Activating Treatment Patents (Class 502/85)
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Patent number: 5518708Abstract: Molecular sieve compositions are prepared by extracting aluminum and substituting chromium and/or tin for extracted aluminum to give molecular sieve products containing framework chromium and/or tin atoms. The process of preparing the chromium and/or tin-containing molecular sieves involves contacting a starting molecular sieve with a solution or slurry of at least one of a fluoro salt of chromium or a fluoro salt of tin under effective process conditions to provide for aluminum extraction and substitution of chromium and/or tin.Type: GrantFiled: November 8, 1994Date of Patent: May 21, 1996Assignee: UOPInventors: Gary W. Skeels, Diane M. Chapman, Edith M. Flanigen
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Patent number: 5516736Abstract: There is provided a method for selectivating a zeolite, such as ZSM-5 which may result in functionalization of the zeolite with at least one organosiliceous group of the formula, SiR.sub.n (OX).sub.4-n, where R is at least one hydrocarbyl group, n is 1 or 2 and X is Si or H. This selectivation method involves vapor phase treatment of a zeolite with an organosilicon compound having at least 2 silicon atoms. This organosilicon compound may be a silicone compound, such as hexamethyldisiloxane, or a silane compound such as hexamethyldisilane. This contacting may take place in the presence of hydrogen and an organic carrier. The functionalized zeolites may provide a catalyst which is both highly active and highly selective for converting aromatic hydrocarbons, especially alkylbenzene compounds, to products comprising the para-isomer of dialkylbenzenes. The disproportionation of toluene is an example of such a reaction.Type: GrantFiled: September 15, 1994Date of Patent: May 14, 1996Assignee: Mobil Oil Corp.Inventors: Clarence D. Chang, Paul G. Rodewald
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Patent number: 5508019Abstract: Crystalline aluminosilicates such as zeolite beta may be readily dealuminated using organic sulfonic acids such as methanesulfonic acid to provide useful catalysts or catalyst precursors. A high degree of aluminum removal with minimal loss of crystallinity is possible even when an organic template is not present in the starting aluminosilicate.Type: GrantFiled: June 30, 1994Date of Patent: April 16, 1996Assignee: ARCO Chemical Technology, L.P.Inventors: Robert J. Saxton, Guy L. Crocco, John G. Zajacek
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Patent number: 5498285Abstract: The invention relates to a process for the synthesis of a layered, clay-like material starting from a silicon oxide containing material in a finely divided state by reacting a glass phase containing material at a pH from 5 to 8, in the presence of water, with a source of layer-forming metal ions and an activator for the formation of clay under atmospheric conditions to obtain a material with a stable structure. Preferably aluminium and/or magnesium ions are employed as layer-forming metal ions. Furthermore, according to a suitable embodiment, boron glass or cullet is employed as a material containing silicon oxide. The conversion of the mixture of materials into a substance having an ordered structure takes place preferably at a pH of approximately 7 and a temperature of 30.degree.-45.degree. C., in which the starting materials appropriately have a particle size of approximately 100 microns. An activator for the formation of clay is added to accelerate the process of conversion.Type: GrantFiled: December 9, 1993Date of Patent: March 12, 1996Assignee: Pelt & Hooykaas B.V.Inventor: Carel W. J. Hooykaas
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Patent number: 5480851Abstract: Disclosed herein is a process of preparing a catalyst having narrow particle size distribution and supported with monodispersed metal particles of which a particle size is about less than 20 .ANG.. In the present invention, propargyl alcohol is employed in place of a sulfur-containing agent for supporting the metal particles on a support thereby avoiding the contamination of the sulfur component and the high temperature treatment for decomposing the sulfur-containing agent. Accordingly, the resulting catalyst contains no sulfur contaminant and substantially no agglomerated metal particles.Type: GrantFiled: July 6, 1993Date of Patent: January 2, 1996Assignees: Tanaka Kikinzoku Kogyo K.K., Stonehart Associates Inc.Inventors: Kazunori Tsurumi, Paul Stonehart
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Patent number: 5476823Abstract: An ex situ selectivated catalytic molecular sieve for enhanced shape selective hydrocarbon conversions in which a catalytic molecular sieve is modified by being exposed to at least two selectivation sequences, each sequence including an impregnation of the molecular sieve with a selectivating agent and a subsequent calcination of the impregnated molecular sieve. The ex situ selectivation method is also described, including the use of low volatility organic carriers for the selectivating agent. Also, a method for moderate steaming of the ex situ selectivated molecular sieve. Also a method for in situ trim-selectivating the ex situ selectivated catalytic molecular sieve. Also described is the process for shape selective hydrocarbon conversion comprising contacting a hydrocarbon feedstream under conversion conditions with the modified catalytic molecular sieve.Type: GrantFiled: May 28, 1993Date of Patent: December 19, 1995Assignee: Mobil Oil Corp.Inventors: Jeffrey S. Beck, David H. Olson, Sharon B. McCullen
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Patent number: 5451391Abstract: Process for the preparation of a crystalline aluminosilicate enriched in silica, having the structure of mazzite, by hydrothermal crystallization of a gel containing sources of silicon, aluminum and alkali metal ions, in the presence of an organic structuring agent, characterized in that the source of aluminum is a zeolite Y in the form of spheres. The mazzite obtained does not contain any silicoalumina debris out of the lattice. It is employed as catalyst for the conversion of hydrocarbons or as molecular sieve.Type: GrantFiled: December 6, 1993Date of Patent: September 19, 1995Assignee: Societe Nationale Elf AquitaineInventors: Francesco Di Renzo, Francois Fajula, Nisso Barbouth, Fredj Fitoussi, Philippe Schulz, Thierry des Courrieres
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Patent number: 5434114Abstract: Molecular sieves are modified by an ion exchange process where metal cations are introduced into the molecular sieves by means of solid state ion exchange. The solid state ion exchange can be carried out as follows: a weighed amount of calcined and activated zeolite is intimately mixed with a precalculated amount of PtCl.sub.2, PdCl.sub.2, RhCl.sub.3, CuCl.sub.2, V.sub.2 O.sub.5 or another compound of the noble metals (e.g., corresponding halides or oxides), the solids mixture is then heated in a current of inert gas (e.g., a current of helium gas or of nitrogen) to temperatures of 400.degree. to 600.degree. C., then cooled down to room temperature and subsequently reduced in a current of hydrogen for 10 to 14 hours at 280.degree. to 350.degree. C. in order to produce small metal clusters from the cationically introduced metal.Type: GrantFiled: February 16, 1994Date of Patent: July 18, 1995Assignee: Degussa AktiengesellschaftInventors: Jens Weitkamp, Stefan Ernst, Thomas Bock, Thomas Kromminga, Akos Kiss, Peter Kleinschmit
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Patent number: 5425934Abstract: Disclosed is a method for treating synthetic zeolite to remove organic template material therefrom and concurrently therewith effect dealumination of the zeolite. The method comprises the steps of providing a body of synthetic zeolite containing organic template material, the zeolite having an SiO.sub.2 /Al.sub.2 O.sub.3 ratio of at least 7:1. The body is treated with a solution comprised of an alcohol selected from methanol, ethanol and propanol and an acid selected from hydrochloric, nitric and sulfuric acid at a temperature and time to remove the organic template material therefrom and to effect dealumination thereof to provide a treated zeolite product. The treated product is washed to remove residual solution and then dried to provide a synthetic zeolite product containing a reduced amount of organic template material and having an SiO.sub.2 /Al.sub.2 O.sub.3 ratio of at least 7:1.Type: GrantFiled: December 27, 1993Date of Patent: June 20, 1995Assignee: Gas Research InstituteInventors: Prakash B. Malla, Sridhar Komarneni
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Patent number: 5403800Abstract: A ex situ selectivated catalytic molecular sieve for enhanced shape selective hydrocarbon conversions in which a catalytic molecular sieve is modified by being exposed to at least two selectivation sequences, each sequence including an impregnation of the molecular sieve with a selectivating agent and a subsequent calcination of the impregnated molecular sieve. The ex situ selectivation method is also described, including the use of aqueous carriers for the selecting agent. Also a method for in situ trim-selectivating the modified catalytic molecular sieve. Also, a method for moderate steaming of the selectivated molecular sieve. Also a method for in situ trim-selectivating the modified catalytic molecular sieve. Also described is the process for shape selective hydrocarbon conversion comprising contacting a hydrocarbon feedstream under conversion conditions with the selectivated molecular sieve.Type: GrantFiled: May 28, 1993Date of Patent: April 4, 1995Assignee: Mobil Oil Corp.Inventors: Jeffrey S. Beck, Sharon B. McCullen, David H. Olson
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Patent number: 5401488Abstract: Molecular sieve compositions are prepared by extracting aluminum and substituting chromium and/or tin for extracted aluminum to give molecular sieve products containing framework chromium and/or tin atoms. The process of preparing the chromium and/or tin-containing molecular sieves involves contacting a starting molecular sieve with a solution or slurry of at least one of a fluoro salt of chromium or a fluoro salt of tin under effective process conditions to provide for aluminum extraction and substitution of chromium and/or tin.Type: GrantFiled: June 26, 1992Date of Patent: March 28, 1995Assignee: UOPInventors: Gary W. Skeels, Diane M. Chapman, Edith M. Flanigen
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Patent number: 5399537Abstract: A method and nickel-containing catalyst are disposed for preparing synthesis gas by the reforming of a hydrocarbyl compound using an oxygen-containing compound.Type: GrantFiled: August 20, 1993Date of Patent: March 21, 1995Assignee: Amoco CorporationInventors: Alakananda Bhattacharyya, Wen-Dong Chang, Mark S. Kleefisch, Carl A. Udovich
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Patent number: 5393718Abstract: The present invention relates to a zeolite beta catalyst characterized by critical limits of weak and strong acid species and exceptionally high catalytic activity. The catalyst is activated at a temperature effective to substantially reduce the concentration of strong acid species, i.e., hydronium cations, without substantially reducing the concentration of weak acid species, i.e., hydroxoaluminum cations, preferably following a calcining step wherein a synthesized zeolite beta catalyst containing a templating agent is calcined at a temperature in the range of from about 200.degree. to 1000.degree. C. in order to remove a substantial portion of the catalyst templating agent and an ion-exchanging step wherein the calcined catalyst is ion-exchanged with a salt solution containing at least one hydrogen forming cation selected from NH.sub.4.sup.+ and quaternary ammonium. Conversion processes utilizing the catalyst of the invention also are disclosed.Type: GrantFiled: July 26, 1993Date of Patent: February 28, 1995Assignee: UOPInventors: Gary W. Skeels, Edith M. Flanigen
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Patent number: 5389357Abstract: A process for the manufacture of a modified aluminosilicate zeolite is disclosed which includes contacting a starting zeolite in an aqueous phase with a dealuminating agent at a pH value of lower than 4 in the presence of a soluble silica. A novel zeolite composition is also disclosed which has increased acid and thermal stability.Type: GrantFiled: June 1, 1994Date of Patent: February 14, 1995Assignee: Catalysts & Chemicals Industries Co., Ltd.Inventors: Goro Sato, Yusaku Arima, Takanori Ida
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Patent number: 5367099Abstract: A process for shape selective hydrocarbon conversion that involves contacting a hydrocarbon feedsteam, including toluene, under conversion conditions with a catalytic molecular sieve which has been modified by being ex situ selectivated with a silicon compound. The ex situ selectivation involves exposing the molecular sieve to at least two silicon impregnation sequences, each sequence comprising an impregnation with a silicon compound followed by calcination. The modified catalyst used in the process may also be steamed. Optionally, the modified catalyst may be trim-selectivated.Type: GrantFiled: May 28, 1993Date of Patent: November 22, 1994Assignee: Mobil Oil Corp.Inventors: Jeffrey S. Beck, David H. Olson, Sharon B. McCullen
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Patent number: 5365004Abstract: A process for shape selective hydrocarbon conversion that involves contacting a hydrocarbon feedsteam, including toluene, under conversion conditions with a catalytic molecular sieve which has been modified by being ex situ selectivated with a silicon compound. The ex situ selectivation involves exposing the molecular sieve to at least two silicon impregnation sequences, each sequence comprising an impregnation with a silicon compound followed by calcination. The modified catalyst used in the process may also be steamed. Optionally, the modified catalyst may be trim-selectivated.Type: GrantFiled: May 28, 1993Date of Patent: November 15, 1994Assignee: Mobil Oil Corp.Inventors: Jeffrey S. Beck, Sharon B. McCullen, David H. Olson
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Patent number: 5349114Abstract: A process for shape selective hydrocarbon conversion involves contacting a hydrocarbon feedsteam under conversion conditions with a modified catalytic molecular sieve which has been modified by being pre-selectivated with a first silicon source, then steamed. The feedstream may also contain a second silicon source which is a high efficiency para-xylene selectivating agent. The method for modifying the molecular sieve is also described.Type: GrantFiled: April 5, 1993Date of Patent: September 20, 1994Assignee: Mobil Oil Corp.Inventors: Rudolph M. Lago, David O. Marler, Sharon B. McCullen
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Patent number: 5271920Abstract: The invention includes a ZSM-5 composition and the preparation thereof which comprises treating ZSM-5 with solutions of salts of weak acids. The resulting ultrasmall crystal size ZSM-5 component has a sorption capacity for 2,2-dimethylbutane of at least 10 mg/g zeolite and a sorption time for 30% capacity zeolitic sorption at 60.degree. C. and P(2,2-dimethylbutane) of 60 torr, of less than about 4 minutes.Type: GrantFiled: January 7, 1992Date of Patent: December 21, 1993Assignee: Mobil Oil CorporationInventors: Clarence D. Chang, Nai Y. Chen, Cynthis T. Chu, Bruce P. Pelrine
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Patent number: 5262141Abstract: Silicon is inserted into the crystal lattice of zeolites containing defect sites by reaction with SiCl.sub.4 in the presence of oxygen. It has been found that by initially dehydrating the starting zeolite and removing the hydroxyl groups existing in the crystal defect sites, the generation of HCl from the SiCl.sub.4 reagent is avoided along with the undesirable aluminum hydrolysis reactions between the HCl thus-generated and the zeolite framework. The prior dehydration and dehydroxylation makes the presence of oxygen essential to the silicon insertion.Type: GrantFiled: December 21, 1992Date of Patent: November 16, 1993Assignee: UOPInventor: Gary W. Skeels
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Patent number: 5242677Abstract: Y-type zeolites with unit cell constants of less than 24.14 .ANG. are prepared by improving the method of dealumination and aluminum ion exchange. Zeolites with such low unit cell constants have not been known previously.Type: GrantFiled: June 11, 1992Date of Patent: September 7, 1993Assignee: PQ CorporationInventors: David A. Cooper, Raymond P. Denkewicz, Elliot P. Hertzenberg
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Patent number: 5242676Abstract: A process for the selective surface dealumination of a zeolite having a Constraint Index greater than 1 by contacting the zeolite with dicarboxylic acid, such as oxalic acid.Type: GrantFiled: May 11, 1992Date of Patent: September 7, 1993Assignee: Mobil Oil Corp.Inventors: Minas R. Apelian, Anthony S. Fung
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Patent number: 5238677Abstract: A process for the dealumination of a zeolite having the structure of mordenite by contacting the zeolite with dicarboxylic acid, such as oxalic acid, and steaming. The process is useful for the dealumination of TEA mordenite.Type: GrantFiled: June 15, 1992Date of Patent: August 24, 1993Assignee: Mobil Oil Corp.Inventors: Minas R. Apelian, Thomas F. Degnan
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Patent number: 5238676Abstract: This invention relates to a method for modifying a synthetic composition of ultra-large pore crystalline material, e.g., silicate, comprising an inorganic, porous, non-layered crystalline phase material exhibiting, after calcination, an X-ray diffraction pattern with at least one peak at a d-spacing greater than 18 Angstrom Units and having a benzene adsorption capacity of greater than 15 grams benzene per 100 grams of said material at 6.7 kPa (50 torr) and 25.degree. C., by contacting with a treatment composition comprising an inorganic oxide of a trivalent element X, e.g., sodium aluminate, or precursor of said inorganic oxide, under sufficient conditions so that the trivalent element X is incorporated in the crystalline phase material. The composition is suited to use for catalytic conversion of organic compounds or as a sorbent.Type: GrantFiled: July 24, 1991Date of Patent: August 24, 1993Assignee: Mobil Oil CorporationInventors: Wieslaw J. Roth, James C. Vartuli, Charles T. Kresge, Michael E. Leonowicz
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Patent number: 5236680Abstract: The invention is a process for preparing amorphous silica alumina spherical particles by mixing sodium silicate or silicic acid gel with sodium aluminate and sodium hydroxide in an aqueous solution to form a gel, homogenizing the formed gel, crystallizing this intermediate product at 85.degree. C. to 200.degree. under atmospheric pressure or under hydrothermal conditions to form spherical zeolite particles with an x-ray diffraction pattern inherent to P-type zeolites and with a notched surface, treating the zeolite particles with acid to remove the sodium, thereby rendering the particles amorphous.Type: GrantFiled: June 18, 1991Date of Patent: August 17, 1993Assignee: Mizusawa Industrial Chemicals, Ltd.Inventors: Tadahisa Nakazawa, Masahide Ogawa, Kiyoshi Abe, Kazuhiko Suzuki, Takashi Tokita, Toshio Ito
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Patent number: 5236880Abstract: A zeolite catalyst with improved hydrocarbon conversion comprising a crystalline aluminosilicate having a SiO.sub.2 /Al.sub.2 O.sub.3 ratio greater than 5 and preferably a MFI or MEL zeolite. The zeolite contains a Group VIIIA metal, preferably nickel, and it has been subjected to severe thermal or hydrothermal treatments under controlled conditions of temperature, time or steam partial pressure so as to effect an increase in the relative surface concentrations of Group VIIIA metal and aluminum. The catalyst can be used in a process for the conversion of paraffinic feedstocks to improve paraffin cracking activity, to increase the aromatic fraction in the C5 to C12 gasoline range products, to improve the calculated octane numbers of the C5 to C12 gasoline range product, and/or to improve the yield of the C5 to C12 gasoline range products.Type: GrantFiled: March 9, 1992Date of Patent: August 17, 1993Assignee: W. R. Grace & Co.-Conn.Inventor: David M. Chapman
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Patent number: 5234872Abstract: A process for the selective surface dealumination of organic-containing zeolites by contacting the zeolite with dicarboxylic acid, such as oxalic acid. The treatment results in a reduction in surface acidity without a significant reduction in overall activity. The organic may be a directing agent used in the zeolite synthesis or introduced into the pores of the zeolite after thermal treatment.Type: GrantFiled: May 11, 1992Date of Patent: August 10, 1993Assignee: Mobil Oil Corp.Inventors: Minas R. Apelian, Thomas F. Degnan, Anthony S. Fung
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Patent number: 5227352Abstract: A crystalline aluminosilicate which has the following characteristics:(A) the SiO.sub.2 /Al.sub.2 O.sub.3 molar ratio as determined by chemical analysis is from 5 to 15;(B) the molar ratio of the Al content in the zeolite framework to the total Al of the aluminosilicate is from 0.3 to 0.6;(C) the unit cell dimension is 24.30 .ANG. or larger but less than 24.45 .ANG.;(D) the alkali metal content in terms of oxide is 0.02% by weight or more but less than 1% by weight in total;(E) the pore distribution yields characteristic peaks at around 50 .ANG. and at around 180 .ANG., with the volume of pores 100 .ANG. or larger but smaller than 600 .ANG. accounting for 10 to 40% of the whole pore volume; and(F) the X ray diffraction pattern thereof yields characteristic peaks of zeolite Y; and a metal modified crystalline aluminosilicate characterized by an X-ray diffraction pattern characteristic of zeolite Y, which is an ion exchanged form or a metal impregnated form containing from 0.Type: GrantFiled: June 28, 1991Date of Patent: July 13, 1993Assignees: Petroleum Energy Center, Cosmo Oil Co., Ltd.Inventors: Mitsugu Tsujii, Nobuki Sekine, Yukihiro Mimura, Yoshihiro Mizutani, Mitsuru Ohi, Seiichi Harima, Masaki Tanno
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Patent number: 5220086Abstract: The invention relates to the treatment of crystals of ZSM-5 with mineral acid to produce ZSM-5 crystals which have an acid activity associated with the pores and channels thereof, the shape selective portion of the crystal, which is greater than the acid activity of the non-shape selective portion of the crystal or the surface of the ZSM-5 crystal, and the effect of the treated zeolite, as a catalyst component, in catalytic hydrocarbon conversions.Type: GrantFiled: December 9, 1991Date of Patent: June 15, 1993Assignee: Mobil Oil CorporationInventor: Paul G. Rodewald
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Patent number: 5206004Abstract: Improved molecular sieves and processes for treatment of molecular sieves which permit use for separation of ethylene and silane without attending formation of ethylsilane. Such treatment includes treatment of sieves with silane at an effective temperature, pressure and time.Type: GrantFiled: July 1, 1991Date of Patent: April 27, 1993Assignee: Ethyl CorporationInventor: Won S. Park
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Patent number: 5204076Abstract: The invention relates to sulfonic acid derivatives of crystalline porous materials having uniform pore size with an average pore size greater than 5 Angstroms or a Constraint Index of ten or less. In a preferred embodiment an acid treated crystalline porous material is reacted with a reagent to form the sulfonic acid derivative. The new products can be used as acid catalysts for acid catalyzed reactions. An example is the use of these materials in acid catalyzed etherification of methanol with isobutene.Type: GrantFiled: July 16, 1991Date of Patent: April 20, 1993Assignee: Mobil Oil CorporationInventors: Maria D. Farnos, Michael E. Landis
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Patent number: 5200168Abstract: A process for the dealumination of a zeolite having the structure of zeolite Beta by contacting the zeolite with dicarboxylic acid, such as oxalic acid.Type: GrantFiled: January 31, 1992Date of Patent: April 6, 1993Assignee: Mobil Oil Corp.Inventors: Minas R. Apelian, Thomas F. Degnan, Anthony S. Fung, Gordon J. Kennedy
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Patent number: 5190904Abstract: Paraffin alkylation using solid, particulate catalyst is carried out by preparing an alkane-catalyst mixture in a wash zone, passing the alkane-catalyst mixture to a plug flow reactor where a minor amount of olefin is introduced to contact the alkane-catalyst mixture and react to form alkylate and the alkane-catalyst-alkylate mixture is passed through the reactor with a minimum of back mixing to restrict the reaction of alkylate with olefin, thus substantially preventing polymerization. The alkane-catalyst-alkylate mixture, substantially free of olefin is passed to a disengaging zone where the liquid is removed and the solid particulate catalyst is recovered and returned to the wash zone for recycle. The alkane is present in the reactor in sufficient molar excess to react substantially all of the olefin. Any unreacted isoalkane is recycled to the reactor with make-up isoalkane added to maintain the molar excess.Type: GrantFiled: November 12, 1991Date of Patent: March 2, 1993Assignee: Chemical Research & Licensing CompanyInventors: Clifford S. Crossland, Alan Johnson, John Woods, Elliot G. Pitt
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Patent number: 5179052Abstract: A method is disclosed wherein t-butanol is reacted with methanol in a reaction zone in one step to provide methyl tert-butyl ether and the improvement of accomplishing the reaction which comprises:a. Using a catalyst consisting of a crystalline aluminosilicate faujasite Y-type zeolite which has been treated with a fluorosulfonic acid;b. continuously contacting said t-butanol and methanol in a molar amount of about 0.1 to 10 moles of methanol per mole of t-butanol with said catalyst at a temperature of about 20.degree. C. to about 250.degree. C. and a pressure of about atmospheric to about 1000 psig to obtain the methyl tert-butyl ether product.Type: GrantFiled: November 29, 1991Date of Patent: January 12, 1993Assignee: Texaco Chemical CompanyInventor: John F. Knifton
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Patent number: 5169812Abstract: A catalyst for converting C.sub.2 to C.sub.6 aliphatic hydrocarbons to aromatics is described. The catalyst contains a zeolite, an aluminum phosphate binder and a gallium component. Examples of zeolites which can be used are the ZSM family of zeolites, with ZSM-5 being a specific example. The catalyst is characterized in that it is tolerant to exposure to hydrogen at tempertures of about 500.degree. to about 700.degree. C. The catalyst's tolerance to hydrogen exposure is the result of treating the catalyst with an aqueous solution of a weakly acidic ammonium salt or a dilute acid solution at a temperature of about 50.degree. to about 100.degree. C. for a time of about 1 to about 48 hours, followed by calcination. A process for preparing the catalyst is also described.Type: GrantFiled: September 16, 1991Date of Patent: December 8, 1992Assignee: UOPInventors: Joseph A. Kocal, Tamotsu Imai, Paul J. Kuchar, Christopher D. Gosling
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Patent number: 5158668Abstract: Recarburizer coke containing not more than 0.1 weight percent sulfur and not more than 0.1 weight percent nitrogen is prepared by the catalytic hydrogenation, thermal cracking, and delayed coking of a mixture of pyrolysis tar and petroleum distillate.Type: GrantFiled: January 6, 1992Date of Patent: October 27, 1992Assignee: Conoco Inc.Inventors: Bharat S. Chahar, John K. Shipley
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Patent number: 5158670Abstract: A catalytic cracking process is provided in which a zeolitic cracking catalyst having the structure of faujasite is first regenerated, then coked at a high catalyst to hydrocarbon weight ratio, and, subsequently utilized to crack a hydrocarbon feed boiling from about 430.degree.F. to 1050.degree. F. at a lower catalyst to hydrocarbon feed ratio.Type: GrantFiled: April 10, 1991Date of Patent: October 27, 1992Assignee: Exxon Research and Engineering CompanyInventors: Ian A. Cody, Gordon F. Stuntz, William G. McKnight
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Patent number: 5143879Abstract: This invention relates to a method for removing organic directing agents from as-synthesized molecular sieves comprising:(a) contacting said porous synthetic material with polar solvent having dissolved therein at least one cation donor, wherein said polar solvent is characterized by solubility parameters f.sub.d, f.sub.p, and f.sub.h wherein the values of solubility parameters f.sub.d, f.sub.p, and f.sub.h are defined by a circular region of the Teas diagram of Figure 41, said circular region having a center defined by the coordinates (f.sub.d =46, f.sub.p =22, f.sub.Type: GrantFiled: July 18, 1991Date of Patent: September 1, 1992Assignee: Mobil Oil CorporationInventor: D. Duayne Whitehurst
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Patent number: 5133952Abstract: Disclosed is a zeolite and a process for modifying a zeolite, which includes alkalizing the zeolite, and calcining the alkalized zeolite. The resultant modified zeolite has improved selectivity characteristics.Type: GrantFiled: October 22, 1990Date of Patent: July 28, 1992Assignee: Vereinigte Aluminium-Werke AktiengesellschaftInventors: Arno Tissler, Klaus K. Unger, Hubertus Schmidt
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Patent number: 5126296Abstract: A method for enhancing the activity of a porous crystalline zeolite having a framework silica-to-alumina mole ratio of 25 or more which comprises contacting the zeolite with a solution comprising a hydrate of trivalent metal fluoride in aqueous media under conditions sufficient to cause incorporation of said metal in the framework of said zeolite.Type: GrantFiled: November 16, 1990Date of Patent: June 30, 1992Assignee: Mobil Oil CorporationInventors: Scott Han, Clarence D. Chang
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Patent number: 5118482Abstract: The instant invention comprises a process for increasing the framework aluminum content of a framework aluminum deficient zeolite containing non-framework aluminum by contacting said zeolite with an aqueous basic solution at a temperature greater than about 25.degree. C. Preferably the aqueous solution comprises ammonium and/or alkali metal hydroxides dissolved in water and the contact temperature ranges between about 60.degree. C. and about 90.degree. C. The instant invention also relates to the zeolites thus prepared by the instant process.Type: GrantFiled: June 30, 1989Date of Patent: June 2, 1992Assignee: Shell Oil CompanyInventors: Mysore Narayana, Brendan D. Murray
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Patent number: 5116794Abstract: The present invention relates to methods for enhancing at least one catalytic property of a crystalline microporous three-dimensional solid catalyst having the structure and composition of zeolite beta for use in hydrocarbon conversion processes. An essential step in the methods of the present invention comprises activating the catalyst which had previously been calcined and subjected to ion-exchange with a hydrogen-forming cation by heating in air or in inert atmosphere at a temperature of from about 575.degree.-657.degree. C. and for a period of time sufficient to enhance at least one catalytic property of the catalyst for use in the hydrocarbon conversion process. Typical of the enhanced catalytic properties which can be achieved in accordance with the present invention are catalytic activity and catalytic selectivity.Type: GrantFiled: June 21, 1990Date of Patent: May 26, 1992Assignee: UOPInventors: Gary W. Skeels, Edith M. Flanigen
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Patent number: 5110776Abstract: A process for preparing a zeolite containing catalyst which has improved attrition resistance, and causes improved octane with no appreciable change in dry gas and coke make when used during catalytic cracking processes is disclosed. The catalyst is prepared by modifying the zeolite with a phosphate containing solution. The zeolite preferably includes an REY large pore zeolite. Treatment of the zeolite is best accomplished in an aqueous solution, at a pH range from about 2 to about 6, containing a water soluble phosphate compound. The phosphate treatment of the zeolite is carried out by deagglomerating the zeolite in an aqueous mixture in the presence of an aqueous phosphate containing solution, such as an aqueous solution of ammonium monohydrogen phosphate. The aqueous mixture containing phosphate modified zeolite is then combined with matrix precursors to form a slurry. The slurry is preferably spray dried to form the catalyst having a diameter less than 200 microns.Type: GrantFiled: March 12, 1991Date of Patent: May 5, 1992Assignee: Mobil Oil Corp.Inventors: Girish K. Chitnis, Joseph A. Herbst
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Patent number: 5100644Abstract: The removal of aluminum and silicon atoms from the framework of crystalline zeolites and the reinsertion of at least some of the removed silicon atoms into the sites vacated by extracted aluminum atoms is accomplished by the process of contacting the zeolite with an aqueous solution of a bifluoride salt, preferably ammonium bifluoride. The treated zeolites have higher crystal destruction temperatures than their precursor starting zeolites.Type: GrantFiled: December 14, 1990Date of Patent: March 31, 1992Assignee: UOPInventors: Gary W. Skeels, Diane M. Chapman-Snyder, Edith M. Flanigen
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Patent number: 5077026Abstract: Ferrisilicate molecular sieves of the ZSM-5 type, having SiO.sub.2 /Fe.sub.2 O.sub.3 mole ratios ranging from 20 to 400, are prepared by adding a silica source and a quaternary ammonium salt in that order to an acedified solution of an iron (III) compound, crystallizing the resulting gel to form a ferrisilicate molecular sieve, and thermally treating the molecular sieve with nitrogen, air and/or steam at 300.degree. to 700.degree. C. Preferred thermal treatment comprises treating with nitrogen first, then with air or steam. Thermally treated molecular sieves contain iron both in and outside the crystal framework; most of the non-framework iron is dispersed as very finely divided iron oxides or internal surfaces. Molecular sieves are useful as catalysts in Fischer-Tropsch and other iron oxide-catalyzed reactions.Type: GrantFiled: July 13, 1990Date of Patent: December 31, 1991Assignee: Georgia Tech Research CorporationInventors: Vinayan Nair, Rosemarie Szostak
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Patent number: 5066630Abstract: Nitrogen-containing organic compounds are removed from crystalline metallosilicates containing the same by firing the crystalline metallosilicates in the presence of a gas containing molecular oxygen and additionally a lower alcohol represented by the formula (I):R--OH (I)wherein R represents an alkyl group of 1-4 carbon atoms.Type: GrantFiled: June 13, 1990Date of Patent: November 19, 1991Assignee: Sumitomo Chemical Company, LimitedInventors: Masaru Kitamura, Hiroshi Ichihashi, Gohfu Suzukamo
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Patent number: 5047139Abstract: This invention pertains to a hydrocracking process for mid-distillate products and to hydrocracking catalysts having improved selectivity, activity and stability for use in the production of mid-distillate products from heavy gas oil feedstocks boiling above 700.degree. F.Type: GrantFiled: December 20, 1989Date of Patent: September 10, 1991Assignee: UOPInventors: Frank P. Gortsema, Regis J. Pellet, Albert R. Springer, Jule A. Rabo
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Patent number: 5043307Abstract: The present invention provides a process for modifying a crystalline aluminosilicate zeolite having a Constraint Index of from about to about 12 which comprises:a) steaming the as synthesized crystalline aluminosilicate zeolite containing organic template material to decompose at least a portion of said template material and to extract zeolitic aluminum; and,b) contacting the zeolite resulting from step (a) in the ammonium, alkali metal or hydrogen form with a dealuminizing agent which forms a water-soluble complex with aluminum to remove a further quantity of zeolitic aluminum therefrom.Type: GrantFiled: September 5, 1989Date of Patent: August 27, 1991Assignee: Mobil Oil Corp.Inventors: Emmerson Bowes, Clarence D. Chang, Scott Han, David S. Shihabi
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Patent number: 5039641Abstract: The invention relates to a process for modifying a molecular sieve, whereby the molecular sieve is brought into contact with a modifying agent containing at least one weak acid, a salt of a weak acid or a derivative of a weak acid of at least one element of Groups III, IV or V of the Periodic Table of Elements, by dry mixing the molecular sieve and the modifying agent, optionally followed by adding liquid to form a slurry or paste, whereafter the resulting mixture is subjected to a thermal treatment.Type: GrantFiled: February 8, 1989Date of Patent: August 13, 1991Assignee: Europese Economische Gemeenschap (E E G)Inventors: Etienne Vansant, Serge Moreau, Jan Verbiest, Paul de Bievre, Jos Philippaerts
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Patent number: 5023066Abstract: Process for introduction of silicon atoms instead of aluminum atoms in the crystal lattice of a zeolite of the faujasite type with a halosilane at temperatures lower than 150.degree. C., then washing. The resulting zeolites are particularly suitable for the conversion of hydrocarbons, above all for cracking. They are distinguished by their ultrastability and good activity.Type: GrantFiled: June 1, 1988Date of Patent: June 11, 1991Assignee: Akzo N.V.Inventors: Moritz Gimpel, Jan W. Roelofsen
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Patent number: 5013535Abstract: Aluminophosphate-based molecular sieve compositions having the crystal structure of AlPO.sub.4 -54 are stabilized against framework collapse or conversion to other crystal structures by treatment in their hydrated state with boric acid or salts thereof. The stabiized products are characterized, in addition to their essential AlPO.sub.4 -54 structure, by the presence of at least 6 ppm of extraneous boron.Type: GrantFiled: April 20, 1989Date of Patent: May 7, 1991Assignee: UOPInventors: Robert L. Bedard, Robert L. Patton, Stephen T. Wilson