And Group Vi Metal Containing (i.e., Cr, Mo, W Or Po) Patents (Class 502/219)
  • Patent number: 5338717
    Abstract: The present invention relates to the preparation of catalysts for heteroatom removal, particularly sulfur, from petroleum and synthetic fuel feedstocks. The catalyst is comprised of at least one Group VIII metal, and at least one Group VI metal, on a refractory support. The catalyst is prepared by: impregnating an inorganic oxide support material with a Group VI heteropolyacid; treating said impregnated support with an aqueous solution of a reducing agent which is capable of at least partially reducing the Group VI metal of the heteropolyacid; drying said treated support at a temperature from about 20.degree. C. to about 200.degree. C. at about atmospheric pressure; impregnating the treated support with a Group VIII metal salt of an acid having an acidity less than that of the Group VI heteropolyacid; drying said impregnated treated support at a temperature from about 20.degree. C. to about 200.degree. C. at about atmospheric pressure; and sulfiding said impregnated support, thereby forming the catalysts.
    Type: Grant
    Filed: October 22, 1993
    Date of Patent: August 16, 1994
    Assignee: Exxon Research and Engineering Company
    Inventors: Clyde L. Aldridge, Kenneth L. Riley
  • Patent number: 5336654
    Abstract: A method for the preparation of catalysts for heteroatom removal, particularly sulfur, from petroleum and synthetic fuel feedstocks. The catalyst is comprised of at least one Group VIII metal, and at least one Group VI metal, on a refractory support. The present method for preparing said catalysts comprises impregnating the Group VIII metal onto the refractory support by use of a Group VIII metal salt of an acid, and impregnating the Group VI metal onto the support by way of a Group VI heteropolyacid, wherein the acid comprising the salt of the Group VIII metal is less acidic than the heteropolyacid. The catalysts are then subjected to a heat treatment which includes a first phase wherein the catalyst is dried of free water and a second phase wherein the catalyst is heated to a temperature up to about 300.degree. C. at a heating rate from about 0.15.degree. C./min to about 15.degree. C./min.
    Type: Grant
    Filed: March 11, 1993
    Date of Patent: August 9, 1994
    Assignee: Exxon Research and Engineering Company
    Inventors: Clyde L. Aldridge, Kenneth L. Riley
  • Patent number: 5292702
    Abstract: The invention relates to an unproved method of presulfurizing a sulfidable metal oxide(s)-containing catalyst which minimizes sulfur stripping upon start-up of a reactor and improves catalyst activity. The method consists of contacting a sulfidable metal oxide(s)-containing catalyst with elemental sulfur at a temperature such that said elemental sulfur is substantially incorporated in the pores of said catalyst by sublimation and/or melting and heating the sulfur-incorporated catalyst in the presence of a liquid olefinic hydrocarbon at a temperature greater than about 150.degree. C.
    Type: Grant
    Filed: October 30, 1992
    Date of Patent: March 8, 1994
    Assignee: CRI International, Inc.
    Inventors: James D. Seamans, Charles T. Adams, Wendy B. Dominguez, Andrew A. Chen
  • Patent number: 5244858
    Abstract: A catalyst composition for the hydrodesulfurization of a hydrocarbon oil, comprising a composite of metal oxides comprising:aluminum; andat least one metal selected from a group consisting of(A) at least one metal belonging to Group VIB of the Periodic Table; and(B) at least one the metal belonging to Group VIII of the Periodic Table;where the at least one metal belonging to Group VIB of the Periodic Table accounts for, in terms of as oxide, from 10 to 60% by weight with respect to the total catalyst, and the at least one metal belonging to Group VIII of the Periodic Table accounts for, in terms of oxide, from 3 to 20% by weight with respect to the total catalyst, and wherein no peak assigned to Y-Al.sub.2 O.sub.3 is present in X-ray diffraction.
    Type: Grant
    Filed: September 24, 1992
    Date of Patent: September 14, 1993
    Assignees: Cosmo Research Institute, Cosmo Oil Co., Ltd.
    Inventors: Kazushi Usui, Takashi Fujikawa, Katsuyoshi Ohki
  • Patent number: 5236881
    Abstract: A coal extract hydrocracking catalyst having particular utility in a two stage coal extracting process which has a first liquid hydrogen donor solvent oil extraction stage and a second stage comprising catalytic hydrocracking of the extract. Desired levels of hydrocracking and hydrogenation of the extract, with an acceptable level of naphthene formation, are achieved by using on the coal extract hydrocracking catalyst a mixture of a promoted W or Mo catalyst with an unpromoted W or Mo catalyst.
    Type: Grant
    Filed: April 13, 1992
    Date of Patent: August 17, 1993
    Assignee: Coal Industry (Patents) Limited
    Inventor: Michael A. Jones
  • Patent number: 5215954
    Abstract: The invention relates to an improved method of presulfurizing a sulfidable metal oxide(s)-containing catalyst which minimizes sulfur stripping upon start-up of a reactor and improves catalyst activity. The method consists of contacting a sulfidable metal oxide(s)-containing catalyst with elemental sulfur at a temperature such that said elemental sulfur is substantially incorporated in the pores of said catalyst by sublimation and/or melting and heating the sulfur-incorporated catalyst in the presence of a liquid olefinic hydrocarbon at a temperature greater than about 150.degree. C.
    Type: Grant
    Filed: July 30, 1991
    Date of Patent: June 1, 1993
    Assignee: CRI International, Inc.
    Inventors: James D. Seamans, Charles T. Adams, Wendy B. Dominguez, Andrew A. Chen
  • Patent number: 5200382
    Abstract: A catalyst is disclosed comprising a thin outer shell of catalytic material bonded to an inner core of catalytically inert material. The catalyst is made by coating a catalytically inert core such as alpha alumina, with a thin layer of finely divided catalytically active material in a slurry of colloidal boehmite/pseudo boehmite then calcining to convert the boehmite/pseudo boehmite into .gamma. alumina thereby bonding it to the inert core. Catalysts made by this technique containing an outer shell of platinum on fluorided alumina in an inert core of alpha alumina .gamma. are attractive isomerization catalysts.
    Type: Grant
    Filed: November 15, 1991
    Date of Patent: April 6, 1993
    Assignee: Exxon Research and Engineering Company
    Inventors: Ian A. Cody, Mahmoud M. Hafez, David N. Zinkie
  • Patent number: 5198100
    Abstract: A hydrotreating process using a sulfided catalyst composition comprised of at least one Group VIII metal and at least one Group VI metal on an inorganic oxide support, which sulfided catalyst is derived from a catalyst precursor comprised of salts and/or complexes of a Group VIII metal(s) with a Group VI metal heteropolyacid on an inorganic oxide support material, wherein the concentration of Group VIII metal ranges from about 2 to 20 wt. %, and the concentration of Group VI metal ranges from 5 to 50 wt. %, which percents are on support and which catalyst composition is substantially free of free water.
    Type: Grant
    Filed: December 24, 1990
    Date of Patent: March 30, 1993
    Assignee: Exxon Research and Engineering Company
    Inventors: Clyde L. Aldridge, Kenneth L. Riley
  • Patent number: 5177047
    Abstract: A catalyst, and method of preparing and using a catalyst, for the hydrodesulfurization of metal-containing heavy feedstocks, which has improved catalytic activity. The catalyst contains Group VIB and Group VIII metals or metal compounds on a support comprising alumina wherein the support has 70 volume percent of its pore volume in pores having a diameter of between 70 and 130 .ANG..
    Type: Grant
    Filed: October 2, 1991
    Date of Patent: January 5, 1993
    Assignee: Chevron Research and Technology Company
    Inventor: Richard S. Threlkel
  • Patent number: 5164075
    Abstract: High activity slurry catalysts for hydroprocessing heavy hydrocarbon oils are produced from Group VIB metal compounds by sulfiding an aqueous mixture of the metal compound with from greater than about 8 to about 14 SCF of hydrogen sulfide per pound of Group VIB metal.
    Type: Grant
    Filed: July 5, 1990
    Date of Patent: November 17, 1992
    Assignee: Chevron Research & Technology Company
    Inventor: Jaime Lopez
  • Patent number: 5162281
    Abstract: Disclosed is a method of preparing a high-activity hydrotreating catalyst for hydrocarbon oil, where metals of Group VI (Mo and/or W) and Group VIII (Co and/or Ni) optionally along with phosphorus, and 0.3 to 3.5 molar times of the total molar amount of the metals of particular carboxylic acid(s) (tartaric acid, citric acid, etc.) and 0.1 times or more of the amount necessary for forming the active metals into their sulfides of particular organic sulfur compound(s) (mercapto-acetic acid, mercapto-succinic acid, etc.) are added to a material consisting essentially of at least one of inorganic acids and their hydrates, and they are kneaded shaped and dried at 200.degree. C. or lower. Using the catalyst, hydrotreatment, desulfurization and denitrogenation of hydrocarbon oil may be effected under mild conditions at a reduced operation cost.
    Type: Grant
    Filed: January 17, 1992
    Date of Patent: November 10, 1992
    Assignee: Sumitomo Metal Mining Co. Ltd.
    Inventors: Tetsuro Kamo, Yuuki Kanai
  • Patent number: 5162282
    Abstract: A process for the preparation of a dispersed Group VI-B metal sulfide hydrocarbon oil hydroprocessing catalyst comprising reacting aqueous ammonia and a Group VI-B metal compound, such as molybdenum oxide or tungsten oxide, to form water soluble compounds such as aqueous ammonium molybdates or tungstates. The aqueous ammonium molybdates or tungstates are sulfided at a relatively low temperature with hydrogen sulfide without feed oil, and wherein the mole ratio of the sulfiding agent to metal salts is greater than 2, to produce molybdenum or tungsten sulfide catalysts of high hydroprocessing activity. The catalyst slurry and feed oil can then be passed to a hydroprocessing reactor or can be further sulfided in additional steps of increasing temperature.
    Type: Grant
    Filed: April 5, 1991
    Date of Patent: November 10, 1992
    Assignee: Chevron Research and Technology Company
    Inventors: Jaime Lopez, Eugene A. Pasek
  • Patent number: 5151259
    Abstract: A crystalline aluminosilicate having its anhydrous state a formula expressed in terms of mol ratios as follows:xQ:0.01-0.1 M.sub.2/n O:0-0.8 Z.sub.2 O.sub.3 :SiO.sub.2 :0.0001-0.5 MeS,wherein:Q is an organic nitrogen compound;Z is aluminium, boron, gallium or mixtures thereof;x is between 0 and 0.5;M is at least one metal cation of valence n; andMe is at least one of the metals which form an insoluble sulfide compound.
    Type: Grant
    Filed: December 18, 1990
    Date of Patent: September 29, 1992
    Assignee: Haldor Topsoe A/S
    Inventor: Niels J. Blom
  • Patent number: 5139983
    Abstract: The invention relates to a process making it possible when a refining catalyst is subject preferably in situ to the conventional activation reaction in the presence of hydrogen (generally at above 100.degree. C.) to carry out, as a result of the in situ presence of hydrogen, the sulphurization at the required stoichiometric or non-stoichiometric level of the active metal or metals in the composition of the catalyst. In the absence of hydrogen, the process consists of incorporating into the porosity of the new or regenerated catalyst at least one sulphurizing agent of general formula:R--S(n)--R'in which n is an integer from 3 to 20 and R represents an organic radical.The invention is characterized in that a critical elementary sulphur quantity is added to the sulphurizing agent.
    Type: Grant
    Filed: March 19, 1991
    Date of Patent: August 18, 1992
    Assignee: Europeenne de Retraitement de Catalyseurs (Eurecat)
    Inventors: Georges Berrebi, Bernard Le Gall
  • Patent number: 5139990
    Abstract: Ex situ presulfidation of hydrotreating catalysts comprising impregnating the catalysts with an aqueous solution of an organic sulfur compound, e.g. the diammonium salt of 2,5-dimercapto-1,3,4-thiadiazole and 2,2'-dithiodiethanol, followed by drying of the impregnated material. The dried material is activated by contacting it with hydrogen gas at elevated temperature.
    Type: Grant
    Filed: March 20, 1991
    Date of Patent: August 18, 1992
    Assignee: Akzo NV
    Inventors: Jan I. de Jong, Ludwig Eisenhuth, Johannes W. F. M. Schoonhoven, Antonius J. van Hengstum
  • Patent number: 5122357
    Abstract: This invention deals with a crystalline oxysulfide composition, a process for preparing the composition, a catalyst using the composition and processes using the composition. The crystalline oxysulfide composition has a three-dimensional microporous framework structure of at least MO.sub.2, MS.sub.2, and MOS tetrahedral units, having an intracrystalline pore system and an empirical formula expressed in molar ratios:(M.sub.s Al.sub.t P.sub.u Si.sub.v)S.sub.w O.sub.2-wwhere M is at least one metal selected from the group consisting of metals which: 1) can be incorporated into the framework structure of a microporous molecular sieve and 2) form hydrolytically stable sulfides; s, t, u, v and w are the mole fractions of M, Al, P, Si and S respectively. The oxysulfide composition is prepared by contacting a molecular sieve having an empirical formula: (M.sub.s Al.sub.t P.sub.u Si.sub.v)O.sub.
    Type: Grant
    Filed: March 18, 1991
    Date of Patent: June 16, 1992
    Assignee: UOP
    Inventors: Robert L. Bedard, Edith M. Flanigen, Stephen T. Wilson
  • Patent number: 5094991
    Abstract: Group VIB metal sulfide slurry catalysts having a pore volume in the pore size range 10 to 300.ANG. radius of at least 0.1 cc/g. Also, Group VIB metal sulfide catalysts having a surface area of at least 20 m.sup.2 /g. Suitable Group VIB metals are molybdenum and tungsten, preferably molybdenum. The Group VIB metal sulfide can be approximately a Group VIB metal disulfide. The slurry catalyst can be promoted with a Group VIII metal, such as nickel or cobalt.
    Type: Grant
    Filed: February 15, 1991
    Date of Patent: March 10, 1992
    Assignee: Chevron Research Company
    Inventors: Jaime Lopez, Eugene A. Pasek
  • Patent number: 5053376
    Abstract: A method for preparing a sulfided molybdenum catalyst concentrate which method comprises: (a) forming a precursor catalyst concentrate by mixing together: (i) a hydrocarbonaceous oil comprising constituents boiling above about 1050.degree. F.; (ii) a metal compound, said metal being selected from the group consisting of Groups II, III, IV, V, VIB, VIIB, and VIII of the Periodic Table of the Elements, in an amount to provide from about 0.2 to 2 wt. % metal, based on said hydrocarbonaceous oil; and (iii) elemental sulfur in an amount such that the atomic ratio of sulfur to metal is from about 1/1 to 8/1; and (b) heating the mixture to an effective temperature to produce a catalyst concentrate.
    Type: Grant
    Filed: June 4, 1990
    Date of Patent: October 1, 1991
    Assignee: Exxon Research & Engineering Company
    Inventors: Roby Bearden, Jr., Clyde L. Aldridge
  • Patent number: 5051389
    Abstract: A catalyst composition prepared by depositing a metal or metal compound onto a preformed carbon support and thereafter converting said metal or metal compounds to an oxide or sulfide having hydrogenation activity. The metal is selected from the group of metals consisting of Groups II-B, IV-B, IV-A, V-A, VI-A, VII-A and VIII-A metals of the Periodic Table of the Elements. The catalyst compositions are useful in hydroconversion and hydrotreating processes.
    Type: Grant
    Filed: June 25, 1990
    Date of Patent: September 24, 1991
    Assignee: Exxon Research and Engineering Company
    Inventors: Robert J. Lang, Claude C. Culross, Lonnie W. Vernon, William E. Winter
  • Patent number: 5041404
    Abstract: An improved method of presulfiding a hydrotreating or hydrocracking catalyst which minimizes sulfur stripping upon start-up of a hydrotreating or hydrocracking reactor utilizing such a catalyst. The method comprises the steps of contacting a hydrotreating or hydrocracking catalyst with elemental sulfur at a temperature below the melting point of sulfur, thereby forming a sulfur-catalyst mixture, and heating the sulfur-catalyst mixture to a temperature above the melting point of sulfur. Preferably, the sulfur-catalyst mixture is first mixed with at least one member selected from the group consisting of high boiling oils and hydrocarbon solvents to form a prewet mixture prior to heating at a temperature above the melting point of sulfur. Tail gas treating catalysts are also presulfided by these methods.
    Type: Grant
    Filed: March 13, 1990
    Date of Patent: August 20, 1991
    Assignee: CRI Ventures, Inc.
    Inventors: James D. Seamans, James G. Welch, Neal G. Gasser, Charles T. Adams
  • Patent number: 5039392
    Abstract: A process for converting a heavy hydrocarbonaceous chargestock to lower boiling products which process comprises reacting the chargestock with a catalyst concentrate in the presence of hydrogen, at hydroconversion conditions, said catalyst concentrate having been prepared by the steps comprising: (a) forming a precursor catalyst concentrate by mixing together: (i) a hydrocarbonaceous oil comprising constituents boiling above about 1050.degree. F.; (ii) a metal compound, said metal being selected from the group consisting of Groups II, III, IV, V, VIB, VIIB, and VIII of the Periodic Table of the Elements, in an amount to provide from about 0.2 to 2 wt. % metal, based on said hydrocarbonaceous oil; (b) heating the precursor concentrate to an effective temperature to produce a catalyst concentrate, wherein elemental sulfur is used an a sulfiding agent in an amount such that the atomic ratio of sulfur to metal is from about 1/1 to 8/1.
    Type: Grant
    Filed: June 4, 1990
    Date of Patent: August 13, 1991
    Assignee: Exxon Research and Engineering Company
    Inventors: Roby Bearden, Jr., Clyde L. Aldridge
  • Patent number: 5017535
    Abstract: Disclosed is a process for the ex situ presulfidation of hydrotreating catalysts employing organic sulfur compounds with a boiling point exceeding 100.degree. C. and satisfying the formulaX--R.sup.1 (S--R.sup.2).sub.p S--R.sup.3 --Y (I)wherein p=0, 1 or 2,R.sup.1, R.sup.2, and R.sup.3 may be the same or different and represent alkylene groups having 1-4 carbon atoms,X and Y may be the same or different and have the meaning of --H, --OH, --OR.sup.4 4 or --C(O)OR.sup.5, whereinR.sup.4 has the meaning of an alkyl group or acyl group with 1-3 carbon atoms, andR.sup.5 has the meaning of --H, an ammonium group or an alkyl group with 1-3 carbon atoms.Also disclosed is a process for activating the thus presulfided catalyst.
    Type: Grant
    Filed: June 20, 1990
    Date of Patent: May 21, 1991
    Assignee: Akzo N.V.
    Inventors: Johannes W. F. M. Schoonhoven, Sonja Eijsbouts, Jacobus J. L. Heinerman, Ludwig Eisenhuth
  • Patent number: 5011807
    Abstract: Catalysts of attractive activities for use in the oxidation of ethylene to ethylene oxide comprise silver supported on a porous heat resisting support, a group VI A transition metal, potassium, rubidium and/or cesium and sulphur.
    Type: Grant
    Filed: August 29, 1989
    Date of Patent: April 30, 1991
    Assignee: Imperial Chemical Industries plc
    Inventors: Percy Hayden, Harry Pinnegar
  • Patent number: 5010049
    Abstract: Hydrodesulfurization/hydrodenitrogenation catalysts and a process for making these is disclosed.The catalysts have (i) overall stoichiometries of M.sub.2x A.sub.1-x S.sub.2, where 0.001.ltoreq.x.ltoreq.0.5, M is Co, Fe, Ni, Cu, Zn, Mn or Ru, and A is Mo or W, or (ii) overall stoichiometries of AS.sub.2-y, where 0.01.ltoreq.y.ltoreq.1.00.To obtain the M.sub.2x A.sub.1-x S.sub.2 catalysts, elemental material M, elemental material A and elemental sulfur are combined in an amount of x moles of M and (1-x)/2 moles of A per mole of S and the mixture is then heated, in the absence of oxygen, to a temperature of from 200.degree. C. to 800.degree. C. for 1 hour to 1 week. To obtain the AS.sub.2-y catalysts, elemental material A and elemental sulfur are mixed in an amount of (2-y) moles of sulfur per mole of A, and a parallel process protocol is followed.
    Type: Grant
    Filed: March 24, 1989
    Date of Patent: April 23, 1991
    Assignee: The Regents of the University of Michigan
    Inventors: Maria A. Villa-Garcia, Johannes Schwank
  • Patent number: 4997801
    Abstract: There is disclosed a catalyst which hydrotreats hydrocarbons without need of presulfiding. The catalyst comprises a carrier of an inorganic oxide containing a sulfurizing agent and a water-soluble compound of two metals one of which belongs to the Group VI of the Periodic Table, while the other belongs to the Group VIII. The carrier has pores in which a precursor of a sulfide is formed. The coordination number of the closest Group VI metal found from the radial distribution function around the Group VI metal is less than 0.25. The function is obtained from the Fourier transform of the extended x-ray absorption fine structure of the precursor.
    Type: Grant
    Filed: April 19, 1989
    Date of Patent: March 5, 1991
    Assignee: Sumitomo Metal Mining Company Limited
    Inventors: Yukuaki Mitarai, Naoto Kinbara, Yasuhito Takahashi, Tomio Kawaguchi, Shigeru Sakai
  • Patent number: 4996108
    Abstract: Compositions of the formula MX.sub.2 :Y, wherein MX.sub.2 is a layer type transition metal dichalcogenide, M is a metal selected from the group consisting of niobium, tantalum, molybdenum and tungsten, X is a chalcogen selected from the group consisting of sulfur and selenium and Y is a material located between layers of MX.sub.2. The compositions may be prepared by the steps of first forming a suspension of the MX.sub.2 in a body of water. A liquid which is immiscible with water is added to the suspension. The suspension and immiscible liquid are agitated together to form a temporary emulsion. The emulsion is allowed to rest until the water and the liquid separate with an interface therebetween. A sheet-like composition of MX.sub.2 :Y forms at the interface. Preferably, the MX.sub.2 is in exfoliated, singular molecular thickness layers suspended in the water.
    Type: Grant
    Filed: January 17, 1989
    Date of Patent: February 26, 1991
    Assignee: Simon Fraser University
    Inventors: W. M. Ranjith Divigalpitiya, Robert F. Frindt, S. Roy Morrison
  • Patent number: 4992403
    Abstract: Catalysts for hydrotreating hydrocarbons are composed of a carrier substance consisting essentially of an oxide of aluminum and/or an oxide hydrate of aluminum, at least one compound selected from water-soluble compounds of metals of Group VI and Group VIII of the Periodic Table and at least one organic compound selected from mercapto-carboxylic acids of formula HS--(CH.sub.2).sub.n --COOR (where n is 1 to 3; R is H, alkali metal, alkaline earth metal or ammonium group or alkyl group with 1-10 carbons), thio-acids of formula R'--COSH (where R' is monovalent hydrocarbon with 1-15 carbons), amino-substituted mercaptans of formula H.sub.2 N--R"--SH (R" is divalent hydrocarbon with 1-15 carbons), dimercaptans of formula HS--R"--SH (R" is same as above) and mercapto-alcohols of formula (R.sup.a S--R"'--(OH).sub.n (where R"' is hydrocarbon with 1-15 carbons; R.sup.a is H or alkyl group with 1-2 carbons; and n is 1-2), and optionally phosphoric acid.
    Type: Grant
    Filed: August 16, 1989
    Date of Patent: February 12, 1991
    Assignee: Sumitomo Metal Mining Company Limited
    Inventors: Yasuhito Takahashi, Tomio Kawaguchi, Shigeru Sakai
  • Patent number: 4983559
    Abstract: Presulfurization of a catalyst used, e.g., for hydrocarbon conversion, wherein a polysulfide is employed as the sulfurization agent. In the first stage of the presulfurization, phosphorous, a halogen, or compounds thereof are introduced.
    Type: Grant
    Filed: July 3, 1989
    Date of Patent: January 8, 1991
    Assignee: Europeene de Retraitement de Catalyseurs Eurecat
    Inventor: Georges Berrebi
  • Patent number: 4983558
    Abstract: The invention relates to a process for treating a new or regenerated catalyst containing a support having as a base at least one metal or metalloid oxide and at least one active metal, comprising treating the catalyst with at least one sulfuration agent dissolved in a solvent.The invention is charcterized in that the sulfuration agent is a polysulfide with the following general formulaR'--S.sub.y --R--S.sub.x --R--S.sub.y).sub.n R'where R is a linear or a branched organic radical comprising from 2 to 12 carbon atoms; R' is an alkyl, alkenyl, arylalkyl or arylalkenyl radical comprising from 1 to 12 carbon atoms, R' possibly comprising at least one heteroatom selected from the group consisting of oxygen, nitrogen, and sulfur; x has a value of from 1 to 4; y has a value of from 1 to 8 and n is such that the average molar mass of the polymer is about 5000.
    Type: Grant
    Filed: February 16, 1989
    Date of Patent: January 8, 1991
    Assignee: Institut Francais du Petrole
    Inventors: Maurice Born, Guy Parc, Herve Toulhoat
  • Patent number: 4981828
    Abstract: A catalyst for the hydrotreatment of a hydrocarbon oil comprises a carrier of an inorganic oxide and an active component supported on the carrier and formed of at least one member selected from the group consisting of water-soluble compounds of molybdenum, tungsten, and the metal of Group 8 in the Periodic Table of Elements and at least one mercapto (--SH) group-containing organic compound selected from the group consisting a mercaptocarboxylic acids represented by the general formula:HS--(CH.sub.2).sub.n --COOR(wherein n stands for an integer in the range of 1 to 3 and R for a hydrogen atom, an alkali metal, an alkaline earth metal, ammonium, or a linear or branched naphthenic alkyl group having 1 to 10 carbon atoms), amino-substituted mercaptans represented by the general formula:H.sub.
    Type: Grant
    Filed: November 28, 1989
    Date of Patent: January 1, 1991
    Inventors: Yasuhito Takahashi, Shigeru Sakai
  • Patent number: 4977117
    Abstract: The invention involves a process comprising regenerating a catalyst comprising (a) a support containing at least one oxide of a metal or metalloid and (b) at least one active metal, said process comprising in a first stage treating said catalyst in the absence of hydrogen with at least one sulfurizing agent comprising a polysulfide of the formulaR--S.sub.(n) --R'wherein n is 2 to 20, R is an organic radical of 1-150 carbon atoms per molecule and R' is independently a radical as defined for R or a hydrogen atom, whereby said agent is incorporated at least in part in said catalyst, in a first portion of a second stage, treating the catalyst in the absence of hydrogen and in the presence of steam, moist air or moist inert gas, at a temperature up to 275.degree. C., and, in a second portion of the second stage, treating the catalyst in the presence of hydrogen at a temperature of at least 275.degree. C., wherein in the first stage a nitrogen compound is added.
    Type: Grant
    Filed: March 29, 1989
    Date of Patent: December 11, 1990
    Assignee: Europeenne de Retraitement de Catalyseurs
    Inventors: Georges Berrebi, Pierre Dufresne
  • Patent number: 4970190
    Abstract: A process for the preparation of a dispersed Group VIB metal sulfide hydrocarbon oil hydroprocessing catalyst comprising reacting aqueous ammonia and a Group VIB metal compound, such as molybdenum oxide or tungsten oxide, to form water soluble compounds such as aqueous ammonium molybdates or tungstates. The aqueous ammonium molybdates or tungstates are sulfided at a relatively low temperature with hydrogen sulfide without feed oil. The slurry stream is then passed through a separator and ammonia is flashed and separated from the system, leaving a separator residue slurry. The separator residue slurry is then mixed with feed oil, hydrogen and hydrogen sulfide and sulfided at a relatively high temperature to produce a dispersed molybdenum sulfide or tungsten sulfide catalyst of high hydroprocessing activity. The catalyst slurry and feed oil can then be passed to a hydroprocessing reactor.
    Type: Grant
    Filed: September 5, 1989
    Date of Patent: November 13, 1990
    Assignee: Chevron Research Company
    Inventors: Jaime Lopez, Eugene A. Pasek
  • Patent number: 4962077
    Abstract: The present invention is based on the discovery that certain transition metal containing complexes thermally decompose to form solids containing the transmission metal, sulfur and carbon and that these transition metal, sulfur and carbon containing solids are particularly suitable as catalysts for hydrodesulfurization, hydrodenitrogenation and aromatics hydrogenation. The transition metal complexes that are thermally decomposed to novel catalysts are complexes of the type represented by the general formula ML.sup.n.sbsp.3, wherein M is selected from Mo, W, Re and mixtures thereof, L is a dithiolene or aminobenzenethiolate ligand, and n represents the total charge of the metal complexes, and is 0, -1, or -2.
    Type: Grant
    Filed: July 11, 1989
    Date of Patent: October 9, 1990
    Assignee: Exxon Research and Engineering Company
    Inventors: Thomas R. Halbert, Russell R. Chianelli, Edward I. Stiefel, Allan J. Jacobson
  • Patent number: 4937221
    Abstract: A mixed-solid solution tri-metallic oxide/sulfide catalyst having the formula:M.sub.I O.sub.a S.sub.b.M.sub.II O.sub.c M.sub.III O.sub.dwherein M.sub.I is iron, nickel, cobalt and mixtures thereof and mixtures with chromium, molybdenum, tungsten, and mixtures thereof; O is oxygen; S is sulfur; a is selected from zero and a number up to a positive real number representing the stoichiometric requirement, and b is selected from zero and a number up to a positive real number representing the stoichiometric requirement, provided one of a and b is a positive real number; M.sub.II is titanium, zirconium, hafnium, and mixtures thereof; c is a positive real number up to the stoichiometric requirement; M.sub.III is lithium, sodium, potassium, rubidium, cesium, francium, beryllium, magnesium, calcium, strontium, barium, radium, zinc, cadmium, mercury, scandium, yttrium, lanthanum, actinium, and mixtures thereof; and d is a positive real number up to the stoichiometric requirement; and wherein M.sub.I O.sub.a S.sub.
    Type: Grant
    Filed: June 9, 1989
    Date of Patent: June 26, 1990
    Assignee: Institute of Gas Technology
    Inventors: Erek J. Erekson, Anthony L. Lee
  • Patent number: 4929585
    Abstract: A mixed-solid solution tri-metallic oxide/sulfide catalyst having the formula:M.sub.I O.sub.a S.sub.b.M.sub.II O.sub.c M.sub.III O.sub.dwherein M.sub.I is vanadium, neodymium, tantalum, chromium, molybdenum, tungsten, and mixtures thereof; O is oxygen; S is sulfur; a is selected from zero and a number up to a positive real number representing the stoichiometric requirement, and b is selected from zero and a number up to a positive real number representing the stoichiometric requirement, provided one of a and b is a positive real number; M.sub.II is titanium, zirconium, hafnium, and mixtures thereof; c is a positive real number up to the stoichiometric requirement; M.sub.III is lithium, sodium, potassium, rubidium, cesium, francium, beryllium, magnesium, calcium, strontium, barium, radium, zinc, cadmium, mercury, scandium, yttrium, lanthanum, actinium, and mixtures thereof; and d is a positive real number up to the stoichiometric requirement; and wherein M.sub.I O.sub.a S.sub.
    Type: Grant
    Filed: June 9, 1989
    Date of Patent: May 29, 1990
    Assignee: Gas Research Institute
    Inventors: Anthony L. Lee, Howard S. Meyer, Vern L. Hill
  • Patent number: 4910181
    Abstract: The catalyst composition comprises a layered metal oxide and/or sulfide of a metal selected from the group consisting of Group VB and VIB metals and containing inserted atomic hydrogen therein, with no chemical bond between said atomic hydrogen and anionic oxygen or anionic sulfur of the oxide or sulfide. It is useful for demetallizing resids.
    Type: Grant
    Filed: October 27, 1988
    Date of Patent: March 20, 1990
    Assignee: Mobil Oil Corporation
    Inventors: Philip J. Angevine, Arthur W. Chester, Thomas F. Degnan, Garry W. Kirker
  • Patent number: 4886772
    Abstract: A method for preparing a mixture of lower aliphatic alcohols from the reaction of carbon monoxide and hydrogen in the presence of a sulfide-containing heavy metal catalyst under carbon-monoxide-hydrogenation conditions in which said catalyst comprises at least one sulfided heavy metal element selected from the group consisting of molybdenum, tungsten, rhenium, and an alkali or alkaline earth promoter which has been treated with a nitrogen-containing compound, or a theramlly stable derivative thereof is provided.
    Type: Grant
    Filed: June 20, 1988
    Date of Patent: December 12, 1989
    Assignee: Texaco Inc.
    Inventors: Guillermo Prada-Silva, Jitendra A. Patel, Ajit K. Bhattacharya
  • Patent number: 4880761
    Abstract: This invention relates to a crystalline composition having a three-dimensional microporous structure of MA.sub.2 units where A is sulfur or selenium and having the empirical formula expressed in molar ratios: xR:MA.sub.2.+-.0.2 :zH.sub.2 O where R represents at least one organic templating agent present in the intracrystalline pore system, x is the moles of R, z is the moles of water and M is germanium or tin. This invention also relates to a composition having the empirical formula expressed in molar ratios: xR:M.sub.1-y M'.sub.y A.sub.2.+-.0.2 :zH.sub.2 O, where M' is a metal such as cobalt, zinc, manganese, iron, nickel, copper, cadmium and gallium. This invention further relates to a method of preparing the crystalline composition.
    Type: Grant
    Filed: December 6, 1988
    Date of Patent: November 14, 1989
    Assignee: UOP
    Inventors: Robert L. Bedard, Lawrence D. Vail, Stephen T. Wilson, Edith M. Flanigen
  • Patent number: 4877762
    Abstract: A catalyst, of especial usefulness in simultaneously reducing the pour point and the organosulfur and/or organonitrogen content of waxy shale oils, comprises a Group VIB metal component on a support comprising a porous refractory oxide and a crystalline silica, such as silicalite.
    Type: Grant
    Filed: August 22, 1988
    Date of Patent: October 31, 1989
    Assignee: Union Oil Company of California
    Inventors: John W. Ward, Timothy L. Carlson
  • Patent number: 4857496
    Abstract: A process for the preparation of a dispersed Group VIB metal sulfide hydrocarbon oil hydroprocessing catalyst comprising reacting aqueous ammonia and a Group VIB metal compound, such as molybdenum oxide or tungsten oxide, to form water soluble compounds such as aqueous ammonium molybdates or tungstates. The aqueous ammonium molybdates or tungstates are sulfided at a relatively low temperature with hydrogen sulfide without feed oil. The slurry stream is then passed through a separator and ammonia is flashed and separated from the system, leaving a separator residue slurry. The separator residue slurry is then mixed with feed oil, hydrogen and hydrogen sulfide and sulfided at a relatively high temperature to produce a dispersed molybdenum sulfide or tungsten sulfide catalyst of high hydroprocessing activity. The catalyst slurry and feed oil can then be passed to a hydroprocessing reactor.
    Type: Grant
    Filed: December 15, 1986
    Date of Patent: August 15, 1989
    Assignee: Chevron Research Company
    Inventors: Jaime Lopez, Eugene A. Pasek
  • Patent number: 4853359
    Abstract: A novel flocculated methanation, hydrogenation or hydrodesulfurization catalyst of the form MS.sub.2 :Y:Z wherein MS.sub.2 is a single layer transition metal dichalcogenide sulfide, Y is a promoter substance and Z is a support substance, is disclosed.
    Type: Grant
    Filed: February 18, 1987
    Date of Patent: August 1, 1989
    Assignee: Simon Fraser University
    Inventors: S. Roy Morrison, Robert F. Frindt, Per Joensen, Michael A. Gee, Bijan K. Miremadi
  • Patent number: 4853357
    Abstract: The additional of redox-active metal components and ligands, alternatively or simultaneously, results in increased conversion and selectivity in the palladium-catalyzed oxidation of olefins to carbonyl products in the presence of polyoxoanions. In preferred modes, heteropolyoxoanions and Isopolyoxoanions containing tungsten, molybdenum and vanadium, individually or in combination, are described. The use of copper as the redox-active metal component shows reduced allylic reactivity. The elimination of chloride from the catalyst system provides substantial engineering advantages over the prior art, particularly, the reduction of corrosion and chloro-organic by-product formation. The use of redox-active metal components and/or ligands makes the palladium-polyoxoanion catalyst system industrially practicable.
    Type: Grant
    Filed: September 30, 1987
    Date of Patent: August 1, 1989
    Assignee: Catalytica Associates
    Inventors: Janis Vasilevskis, Jacques C. De Deken, Robert J. Saxton, Paul R. Wentrcek, Jere D. Fellmann, Lyubov S. Kipnis
  • Patent number: 4845068
    Abstract: Supported catalysts for hydrotreating hydrocarbons comprise (a) at least one member selected from the group consisting of oxides of metals in Groups IV and VIII of the Periodic Table, and (b) at least one organic compound having a mercapto radical or radicals (--SH) selected from the group consisting of mercapto-carboxylic acids, including alkali metal, alkaline earth metal and ammonium salts thereof and esters thereof, bivalent mercaptans, amino-substituted mercaptans, and thiocarboxylic acids. These catalysts can be easily activated by treatment in the presence of hydrogen gas at a temperature in the range from room temperature to 400.degree. C. show higher activity than catalysts activated by conventional methods.
    Type: Grant
    Filed: April 22, 1988
    Date of Patent: July 4, 1989
    Assignee: Sumitomo Metal Mining Company Limited
    Inventors: Yasuhito Takahashi, Shigeru Sakai, Yoshimasa Inoue
  • Patent number: 4839326
    Abstract: This invention relates to a process for the preparation of promoted molybdenum and tungsten sulfide catalysts, the catalysts prepared by such process, and to the use of such catalysts for hydroprocessing processes, particularly hydrotreating. More particularly, this invention relates to the preparation and use of promoted catalysts useful for hydroprocessing processes such as hydrotreating wherein said catalysts are formed by treating molybdenum and tungsten sulfide-containing material (which may be supported) with a low valence promoter metal selected from transition metals particularly the group of Fe, Co, Ni.
    Type: Grant
    Filed: April 22, 1985
    Date of Patent: June 13, 1989
    Assignee: Exxon Research and Engineering Company
    Inventors: Thomas R. Halbert, Edward I. Stiefel, Russell R. Chianelli, Teh C. Ho
  • Patent number: 4831060
    Abstract: Mixed alcohols are produced from carbon monoxide and hydrogen gases using an easily prepared catalyst/co-catalyst metal catalyst. The catalyst metals are molybdenum, tungsten or rhenium. The co-catalyst metals are cobalt, nickel or iron. The catalyst is promoted with a Fischer-Tropsch promoter like an alkali or alkaline earth series metal or a smaller amount of thorium and is further treated by sulfiding. The composition of the mixed alcohols fraction can be selected by selecting the extent of intimate contact among the catalytic components.
    Type: Grant
    Filed: June 6, 1988
    Date of Patent: May 16, 1989
    Assignee: The Dow Chemical Company
    Inventors: Rex R. Stevens, Mark M. Conway
  • Patent number: 4831004
    Abstract: A composition of matter is prepared by a process comprising the steps of impregnating a alumina-containing support material with a thiosulfate (preferably ammonium thiosulfate), drying the thus impregnated material, impregnating the dried material with a transition metal compound, drying and calcining the transition metal impregnated material. This composition of matter is used as catalyst composition for hydrogenating unsaturated hydrocarbon compounds, and as catalyst composition for hydrotreating hydrocarbon-containing feed streams (in particular heavy oils) which contain metal and sulfur compounds as impurities.
    Type: Grant
    Filed: June 29, 1988
    Date of Patent: May 16, 1989
    Assignee: Phillips Petroleum Company
    Inventors: Karlheinz K. Brandes, Simon G. Kukes, Thomas Davis
  • Patent number: 4831002
    Abstract: Self-promoted molybdenum and tungsten sulfide hydrotreating catalysts are prepared by heating one or more water soluble catalyst precursors in a non-oxidizing atmosphere in the presence of sulfur at a temperature of at least about 200.degree. C. The precursors are (Cr.sub.x M.sub.1-x L)[Mo.sub.y W.sub.1-y O.sub.4 ].sub.1+.5x wherein M is a divalent promoter metal selected from the group consisting of Mn, Fe, Co, Ni, Cu, Zn and mixtures thereof, x is any value from about 0.2 to 1, y is any value from 0 to 1, and wherein L is a nitrogen-containing, neutral multidentate, chelating ligand. In a preferred embodiment the lligand L will comprise one or more chelating alkyl di- or triamines and the non-oxidizing atmosphere will comprise H.sub.2 S.
    Type: Grant
    Filed: July 29, 1987
    Date of Patent: May 16, 1989
    Assignee: Exxon Research and Engineering Company
    Inventors: Teh C. Ho, Larry E. McCandlish, Archie R. Young, II, Edward J. Osterhuber
  • Patent number: 4826797
    Abstract: Catalysts comprising a carbon-containing sulfide of molybdenum or tungsten are prepared by contacting, in the presence of sulfur, hydrogen and a hydrocarbon, ammonia and ammonium substituted molybdate, thiomolybdate, tungstate and thiotungstate salts at a temperature of from about 200.degree.-600.degree. C. These catalysts are useful for hydrotreating reactions. In a preferred embodiment, these catalysts will be promoted with certain transition metal sulfides, such as cobalt sulfide, which results in catalysts having greater activity than conventional catalysts such as cobalt-molybdate on alumina.
    Type: Grant
    Filed: November 10, 1986
    Date of Patent: May 2, 1989
    Assignee: Exxon Research and Engineering Company
    Inventors: Russell R. Chianelli, Theresa A. Pecoraro
  • Patent number: 4824820
    Abstract: A composition of matter comprising a mixture of (i) a sulfide of at least one promoter metal selected from the group consisting of Ni, Co, Mn, Cu, Zn and mixture thereof and mixtures thereof with Fe, (ii) an amorphous sulfide of trivalent chromium and (iii) microcrystallites of metal sulfide of a metal selected from the group consisting of molybdenum, tungsten and mixture thereof. These compositions have been found to be useful hydrotreating catalysts having nitrogen removal activity superior to that of commercial catalysts such as cobalt-molybdate on alumina.
    Type: Grant
    Filed: September 24, 1987
    Date of Patent: April 25, 1989
    Assignee: Exxon Research and Engineering Company
    Inventors: Allan J. Jacobson, Teh C. Ho, Russell R. Chianelli, John J. Steger, Angelo A. Montagna
  • Patent number: 4822590
    Abstract: Novel single layer materials of the form MX.sub.2, where MX.sub.2 is a layer-type dichalcogenide such as MoS.sub.2, TaS.sub.2, WS.sub.2, or the like, exfoliated by intercalation of an alkali metal, and immersion in water, are disclosed. MoS.sub.2 has been exfoliated into monolayers by intercalation with lithium followed by reaction with water. X-ray diffraction analysis demonstrates that the exfoliated MoS.sub.2 in suspension is in the form of one-molecule-thick sheets. X-ray patterns from dried and re-stacked films of exfoliated MoS.sub.2 indicate that the layers are randomly stacked. By adsorbing monolayers or precipitating clusters of various species such as compounds of Co, Ni, Pb, Cd, Al, Ce, In and Zn, on MoS.sub.2 while the sulfide is suspended as single layers and then recrystallizing, a new group of inclusion compounds can be formed. In the re-crystallized or re-stacked materials, the inter-layer spacing can be expanded or contracted compared to MoS.sub.2.
    Type: Grant
    Filed: April 23, 1986
    Date of Patent: April 18, 1989
    Assignee: Simon Fraser University
    Inventors: S. Roy Morrison, Robert F. Frindt, Per Joensen, Michael A. Gee, Bijan K. Miremadi