Method of preparation of crystal elemento-alumo-phosphates

FIELD: preparation of crystal elemento-alumo-phosphates, including alumo-phosphates of zeolite-like structure.

SUBSTANCE: alumo-phosphates are designated as ATO according to classification of Structural Commission of International Zeolite Association. Proposed method includes preparation of aqueous reaction mixture containing aluminum source, concentrated phosphoric acid and one or two sources of substituting element, as well as organic structure-forming compound in form of di-n-pentyl amine or mixture of di-n-pentyl amine with other di-n-pentyl amines having common composition expressed in terms of mole ratios: R/Al2O3=0.5-2.0; P2O5/Al2O3=0.8-1.2; MOx/Al2O3=0.1.5; H2O/Al2O3=15-200, where R is organic structure-forming compound; M is substituting element selected from beryllium, magnesium, zinc, chromium, gallium, iron, silicon, titanium, cobalt, manganese and cadmium; x=1, 3/2 or 2. Then, mixture thus prepared is subjected to crystallization, after which material is separated and dried.

EFFECT: possibility of obtaining pure-phase specimens without by-phases.

39 cl, 1 dwg, 7 tbl

 

The present invention relates to a method for preparation of crystalline microporous materials, namely elementalist, including alumophosphates with zeolite like type structure ARE-31, which according to the classification of the Structural Commission of the International Zeolite Association is designated as the ATO, and can be used for the preparation of adsorbents and catalysts in the chemical and petrochemical industries.

It is known that crystalline alumophosphate and substituted alumophosphate with microporous zeolite like structure, used as adsorbents and catalysts in a number of processes associated with the conversion of hydrocarbons. Thus, known processes hydroisomerization various hydrocarbons using catalysts containing crystalline silicoaluminate and a noble metal (platinum or palladium) (U.S. Pat. U.S. No. 4710485, B 01 J 27/18, 1987; 5135638, C 10 G 47/16, 1992; 5139647, C 10 G 11/04, 1992; 5149421, C 10 G 11/02, 1992; 5246566, C 10 G 47/16; 1993; 5413695 C 10 G 73/02, 1995; 6143940, C 10 G 55/04, 2000). In particular, it is noted that one of the preferred silicoaluminate when used in the specified process is silicoaluminate SAPO-31.

Preparation and characteristic properties of crystalline microporous silicoaluminate is described in detail in U.S. Pat. U.S. No. 4440871, B 01 J 27/14, 1984. These siliconium the phosphates have three-dimensional microporous crystal structure, consisting of Vershinskaya tetrahedra PO4/2, AlO4/2and SiO4/2. In accordance with this patent, there are quite a number of different microporous silicoaluminate structures, each of which is characterized by individual characteristics x-ray analysis and adsorption data. Crystalline silicoaluminate commonly referred SAPO, while each of the different crystal structures has its own number.

Known for the synthesis of various silicoaluminate, such as SAPO-5, SAPO-11, SAPO-31, SAPO-37, SAPO-40, SAPO-41, and others (U.S. Pat. U.S. No. 4440871, B 01 J 27/14, 1984). In the examples, is devoted to the preparation of material SAPO-31, having the structure of ATU, it is shown that the target material is observed the formation side of the crystalline phase.

In addition, a method of obtaining substituted silicoaluminate, including the structure of atoms, which optionally enter the various elements (U.S. Pat. U.S. No. 4793984, 01 025/26, 1988). Such materials are designated as ELAPSO, in addition to silicon can contain one or more metals, such as magnesium, manganese, zinc, chromium, cobalt, titanium. However, in the description of this patent also notes that the series ELAPSO-31, containing these elements, as in the case of material SAPO-31, in their x-rays which have the reflexes from the side of impurity crystal phases. Thus, the materials ELAPSO-31, prepared in accordance with techniques described in U.S. Pat. U.S. No. 4793984, are not individual phase-pure samples with the structure of the ATO at any investigated by the authors of the patents variations in the chemical composition of the initial reaction mixture.

Finally, a method of obtaining substituted alumophosphates, including the structure of atoms, which optionally enter the various elements (EP NO. 158977, 01 25/45, 1985), such as metals next row: iron, titanium, cobalt, manganese, magnesium or zinc. In the description of the patent it is noted that when obtaining substituted alumophosphates with the structure of the ATO also observed the formation side of the impurity crystal phases. Therefore, this method also does not allow potowatomie samples with the structure of the ATO at the investigated variations in the composition of the initial reaction mixture.

To study the sorption and catalytic properties of various materials, including microporous silicoaluminate, you must be sustainable and replicable methodology for the synthesis of pure target material that contains no other crystalline phases. However, existing up to the present time the methods of synthesis of the material SAPO-31 and other materials with the structure of the ATO mainly based on the method described in the ATA. U.S. No. 4440971, which leads to the formation in addition to the target phase and also side phase, usually SAPO-11, or equivalent, i.e. materials with AEL structure, in accordance with the international classification. Moreover, to increase the purity of the target in the initial phase of the reaction mixture often add initially obtained crystals with the structure of the ATO (for example, SAPO-31) as the seed material. For example, in aforementioned U.S. Pat. U.S. No. 4440871 to obtain enough pure material SAPO-31 in the original reaction mixture, you need to add at least 10 wt.% crystals of SAPO-31 (see examples 51 and 53).However, in this case, the product of crystallization is not a pure material SAPO-31 and contains the impurity of SAPO-11. If seed crystals of SAPO-31 is added to the initial mixture, the product crystallization contains SAPO-31 only as an impurity phase (see example 52). The separation of the two crystalline phases any reception is impossible due to their similar properties.

Many patents which describe the use as a catalyst material SAPO-31, x-ray data of the prepared catalysts on the basis of this silicoaluminate consistently noted the presence of impurity crystal phases, mainly SAPO-11 (U.S. Pat. U.S. No. 5413695, C 10 G 073/02, 1995). For the preparation of catalysts based on silical is motovate SAPO-31 is also the most often used method of synthesis, described in U.S. Pat. U.S. No. 4440871.

Thus, almost all the methods of synthesis of materials with the structure of ATU is used to produce the target product of the seed crystals having the same structure, and this method cannot provide clean target phase. Therefore, the main disadvantages of the method to obtain materials with the structure of the ATO are the use of seed crystals and the presence of impurity crystal phases in the composition of the resulting product.

The closest to the claimed purpose of the present invention is selected as a prototype method of preparation of substantially pure silicoaluminate SAPO-31 (U.S. Pat. U.S. No. 5230881, 01 33/34, 1993). In accordance with this method substantially pure SAPO-31 is prepared from a reaction mixture containing sources of oxides of silicon, aluminum and phosphorus, and organic structural connections without the use of seed material, and the properties of the original reaction mixture must meet certain requirements. In particular, in accordance with this method the parameters of the original reaction mixture are selected so as to suppress the formation of side-crystalline phases other than SAPO-31. Strict control of reaction parameters allows to obtain substantially pure material SAPO-31.

Recognize the Naya reaction mixture, prepared in accordance with the prototype meets the following molar ratios:

R/Al2O3=0,6-1,2,

P2O5/Al2O3=0,9-1,1,

MOx/Al2O3=0,01-1,0,

H2O/Al2O3=10-35,

where: R is an organic structure-forming compound, which represents a di-n-Propylamine, di-ISO-Propylamine, or a mixture.

It is noted that the term "substantially pure SAPO-31" in relation to the target phase assumes that the product of crystallization at optimal parameters of the reaction can contain up to 10 wt.% another crystalline phase, for example, SAPO-11. Before the crystallization of the reaction mixture must be strict with initial pH of the reaction mixture at a specific interval of values with the aim of suppressing the formation side of the crystalline phases. The range of the used pH values is very narrow and is 4.5 to 5.5. Getting into the specified range of pH values reached by adding to the initial reaction mixture of a solution of a certain acid, which prevents the formation of material SAPO-31. The list of such acids include hydrochloric, nitric, sulphuric acid. However, a detailed study of the x-ray data obtained materials SAPO-31, are shown in Table III of the said Patent shows that the prepared samples, although without using the ZAT is ovocny technology, but invariably contain impurity phase. In accordance with those reported in Table III x-ray diffraction data reflexes with the reflection angles 2theta = 9,7; 13,5; 16,0; 21,5 etc. do not belong to the material SAPO-31, and belong to the impurity phase SAPO-11, and the amount of this impurity phase estimation can be up to 15 wt.%.

It follows that the known method, while excluding the use of seed crystals of SAPO-31 to increase the purity of the target phase, does not lead to obtaining pure material SAPO-31, not containing by-crystalline phases. In addition, in the description of this patent notes that the claimed in the patent is achieved only by keeping the parameters of the original reaction mixture in strictly defined limits. Thus, in particular, the pH of the initial reaction mixture must be within the boundaries of 4.5 to 5.5.

Thus, the main disadvantages of the method of preparation of the material SAPO-31, closest to the proposed invention, is the presence of impurity crystal phases in the composition of the resulting product and the use of additional mineral acids to ensure the pH of the initial reaction mixture in a narrow interval.

The invention solves the problem of creating an improved method of producing phase-pure materials with the structure of the atoms, i.e. retrieve the target material is in without having side-crystalline phases.

The problem is solved by choosing organic structure-forming reagent for the preparation of the initial reaction mixture.

It should be noted that all known methods of synthesis of the material with the structure of the ATO is primarily used as a structure-forming compounds di-n-Propylamine. However, it is known that the same connection is used for synthesis and other microporous aluminophosphate materials, in particular, SAPO-11. Therefore, the synthesis of pure material SAPO-31 using di-n-Propylamine requires the use of seed crystals of SAPO-31 and/or the curing parameters of the original reaction mixture and the conditions of crystallization in strictly defined limits. In General, the use of these methods are aimed at suppressing the education side of the crystalline phase. However, in all cases, the complete suppression of the formation of other crystalline phase is not observed, and the net material SAPO-31 or similar are not formed.

The problem is solved in the following way. Crystalline elementalist with the structure of the ATO is prepared by cooking the aqueous reaction mixture containing sources of aluminum, phosphorus and replacement of the element and organic structure-forming compound, and having a General composition, expressed in terms of molar relationship:

R/Al2/sub> O3=0.5 to 2.0,

P2O5/Al2O3=0,8-1,2,

MOx/Al2O3=0-1,5,

H2O/Al2O3=15-200,

where: R is an organic structure-forming compound, which represents a di-n-pentylamine, or a mixture of di-n-pentylamine with other di-n-alkylamines followed.

M - a placeholder,

with subsequent crystallization prepared mixture under hydrothermal conditions necessary for the formation of crystals with the structure of the atoms.

Organic structure-forming compound is a mixture composed of di-n-pentylamine and other di-n-alkylamines followed, With3-C6alkyl radicals.

The ratio of the number of n-pantiliner radicals in the composition of di-n-pentylamine to the total number of alkyl radicals in the mixture of dialkylamino is within:

Replacement element is at least one element selected from the following range: beryllium, magnesium, zinc, chromium, gallium, iron, silicon, titanium, cobalt, manganese, Nickel, cadmium.

The present invention describes a method of obtaining a crystalline microporous elementalsubstance material with the structure of the atoms that does not contain side-crystalline phases. The purity of the material produced is determined by the absence of powder on radiographs obtained clicks scow, as in the original after the synthesis of organic form and in calcined form, rentgenograficheski definable reflexes from other crystalline phases. As as side phase during the synthesis of materials with the structure of the ATO is most often formed material with AEL structure, the purity of the target material can be determined by the absence of diffraction reflexes, which is characteristic for the material with the structure of the AEL. These characteristic reflexes are those having the x-ray angle of reflection 2theta=9,5; 15,8; 21,2±0,2°. Reflexes with the values of these angles are not present on radiographs fotovista samples with the structure of the ATO. Thus, the method of preparation material with the structure of the ATO in accordance with the present invention allows to obtain samples with the structure of the atoms, x-rays, which have reflexes that are specific to the target phase, i.e. allows to obtain phase-pure samples.

In accordance with the invention potowatomie materials with the structure of the ATO is prepared using the hydrothermal crystallization of the initial reaction mixture containing sources of aluminum, phosphorus, at least one placeholder element: beryllium, magnesium, zinc, chromium, gallium, iron, silicon, titanium, cobalt, manganese, Nickel, cadmium, and di-pentylamine, individually or in a mixture with other di-alkylamines followed as organic strukturoopredelyayuschyaya connection. In the initial reaction mixture additional seed crystals are not added, and the pH of the reaction mixture with additional quantities of mineral acids do not regulate.

The reaction mixture was placed in an autoclave and heated under hydrothermal conditions, i.e. at a temperature of not less than 100°With up to 250°C, and maintained at these conditions for at least 2 hours, up to 14 days. In General, the conditions of hydrothermal synthesis should contribute to the formation of crystals having the structure of ATU. Optimal conditions for production of high quality materials with the structure of the ATO are crystallization temperature of 140-200°and the duration of crystallization 24-72 hours For accelerating crystallization is possible using such known techniques, such as the ageing of the initial reaction mixture or carrying out crystallization by stirring the reaction mixture. After crystallization, the solid product is separated by known methods such as filtration or centrifugation.

After crystallization fotovista material with the structure of the ATO is separated from the solution, washed with water and dried in air. In the crystallization product is porous the th system organic compound. To remove this connection and clean the system then the material used calcining the resulting material at a temperature up to 700°C.

Clean the material with the structure of the ATO is crystallized in the following molar ratios of the components of the original reaction mixture:

R/Al2O3=0.5 to 2.0,

P2O5/Al2O3=0,8-1,2,

MOx/Al2O3=0-1,5,

H2O/Al2O3=10-200.

As the organic structure-forming compounds (R), providing pure material with the structure of the ATO, using di-n-pentylamine, or a mixture of di-n-pentylamine with other organic di-n-alkylamines followed (where the number of carbon atoms in the alkyl group, 3-6) in the ratio of di-n-pentylamine/the sum of all di-n-alkylamines followed = 0.06 to 1.0 in. The use of this specific structure-forming mixture eliminates the use of a variety of ways, inhibiting the formation of other crystalline phases. As an additional alternative element can be used at least one item from the following range: beryllium, magnesium, zinc, chromium, gallium, iron, silicon, titanium, cobalt, manganese, Nickel, cadmium.

Thus, the use of di-n-pentylamine or a mixture of di-n-pentylamine and other di-n-alkylamines followed as organic structure-forming compounds results in the formation of pure material with the structure of the atoms in a wide range of chemical composition of the initial reaction mixture and the conditions of its hydrothermal crystallization. As a source of phosphorus using concentrated phosphoric acid. As the source of aluminum can be used in various hydrated oxides of aluminum, hydroxides of aluminum, aluminum alcoholate, etc. as the source of silicon use various forms of amorphous silicon dioxide hydrates of silicon dioxide or organic salts of silicon. As sources of other metals can be used and their salts or oxides.

Thus prepared material with the structure of the ATO, as synthesized form, and after annealing at temperatures up to 700°has a characteristic set of x-ray reflexes, relevant material with the structure of ATO (in accordance with the designation of the structural Commission of the International Zeolite Association). Typical powder diffraction pattern synthesized by the proposed method material with the structure of the atoms represented in the drawing. X-ray diffraction data are obtained on automatic diffractometer HZG-4c using copper radiation (λ=1.54178), a graphite monochromator and scintillation counter. Recording diffraction data produced by scanning with a step of 0.05 degrees in the 2theta scale, where theta is the Bragg angle, and a counting time at each step is 3 n Velicina 2theta and relative intensity of the reflexes are shown in table 1. As can be seen from the drawing and from the data presented in table 1, on the x-ray absent reflexes, indicates the presence of the side of impurity phases.

The technical effect of the proposed method lies in the fact that the target material is obtained without the presence of other crystalline impurity phases, chemical composition and hence properties of the final material with the structure of the ATO can be adjusted by the composition of the initial reaction mixture.

Introduction in the original reaction mixture of various additional elements allows to obtain materials with catalytic activity in various reactions, the activity and selectivity of the catalysts prepared on the basis of the substituted alumophosphates with the structure of the ATO, can be regulated by the nature and content of additional modifying element.

Materials with the structure of the ATO prepared in accordance with the invention can be used in a number of reactions in the conversion of hydrocarbons: cracking, alkylation, isomerization of normal paraffins structure, the skeletal isomerization of olefins, the migration of double bonds in olefins, isomerization of substituted aromatic hydrocarbons, etc.

The invention is illustrated by the following examples.

Example 1. The initial reaction mixture is prepared by mixing the con is enteromonas phosphoric acid (85 wt%), water and of aluminum isopropylate. The resulting mixture was mixed well, then add Aerosil (Cab-O-Sil M-5, Cabot Corp., USA). After stirring the formed mixture there was added di-n-pentylamine.

The final mixture is stirred until homogeneous. The chemical composition of the prepared mixture, expressed in molar relationships presented in table 2.

The reaction mixture was placed in an autoclave with a Teflon liner and heated at 175°C for 48 hours the product was filtered, washed with water and dried in air. The dried product according to x-ray analysis has a high degree of crystallinity, characterized by a set of reflexes, are shown in table 1, and is tazobactam material SAPO-31.

Example 2. The initial reaction mixture is prepared by mixing concentrated phosphoric acid (85 wt%), water and of aluminum isopropylate. After stirring the formed mixture there was added a mixture of di-n-pentylamine and di-n-butylamine, taken in a molar ratio of di-n-pentylamine/amount di-n-alkylamines followed or=0.6. The final mixture is stirred until homogeneous. The chemical composition of the prepared mixture, expressed in molar relationships presented in table 2.

The reaction mixture was placed in an autoclave with a Teflon liner and heated at 175°C for 48 hours the product was filtered, promyvayut, dried in air and calcined at 620°C. the Calcined product according to x-ray analysis has a high degree of crystallinity, characterized by a set of reflexes, are shown in table 1, and is tazobactam material ARO-31.

Example 3. The initial reaction mixture is prepared by mixing concentrated phosphoric acid (85 wt%), water and of aluminum isopropylate. The resulting mixture was mixed well, then add Aerosil. After stirring the formed mixture there was added a mixture of di-n-pentylamine and di-n-butylamine, taken in a molar ratio of di-n-pentylamine/amount di-n-alkylamines followed=0,1. The final mixture is stirred until homogeneous. The chemical composition of the prepared mixture, expressed in molar relationships presented in table 2.

The reaction mixture was placed in an autoclave with teflonovym liner and heated at 175°With over 78 hours the product was filtered, washed with water, dried in air and calcined at 620°C. the As-synthesized product, and calcined at 650°With the sample, according to x-ray analysis have a high degree of crystallinity, characterized by a set of reflexes, are shown in table 1, and are tazobactam material SAPO-31.

Example 4. The initial reaction mixture is prepared by mixing concentrated phosphoric to the slots (85%), water and of aluminum isopropylate. The resulting mixture was mixed well, then add the tetraethoxysilane. After stirring the formed mixture there was added a mixture of di-n-pentylamine and di-n-hexylamine taken in a molar ratio of di-n-pentylamine/amount di-n-alkylamines followed=0,8. The final mixture is stirred until homogeneous. The chemical composition of the prepared mixture, expressed in molar relationships presented in table 2.

The reaction mixture was placed in an autoclave with a Teflon liner and heated at 150°C for 55 h the resulting product is filtered, washed with water, dried in air and calcined at 620°C. the As-synthesized product, and calcined at 650°With the sample according to x-ray analysis have a high degree of crystallinity, characterized by a set of reflexes, are shown in table 1, and are tazobactam material SAPO-31.

Example 5. The initial reaction mixture is prepared by mixing concentrated phosphoric acid (85 wt%), water and of aluminum isopropylate. The resulting mixture was mixed well, then add Aerosil. After stirring the formed mixture there was added a mixture of di-n-pentylamine and di-n-Propylamine, taken in a molar ratio of di-n-pentylamine/amount di-n-alkylamines followed=0,5. The final mixture is stirred until homogeneous. Chemical status is in the prepared mixture, expressed in molar relationships presented in table 2.

The reaction mixture was placed in an autoclave with a Teflon liner and heated at 200°C for 20 hours the product was filtered, washed with water, dried in air and calcined at 620°C. the As-synthesized product, and calcined at 650°With the sample, according to x-ray analysis have a high degree of crystallinity, characterized by a set of reflexes, are shown in table 1, and are tazobactam material SAPO-31.

Example 6. The initial reaction mixture is prepared by mixing concentrated phosphoric acid (85 wt%), water and hydroxycarbonate aluminum (Reheis Inc., USA). The resulting mixture was mixed well, then add Aerosil. After stirring the formed mixture there was added di-n-pentylamine. The final mixture is stirred until homogeneous. The chemical composition of the prepared mixture, expressed in molar relationships presented in table 2.

The reaction mixture was placed in an autoclave with a Teflon liner and heated at 175°C for 29 hours the product was filtered, washed with water, dried in air and calcined at 600°C. the Calcined product according to x-ray analysis has a high degree of crystallinity, characterized by a set of reflexes, are shown in table 1, and which is tazobactam material SAPO-31.

Example 7. The initial reaction mixture is prepared by mixing concentrated phosphoric acid (85 wt%), water and hydrated aluminum oxide (pseudoboehmite, Catapal, Vista Chemical, USA). The resulting mixture was mixed well, then add Aerosil (Cab-O-Sil M-5, Cabot Corp., USA). After stirring the formed mixture there was added a mixture of di-n-pentylamine and di-n-butylamine, taken in a molar ratio of di-n-pentylamine/amount di-n-alkylamines followed=0,7. The final mixture is stirred until homogeneous. The chemical composition of the prepared mixture, expressed in molar relationships presented in table 2.

The reaction mixture was placed in an autoclave with a Teflon liner and heated at 200°C for 20 hours the product was filtered, washed with water, dried in air and calcined at 620°C. the As-synthesized product, and calcined at 650°With the sample according to x-ray analysis have a high degree of crystallinity, characterized by a set of reflexes, are shown in table 1, and are tazobactam material SAPO-31.

Example 8. The initial reaction mixture is prepared by mixing concentrated phosphoric acid (85 wt%), water and hydrated aluminum oxide. The resulting mixture was mixed well, then add silicic acid. After stirring the mixture formed was added to it is di-n-pentylamine. The final mixture is stirred until homogeneous. The chemical composition of the prepared mixture, expressed in molar relationships presented in table 2.

The reaction mixture was placed in an autoclave with a Teflon liner and heated at 200°C for 20 hours the product was filtered, washed with water, dried in air and calcined at 620°C. the As-synthesized product, and calcined at 650°With the sample according to x-ray analysis have a high degree of crystallinity, characterized by a set of reflexes, are shown in table 1, and are tazobactam material SAPO-31.

Example 9. The initial reaction mixture is prepared by mixing concentrated phosphoric acid (85 wt%), water and hydroxycarbonate aluminum (Reheis Inc., USA). The resulting mixture was mixed well, then there was added an aqueous solution of silicates (30% SiO2). After stirring the formed mixture there was added a mixture of di-n-pentylamine and di-n-hexylamine taken in a molar ratio of di-n-pentylamine/amount di-n-alkylamines followed =0,67. The final mixture is stirred until homogeneous. The chemical composition of the prepared mixture, expressed in molar relationships presented in table 2.

The reaction mixture was placed in an autoclave with a Teflon liner and heated at 175°C for 29 hours the resulting product is filtered, washed in the Oh, dried in air and calcined at 600°C. the Calcined product according to x-ray analysis has a high degree of crystallinity, characterized by a set of reflexes, are shown in table 1, and is tazobactam material SAPO-31.

Example 10. The initial reaction mixture is prepared by mixing concentrated phosphoric acid (85 wt%), water and of aluminum isopropylate.

The resulting mixture was mixed well, then add magnesium acetate. After stirring the formed mixture there was added a mixture of di-n-pentylamine and di-n-Propylamine, taken in a molar ratio of di-n-pentylamine/amount di-n-alkylamines followed =0,32. The final mixture is stirred until homogeneous. The chemical composition of the prepared mixture, expressed in molar relationships presented in table 2.

The reaction mixture was placed in an autoclave with a Teflon liner and heated at 165°C for 48 hours the product was filtered, washed with water, dried in air and calcined at 620°C. the Calcined product according to x-ray analysis has a high degree of crystallinity, characterized by a set of reflexes, are shown in table 1, and is tazobactam material MARO-31.

Example 11. The initial reaction mixture is prepared by mixing concentrated phosphoric acid (85 wt%), water and isopropyl is as aluminum. The resulting mixture was mixed well, then add magnesium acetate. After stirring the formed mixture there was added di-n-pentylamine. The final mixture is stirred until homogeneous. The chemical composition of the prepared mixture, expressed in molar relationships presented in table 2.

The reaction mixture was placed in an autoclave with teflonovym liner and heated at 145°C for 70 hours resulting product at 620°C. the Synthesized product according to x-ray analysis has a high degree of crystallinity, characterized by a set of reflexes, are shown in table 1, and is tazobactam material MARO-31.

Example 12. The initial reaction mixture is prepared by mixing concentrated phosphoric acid (85 wt%), water and hydroxycarbonate aluminum. The resulting mixture was mixed well, then add the magnesium oxide. After stirring the formed mixture there was added a mixture of di-n-pentylamine and di-n-butylamine, taken in a molar ratio of di-n-pentylamine/amount di-n-alkylamines followed =0,06. The final mixture is stirred until homogeneous. The chemical composition of the prepared mixture, expressed in molar relationships presented in table 2.

The reaction mixture was placed in an autoclave with a Teflon liner and heated at 155°With over 43 hours the product was filtered, washed with the water, dried in air and calcined at 620°C. the Calcined product according to x-ray analysis has a high degree of crystallinity, characterized by a set of reflexes, are shown in table 1, and is tazobactam material MARO-31.

Example 13. The reaction mixture is prepared as in example 1, except that additionally add magnesium acetate. The chemical composition of the prepared mixture, expressed in molar relationships presented in table 2.

The reaction mixture was placed in an autoclave with a Teflon liner and heated at 170°C for 46 hours the product was filtered, washed with water, dried in air and calcined at 620°C. the Calcined product according to x-ray analysis has a high degree of crystallinity, characterized by a set of reflexes, are shown in table 1, and is tazobactam magnesiochromite MAPSO-31.

Example 14. The initial reaction mixture is prepared by mixing concentrated phosphoric acid (85 wt%), water and of aluminum isopropylate. The resulting mixture was mixed well, then add beryllium hydroxide. After stirring the formed mixture there was added di-n-pentylamine. The final mixture is stirred until homogeneous. The chemical composition of the prepared mixture, expressed in molar relationship, predstavlen table 2.

The reaction mixture was placed in an autoclave with a Teflon liner and heated at 170°C for 20 hours the product was filtered, washed with water, dried in air and calcined at 620°C. the Calcined product according to x-ray analysis has a high degree of crystallinity, characterized by a set of reflexes, are shown in table 1, and is tazobactum the material Veara-31.

Example 15. The initial reaction mixture is prepared by mixing concentrated phosphoric acid (85 wt%), water and of aluminum isopropylate.

The resulting mixture was mixed well, then add the zinc acetate. After stirring the formed mixture there was added a mixture of di-n-pentylamine and di-n-Propylamine, taken in a molar ratio of di-n-pentylamine/amount di-n-alkylamines followed =0,45. The final mixture is stirred until homogeneous. The chemical composition of the prepared mixture, expressed in molar relationships presented in table 2.

The reaction mixture was placed in an autoclave with a Teflon liner and heated at 140°C for 42 hours the product was filtered, washed with water, dried in air and calcined at 620°C. the Synthesized product according to x-ray analysis has a high degree of crystallinity, characterized by a set of reflexes, are shown in table 1, and assetsfinancial material ZnAPO-31.

Example 16. The initial reaction mixture is prepared by mixing concentrated phosphoric acid (85 wt%), water and of aluminum isopropylate. The resulting mixture was mixed well, then add the zinc oxide. After stirring the formed mixture there was added di-n-pentylamine. The final mixture is stirred until homogeneous. The chemical composition of the prepared mixture, expressed in molar relationships presented in table 2.

The reaction mixture was placed in an autoclave with a Teflon liner and heated at 150°C for 46 hours the product was filtered, washed with water and dried in air. The synthesized product according to x-ray analysis has a high degree of crystallinity, characterized by a set of reflexes, are shown in table 1, and is tazobactam material ZnAPO-31.

Example 17. The initial reaction mixture is prepared by mixing concentrated phosphoric acid (85 wt%), water and hydroxycarbonate aluminum. The resulting mixture was mixed well, then add the zinc acetate. After stirring the formed mixture there was added a mixture of di-n-pentylamine and di-n-butylamine, taken in a molar ratio of di-n-pentylamine/amount di-n-alkylamines followed =0,88. The final mixture is stirred until homogeneous. The chemical composition of the prepared mixture, expressed in molar relationship is, presented in table 2.

The reaction mixture was placed in an autoclave with a Teflon liner and heated at 155°C for 18 hours the product was filtered, washed with water, dried in air and calcined at 620°C. the Calcined product according to x-ray analysis has a high degree of crystallinity, characterized by a set of reflexes, are shown in table 1, and is tazobactam material ZnAPO-31.

Example 18. The reaction mixture prepared according to example 4, except that additionally add zinc acetate. The chemical composition of the prepared mixture, expressed in molar relationships presented in table 2.

The reaction mixture was placed in an autoclave with a Teflon liner and heated at 160°C for 40 hours, the Obtained product was filtered, washed with water, dried in air and calcined at 620°C. the Calcined product according to x-ray analysis has a high degree of crystallinity, characterized by a set of reflexes, are shown in table 1, and is tazobactam cancellaloooooo ZnAPSO-31.

Example 19. The initial reaction mixture is prepared by mixing concentrated phosphoric acid (85 wt%), water and of aluminum isopropylate. The resulting mixture was mixed well, then add chromium nitrate. After stirring educated smusic it was added di-n-pentylamine. The final mixture is stirred until homogeneous. The chemical composition of the prepared mixture, expressed in molar relationships presented in table 2.

The reaction mixture was placed in an autoclave with a Teflon liner and heated at 170°C for 48 hours the product was filtered, washed with water, dried in air and calcined at 620°C, the Calcined product according to x-ray analysis has a high degree of crystallinity, characterized by a set of reflexes, are shown in table 1, and is tazobactam material CrAPO-31.

Example 20. The reaction mixture prepared according to example 6, except that additionally add chromium nitrate. The chemical composition of the prepared mixture, expressed in molar relationships presented in table 2.

The reaction mixture was placed in an autoclave with a Teflon liner and heated at 170°C for 46 hours the product was filtered, washed with water, dried in air and calcined at 620°C. the Calcined product according to x-ray analysis has a high degree of crystallinity, characterized by a set of reflexes, are shown in table 1, and is tazobactam hamiltonization CrAPSO-31.

Example 21. The initial reaction mixture is prepared by mixing concentrated phosphoric acid (85 wt%), water and isopropylate aluminum is tion.

The resulting mixture was mixed well, then add the gallium nitrate. After stirring the formed mixture there was added a mixture of di-n-pentylamine and di-n-butylamine, taken in a molar ratio of di-n-pentylamine/amount di-n-alkylamines followed=0,47. The final mixture is stirred until homogeneous. The chemical composition of the prepared mixture, expressed in molar relationships presented in table 2.

The reaction mixture was placed in an autoclave with a Teflon liner and heated at 170°C for 48 hours the product was filtered, washed with water, dried in air and calcined at 620°C. the Calcined product according to x-ray analysis has a high degree of crystallinity, characterized by a set of reflexes, are shown in table 1, and is tazobactam material GaAPO-31.

Example 22. The reaction mixture prepared according to example 10, except that additionally add gallium oxide. The chemical composition of the prepared mixture, expressed in molar relationships presented in table 2.

The reaction mixture was placed in an autoclave with a Teflon liner and heated at 160°C for 45 hours the product was filtered, washed with water, dried in air and calcined at 620°C. the Calcined product according to x-ray analysis has a high degree of crystallinity is characterized by a set of reflexes, in table 1, and is tazobactam garymarijuanapotdoll GaMAPO-31.

Example 23. The initial reaction mixture is prepared by mixing concentrated phosphoric acid (85 wt%), water and of aluminum isopropylate. The resulting mixture was mixed well, then add the ferric chloride (III). After stirring the formed mixture there was added di-n-pentylamine. The final mixture is stirred until homogeneous. The chemical composition of the prepared mixture, expressed in molar relationships presented in table 2.

The reaction mixture was placed in an autoclave with a Teflon liner and heated at 170°C for 46 hours the product was filtered, washed with water, dried in air and calcined at 620°C. the Calcined product according to x-ray analysis has a high degree of crystallinity, characterized by a set of reflexes, are shown in table 1, and is tazobactam material FeAPO-31.

Example 24. The reaction mixture is prepared as in example 1 except that additionally add the sulphate of iron (III). The chemical composition of the prepared mixture, expressed in molar relationships presented in table 2.

The reaction mixture was placed in an autoclave with a Teflon liner and heated at 170°C for 42 hours the product was filtered, washed with water, dried on Vozduha annealed at 620° C. the Calcined product according to x-ray analysis has a high degree of crystallinity, characterized by a set of reflexes, are shown in table 1, and is tazobactam genesisintermedia FeAPSO-31.

Example 25. The initial reaction mixture is prepared by mixing concentrated phosphoric acid (85 wt%), water and hydroxycarbonate aluminum (Reheis Inc., USA). The resulting mixture was mixed well, then add tetrabutoxide. After stirring the formed mixture there was added a mixture of di-n-pentylamine and di-n-butylamine, taken in a molar ratio of di-n-pentylamine/amount di-n-alkylamines followed=0,7. The final mixture is stirred until homogeneous. The chemical composition of the prepared mixture, expressed in molar relationships presented in table 2.

The reaction mixture was placed in an autoclave with a Teflon liner and heated at 155°C for 46 hours the product was filtered, washed with water, dried in air and calcined at 600°C. the Calcined product according to x-ray analysis has a high degree of crystallinity, characterized by a set of reflexes, are shown in table 1, and is tazobactam material TiAPO-31.

Example 26. The reaction mixture is prepared as in example 1, except that additionally add tetrabutoxide. The chemical composition of the prepared mixture, expressed in molar relationships presented in table 2.

The reaction mixture was placed in an autoclave with a Teflon liner and heated at 170°C for 42 hours the product was filtered, washed with water, dried in air and calcined at 620°C. the Calcined product according to x-ray analysis has a high degree of crystallinity, characterized by a set of reflexes, are shown in table 1, and is tazobactam titanosilicates TiAPSO-31.

Example 27. The initial reaction mixture is prepared by mixing concentrated phosphoric acid (85 wt%), water and of aluminum isopropylate. The resulting mixture was mixed well, then add nitrate of cobalt.

After stirring the formed mixture there was added di-n-pentylamine. The final mixture is stirred until homogeneous. The chemical composition of the prepared mixture, expressed in molar relationships presented in table 2.

The reaction mixture was placed in an autoclave with a Teflon liner and heated at 170°C for 48 hours the product was filtered, washed with water, dried in air and calcined at 600°C. the Calcined product according to x-ray analysis has a high degree of crystallinity, characterized by a set of reflexes, are shown in table 1, and is tazobactam material WITH THE ARO-31.

Example 28. The initial reaction mixture is prepared by mixing concentrated phosphoric acid (85 wt%), water and of aluminum isopropylate. The resulting mixture was mixed well, then add the chloride of cadmium. After stirring the formed mixture there was added di-n-pentylamine. The final mixture is stirred until homogeneous. The chemical composition of the prepared mixture, expressed in molar relationships presented in table 2.

The reaction mixture was placed in an autoclave with a Teflon liner and heated at 160°C for 28 hours the product was filtered, washed with water, dried in air and calcined at 600°C. the Calcined product according to x-ray analysis has a high degree of crystallinity, characterized by a set of reflexes, are shown in table 1, and is tazobactam material CdAPO-31.

Example 29. The initial reaction mixture is prepared by mixing concentrated phosphoric acid (85 wt%), water and hydroxycarbonate aluminum. The resulting mixture was mixed well, then add the manganese nitrate. After stirring the formed mixture there was added a mixture of di-n-pentylamine and di-n-Propylamine, taken in a molar ratio of di-n-pentylamine/amount di-n-alkylamines followed =0,68. The final mixture is stirred until homogeneous. The chemical composition of the prepared mixture, expressed the military in a molar relationship, presented in table 2.

The reaction mixture was placed in an autoclave with teflonovym liner and heated at 150°C for 40 hours, the Obtained product was filtered, washed with water, dried in air and calcined at 630°C. the Calcined product according to x-ray analysis has a high degree of crystallinity, characterized by a set of reflexes, are shown in table 1, and is tazobactam material MnAPO-31.

Example 30. The reaction mixture is prepared as in example 1, except that additionally add nitrate of manganese. The chemical composition of the prepared mixture, expressed in molar relationships presented in table 2.

The reaction mixture was placed in an autoclave with a Teflon liner and heated at 155°C for 44 hours the product was filtered, washed with water, dried in air and calcined at 620°C. the Calcined product according to x-ray analysis has a high degree of crystallinity, characterized by a set of reflexes, are shown in table 1, and is tazobactam margarettelisto MnAPSO-31.

Example 31. The reaction mixture prepared according to example 17, except that additionally add nitrate of manganese. The chemical composition of the prepared mixture, expressed in molar relationships presented in table 2.

The reaction mixture p is meshaut in the autoclave with a Teflon liner and heated at 150° With over 30 hours the product was filtered, washed with water, dried in air and calcined at 620°C. the Calcined product according to x-ray analysis has a high degree of crystallinity, characterized by a set of reflexes, are shown in table 1, and is tazobactam marganetstsinkovyh MnZnAPO-31.

Example 32. The initial reaction mixture is prepared by mixing concentrated phosphoric acid (85 wt%), water and hydroxycarbonate aluminum (Reheis Inc., USA). The resulting mixture was mixed well, then add the Nickel nitrate. After stirring the formed mixture there was added di-n-pentylamine. The final mixture is stirred until homogeneous. The chemical composition of the prepared mixture, expressed in molar relationships presented in table 2.

The reaction mixture was placed in an autoclave with a Teflon liner and heated at 200°C for 20 hours the product was filtered, washed with water, dried in air and calcined at 600°C. the Calcined product according to x-ray analysis has a high degree of crystallinity, characterized by a set of reflexes, are shown in table 1, and is tazobactam material NiAPO-31.

Example 33. The reaction mixture prepared according to example 4, except that additionally add Nickel nitrate. Chemical is the remaining cooked mixture, expressed in molar relationships presented in table 2.

The reaction mixture was placed in an autoclave with a Teflon liner and heated at 180°C for 46 hours the product was filtered, washed with water, dried in air and calcined at 600°C. the Calcined product according to x-ray analysis has a high degree of crystallinity, characterized by a set of reflexes, are shown in table 1, and is tazobactam nickelcreekgallery.com NiAPSO-31.

Example 34. After forming aluminum oxide (pseudoboehmite)of the material prepared in example 1, to prepare extrudates, which are dried and calcined at 560°C for 4 hours Getting Pt-SAPO-31 catalyst is carried out by impregnation of the original calcined material with an aqueous solution of chloride tetrammine platinum (II) at the rate of 1.0 wt.%. Pt in the composition of the final material with subsequent drying and calcination at 530°C for 3 hours To conduct catalytic tests preparing a fraction from 0.5 to 0.8 mm. conditions of the isomerization of n-octane and properties of the prepared catalyst Pt-SAPO-31 are shown in table 3.

Example 35. After forming aluminum oxide (pseudoboehmite) of the material prepared according to example 20 is prepared extrudates, which are dried and calcined at 600°C for 6 hours Getting Pt-CrAPSO-31 catalyst is carried out by impregnation of the original calcined material with an aqueous solution of chloride tetrammine platinum (II) at the rate of 0.6 wt.%. Pt in the composition of the final material with subsequent drying and calcination at 500°C for 2 hours To conduct catalytic tests preparing a fraction from 0.5 to 0.8 mm Conditions for hydrocracking of n-hexadecane and properties of the prepared catalyst Pt-CrAPSO-31 are shown in table 4.

Example 36. After forming aluminum oxide (pseudoboehmite) of the material prepared according to example 13, prepare extrudates, which are dried and calcined at 600°C for 6 hours To conduct catalytic tests preparing a fraction from 0.5 to 0.8 mm. conditions of the isomerization of m-xylene and properties of the prepared catalyst Pt-MAPSO-31 are shown in table 5.

Example 37. After forming aluminum oxide (pseudoboehmite) of the material prepared according to example 16, prepare extrudates, which are dried and calcined at 620°C for 6 hours To conduct catalytic tests preparing a fraction from 0.5 to 0.8 mm Conditions for alkylation of toluene with methanol and properties of the prepared catalyst ZnAPO-31 are shown in table 6.

Example 38. After forming aluminum oxide (pseudoboehmite) of the material prepared according to example 27, prepare extrudates, which are dried and calcined at 600°C for 6 hours. For carrying out catalytic tests preparing a fraction from 0.5 to 0.8 mm Conditions for isomeres the tion of butene-1 and the properties of the prepared catalyst Soara-31 are shown in table 7.

Thus, the advantage of this way of cooking alumophosphates with the structure of the ATO in comparison with the known methods is that in accordance with the present invention it is possible to obtain samples with the structure of the atoms, x-rays, which have reflexes that are specific to the target phase, i.e. the method allows to obtain potowatomie samples that do not contain side of the impurity crystal phases. For obtaining these materials is carried out in a wide range of chemical composition of the initial reaction mixture and in a wide range of conditions to obtain a product of crystallization. In the proposed method does not use the seed crystals and additional mineral acid. The catalysts with the structure of the ATO prepared by the proposed method are highly efficient catalysts for various reactions in the conversion of hydrocarbons.

Table 1

Basic x-ray reflexes samples with the structure of the atoms, obtained by the proposed method (left - ' green ' materials, right - calcined materials).
2thetad,100×I/Io2thetad,100×I/Io
8.44-8.4910.43-10.4431-348.45-8.4910.42-10.4773-93
14.716.01-6.021-314.70-14.755.99-6.017-11
17.01-17.035.19-5.213-817.00-17.055.18-5.2012-13
18.36-18.374.81-4.834-518.37-18.414.80-4.813-5
20.26-20.274.36-4.3844-6020.27-20.314.35-4.3645-71
22.00-22.014.02-4.0438-5222.01-22.054.01-4.0238-55
22.57-22.593.91-3.9410022.56-22.613.91-3.92100
25.15-25.163.51-3.544-825.14-25.193.515-6
25.653.44-3.473-1025.62-at 25.683.44-3.456
At 27.94-27.963.16-3.1912-18At 27.94-27.983.1614-21
29.702.98-3.016-1329.68-29.732.97-2.989-11
31.03-30.940-430.96-31.002.852
31.742.78-2.8223-4031.73-31.782.7826-33
35.14-35.152.51-2.559-13At 35.13-35.182.5110-13
36.17-36.222.44-2.483-736.21-36.242.444-6
37.22-37.272.37-2.41337.25-37.312.373-4
37.62-37.652.35-2.392At 37.63-37.672.352-3
38.21-38.292.31-2.353-438.25-38.32.313-5
39.29-39.32.25-2.29439.30-at 39.342.254-5
39.56-at 39.622.23-2.281-239.58-39.662.232

Table 2
# exampleThe ratio of Al2About3/P2O5The ratio of MOx/Al2O3The ratio R/Al2About3The relation of H2O/Al2About3
110,61,260
20,901,448
31,21,51,6120
40.930,30,715
51,050,150,9120
610,51,6200
71,20,152,040
81.10,051,675
910.61,690
100,90,21,260
110.80,41,475
120,970,11,562
13see Example No. 10,1
140,90.151,360
150,80.351,565
160,950,151,265
170,95 0,251,7120
18see Example No. 40,12
190,850,21,460
20see Example No. 60,1
210,90,11,360
22see Example No. 100,1
230,90,11,260
24see Example No. 10,1
2510,21,790
26see Example No. 10,15
270,850,251,375
280,90,21,450
290,90,151,6150
30see Example No. 10,11,290
31see Example No. 170,151,475
320,950,2 1,8120
33see Example No. 40,15

Table 3

Isomerisation of n-octane on the catalyst Pt-SAPO-31. T=330°C, P=20 ATM, the feed rate of n-octane - 3,5 h-1the ratio of hydrogen/n-octane = 10 (mol.).
Conversion of n-octane wt.%.Selectivity to isomers of octane, wt.%.The selectivity for mono-methylheptane, wt.%.
63,4for 91.386,7
Table 4

Hydrocracking of n-hexadecane catalyst CrAPSO-31. T = 360°C, P = 20 ATM, the feed rate of n-hexadecane - 2,0 h-1the ratio of hydrogen/n-hexadecan = 10 (mol.).
Conversion of n-hexadecane, wt.%.Selectivity for hydrocarbons4-C8wt.%.Selectivity for ISO-hexadecane, wt.%.
98,182,911,3
Table 5

Isomerization of meta-xylene catalyst SAPO-31. T=350°C, P=5 ATM, the feed speed m-xylene - 2,0 h-1.
Conversion of m-xylene, m is S.%. The yield of o-xylene and p-xylene, wt.%.
16,314,9
Table 6

Alkylation of toluene with methanol on the catalyst ZnAPO-31. Toluene:methanol =2:1 (mol.). T=350°C, P=5 ATM, the rate of feed of toluene and 2.0 h-1.
The conversion of toluene wt.%.The yield of xylenes, wt%.
32,219,5
Table 7

Isomerization of butene-1 in the catalyst Soara-31. T=150°S, feed rate of 1-butene to 2,5 h-1.
The conversion of butene-1, wt.%.The output of the isomers of butenes, wt.%.
of 21.218,3

The method of preparation of crystalline elementalist with zeolite like type structure ARE-31 through preparation of an aqueous reaction mixture containing a source of aluminum, phosphoric acid, and one or two sources of replacement of the element and organic structure-forming compound, and having a General composition, expressed in terms of molar relationship:

R/Al2O3=0.5 to 2.0,

P2O5/Al2O3=0,8-1,2,

MOx/Al2O3 =0-1,5,

H2O/Al2O3=15-200,

where R is an organic structure-forming compound;

M - placeholder element selected from beryllium, magnesium, zinc, chromium, gallium, iron, silicon, titanium, cobalt, manganese, Nickel, cadmium;

x is 1, 3/2 or 2,

with subsequent crystallization prepared mixture under hydrothermal conditions necessary for the formation of the crystal structure type AlPO-31, separation and drying of the obtained material, characterized in that the organic structure-forming compound is a di-n-pentylamine, or a mixture of di-n - pentylamine with other di-n-alkylamines followed with the content of carbon atoms in the alkyl group, 3-6, and the ratio of di-n-pentylamine to the total amount of di-n-alkylamines followed in the mixture is 0.06 to 1.0.



 

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