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  • C01B37/00—Compounds having molecular sieve properties but not having base-exchange properties
  • C01B37/02—Crystalline silica-polymorphs, e.g. silicalites dealuminated aluminosilicate zeolites
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  • 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
  • C01B39/026—After-treatment
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  • 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
  • C01B39/46—Other types characterised by their X-ray diffraction pattern and their defined composition
  • C01B39/48—Other types characterised by their X-ray diffraction pattern and their defined composition using at least one organic template directing agent
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  • C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
  • C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
  • C10G11/04—Oxides
  • C10G11/05—Crystalline alumino-silicates, e.g. molecular sieves
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  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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  • C10G29/00—Refining of hydrocarbon oils, in the absence of hydrogen, with other chemicals
  • C10G29/20—Organic compounds not containing metal atoms
  • C10G29/205—Organic compounds not containing metal atoms by reaction with hydrocarbons added to the hydrocarbon oil
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  • 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
  • C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
  • C10G3/42—Catalytic treatment
  • C10G3/44—Catalytic treatment characterised by the catalyst used
  • C10G3/48—Catalytic treatment characterised by the catalyst used further characterised by the catalyst support
  • C10G3/49—Catalytic treatment characterised by the catalyst used further characterised by the catalyst support containing crystalline aluminosilicates, e.g. molecular sieves
• • 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
  • 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
  • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
  • C10G2300/10—Feedstock materials
  • C10G2300/1037—Hydrocarbon fractions
  • C10G2300/1044—Heavy gasoline or naphtha having a boiling range of about 100 - 180 °C
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  • 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
  • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
  • C10G2300/10—Feedstock materials
  • C10G2300/1088—Olefins
• • 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
  • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
  • C10G2300/10—Feedstock materials
  • C10G2300/1096—Aromatics or polyaromatics
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  • 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
  • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
  • C10G2400/02—Gasoline
• • 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
  • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
  • C10G2400/30—Aromatics
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
  • Y02P30/00—Technologies relating to oil refining and petrochemical industry
  • Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock

Definitions

• This invention relates to aluminosilicate zeolites designated UZM-15 and UZM-15HS a method of preparing the zeolites and uses thereof.
• the UZM-15 and UZM-15HS are useful in various hydrocarbon reactions such as the conversion of cyclic hydrocarbons to non-cyclic hydrocarbons, i.e. ring opening reactions.
• Zeolites are crystalline aluminosilicate compositions which are microporous and which are formed from corner sharing AI0 2 and Si0 2 tetrahedra. Numerous zeolites, both naturally occurring and synthetically prepared are used in various industrial processes. Synthetic zeolites are prepared via hydrothermal synthesis employing suitable sources of Si, Al, as well as structure directing agents such as alkali metals, alkaline earth metals, amines, or organoammonium cations. The structure directing agents reside in the pores of the zeolite and are largely responsible for the particular structure that is ultimately formed. These species balance the framework charge associated with aluminum and can also serve as space fillers.
• Zeolites are characterized by having pore openings of uniform dimensions, having a significant ion exchange capacity, and being capable of reversibly desorbing an adsorbed phase which is dispersed throughout the internal voids of the crystal without significantly displacing any atoms which make up the permanent zeolite crystal structure. Zeolites can be used as catalysts for hydrocarbon conversions, which can take place on outside surfaces as well as on internal surfaces within the pore.
• US-A-4,209,498 discloses an aluminosilicate zeolite designated as FU- 1 along with a method of preparing the zeolite and uses for the zeolite.
• FU-1 is prepared using a "methylated quaternary ammonium" cation along with an alkali metal. It is further stated by the patentees that the FU- 1 zeolite has a Si/AI ratio greater than 2.5 and can be used for xylene isomerization.
• An all-silica version of FU-1 was reported in US-A-4,689,207. The synthesis employs the layered silicate magadiite and the Na/ethyltrimethylammonium (ETMA) template system. The solid product was identified as containing 20% FU-1 by x-ray analysis.
• ETMA Na/ethyltrimethylammonium
• Applicants have prepared a family of zeolites, designated UZM-15, which have an x-ray diffraction pattern similar to but distinct from that of FU-1 and is different in other characteristics.
• UZM-15 contains at least one quaternary organoammonium cation template where at least one of the organic groups has at least two carbon atoms.
• Preferred templates are selected from ETMA, DEDMA, TMBA, PEDMA and optionally alkali metals, alkaline earth metals and/or other organoammonium cations.
• the Si/AI ratio of the UZM-15 zeolites ranges from 7 to 50 and the aluminum can be replaced by other metals such as gallium or iron.
• UZM-15HS dealuminated versions of UZM-15.
• the UZM-15HS materials have different properties from the starting UZM-15, including different ion-exchange capacities, acidity, and porosity.
• UZM- 15 a new family of zeolites designated UZM- 15.
• the UZM-15 zeolite has a composition on an anhydrous basis that is represented by the formula:
• M is an exchangeable cation and is selected from the group consisting of alkali and alkaline earth metals.
• M cations include but are not limited to lithium, sodium, potassium, cesium, strontium, calcium, magnesium, barium and mixtures thereof.
• the value of "m" which is the mole ratio of M to (Al + E) varies from 0 to 2.0.
• R is at least one first organoammonium cation comprising at least one organic group having at least two carbon atoms.
• organoammonium cations include but are not limited to ethyltrimethylammonium (ETMA), diethyldimethylammonium (DEDMA), trimethylbutylammonium (TMBA), N.N N'.N'N'-hexamethyl-l ⁇ butanediammonium (DQ ) and propylethyldimethylammonium (PEDMA).
• EMA ethyltrimethylammonium
• DEDMA diethyldimethylammonium
• TMBA trimethylbutylammonium
• DQ N.N N'.N'N'-hexamethyl-l ⁇ butanediammonium
• PEDMA propylethyldimethylammonium
• R may be a mixture of at least one first organoammonium cation and second organoammonium cation selected from the group consisting of quaternary ammonium cations, protonated amines, protonated diamines, protonated alkanolamines, diquaternary ammonium cations, quaternized alkanolammonium cations and mixtures thereof.
• the value of "r” which is the mole ratio of R to (Al + E) varies from 0.25 to 5.0.
• the value of "n” which is the weighted average valence of M varies from +1 to +2.
• the value of "p", which is the average weighted valence of the organic cation has a value from +1 to +2.
• E is an element which is present in the framework and is selected from the group consisting of gallium, iron, boron chromium, indium and mixtures thereof.
• the value of "x” which is the mole fraction of E varies from 0 to 1.0.
• the weighted average valence is the valence of that one metal, i.e. +1 or +2.
• the weighted average valence is the valence of the single R cation, i.e., +1 or +2.
• the total amount of R is given by the equation:
• aluminosilicate zeolites are prepared by a hydrothermal crystallization of a reaction mixture prepared by combining reactive sources of R, aluminum, optionally E and/or M and silicon in aqueous media.
• the aluminum sources include, but are not limited to, aluminum alkoxides, precipitated alumina, aluminum hydroxide, aluminum salts and aluminum metal.
• specific examples of aluminum alkoxides include, but are not limited to aluminum orthosec-butoxide, and aluminum orthoisopropoxide.
• Sources of silica include but are not limited to tetraethylorthosilicate, fumed silicas, precipitated silicas and colloidal silica.
• Sources of the M metals include but are not limited to the halide salts, nitrate salts, acetate salts, and hydroxides of the respective alkali or alkaline earth metals.
• Sources of the E elements include but are not limited to alkali borates, boric acid, precipitated gallium oxyhydroxide, gallium sulfate, ferric sulfate, ferric chloride, chromium chloride, chror ium nitrate, indium chloride and indium nitrate.
• R is a first organoammonium cation having at least one organic group with at least two carbon atoms, e.g.
• the sources include but are not limited to the hydroxide, chloride, bromide, iodide, and fluoride compounds.
• R may also optionally be (in addition to the first organoammonium cation) a second organoammonium compound.
• R (second) is a quaternary ammonium cation or a quaternized alkanolammonium cation
• the sources can be the hydroxide, chloride, bromide, iodide and fluoride compounds.
• Specific examples include without limitation ethyltrimethylammonium hydroxide (ETMAOH), diethyldimethylammonium hydroxide (DEDMAOH), propylethyldimethylammonium hydroxide (PEDMAOH), thmethylpropylammonium hydroxide, trimethylbutylammonium hydroxide (TMBAOH), tetraethylammonium hydroxide, hexamethonium bromide, tetramethylammonium chloride N,N,N,N',N',N'- hexamethyl 1 ,4 butanediammonium hydroxide, methyltriethylammonium hydroxide.
• EMAOH ethyltrimethylammonium hydroxide
• DEDMAOH diethyldimethylammonium hydroxide
• PEDMAOH propylethyldimethylammonium hydroxide
• TMBAOH trimethylbutylammonium hydroxide
• the source of R may also be neutral amines, diamines, and alkanolamines. Specific examples are triethanolamine, triethylamine, and N,N,N',N' tetramethyl-1 ,6-hexanediamine.
• a reagent in the form of an aluminosilicate stock solution may be used. These solutions consist of one or more organoammonium hydroxides and sources of silicon and aluminum that are processed to form a clear homogenous solution that is generally stored and used as a reagent.
• the reagent contains aluminosilicate species that typically don't show up in zeolite reaction mixtures derived directly from separate sources of silicon and aluminum.
• the reagent is generally alkali-free or contains alkali at impurity levels from the silicon, aluminum, and organoammonium hydroxide sources.
• One or more of these solutions may be used in a zeolite synthesis.
• the corresponding metallosilicate solution may also be employed in a synthesis.
• the reaction mixture containing reactive sources of the desired components can be described in terms of molar ratios of the oxides by the formula: aM 2 /nO:bR 2/ pO:(1-c)AI 2 0 3 :cE 2 0 3 :dSi ⁇ 2:eH2 ⁇
• a is the mole ratio of the oxide of M and has a value of 0 to 5
• b is the mole ratio of the oxide of R and has a value of 1.5 to 80
• "d” is the mole ratio of silica and has a value of 10 to 100
• "c” is the mole ratio of the oxide of E and has a value from 0 to 1.0
• e is the mole ratio of water and has a value of 100 to 15000.
• reaction mixture is now reacted at reaction conditions including a temperature of 85°C to 225°C and preferably from 140°C to 175°C for a period of 12 hours to 20 days and preferably for a time of 2 days to 10 days in a sealed reaction vessel under autogenous pressure.
• reaction conditions including a temperature of 85°C to 225°C and preferably from 140°C to 175°C for a period of 12 hours to 20 days and preferably for a time of 2 days to 10 days in a sealed reaction vessel under autogenous pressure.
• the solid product is isolated from the heterogeneous mixture by means such as filtration or centrifugation, and then washed with de-ionized water and dried in air at ambient temperature up to 100°C.
• the crystalline zeolites are characterized by a three-dimensional framework structure of at least Si0 2 and AI0 2 tetrahedral units. These zeolites are further characterized by their x-ray diffraction pattern.
• the x-ray diffraction pattern has at least the diffraction lines with the ⁇ -spacings and relative intensities listed in Table A. TABLE A
• the zeolite will contain some of the exchangeable or charge balancing cations in its pores. These exchangeable cations can be exchanged for other cations, or in the case of organic cations, they can be removed by heating under controlled conditions. Ion exchange involves contacting the zeolites with a solution containing the desired cation (at molar excess) at exchange conditions. Exchange conditions include a temperature of 15°C to 100°C and a time of 20 minutes to 50 hours. Calcination conditions include a temperature of 300°C to 600°C for a time of 2 to 24 hours.
• a special treatment for removing organic cations, which provides the ammonium form of the zeolite is ammonia calcination. Calcination in an ammonia atmosphere can decompose organic cations, presumably to a proton form that can be neutralized by ammonia to form the ammonium cation. The resulting ammonium form of the zeolite can be further ion-exchanged to any other desired form.
• Ammonia calcination conditions include treatment in the ammonia atmosphere at temperatures between 250°C and 600°C and more preferably between 250°C and 450°C for times of 10 minutes to 5 hours.
• the treatments can be carried out in multiple steps within this temperature range such that the total time in the ammonia atmosphere does not exceed 5 hours.
• the treatments should be brief, less than a half hour and more preferably on the order of 5-10 minutes. Extended calcination times above 500°C can lead to unintended dealumination along with the desired ammonium ion-exchange and are unnecessarily harsh as most organoammonium templates easily decompose at lower temperatures.
• the UZM-15 zeolites represented by equation (2) can be further treated in order to remove aluminum and optionally inserting silicon thereby increasing the Si/AI ratio and thus modifying the acidity and ion exchange properties of the zeolites.
• These treatments include: a) contacting with a fluorosilicate solution or slurry; b) calcining or steaming followed by acid extraction or ion-exchange; c) acid extraction or d) any combination of these treatments in any order.
• Fluorosilicate treatment is known in the art and is described in US-A- 6,200,463 B1 , which cites US-A-4, 711 ,770 as describing a process for treating a zeolite with a fluorosilicate salt. Both patents are incorporated by reference in their entirety. General conditions for this treatment are contacting the zeolite with a solution containing a fluorosilicate salt such as ammonium fluorosilicate (AFS) at a temperature of 20°C to 90°C.
• a fluorosilicate salt such as ammonium fluorosilicate (AFS)
• the acids which can be used in carrying out acid extraction include without limitation mineral acids, carboxylic acids and mixtures thereof. Examples of these include sulfuric acid, nitric acid, ethylenediaminetetraacetic acid (EDTA), citric acid, oxalic acid, etc.
• the concentration of acid which can be used is not critical but is conveniently between 1 wt.% to 80 wt.% acid and preferably between 5 wt.% and 40 wt.% acid.
• Acid extraction conditions include a temperature of 10°C to 100°C for a time of 10 minutes to 24 hours.
• the treated UZM-15 zeolite is isolated by means such as filtration, washed with deionized water and dried at ambient temperature up to 100°C.
• the UZM-15 zeolites which have undergone one or more treatments whereby aluminum has been removed and optionally silicon has been inserted into the framework will hereinafter be referred to as UZM-15HS.
• the extent of dealumination obtained from acid extraction depends on the cation form of the starting UZM-15 as well as the acid concentration and the time and temperature over which the extraction is conducted. For example, if organic cations are present in the starting UZM-15, the extent of dealumination will be slight compared to a UZM-15 in which the organic cations have been removed. This may be preferred if it is desired to have dealumination just at the surface of the UZM-15.
• convenient ways of removing the organic cations include calcination, ammonia calcination, steaming and ion exchange. Calcination, ammonia calcination and ion exchange conditions are as set forth above.
• Steaming conditions include a temperature of 400°C to 850°C with from 1% to 100% steam for a time of 10 minutes to 48 hours and preferably a temperature of 500°C to 600°C, steam concentration of 5 to 50% and a time of 1 to 2 hours.
• both calcination and steaming treatments not only remove organic cations, but can also dealuminate the zeolite.
• alternate embodiments for dealumination include: a calcination treatment followed by acid extraction and steaming followed by acid extraction.
• a further embodiment for dealumination comprises calcining or steaming the starting UZM- 15 zeolite followed by an ion-exchange treatment.
• an acid extraction can be carried out concurrently with, before or after the ion exchange.
• the ion exchange conditions are the same as set forth above, namely a temperature of 15°C to 100°C and a time of 20 minutes to 50 hours.
• Ion exchange can be carried out with a solution comprising a cation (M1') selected from the group consisting of alkali metals, alkaline earth metals, rare earth metals, hydrogen ion, ammonium ion, and mixtures thereof.
• M1' cation
• the M1 cation is exchanged for a secondary or different M1' cation.
• the UZM-15HS composition after the steaming or calcining steps is contacted with an ion exchange solution comprising an ammonium salt.
• ammonium salts include but are not limited to ammonium nitrate, ammonium chloride, ammonium bromide, and ammonium acetate.
• the ammonium ion containing solution can optionally contain a mineral acid such as but not limited to nitric, hydrochloric, sulfuric and mixtures thereof.
• the concentration of the mineral acid is that amount necessary to give a ratio of H + to NH + of 0 to 1. This ammonium ion exchange aids in removing any debris present in the pores after the steaming and/or calcination treatments.
• the integrity of the zeolite crystal structure be substantially maintained throughout the dealumination process, and that the zeolite retains at least 50%, preferably at least 70% and more preferably at least 90% of its original crystallinity.
• a convenient technique for assessing the crystallinity of the products relative to the crystallinity of the starting material is the comparison of the relative intensities of the ⁇ f-spacing of their respective X-ray powder diffraction patterns. The sum of the peak intensities, in arbitrary units above the background, of the starting material is used as the standard and is compared with the corresponding peak intensities of the products.
• the numerical sum of the peak heights of the molecular sieve product is 85 percent of the value of the sum of the peak intensities of the starting zeolite, then 85 percent of the crystallinity has been retained.
• Other indications of the retention of crystallinity are surface area and adsorption capacity. These tests may be preferred when the substituted metal significantly changes, e.g., increases, the absorption of x-rays by the sample or when peaks experience substantial shifts such as in the dealumination process.
• the UZM-15HS is usually dried and can be used in various processes as discussed below. Applicants have found the properties of the UZM-
• 15HS can be further modified by one or more additional treatment.
• These treatments include steaming, calcining or ion exchanging and can be carried out individually or in any combination. Some of these combinations include but are not limited to: steam » calcine > ion exchange; calcine ⁇ steam Vintage ion exchange; ion exchange * calcine * steam ion exchange » steam ⁇ calcine; steam » calcine;
• M1 is at least one exchangeable cation selected from the group consisting of alkali, alkaline earth metals, rare earth metals, ammonium ion, hydrogen ion and mixtures thereof
• a is the mole ratio of M1 to (Al + E) and varies from 0.01 to 50
• n is the weighted average valence of M1 and has a value of +1 to +3
• E is an element selected from the group consisting of gallium, iron, boron, chromium, indium and mixtures thereof
• x is the mole fraction of E and varies from 0 to 1 .0
• y' is the mole ratio of Si to (Al + E) and varies from greater than 7.0 to virtually pure silica
• a zeolite is virtually pure silica when y' has a value of at least 3,000, preferably 10,000 and most preferably 20,000. Thus, ranges for y' are from 7 to 3,000 preferably greater than 10 to 3,000; 7.0 to 10,000 preferably greater than 10 to 10,000 and 7.0 to 20,000 preferably greater than 10 to 20,000.
• anhydrous state of the zeolite will be intended unless otherwise stated.
• the term “anhydrous state” is employed herein to refer to a zeolite substantially devoid of both physically adsorbed and chemically adsorbed water.
• the zeolites of this invention are capable of separating mixtures of molecular species based on the molecular size (kinetic diameter) or on the degree of polarity of the molecular species.
• separation is accomplished by the smaller molecular species entering the intracrystalline void space while excluding larger species.
• the kinetic diameters of various molecules such as oxygen, nitrogen, carbon dioxide, carbon monoxide are provided in D.W. Breck, Zeolite Molecular Sieves, John Wiley and Sons (1974) p. 636.
• the crystalline microporous compositions of the present invention can be used as catalysts or catalyst supports in hydrocarbon conversion processes.
• Hydrocarbon conversion processes are well known in the art and include ring-opening, cracking, hydrocracking, alkylation of both aromatics and isoparaffins, isome zation, polymerization, reforming, dewaxing, hydrogenation, dehydrogenation, transalkylation, dealkylation, hydration, dehydration, hydrotreating, hydrodenitrogenation, hydrodesulfurization, methanation and syngas shift process.
• a preferred hydrocarbon conversion process is ring-opening, whereby cyclic hydrocarbons are converted to non-cyclic hydrocarbons, i.e. linear or branched hydrocarbons.
• Other preferred processes include hydroisomerization of normal paraffins to branched paraffins and especially mono-branched paraffins and oligomerization of light olefins to higher molecular weight olefins.
• Interplanar spacings (d) in Angstrom units were obtained from the position of the diffraction peaks expressed as 2 ⁇ where ⁇ is the Bragg angle as observed from digitized data. Intensities were determined from the integrated area of diffraction peaks after subtracting background, "l 0 " being the intensity of the strongest line or peak, and "I" being the intensity of each of the other peaks.
• the determination of the parameter 2 ⁇ is subject to both human and mechanical error, which in combination can impose an uncertainty of ⁇ 0.4 on each reported value of 2 ⁇ and up to ⁇ 0.5 on reported values for nanocrystalline materials. This uncertainty is, of course, also manifested in the reported values of the d-spacings, which are calculated from the ⁇ values. This imprecision is general throughout the art and is not sufficient to preclude the differentiation of the present crystalline materials from each other and from the compositions of the prior art. In some of the X-ray patterns reported, the relative intensities of the c/-spacings are indicated by the notations vs, s, m and w which represent very strong, strong, medium, and weak, respectively.
• the purity of a synthesized product may be assessed with reference to its X-ray powder diffraction pattern.
• a sample is stated to be pure, it is intended only that the X-ray pattern of the sample is free of lines attributable to crystalline impurities, not that there are no amorphous materials present.
• Example 11 An AFS solution was prepared by dissolving 1.47 g (NH 4 ) 2 SiF 6 in 150 g deionized water. A zeolite slurry comprising 14 g of the ammonium exchanged UZM-15 from Example 10 in 200 g deionized water was then added to the AFS solution with mixing. The suspension was stirred for 20 minutes before the reaction mixture was transferred to a teflon bottle, sealed and placed in a shaker bath at 90°C for 17 hr. The product was isolated by filtration, washed with deionized water, and dried in air.
• the dealuminated product of the AFS treatment was identified as UZM- 15HS via x-ray powder diffraction analysis, the pattern was very similar to that of the parent UZM-15 material. Representative diffraction lines are shown in Table 11 below. A 12.55 g portion of the AFS product was calcined at 500°C for 2 hr in nitrogen and an additional 6 hr in air. The x-ray diffraction pattern for the calcined material is also given in Table 11. Slight shifts and some broadening are observed in some of the diffraction lines as further dealumination of the zeolite framework occurs.
• the BET surface area was 356 m 2 /g, while the micropore volume was 0.09 cc/g.
• Example 12 [0041] To a 250 ml solution containing 65 g oxalic acid dihydrate there were added 30 g of the calcined ammonium exchanged UZM-15 from example 10 and the resulting suspension was heated at 71 °C for 2 hr with stirring. The product was isolated by filtration, washed with deionized water and dried at 150°C.
• a 60 g sample of the parent zeolite from example 10 was slurried in 120 ml of 1.57 M HCI and held at 95°C for 1 hr. The product was isolated by filtration and washed thoroughly with deionized water. This process was repeated again, and the product was dried at 95°C. The product was then calcined in nitrogen at 500°C for 2 hr and for another 6 hr in air.
• the BET surface area was 329 m 2 /g and the micropore volume was 0.084 cc/g.
• Example 14 An aluminosilicate stock solution was prepared by adding 25.68g of Aluminum tri sec-butoxide to 712.73 g ETMAOH with vigorous stirring, followed by the addition 257.64 g colloidal silica. The mixture was homogenized for 30 minutes and then reacted at 98°C for 36 hours at autogenous pressures. The resulting clear solution was then cooled to room temperature. A second solution was prepared by dissolving 50.06g of KBr and 32.41 grams of TMABr in 371.60 g of deionized water. It was then added to the entire aluminosilicate solution and mixed for 30 minutes. The mixture was transferred to an autoclave and crystallized at 150°C for 6 days at autogenous pressures.
• the UZM-15 product was isolated by filtration, washed with deionized water, and dried at 70°C. The material was then slurried in a 1.57M aqueous HCI solution for 1 hour at 95°C, filtered and washed. This procedure was repeated 2 times. The material was then washed and dried at 95°C.
• the product was isolated by filtration, washed with de-ionized water, and dried at 98°C.

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