RU2021975C1 - Crystalline aluminophosphate composition and process for preparing same - Google Patents

Abstract

FIELD: chemistry, particlarly, production of molecular sieves. SUBSTANCE: crystalline aluminophosphate composition having three-dimensional microporous crystalline skeleton structure having following chemical constitution, namely: Al₂O₃:(1,0± 0,2)P₂O₅ (molar ratio). Adsorption test data point to the fact that disclosed composition has internal crystalline pores capable of incorporating molecules having kinetic diameter of

. Roentgen radiation diffraction spectrum exhibited by this composition is charcaterized by distance d measured by K-alpha copper radiation method, with 2 θ, at approximately less than 40 deg. Disclosed composition may additionally include structurizing agent. Claimed process prescribes admixing aluminum- and phosphorus-containing components and water to be taken in molar ratio of 10 to 52 mol water to 1 mol aluminum oxide Al₂O₃ to form starting admixture, admixing starting mixture with structurizing agent to produce reaction mixture, conducting reaction under conditions of formation of aluminophosphate composition at temperature of 200 C during 1 h to 10 days, washing out and then drying end product. Disclosed process permits producing metal-substituted aluminophosphate compositions having roentgen radiation diffraction spectrum characterized by same distance d and where oxides of one and more metals are also integrated in oxide lattice and employing silicon, magnesium, zinc or cobalt as substitute taken in amount of 0.3 to 0.5 mol per 1 mol aluminum oxide Al₂O₃. EFFECT: novel promising composition. 10 cl, 13 tbl, 2 dwg

Description

 The invention relates to crystalline aluminophosphate compositions, in particular to large-pore crystalline aluminophosphate compositions and to a method for their preparation.

 Molecular sieves have been well known for many years. As a rule, they are of two types - the zeolite type, including crystalline aluminosilicate molecular sieves, and other molecular sieves that are not related to this crystalline aluminosilicate composition.

Natural and synthetically analogs of zeolites include more than 108 compounds. Zeolites are, by definition, tectosilicates, and that means. that their lattice consists of three-dimensional structures formed by SiO ₄ ^-4 and AlO ₄ ^-5 tetrahedra having oxygen atoms in the corners. Zeolites can be characterized as porous structures with holes of the same size, having an ion-exchange capacity and the ability to reversibly adsorb and desorb molecules in cavities present in crystals through pore openings. These pore openings are determined by bonds of TO ₄ tetrahedra, where T is a silicon or aluminum atom.

 Zeolites are synthesized, as a rule, by a hydrothermal method from reactive components in closed systems. There is a lot of empirical evidence in the literature on the synthesis of compositions and conditions leading to the formation of these zeolites. Practice shows that a wide range of zeolite products can be obtained from one initial composition depending on the raw materials, the mixing method and the crystallization technique.

 Other crystalline molecular sieves other than zeolites are also known. The properties of these aluminophosphates are somewhat similar to zeolite molecular sieves, and therefore are not suitable as catalytic bases or catalysts in some chemical reactions.

 The closest of them to this and the method of its production are described in USSR patent N 1461371 [1].

 Molecular sieve, ion exchange, and catalytic properties similar to those of zeolites were also found in some metal silicates, where instead of silicon or aluminum, elements such as beryllium, boron, gallium, iron, titanium, and phosphorus are present.

. Максимальные отверстия, вероятно, образованы кольцами из 12 ТО₄-тетраэдров. До настоящего времени имеющиеся сообщения о синтезе нецеолитных молекулярных составов с еще большими отверстиями не подтверждены.However, all of the above crystalline materials are known to have openings of about 2.1 to 7.4

. The maximum openings are probably formed by rings of 12 TO ₄ tetrahedrons. To date, the available reports on the synthesis of non-zeolitic molecular compositions with even larger holes have not been confirmed.

 Other materials described as having large pores are Z-21 and N zeolite similar to Z-21. Recently, Russian researchers have described large-pore zeolites using X-ray powder diffraction data.

These crystalline aluminophosphate compositions have a three-dimensional microporous crystal lattice and the following chemical composition, expressed as the ratio of oxides:
Al ₂ O ₃ : (1.0 ± 0.2) P ₂ O ₅
They have a powder X-ray diffraction spectrum when measured using copper K-alpha radiation, as described in Table 1.

The present invention also provides crystalline aluminophosphate compositions having three-dimensional microporous crystalline structures containing a structuring agent, where the chemical composition, expressed as a molar ratio, is as follows:
xR: Al ₂ O ₃ : (1.0 ± 0.2) P ₂ O ₅ , where Al ₂ O ₃ and P ₂ O ₅ form an oxide lattice; R is a structuring agent; x>0; structure is further characterized by X-ray diffraction with the distance d, corresponding to less than about ⁴⁰ ° (2 θ), as measured using copper K-alpha radiation (Table 1).

The present invention also provides a method for producing these crystalline aluminophosphate compositions from an initial mixture having the following chemical composition, expressed as molar ratios of oxides:
Al ₂ O ₃ : (1.0 ± 0.2 P ₂ O ₅ ): (10-100) H ₂ O, and additionally containing 0.02-4.0 mol of a structuring agent per 1 mol of Al ₂ O ₃ . The method includes the steps of mixing a source of aluminum, a source of phosphorus and water to obtain a starting mixture, introducing a structuring agent into the initial mixture to form a reaction mixture and carrying out the reaction in the reaction mixture under conditions under which a crystalline aluminophosphate composition having distances d corresponding to values of 2 θ, less than 40 ^about , when measured using copper K-alpha radiation, as shown in table. 1.

The present invention provides crystalline metal-substituted aluminophosphate compositions having a three-dimensional microporous crystalline structure containing a structuring agent having the following chemical composition, expressed as molar ratios:
xR: Al ₂ O ₃ : (1.0 ± 0.2) P ₂ O ₅ : (0.001-0.5) x
x MO _{Z / 2} : (10-100) H ₂ O, where Al ₂ O ₃ , P ₂ O ₅ and MO _{Z / 2} form an oxide lattice; R is a structuring agent; x>0; M is a metal; Z is an oxidative state of M; MO _{Z / 2} is at least one metal oxide; the chemical composition further includes one charge-compensating particle, or more; These structures are further characterized by X-ray diffraction with the distance d, corresponding to the value 2 θ, less than ^about 40, as measured with copper radiation ispolzvaniem K alpha, as shown in Table 1.

A method is proposed for producing these crystalline metal-substituted aluminophosphate compositions from an initial mixture having the following chemical composition, expressed as molar ratios:
Al ₂ O ₃ : (1.0 ± 0.5) P ₂ O ₅ : (0.001-0.5) x
x MO _{Z / 2} : (10-100) H ₂ O, where M is a metal; Z is an oxidative state of M; MO _{Z / 2} represents at least one metal oxide; the chemical composition additionally includes one charge-compensating particle or more and 0.02-4 mol of structuring agent per 1 mol of Al ₂ O ₃ ; comprising the following stages: mixing sources of aluminum, phosphorus, metal oxide and water to form a starting mixture, mixing the starting mixture with a structuring agent to obtain a reaction mixture and carrying out the reaction in the reaction mixture under conditions of formation of a crystalline metal-substituted aluminophosphate composition having a distance d, corresponding to less than 40 ^about (2 θ) when measured using copper K-alpha radiation, as shown in table 1.

 Figure 1 shows the argon adsorption isotherms for the aluminophosphates of this invention, designated as VP1-5, and for Zeolite X (Na) used for comparison; figure 2 shows the effective pore diameters for aluminophosphates according to this invention VP1-5 and for Zeolite X (Na).

 The compositions of one embodiment of the invention are VP1-5 synthetic crystalline aluminophosphate compounds that are capable of reversibly adsorbing and desorbing large molecules such as triisopropylbenzene in intracrystalline pores. These materials have a three-dimensional microporous crystalline lattice structure.

Aluminophosphate materials can be characterized in many ways. As a rule, the basic chemical composition of molecular sieves can be represented as follows in the form of molar ratios
Al ₂ O ₃ : (1.0 ± 0.2) P ₂ O ₅ , these compositions have a crystalline structure, determined by X-ray diffraction by powders, with distances d.

Table 1 shows the characteristic d-distances for VP1-5 in the range from 2 θ of about 3 ^about 2 θ of about 40 ^about when measured using copper radiation of K-alpha. The expressions “characteristic” and “characterizing” refer to distances d corresponding to all peaks having a relative intensity relative to the intensity of the largest peak greater than 1:10. These peaks are described as VS for very intense and m for medium. Peaks of lower intensity, denoted as weak w, are thus excluded from the definition. Distances d remain virtually unchanged after VP1-5 temperatupy heating to not lower than 600 ° ^C. This heating can be carried out, e.g., in vacuum, in air or air-steam mixture. Experimental X-ray diffraction spectra were obtained from an automatic powder diffraction cell using K-alpha copper radiation.

Another characteristic of the aluminophosphates according to this invention, characterized by x-ray diffraction distances d on the powder, mainly as shown in Table 1, is their following chemical composition:
xR: Al ₂ O ₃ : (1.0 ± 0.2) P ₂ O ₅ , where R is a structuring agent used in the synthesis of large-pore material, and x is the molar ratio of R to Al ₂ O ₃ , where x> 0 Since the structuring agent is involved in the production reaction, as will be described below, its amount in the composition will be partially determined by its possible partial desorption or decomposition.

 In FIG. 1 shows argon adsorption isotherms on VP1-5 aluminophosphate according to this invention and on Zeolite X (Na). Figure 2 shows the effective pore diameters for VP1-5 and Zeolite X. Adsorption isotherms and pore size distribution were obtained using Horwatz-Kawazoe analysis. Zeolite X (Na) is a structure with pore openings bounded by a 12-membered ring of tetrahedrons and having a size of about 0.8 nm. This size is in good agreement with the data presented in figure 2. Obviously, VP1-5 has a pore size significantly larger than Zeolite X (Na).

 Thus, it follows from the experiments described above that VP1-5 compositions have a crystalline structure with such a pore system that some of the pore cavities are large enough to accommodate triisopropylbenzene molecules. Additional pore spaces are available for smaller molecules.

Metal-substituted aluminophosphates are also characterized by x-ray diffraction. The spectra obtained on the powder have the same characteristic distances d as the unsubstituted VP1-5, as shown in Table 1. These metal-substituted aluminophosphates have similar molar ratios of Al ₂ O ₃ to P ₂ O ₅ . Typically, these compositions are determined by the following molar relationships:
Al ₂ O ₃ : (1.0 ± 0.2) P ₂ O ₅ : (0.001-0.5) x
x MO _{Z / 2} : (10-100) H ₂ O
In this formula, M is a metal, Z is the oxidative state of M, MO _{Z / 2} is an oxide of at least one metal. For example, the molar ratio formula for silicoaluminophosphate is as follows:
Al ₂ O ₃ : (1.0 ± 0.2) P ₂ O ₅ : (0.001-0.5) SiO ₂ :
: (10-100) H ₂ O.

 The structuring agent is present in the same ratio in metal-substituted aluminophosphates as in unsubstituted aluminophosphate compositions, and the same sources of aluminum, phosphorus and the same structuring agent can be selected. Similarly, the structuring agent may or may not be retained in the resulting silicon aluminophosphate composition VP1-5 depending on whether or not desorption or decomposition occurs. The chemical composition additionally includes one particle that compensates for the charge of the aluminophosphate particles replaced by the metal, or more, as a result of which the charges are balanced. These charge balancing particles can be selected from various cations or anions, including, for example, sodium, potassium ions, hydroxides, chlorides, etc., which is well known to specialists in this field.

 Other elements from sources capable of forming oxides can also be introduced into the main crystalline skeleton structure of aluminophosphate VP1-5 without significantly changing the X-ray diffraction spectrum of the powder of the main oxide structure. They include, for example, substitute metals such as titanium, tin, cobalt, zinc, magnesium, zirconium, and mixtures thereof.

 The invention also includes a method for preparing compositions VP1-5 described herein. Typically, the specific molar ratios of the reactants are important to obtain the resulting crystalline solid compound that meets the above characterization data. Briefly, the crystalline aluminophosphates of this invention are prepared by displacing sources of aluminum and phosphorus, a structuring agent and water to form a reaction mixture and carrying out the reaction in the reaction mixture under conditions where a crystalline aluminophosphate composition is formed, characterized by such distances d as described in Table 1.

 The combination of components to obtain the described compositions VP1-5 can be achieved in various ways. For example, an aluminum source can be mixed with water, and a phosphorus source can be mixed with water separately. In a preferred embodiment, the mixture of the source of phosphorus with water can then be added to the mixture of the source of aluminum with water with stirring until homogeneity is achieved. You can also add the source of aluminum to the mixture of the source of phosphorus with water or add the mixture of the source of aluminum with water to the mixture of the source of phosphorus with water. Other blending orders may also be used.

 After obtaining a carefully mixed mixture of phosphorus and aluminum sources with water, it is preferable to maintain the initial mixture to stabilize its pH. This aging can be carried out with or without stirring, but it is preferable not to stir for the time necessary to stabilize the pH. The aging is preferably carried out at room temperature for 1-5 hours

 In the preparation of the metal-substituted aluminophosphates of the present invention, the metal source can, for example, be preferably added to the initial mixture of aluminum and phosphorus sources with water after the above exposure of the mixture. You can also add the metal source to a mixture of an aluminum source with water or to a mixture of a phosphorus source with water before combining the mixtures. In addition, a metal source can also be added at any stage of the synthesis.

The starting compounds for preparing aluminophosphate or metal-substituted aluminophosphate compositions of this invention can be taken from various sources. Possible sources of phosphorus include, for example, elemental phosphorus, phosphoric acid (H ₃ PO ₄ ), phosphorus oxide, phosphoric acid esters and mixtures thereof. Of these, phosphoric acid is preferred. Preferred sources of aluminum are aluminum hydrates, such as boehmite, pseudoboehmite, gibboite, baerite, and mixtures thereof. Other possible sources include elemental aluminum, alkoxides and aluminum oxides, and mixtures thereof. Sources of phosphorus and aluminum, as well as in the case of silicoaluminophosphate VP1 -5, silicon sources must be able to form metal oxide after being introduced into the aluminophosphate matrix. Preferred sources of silicon are aerosil, aqueous colloidal silicon dioxide, tetraethylorthosilicate and other reactive types of silicon dioxide. Other silicon compounds may also be used. In other metal-substituted embodiments of the invention, metal acetate dihydrates or tetrahydrates are preferred, for example cobalt acetate tetrahydrate, zinc acetate dihydrate or magnesium acetate tetrahydrate, but other metal-containing compounds are possible sources. Metals can also be introduced as a complex ion, such as a metal oxalate, a complex with ethylenediaminetetraacetic acid, and the like.

 The next step in the synthesis is the addition of a structuring agent. It is preferably added to the aged aging starting mixture. However, you can also add it earlier. A structuring agent combined with all other starting compounds is called a reaction mixture. It is preferable to subject this mixture to aging 1-2 hours also to stabilize the pH.

 Various effective structuring agents are dipropylamine, diisopropylamine, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, dipentylamine, trypentylamine, tributylamine, generally alkylammonium and alkylphosphonium compounds and mixtures thereof. Of these, dipropylamine, tetrabutylammonium hydroxide and dipentylamine are preferred, and tetrabutylammonium hydroxide is more preferred. Similar molecules may also appear as structuring agents in the present invention.

The ratio of reagents can vary in a given interval. Based on 1 mol of Al ₂ O _{3, the} content of the structuring agent (R) is preferably 0.02-4 mol, more preferably 0.2-2 mol and most preferably 1; the content of P ₂ O _{5 is} preferably 90.8-1.2 mol, more preferably 0.9-1.1 mol, and most preferably 1; the molar ratio of water to Al ₂ O _{3 is} preferably 10-100, more preferably 30-70, most preferably 35-55. If silicon or another metal (M) is added to produce the metal-substituted aluminophosphate of the present invention, the above ratios are also applicable and in addition the molar ratio of MO _{Z / 2} to Al ₂ O ₃ may preferably be 0.001-0.5. In this general preferred range, there are differences between substitution with silicon and most other metals. Thus, it is more preferable that the ratio to Al ₂ O ₃ be 0.2-0.5 for silicon dioxide and most preferably 0.3-0.4, while for most oxides of other metals, the range of ratios to Al _{2 is} more preferable. O ₃ equal to 0.001-0.1, most preferably 0.02.

 In another embodiment of the present invention, part of the water can be replaced with a polar organic solvent. To do this, you can use an alcohol such as hexanol, or ketone, or another polar solvent. In this case, it is preferable to dissolve the structuring agent directly in the solvent before introducing the agent into the initial oxide mixture.

After combining the minimum necessary components of the reaction mixture. namely, sources of aluminum, phosphorus, a structuring agent, water, and possibly an additional metal source, the formation of the reaction mixture and its aging to achieve a practically constant pH, the reaction mixture is subjected to reaction under conditions of formation of a crystalline solid material with such a spectrum of x-ray diffraction and powder, as defined for composition VP1-5. For this, it is preferable to use known heating methods. To achieve this, an effective and convenient means is autoclaving in a teflon-coated bomb. In addition, other types of reactors may be used. The temperature preferably lies in the range 50-200 ^{° C,} more preferably 100-150 ^C. The reaction is preferably carried out under pressure, for example under the self-developing pressure or at atmospheric pressure.

The reaction time varies in part depending on the temperature used. Inadequate heating can lead to the formation of amorphous products. excessive heating can lead to the formation of amorphous products or undesirable phases. Preferably, the time is 2-50 hours at a temperature of 100-150 ^about With depending on the reagents and the composition of the reaction mixture.

 After crystallization, the product is separated and isolated in the usual way. Separation from the mother liquor is usually carried out by filtration, but centrifugation, precipitation, decantation and similar methods can also be used. Subsequent isolation of the VP1-5 crystalline compositions may include conventional washing with acidic solutions, such as HCl or boric acid, organic solvents such as acetone or methanol, salt solutions such as magnesium acetate solutions, or deionized water, and drying and / or heat treatment. These post-synthesis treatments can help remove the structuring agent, if necessary, and can also impart some physical and chemical properties to the resulting product. The resulting crystalline aluminophosphate compositions will have catalytic adsorption, ion exchange and / or molecular sieve properties and can be used for catalytic reactions of various organic compounds.

 The following examples more fully illustrate various embodiments of the present invention. They are provided for illustrative purposes only and are not intended to limit the scope of this invention.

Example 1. A suspension of 55.0 g of alumina hydrate, 150 g of water was added to a solution of 90 g of phosphoric acid (85% H ₃ PO ₄ ) and 100 g of water. The resulting starting mixture is aged 2 hours without stirring at room temperature. 186 g of 55% tetrabutylammonium hydroxide (TBA) were added to the starting mixture and stirred for 2.5 hours at room temperature. The composition of the reaction mixture:
TVA: Al ₂ O ₃ : P ₂ O ₅ : 20 H ₂ O
The reaction mixture is heated at 145 ° C. ^for 24 hours in a Teflon-coated stainless steel autoclave. The product is taken out, washed with water and dried overnight at room temperature. The resulting x-ray diffraction spectrum is characterized by distances d, basically the same as shown in table. 1.

PRI me R 2. 7 suspensions of alumina hydrate are obtained as indicated in the table. 2. Each suspension was added to a solution of 11.38 g of phosphoric acid (85% H ₃ PO ₄ ) and 11.0 g of water and aged 5 hours at room temperature without stirring. 23.54 g of 55% tetrabutylammonium hydroxide (TBA) are added to each feed mixture with stirring, and reaction mixtures of the compositions shown in Table 2 are obtained.

The reaction mixture was heated 18 hours at 150 ^C in a Teflon coated stainless steel reactors. White solid compounds are recovered by suspending the contents of each deionized water reactor and then precipitating solid particles. The solid compounds are dried at room temperature overnight in air. The resulting crystalline product has an X-ray diffraction spectrum with distances d substantially the same as shown for VIP-5 in Table 1.

 PRI me R 3. About 8.9 g of aqueous phosphoric acid (concentration of 85%) is dissolved and approximately 6.0 g of distilled water. Separately, a suspension is prepared by mixing 5.3 g of alumina dihydrate with approximately 6.0 g of distilled water. Then, with stirring at room temperature, an acid solution is added to the suspension. The resulting starting mixture was stirred on a magnetic stirrer for approximately 30 minutes.

Another solution is prepared by combining about 18.3 g of an aqueous 55% solution of tetrabutylammonium hydroxide (TBA) and about 10.9 g of distilled water. This solution is then added with stirring to the starting mixture. Stirring is then continued for approximately 1.5 hours at room temperature in air. At this moment, the mixture has the following molar ratios: 1.0 TBA: Al ₂ O ₃ : P ₂ O ₅ : 52 H ₂ O.

Aliquots of this gel (each approximately 25% of the total amount) are placed in autoclaves, coated with Teflon with a capacity of about 15 ml, and sealed. Autoclaves heated to about 44 hours at about 150 ° ^C. The resulting product was isolated as in Example 1 and characterized as shown in Table 1.

Example 4. About 11.50 g of phosphoric acid (85% H ₃ PO ₄ ) are dissolved in approximately 9.8 g of water. The solution was stirred for about 5 minutes to a pH of about 0. This solution was then added to the suspension obtained by mixing 6.875 g of aluminum oxide dihydrate in 20.0 g of water for about 5 minutes. The pH of the suspension before it is mixed with an acid solution is approximately 7. The resulting initial mixture is homogenized first by hand, and then on a magnetic stirrer and the pH of the reaction mixture is measured for 110 minutes, as shown in Table 3.

About 5.075 g of dipropylamine (DPrA) are added to the above starting mixture with stirring. The resulting white reaction mixture (pH about 3.8) is further homogenized for approximately 82 minutes. The result is the following composition, expressed in terms of moles of oxides
DPrA: Al ₂ O ₃ : P ₂ O ₅ : 40 H ₂ O
The reaction mixture was then transferred to a 5 Teflon coated stainless steel autoclaves labeled, respectively, 1.2, 3.4, 5, and self-developing is heated under pressure at 142 ^{° C} for the time specified in the Table. 4, the pH measured for each serving is 7.0.

A white solid compound is isolated by separately suspending the contents of each autoclave in deionized water, stirring for several minutes to settle solid particles and discarding the supernatant liquid. These solids were then filtered, dried in an oven at ¹⁰⁰ ° C and characterized as in Table 1.

 PRI me R 5. 5 solutions of phosphoric acid (concentration of 85%) are obtained as shown in table.5. Each solution is added dropwise to a suspension of alumina dihydrate and water. The resulting starting mixture is heated at a temperature and for the time indicated in Table 5. Dipropylamine was added dropwise in the amount indicated in Table 5, and the resulting reaction mixture was stirred for several minutes.

 Then, each reaction mixture is heated at a temperature and for the time indicated in Table 6. in a teflon-coated autoclave. White solids are isolated by suspending the contents of each reactor and deionized water and leave solids to settle. Then the solid product is dried overnight in air at room temperature. The resulting crystalline solid product has an X-ray diffraction spectrum substantially as indicated in Table 1.

The reaction composition of all experiments DPrA: Al ₂ O ₃ : P ₂ O ₅ : 37 H ₂ O is additionally characterized as in table 1.

PRI me R 6. 4 solution of orthophosphoric acid (7 85% H ₃ PO ₄ ) and water obtained using the components listed in table 7. Each solution is added dropwise to a suspension of alumina dihydrate and water in the same manner as indicated in this table. The resulting starting mixture is mixed and its pH is measured. Then dipentylamine (DPtA) was added dropwise and each of the resulting starting mixtures was again stirred for the indicated time.

 The reaction mixtures are heated in Teflon-coated stainless steel autoclaves for the time indicated in Table 8. A white solid product is isolated by suspending the contents of each reactor with deionized water, standing until settling, and washing with acetone. Solid products are dried overnight in air at room temperature and are characterized as shown in table 1.

PRI me R 7. About 8.9 g of phosphoric acid (H ₃ PO ₄ ) is dissolved in approximately 6.0 g of distilled water. Separately, about 5.3 g of alumina dihydrate is mixed with about 6.0 g of distilled water. Then the phosphorus-containing mixture is added to the aluminum-containing mixture and the resulting initial mixture is homogenized for about 20 minutes on a magnetic stirrer.

About 7.89 g of aqueous 95% dipentylamine are then added to the homogeneous starting mixture with stirring, and then about 10.9 g of distilled water. Stirring of the resulting reaction mixture was continued for another 4.5 hours in air at room temperature. The reaction mixture has the following composition in molar ratios: DPtA: Al ₂ O ₃ : P ₂ O ₅ :: 40 H ₂ O.

Aliquots (each about 25% of the total) aged mixture was transferred to an autoclave coated with Teflon, and heated at ¹⁵⁰ ° C and a pressure of self-developing.

The solids are then separated from the mother liquor by filtration and isolated by suspending the contents of each autoclave in approximately 100 ml of distilled water, stirring for several minutes, allowing the particles to settle under gravity and then discarding the supernatant liquid. Then the solid product is filtered and dried for about 30 minutes in air at 100 ^about C.

 Example 8. Using the same procedure as in the previous examples, phosphoric acid solutions were prepared and then added to suspensions of alumina dihydrate. The amounts of starting compounds are shown in table. 9. Stirring at room temperature and heating are carried out as described in table 10, and the reaction mixtures have the compositions shown in table 11. Aliquots of the reaction mixture are placed in Teflon-coated autoclaves with an internal capacity of about 15 ml and sealed. Autoclaves are heated at the indicated temperatures and times. The resulting white solid products are isolated by suspending the contents of the reactors in deionized water and holding solid particles to settle. They are dried overnight in air at room temperature.

 In the table. 11 shows the calculation results from the above information for molar ratios in the reaction mixture, and these compositions are additionally characterized in table 1.

Example 9. A solution obtained from 8.9 g of phosphoric acid (85% H ₃ PO ₄ ) and 6.0 g of water was added to a suspension of 5.3 g of alumina dihydrate in 6.0 g of water. This stock mixture is homogenized for several minutes. The second solution is obtained by adding 18.3 g of an aqueous 55 wt.% Solution of tetrabutylammonium hydroxide (TBA) and 0.928 g of soot to 10.9 g of water. This second solution is added with stirring and the resulting reaction mixture is homogenized for 90 minutes. The reaction mixture has the following composition:
1.0 TVA: Al ₂ O ₃ : P ₂ O ₅ : 0.5 SiO ₂ : 52 H ₂ O
Parts of the mixture are transferred to Teflon-coated autoclaves with a capacity of 15 ml and fill about 60% of the volume. The autoclaves are heated at 150 ^o C and a self-developing pressure of more than 44 hours. The product is isolated analogously to example 8, and it is characterized by table 1.

PRI me R 10. Get a solution of 8.9 g of 85% orthophosphoric acid and 6 g of water. It is added to a suspension of 5.3 g of alumina dihydrate in 6 g of water. The mixture was homogenized for several minutes and 2.5 g of low sodium 40% colloidal silica was added. The resulting gel is aged at room temperature without stirring for 1 hour. Then a solution of 10.9 g of water and 18.3 g of 55% tetrabutylammonium hydroxide are added. The reaction mixture has the following composition:
TVA: Al ₂ O ₃ : P ₂ O ₅ : 0.4 SiO ₂ : 50 H ₂ O.

The gel is heated for 41 hours at ¹⁵⁰ ° C as described in previous examples. A white solid product is isolated by suspending the contents of the reactor in deionized water and allowing the solids to settle. The solid product characterized by tab. 1, obtained by drying overnight in air at room temperature.

PRI me R 11. A solution is obtained by mixing for 20 minutes 11.5 g of phosphoric acid (85% H ₃ PO ₄ ) and 9.8 g of water. A suspension of 6.8 g of alumina dihydrate in 20 g of water is stirred for 15 minutes. Then, with stirring, a solution of phosphoric acid is added to the aluminum-containing mixture. After this, 0.93 g of soot is added. The silicoaluminophosphate starting mixture is homogenized for 2 hours, and during this time the pH of the mixture rises from 0.9 to 1.6, stabilizing at 1.6.

Then, with constant stirring, 6.87 ml of dipropylamine DPrA are added to the mixture. The gel is homogenized for another 4 hours. This gel has the following oxide composition:
DPrA: Al ₂ O ₃ : P ₂ O ₅ : 0.3 SiO ₂ : 40 H ₂ O.

This mixture was transferred in portions Teflon coated autoclave and heated a minimum of 24 hours at 142 ^{° C} and self-developing davlenii.Bely solid product was isolated by suspending the contents of each autoclave in water, stirring a few minutes, leaving the solid particles to settle and discarding the supernatant liquid. The solid product is then filtered and dried in an oven at 100 ^about C, it is characterized by table 1.

PRI me R 12. About 11.5 g of phosphoric acid (85% H ₂ PO ₄ ) is dissolved in 9.7 g of water and stirred. This solution was added dropwise to a suspension of 6.7 g of alumina dihydrate in 20 g of water. The resulting starting mixture is aged with stirring at room temperature for the time indicated in Table 13. At this point, the metal compound is added in the amount indicated in the same table, with stirring and room temperature. The total mixing time, which is the mixing time of the Al ₂ O ₃ / P ₂ O ₅ mixture before and after adding all the compounds, is shown in the table. Separate reaction mixtures are prepared using magnesium, cobalt and zinc, respectively varying the ratios. The water content is also shown. In all cases, use water. The determined amount of dipropylamine (DPrA) indicated in the table is then added dropwise. The reaction mixture is heated in Teflon-coated stainless steel autoclaves for the time indicated in the table. The resulting solid product is isolated by suspending the contents of the reactor in deionized water and leaving the solid particles to settle. The solid product is dried overnight in air at room temperature, and it is characterized by table 1. Specific reagents and process details are shown in Table 12.

PRI me R 13. For a better understanding of the nature of the compositions VP1-5 according to this invention, having a unique x-ray diffraction spectrum shown in table 1, adsorption experiments were carried out with samples VP1-5, preheated to a minimum of 350 ^about With for at least 1 h and then cooled to room temperature under vacuum. Then the samples are placed in the atmosphere of this adsorbate until equilibrium is reached. The equilibrium was determined as the constancy of the weight of the adsorbate and the sample for at least 2 hours. The results of these experiments are shown in Table 13, which includes data on the adsorption of water, oxygen, nitrogen, cyclohexane, neopentane, and triisopropylbenzene.

могут входить во внутрикристаллические свободные поры VР1-5.This table shows the adsorption data for VP1-5 obtained using two different structuring agents, namely dipropylamine and tetrabutylammonium hydroxide. It also shows adsorption data for three other known materials, namely zeolite (described in U.S. patent N 3,216,789) and molecular sieve AlPO ₄ -5 and -8 AlRO ₄ (described in U.S. Patent N 3,414,602). From the table it follows that molecules with a kinetic diameter of approximately 3-14

can enter intracrystalline free pores of VR1-5.

Claims (9)

1. A crystalline aluminophosphate composition having a microporous skeleton structure characterized by a chemical composition expressed as molar ratios of oxides: Al ₂ O ₃ : (1.0 ± 0.2) P ₂ O ₅ , characterized in that its structure is characterized by the following spectrum X-ray diffraction:
Angle of Incidence Interplanar - Relative -
and reflection distance inten-
beam / hail. /

sivnost /%
5.36 16.48 v _in
9.32 9.49 w
10.75 8.23 m
14.35 6.17 m
16.16 5.48 w
18.68 4.75 m
21.66 4.10 m
21.92 4.05 m
22.39 3.97 m
22.56 3.94 m
23.59 3.77 m
24.46 3.64 w
26.12 3.41 w
27.17 3.28 m
28.19 3.17 w
28.96 3.08 w
29.48 3.03 w
30.28 2.95 w
30.88 2.90 w
32.71 2.74 m
34.05 2.63 w
35.86 2.50 w
38.32 2.35 w
2. The composition according to claim 1, characterized in that it has intracrystalline free micropores the size of which allows to contain molecules with a kinetic diameter of 3 to 14

.  3. The composition according to claim 1, characterized in that its frame structure has the form of a lattice. 4. The composition according to claim 3, characterized in that it additionally contains dipropylamine, or diisopropylamine, or tetrabutylammonium hydroxide, or tetrapropylammonium hydroxide, or dipentylamine, or tripentylamine, or tributylamine and has a molar composition: (0.02 - 4) R: Al ₂ O ₃ : (1.0 ± 0.2) P ₂ O ₅ ,
where R is organic matter.  5. The composition according to paragraphs. 1 to 4, characterized in that it further comprises silicon oxide, or magnesium oxide, or titanium oxide, or cobalt oxide, or tin oxide, or zirconium oxide or its frame structure has a lattice shape.  6. The composition according to claim 5, characterized in that it contains silicon oxide in the form of white soot, or aqueous colloidal silica, or tetraethylorthosilicate. 7. A method of obtaining a crystalline aluminophosphate composition, comprising mixing sources of aluminum, phosphorus and water, introducing a nitrogen-containing organic structuring substance, heating the mixture, separating and washing the precipitate, characterized in that hydrate or dihydrate of aluminum oxide is used as a source of aluminum, as a source of phosphorus use phosphoric acid, dipropylamine, or diisopropylamine, or tetrabutylammonium hydroxide, or tetrapropyl hydroxide, are used as organic matter Monia, or dipentylamine, tripentylamine, or, mixing is carried out at the following molar ratios of reactants:
R: Al ₂ O ₃ : (1.0 ± 0.2) P ₂ O ₅ : (20-52) H ₂ O ,,
where R is organic matter
heating is carried out at 50 - 200 ^o C for 1 h to 10 days and after washing the product is dried.  8. The method according to claim 7, characterized in that the source of aluminum is mixed with water, the source of phosphorus is mixed with water separately, and both mixtures are combined.  9. The method according to claim 7, characterized in that the mixing additionally serves a source of silicon, or magnesium, or cobalt, or zinc in an amount in terms of oxide 0.3 - 0.5 mol per 1 mol of aluminum oxide.  10. The method according to claim 7, characterized in that as the source of silicon using white carbon black.

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