JP5646366B2 - UZM-16: crystalline aluminosilicate zeolitic material - Google Patents

Description

  This invention relates to an aluminosilicate zeolitic material designated as UZM-16. The material can be dealuminated to form UZM-16HS that exhibits different acidity, porosity and ion exchange properties. UZM-16 and UZM-16HS are useful in hydrocarbon conversion processes.

Zeolite is a crystalline aluminosilicate composition having porosity, and is formed by a tetrahedron in which AlO ₂ and SiO ₂ share a vertex. A number of natural and synthetic zeolites are used in various production processes. Synthetic zeolites are produced via hydrothermal synthesis using suitable Al, Si raw materials and structure-dominating materials such as alkali metals, alkaline earth metals, amines or organic ammonium cations. The structure-dominating substance is present in the pores of the zeolite and contributes to the special structure that is finally formed. These species, in combination with aluminum, balance the skeletal charge and serve as a spatial filter. Zeolite has uniform sized pores, has outstanding ion exchange performance, and is dispersed throughout the internal voids of the crystal without significant substitution with permanent zeolite crystal constituent atoms It has the feature of having the ability to reversibly desorb the adsorbed phase. Zeolites are used as catalysts for hydrocarbon conversion, which can be carried out on the outer surface or the inner surface of the pores.

Synthetic zeolite represented by zeolite T is prepared in the Na, K system and is disclosed by BRECK and Acara in US Pat. No. 2,950,952. Subsequent crystallographic studies using electron diffraction (JM Bennett and JA Gard, Nature, 214, 1005 (1967)) showed specificity and confirmed the specialities of the offretite and erionite skeletons. Classified as zeolite T as an internal growth of structure. Synthetic zeolites with offretite without erionite ingrowth were prepared in Na, K, TMA and K, TMA systems (R. Aiello and R. Barrer, J. Chem. Soc. (A), 1470, (1970)).
Rubin and Rosinsky were able to prepare materials related to erionite in the benzyltrimethylammonium (BzTMA), Na, K system (US Pat. No. 3,699,139). In a similar system of studies, an offretite without erionite X-ray diffraction lines was prepared (ML Occelli, RA Innes, SS Pollack, and JV Sanders, Zeolites, 7, 265 (1987)). An offretite, erionite, and offretite-erionite electron diffraction study with synthetic results involving six organic template systems, including BzTMA, characterized several defects occurring in this system (JV Sanders, ML Occelli, RA Innes, and SS Pollack, Studies in Surface and Catalysis, Y. Murakami, A. Iijima, and JW Ward, Elsevier, New York, 28,429 (1986)).

  We have prepared a zeolite designated UZM-16 which has some similarities to offretite but is given a unique structure and has sufficient differences. UZM-16 was prepared in benzyltrimethylamine (BzTMA) with a small amount of potassium added. The X-ray diffraction pattern was the same as that of offretite, but there was no line related to erionite, and the pattern centered around d = 21.5 including an unidentified peak extending in the range of d = 18 to 27%. A wide line in the pattern is included. This aspect was observed as light fringes in a lattice image with high resolution in the electron diffraction pattern of the crystal. In addition, in the electron diffraction of UZM-16, a peculiar periodicity not known for offretite and erionite was observed in the ab plane. UZM-16 has more intermediate pore properties than offretite. UZM-16 zeolite is also dealuminated to form UZM-16HS zeolite with different acidity, porosity, and ion exchange properties. Both UZM-16 and UZM-16HS can be used in various hydrocarbon conversion processes.

  The inventors have synthesized a new family of zeolites designated UZM-16. In the as-synthesized form, UZM-16 has a composition on an anhydride basis represented by the following formula.

  Wherein M is an exchangeable cation and is selected from the group consisting of alkali metals and alkaline earth metals. Specific examples of M cations include, but are not limited to, lithium, sodium, potassium, cesium, strontium, calcium, magnesium, barium and mixtures thereof, of which potassium and sodium are preferred. The value of “m” is the molar ratio of M to (Al + E) and varies between 0 and 0.75. R is from benzyltrimethylammonium (BzTMA) cation or BzTMA and quaternary ammonium, protonated amine, protonated diamine, protonated alkanolamine, diquaternary ammonium cation, quaternized alkanol ammonium cation and mixtures thereof. A combination with at least one organic ammonium cation selected from the group consisting of: The value of “r” is the molar ratio of R to (Al + E) and varies between 0.25 and 5.0. The value of “n” is the weighted average valence of M and varies between +1 and +2. The value of “p” is the weighted average valence of the organic cation and has a value between +1 and +2. E is a component present in the skeleton, and is selected from the group consisting of gallium, iron, boron, chromium, indium and mixtures thereof. The value of “x” is the mole fraction of E and varies between 0 and 1.0. The ratio of silicon to (Al + E) is represented by “y” and varies from greater than 3 to 25, while the molar ratio of O to (Al + E) is represented by “z”, the value of which is Is given by the equation.

  If M is only one metal, the weighted average atomization is the valence of that one metal, ie +1 or +2. However, if more than one M metal is present, it is the total amount shown by the following equation:

The weighted average valence “n” is given by the following equation:

  Similarly, if only one R organic cation is present, the weighted average valence is that of a single R cation, ie +1 or +2. When more than one R cation is present, the total amount of R is given by the following equation:

The weighted average valence “p” is given by the following equation:

These aluminosilicate zeolites are prepared by hydrothermal crystallization of a reaction mixture obtained by reacting a reaction raw material of R with aluminum, optional components E and / or M, and silicon in a liquid solvent. The raw material of aluminum includes, but is not limited to, aluminum alkoxide, precipitated alumina, aluminum hydroxide, aluminum salt, and aluminum metal. Specific examples of aluminum alkoxides include, but are not limited to, aluminum ortho sec-butoxide and aluminum orthoisopropoxide. Silica raw materials include, but are not limited to, tetraethylorthosilicate, fumed silica, precipitated silica and colloidal silica. A preferred silica source is Ultrasil VN SP (89% SiO ₂ ). The raw materials for M metal include, but are not limited to, alkali metal or alkaline earth metal halides, nitrates, acetates, and hydroxides. In particular, M metal occurs as an impurity in certain organic ammonium raw materials as well as certain silica raw materials. For example, Ludox AS-40 colloidal silica contains about 0.05% Na, while benzyltrimethylammonium hydroxide from Aldrich Chemical is contaminated with about 0.5% K. The raw materials for the E component include, but are not limited to, alkali borates, boric acid, precipitated gallium oxyhydroxide, gallium sulfate, iron chloride, chromium chloride, chromium nitrate, indium chloride, and indium nitrate. When benzyltrimethylammonium already described is a raw material for R, it is not limited, but includes hydroxide, chloride, bromide, iodide and fluoride compounds. R is also included as a blend of benzyltrimethylammonium and at least one other organic ammonium. When R is a quaternary ammonium cation or a quaternized alkanol ammonium, the raw material is a hydroxide, chloride, bromide or iodide compound. Specific examples include, but are not limited to, diethyldimethylammonium hydroxide, tetraethylammonium hydroxide, hexamethonium bromide, tetraethylammonium chloride, methyltriethylammonium hydroxide. Moreover, as a raw material of R, it may be a neutral amine, diamine, and alkanolamine. Specific examples include triethanolamine, triethylamine, and N, N, N ′, N′-tetramethyl-1,6-hexanediamine. In special cases, the reagent is used in the form of an aluminosilicate stock solution. These solutions consist of one or more organic ammonium hydroxides, and silicon and aluminum raw materials are made and stored in the form of a clear homogeneous solution and used as reagents. The reagent contains an aluminosilicate species, but typically no zeolite reaction mixture is found due to the individual sources of silicon and aluminum. The reagents generally do not contain alkalis or only contain alkalis to the extent of impurities from silicon, aluminum and organoaluminum hydroxide raw materials. One or more of these solutions are used for the synthesis of zeolite. If Al is replaced by E, the corresponding metallosilicate solution is used for synthesis.

  The reaction mixture containing the reaction raw materials of the desired components can be described in terms of the molar ratio of oxides below.

  Where “a” is the molar ratio of the oxide of M and has a value from 0 to 5, and “b” is the molar ratio of the oxide of R and has a value from 1 to 120. , "D" is a silica molar ratio having a value of 5 to 100, "c" is an E oxide molar ratio having a value of 0 to 1.0, and "e" "Is the molar ratio of water and has a value from 50 to 15000. The reaction mixture is reacted in a sealed reaction vessel under autogenous pressure at reaction temperatures of 80 ° C. to 160 ° C., preferably 95 ° C. to 125 ° C., under reaction conditions of 2 days to 30 days, preferably 5 days to 15 days. When crystallization is complete, the solid reactant is separated from the heterogeneous mixture by methods such as filtration or centrifugation, washed with ionic water, and air dried at an external temperature of 100 ° C. or lower.

Crystalline zeolites are characterized by a three-dimensional framework structure of at least SiO ₂ and AlO ₂ tetrahedral units. The characteristics of these zeolites are further demonstrated by their X-ray diffraction patterns. The X-ray diffraction pattern has at least diffraction lines having a d-space and relative intensity shown in Table A below.

  The as-synthesized zeolite contains some exchangeable or charge-balanced cations in its pores. Exchangeable cations can be exchanged with other cations, and in the case of organic cations, these can be removed by heating under controlled conditions. Ion exchange is carried out by contacting the zeolite with a solution containing the desired cation (in molar excess) under exchange conditions. The exchange conditions are a temperature of 15 ° C. to 100 ° C. and a time of 20 minutes to 50 hours. Firing conditions are a temperature of 300 ° C. to 600 ° C. and a time of 2 to 24 hours.

  A special treatment to remove organic cations that provide zeolite in ammonium form is ammonia calcination. In calcination in ammonia, it is presumed that the organic cation is decomposed into a proton form, which is neutralized by ammonia to form an ammonia cation. The resulting ammonium form zeolite can be further ion exchanged to other desired cations. Ammonia calcination conditions include treatment in an ammonia atmosphere between 250 ° C. and 600 ° C., preferably between 250 ° C. and 450 ° C., for 10 minutes to 5 hours. Optionally, the treatment can be performed in this temperature range, with a total time in an ammonia atmosphere of no more than 5 hours, and in multiple stages. At 500 ° C. or higher, the treatment must be performed within a short time of 30 minutes or less, preferably about 5 to 10 minutes. Long firing at 500 ° C. or higher causes unintentional dealumination in the desired ammonium ion exchange, and most of the organic ammonium decomposes at a lower temperature and becomes unnecessarily coarse.

The ion exchanged form of UZM-16 is shown by the following empirical formula.

  In the formula, R, x, y, and E are as described above, m ′ has a value of 0 to 5.75, and M ′ is an alkali metal, an alkaline earth metal, or a rare earth metal. A cation selected from the group consisting of hydrogen ions, ammonium ions, and mixtures thereof. n ′ is the weighted average valence of M ′ and varies from 1 to 3, r ′ has a value from 0 to 5.75, r ′ + m ′> 0, and p is the weighted average of R The valence varies from +1 to +2. The value of z 'is given by the following equation:

  The UZM-16 zeolite represented by formula (2) is further processed to remove aluminum and optionally insert silicon. This raises the Si / Al ratio and improves the acidity and ion exchange performance of the zeolite. These treatments can include a) contacting a fluorosilicate solution or slurry, b) acid extraction or ion exchange after calcination or steam treatment, c) acid extraction, or d) any of these treatments in any order. Can be done in combination.

  Fluorosilicate treatment is known and this treatment is described in US Pat. No. 6,200,463 which refers to US Pat. No. 4,711,770 which describes a method for treating zeolite with a fluorosilicate salt. A common condition for this treatment is to contact the zeolite with a solution containing a fluorosilicate salt such as ammonium fluorosilicate (AFS) at a temperature of 20 ° C to 90 ° C.

  Acids that can be used to perform the acid extraction include, but are not limited to, mineral acids, carboxylic acids, and mixtures thereof. Examples of these acids include sulfuric acid, nitric acid, ethylenediaminetetraacetic acid (EDTA), citric acid, and succinic acid. The acid concentration that can be used is not limited, but for convenience is between 1% and 80% by weight, preferably between 5% and 40%. The treatment conditions for the acid extraction are a temperature of 10 ° C. to 100 ° C. and a time of 10 minutes to 24 hours. After the acid treatment, the treated UZM-16 zeolite is separated by means such as filtration, washed with deionized water, and dried at ambient temperature up to 100 ° C. UZM-16 zeolite that has undergone one or more treatments in which the aluminum has been removed and silicon has been inserted into the tissue as needed is hereinafter referred to as UZM-16HS.

  The degree of dealumination is obtained from the acid extraction based on the cationic form of the starting UZM-16, as well as the acid concentration and time and temperature at which the extraction was performed. For example, when an organic cation is present in the starting UZM-16, the degree of dealumination is less than that of UZM-16 from which the organic cation has been removed. This is preferred when desalinization is desired at the immediate surface of UZM-16. As described above, convenient methods for removing organic cations include calcination, ammonia calcination, steam treatment and ion exchange. Calcination, ammonia calcination and ion exchange are as described above. Steam treatment conditions are 1% to 100% steam concentration, 400 ° C. to 850 ° C. for 10 minutes to 48 hours, and preferred treatment conditions are 500 ° C. to 600 ° C. treatment temperature, 5 to 50%. Vapor concentration, processing time of 1-2 hours.

  It should be noted that both calcination and steam treatment can not only remove organic cations but also dealumination. Thus, in other embodiments for dealumination, acid extraction after calcination or acid extraction after steam treatment. In yet another dealumination embodiment, the ion exchange treatment is performed after calcination or steam treatment of the starting UZM-16 zeolite. Of course, acid extraction can be performed both before and after ion exchange.

The ion exchange conditions are the same as those set above, that is, the treatment is performed at 15 to 100 ° C. for 20 minutes to 50 hours. The ion exchange can be carried out in a solution comprising a cation (M1 ′) selected from alkali metals, alkaline earth metals, rare earth metals, hydrogen ions, ammonium ions and mixtures thereof. By performing ion exchange, the M1 cation is exchanged for a second cation or a different M1 ′ cation. In a preferred embodiment, the steamed or calcined UZM-16HS composition 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 optionally includes mineral acids such as, but not limited to, nitric acid, hydrochloric acid, sulfuric acid and mixtures thereof. The concentration of the mineral acid is that amount necessary to provide the H ⁺ versus NH ₄ ⁺ ratio of 0-1. Due to the contribution of this ammonium ion exchange, any residue remaining in the pores after the steam treatment and / or calcination treatment is removed.

  As is apparent from the foregoing, with respect to effective processing conditions, the integrity of the crystal structure of the zeolite is substantially maintained during the dealumination process, and the zeolite is 50% of the initial crystallinity, preferably 70%. More preferably, 90% is maintained. A convenient technique for assessing the crystallinity of the product in relation to the crystallinity of the starting material is a comparison of the relative intensities of the d-spaces of the respective X-ray powder diffraction patterns. The starting material peak intensity value is used as a standard in arbitrary units on the background and compared to the corresponding peak intensity of the product. For example, when the total peak height value of the molecular sieve product is 85% of the starting zeolite peak intensity value, 85% of the crystallinity is maintained. In practice, only a few peaks are normally used for this purpose. Other indices for maintaining crystallinity are surface area and absorption capacity. These tests are suitable when the displacement metal changes significantly, i.e. when the absorption of X-rays by the sample increases, or when the peak content changes significantly, e.g., dealumination.

After performing the dealumination process as described above, UZM-16HS is usually dried and can be used in various processes as discussed below. The inventors have discovered that the properties of UZM-16HS can be further modified by one or more additional treatments. These treatments include steam treatment, calcination, and ion exchange, which are performed individually or in combination. Some of these combinations are, but not limited to, the following.
Steam treatment → Firing treatment → Ion exchange;
Firing treatment → Steam treatment → Ion exchange;
Ion exchange → Firing treatment → Steam treatment;
Ion exchange → Steam treatment → Baking treatment;
Steam treatment → Firing treatment;

  It should be pointed out that the above dealumination treatment does not necessarily give the same results to produce the zeolite of the present invention, but can be combined in any order. For example, a specific processing sequence such as AFS, acid extraction, steam, and calcination can be repeated as many times as necessary to obtain the desired properties. Of course, it is possible to repeat AFS two or more times before repeating one process without repeating other processes, for example, before performing a steam process or a baking process. Ultimately, the final properties of the UZM-16HS composition are determined by the order and / or repetition of processing.

  UZM-16HS prepared as described above is represented by an empirical formula on an anhydride basis.

  Here, Ml is at least one exchangeable cation selected from the group consisting of alkali, alkaline earth metal, rare earth metal, ammonium ion, hydrogen ion and mixtures thereof, and a is a molar ratio of M1 to (Al + E). N is a weighted average valence of M1 and has a value of +1 to +3, and E is selected from the group consisting of gallium, iron, boron, chromium, indium and mixtures thereof. X is a molar fraction of E having a value of 0 to 1.0, and y ′ is a Si to (Al + E) molar ratio greater than 3 and substantially up to (pure silica). Z "is the molar ratio of O to (Al + E), with the value determined by the equation below.

  Zeolite is characterized by having an X-ray diffraction pattern having at least an intensity relative to the d-space shown in Table B.

  Pure silica means that substantially all of the aluminum and / or E metal has been removed from the framework. It is known that it is virtually impossible to remove all aluminum and / or E metal. Numerically, the zeolite is substantially pure silica if y 'takes a value of at least 3,000, preferably 10,000, most preferably 20,000. Accordingly, the range of y ′ is 3 to 3,000, preferably greater than 10 to 3,000, 3 to 10,000, preferably greater than 10 to 10,000, and 3 to 20,000, preferably Is greater than 10 to 20,000.

  When specifying the ratio of zeolite starting materials or the adsorption characteristics of the zeolite product, the “anhydrous state” of the zeolite is intended unless otherwise specified. As used herein, the term “anhydrous state” refers to the fact that the zeolite lacks substantially physically adsorbed water and chemically adsorbed water.

  The zeolites of the present invention (UZM-16 and UZM-16HS) can separate a mixture of molecular species based on molecular size (kinetic diameter) or polarity of molecular species. If the separation of molecular species is by molecular size, the separation is performed by eliminating larger molecular species and allowing smaller molecular species to enter the space within the crystal. The kinetic diameters of various molecules such as oxygen, nitrogen, carbon, dioxide, carbon monoxide are published by DW Greck, Zeolite Molecular Sieves, John Wiley and Sons (1974) p.636. .

  The crystalline pore composition of the present invention (both UMZ-16 and UZM-16HS) can be used as a catalyst in a hydrocarbon conversion process, either as synthesized, after calcination or after any of the above treatments. Alternatively, it is used as a catalyst support. Hydrocarbon conversion processes are well known in the art and include ring opening, cracking, hydrogenolysis, alkylation of both aromatics and isoparaffins, isomerization, polymerization, reforming, dewaxing, hydrogenation, Includes dehydrogenation, transalkylation, dealkylation, hydration, dehydration, hydrotreatment, hydrodenitrogenation, hydrodesulfurization, methanation and syngas shift treatment. Specific reaction conditions and feed types used in these processing methods are described in US Pat. No. 4,310,440 and US Pat. No. 4,440,871. A preferred hydrocarbon conversion process is ring opening, whereby cyclic hydrocarbons are converted to non-cyclic hydrocarbons such as, for example, linear hydrocarbons or branched hydrocarbons.

Other reactions are catalyzed by these crystalline pore compositions, which include base-catalyzed side-chain alkylation, aldol condensation, olefin double bond isomerization and acetylene isomerization of alkylaromatic compounds. , Including alcohol dehydrogenation and olefin dimerization, oligomerization and conversion of alcohol to olefin. Suitable ion exchange forms of these materials catalyze the reduction of NO _x to N ₂ in automotive and industrial exhaust streams. Some reaction conditions and feed types used in these processes are described in U.S. Pat.No. 5,015,796 and by H. Pines, THE CHEMISTRY OF CATALYTIC HYDROCARBON CONVERSION, Academic Press (1981) pp.123-154, and references contained therein.

The X-ray patterns described in the following examples (and the above table) were obtained using standard X-ray powder diffraction techniques. The radiation source is a high intensity X-ray tube operated at 45 kV and 35 ma. The diffraction pattern from copper K-alpha radiation was obtained by appropriate computer-based techniques. The flatly compressed powder sample was subsequently scanned from 2 ° to 70 ° (2θ) at 2 ° (2θ) per minute. The lattice spacing (d) in angstrom units was obtained from the position of the diffraction peak expressed as 2θ when θ is the Bragg angle as seen from the digitized data. The intensity is measured from the concentrated location of the diffraction peak after subtracting the background. In the intensity, “I ₀ ” is the strongest line or peak, and “I” is each other peak.

As will be appreciated by those skilled in the art, parameter 2θ measurement methods are prone to human and mechanical errors, and these errors can combine to impose an uncertainty of ± 0.4 for each reported value of 2θ. it can. Needless to say, this uncertainty is recognized in the reported value of d-space calculated from the θ value. This inaccuracy is common throughout this field of technology and is not sufficient to rule out differences in the crystalline materials of the present invention and differences from prior art compositions. is there. In some reported X-ray patterns, the relative intensity of d-space is expressed as vs, s, m, and w, indicating that the intensity is very strong, strong, medium, and weak, respectively. With respect to 100 × I / I ₀ , the above symbolic representation is defined as w = 0-15, m = 15-60, s = 60-80, vs = 80-100. In one example, the purity of the synthesis product will be evaluated with respect to an X-ray powder diffraction pattern. Thus, for example, if the sample is stated to be pure, it is only intended that the absence of a line in the sample's X-ray pattern is due to crystalline impurities, and no amorphous material is present. Not that.

  The following examples are presented in order to more fully illustrate the present invention. These examples are illustrative only and do not place undue limitations on the broad scope of the invention as set forth in the appended claims.

The aluminosilicate reaction mixture was stirred vigorously by adding 2.33 g Al (Osec-Bu) ₃ (95 +%) to 63.35 g BzTMAOH (40%) and then 28 g colloidal silica (LUDOX ^™ AS). −40, 40% SiO ₂ ) was added. Next, 6 g of water was slowly added to the aluminosilicate reaction mixture and further mixed. This mixture was stirred at high speed and homogenized for an additional 30 minutes and distributed to three Teflon-coated autoclaves placed in an oven at 125 ° C., and the mixture was 3, 6, Digested for 10 days. The solid product was separated by filtration, washed with deionized water and dried at 95 ° C.

The product from all three reactions showed that the X-ray diffraction pattern was a zeolite identified as UZM-16. The diffraction lines exhibited by the 3-day sample are shown in Table 1 below. The BET surface area of the calcined material measured by N ₂ adsorption was 523 m ² / g and the pore volume was 0.26 cc / g.

  The difference between the offrite structure and UZM-16 was further identified by electron diffraction. As shown, a comparison of electron diffraction patterns along [001] of UZM-16 (FIG. 1B) and offretite (FIG. 1A) shown in the (001) and (110) directions in the plane is shown in FIG. . It is clear that the periodicity in the (110) direction in UZM-16 is different from the periodicity of offretite, and the interval is large by a factor of 3. The electron diffraction pattern of the offretite shown here is consistent with that shown in literature with the same orientation (JV Sanders, ML Occeli, RA Innes, and SS Pollack, Studies in Surface Science and Catalysis. Research on Chemistry and Catalysts), Ed. Y. Murakamai, A. Iijima, and JW Ward, Elsever, New York, 28,429, (1989)).

  Larger spacing is readily observed in the UZM-16 lattice image. FIG. 2 shows a lattice image of UZM-16 along [110]. The grating fringes extending vertically in the image correspond to the 19.3 species shown by reflection at 1/3 (110) in FIG. 1b. This interval is three times the (110) interval expected for offretite and will be 6.65 mm.

This example shows a modification by preparation of UZM-16, calcination to produce UZM-16HS, ion exchange, and steam treatment, and then a modification by acid extraction to produce another different UZM-16HS. Indicates. The aluminosilicate reaction mixture was prepared by adding 927.47 g BzTMAOH (40%) to 35.21 g Al (Osec-Bu) ₃ (95% +) and stirring vigorously. After the aluminum reagent was dissolved, 416.45 g of colloidal silica (LUDOX ^™ AS-40, 40% SiO ₂ ) was added and the resulting mixture was stirred at high speed and homogenized for 30 minutes. The mixture was crystallized at 125 ° C. for 6 days in a 2 L PARR ^™ stirred reactor under autogenous pressure. The solid product was isolated by filtration, washed with deionized water and dried at 95 ° C. Powder X-ray diffraction confirmed that the product was UZM-16. The diffraction lines showing the characteristics of the pattern are shown in Table 2 below. In elemental analysis, this parent UZM-16 material showed a Si / Al ratio of 5.83. 62.5 g portion of UZM-16 was first raised to 250 ° C. while raising the temperature at 1 ° C. per minute in a flowing nitrogen atmosphere, held at 250 ° C. for 2 hours, and further raised to 1 ° C. per minute for 500 minutes. The temperature was raised to 50 ° C. and maintained at 500 ° C. for 3 hours, and the atmosphere was changed to an air flow, and further maintained at 500 ° C. for 3 hours. The BET surface area of the fired material was 676 m ² / g, and the pore volume was 0.33 cc / g. A 51 g portion of the calcined material was ammonium exchanged by suspending in a solution containing 52 g NH ₄ NO ₃ dissolved in 500 g deionized water. The slurry was heated to 85 ° C. for 7 hours, then separated by filtration and washed thoroughly with deionized water. This exchange process was further repeated twice at 85 ° C. for 2 hours and a half.

A 40 g portion of ammonium exchange calcined UZM-16 was steamed at 600 ° C. for 2 hours with 50% steam using a horizontal steam processor. Powder X-ray diffraction was performed and the product was confirmed to be UZM-16HS. The characteristics of the diffraction line of this product are shown in Table 2. In nitrogen adsorption measurements, the steam treated ammonium-exchanged calcined UZM-16HS material showed a BET surface area of 424 m ² / g and a micropore volume of 0.20 cc / g.

A 20 g portion of UXM-16HS obtained by the steam treatment was further subjected to an acid treatment. The acidic solution was prepared by diluting 19.7 g HNO ₃ (69%) in 350 g deionized water. The solution was heated to 90 ° C. before adding the steamed UZM-16. The resulting slurry is stirred for 1 hour at 90 ° C. The product was isolated by filtration, washed with deionized water and dried at 98 ° C. The deformation product was identified as UZM-16HS by X-ray powder diffraction analysis. The characteristics of the diffraction line of this product are shown in Table 2. Elemental analysis by steam / acid cleaning showed the product to have a Si / Al ratio of 14.76.

An aluminosilicate reaction mixture was prepared by adding 35.21 g Al (Osec-Bu) ₃ (95 +%) to 927.47 g BzTMAOH (40%) and then stirring vigorously. After the aluminum reagent had dissolved, 416.45 g of colloidal silica (LUDOX ^™ AS-40, 40% SiO ₂ ) was added and the resulting mixture was stirred at high speed and homogenized for an additional 30 minutes. The mixture was crystallized at 105 ° C. for 12 days in a 2 L PARR ^™ stirred reactor at autogenous pressure. The solid product was isolated by filtration, washed with deionized water and dried at 95 ° C. It was confirmed by powder X-ray diffraction that the product was UZM-16. The diffraction lines showing the characteristics of the pattern are shown in Table 3 below. In elemental analysis, the parent UZM-16 composition showed a Si / Al element molar ratio of 5.7. 62.5 g of UZM-16 was first raised to 350 ° C. while raising the temperature at 1 ° C. per minute in a flowing nitrogen atmosphere, held at 350 ° C. for 1 hour, and 500 ° C. while raising the temperature at 1 ° C. per minute. The temperature was raised to 500 ° C. for 6 hours, the atmosphere was changed to an air flow, and the temperature was further maintained at 500 ° C. for 6 hours. The fired material has a BET surface area of 574 m ² / g and a pore volume of 0.24 cc / g. 98g portion of the baked product is ammonium exchanged by suspending in a solution containing 100 g NH ₄ NO _3, which was dissolved in deionized water 1000 ml.
The slurry is heated to 80 ° C. for 5 hours, then separated by filtration and washed thoroughly with deionized water. This exchange was repeated three more times at 85 ° C.

An 18 g portion of ammonium exchange calcined UZM-16 was steamed at 600 ° C. for 2 hours with 50% steam using a horizontal steam processor. A 12 g portion of the steamed material was further acid extracted. The acidic solution was prepared by diluting 10 g HNO ₃ (69%) in 300 g deionized water. The solution was heated to 90 ° C. before adding the steamed UZM-16. The resulting slurry was stirred for 1 hour at 90 ° C. The product was isolated by filtration, washed with deionized water and dried at 98 ° C. The deformation product was confirmed to be UZM-16HS by X-ray powder diffraction. The characteristics of the diffraction line of this product are shown in Table 3. Elemental analysis indicated that the final dealuminated product had a Si / Al ratio of 11.56. Nitrogen adsorption measurements showed a BET surface area of 466 m ² / g and a micropore volume of 0.19 cc / g.

1A and 1B are diagrams showing electron diffraction patterns obtained along the [110] direction of offretite and UZM-16 described in Example 1, respectively. FIG. 2 shows a lattice image obtained by the UZM-16 high-resolution electron microscope described in Example 1.

Claims (4)

A porous crystalline zeolite characterized in that the molar representation of the component on an anhydride basis has the composition of the following empirical formula:
Wherein M1 is at least one exchangeable cation selected from the group consisting of alkali metals, alkaline earth metals, rare earth metals, ammonium ions, hydrogen ions, and mixtures thereof, and a is M1 to Al . The molar ratio varies from 0.01 to 50 , n is the weighted average valence of M1 and varies from +1 to +3, y ′ is the molar ratio of Si to Al and is greater than 3. And z ″ is the molar ratio of O to Al , having the value given by the equation
The zeolite has an X-ray diffraction pattern having at least d-space and strength shown in Table B below, and is a porous crystalline zeolite.
  The zeolite according to claim 1, wherein y 'has a value of 3 to 20,000.   A method for converting a hydrocarbon comprising the step of contacting the hydrocarbon with a catalyst complex under hydrocarbon conversion conditions such that a conversion product is obtained, said catalyst complex according to claim 1. A method comprising a porous crystalline zeolite. The hydrocarbon conversion method is selected from the group consisting of alkylation of aromatic compounds, xylene isomerization, naphtha decomposition, ring opening, alkyl exchange, isoparaffin alkylation and ethylbenzene isomerization. The method according to claim 3 .