JPH0480856B2 - - Google Patents

Description

[Detailed description of the invention]

<Industrial Application Field> The present invention is directed to a novel synthetic crystalline silicophosphoalumi-nate molecular sieve called "MCM-9" containing aluminum, silicon and phosphorus in its framework structure. Concerning substances and their use in catalytic conversion reactions of organic compounds. The crystalline material of the present invention exhibits ion exchange properties and can be easily converted into a catalytically active material. BACKGROUND OF THE INVENTION Zeolite materials, both natural and synthetic, have been shown to have catalytic properties for various types of hydrocarbon conversion reactions. Certain zeolite materials are ordered, porous materials with a well-defined crystal structure, identified by X-ray diffraction, in which there are many small cavities that can be interconnected by many smaller pore channels or pores. It is a crystalline aluminosilicate. Within each particular zeolite, these cavities and pores are uniform in size. Because the dimensions of these pores allow adsorbed molecules of a certain size while rejecting molecules of larger size, these materials have become known as "molecular sieves" and have these properties. It is used in a variety of applications. Such molecular sieves include a wide variety of cation-containing crystalline aluminosilicates, both natural and synthetic. These aluminosilicates have tetrahedra that are crosslinked by sharing oxygen atoms, and the ratio of total (aluminum + silicon) atoms to oxygen atoms is 1:2.
A strong three-dimensional (reticular) structure of SiO ₄ and AlO ₄
It can be described as a framework structure. The ionic valence of the aluminum-containing tetrahedron is balanced by the presence of cations such as alkali metal or alkaline earth metal cations within the crystal. This is true for aluminum and various cations such as Ca/2,
It can be shown that the ratio to the number of Sr/2, Na, K or Li is equal to 1. One type of cation can be completely or partially exchanged for another type of cation using well-known ion exchange techniques. By using such cation exchange means, it is possible to change the properties of a given aluminosilicate by appropriately selecting the cation. Before dehydration, the spaces between the tetrahedra are occupied by water molecules. A wide variety of synthetic zeolites have been formed by prior art methods. Zeolites include Zeolite A (US Patent No. 2,882,243), Zeolite X (US Patent No. 2,882,244), Zeolite Y (US Patent No.
3130007), Zeolite ZK-5 (U.S. Patent No.
3247195), Zeolite ZK-4 (U.S. Patent No.
3314752), Zeolite ZSM-5 (U.S. Patent No.
3702886), Zeolite ZSM-11 (U.S. Patent No.
3709979), Zeolite ZSM-12 (U.S. Patent No.
3832449), Zeolite ZSM-20 (U.S. Patent No.
No. 3972983), Zeolite ZSM-35 (U.S. Patent No.
4016245), Zeolite ZSM-38 (U.S. Patent No.
No. 4,046,859), and zeolite ZSM-23 (U.S. Pat. No. 4,076,842), to name a few. The silicophosphoaluminate of the present invention is not an aluminosilicate zeolite, but it is a molecular sieve material with an ordered pore structure that admits certain molecules while rejecting others. Aluminum phosphate, for example, US Pat. No. 4,310,440
No. 4,385,994. Aluminum phosphate materials have an electrically neutral lattice and are therefore not effective as ion exchangers or as catalyst components. US Pat. No. 3,801,704 teaches aluminum phosphate treated in a manner to impart acidity. Canadian Patent No. 911416; No. 911417 and No.
The phosphorus-substituted zeolite of No. 911418 is “aluminosilicophosphate”
It is called zeolite. It has become clear that some of the phosphorus in it is occluded and is not structural. U.S. Pat. No. 4,363,748 describes silica and aluminum-calcium-cerium phosphate.
A combination of calcium and cerium phosphate is described as a low acid activity catalyst for oxidative dehydrogenation.
British Patent No. 2068253 covers silica and aluminum phosphate-calcium-tungsten (aluminum-calcium-tungsten).
(calcium-tungsten phosph-ate) as a low acid activity catalyst for oxidative dehydrogenation. U.S. Pat. No. 4,228,036 teaches an alumina-aluminum phosphate-silica matrix as an amorphous body mixed with zeolite for use as a cracking catalyst. US Pat. No. 3,213,035 teaches hardness improvement of aluminosilicate catalysts by treatment with phosphoric acid. This catalyst is amorphous. U.S. Pat. No. 2,876,266 describes an active silicophosph-oric acid or salt phase of amorphous material prepared by absorption of phosphoric acid with a preformed silicate or aluminosilicate. Aluminum phosphate is disclosed in U.S. Pat. No. 4,365,095;
No. 4361705; No. 4222896; No. 4210560; No.
No. 4179358; No. 4158621; No. 4071471; No.
No. 4014945, No. 3904550 and No. 3697550 are well known in the art. Because their neutral framework structure lacks ion exchange properties, they are used as catalyst supports or matrices. The crystalline silicophosphoaluminates synthesized herein have a molecular sieve framework structure with ion exchange properties and are easily and conveniently converted into materials with inherent catalytic activity. <Characteristics of the Invention> The present invention provides a novel synthetic crystalline silicophosphoaluminate molecular sieve material containing aluminum, silicon and phosphorus, hereinafter referred to as "MCM-9", and an organic, e.g. hydrocarbon, compound. and its use as a catalyst component in catalytic conversion reactions. Anhydrous crystalline MCM-9 has the general formula: M ^m+ _x/n : (AlO ₂ ) ^- _1-y : (PO ₂ ) ⁺ _1-x : (SiO ₂ ) _x+y : N ^n
- _y/o [However, M is a cation with valence m, N is an anion with valence n, and x and y are greater than -1 and less than +1, and (1) x is 0. In this case, y is not 0, (2) If y is 0, x is not 0, and (3) x + y is greater than 0.01 and less than 1. is the number of In the above composition, when x is greater than y, the silicophosphoaluminate is a cation converter that has potential use as an acidic catalyst. When x is less than y, the silicophosphoaluminate is an anion converter with potential use as a basic catalyst. Such MCM-9 crystalline material, in its calcined form, has a unique X-ray diffraction pattern as shown in Table 1-B below. MCM-9 as synthesized (“as synthesized”)
After the synthesis reaction, it is separated from the reaction mixture, washed with water,
In the dry form), the silicophosphoaluminate may also contain organic substances, A, and water molecules that are trapped and fill the microporous voids. Therefore, it has the general formula: vA: M ^m+ _x/n : (AlO ₂ ) _1-y : (PO ₂ )
_1-x : (SiO ₂ ) _x+y : N ^n- _y/o : wH ₂ O [where v is derived from the organic directing agent or solvent used during the synthesis of MCM-9 and is the number of moles of adsorbed organic material, A, filling the microporous voids, which can be removed by calcination, and w is, for example, from 0 to about 5 moles of H ₂ O; , and x and y are the numbers defined above], in its as-synthesized form, exhibits characteristic X-ray diffraction characteristics as shown in Table 1-A below. Has a pattern. The crystalline silicophosphoaluminate of the present invention is a unique material that exhibits a combination of catalytic, adsorption, and ion exchange properties that distinguish it from known aluminum phosphates. The silicophosaluminate materials of the present invention have a molecular weight of less than 1 and greater than 0, such as from about 0.001 to about
At a silicon/(aluminum and phosphorus) atomic ratio of 0.99, it exhibits unique and useful catalytic, adsorption, and shape-selective properties. It is well known that aluminum phosphate exhibits a phosphorus/aluminum atomic ratio of only 0.8 to 1.2 and contains no silicon. Also, phosphorus-substituted zeolite compositions, sometimes called "aluminosilicophosphate zeolites," have a
Silicon/aluminum atomic ratio of 8.0 and greater than 0
It has a phosphorus/aluminum atomic ratio of up to 1.0. The original cations of as-synthesized MCM-9 can be replaced, at least in part, by ion exchange with other ions, by methods well known to those skilled in the art. Preferred substituted cations include metal ions,
Included are hydrogen ions, hydrogen precursors such as ammonium ions, and mixtures thereof. Particularly preferred cations are those that render MCM-9 catalytically active, particularly with respect to hydrocarbon conversion reactions. These include hydrogen, rare earth metals, and
Group, Group A, Group A, Group A, Group B,
Group B, Group B, Group B and Group metals are included. A typical ion exchange method is to contact synthetic MCM-9 with a salt of one or more desired substituted cations. Examples of such salts include halides such as chlorides, nitrates and sulfates. The morphology of the framework structure of MCM-9, which contains silicon, phosphorus, and aluminum with tetrahedrally coordinated structural positions, is similar to the synthetic aluminum phosphate described in US Pat. No. 4,310,440. The crystalline MCM-9 of the present invention can be effectively heat treated before or after ion exchange. This heat treatment heats the silicophosphoaluminate in an atmosphere such as air, nitrogen, hydrogen, steam, etc. from about 300°C to about 1100°C.
, preferably from about 350°C to about 750°C, for a period of from about 1 hour to about 20 hours. Although reduced pressure or increased pressure can be used for this heat treatment, normal pressure is preferred for convenience. MCM-9 exhibits a distinct X-ray diffraction pattern that distinguishes it from other crystalline materials. As-synthesized
The X-ray diffraction pattern of MCM-9 has the following characteristic values:

[Table] Table 1-B shows MCM-9 calcination (450℃ in nitrogen,
The figure shows the characteristic diffraction lines of MCM-9 in the form of MCM-9 (at normal pressure for 4 hours).

【table】

Table: These X-ray diffraction data were collected using a Rigaku X-ray system using copper K-α radiation. The position of the peak in 2θ° (θ is Bragg's angle) was measured by step scanning with a 2θ interval of 0.02° and a measurement time of 1 second at each step. The lattice spacing, d, measured in angstroms (A), and the relative strength of the line, minus the background ground, / ₀ (where ₀ is 1/100 of the strength of the strongest line) are calculated using the profile fitting method. lead. The relative strength is the symbol vs = extremely strong (75−100
%), s = strong (50-74%), m = moderate (25-49
%) and w=weak (0-24%).
It should be understood that this X-ray diffraction pattern is unique to all types of MCM-9 compositions synthesized in accordance with the present invention. Ion exchange of the cations of the silicophosphoaluminate with other ions gives essentially the same X-ray diffraction pattern with some slight shifts in lattice spacing and changes in relative intensity. Other slight variations may occur depending on the silicon/aluminum and phosphorus/aluminum ratios of the individual samples and the degree of thermal history. The crystalline MCM-9 material of the present invention can be converted into a dry, hydrogen form by the heat treatment described above, either in an organic cation-containing form or in a hydrogen ion precursor form obtained from ion exchange. Generally, the silicophosphoaluminates of the present invention are prepared from a two-phase reaction mixture comprising sources of aluminum, phosphorus and silicon and an organic directing agent(s), and a substantially water-immiscible organic solvent. Can be manufactured. The overall molar composition of the two-phase synthesis mixture in terms of oxide and organic components is as follows. ( _A ) _a : ( _M2O ) _b : ( _Al2O3 ) _{c :} ( _SiO2 ) _d : ( _P2O5 ) _e : (solvent) _f : (anion source) _g : ( _H2O ) _o However, a/(c+d+e) is less than 4,
b/(c+d+e) is less than 2, and d/(c
+e) is less than 2, and f/(c+d+e) is
0.1 to 15, g/(c+d+e) is less than 2, and h/(c+d+e) is 3 to
It is 150. A "solvent" is an organic solvent, and "A" is an organic compound or substance derived from an organic directing agent or an organic solvent.
The anions are not necessarily added separately to the two-phase system, but may or may not appear in the product crystals from one or more of the other component sources. The reaction conditions are a rate of 5°C to 200°C per hour, approximately 80°C
°C to about 300 °C and at that temperature for about 5 hours to about 300 °C until crystals of MCM-9 form.
It consists of carefully heating the aforementioned reaction mixture for a period of 500 hours. A more preferred temperature range is approximately
100°C to about 200°C, and the time at such temperature range is about 24 hours to about 168 hours. The PH must be carefully controlled from about 2 to about 9 while heating the reaction mixture and holding it at the desired temperature. Control of PH can be achieved by adjusting the concentration of added organic and/or inorganic base. The reaction is carried out until the desired MCM-9 crystals are formed. The crystalline product is recovered by separating it from the reaction medium by cooling the whole to room temperature, filtering and washing with water before drying. The above reaction mixture composition can be prepared using materials that provide the appropriate components. The water phase components are elemental silicon,
It is possible to include sources of phosphorus or aluminum that are not present in the organic phase. The organic phase contains an organic solvent and at least one source of the elements silicon, phosphorus or aluminum which is insoluble in the aqueous phase under the reaction conditions. The aqueous phase also contains the necessary organic and/or inorganic directing agents. Useful sources of aluminum include, by way of non-limiting example, known forms of aluminum oxide or hydroxide, organic or inorganic salts or compounds. Useful silicon sources include, by way of non-limiting example, known forms of silicon dioxide or silicic acid, silicon alkoxy- or other compounds. Useful sources of phosphorus include, by way of non-limiting example, known forms of phosphorous or oxidized phosphorus, phosphates and cophosphates, and organic derivatives of phosphorus. The organic solvent is a _C5 - _C10 alcohol or a liquid organic compound that is substantially immiscible with water. The organic directing agent is an organic mono-, di-, or polyamine and has _the following formula: R ₄ M ⁺ X ^- or (R ₃ M ⁺ R′M ⁺ R ₃ ) atomic alkyl, heteroalkyl of 1 to 20 carbon atoms, aryl, heteroaryl, cycloalkyl of 3 to 6 carbon atoms, cycloheteroalkyl of 3 to 6 carbon atoms, or combinations thereof. M is a tetracoordinate element (e.g. nitrogen, phosphorus, arsenic, antimony or bismuth) or a heteroatom in an alicyclic, heteroalicyclic or heteroaromatic structure (e.g. N, O, S, Se, P ,
As, etc.); and X is an anion (e.g.,
fluoride, chloride, bromide, iodide, hydroxide,
acetates, sulfates, carboxylates, etc.). When M is a heteroatom in a cycloaliphatic, heterocycloaliphatic, or heteroaromatic structure, such structure may include, by way of non-limiting example,

[Formula] or [However, R′ is alkyl of 1 to 20 carbon atoms,
heteroalkyl, aryl, heteroaryl of 1 to 20 carbon atoms, cycloalkyl of 3 to 6 carbon atoms, or cycloheteroalkyl of 3 to 6 carbon atoms]. Particularly preferred directing agents for the method of the invention include those in which R is 1 to 4 carbon atoms and M is nitrogen;
and onium compounds as defined above where X is a halide or hydroxide are included. Non-limiting examples of these include tetrapropylammonium hydroxide, tetraethylammonium hydroxide and tetrapropylammonium bromide. Inorganic hydroxides or salts of suitable composition can also be used as supplemental directing agents, non-limiting examples being CsOH, KOH, CsCl, KCl and the like. MCM-9 crystals produced according to the present invention can be formed into a wide variety of particle sizes. Generally speaking, the particles are in the form of powders, granules, or molded articles, such as extrudates having a particle size that passes well through a 2-mesh (Tyler) sieve and retains on a 400-mesh (Tyler) sieve. I can do it. When the catalyst is molded, for example, by extrusion molding, the catalyst can be extruded before being dried, or it can be partially dried and then extruded. It would be desirable to composite the new MCM-9 crystals with other materials or matrices that are resistant to the temperatures and other conditions used in various organic conversion processes. Such materials include active and inert materials and synthetic or naturally occurring zeolites as well as inorganic materials such as clays, silica and/or metal oxides such as alumina. The latter may be of natural origin or in the form of a gel-like precipitate or a gel containing a mixture of silica and metal oxides. Catalyst compositions containing MCM-9 crystals generally consist of about 1 to 90% by weight MCM-9 material and about 10 to 99% by weight matrix material. More particularly, such catalysts contain about 2 to 80% new
It consists of MCM-9 material and about 20-98% by weight matrix. The use of active materials in combination with the novel MCM-9 crystals tends to alter the overall conversion and/or selectivity of the catalyst in certain organic conversion processes. Inert substances serve well as diluents to control the amount of conversion in a given reaction, so that the product can be obtained economically and regularly without the use of other means of controlling the rate of reaction. . These materials may be incorporated into naturally occurring clays such as bentonite and kaolin to improve the crush strength of the catalyst under productive operating conditions. The materials, ie clays, oxides, etc., act as binders for the catalyst. Since it is desirable to prevent catalysts from disintegrating into powdered materials for commercial production use, it would be desirable to provide catalysts with good crush strength. These clay binders are normally used only to improve the crush strength of the overall catalyst. Naturally occurring clays that can be composited with the new crystals include montmorionite and the kallion family, which includes subbentonite and kaolin, known as Dixie, McNamee, Jiyojia and Florida clays, or whose main mineral component is halloysite, Includes other minerals that are kaolinite, zitzkite, nacrite, or anauxite. Such clay can be used in its crude, as-mined state, or in calcined, acid-treated or chemically modified form. In addition to the aforementioned materials, crystalline MCM-9 may be made of porous matrix materials such as aluminum phosphate, silica-alumina, silica-magnesia, silica-zirconia, silica-thoria, silica-beryria,
It can be composited with silica-titania and ternary compositions such as silica-alumina-thoria, silica-alumina-zirconia, silica-alumina-magnesia and silica-magnesia-zirconia. The relative proportions of the finely divided crystalline material and the inorganic oxide gel matrix range from about 1 to about 90% by weight of the composite, and more commonly, especially when the composite is made in bead form, about Crystal contents vary widely, ranging from 2 to about 80% by weight. When the catalytically active form of the novel MCM-9 material of the present invention is used as a catalyst component, the catalyst likely contains an additional hydrogenation component, and the reformed feedstock is heated between about 370°C and about 540°C. Temperature, approximately 100 psig
from about 1000 psig (791 to 6996 kPa), preferably from about 200 psig to about 700 psig (1480 to 4928 kPa)
, a liquid hourly space velocity of about 0.1 to about 10, preferably about 0.5 to about 4, and a hydrogen/hydrocarbon molar ratio of about 1 to about 20, preferably about 4 to about 12. Catalysts comprising the MCM-9 material of the present invention are n-
It can also be used for the hydrogenation isomerization of paraffin. Such hydroisomerization is carried out at a temperature of from about 90°C to about 375°C, preferably from about 145°C to about 290°C, and at a temperature of from about 0.01 to about 2
, preferably using a liquid hourly space velocity of about 0.25 to about 0.50 and a hydrogen/hydrocarbon molar ratio of about 1:1 to about 5:1. Furthermore, such a catalyst is about
Temperatures from 200°C to about 480°C can be used for olefin or aromatic isomerization. Such catalysts can also be used to lower the pour point of light oil. This reaction has a liquid hourly space velocity of about 10 to about 30 and a
It is carried out at a temperature of 425°C to about 595°C. MCM of the present invention containing a metal such as platinum
Other reactions that can be accomplished using catalysts consisting of (eg dimethyl ether) to hydrocarbons and the alkylation of aromatics in the presence of an alkylating agent (eg ethylene). In order to more fully illustrate the nature of the invention and the manner in which it may be carried out, the following examples are presented. Example When obtaining adsorption data in order to compare the adsorption capacities of various adsorbents, it was obtained as follows. A weighed sample of the calcined adsorbent was contacted with a flowing stream of 25°C equilibrium vapor of adsorbate mixed with dry nitrogen. The adsorbate is water vapor, n-hexane, 2-methylbentane, xylene or cyclohexane vapor. For adsorbates other than o-xylene and water, the sample temperature was maintained at 90°C. The temperature was 120°C for o-xylene and 60°C for water. The weight gain was determined gravimetrically and converted to adsorption capacity of the sample as weight percent of calcined adsorbent. When alpha values are tested, the alpha values are a rough measure of the catalytic cracking activity of the catalyst compared to standard catalysts, and the alpha values are the relative rate constants (rate of n-hexane conversion per unit time, per volume of catalyst). ). The activity of the highly active silica-alumina decomposition catalyst is based on Alpha's 1 (rate constant = 0.016 sec ^-1 ). In the case of zeolite HZSM-5, only 174 ppm of tetrahedrally coordinated Al ₂ O ₃ was required to give an alpha value of 1.
The alpha test is described in U.S. Patent No. 3,354,078 and in The Journal of Catalyst.
Journal of Catalysis, Volume 4, Pages 522-529 (August 1965). Ion exchange capacity was tested by titrating the gaseous ammonia generated during temperature-programmed decomposition of the ammonium form of silicophosphoaluminate with a sulfamic acid solution. This method is described by GT Kerr and AW Chester in Thermochimica Acta, Vol. 3, pp. 113-124 (1971). Example 1 An organic phase consisting of 10 g of Si( _OC2H5 ) ₄ and 60 g of 1-hexanol, and _{23.1 g} of _H3PO4 (85%),
A two-phase reaction mixture was prepared using an aqueous phase consisting of 13.7 _g Al2O3, 10.1 g di-n-propylamine _, and 59.6 g _H2O . The reaction mixture as a whole is atomic%
It had a composition containing 9.3% Si, 38.8% P and 51.9% Al. The directing agent was di-n-propylamine. The starting PH was between 5 and 7. The reaction mixture was heated to 130°C at 50°C/hr and held at that temperature for 24 hours. Next, heat it to 200℃,
The temperature was maintained for 24 hours until crystals of silicophosphoaluminate formed. The crystalline product was separated from the reaction mixture by filtration, washed with water and dried at 80°C. Analysis of the product crystals revealed 13.1% Si, 42.7% P and 44.2% Al.
It contained atomic percent of When a sample of the as-synthesized silicophosphoaluminate was subjected to X-ray analysis, it was revealed that it had a molecular sieve structure exhibiting the diffraction lines shown in Table 2.

【table】

Table: Example 2 The synthesis of Example 1 was repeated, keeping the reaction mixture at 200° C. for 48 hours. Crystalline silicophosphoaluminate contains 14.5% Si, 42.4% P and 43.1% in atomic percent
Analysis revealed that it contains Al. When a sample of the as-synthesized silicophosphoaluminate was subjected to X-ray analysis, it was found to have a molecular sieve structure exhibiting the diffraction lines shown in Table 3.

【table】

Table: Example 3 A portion of the crystalline silicophosphoaluminate of Example 2 was calcined in nitrogen at 450° C. for 4 hours and then subjected to X-ray analysis. The results are shown in Table 4.

【table】

[Table] Example 4 A portion of the crystalline silicophosphoaluminate of Example 1 was calcined in the manner described in Example 3, and
Ammonium exchange was performed using 1M NH ₄ NO ₃ solution. The ion exchange capacity, measured from ammonia evolution, was determined to be 0.22 meq/g. Example 5 The ion exchange capacity of the crystalline silicophosphoaluminate of Example 2 was determined as described in Example 4.
It was 0.105meq/g. Example 6 A portion of the crystalline silicophosphoaluminate of Example 5 was tested in an alpha experiment. Its alpha value was 1.4. Example 7 A portion of the crystalline silicophosphoaluminate of Example 5 was prepared using a constraint factor (as disclosed in U.S. Pat. No. 4,385,195, herein incorporated by reference).
index) was used to conduct the test. The constraint coefficient is
0.4, indicating the presence of large pores. Example 8 A sample of the crystalline silicophosphoaluminate calcined product of Example 1 was evaluated for adsorption properties to confirm its molecular sieve properties. The results, expressed in weight percent, were as follows: Water (60°C): 1.73 N-hexane (90°C): 1.00 Example 9 A sample of the calcined product of Example 2 was also evaluated for adsorption properties. The results expressed in weight percent were as follows: Water (60°C): 3.8 n-hexane (90°C): 1.1

Claims (1)

[Scope of Claims] 1. Containing silicon, phosphorus, and aluminum, characterized in that an X-ray diffraction pattern measured as synthesized exhibits a unique X-ray diffraction pattern shown in Table 1-A herein. Synthetic crystalline substance. 2. The synthetic crystalline material of claim 1, wherein the X-ray diffraction pattern measured after calcination exhibits the characteristic X-ray diffraction pattern shown in Table 1-B herein. Tertiary formula: vA: M ^m+ _x/n : (AlO ₂ ) ^- _1-y : (PO ₂
) ⁺ _1-x : (SiO ₂ ) _x+y : N ^n- _y/o : wH ₂ O [However, M is a cation with a valence of m, N is an anion with a valence of n, and A is an organic a directing agent, v is the number of moles of A, w is the number of moles of H ₂ O, and x and y are greater than -1 and less than +1, and (1) when x is 0; is a number that satisfies the following relationships: y is not 0, (2) if y is 0, x is not 0, and (3) x+y is greater than 0.001 and less than 1. A synthetic crystalline material according to claim 1, having the composition: 4 The following formula in anhydrous state: M ^m+ _x/n : (AlO ₂ ) ^- _1-y : (PO ₂ ) ⁺ _1-x : (SiO ₂ ) _x+y : N ^n
- _y/o [where M is a cation of valence m, N is an anion of valence n, and x and y are -1
greater than and less than +1, and (1) if x is 0, y is not 0; (2) if y is 0, then x is not 0; and (3) x+y is 0.001. The synthetic crystalline material according to claim 2, which has a composition of: greater than and less than 1, satisfying the following relationships. 5. At least a portion of the original cation, hydrogen and hydrogen precursors, rare earth metals and groups A, A, A, B of the Periodic Table of the Elements.
Any one of claims 1 to 4 substituted with at least one cation selected from the group consisting of metals of Group B, Group B, Group B, and Group B. The crystalline substance described. 6. A synthetic crystalline material containing silicon, phosphorus, and aluminum, characterized in that an X-ray diffraction pattern measured as synthesized exhibits a unique X-ray diffraction pattern shown in Table 1-A herein. hydrogen and hydrogen precursors, rare earth metals and group IA of the periodic table of the elements, group A,
Substituted with at least one cation selected from the group consisting of Group A, Group A, Group B, Group B, Group B, Group B, and Group metals,
A crystalline substance obtained by heat treatment. 7. A synthetic crystalline material containing silicon, phosphorus, and aluminum, characterized in that the X-ray diffraction pattern measured as synthesized exhibits the characteristic X-ray diffraction pattern shown in Table 1-A herein. A catalyst consisting of 8 Claim No. 7 for conversion of organic compounds
Catalysts as described in section.