Patents Represented by Attorney, Agent or Law Firm Robert A. Maggio
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Patent number: 8309749Abstract: Processes for preparing aluminoxane comprising: bringing into contact under reaction conditions in an inert atmosphere a liquid containing reaction mixture comprising: (i) a water in oil emulsion comprising water and at least one emulsifier in a first hydrocarbon solvent; and (ii) an organoaluminum compound capable of forming aluminoxane in a second hydrocarbon solvent; provided that the aluminoxane produced by the reaction is present in solution under the reaction conditions. In a preferred embodiment a support carrier for the aluminoxane: (i) is present during the contact step or (ii) is introduced following contact. A polymerization catalyst can be prepared wherein the support carrier is SiO2 and a Group 3 to Group 10 metal containing single site complex is mixed with the aluminoxane. Catalysts suitable for polymerizing an olefin such as ethylene or copolymerizing an olefin with at least one C3 to C20 alpha-olefin can be produced.Type: GrantFiled: June 9, 2010Date of Patent: November 13, 2012Assignee: W R Grace & Co-ConnInventors: Xinggao Fang, Timothy A. Boyer, John Henry Hain, Jr.
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Patent number: 8021538Abstract: Stable catalyst carrier impregnating solutions can be prepared using a component of a Group VIB metal, e.g., molybdenum, at high concentration, a component of a Group VIII metal, e.g., nickel, at low concentration, and a phosphorous component, e.g., phosphoric acid, at low concentration, provided that the Group VIII metal is in a substantially water-insoluble form and a particular sequence of addition of the components is followed, even when a substantially water-insoluble form of the Group VIB component is used. The resulting stabilized impregnating solution can be supplemented with additional Group VIII metal in water-soluble form to achieve increased levels of such metal in the final catalyst. Furthermore, uncalcined catalyst carriers impregnated with the stable solution and subsequently shaped, dried and calcined, have unexpectedly improved performance when used in the hydroprocessing of heavy hydrocarbon feedstocks.Type: GrantFiled: April 16, 2008Date of Patent: September 20, 2011Assignee: Advanced Refining Technologies LLCInventor: Darryl P. Klein
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Patent number: 7642212Abstract: Stable catalyst carrier impregnating solutions can be prepared using a component of a Group VIB metal, e.g., molybdenum, at high concentration, a component of a Group VIII metal, e.g., nickel, at low concentration, and a phosphorous component, e.g., phosphoric acid, at a low concentration, provided that the Group VIII metal is in a substantially water-insoluble form and a particular sequence of addition of the components is followed, even when a substantially water-insoluble form of the Group VIB component is used. The resulting stabilized impregnating solution can be supplemented with additional Group VIII metal in water-soluble form to achieve increased levels of such metal in the final catalyst. Furthermore, uncalcined catalyst carriers impregnated with the stable solution and subsequently shaped, dried and calcined, have unexpectedly improved performance when used in the hydroprocessing of heavy hydrocarbon feedstocks.Type: GrantFiled: April 16, 2008Date of Patent: January 5, 2010Assignee: Advanced Refining Technologies LLCInventor: Darryl P. Klein
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Patent number: 7560407Abstract: Stable catalyst carrier impregnating solutions can be prepared using a component of a Group VIB metal, e.g., molybdenum, at high concentration, a component of a Group VIII metal, e.g., nickel, at low concentration, and a phosphorous component, e.g., phosphoric acid, at low concentration, provided that the Group VIII metal is in a substantially water-insoluble form and a particular sequence of addition of the components is followed, even when a substantially water-insoluble form of the Group VIB component is used. The resulting stabilized impregnating solution can be supplemented with additional Group VIII metal in water-soluble form to achieve increased levels of such metal in the final catalyst. Furthermore, uncalcined catalyst carriers impregnated with the stable solution and subsequently shaped, dried and calcined, have unexpectedly improved performance when used in the hydroprocessing of heavy hydrocarbon feedstocks.Type: GrantFiled: April 16, 2008Date of Patent: July 14, 2009Assignee: Advanced Refining Technologies, LLCInventor: Darryl P. Klein
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Patent number: 7390766Abstract: Stable catalyst carrier impregnating solutions can be prepared using a component of a Group VIB metal, e.g., molybdenum, at high concentration, a component of a Group VIII metal, e.g., nickel, at low concentration, and a phosphorous component, e.g., phosphoric acid, at low concentration, provided that the Group VIII metal is in a substantially water-insoluble form and a particular sequence of addition of the components is followed, even when a substantially water-insoluble form of the Group VIB component is used. The resulting stabilized impregnating solution can be supplemented with additional Group VIII metal in water-soluble form to achieve increased levels of such metal in the final catalyst. Furthermore, uncalcined catalyst carriers impregnated with the stable solution and subsequently shaped, dried and calcined, have unexpectedly improved performance when used in the hydroprocessing of heavy hydrocarbon feedstocks.Type: GrantFiled: November 20, 2003Date of Patent: June 24, 2008Inventor: Darryl P. Klein
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Patent number: 6943224Abstract: A process for forming a coordination catalyst system comprising sequentially or substantially simultaneously contacting: (I) pre-catalyst reactants comprising (a) at least one first ligand-containing reactant; and (b) at least one first transition metal reactant suitable to form at least one metallocene or constrained geometry pre-catalyst compound (e.g., rac-ethylene bis(indenyl)zirconiUm dichloride); an optionally (c) at least one second ligand-containing reactant and (d) at least one second transition metal reactant suitable to form at least one non-metallocene, non-constrained geometry, bidentate or tridentate transition metal compound (e.g., tridentate 2,6-diacetylpyridine-bis(2,4,6-trimethylanaline)FeCl2) and (II) further contacting, jointly or individually, the pre-catalyst compound(s) and optional bidentate or tridentate compound(s) with at least one support-activator agglomerate (e.g., spray dried silica/clay agglomerate).Type: GrantFiled: April 10, 2002Date of Patent: September 13, 2005Assignee: W. R. Grace & Co.-Conn.Inventor: Keng-Yu Shih
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Patent number: 6734131Abstract: A chromium containing catalyst wherein the chromium atom is in one of its higher valence states and is immobilized to a support-agglomerate composed of at least one inorganic oxide component and at least one ion-containing layered component.Type: GrantFiled: April 10, 2002Date of Patent: May 11, 2004Assignee: W. R. Grace & Co.-Conn.Inventors: Keng-Yu Shih, Dean Alexander Denton, Rimantas Glemza
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Patent number: 6686306Abstract: A coordination catalyst system comprising at least one metallocene or constrained geometry pre-catalyst transition metal compound, (e.g., rac-ethylene bis(indenyl)zirconium dichloride), at least one non-metallocene, non-constrained geometry, bidentate transition metal compound or tridentate transition metal compound (e.g., tridentate 2,6-diacetylpyridine-bis(2,4,6-trimethylanaline)FeCl2), at least one support-activator (e.g., spray dried silica/clay agglomerate), and optionally at least one organometallic compound (e.g., triisobutyl aluminum), in controlled amounts, and methods for preparing the same. The resulting dual transition metal catalyst system is suitable for addition polymerization of ethylenically and acetylenically unsaturated monomers into polymers; for example, polymers having a broad molecular weight distribution, Mw/Mn, and good polymer morphology.Type: GrantFiled: April 10, 2002Date of Patent: February 3, 2004Assignee: W.R. Grace & Co.- Conn.Inventor: Keng-Yu Shih
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Patent number: 6670302Abstract: High melt index polyolefins have been obtained with chromium silica catalysts under conventional polymerization conditions without the use of titanium or other additives. The useful chromium silica catalysts have a pore volume in the range of 1.9-2.9 cc/g and a narrow pore size distribution. The silica is a silica gel preferably obtained from a low solids, rapid gelation process.Type: GrantFiled: October 31, 2002Date of Patent: December 30, 2003Assignee: W. R. Grace & Co.-ConnInventors: Rimantas Glemza, Dean A. Denton
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Patent number: 6660683Abstract: Compositions for reduction of gas phase reduced nitrogen species and NOx generated during a partial or incomplete combustion catalytic cracking process, preferably, a fluid catalytic cracking process, are disclosed. The compositions comprise (i) an acidic metal oxide containing substantially no zeolite, (ii) an alkali metal, alkaline earth metal, and mixtures thereof, (iii) an oxygen storage component, and (iv) a noble metal component, preferably rhodium or iridium, and mixtures thereof, are disclosed. Preferably, the compositions are used as separate additives particles circulated along with the circulating FCC catalyst inventory. Reduced emissions of gas phase reduced nitrogen species and NOx in an effluent off gas of a partial or incomplete combustion FCC regenerator provide for an overall NOx reduction as the effluent gas stream is passed from the FCC regenerator to a CO boiler, whereby as CO is oxidized to CO2 a lesser amount of the reduced nitrogen species is oxidized to NOx.Type: GrantFiled: October 21, 2002Date of Patent: December 9, 2003Assignee: W.R. Grace & Co.-Conn.Inventors: George Yaluris, John Allen Rudesill
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Patent number: 6589156Abstract: A composition for transforming a chrysotile asbestos-containing material into a non-asbestos material is disclosed, wherein the composition comprises water, at least about 30% by weight of an acid component, at least about 0.1% by weight of a source of fluoride ions, and a stable foam forming amount of a foaming agent system composed of a non-ionic alkyl polyglycoside alone or with additional non-ionic foaming agents. A method of transforming the asbestos-containing material into a non-asbestos material using the present composition in the form of a foam also disclosed.Type: GrantFiled: December 21, 2000Date of Patent: July 8, 2003Assignee: W. R. Grace & Co.-Conn.Inventor: Lawrence Joseph Kindt
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Patent number: 6489410Abstract: In accordance with this invention are methods for making the novel compositions and methods of using the compositions for polymerization of olefins. In its broadest form, the method of producing the supported catalytic composition of the present invention comprises treating an inorganic or inorganic oxide support which has incorporated uniformly therein a Group 3-10 transition metal from the Periodic Table with a metal alkylating reagent wherein the reaction product is then treated with a halogenating reagent. The resultant reaction product can be recovered and is available for use in conjunction with the activating co-catalyst for the polymerization of polyolefins.Type: GrantFiled: June 7, 1995Date of Patent: December 3, 2002Assignee: W. R. Grace & Co.-Conn.Inventors: Michael John Carney, David George Ward
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Patent number: 6451200Abstract: Porous composite particles are provided which comprise an aluminum oxide component, e.g., crystalline boehmite, and a swellable clay component, e.g., synthetic hectorite, intimately dispersed within the aluminum oxide component at an amount effective to increase the hydrothermal stability, pore volume, and/or the mesopore pore mode of the composite particles relative to the absence of the swellable clay. Also provided is a method for making the composite particles, agglomerate particles derived therefrom, and a process for hydroprocessing petroleum feedstock using the agglomerates to support a hydroprocessing catalyst.Type: GrantFiled: July 16, 2001Date of Patent: September 17, 2002Assignee: W. R. Grace & Co.-Conn.Inventors: Roger Jean Lussier, Stanislaw Plecha, Charles Cross Wear, Gordon Dean Weatherbee
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Patent number: 6403526Abstract: Porous composite particles are provided which comprise an aluminum oxide component, e.g., crystalline boehmite having a crystallite size of from about 20 to about 200 Angstroms and additive component residue, e.g., silicate, phosphate, of a crystal size growth inhibitor, intimately dispersed within the aluminum oxide component. The aluminum oxide component of the composite particles are derived from a mixture of alumina trihydrate (e.g., gibbsite) and an alumina seed component, i.e., active alumina, which are both converted to crystalline boehmite in the presence of the additive component. Also provided is a method for making the composite particles, agglomerate particles derived therefrom, and a process for hydroprocessing petroleum feedstock using the agglomerates.Type: GrantFiled: January 13, 2000Date of Patent: June 11, 2002Assignee: W. R. Grace & Co.-Conn.Inventors: Roger Jean Lussier, Michael David Wallace
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Patent number: 6399535Abstract: The present invention is directed to a coordinating catalyst system comprising at least one bidentate or tridentate ligand containing pre-catalyst transition metal compound, (e.g., 2,6-bis (2,4,6-trimethylarylamino)pyridyl iron dichloride), at least one support-activator (e.g., spray dried silica/clay agglomerate), and optionally at least one organometallic compound (e.g., triisobutyl aluminum), in controlled amounts, and methods for preparing the same. The resulting catalyst system exhibits enhanced activity for polymerizing olefins and yields polymer having very good morphology.Type: GrantFiled: November 1, 1999Date of Patent: June 4, 2002Assignee: W. R. Grace & Co.-Conn.Inventors: Keng-Yu Shih, Michael John Carney, Dean Alexander Denton
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Patent number: 6395403Abstract: A novel precious metal doped porous metal catalyst is disclosed. The precious metal is present in from 0.01 to 1.5 weight percent and distributed throughout the particles of porous metal to provide a surface to bulk ratio distribution of not greater than 60. The present invention is further directed to a process of forming said doped catalyst and to improved processes of catalytic hydrogenation of organic compounds.Type: GrantFiled: July 6, 2001Date of Patent: May 28, 2002Assignee: W. R. Grace & Co.Inventor: Stephen Raymond Schmidt
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Patent number: 6329315Abstract: Frangible, spray dried agglomerate catalyst supports are provided, e.g. of silica gel, which possess a controlled morphology of microspheroidal shape, rough, scabrous appearance, and interstitial void spaces which penetrate the agglomerate surface and are of substantially uniform size and distribution. The agglomerates also possess a 1-250 micron particle size, 1-1000 m2/gm. surface area, and an Attrition Quality Index (AQI) of at least 10. The agglomerates are derived from a mixture of dry milled inorganic oxide particles, e.g. silica gel, and optionally but preferably wet milled inorganic oxide particles, e.g. silica gel particles, (which preferably contain a colloidal segment of <1 micron particles) slurried in water for spray drying. The high AQI assures that the agglomerates are frangible and that polymerization performance is improved.Type: GrantFiled: June 19, 1997Date of Patent: December 11, 2001Assignee: W. R. Grace & Co.-Conn.Inventors: Dean Alexander Denton, Michael J. Carney
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Patent number: 6313061Abstract: A method of making frangible, spray dried agglomerate catalyst supports is provided, e.g. of silica gel, which possess a controlled morphology of microspheroidal shape, preferably a rough, scabrous appearance, and interstitial void spaces which penetrate the agglomerate. The agglomerates also possess a 4-250 micron particle size, 1-1000 m2/gm. surface area, and an Attrition Quality Index (AQI) of at least 10. The method comprises dry milling inorganic oxide particles, e.g. silica gel, wet milling the dry milled inorganic oxide particles (to preferably impart a colloidal segment of <1 micron particles), and spray drying the particles. The high AQI assures that the agglomerates are frangible and that polymerization performance is improved. The controlled morphology is believed to permit the constituent particles of the agglomerates to be more uniformly impregnated or coated with conventional olefin polymerization catalysts.Type: GrantFiled: December 22, 1998Date of Patent: November 6, 2001Assignee: W. R. Grace & Co.-Conn.Inventors: Dean A. Denton, Michael J. Carney
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Patent number: 6309758Abstract: A novel precious metal doped porous metal catalyst is disclosed. The precious metal is present in from 0.01 to 1.5 weight percent and distributed throughout the particles of porous metal to provide a surface to bulk ratio distribution of not greater than 60. The present invention is further directed to a process of forming said doped catalyst and to improved processes of catalytic hydrogenation of organic compounds.Type: GrantFiled: May 6, 1999Date of Patent: October 30, 2001Assignee: W. R. Grace & Co.-Conn.Inventor: Stephen Raymond Schmidt
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Patent number: 6303531Abstract: Porous composite particles are provided which comprise an aluminum oxide component, e.g., crystalline boehmite, and a swellable clay component, e.g., synthetic hectorite, intimately dispersed within the aluminum oxide component at an amount effective to increase the hydrothermal stability, pore volume, and/or the mesopore pore mode of the composite particles relative to the absence of the swellable clay. Also provided is a method for making the composite particles, agglomerate particles derived therefrom, and a process for hydroprocessing petroleum feedstock using the agglomerates to support a hydroprocessing catalyst.Type: GrantFiled: January 13, 2000Date of Patent: October 16, 2001Assignee: W. R. Grace & Co.-Conn.Inventors: Roger Jean Lussier, Stanislaw Plecha, Charles Cross Wear