EP1742875A1 - Crystalline aluminosilicate zeolitic composition: uzm-15 - Google Patents

Crystalline aluminosilicate zeolitic composition: uzm-15

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Publication number
EP1742875A1
EP1742875A1 EP04750374A EP04750374A EP1742875A1 EP 1742875 A1 EP1742875 A1 EP 1742875A1 EP 04750374 A EP04750374 A EP 04750374A EP 04750374 A EP04750374 A EP 04750374A EP 1742875 A1 EP1742875 A1 EP 1742875A1
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European Patent Office
Prior art keywords
zeolite
value
uzm
varies
group consisting
Prior art date
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Withdrawn
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EP04750374A
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German (de)
French (fr)
Inventor
Lisa M. Rohde
Gregory J. Lewis
Stephen T. Wilson
Deng Yang Jan
R. Lyle Patton
Susan C. Koster
Jamie G. Moscoso
Mark A. Miller
Michael G. Gatter
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Honeywell UOP LLC
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Honeywell UOP LLC
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Priority to PCT/US2004/012153 priority Critical patent/WO2005113440A1/en
Publication of EP1742875A1 publication Critical patent/EP1742875A1/en
Application status is Withdrawn legal-status Critical

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    • C01B39/02Crystalline 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
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    • C10G29/00Refining of hydrocarbon oils in the absence of hydrogen, with other chemicals
    • C10G29/20Organic compounds not containing metal atoms
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    • C10G3/42Catalytic treatment
    • C10G3/44Catalytic treatment characterised by the catalyst used
    • C10G3/48Catalytic treatment characterised by the catalyst used further characterised by the catalyst support
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    • C10G45/00Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/58Refining 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
    • C10G45/60Refining 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
    • C10G45/64Refining 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
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Abstract

An aluminosilicate zeolite and substituted versions designated UZM-15 have been synthesized. These zeolites are prepared using an organo-ammonium cation as a template in which at least one organic group has at least 2 carbon atoms. An example of such a cation is diethyldimethyl-ammonium cation. The template can optionally comprise other organoammonium cations, alkali metals and alkaline earth metals. These UZM-15 materials can be dealuminated by various processes to provide UZM-15HS compositions. Both the UZM-15 and UZM-15HS compositions are useful as catalysts or catalyst supports in various process such as the conversion of cyclic hydrocarbons to non-cyclic hydrocarbons and olefin oligomerization.

Description

"CRYSTALLINE ALUMINOSILICATE ZEOLITIC COMPOSITION: UZM-15"

BACKGROUND OF THE INVENTION

[0001] 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.

[0002] Zeolites are crystalline aluminosilicate compositions which are microporous and which are formed from corner sharing AI02 and Si02 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.

[0003] 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. The '498 patent states that 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. [0004] 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.

[0005] A number of applications have been identified for the FU-1 zeolite. Besides the xylene isomerization mentioned above and disclosed in GB1563346, the conversion of alkylbenzenes, such as xylenes and ethylbenzene is described in GB2052554A, GB2006818, GB2042490, and GB2006262. US-A-4, 172,856 describes the use of FU-1 to make olefins from methanol or dimethylether as preferred feedstocks while US-A-4,191 ,709, US-A-4,205,012, and GB2013660A describe the synthesis of amines from alcohols using a FU-1 based catalyst. Finally, FU-1 based catalysts have been described for the cracking of heavy fractions to naphtha-type products in US-A-4, 197, 186.

[0006] 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. One difference is that the as-synthesized 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.

[0007] Applicants have also prepared dealuminated versions of UZM-15 designated UZM-15HS. The UZM-15HS materials have different properties from the starting UZM-15, including different ion-exchange capacities, acidity, and porosity. DETAILED DESCRIPTION OF THE INVENTION

[0008] Applicants have synthesized a new family of zeolites designated UZM- 15. In its as-synthesized form, the UZM-15 zeolite has a composition on an anhydrous basis that is represented by the formula:

Mn:Rr P+A -x)ExSiyOz0) where M is an exchangeable cation and is selected from the group consisting of alkali and alkaline earth metals. Specific examples of the 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. Examples of these 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). Optionally, 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 ratio of silicon to (Al+E) is represented by "y" which varies from 7 to 50, while the mole ratio of O to (Al+E) is represented by "z" and has a value given by the equation: z = (m»n + r*p + 3 + 4*y)/2.

[0009] When M is only one metal, then the weighted average valence is the valence of that one metal, i.e. +1 or +2. However, when more than one M metal is present, the total amount of:

Mm = „„ + m2 + Ma3 + and the weighted average valence "n" is given by the equation: [0010] Similarly when only one R organic cation is present, the weighted average valence is the valence of the single R cation, i.e., +1 or +2. When more than one R cation is present, the total amount of R is given by the equation:

R;' =RT+RT +R and the weighted average valence "p" is given by the equation:

[0011] These 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. Accordingly, 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. When R is a first organoammonium cation having at least one organic group with at least two carbon atoms, e.g. DEDMA, ETMA, TMBA, DQ and PEDMA, 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. In the case where 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 (either first or second cation) 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. 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. In a special case, 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. In the case of substitution of Al by E, the corresponding metallosilicate solution may also be employed in a synthesis.

[0012] The reaction mixture containing reactive sources of the desired components can be described in terms of molar ratios of the oxides by the formula: aM2/nO:bR2/pO:(1-c)AI203:cE203:dSiθ2:eH2θ where "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, and "e" is the mole ratio of water and has a value of 100 to 15000. The 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. After crystallization is complete, 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.

[0013] The crystalline zeolites are characterized by a three-dimensional framework structure of at least Si02 and AI02 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 α-spacings and relative intensities listed in Table A. TABLE A

[0014] As-synthesized, 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.

[0015] 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. Optionally, 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. Above 500°C, 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.

[0016] The ion exchanged form of UZM-15 can be described by the empirical formula:

M R;p Ah-x)ExSiyOA ) where R, x, y, and E are as described above and m' has a value from 0 to 7.0, M' is a cation selected from the group consisting of alkali metals, alkaline earth metals, rare earth metals, hydrogen ion, ammonium ion, and mixtures thereof, n' is the weighted average valence of M' and varies from 1 to 3, r' has a value from 0 to 7.0, r' + m' > 0, and p is the weighted average valence of R and varies from +1 to +2. The value of z' is given by the formula: z' = (m' • n' + r' • p + 3 + 4 • y)/2.

[0017] 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.

[0018] 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.

[0019] 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. Once treated with the acid, 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.

[0020] 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. As stated above, 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.

[0021] It should be pointed out that both calcination and steaming treatments not only remove organic cations, but can also dealuminate the zeolite. Thus, 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. Of course an acid extraction can be carried out concurrently with, before or after the ion exchange.

[0022] 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. By carrying out this ion exchange, the M1 cation is exchanged for a secondary or different M1' cation. In a preferred embodiment, the UZM-15HS composition after the steaming or calcining steps is contacted with an ion exchange solution comprising an ammonium salt. Examples of 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.

[0023] It is apparent from the foregoing that, with respect to effective process conditions, it is desirable that 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 αf-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. When, for example, 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. In practice it is common to utilize only a portion of the peaks for this purpose, as for example, five or six of the strongest peaks. 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. [0024] After having undergone any of the dealumination treatments as described above, 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 ». ion exchange; ion exchange * calcine * steam ion exchange » steam ► calcine; steam » calcine;

[0025] The dealumination treatment described above can be combined in any order to provide the zeolites of the invention although not necessarily with equivalent result. It should be pointed out that the particular sequence of treatments, e.g., AFS, acid extraction, steaming, calcining, etc., can be repeated as many times as necessary to obtain the desired properties. Of course one treatment can be repeated while not repeating other treatments, e.g., repeating the AFS two or more times before carrying out steaming or calcining; etc. Finally, the sequence and/or repetition of treatments will determine the properties of the final UZM-15HS composition.

[0026] The UZM-15HS as prepared above is described by the empirical formula on an anhydrous basis of Mi +Al -,)ExSiyOz-. (3)

where 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 and z" is the mole ratio of O to (Al + E) and has a value determined by the equation: z" = (a • n + 3 + 4 • y')/2. [0027] By virtually pure silica is meant that virtually all the aluminum and/or the E metals have been removed from the framework. It is well know that it is virtually impossible to remove all the aluminum and/or E metal. Numerically, 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.

[0028] In specifying the proportions of the zeolite starting material or adsorption properties of the zeolite product and the like herein, the "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.

[0029] The zeolites of this invention (both UZM-15 and UZM-15HS) 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. When the separation of molecular species is based on molecular size, 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.

[0030] The crystalline microporous compositions of the present invention either as-synthesized or after modification 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. Specific reaction conditions and the types of feeds which can be used in these processes are set forth in US-A-4,310,440 and US-A-4,440,871 which are incorporated by reference. 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.

[0031] Other reactions may be catalyzed by these crystalline microporous compositions, including base-catalyzed side chain alkylation of alkylaromatics, aldol-condensations, olefin double bond isome zation and isomerization of acetylenes, alcohol dehydrogenation, and olefin dimerization, oligomerization and conversion of alcohol to olefins. Suitably ion exchanged forms of these materials can catalyze the reduction of NOx to N2 in automotive and industrial exhaust streams. Some of the reaction conditions and types of feeds that can be used in these processes are set forth in US-A-5, 015,796 and in H. Pines, THE CHEMISTRY OF CATALYTIC HYDROCARBON CONVERSIONS, Academic Press (1981) pp. 123-154 and references contained therein, which are incorporated by reference. [0032] The X-ray patterns presented in the following examples (and tables above) were obtained using standard X-ray powder diffraction techniques. The radiation source was a high-intensity X-ray tube operated at 45 kV and 35 ma. The diffraction pattern from the copper K-alpha radiation was obtained by appropriate computer based techniques. Flat compressed powder samples were continuously scanned at 2° (2Θ) per minute from 2° to 70°(2Θ), or optionally from 3° to 40° (2Θ) in 0.05° steps at 3° (2Θ) per minute. Interplanar spacings (d) in Angstrom units were obtained from the position of the diffraction peaks expressed as 2Θ where θ is the Bragg angle as observed from digitized data. Intensities were determined from the integrated area of diffraction peaks after subtracting background, "l0" being the intensity of the strongest line or peak, and "I" being the intensity of each of the other peaks.

[0033] As will be understood by those skilled in the art, the determination of the parameter 2Θ is subject to both human and mechanical error, which in combination can impose an uncertainty of ±0.4 on each reported value of 2Θ 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 θ 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. In terms of 100 X l/l0, the above designations are defined as w = 0- 15; m = 15-60; s = 60-80 and vs = 80-100. In certain instances the purity of a synthesized product may be assessed with reference to its X-ray powder diffraction pattern. Thus, for example, if 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.

[0034] In order to more fully illustrate the invention, the following examples are set forth. It is to be understood that the examples are only by way of illustration and are not intended as an undue limitation on the broad scope of the invention as set forth in the appended claims. Example 1 - 8

[0035] A series of examples were carried out to prepare UZM-15 compositions using different templates, conditions and silicon sources. The general process involved forming a mixture of AI(OSec-Bu)3 and an organic templating agent, e.g. DEDMAOH. To this there was added a silicon source and the mixture was homogenized. If the silicon source was TEOS, the solution was concentrated by removing the ethanol and sec-butanol and some water which formed as hydrolysis products of the alkoxides. Optionally the solution/mixture was aged followed by the addition of a second templating agent and finally crystallization. The solid product was collected, washed, dried and then characterized by several analytical methods including x-ray diffraction analysis. The specific conditions for each example are presented in Table 1 and the characterization data are presented in Table 2-8. Table 1 Reaction Mixture Compositions and Reaction Conditions

Table 2 Analytical Results for UZM-15 Compositions

Table 4 X-Ray Diffraction Tables

Table 4 X-Ray Diffraction Tables

Table 5 X-Ray Diffraction Tables

Example 9

[0036] A portion of the Example 1 product was treated with an HCI solution, employing 2mL of 5 wt. % HCI per gram product. The slurry was heated to 95°C and held at that temperature for 1 hr. with stirring. The solid was collected and washed with de-ionized water and the above procedure was repeated. The washed material was dried at 95°C. The material was then calcined at 450°C for 17 hr. in air. The HCI treated and calcined material had a composition in terms of mole ratios Si/AI=13.09, Na/AI=0.01 , and N/AI=0.07. The BET surface area was determined to be 372 m2/g and the micropore volume was 0.13 cc/g. The x-ray diffraction pattern showed it to be UZM-15HS (Table 9).

Table 9

Example 10

[0037] To an aluminosilicate stock solution, 569.7 g, containing ETMAOH, Si and Al with an Si/AI ratio of 15.79 there was added a solution containing 32.41 g TMABr and 50.06 g KBr in 371.06 g deionized water. The resulting mixture was transferred to a Parr 2-liter stirred reactor and the mixture was reacted at 150°C for 48 hr and then cooled. The product was isolated by filtration, washed with deionized water, and dried.

[0038] The product was identified as UZM-15 via powder x-ray diffraction analysis. Representative diffraction lines in the pattern are shown below in Table 10. Elemental analysis showed the material to consist of the elemental mole ratios Si/AI = 11.07, K/AI = 0.81 , Na/AI = 0.03, N/AI = 1.06 and C/N = 4.89. A 75 g portion of the product was ammonium exchanged twice in an ammonium nitrate solution (75 g NH4N03 dissolved in 750 g deionized water) for 2 hr at 80°C. This ammonium exchanged product of the UZM-15 was used for several of the modifications below. A 50 g portion of this product was calcined at 500°C for 2 hr in N2 and then in air also at 500°C for another 6 hr. Elemental analyses showed the calcined, exchanged UZM-15 product to contain the elemental mole ratios Si/AI = 11.07, K/AI = 0.01 , and Na/AI = 0.003. The BET surface area determined by nitrogen adsorption measurements was 361 m2/g and the micropore volume was 0.09 cc/g.

Table 10

* impurity peaks

Example 11 [0039] An AFS solution was prepared by dissolving 1.47 g (NH4)2SiF6 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.

[0040] 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. Elemental analyses of the calcined product yielded an elemental mole ratio of Si/AI = 13.57, showing that 18% of the Al had been removed from the parent material. The BET surface area was 356 m2/g, while the micropore volume was 0.09 cc/g.

Table 11

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.

[0042] The product was identified as UZM-15HS by powder x-ray diffraction. Representative diffraction lines are given in Table 12 below. A portion of the sample was calcined in air at 375°C for 3 hr. The x-ray diffraction pattern of the calcined material was similar to the treated product and representative diffraction lines are also given in Table 12. Elemental analyses showed the calcined material to consist of the elemental mole ratios Si/AI = 15.88, K/AI = 0.02, and Na/AI = 0.007. The extent of dealumination is such that this material contains 28% less Al than the parent material from example 10. The BET surface area was 340 m2/g and the micropore volume was 0.093 cc/g.

Table 12

Example 13

[0043] 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.

[0044] The product was identified as UZM-15HS by powder x-ray diffraction analysis. Representative diffraction lines are given in Table 13. Elemental analysis showed the product to contain the elemental mole ratios Si/AI = 13.21 , K/AI = 0.03, and Na AI = 0.003. This dealumination resulted in the removal of 15% of the aluminum from the zeolite. The BET surface area was 329 m2/g and the micropore volume was 0.084 cc/g.

Table 13

Example 14 [0045] 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.

[0046] The acid extracted product was identified as UZM-15HS by powder x- ray diffraction analysis. Representative diffraction lines for the product are listed in Table 14. Elemental analysis showed the product to consist of the elemental mole ratio Si/AI =14.25. The BET surface area of the calcined material determined by nitrogen adsorption was 380 m2/g and the micropore volume was 0.11 cc/g.

[0047] Further dealumination of the above sample was carried out by steaming 60g of the sample at 600°C for 4 hrs with 50% steam using a horizontal steamer. Nitrogen adsorption showed the BET surface area of the steamed sample to be 275 m2/g, while the micropore volume is 0.063 cc/g. A 20 g portion of the steamed UZM-15HS was acid extracted using a solution prepared by diluting 19.7g HN03 (69%) in 350 g de-ionized water. The solution was heated to 90°C before the addition of the steamed UZM-15HS. The resulting slurry was stirred for 1 hr at 90°C. The product was isolated by filtration, washed with de-ionized water, and dried at 98°C. The modified product was determined to be UZM-15HS via x-ray powder diffraction analysis. Characteristic diffraction lines for the product are listed in Table 14. Elemental analyses showed the product to have the elemental mole ratio Si/AI = 20.1.

Table 14

Claims

WE CLAIM AS OUR INVENTION: 1. A microporous crystalline zeolite having a composition in the as- synthesized and anhydrous form in terms of mole ratios of the elements of:
M° R?A -*ExSi,Ot where M is at least one exchangeable cation selected from the group consisting of alkali and alkaline earth metals, "m" is the mole ratio of M to (Al + E) and varies from 0 to
2.0, R is at least one first quaternary organoammonium cation comprising at least one organic group having at least 2 carbon atoms, and optionally a second organoammonium cation selected from the group consisting of quaternary ammonium cations, protonated amines, protonated diamines, protonated alkanolamines, diquatemaryammonium cations, quaternized alkanolamines and mixtures thereof, "r" is the mole ratio of R to (Al + E) and has a value of 0.25 to 5.0, E is an element selected from the group consisting of Ga, Fe, In, Cr, B, and mixtures thereof, "x" is the mole fraction of E and varies from 0 to 1.0, "n" is the weighted average valence of M and has a value of +1 to +2, "p" is the weighted average valence of R and has a value of +1 to +2, "y" is the mole ratio of Si to (Al + E) and varies from 7 to 50 and "z" is the mole ratio of O to (Al + E) and has a value determined by the equation: z = (m*n + r»p + 3 + 4»y)/2; the zeolite characterized in that it has an x-ray diffraction pattern having at least the d-spacings and relative intensities set forth in Table A;
TABLE A
2. The zeolite of claim 1 where "m" is zero.
3. The zeolite of claim 3 where R is only a first organoammonium cation selected from the group consisting of diethyldimethylammonium, ethyltrimethylammonium, trimethylbutylammonium, propylethyldimethylammonium N,N,N'N',N',N'-hexamethyl-1 ,4 butanediammonium cations and mixtures thereof.
4. A process for preparing the microporous crystalline zeolite of claim 1 comprising forming a reaction mixture containing reactive sources of R, Al, Si and optionally E and/or M and heating the reaction mixture at a temperature of 85°C to 225°C, the reaction mixture having a composition expressed in terms of mole ratios of the oxides of: aM2 nO:bR2 pO:(1-c)Al2θ3:cE203:dSiθ2:eH20 where "a" has a value of 0 to 5.0, "b" has a value of 1.5 to 80, "c" has a value of 0 to 1.0, "d" has a value of 10 to 100, and "e" has a value of 100 to 15000.
5. A microporous crystalline zeolite having an empirical composition on an anhydrous basis in terms of mole ratios of the elements of:
M +AU-x)ExSiy Oz* where M1 is at least one exchangeable cation selected from the group consisting of alkali metals, 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, 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, n is the weighted average valence of M1 and has a value of +1 to +3, y' is the mole ratio of Si to (Al + E) and is greater than 7and z" is the mole ratio of O to (Al + E) and has a value determined by the equation: z" = (a • n + 3 + 4«y')/2; the zeolite characterized in that it has an x-ray diffraction pattern having at least the α-spacings and relative intensities set forth in Table B; TABLE B
6. The zeolite of claim 5 where y' has a value from 7 to 20,000.
7. A process for preparing the microporous crystalline zeolite of claim 5 comprising treating a starting zeolite at treating conditions thereby removing at least a portion of the framework aluminum and optionally inserting silicon into the framework to provide the microporous crystalline zeolite; the starting zeolite having an empirical formula on an anhydrous basis of: M R;P AI{X_X)EXS OZ where M' is an exchangeable cation selected from the group consisting of ammonium ion, hydrogen ion, alkali metals, alkaline earth metals, rare earth metals and mixtures thereof, n is the weighted average valence of M' and varies from +1 to +3, m' is the mole ratio of M' to (Al + E) and varies from 0 to 7.0, R is at least one first quaternary organoammonium cation comprising at least one organic group having at least 2 carbon atoms and optionally a second organoammonium cation selected from the group consisting of protonated amines, protonated diamines, protonated alkanolamines, quaternary ammonium ions, diquartemary ammonium ions, quaternized alkanolammonium ions and mixtures thereof, p is the average weighted valence of the organic cation and varies from +1 to +2, r' is the mole ratio of R to (Al + E) and varies from 0 to 7.0, r' + m' > 0, y' is the ratio of Si to (Al + E) and varies from 7 to 50 and z' is the mole ratio of O to (Al + E) and has a value given by the equation: z' = (nrf • n + r' • p + 3 + 4 • y')/2. the zeolite characterized in that it has an x-ray diffraction pattern having at least the c/-spacings and relative intensities set forth in Table A.
TABLE A
8. The process of claim 7 where the treating step is selected from the group consisting of treatment with a fluorosilicate solution or slurry, extraction with a weak, strong or complexing acid, calcination plus ion-exchange, calcination plus acid extraction, steaming plus ion-exchange, steaming plus acid extraction and mixtures thereof.
9. A hydrocarbon conversion process comprising contacting a hydrocarbon stream with a catalytic composite at hydrocarbon conversion conditions to give a converted product, the catalytic composite comprising the microporous crystalline zeolite of claim 1 or claim 5 or mixtures thereof.
10. The process of claim 9 where the hydrocarbon conversion process is selected from the group consisting of alkylation of aromatics, isomehzation of xylenes, naphtha cracking, ring opening, transalkylation, alkylation of isoparaffins, and isomehzation of ethyl benzene and olefin oligomerization.
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WO2005113440A1 (en) 2005-12-01
CN1972868B (en) 2010-04-21
JP5027655B2 (en) 2012-09-19

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