Activating Treatment Patents (Class 502/85)
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Patent number: 4559314Abstract: The activity of a zeolite catalyst is enhanced by forming the catalyst into a composite with a binder such as alumina and steaming the composite. The zeolites have a Constraint Index of 1 to 12 and a silica:alumina ratio of at least 12 and ZSM-5 is preferred. The enhancement of the activity is greatest at the high silica:alumina ratio, especially at ratios above 1200.Type: GrantFiled: January 23, 1984Date of Patent: December 17, 1985Assignee: Mobil Oil CorporationInventor: David S. Shihabi
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Patent number: 4556550Abstract: A process is provided for achieving a high degree of exchange for zeolites, e.g., Zeolites F and W. After preparation of the ammonium form, the zeolite is contacted with a solution containing the desired metal cation while simultaneously maintaining the pH at between about 9.0 and 12.0 to provide a final product zeolite wherein the desired metal cation will correspond to at least about 0.5 of the total zeolitic cations.Type: GrantFiled: October 19, 1983Date of Patent: December 3, 1985Assignee: Union Carbide CorporationInventors: Ronald J. Ross, John D. Sherman
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Patent number: 4554260Abstract: A process for improving the catalyst life of zeolites employed in the conversion of alcohols (e.g. methanol) and/or their ether derivatives (e.g., dimethyl ether) wherein a suitable zeolite is modified in a 2-stage procedure by providing a controlled low amount of a coke precursor deposit on the external surface of the zeolite, and then heating this treated zeolite in an inert gas at specifically controlled temperatures for a minimum time is disclosed. A process of employing this modified zeolite to produce lower olefins is also disclosed.Type: GrantFiled: July 13, 1984Date of Patent: November 19, 1985Assignee: Exxon Research & Engineering Co.Inventors: Wim J. M. Pieters, Yoshiharu Okumura
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Patent number: 4550092Abstract: A crystalline high silica-containing zeolite such as ZSM-5 is treated with an ammoniacal alkali metal aluminate so as to enhance the catalytic activity thereof.Type: GrantFiled: November 25, 1983Date of Patent: October 29, 1985Assignee: Mobil Oil CorporationInventors: Clarence D. Chang, Joseph N. Miale
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Patent number: 4550091Abstract: Surface-active catalytic sites are deactivated on catalyst support materials wherein the catalyst comprises crystalline aluminosilicate or borosilicate molecular sieve catalytic compositions without deactivating all acidic sites of the molecular sieve. Resulting catalyst compositions are useful in dehydrogenating and/or isomerizing hydrocarbons.Type: GrantFiled: June 25, 1984Date of Patent: October 29, 1985Assignee: Standard Oil Company (Indiana)Inventor: David L. Sikkenga
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Patent number: 4548914Abstract: A method is provided for treating modified ZSM-5 type zeolite catalysts with water vapor in order to enhance the aromatics conversion activity and/or the para-selective properties of such catalysts for the conversion of aromatic materials. The modified zeolites so treated are those which contain a minor proportion of a difficultly reducible oxide such as magnesium oxide, calcium oxide and/or phosphorus oxide. Such catalyst compositions can be used in alkylation, transalkylation or disproportionation processes to provide improved yields of alkylated aromatic product mixtures having exceptionally high concentrations of the para-dialkylbenzene isomer.Type: GrantFiled: March 4, 1985Date of Patent: October 22, 1985Assignee: Mobil Oil CorporationInventor: Chin-Chiun Chu
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Patent number: 4539304Abstract: A pretreatment process is disclosed for increasing conversion of reforming catalysts wherein the catalyst is treated at from 120.degree. C. to 260.degree. C.; then the temperature of the treated catalyst is maintained at a temperature of from 370.degree. C. to 600.degree. C. in a reducing atmosphere prior to starting the hydrocarbon feed. Preferably, the catalyst is treated in the presence of hydrogen at atmospheric pressure for at least twenty minutes; then the temperature of the treated catalyst is maintained at 475.degree. C. in a reducing atmosphere for at least ten minutes prior to starting the hydrocarbon feed.Type: GrantFiled: March 8, 1984Date of Patent: September 3, 1985Assignee: Chevron Research CompanyInventor: Leslie A. Field
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Patent number: 4539305Abstract: A pretreatment method is disclosed for enhancing the selectivity and increasing the stability of a reforming catalyst comprising a large-pore zeolite containing at least one Group VIII metal. In this method, the catalyst is reduced in reducing atmosphere at a temperature of from 250.degree. C. to 650.degree. C., exposed to an oxygen-containing gas, treated in a reducing atmosphere at from 120.degree. C. to 260.degree. C., and maintained at a temperature of from 370.degree. C. to 600.degree. C. in a reducing atmosphere.Type: GrantFiled: March 8, 1984Date of Patent: September 3, 1985Assignee: Chevron Research CompanyInventors: Charles R. Wilson, Waldeen C. Buss, Leslie A. Field
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Patent number: 4526880Abstract: The acid activity of a high silica content crystalline zeolite that contains framework boron is increased by hydrolyzing a portion of the boron before compositing the crystals with a binder that contains alumina.Type: GrantFiled: July 16, 1984Date of Patent: July 2, 1985Assignee: Mobil Oil CorporationInventors: Pochen Chu, Gunter H. Kuhl
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Patent number: 4524140Abstract: Substitution of aluminum or gallium for boron or iron contained in the framework of a high silica content zeolite is effected by treating the zeolite in liquid water in the presence of a compound of aluminum or gallium.Type: GrantFiled: July 16, 1984Date of Patent: June 18, 1985Assignee: Mobil Oil CorporationInventors: Clarence D. Chang, Joseph N. Miale
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Patent number: 4524055Abstract: A novel crystalline aluminosilicate zeolite characterized by having(a) a silica/alumina mole ratio in the range of from 10 to 100,(b) X-ray lattice distances d shown in Table A in the specification, and(c) a (cyclohexane/n-hexane) adsorption ratio of at least 0.7. This crystalline aluminosilicate zeolite is useful, for example, as a catalyst in the isomerization reaction or transalkylation reaction of alkylbenzenes or alkylnaphthalenes, and can be prepared by heating a crystalline aluminosilicate zeolite ZSM-5 having a silica/alumina mole ratio of from 20 to 300 at a temperature between 80.degree. C. and 250.degree. C. in an aqueous solution containing 0.1 to 1 g, per gram of the ZSM-5 zeolite, of an alkali metal hydroxide.Type: GrantFiled: February 22, 1983Date of Patent: June 18, 1985Assignee: Teijin Petrochemical Industries Ltd.Inventors: Tamio Onodera, Tokuji Sakai, Yasuo Yamasaki, Koji Sumitani
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Patent number: 4522929Abstract: A zeolite of improved stability for use in acid-catalyzed reactions is prepared by mildly presteaming the catalyst under controlled conditions of temperature, time, and steam partial pressure. The resulting catalyst retains nearly the same activity as that of a fresh unsteamed catalyst.Type: GrantFiled: October 6, 1983Date of Patent: June 11, 1985Assignee: Mobil Oil CorporationInventors: Arthur W. Chester, Yung F. Chu
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Patent number: 4520118Abstract: This invention relates to a method of improving the catalytic activity of a freshly made zeolite loaded with gallium ions by first treating with steam and then with hydrogen. Steam and hydrogen treatment may be carried out before or after loading with gallium simultaneously or successively. It has been found that a combination of steam and hydrogen treatments gives high conversions of hydrocarbon feeds and high selectivity to aromatics.Type: GrantFiled: February 16, 1984Date of Patent: May 28, 1985Assignee: The British Petroleum Company p.l.c.Inventors: Brian R. Gane, Philip Howard
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Patent number: 4513091Abstract: In the process for activating high-silica zeolite catalyst with an ionized activating agent wherein a crystalline zeolite catalyst having a silica:alumina ratio greater than 70 and a constraint index of 1 to 12 is contacted with the activating agent at elevated temperature, an improvement which comprises: hydrothermally treating an intimate mixture of zeolite catalyst and an effective amount of activating agent in contact with an aqueous liquid phase under reaction conditions to increase the cracking activity of the catalyst.The activated catalyst product may be produced by hydrothermal treatment of a composite mixture of zeolite and hydrated alumina or other activating metal oxide binder material. The preferred zeolites are acid ZSM-5 type crystalline materials having a silica:alumina ratio of at least 1600:1.Type: GrantFiled: February 14, 1983Date of Patent: April 23, 1985Assignee: Mobil Oil CorporationInventors: Clarence D. Chang, Joseph N. Miale
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Patent number: 4503023Abstract: Aluminum from AlO.sub.4 -tetrahedra of as-synthesized zeolites is extracted and substituted with silicon to form zeolite compositions having higher SiO.sub.2 /Al.sub.2 O.sub.3 molar ratios and exhibiting distinctive chemical and physical properties. The preparative procedure involves contact of the starting zeolite with an aqueous solution of a fluorosilicate salt using controlled proportions and temperature and pH conditions which avoid aluminum extraction without silicon substitution.Type: GrantFiled: October 28, 1981Date of Patent: March 5, 1985Assignee: Union Carbide CorporationInventors: Donald W. Breck, deceased, by Harold Blass, executor, Gary W. Skeels
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Patent number: 4497903Abstract: Synthesis gas conversion catalyst prepared from synthetic layered aluminosilicate having a montmorillonite-type structure and containing cobalt substituted in the crystal lattice are activated for the conversion of synthesis gas by a sequential reduction, oxidation and reduction treatment. A Group VIII noble metal such as ruthenium can be impregnated on the catalyst prior to the final reduction stage. The catalyst is used in the production of liquid hydrocarbons from synthesis gas.Type: GrantFiled: December 17, 1982Date of Patent: February 5, 1985Assignee: Gulf Research & Development CompanyInventors: Charles L. Kibby, Thaddeus P. Kobylinski
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Patent number: 4487843Abstract: The present invention relates to a method of improving catalytic activity of a zeolite by first steam treating the zeolite and then loading the zeolite so treated with a Group IIIb metal, especially gallium. It has been found that steam treatment prior to gallium loading gives a catalyst which has a higher conversion and selectivity of hydrocarbon feeds to aromatics than otherwise.Type: GrantFiled: February 13, 1984Date of Patent: December 11, 1984Assignee: British Petroleum Company, p.l.c.Inventors: Clive D. Telford, Dennis Young
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Patent number: 4486616Abstract: A process for alkylation of aromatic hydrocarbon reactants to dialkylbenzene products, whereby chemically modified zeolite catalysts are treated with an organic acid to enhance their intrinsic para-selectivity in the alkylation reaction. The modified zeolites which may be so reselectivated or improved comprise those crystalline zeolites having a constraint index of 1 to 12, a silica to alumina mole ratio of at least 12, and having a minor proportion of the oxide form of one or more chemical elements (e.g. phosphorus and magnesium) deposited thereon.Type: GrantFiled: May 12, 1983Date of Patent: December 4, 1984Assignee: Mobil Oil CorporationInventors: Chin-Chiun Chu, Warren W. Kaeding
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Patent number: 4481018Abstract: The invention relates to faujasite-containing compositions in which the original hydrogen or monovalent forms are ion exchanged to their polyvalent form and then thermally activated to promote dehydration and dehydroxylation of the faujasite while maintaining substantially the same zeolite content. The resulting compositions containing faujasites substantially in their dehydrated/dehydroxylated state have been found to have surprisingly high selectivities and capacities for the separation of air into nitrogen and oxygen.Type: GrantFiled: November 15, 1982Date of Patent: November 6, 1984Assignee: Air Products and Chemicals, Inc.Inventors: Charles G. Coe, Steven M. Kuznicki
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Patent number: 4478949Abstract: A process is provided for modifying ZSM-5 type zeolite catalysts with sulfur-based treating agents in order to enhance the para-selective properties of such catalysts for the conversion of aromatic materials to dialkyl-substituted benzene compounds. Sulfur-based treating agents include hydrogen sulfide and sulfur dioxide. Catalyst compositions so treated can be used in alkylation, transalkylation or disproportionation processes to provide product mixtures having exceptionally high concentrations of the para-dialkylbenzene isomer.Type: GrantFiled: August 30, 1982Date of Patent: October 23, 1984Assignee: Mobil Oil CorporationInventor: Warren W. Kaeding
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Patent number: 4478950Abstract: A crystalline high silica-containing zeolite, such as ZSM-5, is hydrothermally treated with aluminate ion to enhance the catalytic activity.Type: GrantFiled: April 25, 1983Date of Patent: October 23, 1984Assignee: Mobil Oil CorporationInventor: Pochen Chu
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Patent number: 4477585Abstract: A process is provided for modifying ZSM-5 type zeolite catalysts with carbon dioxide treating agent in order to enhance the para-selective properties of such catalysts for the conversion of aromatic materials to dialkyl-substituted benzene compounds. Catalyst compositions so treated can be used in alkylation, transalkylation or disproportionation processes to provide product mixtures having exceptionally high concentrations of the para-dialkylbenzene isomer.Type: GrantFiled: August 30, 1982Date of Patent: October 16, 1984Assignee: Mobil Oil CorporationInventor: Warren W. Kaeding
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Patent number: 4477584Abstract: A process is provided for modifying ZSM-5 type zeolite catalysts with gaseous nitrogen-based treating agents in order to enhance the para-selective properties of such catalysts for the conversion of aromatic materials to dialkyl-substituted benzene compounds. Nitrogen-based treating agents include nitrogen dioxide and ammonia. Catalyst compositions so treated can be used in alkylation, transalkylation or disproportionation processes to provide product mixtures having exceptionally high concentrations of the para-dialkylbenzene isomer.Type: GrantFiled: August 30, 1982Date of Patent: October 16, 1984Assignee: Mobil Oil CorporationInventor: Warren W. Kaeding
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Patent number: 4468475Abstract: In the process for activating high-silica zeolite catalyst with alumina activating agent wherein a crystalline zeolite catalyst having a silica:alumina ratio greater than 70 and a constraint index of 1 to 12 is contacted with the activating agent at elevated temperature, the improvement which comprises: hydrothermally treating an intimate mixture of zeolite catalyst and an effective amount of activating agent in contact with an aqueous liquid phase under reaction conditions to increase the cracking activity of the catalyst.The activated catalyst product may be produced by hydrothermal treatment of a composite mixture of zeolite and hydrated alumina binder material. The preferred zeolites are acid ZSM-5 type crystalline materials having a silica:alumina ratio of at least 2000:1.Type: GrantFiled: July 11, 1983Date of Patent: August 28, 1984Assignee: Mobil Oil CorporationInventor: Guenter H. Kuehl
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Patent number: 4458026Abstract: Heat treated anionic clay mineral is an improved catalyst for the conversion of acetone to mesityl oxide and isophorone as well as for the aldo condensation of other carbonyl-containing compounds.Type: GrantFiled: May 25, 1983Date of Patent: July 3, 1984Assignee: Union Carbide CorporationInventor: Walter T. Reichle
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Patent number: 4452910Abstract: Expanded layer, smectite clay having a regular pore structure suitable for catalytic uses and a process for preparing said expanded clay by treating a suspension of commercial smectite clay with a chromium-oligomer solution and subjecting the treated clay to a stabilization heat treatment in an inert gas atmosphere.Type: GrantFiled: June 15, 1982Date of Patent: June 5, 1984Assignee: Standard Oil Company (Indiana)Inventors: P. Donald Hopkins, Bernard L. Meyers, Donna M. Van Duch
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Patent number: 4443554Abstract: Inactive zeolites such as NaZSM-5 are activated by steaming in the presence of a binder such as alumina.Type: GrantFiled: May 28, 1982Date of Patent: April 17, 1984Assignee: Mobil Oil CorporationInventor: Ralph M. Dessau
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Patent number: 4440867Abstract: This invention is concerned with production and use of high surface area particulate matter by calcining a charge of clay mineral, feldspar, zeolite, coal ash, fly ash, pozzolan or volcanic ash for a time to develop fractures which increase the surface area of the particles. Vacuum calcining decreases the calcining time. The calcined matter desirably has an analysis including: calcium oxide, about 20-40 weight %; aluminum oxide, about 15-35 weight %; and silicon oxide, about 20-40 weight %.The calcined particulate matter can be used in the treatment of impure aqueous materials; the matter is denser than water and sludge settles rapidly and completely. The calcined matter interacts with heavy metal ions to form tightly bound sludge that is nonhazardous for landfill disposal. The calcined matter can be combined with conventual coagulants, flocculants, filter aids, or activated carbon to obtain a multipurpose treating agent.Type: GrantFiled: May 14, 1982Date of Patent: April 3, 1984Assignee: Ensotech, Inc.Inventor: Inderjit H. Sabherwal
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Patent number: 4440958Abstract: The activity of cation-exchangeable layered clay or crystalline aluminosilicate catalyst in esterification, etherification, hydration, and cracking reactions is promoted by addition of a strong acid such as sulphuric acid, phosphoric acid, hydrochloric acid, hydrofluoric acid or para-toluene sulphonic acid. The further addition of water to the reaction can extend the life of the clay catalyst and in some cases its catalytic activity.Type: GrantFiled: July 29, 1981Date of Patent: April 3, 1984Assignee: The British Petroleum Company LimitedInventors: Reginald Gregory, David J. Westlake
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Patent number: 4435311Abstract: A process to reactivate a noble metal-containing AMS-1B crystalline borosilicate catalyst comprising contacting such catalyst with water.Type: GrantFiled: September 24, 1982Date of Patent: March 6, 1984Assignee: Standard Oil Company (Indiana)Inventor: David L. Sikkenga
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Patent number: 4420418Abstract: A process is provided for treating modified ZSM-5 type zeolite catalysts with carboxylic acid (or anhydride) and water vapor treating agents in order to enhance the para-selective properties of such catalysts for the alkylation of aromatic materials without significantly diminishing catalyst activity. The modified zeolites so treated are those which contain a minor proportion of a difficulty reducible oxide such as magnesium oxide, calcium oxide and/or phosphorus oxide. Such catalyst compositions can be used in alkylation processes to provide alkylated aromatic product mixtures having exceptionally high concentrations of the para-dialkylbenzene isomer.Type: GrantFiled: November 19, 1981Date of Patent: December 13, 1983Assignee: Mobil Oil CorporationInventor: Chin-Chiun Chu
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Patent number: 4415479Abstract: A catalyst and process for purifying crude terephthalic acid wherein the catalyst comprises palladium metal crystallites deposited upon a carbon support wherein the catalyst is prepared by contacting a carbonaceous support with an aqueous solution of a palladium amine complex in the presence of acetic acid.Type: GrantFiled: October 29, 1981Date of Patent: November 15, 1983Assignee: Standard Oil Company (Indiana)Inventors: Imre Puskas, David E. James
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Patent number: 4414189Abstract: A method is provided for effectively tailoring the catalytic activity of synthetic crystalline zeolites. The method involves synthesizing the zeolite from a reaction mixture containing a source of bulky organic cations, contacting the synthesized zeolite with hydrogen fluoride solution, calcining the hydrogen fluoride solution contacted zeolite, contacting the calcined zeolite with an ammonium exchange solution, and then calcining the ammonium exchange solution contacted zeolite.Type: GrantFiled: May 27, 1982Date of Patent: November 8, 1983Assignee: Mobil Oil CorporationInventors: George T. Kokotailo, Albert C. Rohrman, Jr., Stephen Sawruk