JPS60151219A - Crystalline silicophosphoaluminate - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

Detailed Description of the Invention <Industrial Application Field> The present invention is a novel synthetic crystalline silicophosphoaluminate (called "MCM-10") containing aluminum, silicon and phosphorus in its framework structure. silicophos
phoalumi-nate) molecular sheep materials 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.

PRIOR ART Zeolite materials, both natural and synthetic, have catalytic properties for various types of hydrocarbon conversion reactions.
) has been shown so far. 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 interconnected by many smaller pore channels or pores. It is a crystalline aluminosilicate. In each particular zeolite (well, the size of these cavities and pores are uniform; the dimensions of these pores accept adsorbed molecules of a certain size while rejecting molecules of larger size). , these substances are called “molecular sheep” (
These properties have come to be known as molecular sieves and have been used in a variety of ways to apply these properties.

Such molecular sieves include natural and synthetic products.
A wide variety of cation-containing crystalline aluminosilicates are included. These aluminosilicates (well, 5i06 and AI!04, in which the tetrahedrons are crosslinked by sharing oxygen atoms, and the ratio of the total number of (aluminum + silicon) atoms to oxygen atoms is 1:2. It can be described as a strong three-dimensional (slender) 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 means that aluminum and various cations such as CCLA, S r /l
, Ha, 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 means of such cation exchange, 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 (U.S. Pat. No. 2,882,243), Zeolite X (U.S. Pat. No. 2,882.244), Zeolite Y (U.S. Pat. No.
, 130,007), Zeolite ZK-5 <U.S. Patent No. 3,247,195), Zeolite ZK-4C U.S. Patent No. 3,314,752), Zeolite ZSM-5
(U.S. Patent No. 3,702,886), Zeolite ZS
M-11 (U.S. Patent No. 3,709,979), Zeolite ZSM-12 (U.S. Patent No. 3,832,449)
, Zeolite ZSM-20C U.S. Patent No. 3,972,9
No. 83), Zeolite ZSM-35 (U.S. Pat. No. 4,0
No. 16,245), Zeolite ZSM-38C U.S. Pat. No. 4,046,859), and Zeolite ZSM-2
3C U.S. Pat. No. 4,076,842), to name a few, may be named by letters or convenient symbols.

The silicophosphoaluminate of the present invention is not an aluminosilicate-zeolite, but it is a molecular sieve material that has an ordered pore structure that accepts some glaze molecules while rejecting others.

Aluminum phosphate is an example of U.S. Pat. No. 4,310,44.
No. 0 and No. 4,385,994. Aluminum phosphate materials have an electrically neutral lattice and are therefore not effective as ion exchangers or as catalyst components. U.S. Pat. No. 3,801,704 teaches aluminum phosphate treated in a manner to impart acidity.

Canadian Patent No. 911,416: The phosphorus-substituted zeolites of Canadian Patent Nos. 911,417 and 911.418 are "aluminosilicophosphates"? (Alwminosilic
ophosphate) - 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 (alum, inum-
calciwm-ceτ1urn phosphate
The force combination is described as a low acid activity catalyst for oxidative dehydrogenation. British Patent No. 2,068,253 discloses that silica and aluminum-calcium phosphate
iniurn-calcium, -tungsten
phosphate) as a low acid activity catalyst for oxidative dehydrogenation. U.S. Patent 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 Patent 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 discloses an amorphous material prepared by the absorption of phosphoric acid by a preformed silicate or aluminosilicate.
ophospho-ric acid) or salt phase.

Aluminum phosphate is disclosed in US Pat. No. 4,365,095: No. 4
．． 361,705'P18; No. 4,222,896;
No. 4.210.560: No. 4179358; No. 4,
No. 158,621; No. 4.071,471; No. 4.0
No. 14,945; No. 3,904,550, they are used as catalyst supports or IJ socks. The crystalline silicophosphoaluminate synthesized herein has a molecular sieve skeleton structure with ion exchange properties and is easily and selectively converted into a substance having inherent catalytic activity ya'.

Novel synthetic crystalline silicophosphoaluminate molecular sheep material containing silicon and phosphorus and organic,
For example, it relates to its use as a catalyst component in catalytic conversion reactions of hydrocarbons and compounds.

Anhydrous crystalline MC! 1l-10 is a general formula: % formula %: [where M is a cation with a valence of m, N is an anion with a valence of 1, and X and y are +1 in dog than -1
and (1) when z is 00, y is not 0, (2) when y is 0, X is not 0, and (31Al/P atomic ratio is greater than 1) In the case, (+, 10y) is 0.001
is greater than and y+0.6e is less than 0.4,
And if the atomic ratio of (43All/P is less than 1), (
x + y) is larger than 0.001, and z+〇, 5y is smaller than 0.5, which is a number that satisfies the following relationships].

In the above composition, when X is greater than y, the silicophosphoalbanate is a cation exchanger with potential use as an acidic catalyst. When X is less than y, the silicophosphoaluminate is an anion exchanger with potential use as a basic catalyst. Such 44 cM-10 crystalline material, in its calcined form, has a unique Xn1 diffraction pattern as shown in unwritten Table 1-B.

The synthesized 11 of Afcu-1o ("as-synthesized" may also contain combined organic materials, A1 and water molecules. Therefore, it has the general formula: % formula % [where τ is The moles of adsorbed organic material, A, arising from the organic directing agent or solvent used and filling the microporous voids of MCM-10, can be removed by baking, and W is e.g. It has a unique X-ray diffraction pattern as shown in unwritten Table 1-A.

The crystalline silicophosphoaluminate of the present invention is a unique material that exhibits a combination of catalytic attachment and ion exchange properties that distinguish it from known aluminum phosphates.

The silicophosphoaluminate materials of the present invention have less than one
For example, about 0. Silicon/(aluminum and phosphorus) atomic ratios of UOl to about 0.99 exhibit unique and useful catalyst adhesion and shape-selective properties. When synthesized with aluminum/phosphorus atomic ratios greater than 1, crystalline silicophosphoaluminates exhibit aluminum/silicon atomic ratios greater than 1.5 and usually in the range of 1.6 to 600. aluminum/
When the phosphorus atomic ratio is less than 1, it indicates a phosphorus/silicon atomic ratio greater than 1, usually in the range of 1.2 to 600. 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 referred to as "aluminosilicophosphate zeolites," have silicon/aluminum atomic ratios of 0.66 to aO and phosphorus/aluminum atomic ratios greater than O up to 1.0.

The original cations of as-synthesized MCM-10 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, hydrogen ions, hydrogen precursors such as ammonium ions, and mixtures thereof.

Particularly preferred cations are those that render MCM-10 catalytically active, particularly with respect to hydrocarbon conversion reactions. These include hydrogen, rare metals, Group 1A, Group ■A, Group ■A, Group 1VA, Group 1B of the periodic table of elements, and mUB.
Tribe? Included are group amB, group 1VB and group 1 metals.

A typical ion exchange method is to contact synthetic MCM-10 with a salt of one or more desired substituted cations. Examples of such salts include halides such as chlorides, nitrates and sulfates.

The crystalline MCM-10 of the present invention can be effectively heat treated before or after ion exchange. This heat treatment involves heating the silicophosphoaluminate to a temperature of about 300°C to about 1100°C, preferably about 350°C to about 750°C, in an atmosphere such as air, nitrogen, hydrogen, steam, etc., for about 1 hour to about 1 hour. 20
It is carried out by heating for a period of time. Although reduced pressure or increased pressure can be used for this heat treatment, normal pressure is preferred from the point of view of convenience.

MCM-1O shows a distinct X-ray diffraction pattern that distinguishes it from other crystalline materials.
The X-ray diffraction pattern of has the following characteristic values: Table 1 - A ll, 85±o, i w l 0.20±0.1 5-vs 7°65±0.05 vs 6.86±( LO5m 5.93±0.05 w 5゜67±0.05 m 5, 110, (J 5 m 5.01±0.05 m 4.49±0.05 w 4.37±0.05 vs - 4,09±0.05 vs 3.95±0.03 w 3.80±0.03 vs 3.73±(LO3w 3.43±0.03 m 3.22±0.03 m 3. 16 0.03 w l, 99 ± 0.02 w l, 97 ± 0.02 w l, 93 ± 0.02 vs 2.85 ± (LO2m 2.75 100-02 w l, 68 ± (102 m 2 .59±0.02 w Table i-B shows the characteristic diffraction of MCM-210 in the calcined form of MCM-10 (450° C. in nitrogen, atmospheric pressure, 4 hours).

Table 1-B 11.75±0.1 w lo, 11shio, i v8 7.56±0.05v.

6.81±0.05 8 5.65±0.05rn 5.08±0.05rIL 4.94±0.05 vs.

4.46±0.05 w 4.35±0.05v.

4.28±0.05rn 4.08±0.05 , 8 3.85±ILO3w 3.75±0.03 w 3.41±0.03 yyt 3.18±0.03 8 2.96±0 .02 m 2.92±0.02 rrL 2.88±0.02 w 2.83±0.02 m 2.66±0.02 m 2.58±0.02 w These X-ray diffraction data are Using alpha irradiation on copper,
2θ collected using a Rigakw X-ray system.

The position of the peak expressed by (θ is Bragg's angle) is 0.
Measurements were made by step scanning with a 2θ interval of 0.02° and a measurement time of 1 second at each step. Angstrom unit (
The lattice spacing obtained in step 3), d, and the relative strength of the line after subtracting the background, I/Io (Io is the strength of the strongest string, K...) are derived using the profile fitting method. In addition, the relative strength is the symbol vs = extremely strong (75-
100%), 8 = strong (50-74%), m = moderate (2
5-49%) and W=weak (0-24%). It should be understood that this X-ray diffraction pattern is unique to all rice MCM-10 compositions synthesized according to 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. Silicon of individual samples/
Other slight variations may occur depending on the aluminum and g4/aluminum ratio and the degree of thermal history.

The crystalline MCM-1O 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 by ion exchange.

Generally, the silicophosphoaluminates of the present invention are derived from a two-phase reaction mixture comprising 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.

(Circle: (AftCJ)6'CAA'Os). :(Sac
)2)c('(P2QIl)g:(solvent)f:(anion source), :(RtO)n However, L/(c+d×g) is smaller than 4, and b/(
c+d tentt) is less than 2, and d/(c teng
) is less than 2, //(C+d0g) is 01 to 1
5, g/(c+d×g) is less than 2, and h/(c+d++s) is 3 to 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 as described above at a rate of 5°C to 200°C per hour to a temperature of about 80°C to about 300°C and at that temperature for about 5 hours to about 500 hours until crystals of MCM-10 are formed. and carefully heating the reaction mixture.

A more preferred temperature range is from about 100°C to about 200°C, and the time at such temperature is from about 24 hours to about 16 hours.
It is 8 hours. The pH must be carefully controlled from about 2 to about 9 while heating the reaction mixture and maintaining it at the desired temperature.

Control of pli can be achieved by adjusting the concentration of added organic and/or inorganic base.

The reaction is carried out until the desired crystals of A4CM-10 are formed. The crystalline product is recovered by separating it from the reaction medium by cooling the whole to room temperature, allowing and washing with water before drying.

The above reaction mixture composition can be prepared using materials that supply the appropriate components. The aqueous phase components can include elements not included in the organic phase, such as from the origins of the elements silicon, phosphorus, or aluminum. 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 sources of silicon include, by way of non-limiting example, known forms of silicon dioxide or organic derivatives including silicic acid, alkoxy- or other compounds of silicon. Organic solvent is C3-C
,. Alco & M+X- or (RsM+R'M+
Rs ) -￥t [However, R or R' is 1 to 20
alkyl of 1 to 20 carbon atoms, heteroalkyl, aryl, heteroaryl of 1 to 20 carbon atoms, cycloargyl 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 8%Se, P, As, etc.); and X is an anion (e.g. fluoride, chloride, bromide, iodide,
hydroxide, acetate, sulfate, carboxylate, etc.) and M is a heteroatom in a cycloaliphatic, heteroalicyclic, or heteroaromatic structure, such structures include, by way of non-limiting example, , [However, R' is alkyl of 1 to 20 carbon atoms, 1 to 2
heteroalkyl of 0 carbon atoms, aryl, heteroaryl, 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 R 1 to 4;
carbon atoms, M is nitrogen, and X is -.
Included are onium compounds as defined above which are rogides or hydroxides. 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 include C8υH1
KOH, C5CL KCII and similar.

A4CM-10 crystals produced according to the present invention can be formed into a wide variety of grain 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 ldcM~10 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-LO crystals generally contain about 1 to 90% by weight AICM-10 material and about 10 to 99% by weight AICM-10 material.
(% by weight) Made of IJ sock material. More particularly,
Such catalysts consist of about 2 to 80 weight percent MCkf-10 material and about 20 to 98 weight percent matrix.

The use of active materials in combination with the novel McM-10 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 crushing 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 this new crystal include montmorionite and the kaolin family, which includes subbentonite and kaolin, known as Dixie, McNamee, Jorja and Florida clays, or whose main mineral constituents are halloysite, Includes other minerals that are kaolinite, dickite, nacrite, or anauxite.

Such clays can be used in their crude, as-mined state, or in calcined, acid-treated or chemically modified forms.

In addition to the aforementioned materials, crystalline MCM-10 is also a porous material.
IJ socks such as aluminum phosphate, silica-alumina, silica-madanesia, silica-zirconia, silica-thoria, silica-beryria, silica-titania and ternary compositions such as silica-alumina-thoria, silica-alumina-zirconia, silica -Can be combined with 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 usually are active as catalysts, particularly for the novel MCM-10 materials of the present invention. When this form is used as a catalyst component,
The catalyst likely contains additional hydrogenation components;
The reformed raw material is heated at a temperature of about 370°C to about 540°C, about 100°C.
psig to approximately 1000 psig (791 to 69
96 kPa, l), preferably from about 200 psig to about 700 psig (1480 to 4928 kPa
) of about 0.1 to about 10, preferably about 0.5
Reforming can be performed using a liquid hourly space velocity of from about 4 to about 4 and a hydrogen/hydrocarbon molar ratio of from about 1 to about 20, preferably from about 4 to about 12.

The MCM-10 molecular sieve catalyst of the present invention, when provided with a hydrogenation component such as platinum,
It can also be used for hydrogenoisomerization of luparaffin. Such hydroisomerization is carried out at a temperature of about 90°C to about 375°C, preferably about 1
a liquid hourly space velocity of about 0.01 to about 2, preferably about 0.25 to about 0.50 and a hydrogen/hydrocarbon ratio of about 1:1 to about 5:1 at a temperature of 45°C to about 290°C. It is carried out using molar ratios. Additionally, such catalysts can be used for olefin or aromatic isomerization using temperatures of about 200°C to about 480°C.

Such catalysts can also be used to lower the pour point of light oil. The reaction is carried out at a liquid hourly space velocity of about 10 to about 30 and a temperature of about 425°C to about 595°C.

Other reactions that can be accomplished using the MCM-10 catalyst of the present invention containing metals such as platinum include hydrogenation-dehydrogenation and desulfurization reactions, olefin polymerization (oligomerization), and other organic compound reactions. Conversion reactions include, for example, the conversion of alcohols (eg methanol) or ethers (eg dimethyl ether) to hydrocarbons, and the alkylation of aromatics in the presence of alkylating agents (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 collecting adsorption data to compare the adsorption abilities of various adsorbents, it was done as follows.

n-hexane, 2-methylpentane, xylene or cyclohexane vapor. For adsorbates other than 0-xylene and water, the sample temperature was maintained at 90°C. The temperature was 120°C for 0-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 11α was tested7, the alpha value is a rough measure of the catalytic cracking activity of the catalyst compared to a standard catalyst, and the alpha value is the relative rate constant (rhexanes per unit time, per volume of catalyst). Please be careful to show the conversion rate). The activity of the highly active silica-alumina decomposition catalyst was determined by alpha's 1 (rate constant = 0.016 se (
Zeolite HzsM-
5, it takes only 1 to give an alpha value of 1.
74 ppm of tetrahedrally coordinated A4Qs L was not required. The alpha test is based on U.S. Patent No. 3,35
4,078 and The Journal of Catalysis (1'he Journal of Catalysis)
s) Volume 4.

No. 522-529 (August 1965).

When testing ion exchange capacity, the temperature of the ammonium form of silicophosphoaluminate is determined by titration with a solution of ammoniacal sulfamic acid generated during program-controlled decomposition. This method was developed by G.T. Kerr and N.W. Chester.
thermostain force/actor (1'hermo
chimica Acta) Volume 3, No. 113-124
Page (1971).

Example 1 60 g of Ruhexanol and 5iCOCtH5) 411
an organic phase consisting of HsP O+ (85%) 23
．． 1 g, AToOslog, 3.6 N, Di q
uat -7(OHt (i.e. 011CCIis)sN
ccH2)tNccHs)s<OR)) of 154.4
A two-phase synthesis reaction mixture was prepared using aqueous phase 7 consisting of fJ. The reaction mixture as a whole contained 10.8% S by atoms.
i % It had a composition containing 45% P and 44.2% Al. The directing agent is Diaqut-7C0Ii)t
Met. The starting pH was slightly above 6.

The reaction mixture was heated to 130°C at 50°C/hτ and held at that temperature for 24 hours. Next, heat to 180℃ and 144℃
Holded there for an hour. Stirring was performed at 80 Urp during this time.

The crystalline product was separated from the reaction mixture by filtration, washed with water and dried at 80°C. The product crystalline silicophosphoaluminate had a composition containing 19.9% Si, 321SP, 4a, and 0% Al. A sample of the synthesized 1/7 lycophosphoaluminate was then subjected to X-ray analysis.

This is a crystalline molecular compound showing the diffraction lines shown in Table 2.
It is revealed that it is Sheev.

Table 2 Lattice spacing Measured relative strength d(A) 2Xθ I/IO 1184467,45717,04 10,l 960 8-665 78.407.648
9 11.559 84.856.8567 12.9
00 24.395.9273 14.934 13.
315.6856 15-573 35.975.10
59 17.354 57.485-0091 17.
692 64.214.4885 19.763 10
．． 914.3742 20.2B5 85.604.0
918 21.701 100.003-9534 2
2.471 11.663.7982 23.402
42.703.7262 23.861 13.623
．． 4249 25.995 26.693.2165
27.711 81.463.1626 28.193
8.652.9904 29.854 20.842
．． 9657 30.108 21.062.9347
30.433 32.192.8448 31.420
36.842.7B46 32.118 7.4.1
2.6813 33.390 42-382.5893
34.614 19.50 Example 2 The synthesis of Example 1 was repeated with the addition of only 31 parts of water.

The crystalline product obtained had an X-ray diffraction pattern of 7 showing lines similar to those shown in Table 2. Product C5
It had zero crystallinity.

Example 3 A portion of the crystalline silicophosphoaluminate of Example 1 was calcined in nitrogen at 450° C. for 4 hours and then subjected to X-ray analysis. The results are shown in Table 3.

Table 3 Lattice spacing Actual measured relative strength 11.7521 7.516 20.8110.107
0 8.742 85.447.5640 11.69
0 100.006.8057 12.997 71.
805.6522 15.665 25.385.07
70 17.453 29.024.9416 17.
935 78.184.4564 19.907 16
．． 584.3515 20.392 99.634.2
756 20.758 25.684.0759 21
．． 787 83.253.8546 23.055 1
5.883.7499 23.707 21.15:(
,408926,11942,383,177828,
05668,19 2,96163 (L151 29.912.9230
30.558 51.092.8835 30.988
10.992.8321 31.564 36.78
2.6565 33.711 43.092.5795
34.749 19.66 Example 4 A portion of the calcined product silicophosphoalnate of Example 3 was evaluated for adsorption properties to confirm molecular sieve properties. The results clearly showing the shape selectivity in weight percent were as follows: Hexano (90°C): 4.75 Cyclohexane (90°C): 2.05 Example 5 Crystalline silicophosphor of Example 1 A portion of the aluminate was calcined in the manner described in Example 3 and I A/N11+
Ammonium exchange was performed using an aqueous NOs solution. The ion exchange capacity measured from the generation of ammonia is 1.51
It was determined that me q/fj.

Applicant: Mobil Oil Corporation -,・
fart

Claims (1)

[Claims] 1. silicon, characterized in that its diffraction pattern exhibits the unique X-ray diffraction pattern shown in Table 1-A herein;
A synthetic crystalline substance containing phosphorous aluminum. 2. The synthetic crystalline material of claim 1, wherein the X-ray diffraction pattern determined by calcination shows the characteristic X-ray diffraction pattern shown in Table 1-B herein. 3. The following formula: %Formula% [However, M is a cation with a valence of m, and N is a cation with a valence of n
, A is an organic directing agent or an organic solvent that is immiscible with water, υ is the number of moles of A, and W is H
is the molar value of 2O, and X and y are + in dog than -1
is less than 1 and (1) when x is 0, y is not 0, (2) when y is 0, π is not O, and (3) the atomic ratio of Al/P is (4) If the atomic ratio of AllIP is less than 1, then z
+3' is a dog from 0.001, and z+〇, 5Y is 0
．． A synthetic crystalline material according to claim 1, which has a composition of less than 5 and satisfying the following relationships. 4. In an anhydrous state, the following formula: % formula % [However, M is a cation with a valence of m, and N is a cation with a valence of n
is an anion, and 2 and y are greater than = 1 and +1
and (1) when z is 0, y is not 0, (2) when y is 0, 2 is not 0, and (31Al/P atomic ratio is more than 1). (4) If the atomic ratio of Al/P is less than 1, then Z0'/ is greater than 0.001 and 3100-6z is less than 0.4 , Z-
1-y is a dog than 0.001 and z+0.5y is 0
．． The synthetic crystalline material according to claim 2, which has a composition of less than 5 and satisfying the following relationships. 5. At least a portion of the initial cation, hydrogen and hydrogen precursors, rare earth metals and elements of Group 1A, 1 of the Periodic Table of the Elements
Group 1A, Group [[[ Group A, Group 1V, Group 4, Group 1B, Group ■
Claims 1 to 4 are substituted with at least one cation selected from the group consisting of metals of Group B, Group mE, Group 1VB, and Group Vl. crystalline substance. 6. Silicon, phosphorus and At least a portion of the initial cation y of a synthetic crystalline material containing aluminum χ, hydrogen and hydrogen precursors, rare earth metals and groups 1A, 11A, mA, NA of the periodic table of the elements, Group 1B, HBtS% Group ■B, NB
At least l selected from the group consisting of metals of Groups 1 and 2.
A crystalline substance obtained by substitution with a cation and heat treatment. 7, silicon characterized by O, which is called ucu-1o and whose X-ray diffraction butter 7 measured with synthesized -22 exhibits the characteristic X-ray diffraction pattern shown in Table 1-A herein; A catalyst consisting of a synthetic crystalline material containing phosphorus and aluminum. 8. The catalyst according to claim 7, which is used for converting organic compounds.