Phillips Petroleum Company
    Inventors: Rickey D. Badley, Kent W. Rollmann, Max P. McDaniel
  • Patent number: 5571769
    Abstract: A process for preparing a metal catalyst for the hydrogenation of oils and ats comprises causing a soluble Ni salt to react with an alkylsilane and an organic orthosilicate, so as to generate the catalyst support in Situ.
    Type: Grant
    Filed: June 15, 1994
    Date of Patent: November 5, 1996
    Assignee: Ministero Dell `Universita` e Della Ricerca Scientifica e Technologica
    Inventors: Giuseppe Gubitosa, Maurizio Giampeitri, Giuliano Vecchiato
  • Patent number: 5527867
    Abstract: A process is provided to produce polyolefins having a multimodal molecular weight distribution at the molecular level by contacting at least one mono-1-olefin in a polymerization zone, under polymerization conditions, with dual site supported chromium polymerization catalyst system. Such a polymerization catalyst system comprises an inorganic oxide supported chromium oxide catalyst system and a chromocene compound, wherein the supported catalyst system and chromocene compound are contacted in a polymerization reactor. The resultant, recovered polymer has at least a bimodal, or broad, molecular weight distribution.
    Type: Grant
    Filed: September 15, 1995
    Date of Patent: June 18, 1996
    Assignee: Phillips Petroleum Company
    Inventor: Joseph J. Bergmeister
  • Patent number: 5480852
    Abstract: A novel Phillips catalyst for the copolymerization of ethylene with .alpha.-olefins, contains, as a catalytically active component, a finely divided, aluminum silicate-supported, phosphorus-containing chromium catalyst. This can be prepared by applying at least one organic phosphorus(III), (IV) and/or (V) compound and at least one chromium(III) compound which does not react with said phosphorus compounds under the reaction conditions used, in succcession in any order or simultaneously, to a finely divided aluminum silicate hydrogel or xerogel with formation of a catalyst intermediate and activating the catalyst intermediate at elevated temperatures in an oxidizing atmosphere, with the result that the chromium catalyst is formed. The novel Phillips catalyst gives ethylene/.alpha.-olefin copolymers in which the comonomers are more uniformly distributed over the copolymer chains than is the case with ethylene/.alpha.-olefin copolymers which have been prepared with the aid of conventional Phillips catalysts.
    Type: Grant
    Filed: May 23, 1994
    Date of Patent: January 2, 1996
    Assignee: BASF Aktiengesellschaft
    Inventors: Hans-Joachim Mueller, Kaspar Evertz, Siegfried Weber, Guido Funk, Rainer Konrad, Roland Saive
  • Patent number: 5455216
    Abstract: A process for the preparation of a supported catalyst for the polymerization of .alpha.-olefins, in which(1) a silicon dioxide-containing support gel is prepared by(1.1) introducing a sodium water glass or potassium water glass solution into a swirling stream of an aqueous mineral acid longitudinally and tangentially to the stream, spraying the resultant silica hydrosol in drop form into a gaseous medium and allowing it to solidify to form a hydrogel, and freeing the resultant hydrogel from salts by washing without prior ageing,(1.2) drying the hydrogel resulting from (1.1) to form the support gel,(2) the support gel (1) is charged with chromium trioxide or a chromium compound which can be converted into chromium trioxide under the conditions of process step (3), giving a chromium-containing support gel, and(3) the chromium-containing support gel (2) is heated at from 400.degree. to 1100.degree. C.
    Type: Grant
    Filed: September 21, 1993
    Date of Patent: October 3, 1995
    Assignee: BASF Aktiengesellschaft
    Inventors: Hans-Joachim Mueller, Godofredo Follmer, Rainer Konrad, Roland Saive, Martin Lux, Hans-Helmut Goertz, Guido Funk
  • Patent number: 5434118
    Abstract: A catalytically active gel product is described consisting of a silica matrix which is amorphous to x-rays with uniform porosity, monomodal pore distribution and high surface area, within which one or more metal oxides possessing catalytic activity are dispersed. A process for preparing this catalytic gel is also described.
    Type: Grant
    Filed: October 12, 1993
    Date of Patent: July 18, 1995
    Assignees: Eniricerche S.p.A., Snamprogetti SpA
    Inventors: Angela Carati, Enrico Davini, Mario G. Clerici, Giuseppe Bellussi
  • Patent number: 5376611
    Abstract: A process for preparing pillared chromium ribbon-like silicate clay .alpha.-olefin catalysts is disclosed which comprises contacting a ribbon-like clay selected from the group consisting of sepiolites with a chromium solution. Preparation of said chromium solution comprises the steps of:a) dissolving a chromium salt and a base in water by heating solution at a temperature in the range of about 20.degree. C. to about 100.degree. C. thereby producing a first chromium solution having a pH in the range of about 1.5 to 2.5;b) diluting said first chromium solution with water so as to produce a second chromium solution wherein first chromium solution is diluted such that the ratio of added water to first chromium solution is in the range of about 5 ml H.sub.2 O to about 10 mls H.sub.2 O to per ml first solution, and thereafter heating said second chromium solution at a temperature in the range of about 60.degree. C. to about 95.degree. C.
    Type: Grant
    Filed: May 6, 1993
    Date of Patent: December 27, 1994
    Assignee: Phillips Petroleum Company
    Inventor: Joseph S. Shveima
  • Patent number: 5372983
    Abstract: A method for preparing silica, silica-chromium and silica-titanium-chromium polyolefin catalysts and catalyst supports wherein an alcohol-treated hydrogel is heated under partial oxidation conditions to reduce the carbon level to below about one weight percent prior to activation.
    Type: Grant
    Filed: May 24, 1993
    Date of Patent: December 13, 1994
    Assignee: W. R. Grace & Co.-Conn.
    Inventors: Jeffrey D. Mullen, Joel L. Kitaguchi, Darvin R. Moran
  • Patent number: 5364915
    Abstract: A process to produce a polyethylene composition that has less than 2 weight percent fines, based on the weight of said polyethylene composition, and a fluff bulk density greater than 25 pounds per cubic foot, said process comprising polymerizing ethylene in the presence of a trialkylaluminum compound, and a diluent that is essentially saturated with ethylene under slurry polymerization conditions that comprise a polymerization temperature from 104.degree. C. to 116.degree. C., with an activated catalyst system comprising (a) a catalyst support that comprises a silica compound, wherein said catalyst support has a pore volume less than 2 cubic centimeters per gram, (b) a catalyst that comprises a chromium compound, wherein the amount of chromium in said catalyst system is from about 0.1 to about 20 weight percent, wherein said weight percent is based on the total weight of said catalyst and catalyst support, and (c) a fluorine compound, wherein the amount of fluorine used is from about 0.
    Type: Grant
    Filed: September 25, 1992
    Date of Patent: November 15, 1994
    Assignee: Phillips Petroleum Company
    Inventors: Elizabeth A. Benham, Max P. McDaniel
  • Patent number: 5364825
    Abstract: Multimetal oxide compositions of the formula I[X.sup.1.sub.a X.sup.2.sub.b O.sub.x ].sub.p [X.sup.3.sub.c X.sup.4.sub.d X.sup.5.sub.e X.sup.6.sub.f X.sup.7.sub.g X.sup.2.sub.h O.sub.y ].sub.q(I)whereX.sup.1 is bismuth, tellurium, antimony, tin and/or copper,X.sup.2 is molybdenum and/or tungsten,X.sup.3 is an alkali metal, thallium and/or samarium,X.sup.4 is an alkaline earth metal, nickel, cobalt, copper, manganese, zinc, tin, cadmium and/or mercury,X.sup.5 is iron, chromium, cerium and/or vanadium,X.sup.6 is phosphorus, arsenic, boron and/or antimony,X.sup.7 is a rare-earth metal, titanium, zirconium, niobium, tantalum, rhenium, ruthenium, rhodium, silver, gold, aluminum, gallium, indium, silicon, germanium, lead, thorium and/or uranium,a is from 0.01 to 8,b is from 0.
    Type: Grant
    Filed: May 21, 1993
    Date of Patent: November 15, 1994
    Assignee: BASF Aktiengesellschaft
    Inventors: Hans-Peter Neumann, Hans Martan, Hermann Petersen, Walter Doerflinger
  • Patent number: 5310712
    Abstract: In a novel process for the preparation of a supported catalyst for the polymerization of .alpha.-olefins, a carrier gel (1) is first prepared by a method in which a sodium or potassium waterglass solution is introduced into a stream of an aqueous mineral acid which is subjected to angular momentum and may contain aluminum ions, longitudinally and tangentially to the stream, the resulting silica hydrosol sprayed in the form of drops into a gaseous medium and allowed to solidify into a hydrogel, and the resulting hydrogel is freed from salts by washing without prior aging and, if necessary, freed from some of the water by extraction with alcohols and/or ketones and is then dried. This gives the carrier gel (1), which is milled and is fractionated according to particle size. In a second process step, the carrier gel (1) is laden with chromium trioxide or with a chromium compound which can be converted into chromium trioxide, after which the resulting chromium-containing carrier gel (2) is heated at from 400.
    Type: Grant
    Filed: September 30, 1992
    Date of Patent: May 10, 1994
    Assignee: BASF Aktiengesellschaft
    Inventors: Guido Funk, Rainer Hemmerich, Hans Gropper, Erich Kolk, Godofredo Follmer
  • Patent number: 5290748
    Abstract: The present invention concerns a polymerization catalyst of olefins, said catalyst containing an active chromium compound on an inorganic support. The catalyst in accordance with the invention is prepared by vaporizing a precursor of chromium oxide such as chromyl chloride and allowing the chromium oxide vapor to react with the surface of, e.g., silica gel support material at 160.degree. . . . 500.degree. C. A selective binding of the chromium oxide to the support material is achieved by keeping the vapor pressure sufficiently high and the duration of interaction with the support sufficiently long so as to maintain an excess of the chromium compound in relation to the number of available binding sites on the support material. The activity of a catalyst in accordance with the invention even with a very low content of catalytic metal is as high as the activity of a catalyst of an appreciably higher metal content that has been prepared by the methods of the conventional technology.
    Type: Grant
    Filed: July 16, 1992
    Date of Patent: March 1, 1994
    Assignee: Neste Oy
    Inventors: Hilkka Knuuttila, Eeva-Liisa Lakomaa
  • Patent number: 5284811
    Abstract: An improved supported chromium oxide catalyst, a process for preparing the catalyst and a process for polymerizing olefin monomers utilizing the catalyst are provided. In accordance with the preparation process, chromium oxide and a support containing one or more of silica, titania, thoria, alumina, zirconia or aluminophosphates are combined, impregnated with a metal salt and activated. The metal salt is selected from the group consisting of alkali metal salts, alkaline earth metal salts and mixtures thereof.
    Type: Grant
    Filed: June 1, 1993
    Date of Patent: February 8, 1994
    Assignee: Phillips Petroleum Company
    Inventors: Donald R. Witt, Elizabeth A. Benham, Max P. McDaniel
  • Patent number: 5283043
    Abstract: There is provided a method for preparing organic-swelled layered silicate by direct crystallization from an alkaline reaction mixture containing a source of silicon oxide and organic onium compound, e.g., a cetyltrimethylammonium salt. Layered silicates containing interlayer polymeric chalcogenide are prepared by contacting the organic-swelled layered silicate with a source of polymeric chalcogenide, e.g., tetraethylorthosilicate.
    Type: Grant
    Filed: April 16, 1992
    Date of Patent: February 1, 1994
    Assignee: Mobil Oil Corp.
    Inventors: Ivy D. Johnson, Michael E. Landis
  • Patent number: 5240889
    Abstract: A composition useful for catalyzing alkylation and transalkylation reactions comprises a molecular sieve having alkylation and/or transalkylation activity, an inorganic refractory oxide component and greater than 3.5 weight percent water. Such a catalyst has been found to maintain a long life when used to produce ethylbenzene in an integrated process in which benzene is alkylated with ethylene and transalkylated with diethylbenzene. The catalyst can also be used to produce cumene via an integrated process in which benzene is alkylated with propylene and transalkylated with diisopropylbenzene.
    Type: Grant
    Filed: July 12, 1991
    Date of Patent: August 31, 1993
    Assignee: Union Oil Company of California
    Inventors: Martin West, Suheil F. Abdo
  • Patent number: 5232883
    Abstract: Process for obtaining monodisperse microspheroidal particles, comprising spraying an electrostatically charged gellable liquid material through a spraying orifice and into a chamber, so as to produce macrodrops which break up into microdrops which fall in the chamber and within which gelling is produced after spraying. The microspheroidal particles thus obtained can be collected on a solid surface or preferably in a liquid medium and find application in the manufacture of silica-based microspheroidal particles. These microspheroidal particles can be employed as catalyst supports for alpha-olefin polymerization.
    Type: Grant
    Filed: March 9, 1992
    Date of Patent: August 3, 1993
    Assignee: Solvay (Societe Anonyme)
    Inventors: Helmut Derleth, Abel Grosjean
  • Patent number: 5231066
    Abstract: A bimodal silica gel particle, its method of preparation and its use as a catalyst support in the polymerization of olefins is disclosed. The bimodal silica gel particle exhibits a bimodal pore radius distribution, wherein the silica gel particle has a first average pore radius and a second average pore radius differing by at least about 20 .ANG.. The bimodal silica gel particle is useful as a support for a transition metal-based catalyst to provide a polyolefin having a broad or bimodal molecular weight distribution.
    Type: Grant
    Filed: September 11, 1991
    Date of Patent: July 27, 1993
    Assignee: Quantum Chemical Corporation
    Inventors: Louis J. Rekers, Roger D. Laib
  • Patent number: 5202299
    Abstract: A catalyst for treatment of exhaust emissions from diesel engines includes a washcoat layer with a catalytically active metal. The washcoat layer has refractory oxide particles with catalytically active metal particles dispersed thereon, and colloidal silica disposed in a thin layer over the refractory oxide and metal particles. The refractory oxide particles and colloidal silica are each characterized by respective surface charges at a selected pH to cause the colloid to form the layer over the refractory oxide and metal particles. Preferably, the pH is selected to provide opposite and attractive surface charges between the colloidal silica and the refractory oxide particles. Preferably, the metal particles are at least one of the group consisting essentially of platinum, palladium, rhodium, ruthenium, copper and chromium.
    Type: Grant
    Filed: December 23, 1991
    Date of Patent: April 13, 1993
    Assignee: General Motors Corporation
    Inventors: Walter T. Symons, Richard F. Beckmeyer
  • Patent number: 5198400
    Abstract: Mixed catalyst compositions comprised of a first supported chromium-containing catalyst component and a second supported chromium-containing catalyst component and which additionally have one or more metallic or non-metallic catalytic agents associated therewith are provided. The additional metallic or non-metallic elements associated with the catalyst components can be aluminum, titanium, zirconium, boron, phosphorous or combinations thereof. The pore volume of the silica supports used for the first and second catalyst components differs by at least 0.3 cc/g. The mixed catalyst compositions of the invention are useful for the preparation of polyolefins. They are particularly useful of polymerization of ethylene in particle form polymerizations to produce high density polyethylene blow molding resins having good processability and physical properties. The improved particle form polymerization process and products obtained thereby using the above-described mixed catalyst compositions are also described.
    Type: Grant
    Filed: March 26, 1991
    Date of Patent: March 30, 1993
    Assignee: Quantum Chemical Corporation
    Inventors: Stanley J. Katzen, Thomas J. Pullukat, Michael W. Lynch, Louis J. Rekers
  • Patent number: 5189123
    Abstract: The present invention relates to a novel catalyst for the preparation of high molecular weight homopolymers and copolymers of ethene, which catalyst is obtainable by(1) loading a support based on silicon dioxide with(2) either chromium trioxide or a chromium compound capable of being converted to chromium trioxide under the conditions of stage (3) below and then(3) heating the resulting intermediate in a gas stream containing oxygen.the support (1) being a special silica xerogel obtained by extracting not more than 30% of the water from a silica hydrogel by means of an alkanol, an alkanone or a mixture thereof followed by drying, comminution and fractional screening.
    Type: Grant
    Filed: October 19, 1990
    Date of Patent: February 23, 1993
    Assignee: BASF Aktiengesellschaft
    Inventors: Hans Gropper, Guido Funk, Erich Kolk, Dieter Oeder
  • Patent number: 5169823
    Abstract: Disclosed herein is a method for the stabilizing treatment of a catalyst comprising washing the catalyst with hot washing water following the preparation of the catalyst, the catalyst being composed principally of chromium oxide and used in the production of chlorine by the oxidation of hydrogen chloride with an oxygen-containing gas, thereby improving its catalytic activity and prolonging its life.
    Type: Grant
    Filed: July 1, 1991
    Date of Patent: December 8, 1992
    Assignee: Mitsui Toatsu Chemicals, Inc.
    Inventors: Yukihiro Yoshikawa, Tooru Hihara, Teruo Hirayama, Kunihiro Yamada, Shinji Takenaka
  • Patent number: 5164353
    Abstract: A supported catalyst for ethene polymerization by Phillips catalysis is disclosed. The supported catalyst is prepared by (1) mixing a porous silicate in an inert, organic liquid to produce a silicate suspension, (2) providing an ester of phosphoric acid or phosphorous acid, (3) mixing an organic liquid, a chromium compound, and a trialkylaluminum compound to produce a chromium compound/aluminum compound and combining the silicate suspension, the phosphorus compound and the chromium compound/aluminum compound suspension. This resulting suspension is evaporated to dryness to form a catalyst intermediate. The catalyst intermediate is heated in nitrogen, then heated in an oxygen-containing atmosphere, and then heated again in nitrogen to produce an activated catalyst. The activated catalyst is suspended in an organic liquid and treated with an alkyl boron compound to produce the desired supported catalyst.
    Type: Grant
    Filed: November 14, 1989
    Date of Patent: November 17, 1992
    Assignee: BASF Aktiengesellschaft
    Inventors: Siegfried Weber, Guido Funk
  • Patent number: 5096868
    Abstract: A supported catalyst for polymerizing 1-olefins, for example, ethylene, is prepared by depositing a chromium compound and a titanium compound on a refractory oxide support which is substantially non-spherical, and which has a relatively broad particle size distribution range. The catalyst is preferably combined, either outside of the polymerization vessel or in situ, with a sufficient amount of at least one magnesium composition of the formula RMgR', where R and R' are the same or different and they are C.sub.1 to C.sub.12 hydrocarbyl groups, to provide a molar ratio of magnesium to chromium in the catalyst composition of about 0.01:1 to about 25:1. The resulting catalyst composition has good feedability and fluidization characteristics, and it produces resins of relatively high HLMI at relatively low temperatures.
    Type: Grant
    Filed: April 27, 1990
    Date of Patent: March 17, 1992
    Assignee: Mobil Oil Corporation
    Inventors: John T. T. Hsieh, Jeanne C. Simondsen
  • Patent number: 5093300
    Abstract: A method for activating supported chromium oxide catalysts in which a chromium-containing catalyst on a silica-containing base is first heated in an oxidizing atmosphere at temperatures up to about 850.degree. C. and then cooled down. During the cooling step of the catalyst, the oxidizing atmosphere is replaced by a non-oxidizing one, leading to an activated catalyst. A process for the polymerization of alpha-olefins, especially ethylene, in which at least one alpha-olefin is contacted, under polymerization conditions, with the catalyst activated by the method described above.
    Type: Grant
    Filed: June 3, 1988
    Date of Patent: March 3, 1992
    Assignee: Solvay & Cie (Societe Anonyme)
    Inventors: Claude Vogels, Luc Lerot
  • Patent number: 5081089
    Abstract: Improved mixed chromium catalysts useful in particle form polymerizations to produce readily processable high density polyolefin resins which also have high resistance to environmental stress cracking are provided. First and second chromium-containing catalyst components obtained using silica supports of different pore volumes and wherein one of the catalyst components also contains aluminum are employed for the preparation of the mixed catalysts. The polymerization process and products obtained using the above-described mixed catalysts are also described.
    Type: Grant
    Filed: August 22, 1990
    Date of Patent: January 14, 1992
    Assignee: National Distillers and Chemical Corporation
    Inventors: Louis J. Rekers, Stanley J. Katzen
  • Patent number: 5079317
    Abstract: A process for producing polyethylene is disclosed in which ethylene is polymerized in the presence of a composite catalyst. The catalyst is made up of a solid catalyst component typified by a selected chromium compound, a modified aluminum compound typified by a trialkylaluminum and an R.sub.n.sup.1 Al(OR.sup.2).sub.3-n compound wherein R.sup.1 and R.sup.2 are represented by selected hydrocarbon groups and n by 0.ltoreq.n.ltoreq.3. The polymer has improved melt index, flow parameter and melt tension characteristics.
    Type: Grant
    Filed: October 11, 1989
    Date of Patent: January 7, 1992
    Assignee: Nippon Oil Co., Ltd.
    Inventors: Yoshino Tajima, Kazutoshi Nomiyama, Nobuyuki Kuroda, Kazuo Matsuura
  • Patent number: 5073531
    Abstract: Sodium-free olefin polymerization catalysts having high polymerization activities and methods of preparing such catalysts are provided. A hydrolyzable silicate ester and a hydrolyzable acid-generating chromium compound are combined with water and an organic solvent whereby a hydrolysis reaction solution is formed comprising silica and chromium. Sufficient acid-neutralizing gelling agent is added to the solution to form a gelled silica-chromium catalyst and the catalyst is aged to stabilize its structure. Water and solvent are removed from the catalyst and the catalyst is activated.
    Type: Grant
    Filed: May 7, 1990
    Date of Patent: December 17, 1991
    Assignee: Phillips Petroleum Company
    Inventor: Donald R. Witt
  • Patent number: 5061673
    Abstract: The present invention pertains to novel solid solutions involving Cr.sub.2 O.sub.3, V.sub.2 O.sub.3 and TiO.sub.2 and the method for their preparation. The solid compositions involving Cr.sub.2 O.sub.3, V.sub.2 O.sub.3 and TiO.sub.2 fall within the shaded area of a polygon in a ternary composition diagram of Cr.sub.2 O.sub.3, V.sub.2 O.sub.3 and TiO.sub.2 as shown in the drawing herein e.g., FIG. 1. The composition may be used as an oxidation catalyst or in the manufacture of high temperature refractories.
    Type: Grant
    Filed: June 1, 1990
    Date of Patent: October 29, 1991
    Assignee: Texaco Inc.
    Inventors: Arnulf Muan, Mitri S. Najjar
  • Patent number: 5034364
    Abstract: An olefin, particularly alpha-olefin, polymerization catalyst composition, supported on a refractory oxide support comprises two chromium specie: (1) CrO.sub.3 or any chromium compound calcinable to CrO.sub.3 ; and (2) at least one silylchromate compound. The composition is prepared by sequentially depositing specie (1) and (2) onto the same support.
    Type: Grant
    Filed: November 9, 1989
    Date of Patent: July 23, 1991
    Assignee: Mobil Oil Corporation
    Inventors: Bohumil V. Kral, Grace O. Tsien, Chisung Wu
  • Patent number: 4988657
    Abstract: Olefins are polymerized with a catalyst composition which forms on mixing a supported chromium oxide catalyst system and a silane compound. This composition allows the production of one or more comonomers in-situ. The resultant polymer has a lower density, a higher melt index, and a higher high load melt index than polymers produced with a similar catalyst system in the absence of a silane compound.
    Type: Grant
    Filed: October 6, 1989
    Date of Patent: January 29, 1991
    Assignee: Phillips Petroleum Company
    Inventors: Shirley J. Martin, Elizabeth A. Benham, Max P. McDaniel, Bruce W. Gerhold
  • Patent number: 4976848
    Abstract: For a heavy hydrocarbonaceous feed, especially good hydrodemetalation and hydrodesulfurization are achieved, as well as MCR reduction, using a catalyst having 5 to 11 percent of its pore volume in the form of macropores, and a surface area greater than 75 m.sup.2 /g. Preferably the catalyst has a peak mesopore diameter greater than 165 .ANG., as determined by mercury porosimetry, and an average mesopore diameter greater than 160 .ANG..
    Type: Grant
    Filed: October 4, 1988
    Date of Patent: December 11, 1990
    Assignee: Chevron Research Company
    Inventor: David R. Johnson
  • Patent number: 4855273
    Abstract: Process for the production of a new copper (II) chromite spinel catalyst using colloidal silica gel and to its use for the direct fixed-bed hydrogenation of fatty acids to fatty alcohols of corresponding chain length.
    Type: Grant
    Filed: March 1, 1988
    Date of Patent: August 8, 1989
    Assignee: Henkel Kommanditgesellschaft auf Aktien
    Inventors: Joachim Pohl, Franz-Josef Carduck, Gerd Goebel
  • Patent number: 4829040
    Abstract: Mild hydrocracking is accomplished with a catalyst containing an intermediate pore molecular sieve, such as silicalite or a ZSM-5 type zeolite.
    Type: Grant
    Filed: June 19, 1987
    Date of Patent: May 9, 1989
    Assignee: Union Oil Company of California
    Inventor: John W. Ward
  • Patent number: 4828815
    Abstract: Chlorine can be efficiently produced at a low temperature and with a high hourly space velocity by oxidizing hydrogen chloride with an oxygen-containing gas in the presence of a catalyst obtained by calcining a compound, which has in turn been obtained by reacting chromium nitrate, chromium chloride, the chromium salt of an organic acid or the like with ammonia, or by calcining a mixture of the compound and a silicon compound, preferably, at a temperature lower than 800.degree. C.
    Type: Grant
    Filed: December 10, 1987
    Date of Patent: May 9, 1989
    Assignee: Mitsui Toatsu Chemicals, Incorporated
    Inventors: Tadamitsu Kiyoura, Masanobu Ajioka, Naoshi Fujimoto, Toshihide Suzuki, Yasuo Kogure, Tokio Nagayama, Kazuo Kanaya
  • Patent number: 4800189
    Abstract: A mass for removal through chemical sorption of oxygen and water vapor and their reactive hydrides consists of a heat-resistant oxidic carrier having a large surface area and is doped with a component that is activated with molecular oxygen at from 300.degree. C. to 600.degree. C. and afterwards is treated with a reducing gas at a temperature between 200.degree. C. and below the activation temperature. Before being used as a chemical sorption agent the mass is additionally treated with a reactable gaseous hydride.
    Type: Grant
    Filed: May 27, 1987
    Date of Patent: January 24, 1989
    Assignee: Messer Griesheim GmbH
    Inventors: Manfred Eschwey, Werner Schleser
  • Patent number: 4746643
    Abstract: The invention relates to a method for the preparation of a catalyst for the dehydrogenation of C.sub.3 -C.sub.5 paraffins consisting in impregnating calcined aluminum oxide with a solution of chromium and potassium compounds, in drying and then impregnating the product obtained with a solution of a compound of silicon, the catalyst obtained being finally dried and calcined.
    Type: Grant
    Filed: June 16, 1986
    Date of Patent: May 24, 1988
    Assignees: Snamprogetti S.p.A., Niimsk
    Inventors: Franco Buonomo, Rodolfo Jezzi, Bruno Notari, Gheorghiy R. Kotelnikov, Konstantinovic R. Michailov, Victor A. Patanov
  • Patent number: 4701435
    Abstract: A method for producing a catalyst for use in the hydrotreatment, hydrodemetallization and hydrocracking of heavy hydrocarbon feedstocks containing high metal levels of vanadium, nickel and sulfur comprises the steps of preparing a carrier from a naturally occurring material consisting essentially of magnesium silicate having a sheet-type structure, iron and nickel wherein the carrier is prepared directly from the above naturally occurring material or, in the alternative, it can be prepared from the naturally occurring material in combination with a catalyst component. In the event the carrier for the catalyst is prepared from the above naturally occurring material without the addition of the catalyst component, the carrier can be impregnated with the catalyst component. The resultant catalyst is particularly useful in the treatment of heavy hydrocarbon feedstocks.
    Type: Grant
    Filed: April 7, 1986
    Date of Patent: October 20, 1987
    Assignee: Intevep, S.A.
    Inventors: Juan J. Garcia, Roberto E. Galiasso, Magdalena M. Ramirez de Agudelo, Luis Rivas, Juan Hurtado
  • Patent number: 4683050
    Abstract: Mild hydrocracking is accomplished with a catalyst containing an intermediate pore molecular sieve, such as silicalite or a ZSM-5 type zeolite.
    Type: Grant
    Filed: August 22, 1985
    Date of Patent: July 28, 1987
    Assignee: Union Oil Company of California
    Inventor: John W. Ward
  • Patent number: 4659690
    Abstract: Fines are reduced in refractory materials by mixing the refractory material with an acid composition in a liquid polar organic compound and thereafter working the mixture until a decrease in volume occurs. The resulting product can be shaped and subjected to conventional finishing treatments. The resulting product exhibits reduced fines and thus is an improved material for use as a catalyst support. The resulting catalyst is of particular utility in the production of film grade ethylene polymer.
    Type: Grant
    Filed: December 24, 1984
    Date of Patent: April 21, 1987
    Assignee: Phillips Petroleum Company
    Inventors: Max P. McDaniel, Emory W. Pitzer