Activating Treatment Patents (Class 502/85)
  • Patent number: 5518708
    Abstract: 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: Grant
    Filed: November 8, 1994
    Date of Patent: May 21, 1996
    Assignee: UOP
    Inventors: Gary W. Skeels, Diane M. Chapman, Edith M. Flanigen
  • Patent number: 5516736
    Abstract: 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: Grant
    Filed: September 15, 1994
    Date of Patent: May 14, 1996
    Assignee: Mobil Oil Corp.
    Inventors: Clarence D. Chang, Paul G. Rodewald
  • Patent number: 5508019
    Abstract: 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: Grant
    Filed: June 30, 1994
    Date of Patent: April 16, 1996
    Assignee: ARCO Chemical Technology, L.P.
    Inventors: Robert J. Saxton, Guy L. Crocco, John G. Zajacek
  • Patent number: 5498285
    Abstract: 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: Grant
    Filed: December 9, 1993
    Date of Patent: March 12, 1996
    Assignee: Pelt & Hooykaas B.V.
    Inventor: Carel W. J. Hooykaas
  • Patent number: 5480851
    Abstract: 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: Grant
    Filed: July 6, 1993
    Date of Patent: January 2, 1996
    Assignees: Tanaka Kikinzoku Kogyo K.K., Stonehart Associates Inc.
    Inventors: Kazunori Tsurumi, Paul Stonehart
  • Patent number: 5476823
    Abstract: 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: Grant
    Filed: May 28, 1993
    Date of Patent: December 19, 1995
    Assignee: Mobil Oil Corp.
    Inventors: Jeffrey S. Beck, David H. Olson, Sharon B. McCullen
  • Patent number: 5451391
    Abstract: 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: Grant
    Filed: December 6, 1993
    Date of Patent: September 19, 1995
    Assignee: Societe Nationale Elf Aquitaine
    Inventors: Francesco Di Renzo, Francois Fajula, Nisso Barbouth, Fredj Fitoussi, Philippe Schulz, Thierry des Courrieres
  • Patent number: 5434114
    Abstract: 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: Grant
    Filed: February 16, 1994
    Date of Patent: July 18, 1995
    Assignee: Degussa Aktiengesellschaft
    Inventors: Jens Weitkamp, Stefan Ernst, Thomas Bock, Thomas Kromminga, Akos Kiss, Peter Kleinschmit
  • Patent number: 5425934
    Abstract: 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: Grant
    Filed: December 27, 1993
    Date of Patent: June 20, 1995
    Assignee: Gas Research Institute
    Inventors: Prakash B. Malla, Sridhar Komarneni
  • Patent number: 5403800
    Abstract: 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: Grant
    Filed: May 28, 1993
    Date of Patent: April 4, 1995
    Assignee: Mobil Oil Corp.
    Inventors: Jeffrey S. Beck, Sharon B. McCullen, David H. Olson
  • Patent number: 5401488
    Abstract: 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: Grant
    Filed: June 26, 1992
    Date of Patent: March 28, 1995
    Assignee: UOP
    Inventors: Gary W. Skeels, Diane M. Chapman, Edith M. Flanigen
  • Patent number: 5399537
    Abstract: 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: Grant
    Filed: August 20, 1993
    Date of Patent: March 21, 1995
    Assignee: Amoco Corporation
    Inventors: Alakananda Bhattacharyya, Wen-Dong Chang, Mark S. Kleefisch, Carl A. Udovich
  • Patent number: 5393718
    Abstract: 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: Grant
    Filed: July 26, 1993
    Date of Patent: February 28, 1995
    Assignee: UOP
    Inventors: Gary W. Skeels, Edith M. Flanigen
  • Patent number: 5389357
    Abstract: 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: Grant
    Filed: June 1, 1994
    Date of Patent: February 14, 1995
    Assignee: Catalysts & Chemicals Industries Co., Ltd.
    Inventors: Goro Sato, Yusaku Arima, Takanori Ida
  • Patent number: 5367099
    Abstract: 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: Grant
    Filed: May 28, 1993
    Date of Patent: November 22, 1994
    Assignee: Mobil Oil Corp.
    Inventors: Jeffrey S. Beck, David H. Olson, Sharon B. McCullen
  • Patent number: 5365004
    Abstract: 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: Grant
    Filed: May 28, 1993
    Date of Patent: November 15, 1994
    Assignee: Mobil Oil Corp.
    Inventors: Jeffrey S. Beck, Sharon B. McCullen, David H. Olson
  • Patent number: 5349114
    Abstract: 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: Grant
    Filed: April 5, 1993
    Date of Patent: September 20, 1994
    Assignee: Mobil Oil Corp.
    Inventors: Rudolph M. Lago, David O. Marler, Sharon B. McCullen
  • Patent number: 5271920
    Abstract: 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: Grant
    Filed: January 7, 1992
    Date of Patent: December 21, 1993
    Assignee: Mobil Oil Corporation
    Inventors: Clarence D. Chang, Nai Y. Chen, Cynthis T. Chu, Bruce P. Pelrine
  • Patent number: 5262141
    Abstract: 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: Grant
    Filed: December 21, 1992
    Date of Patent: November 16, 1993
    Assignee: UOP
    Inventor: Gary W. Skeels
  • Patent number: 5242677
    Abstract: 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: Grant
    Filed: June 11, 1992
    Date of Patent: September 7, 1993
    Assignee: PQ Corporation
    Inventors: David A. Cooper, Raymond P. Denkewicz, Elliot P. Hertzenberg
  • Patent number: 5242676
    Abstract: 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: Grant
    Filed: May 11, 1992
    Date of Patent: September 7, 1993
    Assignee: Mobil Oil Corp.
    Inventors: Minas R. Apelian, Anthony S. Fung
  • Patent number: 5238677
    Abstract: 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: Grant
    Filed: June 15, 1992
    Date of Patent: August 24, 1993
    Assignee: Mobil Oil Corp.
    Inventors: Minas R. Apelian, Thomas F. Degnan
  • Patent number: 5238676
    Abstract: 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: Grant
    Filed: July 24, 1991
    Date of Patent: August 24, 1993
    Assignee: Mobil Oil Corporation
    Inventors: Wieslaw J. Roth, James C. Vartuli, Charles T. Kresge, Michael E. Leonowicz
  • Patent number: 5236680
    Abstract: 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: Grant
    Filed: June 18, 1991
    Date of Patent: August 17, 1993
    Assignee: Mizusawa Industrial Chemicals, Ltd.
    Inventors: Tadahisa Nakazawa, Masahide Ogawa, Kiyoshi Abe, Kazuhiko Suzuki, Takashi Tokita, Toshio Ito
  • Patent number: 5236880
    Abstract: 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: Grant
    Filed: March 9, 1992
    Date of Patent: August 17, 1993
    Assignee: W. R. Grace & Co.-Conn.
    Inventor: David M. Chapman
  • Patent number: 5234872
    Abstract: 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: Grant
    Filed: May 11, 1992
    Date of Patent: August 10, 1993
    Assignee: Mobil Oil Corp.
    Inventors: Minas R. Apelian, Thomas F. Degnan, Anthony S. Fung
  • Patent number: 5227352
    Abstract: 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: Grant
    Filed: June 28, 1991
    Date of Patent: July 13, 1993
    Assignees: Petroleum Energy Center, Cosmo Oil Co., Ltd.
    Inventors: Mitsugu Tsujii, Nobuki Sekine, Yukihiro Mimura, Yoshihiro Mizutani, Mitsuru Ohi, Seiichi Harima, Masaki Tanno
  • Patent number: 5220086
    Abstract: 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: Grant
    Filed: December 9, 1991
    Date of Patent: June 15, 1993
    Assignee: Mobil Oil Corporation
    Inventor: Paul G. Rodewald
  • Patent number: 5206004
    Abstract: 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: Grant
    Filed: July 1, 1991
    Date of Patent: April 27, 1993
    Assignee: Ethyl Corporation
    Inventor: Won S. Park
  • Patent number: 5204076
    Abstract: 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: Grant
    Filed: July 16, 1991
    Date of Patent: April 20, 1993
    Assignee: Mobil Oil Corporation
    Inventors: Maria D. Farnos, Michael E. Landis
  • Patent number: 5200168
    Abstract: 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: Grant
    Filed: January 31, 1992
    Date of Patent: April 6, 1993
    Assignee: Mobil Oil Corp.
    Inventors: Minas R. Apelian, Thomas F. Degnan, Anthony S. Fung, Gordon J. Kennedy
  • Patent number: 5190904
    Abstract: 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: Grant
    Filed: November 12, 1991
    Date of Patent: March 2, 1993
    Assignee: Chemical Research & Licensing Company
    Inventors: Clifford S. Crossland, Alan Johnson, John Woods, Elliot G. Pitt
  • Patent number: 5179052
    Abstract: 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: Grant
    Filed: November 29, 1991
    Date of Patent: January 12, 1993
    Assignee: Texaco Chemical Company
    Inventor: John F. Knifton
  • Patent number: 5169812
    Abstract: 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: Grant
    Filed: September 16, 1991
    Date of Patent: December 8, 1992
    Assignee: UOP
    Inventors: Joseph A. Kocal, Tamotsu Imai, Paul J. Kuchar, Christopher D. Gosling
  • Patent number: 5158668
    Abstract: 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: Grant
    Filed: January 6, 1992
    Date of Patent: October 27, 1992
    Assignee: Conoco Inc.
    Inventors: Bharat S. Chahar, John K. Shipley
  • Patent number: 5158670
    Abstract: 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: Grant
    Filed: April 10, 1991
    Date of Patent: October 27, 1992
    Assignee: Exxon Research and Engineering Company
    Inventors: Ian A. Cody, Gordon F. Stuntz, William G. McKnight
  • Patent number: 5143879
    Abstract: 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: Grant
    Filed: July 18, 1991
    Date of Patent: September 1, 1992
    Assignee: Mobil Oil Corporation
    Inventor: D. Duayne Whitehurst
  • Patent number: 5133952
    Abstract: 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: Grant
    Filed: October 22, 1990
    Date of Patent: July 28, 1992
    Assignee: Vereinigte Aluminium-Werke Aktiengesellschaft
    Inventors: Arno Tissler, Klaus K. Unger, Hubertus Schmidt
  • Patent number: 5126296
    Abstract: 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: Grant
    Filed: November 16, 1990
    Date of Patent: June 30, 1992
    Assignee: Mobil Oil Corporation
    Inventors: Scott Han, Clarence D. Chang
  • Patent number: 5118482
    Abstract: 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: Grant
    Filed: June 30, 1989
    Date of Patent: June 2, 1992
    Assignee: Shell Oil Company
    Inventors: Mysore Narayana, Brendan D. Murray
  • Patent number: 5116794
    Abstract: 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: Grant
    Filed: June 21, 1990
    Date of Patent: May 26, 1992
    Assignee: UOP
    Inventors: Gary W. Skeels, Edith M. Flanigen
  • Patent number: 5110776
    Abstract: 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: Grant
    Filed: March 12, 1991
    Date of Patent: May 5, 1992
    Assignee: Mobil Oil Corp.
    Inventors: Girish K. Chitnis, Joseph A. Herbst
  • Patent number: 5100644
    Abstract: 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: Grant
    Filed: December 14, 1990
    Date of Patent: March 31, 1992
    Assignee: UOP
    Inventors: Gary W. Skeels, Diane M. Chapman-Snyder, Edith M. Flanigen
  • Patent number: 5077026
    Abstract: 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: Grant
    Filed: July 13, 1990
    Date of Patent: December 31, 1991
    Assignee: Georgia Tech Research Corporation
    Inventors: Vinayan Nair, Rosemarie Szostak
  • Patent number: 5066630
    Abstract: 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: Grant
    Filed: June 13, 1990
    Date of Patent: November 19, 1991
    Assignee: Sumitomo Chemical Company, Limited
    Inventors: Masaru Kitamura, Hiroshi Ichihashi, Gohfu Suzukamo
  • Patent number: 5047139
    Abstract: 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: Grant
    Filed: December 20, 1989
    Date of Patent: September 10, 1991
    Assignee: UOP
    Inventors: Frank P. Gortsema, Regis J. Pellet, Albert R. Springer, Jule A. Rabo
  • Patent number: 5043307
    Abstract: 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: Grant
    Filed: September 5, 1989
    Date of Patent: August 27, 1991
    Assignee: Mobil Oil Corp.
    Inventors: Emmerson Bowes, Clarence D. Chang, Scott Han, David S. Shihabi
  • Patent number: 5039641
    Abstract: 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: Grant
    Filed: February 8, 1989
    Date of Patent: August 13, 1991
    Assignee: Europese Economische Gemeenschap (E E G)
    Inventors: Etienne Vansant, Serge Moreau, Jan Verbiest, Paul de Bievre, Jos Philippaerts
  • Patent number: 5023066
    Abstract: 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: Grant
    Filed: June 1, 1988
    Date of Patent: June 11, 1991
    Assignee: Akzo N.V.
    Inventors: Moritz Gimpel, Jan W. Roelofsen
  • Patent number: 5013535
    Abstract: 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: Grant
    Filed: April 20, 1989
    Date of Patent: May 7, 1991
    Assignee: UOP
    Inventors: Robert L. Bedard, Robert L. Patton, Stephen T. Wilson