EP0592392A1 - Zeolithe beta de boron pauvre en aluminium - Google Patents

Zeolithe beta de boron pauvre en aluminium

Info

Publication number
EP0592392A1
EP0592392A1 EP90911359A EP90911359A EP0592392A1 EP 0592392 A1 EP0592392 A1 EP 0592392A1 EP 90911359 A EP90911359 A EP 90911359A EP 90911359 A EP90911359 A EP 90911359A EP 0592392 A1 EP0592392 A1 EP 0592392A1
Authority
EP
European Patent Office
Prior art keywords
zeolite
accordance
oxide
catalyst
beta
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP90911359A
Other languages
German (de)
English (en)
Other versions
EP0592392A4 (fr
Inventor
Stacey I. Zones
Dennis L. Holtermann
Lawrence W. Jossens
Donald S. Santilli
Andrew Rainis
James N. Ziemer
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Chevron USA Inc
Original Assignee
Chevron USA Inc
Chevron Research and Technology Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Chevron USA Inc, Chevron Research and Technology Co filed Critical Chevron USA Inc
Publication of EP0592392A4 publication Critical patent/EP0592392A4/fr
Publication of EP0592392A1 publication Critical patent/EP0592392A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
    • C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
    • C10G47/10—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used with catalysts deposited on a carrier
    • C10G47/12—Inorganic carriers
    • C10G47/16—Crystalline alumino-silicate carriers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/86—Borosilicates; Aluminoborosilicates
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B35/00—Boron; Compounds thereof
    • C01B35/08—Compounds containing boron and nitrogen, phosphorus, oxygen, sulfur, selenium or tellurium
    • C01B35/10—Compounds containing boron and oxygen
    • C01B35/1009—Compounds containing boron and oxygen having molecular-sieve properties
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
    • C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
    • C01B39/06—Preparation of isomorphous zeolites characterised by measures to replace the aluminium or silicon atoms in the lattice framework by atoms of other elements, i.e. by direct or secondary synthesis
    • C01B39/12—Preparation of isomorphous zeolites characterised by measures to replace the aluminium or silicon atoms in the lattice framework by atoms of other elements, i.e. by direct or secondary synthesis the replacing atoms being at least boron atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
    • C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
    • C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
    • C07C2/08—Catalytic processes
    • C07C2/12—Catalytic processes with crystalline alumino-silicates or with catalysts comprising molecular sieves
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/54—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition of unsaturated hydrocarbons to saturated hydrocarbons or to hydrocarbons containing a six-membered aromatic ring with no unsaturation outside the aromatic ring
    • C07C2/64—Addition to a carbon atom of a six-membered aromatic ring
    • C07C2/66—Catalytic processes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C6/00—Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions
    • C07C6/08—Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions by conversion at a saturated carbon-to-carbon bond
    • C07C6/12—Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions by conversion at a saturated carbon-to-carbon bond of exclusively hydrocarbons containing a six-membered aromatic ring
    • C07C6/126—Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions by conversion at a saturated carbon-to-carbon bond of exclusively hydrocarbons containing a six-membered aromatic ring of more than one hydrocarbon
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G35/00—Reforming naphtha
    • C10G35/04—Catalytic reforming
    • C10G35/06—Catalytic reforming characterised by the catalyst used
    • C10G35/065—Catalytic reforming characterised by the catalyst used containing crystalline zeolitic molecular sieves, other than aluminosilicates
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/58—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins
    • C10G45/60—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used
    • C10G45/64—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used containing crystalline alumino-silicates, e.g. molecular sieves
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00—Catalysts comprising molecular sieves
    • C07C2529/86—Borosilicates; Aluminoborosilicates

Definitions

  • Natural and synthetic zeolitic crystalline aluminosilicates are useful as catalysts and adsorbents.
  • aluminosilicates have distinct crystal structures which are demonstrated by X-ray diffraction.
  • the crystal structure defines cavities and pores which are characteristic of the different species.
  • the adsorptive and catalytic properties of each crystalline aluminosilicate are determined in part by the dimensions of its pores and cavities.
  • the utility of a particular zeolite in a particular application depends at least partly on its crystal structure. Because of their unique molecular sieving characteristics, as well as their catalytic properties, crystalline
  • aluminosilicates are especially useful in such applications as gas drying and separation and hydrocarbon conversion.
  • many different crystalline aluminosilicates and silicates have been disclosed, there is a continuing need for new zeolites and silicates with desirable properties for gas separation and drying, hydrocarbon and chemical
  • Crystalline aluminosilicates are usually prepared from aqueous reaction mixtures containing alkali or alkaline earth metal oxides, silica, and alumina. "Nitrogenous zeolites" have been prepared from reaction mixtures
  • Beta zeolite is a known synthetic crystalline
  • Synthetic zeolitic crystalline borosilicates are useful as catalysts. Methods for preparing high silica content zeolites that contain framework boron are known and
  • the amount of boron contained in the zeolite usually may be made to vary by incorporating different amounts of borate ion in the zeolite forming solutioa.
  • U.S. Patent No. 4,788,169 describes a method for preparing beta zeolite containing boron. This boron beta zeolite contains 7000 parts per million of aluminum according to the analyses given therein.
  • European Patent Application No. 188,913 claims compositions for various intermediate pore boron-containing zeolites with an aluminum content of less than 0.05% by weight.
  • composition (B)Beta
  • (B)Beta has a mole ratio of an oxide selected from silicon oxide, germanium oxide, and mixtures thereof to an oxide selected from boron oxide or mixtures of boron oxide with aluminum, gallium, or iron oxide, greater than about 10:1 and wherein the amount of aluminum is less than 0.10% by weight and having the X-ray diffraction lines of Table 1(a) below.
  • An aluminum-free boron beta zeolite can also be made using the novel method disclosed herein. The amount of aluminum contained in the zeolite depends simply upon the aluminum impurity present in the silica source.
  • This zeolite further has a composition, as synthesized and in the anhydrous state, in terms of mole ratios of oxides as follows: (1.0 to 5.0)Q 2 O:(0.1 to 2.0)M 2 O:W 2 O 3 : (greater than 10)YO 2 wherein M is an alkali metal cation, W is selected from boron, Y is selected from silicon, germanium and mixtures thereof, and Q is a diquatemary ammonium ion, or mixtures of diquarternary ammonium cation, and
  • Beta zeolites preferably have a silicarboria ratio typically in the range of 10:1 to about 100:1. Higher mole ratios can be obtained by treating the zeolite with
  • chelating agents or acids to extract boron from the zeolite lattice The silicarboria mole ratio can also be increased by using silicon and carbon halides and other similar compounds.
  • the boron in the crystalline network may also be replaced by aluminum, gallium or iron. Procedures for incorporating aluminum are described in U.S. Patent Nos. 4,559,315 and 4,550,092 which are hereby incorporated by reference. A method for preparing boron beta zeolite is described in U.S. Patent No. 4,788,169. A tetraethyl ammonium template is used to make this zeolite which contains 7000 parts per million of aluminum. The method described in U.S. Patent No. 4,788,169, however, cannot be used to make boron beta zeolite containing less than 1000 parts per million
  • a method for making (B)beta zeolites comprising preparing an aqueous mixture containing sources of a
  • diquatemary ammonium ion an oxide selected from boron oxide, and an oxide selected from silicon oxide, germanium oxide, and mixtures thereof, and having a composition, in terms of mole ratios of oxides, falling within the following ranges: YO 2 /W 2 O 3 , 10:1 to 100:1; wherein Y is selected from silicon, germanium, and mixtures thereof, W is selected from boron, and Q is a diquatemary ammonium ion; maintaining the mixture at a temperature of at least 100°C until the
  • the present invention is based on our finding that low-aluminum boron beta zeolite can be
  • Typical (B)Beta borosilicate and boroaluminosilicate zeolites have the X-ray diffraction pattern of Tables 2 and 4 below. The d-spacings are shown in Table 8 and
  • the X-ray powder diffraction patterns were determined by standard techniques.
  • the radiation was the K-alpha/doublet of copper and a scintillation counter spectrometer with a strip-chart pen recorder was used.
  • the peak heights I and the positions, as a function of 2 ⁇ where ⁇ is the Bragg angle, were read from the spectrometer chart. From these measured values, the relative intensities, 100I/I o' where I o is the intensity (peak height) of the strongest peak, and d/n, related to interplanar spacings in Angstroms
  • the X-ray diffraction pattern of Table 1(a) is characteristic of (B)Beta zeolites.
  • the zeolite produced by exchanging the metal or other cations present in the zeolite with various other cations yields substantially the same diffraction pattern although there can be minor shifts in interplanar spacing and minor variations in relative intensity. Minor variations in the diffraction pattern can also result from variations in the organic compound used in the preparation and from variations in the silica-to-boria mole ratio from sample to sample. Calcination can also cause minor shifts in the X-ray diffraction pattern. Notwithstanding these minor perturbations, the basic crystal lattice structure remains unchanged.
  • (B)Beta zeolites can be suitably prepared from an aqueous solution containing sources of an alkali metal borate, a bis(l-Azonia, bicyclo[2.2.2] octane- ⁇ , ⁇ alkane diquatemary ammonium ion, and an oxide of silicon or germanium, or mixture of the two.
  • the reaction mixture should have a composition in terms of mole ratios falling within the following ranges: Broad Preferred YO 2 /W 2 O 3 10-200 30-100
  • Q is a diquatemary ammonium ion, or mixture with tetramethylammonium cation
  • Y is silicon, germanium or both
  • W is boron
  • M is an alkali metal, preferably sodium.
  • crystallization mixture is derived from the quaternary ammonium compound.
  • the diquatemary ammonium ion is derived from a compound of the formula:
  • the quaternary ammonium compounds are prepared by methods known in the art, an example of which can be found in U.S. No. 4,508,837.
  • the reaction mixture is prepared using standard zeolitic preparation techniques.
  • Sources of boron for the reaction mixture include borosilicate glasses and most particularly, other reactive borates and borate esters.
  • Typical sources of silicon oxide include silicates, silica hydrogel, silicic acid, colloidal silica, tetra-alkyl orthosilicates, and silica hydroxides.
  • the reaction mixture is maintained at an elevated
  • the temperatures during the hydrothermal crystallization step are typically maintained from about 140°C to about 200°C, preferably from about 150°C to about 170°C and most preferably from about 135°C to about 165°C.
  • crystallization period is typically greater than one day and preferably from about three days to about seven days.
  • the hydrothermal crystallization is conducted under pressure and usually in an autoclave so that the reaction mixture is subject to autogenous pressure.
  • the reaction mixture can be stirred during crystallization.
  • the solid product is separated from the reaction mixture by standard mechanical separation techniques such as filtration.
  • the crystals are water-washed and then dried, e.g., at 90°C to 150°C from 8 to 24 hours, to obtain the as synthesized, (B)Beta zeolite crystals.
  • the drying step can be performed at atmospheric or subatmospheric pressures.
  • the (B)Beta crystals can be allowed to nucleate spontaneously from the reaction mixture.
  • the reaction mixture can also be seeded with (B)Beta crystals both to direct, and accelerate the crystallization, as well as to minimize the formation of undesired aluminosilicate contaminants.
  • the synthetic (B)Beta zeolites can be used as synthesized or can be thermally treated (calcined). Usually, it is
  • the zeolite can be leached with chelating agents, e.g., EDTA or dilute acid solutions, to increase the
  • the zeolite can be used in
  • hydrogenating components such as tungsten, vanadium, molybdenum, rhenium, nickel, cobalt, chromium, manganese, or a noble metal, such as palladium or platinum, for tlbose applications in which a
  • Typical replacing cations can include metal cations, e.g., rare earth, Group IIA and Group VIII metals, as well as their mixtures.
  • metal cations e.g., rare earth, Group IIA and Group VIII metals, as well as their mixtures.
  • replacing metallic cations cations of metals such as rare earth, Mn, Ca, Mg, Zn, Cd, Pt, Pd, Ni, Co, Ti, Al, Sn, Fe, and Co are particularly preferred.
  • the hydrogen, ammonium, and metal components can be
  • the zeolite can also be
  • the metals can be any metals, or, the metals can be any metals, or, the metals.
  • the metals can be occluded in the crystal lattice by having the desired metals present as ions in the reaction mixture from which the
  • (B)Beta zeolite is prepared.
  • Typical ion exchange techniques involve contacting the synthetic zeolite with a solution containing a salt of the desired replacing cation or cations.
  • a wide variety of salts can be employed, chlorides and other halides, nitrates, and sulfates are particularly preferred.
  • Representative ion exchange techniques are disclosed in a wide variety of patents including U. S . Nos . 3 , 140 , 249 ;
  • the zeolite is typically washed with water and dried at temperatures ranging from 650°C to about
  • the zeolite can be calcined in air or inert gas at temperatures ranging from about 200°C to 820°C for periods of time ranging from 1 to 48 hours, or more, to produce a catalytically active product especially useful in hydrocarbon conversion processes.
  • the spatial arrangement of the atoms which form the basic crystal lattice of the zeolite remains essentially unchanged.
  • the exchange of cations has little, if any, effect on the zeolite lattice structures.
  • the Beta borosilicate and subsequent metalloborosilicate can he formed into a wide variety of physical shapes.
  • the zeolite can be in the form of a powder, a granule, or a molded product, such as extrudate having particle size sufficient to pass through a 2-mesh (Tyler) screen and be retained on a 400-mesh (Tyler) screen.
  • the borosilicate can be extruded before drying, or, dried or partially dried and then
  • the zeolite can be composited with other materials
  • Such matrix materials include active and inactive materials and
  • synthetic or naturally occurring zeolites as well as inorganic materials such as clays, silica and metal oxides.
  • the latter may occur naturally or may be in the form of gelatinous precipitates, sols, or gels, including mixtures of silica and metal oxides.
  • Use of an active material in conjunction with the synthetic zeolite, i.e., combined with it, tends to improve the conversion and selectivity of the catalyst In certain organic conversion processes.
  • Inactive materials can suitably serve as diluents to control the amount of coaversion in a given process so that products can be obtained economically without using other means for controlling the rate of reaction.
  • zeolite materials have been incorporated into naturally occurring clays, e.g., bentonite and kaolin.
  • Naturally occurring clays which can be composited with the synthetic zeolites of this invention include the
  • montmorillonite and kaolin families which families include the sub-bentonites and the kaolins commonly known as Dixie, McNamee, Georgia, and Florida clays or others in which the main mineral constituent is halloysite, kaolinite, dickite, nacrite, or anauxite.
  • Fibrous clays such as sepiolite and attapulgite can also be used as supports. Such clays can be used in the xaw state as originally mined or can be
  • the (B)Beta zeolites can be composited with porous matrix materials and mixtures of matrix materials such as silica, alumina, titania, magnesia, silica:alumina, silica-magnesia, silica-zirconia, silica-thoria, silica-beryllia, silica-titania,
  • titania-zirconia as well as ternary compositions such as silica-alumina-thoria, silica-alumina-zirconia,
  • the matrix can be in the form of a cogel.
  • the (B)Beta zeolites can also be composited with other zeolites such as synthetic and natural faujasites (e.g., X and Y), erionites, and mordenites. They can also be
  • (B)Beta zeolites are useful in hydrocarbon conversion reactions. Hydrocarbon conversion reactions are chemical and catalytic processes in which carbon-containing compounds are changed to different carbon-containing compounds.
  • hydrocarbon conversion reactions examples include
  • the catalysts are useful in other petroleum refining and hydrocarbon conversion reactions such as isomerizing n-paraffins and naphthenes, polymerizing and oligomerizing olefinic or acetylenic compounds such as isobutylene and butene-1, reforming, alkylating, isomerizing polyalkyl substituted aromatics (e.g., ortho xylene), and disproportionating aromatics (e.g., toluene) to provide mixtures of benzene, xylenes, and higher methylbenzenes.
  • isomerizing n-paraffins and naphthenes polymerizing and oligomerizing olefinic or acetylenic compounds such as isobutylene and butene-1
  • reforming alkylating
  • isomerizing polyalkyl substituted aromatics e.g., ortho xylene
  • disproportionating aromatics e.g., toluene
  • the (B)Beta catalysts have high selectivity, and under hydrocarbon conversion conditions can provide a high percentage of desired products relative to total products.
  • (B)Beta zeolites can be used in processing hydrocarbonaceous feedstocks.
  • Hydrocarbonaceous feedstocks contain carbon compounds and can be from many different sources, such as virgin petroleum fractions, recycle petroleum fractions, shale oil, liquefied coal, tar sand oil, and in general, can be any carbon containing fluid susceptible to zeolitic catalytic reactions.
  • the hydrocarbonaceous feed is to undergo the feed can contain metal or be free of metals, it can also have high or low nitrogen or sulfur impurities. It can be appreciated, however, that in general processing will be more efficient (and the catalyst more active) the lower the metal,
  • hydrocracked at hydrocracking conditions including a
  • the hydrocracking catalysts contain an effective amount of at least one hydrogenation catalyst (component) of the type commonly employed in hydrocracking catalysts.
  • hydrogenation component is generally selected from the group of hydrogenation catalysts consisting of one or more metals of Group VIB and Group VIII, including the salts, complexes, and solutions containing such.
  • the hydrogenation catalyst is preferably selected from the group of metals, salts, and complexes thereof of the group consisting of at least one of platinum, palladium, rhodium, iridium, and mixtures thereof or the group consisting of at least one of nickel,
  • the hydrogenation catalyst is present in an effective amount to provide the hydrogenation function of the hydrocracking catalyst and preferably in the range of from 0.05% to 25% by weight.
  • the catalyst may be employed in conjunction with traditional hydrocracking catalysts, e.g., any aluminosilicate
  • zeolitic aluminosilicates include Zeolite Y (including steam stabilized, e.g., ultra-stable Y), Zeolite X, Zeolite beta (U.S. Patent No. 3,308,069), Zeolite ZK-20 (U.S. Patent No. 3,445,727), Zeolite ZSM-3 (U.S. Patent No. 3,415,736), faujasite, LZ-10 (U.K.
  • ZSM-5-type zeolites e.g., ZSM-5, ZSM-11, ZSM-12, ZSM-23, ZSM-35, ZSM-38, ZSM-48, crystalline silicates such as silicalite (U.S. Patent No. 4,061,724), erionite, mordenite, offretite, chabazite, FU-1-type zeolite, NU-type zeolites, LZ-210-type zeolite, and mixtures thereof.
  • Traditional hydrocracking catalysts containing amounts of Na 2 O less than about one percent by weight are generally preferred.
  • the relative amounts of the (B)Beta component and traditional hydrocracking component, if any, will depend at least in part, on the selected hydrocarbon feedstock and on the desired product distribution to be obtained therefrom, but in all instances an effective amount of (B)Beta is employed.
  • the hydrocracking catalysts are typically employed with an inorganic oxide-matrix component which may be any of the inorganic oxide matrix components which have been employed heretofore in the formulation of hydrocracking catalysts including: amorphous catalytic inorganic oxides, e.g., catalytically active silica-aluminas, clays, silicas, aluminas, silica-aluminas, silica-zirconias,
  • the traditional hydrocracking catalyst component (TC) and (B)Beta may be mixed separately with the matrix component and then mixed or the TC component and (B)Beta may be mixed and then formed with the matrix component.
  • (B)Beta can be used to dewax hydrocarbonaceous feeds by selectively removing or transforming straight chain
  • the catalytic dewaxing conditions are dependent in large measure on the feed used and upon the desired pour point.
  • the temperature will be between about 200°C and about 475°C, preferably between about 250°C and about 450°C.
  • the pressure is typically between about 15 psig and about 3000 psig, preferably between about 200 psig and 3000 psig.
  • the LHSV preferably will be from 0.1 to 20, preferably between about 0.2 and about 10.
  • Hydrogen is preferably present in the reaction zone during the catalytic dewaxing process.
  • the hydrogen to feed ratio is typically between about 500 and about 30,000 SCF/bbl (standard cubic feet per barrel), preferably about 1,000 to about 20,000 SCF/bbl.
  • the (B)Beta hydrodewaxing catalyst may optionally contain a hydrogenation component of the type commonly employed in dewaxing catalysts.
  • the hydrogenation component may be selected from the group of hydrogenation catalysts
  • catalyst is at least one of the group of metals, salts, and complexes selected from the group consisting of at least one of platinum, palladium, rhodium, iridium, and mixtures thereof or at least one from the group consisting of nickel, molybdenum, cobalt, tungsten, titanium, chromium, and mixtures thereof.
  • Reference to the catalytically active metal or metals is intended to encompass such metal or metals in the elemental state or in some form such as an oxide, sulfide, halide, carboxylate, and the like.
  • the hydrogenation component is present in an effective amount to provide an effective hydrodewaxing catalyst preferably in the range of from about 0.05 to 5% by weight.
  • (B)Beta can be used to convert straight run naphthas and similar mixtures to highly aromatic mixtures.
  • normal and slightly branched chained hydrocarbons preferably having a boiling range above about 40°C and less than about 200°C, can be converted to products having a substantial aromatics content by contacting the hydrocarbon feed with the zeolite at a temperature in the range of from about 400°C to 600°C, preferably 480°C-550°C at pressures ranging from atmospheric to 10 bar, and LHSV ranging from 0.1 to 15.
  • the hydrogen to hydrocarbon ratio will range between 1 and 10.
  • (B)Beta can be used in a fixed, fluid or moving bed reformer.
  • the conversion catalyst preferably contain a Group VIII metal compound to have sufficient activity for commercial use.
  • Group VIII metal compound as used herein is meant the metal itself or a compound thereof.
  • the Group VIII noble metals and their compounds, platinum, palladium, and iridium, or combinations thereof can be used.
  • the most preferred metal is platinum.
  • the amount of Group VIII metal present in the conversion catalyst should be within the normal range of use in reforming catalysts, from about 0.05 to 2.0 wt. %, preferably 0.2 to 0.8 wt. %.
  • the performance of the noble metal in (B)Beta may be further enhanced by the presence of other metals as promotors for aromatization selectivity.
  • the zeolite/Group VIII metal conversion catalyst can be used without a binder or matrix.
  • the preferred inorganic matrix, where one is used, is a silica-based binder such as
  • Cab-O-Sil or Ludox Other matrices such as magnesia and titania can be used.
  • the preferred inorganic matrix is nonacidic. It is critical ito the selective production of aromatics in useful quantities that the conversion catalyst be
  • the zeolite is usually prepared from mixtures containing alkali metal hydroxides and thus, have alkali metal contents of about 1-2 wt. %. These high levels of alkali metal, usually sodium or potassium, are unacceptable for most catalytic applications because they greatly deactivate the catalyst for crarcking reactions. Usually, the alkali metal is removed to low levels by ion exchange with hydrogen or ammonium ions.
  • alkali metal compound as used herein is meant elemental or ionic alkali metals or their basic compounds.
  • catalytic cracking process which consists of contacting a hydrocarbon feedstock with a catalyst in a reaction zone in the absence of added hydrogen at average catalyst
  • the (B)Beta can be employed in conjunction with traditional cracking catalysts either as an
  • the catalyst may be employed in conjunction with traditional cracking catalysts, comprising any aluminosilicate
  • zeolitic aluminosilicates employed as a component in cracking catalysts.
  • Representative of the zeolitic aluminosilicates disclosed heretofore as employable as component parts of cracking catalysts are Zeolite Y (including steam stabilized Y, rare earth Y, chemically modified Y, ultra-stable Y or combinations thereof).
  • Zeolite X Zeolite beta (U.S. Patent No. 3,308,069), Zeolite ZK-20 (U.S. Patent No. 3,445,727), Zeolite ZSM-3 (U.S. Patent No. 3,415,736), faujasite, LZ-10 (U.K.
  • ZSM-5-Type Zeolites e.g., ZSM-5, ZSM-11, ZSM-12, ZSM-23, ZSM-35, ZSM-38, ZSM-48, crystalline silicates such as silicalite (U.S. Patent No. 4,061,724), erionite, mordenite, offretite, chabazite,
  • FU-1-type zeolite NU-type zeolite, LZY-210 type zeolite or other dealuminated zeolite of 24.5A unit cell size or lower, or zeolite grown "in-situ" in matrix materials (U.S. Patent Nos. 3,647,718 and 4,493,902), and the mixtures thereof.
  • zeolite as used herein contemplates not only aluminosilicates but substances in which the aluminum is replaced by gallium or boron and substances in which silicon is replaced by germanium.
  • Other representative acidic aluminosilicates also deemmed employable as component parts are amorphous silica-alumina catalysts, synthetic
  • mica-montmorillonite catalysts as defined in U.S. Patent No. 3,252,889
  • cross-linked or pillared clays as defined in U.S. Patent Nos. 4,176,090; 4,248,739; 4,238,364 and 4 , 216 , 188
  • acid activated clays - - bentonite
  • the relative amounts of the (B)Beta component and traditional cracking component (TC), if any, will depend at least in part, on the selected hydrocarbon feedstock and on the desired product distribution to be obtained
  • the relative weight ratio of the TC to the (B)Beta is generally between about 1:10 and about 500:1, desirably between about 1:10 and about 200:1, preferably between about 1:2 and about 50:1, and most preferably is between about 1:1 and about 20:1.
  • the cracking catalysts are typically employed with an inorganic oxide matrix component which may be any of the inorganic oxide matrix components which have been employed heretofore in the formulation of FCC catalysts including: amorphous catalytic inorganic oxides, e.g., catalytically active silica-aluminas, clays, synthetic or acid activated clays, silicas, aluminas, silica-aluminas, silica-zirconias, silica-magnesias, alumina-borias, alumina-titanias, pillared or cross-linked clays, and the like and mixtures thereof.
  • amorphous catalytic inorganic oxides e.g., catalytically active silica-aluminas, clays, synthetic or acid activated clays, silicas, aluminas, silica-aluminas, silica-zirconias, silica-magnesias, alumina-borias,
  • the TC component and (B)Beta may be mixed separately with their respective matrix component and then mixed together or the TC component and (B)Beta may be mixed together and then formed with the matrix component.
  • the mixture of a traditional cracking catalyst and (B)Beta may be carried out in any manner which results in the coincident presence of such in contact with the crude oil feedstock under catalytic cracking conditions.
  • a catalyst may be employed containing the traditional cracking catalyst component and (B)Beta in single catalyst particles or (B)Beta with or without a matrix component may be added as a discrete component to a traditional cracking catalyst provided its particle has appropriate density and particle size distribution.
  • (B)Beta can also be used to oligomerize straight and
  • the oligomers which are the products of the process are medium to heavy olefins which are useful for both fuels, i.e., gasoline or a gasoline blending stock and chemicals.
  • the oligomerization process comprises contacting the olefin feedstock in the gaseous state phase with (B)Beta at a temperature of from about 450°F to about 1200°F, a WHSV of from about 0.2 to about 50 and a hydrocarbon partial
  • oligomerize the* feedstock when the feedstock is in the liquid phase when contacting the zeolite catalyst.
  • temperatures of from about 50°F to about 450°F, and preferably from 80-400°F may be used and a WHSV of from about 0.05 to 20 and preferably 0.1 to 10. It will be appreciated that the pressures employed must be
  • the pressure will be a function of the number of carbon atoms of the feed olefin and the
  • Suitable pressures include from about 0 psig to about 3000 psig.
  • the zeolite can have the original cations associated
  • Typical cations would include hydrogen, ammonium, and metal cations including mixtures of the same.
  • metallic cations particular preference is given to cations of metals such as rare earth metals, manganese, calcium, as well as metals of Group II of the Periodic Table, e.g., zinc, and Group VIII of the Periodic Table, e.g., nickel.
  • metals such as rare earth metals, manganese, calcium, as well as metals of Group II of the Periodic Table, e.g., zinc, and Group VIII of the Periodic Table, e.g., nickel.
  • One of the prime requisites is that the zeolite nave a fairly low aromatization activity, i.e., in which the amount of
  • aromatics produced is not more than about 20 wt. %. This is accomplished by using a zeolite with controlled acid
  • alpha value of from about 0.1 to about 120, preferably from about 0.1 to about 100, as measured by its ability to crack n-hexane.
  • Alpha values are defined by a standard test known in the art, e.g., as shown in U.S. Patent No. 3,960,978 which is incorporated totally herein by reference. If required, such zeolites may be obtained by steaming, by use in a conversion process or by any other method which may occur to one skilled in this art .
  • (B)Beta can be used to convert light gas C 2 -C 6 paraffins and/or olefins to higher molecular weight hydrocarbons including aromatic compounds. Operating temperatures of 100-700°C, operating pressures of 0-1000 psig and space velocities of 0.5-40 hr -1 WHSV can be used to convert the C 2- C 6 Paraffin and/or olefins to aromatic compounds.
  • the zeolite will contain a catalyst metal or metal oxide wherein said metal is selected from the group consisting of Group IB, IIB, VIII, and IIIA of the Periodic Table, and most preferably, gallium or zinc and in the range of from about 0.05-5 wt. %.
  • B)Beta can be used to condense lower aliphatic alcohols having 1-10 carbon atoms to a gasoline boiling point
  • hydrocarbon product comprising mixed aliphatic and aromatic hydrocarbon.
  • the condensation reaction proceeds at a temperature of about 500-1000°F, a pressure of about
  • the catalyst may be in the hydrogen form or may be base exchanged or impregnated to contain amonium or a metal cation complement, preferably in the range of from about 0.05-5 wt. %.
  • the metal cations that may be present include any of the metals of the Groups I-VIII of the Periodic
  • the catalyst can be made highly active and highly selective for isomerizing, C 4 to C 7 hydrocarbons.
  • the activity means that the catalyst can operate at relatively low temperatures which thermodynamically favors highly branched paraffins. Consequently, the catalyst can produce a high octane
  • the high selectivity means that a relatively high liquid yield can be achieved when the catalyst is run at a high octane.
  • the present process comprises contacting the isomerization catalyst with a hydrocarbon feed under isomerization
  • the feed is preferably a light straight run fraction, boiling within the range of 30-250°F and
  • the hydrocarbon feed for the process comprises a substantial amount of C 4 to C 7 normal and slightly branched low octane hydrocarbons, more preferably C 5 and C 6 hydrocarbons.
  • the pressure in the process is preferably between 50-1000 psig, more preferably between 100-500 psig.
  • the LHSV is preferably between about 1 to about 10 with a value in the range of about 1 to about 4 being more preferred. It is also preferable to carry out the isomerization reaction in the presence of hydrogen.
  • hydrogen is added to give a hydrogen to hydrocarbon ratio (H 2 /HC) of between 0.5 and 10 H 2 /HC, more preferably between 1 and 8 H 2 /HC.
  • the temperature is preferably between about 200°F and about 1000°F, more preferably between 400-600°F.
  • the initial selection of the temperature within this broad range is made primarily as a function of the desired conversion level considering the characteristics of the' feed and of the catalyst .
  • the temperature may have to be slowly increased during the run to compensate for any deactivation that occurs.
  • a low sulfur feed is especially preferred in the present process.
  • the feed preferably contains less than 10 ppm, more preferably less than 1 ppm, and most preferably less than 0.1 ppm sulfur. In the case of a feed which is not already low in sulfur, acceptable levels can be reached by hydrogenating the feed in a presaturation zone with a hydrogenating catalyst which is resistant to sulfur
  • An example of a suitable catalyst for this hydrodesulfurization process is an alumina-containing support and a minor catalytic proportion of molybdenum oxide, cobalt oxide and/or nickel oxide.
  • a platinum on alumina hydrogenating catalyst can also work. in which case, a sulfur sorber is preferably placed downstream of the hydrogenating catalyst, but upstream of the present
  • isomerization catalyst examples of sulfur sorbers are alkali or alkaline earth metals on porous refractory inorganic oxides, zinc, etc. Hydrodesulfurization is typically conducted at 315-455°C, at 200-2000 psig, and at a LHSV of 1-5. It is preferable to limit the nitrogen level and the water content of the feed. Catalysts and processes which are suitable for these purposes are known to those skilled in the art. After a period of operation, the catalyst can become
  • the isomerization catalyst preferably contains a Group VIII metal compound to have sufficient activity for commercial use.
  • Group VIII metal compound as used herein is meant the metal itself or a compound thereof.
  • the Group VIII noble metals and their compounds, platinum, palladium, and iridium, or combinations thereof can be used. Rhenium and tin may also be usd in conjunction with the noble metal.
  • the most preferred metal is the amount of Group VIII metal present in the conversion catalyst should be within the normal range of use in isomerizing catalysts, from about 0.05-2.0 wt. %.
  • (B)Beta can be converted to a catalyst for use in a process for the alkylation or transalkylation of an aromatic hydrocarbon.
  • the process comprises contacting the aromatic hydrocarbon with a C 2 to C 20 olefin alkylating agent or a polyalkyl aromatic hydrocarbon transalkylating agent, under at least partial liquid phase conditions, and in the presence of a catalyst comprising (B)Beta.
  • the (B)Beta zeolite should be predominantly in its hydrogen ion form. Generally, the zeolite is converted to its hydrogen form by ammonium exchange followed by calcination. If the zeolite is
  • the pure (B)Beta zeolite may be used as a catalyst, but generally, it is preferred to mix the zeolite powder with an inorganic oxide binder such as alumina, silica,
  • the final catalyst may contain from 1-99 wt. % (B)Beta zeolite. Usually the zeolite content will range form 10-90 wt. %, and more typically from 60-80 wt. %.
  • the preferred inorganic binder is alumina.
  • the mixture may be formed into tablets or extrudates having the desired shape by methods well known in the art.
  • suitable aromatic hydrocarbon feedstocks which may be alkylated or transalkylated by the process of the invention include aromatic compounds such as benzene, toluene, and xylene.
  • the preferred aromatic hydrocarbon is benzene. Mixtures of aromatic hydrocarbons may also be employed. Suitable olefins for the alkylation of the aromatic
  • hydrocarbon are those containing 2-20 carbon atoms, such as ethylene, propylene, butene-1, transbutene-2, and
  • olefins cis-butene-2, and higher olefins or mixtures thereof.
  • the preferred olefin is propylene. These olefins may be present in admixture with the corresponding C 2 to C 20 paraffins, but it is preferable to remove any dienes, acetylenes, sulfur compounds or nitrogen compounds which may be present in the olefin feedstock stream to prevent rapid catalyst
  • the transalkylating agent is a polyalkyl aromatic hydrocarbon containing two or more alkyl groups that each may have from two to about four carbon atoms.
  • suitable polyalkyl aromatic hydrocarbons include di-, tri-, and tetra-alkyl aromatic hydrocarbons, such as diethylbenzene, triethylbenzene, diethylmethylbenzene (diethyltoluene), di-isopropylbenzene, di-isopropyltoluene, dibutylbenzene, and the like.
  • Preferred polyalkyl aromatic hydrocarbons are the dialkyl benzenes.
  • a particularly preferred polyalkyl aromatic hydrocarbon is di-isopropylbenzene.
  • Reaction products which may be obtained include ethylbenzene from the reaction of benzene with either ethylene or
  • polyethylbenzenes cumene from the reaction of benzene with propylene or polyisopropylbenzenes
  • ethyltoluene from the reaction of toluene with ethylene or polyethyltoluenes
  • cymenes from the reaction of toluene with propylene or polyisopropyltoluenes
  • secbutylbenzene from the reaction of benzene and n-butenes or polybutylbenzenes.
  • the aromatic hydrocarbon feed should be present in stoichiometric excess. It is preferred that molar ratio of aromatics to olefins be greater than four-to-one to prevent rapid catalyst fouling.
  • the reaction temperature may range from 100-600°F, preferably, 250-450°F.
  • the reaction pressure should be sufficient to maintain at least a partial liquid phase in order to retard catalyst fouling. This is typically 50-1000 psig depending on the feedstock and reaction temperature.
  • Contact time may range from 10 seconds to 10 hours, but is usually from five minutes to an hour.
  • the WHSV in terms of grams (pounds) of aromatic hydrocarbon and olefin per gram (pound) of catalyst per hour, is generally within the range of about 0.5 to 50.
  • the molar ratio of aromatic hydrocarbon will generally range from about 1:1 to 25:1, and preferably from about 2:1 to 20:1.
  • the reaction temperature may range from about 100-600°F, but it is preferably about 250-450°F.
  • the reaction pressure should be sufficient to maintain at least a partial liquid phase, typically in the range of about 50-1000 psig, preferably 300-600 psig.
  • the WHSV will range from about 0.1-10.
  • the conversion of hydrocarbonaceous feeds can take place in any convenient mode, for example, in fluidized bed, moving bed, or fixed bed reactors depending on the types of process desired.
  • the formulation of the catalyst particles will vary depending on the conversion process and method of operation.
  • (B)Beta can also be used as an adsorbent, as a filler in paper, paint, and toothpastes, and as a water-softening agent in detergents.
  • the following examples illustrate the preparation and use of (B)Beta.
  • Example 2 10.85 g of a 0.90M solution of the template from Example 1 is diluted with 3.95 ml H 2 O. 0.23 g of Na 2 B 4 O 7 ⁇ 18H 2 O are dissolved in this solution and then 1.97 g of Cabosil M5 are blended in last.
  • Example 3 The same experiment is set up as in Example 2 except the diquat in Example 2 is replaced by an equivalent amount of TEAOH. The experiment is run under analogous conddtions although this time the crystallization is complete in 6 days.
  • the product is ZSM-5 by XRD. This shows that TEAOH doesn't have enough selectivity for Beta in the borosilicate system.
  • TEAOH is the template used in the prior art for synthesis of Beta.
  • Example 4 202 g of a 0.84M solution of the template from Example 1 is mixed with 55 g of H 2 0, and 4.03 g of Na 2 B 4 O 7 "10H 2 O. 35 g of Cabosil M5 is blended in last and the reaction is run in a Parr 600-cc stirred autoclave with liner for 6 days at 150°C and stirred at 50 rpm. The product is
  • Example 5-10 Very Broad Examples 5-10 are given in Table 3, demonstrating the utility of the method of the invention. Examples 5-7 show that (B)Beta can be made at very low SiO 2 /B 2 O, values and that higher values eventually lead to some ZSM-12 formation as well. Example 8 shows that the desired product can be obtained using Ludox AS-30 as silica source. Now the aluminum impurity has risen to 530 ppm. Examples 9 and 10 show that providing the diquat as a salt to supplement TEAOH can insure formation of pure Boron Beta. Example 9 shows that is the case even without seeding. Table 4 shows the XRD data for the product of Example 5 and Table 5 is of Example 6, both in the as-synthesized form.
  • VB Very Broad XRD patterns for the calcined products of Examples 5 and 6 appear in Tables 6 and 7, respectively.
  • the presence of the boron in the framework of beta zeolite can be indicated by changes in d-spacings.
  • Table 8 compares the d-spacings before and after calcination for some of the sharper peaks of the products of Examples 4, 5 and 6. Also shown are the values for an aluminum beta zeolite prepared by the prior art reference (Re 28,341). It can be seen that the Boron Betas show d-spacings consistently smaller than the aluminum Beta. TABLE 6
  • Example 4 The product of Example 4 was calcined as follows. The sample was heated in a muffle furnace in nitrogen from room temperature up to 540°C at a steadily increasing rate over a 7-hour period. The sample was maintained at 540°C for four more hours and then taken up to 600°C for an additional four hours. Nitrogen was passed over the zeolite at a rate of 20 standard cfm during heating. The calcined product had the X-ray diffraction lines indicated in Table 9 below. TABLE 9
  • Example 12 Ion exchange of the calcined material from Example 4 was carried out using NH 4 NO 3 to convert the zeolites from Na form to NH.. Typically the same mass of NH 4 NO 3 as zeolite was slurried into H 2 O at ratio of 50:1 H-O zeolite. The exchange solution was heated at 100°C for two hours and then filtered. This process was repeated two times. Finally, after the last exchange, the zeolite was washed several times with H 2 O and dried.
  • Example 13 Constraint Index Determination 0. 50 g of the hydrogen form of the zeolite of Example 4 (after treatment according to Examples 11 and 12 was packed into a 3/8-inch stainless steel tube with alundum on both sides of the zeolite bed.
  • a Lindburg furnace was used to heat the reactor tube. Helium was introduced into the reactor tube at 10 cc/minute and atmospheric pressure. The reactor was taken to 250°F for 40 minutes and then raised to 800°F. Once temperature equilibration was achieved a 50/50, w/w feed of n-hexane and 3-methylpentane was introduced into the reactor at a rate of 0.62 cc/hour. Feed delivery was made via syringe pump. Direct sampling onto a gas
  • Example 14 The product of Example 4 after treatment as in Examples 11 and 12 is refluxed overnight with Al(NO 3 ) 3 ⁇ 9H 2 O with the latter being the same mass as the zeolite and using the same dilution as in the ion exchange of Example 12. The product is filtered, washed, and calcined to 540°C. After
  • Example 13 pelletizing the zeolite powder and retaining the 20-40 mesh fraction, the catalyst is tested as in Example 13. Data for the reaction is given in Table 10 along with a variety of catalysts made from analogous treatments with other metal salts. Examples 15-22 Please refer to Table 10 and Table 11. TABLE 10 Constraint Index Determination
  • the borosilicate version of (B)Beta was evaluated as a reforming catalyst.
  • the zeolite powder was impregnated with Pt(NH 3 ) 4 ⁇ 2NO 3 to give 0.8 wt. % Pt.
  • the material was calcined up to 550°F in air and maintained at this
  • the powder was pelletized on a Carver press at 1000 psi and broken and meshed to 24-40.
  • Aromatization Selectivity % 25.4 54.5 25.3
  • Example 24 The product of Example 18 now contained a second metal due to cobalt incorporation. The catalyst was calcined to
  • Example 12 A product was prepared as in Example 12. Next, the catalyst was dried at 600oF, cooled in a closed system, and then vacuum impregnated with an aqueous solution of Pd(NH 3 ) 4 ⁇ 2NO 3 to give 0.5 wt. % loading of palladium. The catalyst was then calcined slowly, up to 900°F in air and held there for three hours. Table 14 gives run conditions and product data for the hydrocracking of hexadecane. The catalyst is quite stable at the temperatures given.
  • EP 654°C Table 16 shows calculated research and motor octane numbers from the fixed fluidized cyclic tests.

Abstract

Une zéolithe bêta de boron pauvre en aluminium et cristalline est préparée par l'utilisation d'un ion quaternaire en tant que gabarit.
EP90911359A 1989-07-07 1990-07-03 Zeolithe beta de boron pauvre en aluminium Withdrawn EP0592392A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US37735989A 1989-07-07 1989-07-07
US377359 1989-07-07
PCT/US1990/003764 WO1991000777A1 (fr) 1989-07-07 1990-07-03 Zeolithe beta de boron pauvre en aluminium

Publications (2)

Publication Number Publication Date
EP0592392A4 EP0592392A4 (fr) 1992-10-05
EP0592392A1 true EP0592392A1 (fr) 1994-04-20

Family

ID=23488797

Family Applications (1)

Application Number Title Priority Date Filing Date
EP90911359A Withdrawn EP0592392A1 (fr) 1989-07-07 1990-07-03 Zeolithe beta de boron pauvre en aluminium

Country Status (9)

Country Link
EP (1) EP0592392A1 (fr)
JP (1) JPH05500650A (fr)
KR (1) KR920703201A (fr)
AU (1) AU6052190A (fr)
BR (1) BR9007515A (fr)
CA (1) CA2062947A1 (fr)
NZ (1) NZ234405A (fr)
WO (1) WO1991000777A1 (fr)
ZA (1) ZA905369B (fr)

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE69023778T2 (de) * 1990-01-24 1996-05-02 Mobil Oil Corp Verfahren zur dehydrierung/dehydrocyclisierung von aliphaten.
DE4115263C2 (de) * 1991-05-10 1995-04-06 Taiwan Styrene Monomer Corp Modifizierter Beta-Zeolith
US5227569A (en) * 1991-08-19 1993-07-13 Texaco Inc. Skeletal isomerization of n-butylenes to isobutylene on boron-beta zeolites
IT1265041B1 (it) * 1993-07-23 1996-10-28 Eniricerche Spa Catalizzatore bifunzionale efficace nella idroisomerizzazione di cere e procedimento per la sua preparazione
IT1270230B (it) * 1994-06-16 1997-04-29 Enichem Sintesi Composizione catalitica e processo per l'alchilazione di composti aromatici
DE10256431A1 (de) * 2002-05-31 2004-01-15 SCHÜMANN SASOL GmbH Mikrokristallines Paraffin, Verfahren zur Herstellung von mikrokristallinen Paraffine und Verwendung der mikrokristallinen Paraffine
JP2004010537A (ja) * 2002-06-06 2004-01-15 Mitsubishi Chemicals Corp 水熱合成用テンプレート、ケイ素含有層状化合物の製造方法及びケイ素含有層状化合物
US8212099B2 (en) * 2009-11-05 2012-07-03 Chevron U.S.A. Inc. N-paraffin selective hydroconversion process using borosilicate ZSM-48 molecular sieves
CN108367931B (zh) * 2015-12-08 2022-01-18 巴斯夫欧洲公司 具有bea框架结构的含锡沸石材料
ES2692818B2 (es) 2017-06-05 2019-11-28 Univ Valencia Politecnica Sintesis de la zeolita beta en su forma nanocristalina, procedimiento de sintesis y su uso en aplicaciones cataliticas

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2429182A1 (fr) * 1978-06-22 1980-01-18 Snam Progetti Materiaux synthetiques a base de silice
EP0055046A1 (fr) * 1980-12-19 1982-06-30 Imperial Chemical Industries Plc Zéolites
EP0251589A2 (fr) * 1986-06-26 1988-01-07 Mobil Oil Corporation Synthèse d'oxydes binaires cristallins

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4554145A (en) * 1984-04-16 1985-11-19 Mobil Oil Corporation Preparation of crystalline silicate zeolite Beta
US4683214A (en) * 1984-09-06 1987-07-28 Mobil Oil Corporation Noble metal-containing catalysts
US4717466A (en) * 1986-09-03 1988-01-05 Mobil Oil Corporation Multiple riser fluidized catalytic cracking process utilizing hydrogen and carbon-hydrogen contributing fragments
US4788169A (en) * 1987-10-26 1988-11-29 Mobil Oil Corporation Low acidity alumina-bound zeolites containing tetrahedral boron, gallium, indium and/or thallium

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2429182A1 (fr) * 1978-06-22 1980-01-18 Snam Progetti Materiaux synthetiques a base de silice
EP0055046A1 (fr) * 1980-12-19 1982-06-30 Imperial Chemical Industries Plc Zéolites
EP0251589A2 (fr) * 1986-06-26 1988-01-07 Mobil Oil Corporation Synthèse d'oxydes binaires cristallins

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of WO9100777A1 *

Also Published As

Publication number Publication date
BR9007515A (pt) 1992-06-23
KR920703201A (ko) 1992-12-17
ZA905369B (en) 1991-06-26
EP0592392A4 (fr) 1992-10-05
NZ234405A (en) 1992-05-26
AU6052190A (en) 1991-02-06
CA2062947A1 (fr) 1991-01-08
WO1991000777A1 (fr) 1991-01-24
JPH05500650A (ja) 1993-02-12

Similar Documents

Publication Publication Date Title
US5393407A (en) Hydrocarbon conversion utilizing a low-aluminum boron beta zeolite
US4963337A (en) Zeolite SSZ-33
US5106801A (en) Zeolite SSZ-31
US5215648A (en) Hydrocarbon conversion processes using SSZ-31
EP0374206B1 (fr) Nouveau zeolite ssz-26
US5391287A (en) Hydrocarbon conversion process using zeolite SSZ-35
US4826667A (en) Zeolite SSZ-25
US5252527A (en) Zeolite SSZ-32
US5053373A (en) Zeolite SSZ-32
US5254514A (en) Zeolite SSZ-37
US5202014A (en) Zeolite SSZ-25
US5200377A (en) Zeolite SSZ-28
US5007997A (en) Zeolite SSZ-26
US5120425A (en) Use of zeolite SSZ-33 in hydrocarbon conversion processes
WO1991000777A1 (fr) Zeolithe beta de boron pauvre en aluminium
US5691463A (en) Alkylation process using zeolite SSZ-25
EP0522196B1 (fr) Zéolithe SSZ-32
US6005154A (en) Isomerization process using zeolite SSZ-25
WO1991000844A1 (fr) Zeolithe (b)ssz-24
CA1335600C (fr) Zeolite ssz-26

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 19920129

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE CH DE DK ES FR GB IT LI LU NL SE

17Q First examination report despatched

Effective date: 19941220

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: CHEVRON U.S.A. INC.

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 19960326