A SAPO-35 / SAPO-5 symbiotic molecular sieve, its preparation method and application, and a molecular sieve composition and its application

Abstract

The present invention belongs to the field of molecular sieves, and specifically discloses a SAPO-35 / SAPO-5 symbiotic molecular sieve and its preparation method and application, as well as a molecular sieve composition and its application. The SAPO-35 / SAPO-5 (LEV / AFI) symbiotic molecular sieve has the following anhydrous chemical composition: (Al x P y Si z )O2·mR, where R is methyltriethylammonium hydroxide, x, y, and z respectively represent the molar fractions of the sum of the molar numbers of Al, P, and Si, x = 0.35 - 0.55, y = 0.30 - 0.55, z = 0.005 - 0.15, x + y + z = 1, m is the molar fraction of R, m = 0.005 - 0.05. The peak intensity of the characteristic peaks belonging to the SAPO-5 (AFI) structure in the SAPO-35 / SAPO-5 symbiotic molecular sieve is higher than the peak intensity of the characteristic peaks belonging to the SAPO-35 (LEV) structure. The SAPO-5 molecular sieve accounts for 55 - 90% in the SAPO-35 / SAPO-5 symbiotic molecular sieve. After calcination, the specific surface area of the symbiotic molecular sieve is 300 - 450 m 2 / g, and the acid amount is 200 - 1000 μmol / g. The molecular sieve of the present invention is used in the cumene cracking reaction, having the advantages of high activity and high benzene selectivity.

Description

Technical Field

[0001] The present invention relates to a SAPO-35 / SAPO-5 symbiotic molecular sieve, a preparation method and application thereof, and a molecular sieve composition and application thereof. Background Art

[0002] Aluminum phosphate molecular sieves (AlPO series molecular sieves) are a type of molecular sieves whose framework is composed of alternately connected phosphorus-oxygen tetrahedrons and aluminum-oxygen tetrahedrons. Since the molecular sieve framework is electrically neutral, it has no cation exchange performance and catalytic reaction performance. Introducing silicon into the aluminum phosphate molecular sieve framework results in the SAPO series molecular sieves (US4440871). The framework is negatively charged and there are balancing cations outside the framework, so it has cation exchange performance and catalytic reaction performance. Currently, SAPO series molecular sieves are widely used in the fields of oil refining and petrochemical industry such as catalytic cracking, hydrocracking, isomerization, and aromatic alkylation.

[0003] The topological structure of SAPO-35 is the intergrowth chabazite type (LEV), with the space group of R-3m. It has mutually intersecting eight-membered ring channels with a pore size of 0.36×0.48 nm. The framework of the molecular sieve is composed of LEV cages connected by single six-membered rings and double six-membered rings. The pore channels have a large micropore volume due to the presence of heptadecahedral pores. There are two different T atom positions in the molecular sieve framework, one in the double six-membered ring and the other in the single six-membered ring, and the distribution ratio of these two positions is 2:1. SAPO-35 molecular sieves generally use hydrothermal or solvothermal methods, with water or alcohol as the solvent, and a mixture composed of an aluminum source, a silicon source, a phosphorus source, an organic structure-directing agent, and deionized water is synthesized in a reaction kettle under its own pressure. The selection of the organic structure-directing agent will have a certain impact on the microstructure, element composition, and morphology of the synthesized molecular sieve, and thus affect its catalytic performance. The topological structure of SAPO-5 is the AFI type, and its framework structure is a one-dimensional pore channel system of twelve-membered rings composed of alternately two four-membered rings and six-membered rings, with a pore size of 0.80 nm, belonging to macroporous molecular sieves. It has unique catalytic performance and has good catalytic performance in reactions such as meta-xylene isomerization and n-hexane catalytic cracking.

[0004] Molecular sieves with LEV topological structure and AFI topological structure have two sets of pore size structure systems of different sizes. The symbiotic combination of the two molecular sieves may affect the element distribution in the pore channels of the molecular sieve.

[0005] CN103706394A discloses a submicron SAPO-5 / SAPO-18 composite molecular sieve and a preparation method thereof. There is only one type of medium strong acid center in the SAPO-5 molecular sieve with AFI structure, and the L acid center is in the majority. The SAPO-35 molecular sieve with LEV topological structure has strong acid and weak acid. Therefore, the symbiotic molecular sieve with LEV topological structure and AFI topological structure can achieve complementarity in acidity and may have a beneficial effect on the performance of the catalyst. Summary of the Invention

[0006] The technical problem to be solved by the present invention is to provide a SAPO-35 / SAPO-5 symbiotic molecular sieve with adjustable composition ratio, specific surface area, micropore volume and acid amount, and to provide a preparation method of the SAPO-35 / SAPO-5 symbiotic molecular sieve that is simple and feasible to operate.

[0007] According to the first aspect of the present invention, a SAPO-35 / SAPO-5 symbiotic molecular sieve of the present invention

[0008] The SAPO-35 / SAPO-5 symbiotic molecular sieve has the following anhydrous chemical composition: (Al x P y Si z )O 2 ·mR, where R is methyltriethylammonium hydroxide, x, y and z respectively represent the mole fractions of the sum of the moles of Al, P and Si, x = 0.35 - 0.55, y = 0.30 - 0.55, z = 0.005 - 0.15, x + y + z = 1, and m is the mole fraction of R, m = 0.005 - 0.05;

[0009] Preferably, the SAPO-35 / SAPO-5 symbiotic molecular sieve has an X-ray diffraction pattern attributed to the AFI structure of the SAPO-5 molecular sieve and the LEV structure of the SAPO-35 molecular sieve as shown in the following table;

[0010]

[0011] a: ±0.30°, b: varies with 2θ.

[0012] In the present invention, in the X-ray diffraction pattern, vw, w, m, s, vs represent the diffraction peak intensity, vw is very weak, w is weak, m is medium, s is strong, and vs is very strong; generally speaking, vw is less than 5%, w is 5% - 20%, m is 20% - 40% (including 20% and 40%), s is 40% - 70%, and vs is greater than 70% (including 70%).

[0013] The data in the above table represents the SAPO-35 / SAPO-5 intergrown molecular sieve at 2θ (°) (a) is 7.40, and the d-spacing is 11.941, and the relative intensity (I / I 0 ×100) is m-vs (medium strong), and so on. Those skilled in the art are well aware of the representation method of this table, and the present invention will not elaborate on it one by one here.

[0014] The SAPO-35 / SAPO-5 intergrown molecular sieve of the present invention has a unique chemical composition, adjustable composition ratio and acid amount, and has good industrial application prospects.

[0015] According to a preferred embodiment of the present invention, x = 0.38 - 0.52, y = 0.38 - 0.52, z = 0.01 - 0.15, x + y + z = 1, and m = 0.01 - 0.05. The SAPO-35 / SAPO-5 intergrown molecular sieve of the present invention has an adjustable composition ratio and has good industrial application prospects.

[0016] According to a preferred embodiment of the present invention, the peak intensity of the characteristic peaks belonging to the AFI structure of the SAPO-5 molecular sieve in the SAPO-35 / SAPO-5 intergrown molecular sieve is higher than the peak intensity of the characteristic peaks belonging to the LEV structure of the SAPO-35 molecular sieve.

[0017] According to a preferred embodiment of the present invention, preferably, the SAPO-5 molecular sieve accounts for 55 - 90% by weight in the SAPO-35 / SAPO-5 intergrown molecular sieve. For the SAPO-35 / SAPO-5 intergrown molecular sieve of the present invention, the proportion of the SAPO-5 molecular sieve in the SAPO-35 / SAPO-5 intergrown molecular sieve is adjustable, and it has good industrial application prospects.

[0018] The SAPO-35 / SAPO-5 intergrown molecular sieve having the aforementioned structure and composition of the present invention can achieve the purpose of the present invention, and there are no special requirements for its preparation method. According to a preferred embodiment of the present invention, the present invention provides a preparation method of the SAPO-35 / SAPO-5 intergrown molecular sieve, and this method includes the following steps:

[0019] Performing heat crystallization treatment on a mixture containing an aluminum source, a phosphorus source, a silicon source, methyltriethylammonium hydroxide and water, and performing post-treatment to obtain the SAPO-35 / SAPO-5 intergrown molecular sieve;

[0020] Among them, the aluminum source is calculated as Al 2 O 3 calculated, the phosphorus source is calculated as P 2 O 5 calculated, and the silicon source is calculated as SiO 2Calculated as Al, methyltriethylammonium hydroxide R and water, with a molar ratio of Al 2 O 3 :P 2 O 5 :SiO 2 :R:H 2 O = 1:0.65 - 1.40:0.02 - 0.65:0.60 - 1.45:28 - 100.

[0021] The present invention provides a simple and feasible method for preparing SAPO-35 / SAPO-5 symbiotic molecular sieve, using relatively inexpensive methyltriethylammonium hydroxide as the organic structure-directing agent, with the crystallization solution being nearly neutral and the post-treatment being relatively simple and environmentally friendly.

[0022] The present invention can carry out crystallization under nearly neutral conditions. For the present invention, the pH value of the mixture is 5.5 - 8.0.

[0023] In the present invention, there are no special requirements for the crystallization conditions of the mixture, and conventional crystallization conditions can be used for the present invention. According to a preferred embodiment of the present invention, the crystallization conditions of the mixture include crystallization at 150 - 205 °C for 0.5 - 7 days, preferably crystallization at 155 - 200 °C for 0.5 - 6 days, and more preferably crystallization at 160 - 195 °C for 0.75 - 5 days.

[0024] The method of the present invention can be carried out under seedless conditions. For the present invention, it is preferred that the mixture does not contain seeds.

[0025] In the present invention, the optional ranges of the amounts of each substance are relatively wide and can be adjusted according to needs. According to a preferred embodiment of the present invention, the aluminum source is calculated as Al 2 O 3 calculated, the phosphorus source is calculated as P 2 O 5 calculated, the silicon source is calculated as SiO 2 calculated, methyltriethylammonium hydroxide R and water, with a molar ratio of Al 2 O 3 :P 2 O 5 :SiO 2 :R:H 2 O = 1:0.70 - 1.40:0.04 - 0.60:0.65 - 1.40:30 - 90.

[0026] In the present invention, there are no special requirements for the optional types of the aluminum source, phosphorus source, and silicon source, and common types can be used for the present invention.

[0027] According to a preferred embodiment of the present invention, the aluminum source is at least one selected from pseudoboehmite, alkoxyaluminum, aluminum salts, alumina, and aluminum hydroxide, and preferably pseudoboehmite.

[0028] According to a preferred embodiment of the present invention, the phosphorus source is selected from at least one of phosphoric acid, ammonium hydrogen phosphate, ammonium dihydrogen phosphate, and organic phosphorus compounds, and is preferably phosphoric acid.

[0029] According to a preferred embodiment of the present invention, the silicon source is selected from at least one of silica sol, silica gel, and tetraethyl orthosilicate, and is preferably silica sol.

[0030] In the present invention, for the post-treatment after the crystallization step in the preparation method, the SAPO-35 / SAPO-5 co-crystalline molecular sieve can be separated from the obtained mixture by any conventionally known post-treatment method. As the post-treatment method, for example, a method of separating, filtering, washing, and drying the mixture obtained after the crystallization step can be cited. Here, the filtration, washing, and drying can be carried out in any manner conventionally known in the art. Specifically, for example, as the filtration, the obtained product mixture can be simply suction-filtered. As the washing, for example, washing with deionized water and / or ethanol for 2 to 3 times can be cited. As the drying temperature, for example, 40 to 110 °C can be cited, and as the drying time, for example, 4 to 24 h can be cited. This drying can be carried out under normal pressure or under reduced pressure.

[0031] According to the requirements of the present invention, the molecular sieve prepared by the foregoing method can also be calcined to remove the organic structure-directing agent and possible moisture, etc. The calcination can be carried out in any manner conventionally known in the art. For example, the calcination temperature is generally 300 to 800 °C, preferably 400 to 650 °C, and the calcination time is generally 1 to 10 hours, preferably 3 to 6 hours. In addition, the calcination is generally carried out in an oxygen-containing atmosphere, such as an air or oxygen atmosphere.

[0032] The present invention provides the SAPO-35 / SAPO-5 co-crystalline molecular sieve prepared by the preparation method of the present invention.

[0033] As described above, according to a preferred embodiment of the present invention, the SAPO-35 / SAPO-5 co-crystalline molecular sieve has the following anhydrous chemical composition: (Al x P y Si z )O 2 ·mR, where R is methyltriethylammonium hydroxide, x, y, and z respectively represent the mole fractions of the sum of the moles of Al, P, and Si, x = 0.35 to 0.55, y = 0.30 to 0.55, z = 0.005 to 0.15, x + y + z = 1, m is the mole fraction of R, and m = 0.005 to 0.05;

[0034] The SAPO-35 / SAPO-5 intergrown molecular sieve has an X-ray diffraction pattern including the AFI structure attributed to the SAPO-5 molecular sieve and the LEV structure attributed to the SAPO-35 molecular sieve as shown in the following table;

[0035]

[0036] a: ±0.30°, b: varies with 2θ.

[0037] According to a preferred embodiment of the present invention, x = 0.38 to 0.52, y = 0.38 to 0.52, z = 0.01 to 0.15, x + y + z = 1, m = 0.01 to 0.05.

[0038] According to a preferred embodiment of the present invention, in the SAPO-35 / SAPO-5 intergrown molecular sieve, the peak intensity of the characteristic peak belonging to the AFI structure of the SAPO-5 molecular sieve is higher than that of the characteristic peak belonging to the LEV structure of the SAPO-35 molecular sieve. Preferably, the SAPO-5 molecular sieve accounts for 55 to 90% by weight in the SAPO-35 / SAPO-5 intergrown molecular sieve.

[0039] According to a preferred embodiment of the present invention, after calcination at 300 to 800 °C, preferably 400 to 650 °C, for 1 to 10 hours, preferably 3 to 6 hours: the specific surface area of the SAPO-35 / SAPO-5 intergrown molecular sieve is 300 to 450 m 2 / g.

[0040] According to a preferred embodiment of the present invention, after calcination at 300 to 800 °C, preferably 400 to 650 °C, for 1 to 10 hours, preferably 3 to 6 hours: the total pore volume of the SAPO-35 / SAPO-5 intergrown molecular sieve is 0.20 to 0.50 cm 3 / g, preferably 0.20 to 0.45 cm 3 / g.

[0041] According to a preferred embodiment of the present invention, after calcination at 300 to 800 °C, preferably 400 to 650 °C, for 1 to 10 hours, preferably 3 to 6 hours: the micropore volume of the SAPO-35 / SAPO-5 intergrown molecular sieve is 0.10 to 0.25 cm 3 / g, preferably 0.11 to 0.20 cm 3 / g.

[0042] According to a preferred embodiment of the present invention, after calcination at 300 - 800 °C, preferably 400 - 650 °C, for 1 - 10 hours, preferably 3 - 6 hours: the acid amount of the SAPO-35 / SAPO-5 intergrown molecular sieve is 200 - 1000 μmol / g, preferably 300 - 900 μmol / g.

[0043] The molecular sieve of the present invention can be used alone or mixed with a binder or formed for use. Therefore, the present invention provides a molecular sieve composition comprising the SAPO-35 / SAPO-5 intergrown molecular sieve of the present invention and a binder.

[0044] The present invention provides the application of the SAPO-35 / SAPO-5 intergrown molecular sieve of the present invention or the molecular sieve composition of the present invention as a catalyst in the conversion reaction of organic substances, preferably in the cracking reaction, and particularly preferably in the application of preparing benzene by cumene cracking reaction.

[0045] The molecular sieve of the present invention is particularly suitable for the conversion of organic substances, for example, used in the cumene cracking reaction. It has the advantages of high activity and high benzene selectivity.

[0046] The present invention provides a SAPO-35 / SAPO-5 intergrown molecular sieve with a unique chemical composition. The composition ratio of the two molecular sieves can be adjusted, and the acid amount can be adjusted, having good industrial application prospects. The preparation method of the SAPO-35 / SAPO-5 intergrown molecular sieve of the present invention is simple and feasible, uses relatively inexpensive methyltriethylammonium hydroxide as the organic structure-directing agent, the crystallization solution is nearly neutral, and the post-treatment is relatively simple and environmentally friendly. Description of the Drawings

[0047] Figure 1 It is the X-ray diffraction pattern of the molecular sieve obtained in Example 1;

[0048] Figure 2 It is the X-ray diffraction pattern of the molecular sieve obtained in Example 2;

[0049] Figure 3 It is the X-ray diffraction pattern of the molecular sieve obtained in Example 3;

[0050] Figure 4 It is the X-ray diffraction pattern of the molecular sieve obtained in Example 4. Detailed Embodiments

[0051] The endpoints and any values disclosed in this text for a range are not limited to the exact range or value. These ranges or values should be understood to include values close to these ranges or values. For numerical ranges, between the endpoint values of each range, between the endpoint values of each range and individual point values, and between individual point values, they can be combined with each other to obtain one or more new numerical ranges, and these numerical ranges should be regarded as specifically disclosed in this text.

[0052] The following will elaborate on the specific embodiments of the present invention. However, it should be noted that the protection scope of the present invention is not limited by these specific embodiments, but is determined by the appended claims.

[0053] All publications, patent applications, patents, and other references mentioned in this specification are hereby incorporated by reference. Unless otherwise defined, all technical and scientific terms used in this specification have the meanings commonly understood by those skilled in the art. In case of conflict, the definitions in this specification shall prevail.

[0054] When this specification uses prefixes such as "known to those skilled in the art", "prior art", or similar terms to introduce materials, substances, methods, steps, devices, or components, etc., the objects introduced by these prefixes cover those commonly used in the art at the time when this application is filed, but also include those that are not commonly used currently but will become recognized in the art as suitable for similar purposes.

[0055] According to a preferred embodiment of the present invention, the present invention provides a SAPO-35 / SAPO-5 (LEV / AFI) intergrown molecular sieve having the following anhydrous chemical composition: (Al x P y Si z )O 2 ·mR, where R is methyltriethylammonium hydroxide, x, y, and z respectively represent the mole fractions of the sum of the moles of Al, P, and Si, x = 0.35 - 0.55, y = 0.30 - 0.55, z = 0.005 - 0.15, x + y + z = 1, and m is the mole fraction of R, m = 0.005 - 0.05.

[0056] According to a preferred embodiment of the present invention, in the chemical composition, x = 0.38 - 0.52, y = 0.38 - 0.52, z = 0.01 - 0.15, x + y + z = 1, and m = 0.01 - 0.05.

[0057] According to a preferred embodiment of the present invention, the molecular sieve has an X-ray diffraction pattern attributed to the SAPO-5 molecular sieve (AFI) structure as shown in the following table,

[0058]

[0059] a: ±0.30°, b: varies with 2θ.

[0060] According to a preferred embodiment of the present invention, the molecular sieve has an X-ray diffraction pattern attributed to the SAPO-35 molecular sieve (LEV) structure as shown in the following table,

[0061]

[0062]

[0063] a: ±0.30°, b: varies with 2θ.

[0064] According to a preferred embodiment of the present invention, in the SAPO-35 / SAPO-5 intergrown molecular sieve, the peak intensity of the characteristic peaks belonging to the SAPO-5 (AFI) structure is higher than that of the characteristic peaks belonging to the SAPO-35 (LEV) structure, and the SAPO-5 molecular sieve accounts for 55-90% in the SAPO-35 / SAPO-5 intergrown molecular sieve.

[0065] According to a preferred embodiment of the present invention, after calcining at 300-800 °C, preferably 400-650 °C, for 1-10 hours, preferably 3-6 hours: the specific surface area of the SAPO-35 / SAPO-5 intergrown molecular sieve is 300-450 m 2 / g, the total pore volume is 0.20-0.50 cm 3 / g, preferably 0.20-0.45 cm 3 / g, the micropore volume is 0.10-0.25 cm 3 / g, preferably 0.11-0.20 cm 3 / g.

[0066] According to a preferred embodiment of the present invention, after calcining at 300-800 °C, preferably 400-650 °C, for 1-10 hours, preferably 3-6 hours: the acid amount of the SAPO-35 / SAPO-5 intergrown molecular sieve is 200-1000 μmol / g, preferably 300-900 μmol / g.

[0067] According to a preferred embodiment of the present invention, the present invention provides a preparation method of a SAPO-35 / SAPO-5 intergrown molecular sieve, comprising the following steps:

[0068] Performing one-step heating crystallization treatment on a mixture formed by an aluminum source, a phosphorus source, a silicon source, methyltriethylammonium hydroxide and water, and performing post-treatment to obtain the SAPO-35 / SAPO-5 intergrown molecular sieve;

[0069] According to a preferred embodiment of the present invention, the aluminum source is in the form of Al2 O 3 Calculated as P for the phosphorus source 2 O 5 Calculated as SiO for the silicon source 2 Calculated as aluminum, phosphorus source as P 2 O 3 : P 2 O 5 : SiO 2 : R: H 2 O = 1: 0.65 to 1.40: 0.02 to 0.65: 0.60 to 1.45: 28 to 100.

[0070] According to a preferred embodiment of the present invention, the aluminum source is calculated as Al 2 O 3 Calculated as P for the phosphorus source 2 O 5 Calculated as SiO for the silicon source 2 Calculated as aluminum, phosphorus source as P 2 O 3 : P 2 O 5 : SiO 2 : R: H 2 O = 1: 0.70 to 1.40: 0.04 to 0.60: 0.65 to 1.40: 30 to 90.

[0071] According to a preferred embodiment of the present invention, the aluminum source is at least one selected from pseudoboehmite, alkoxyaluminum, aluminum salts, alumina, and aluminum hydroxide, the phosphorus source is at least one selected from phosphoric acid, ammonium hydrogen phosphate, ammonium dihydrogen phosphate, and organic phosphides, and the silicon source is at least one selected from silica sol, silica gel, and tetraethyl orthosilicate.

[0072] According to a preferred embodiment of the present invention, the aluminum source is at least one selected from pseudoboehmite and aluminum isopropoxide, the phosphorus source is phosphoric acid, and the silicon source is silica sol.

[0073] According to a preferred embodiment of the present invention, the pH value of the mixture is 5.5 to 8.0.

[0074] According to a preferred embodiment of the present invention, the crystallization conditions of the mixture are crystallization at 150 to 205 °C for 0.5 to 7 days, preferably crystallization at 155 to 200 °C for 0.5 to 6 days, more preferably crystallization at 160 to 195 °C for 0.75 to 5 days.

[0075] According to a preferred embodiment of the present invention, the mixture does not contain seeds.

[0076] According to a preferred embodiment of the present invention, the present invention provides a SAPO-35 / SAPO-5 symbiotic molecular sieve obtained by the above preparation method. The SAPO-35 / SAPO-5 (LEV / AFI) symbiotic molecular sieve has the following anhydrous chemical composition: (Al x P y Si z )O 2 ·mR, where R is methyltriethylammonium hydroxide, x, y, and z respectively represent the molar fractions of the sum of the molar amounts of Al, P, and Si. x = 0.35 to 0.55, y = 0.30 to 0.55, z = 0.005 to 0.15, x + y + z = 1, and m is the molar fraction of R, m = 0.005 to 0.05.

[0077] According to a preferred embodiment of the present invention, in the chemical composition, x = 0.38 to 0.52, y = 0.38 to 0.52, z = 0.01 to 0.15, x + y + z = 1, and m = 0.01 to 0.05.

[0078] According to a preferred embodiment of the present invention, in the SAPO-35 / SAPO-5 symbiotic molecular sieve, the peak intensity of the characteristic peak belonging to the SAPO-5 (AFI) structure is higher than the peak intensity of the characteristic peak belonging to the SAPO-35 (LEV) structure, and the SAPO-5 molecular sieve accounts for 55 to 90% in the SAPO-35 / SAPO-5 symbiotic molecular sieve.

[0079] According to a preferred embodiment of the present invention, after calcining at 300 to 800 °C, preferably 400 to 650 °C, for 1 to 10 hours, preferably 3 to 6 hours: the specific surface area of the SAPO-35 / SAPO-5 symbiotic molecular sieve is 300 to 450 m 2 / g, the total pore volume is 0.20 to 0.50 cm 3 / g, preferably 0.20 to 0.45 cm 3 / g, and the micropore volume is 0.10 to 0.25 cm 3 / g, preferably 0.11 to 0.20 cm 3 / g.

[0080] According to a preferred embodiment of the present invention, after calcining at 300 to 800 °C, preferably 400 to 650 °C, for 1 to 10 hours, preferably 3 to 6 hours: the acid amount of the SAPO-35 / SAPO-5 symbiotic molecular sieve is 200 to 1000 μmol / g, preferably 300 to 900 μmol / g.

[0081] According to a preferred embodiment of the present invention, the present invention further provides a molecular sieve composition, comprising the SAPO-35 / SAPO-5 intergrown molecular sieve provided by the present invention or a binder.

[0082] The present invention provides the application of the SAPO-35 / SAPO-5 intergrown molecular sieve or the molecular sieve composition of the present invention as a catalyst in the organic matter conversion reaction, preferably in the cracking reaction, and particularly preferably in the application of preparing benzene by cumene cracking reaction.

[0083] The molecular sieve of the present invention is particularly suitable for the conversion of organic matter, for example, for the cumene cracking reaction. It has the advantages of high activity and high benzene selectivity.

[0084] The present invention provides a SAPO-35 / SAPO-5 intergrown molecular sieve, which has a unique chemical composition. The composition ratio and acid amount of the two molecular sieves can be adjusted, and it has good industrial application prospects. The preparation method of the SAPO-35 / SAPO-5 intergrown molecular sieve of the present invention is simple and feasible. Using relatively inexpensive methyltriethylammonium hydroxide as the organic structure directing agent, the crystallization solution is nearly neutral, and the post-treatment is relatively simple and environmentally friendly.

[0085] In the context of this specification, except for the expressly stated content, any matter or thing not mentioned shall directly apply those known in the art without any change. Moreover, any embodiment described herein can be freely combined with one or more other embodiments described herein, and the resulting technical solution or technical idea shall be regarded as part of the original disclosure or original record of the present invention, and shall not be regarded as new content not disclosed or anticipated herein, unless those skilled in the art consider that the combination is obviously unreasonable.

[0086] In the context of this specification, for a molecular sieve, before other substances (such as organic structure directing agent molecules, etc.) filled in the pores during the synthesis of the molecular sieve other than water and metal ions in the pores are removed, it is called a "precursor".

[0087] In the context of this specification, the structure of the molecular sieve is determined by the X-ray diffraction pattern (XRD), and the X-ray diffraction pattern (XRD) is measured by an X-ray powder diffractometer, using a Cu-Kα ray source and a nickel filter. Before the sample test, the crystallization of the molecular sieve sample is observed by a scanning electron microscope (SEM) to confirm that there is only one kind of crystal in the sample, that is, the molecular sieve sample is a pure phase. On this basis, the XRD test is carried out to ensure that there are no interference peaks of other crystals in the diffraction peaks of the XRD pattern.

[0088] In the context of this specification, in the XRD data of the molecular sieve, w, m, s, and vs represent the diffraction peak intensities. w is weak, m is medium, s is strong, and vs is very strong, which are well-known to those skilled in the art. Generally, w is less than 20; m is 20 - 40; s is 40 - 70; vs is greater than 70.

[0089] In the context of this specification, including in the following examples and comparative examples, the model of the X-ray powder diffractometer for the molecular sieve is the Panalytical X PERPRO type X-ray powder diffractometer, which analyzes the phase of the sample, with a CuKα ray source , a nickel filter, a 2θ scanning range of 2 - 50°, an operating voltage of 40 KV, a current of 40 mA, and a scanning rate of 10° / min.

[0090] In the context of this specification, including in the following examples and comparative examples, the model of the inductively coupled plasma atomic emission spectrometer (ICP) for the molecular sieve is the Varian 725-ES. The analysis sample is dissolved with hydrofluoric acid to detect the elemental content in moles.

[0091] In the context of this specification, including in the following examples and comparative examples, the micropore volume and specific surface area of the molecular sieve are measured by the nitrogen physical adsorption - desorption method (BET method): The nitrogen physical adsorption - desorption isotherm of the molecular sieve is measured using a physical adsorption instrument (such as the Micromeretic ASAP2020M physical adsorption instrument), and then calculated by the BET equation and the t-plot equation. The experimental conditions for the SAPO-35 / SAPO-5 intergrown molecular sieve are: the measurement temperature is -169°C. The molecular sieve is first heat-treated in an air atmosphere at 550°C for 6 hours before measurement, and then pre-treated in vacuum at 350°C for 4 hours.

[0092] In the context of this specification, including in the following examples and comparative examples, the acid amount of the molecular sieve is determined by NH 3 -TPD chemical adsorption - desorption curves are measured using an Altamira AMI-3300 type instrument. The sample is activated at 550°C for 1 h before testing, adsorbed with ammonia at 100°C for 20 min, and then desorbed and detected at 100 - 600°C.

[0093] In the context of this specification, including in the following examples and comparative examples, when the catalyst undergoes the cumene cracking reaction:

[0094] The conversion rate of cumene % = (the molar amount of cumene in the feed - the molar amount of cumene in the product of the discharge) / (the molar amount of methanol in the feed) × 100%.

[0095] Selectivity of benzene % = (molar amount of benzene in the product) / (molar amount of aromatic hydrocarbons in the product) × 100%.

[0096] Among them, the aromatic hydrocarbons in the product do not include the raw material cumene.

[0097] The present invention will be further described in detail by the following examples, but the present invention is not limited to these examples.

[0098] Example 1

[0099] Mix 22.13 g of deionized water, 11.96 g of methyltriethylammonium hydroxide solution (containing 40 wt% of methyltriethylammonium hydroxide), 5.466 g of pseudo-boehmite (containing 67.0 wt% of Al 2 O 3 ), 8.28 g of phosphoric acid (containing 85 wt% of H 3 PO 4 ), and 2.16 g of silica sol (containing 40 wt% of SiO 2 ) evenly. After stirring at room temperature for 3 hours, a mixture is obtained. The pH value of the mixture is 6.5. The final material ratio (molar ratio) is:

[0100] P 2 O 5 / Al 2 O 3 = 1.00

[0101] SiO 2 / Al 2 O 3 = 0.40

[0102] R / Al 2 O 3 = 1.00

[0103] H 2 O / Al 2 O 3 = 52

[0104] Put the mixture into a stainless steel autoclave and crystallize it by rotation at 180 °C for 3 days. After the crystallization is completed, centrifuge and wash three times, and dry it in an oven at 110 °C. The XRD spectrum data of the obtained sample are shown in Table 1 and Figure 1 . It is a symbiotic zeolite of SAPO-35 / SAPO-5 with LEV and AFI structures. Among them, the SAPO-5 zeolite accounts for 60 wt% in the symbiotic zeolite of SAPO-35 / SAPO-5. The phosphorus-aluminum molar ratio (P 2 O 5 / Al 2 O 3 ) of the sample measured by inductively coupled plasma atomic emission spectrometry (ICP) is 0.92, and the silicon-aluminum molar ratio (SiO2 / Al 2 O 3 ) is 0.36, and the chemical composition of the molecular sieve is (Al 0.48 P 0.44 Si 0.08 )O 2 ·0.02R.

[0105] Table 1

[0106]

[0107] After calcination at 550 °C for 6 hours, the specific surface area of the obtained sample is 411 m 2 / g, the micropore volume is 0.13 cm 3 / g, and the total pore volume is 0.33 cm 3 / g. The total acid amount of the sample measured by NH 3 -TPD is 771 μmol / g.

[0108] Example 2

[0109] 14.33 g of deionized water, 15.04 g of methyltriethylammonium hydroxide solution (containing 40 wt% of methyltriethylammonium hydroxide), 4.909 g of pseudoboehmite (containing Al 2 O 3 67.0 wt%), 7.81 g of phosphoric acid (containing H 3 PO 4 85 wt%) and 2.91 g of silica sol (containing SiO 2 40 wt%) were mixed evenly, and the mixture was stirred at room temperature for 3 hours to obtain a mixture. The pH value of the mixture was 6.5, and the final material ratio (molar ratio) was:

[0110] P 2 O 5 / Al 2 O 3 = 1.05

[0111] SiO 2 / Al 2 O 3 = 0.60

[0112] R / Al 2 O 3 = 1.40

[0113] H 2 O / Al 2 O 3 = 48

[0114] The mixture was charged into a stainless-steel reactor and crystallized by rotation at 180 °C for 3 days. After crystallization, it was centrifuged and washed three times, and then dried in an oven at 110 °C to obtain the XRD spectral data of the sample. As shown in Table 2 and Figure 2 The symbiotic zeolite SAPO-35 / SAPO-5 with LEV and AFI structures was obtained. Among them, the SAPO-5 zeolite accounted for 65 wt% in the symbiotic zeolite SAPO-35 / SAPO-5. The phosphorus-aluminum molar ratio (P 2 O 5 / Al 2 O 3 ) of the sample was measured to be 0.93 by inductively coupled plasma atomic emission spectrometry (ICP), and the silicon-aluminum molar ratio (SiO 2 / Al 2 O 3 ) was 0.56. The chemical composition of the zeolite was (Al 0.45 P 0.42 Si 0.13 )O 2 ·0.02R.

[0115] Table 2

[0116]

[0117] After calcination at 550 °C for 6 hours, the specific surface area of the sample was 389 m 2 / g, the micropore volume was 0.12 cm 3 / g, and the total pore volume was 0.30 cm 3 / g. The total acid amount of the sample measured by NH 3 -TPD was 826 μmol / g.

[0118] Example 3

[0119] 22.25 g of deionized water, 12.39 g of methyltriethylammonium hydroxide solution (containing 40 wt% of methyltriethylammonium hydroxide), 5.661 g of pseudoboehmite (containing 67.0 wt% of Al 2 O 3 ), 8.58 g of phosphoric acid (containing 85 wt% of H 3 PO 4 ) and 1.12 g of silica sol (containing 40 wt% of SiO 2 ) were mixed evenly and stirred at room temperature for 3 hours to obtain a mixture. The pH value of the mixture was 6.5, and the final material ratio (molar ratio) was:

[0120] P 2 O 5 / Al 2 O 3 = 1.00

[0121] SiO 2 / Al 2 O 3 = 0.20

[0122] R / Al 2 O 3 = 1.00

[0123] H 2 O / Al 2 O 3 = 50

[0124] The mixture was charged into a stainless-steel autoclave and crystallized by rotation at 180 °C for 3 days. After crystallization, it was centrifuged and washed three times, and then dried in an oven at 110 °C to obtain the XRD spectrum data of the sample as shown in Table 3 and Figure 3 shown, which is a symbiotic zeolite of LEV and AFI-type SAPO-35 / SAPO-5. Among them, the SAPO-5 zeolite accounts for 75 wt% in the symbiotic SAPO-35 / SAPO-5 zeolite. The phosphorus-aluminum molar ratio (P 2 O 5 / Al 2 O 3 ) of the sample was measured to be 0.91 by inductively coupled plasma atomic emission spectrometry (ICP), and the silicon-aluminum molar ratio (SiO 2 / Al 2 O 3 ) was 0.19. The chemical composition of the zeolite was (Al 0.50 P 0.45 Si 0.05 )O 2 ·0.03R.

[0125] Table 3

[0126]

[0127]

[0128] After calcination at 550 °C for 6 hours, the specific surface area of the sample was 386 m 2 / g, the micropore volume was 0.11 cm 3 / g, and the total pore volume was 0.31 cm 3 / g. The total acid amount of the sample measured by NH 3 -TPD was 568 μmol / g.

[0129] Example 4

[0130] 7.98 g of deionized water, 10.04 g of methyltriethylammonium hydroxide solution (containing 40 wt% of methyltriethylammonium hydroxide), and 4.585 g of pseudoboehmite (containing Al 2 O3 67.0 wt%, 6.95 g of phosphoric acid (containing H 3 PO 4 85 wt%) and 0.45 g of silica sol (containing SiO 2 40 wt%) were mixed evenly, and the mixture was prepared after stirring at room temperature for 3 hours. The pH value of the mixture was 6.5, and the final material ratio (molar ratio) was:

[0131] P 2 O 5 / Al 2 O 3 = 1.00

[0132] SiO 2 / Al 2 O 3 = 0.10

[0133] R / Al 2 O 3 = 1.00

[0134] H 2 O / Al 2 O 3 = 31

[0135] The mixture was loaded into a stainless steel autoclave and crystallized by rotation at 180 °C for 3 days. After the crystallization was completed, it was centrifuged and washed three times, and then dried in an oven at 110 °C. The XRD spectrum data of the sample are shown in Table 4 and Figure 4 It is a symbiotic zeolite of LEV and AFI-type SAPO-35 / SAPO-5. Among them, the SAPO-5 zeolite accounts for 85 wt% in the symbiotic zeolite of SAPO-35 / SAPO-5. The phosphorus-aluminum molar ratio (P 2 O 5 / Al 2 O 3 ) of the sample was measured to be 1.05 by inductively coupled plasma atomic emission spectrometry (ICP), and the silicon-aluminum molar ratio (SiO 2 / Al 2 O 3 ) was 0.11. The chemical composition of the zeolite was (Al 0.47 P 0.50 Si 0.03 )O 2 ·0.04R.

[0136] Table 4

[0137]

[0138]

[0139] After calcination at 550 °C for 6 hours, the specific surface area of the obtained sample is 426 m 2 / g, the micropore volume is 0.11 cm 3 / g, and the total pore volume is 0.32 cm 3 / g. The total acid amount of the sample measured by NH 3 -TPD is 428 μmol / g.

[0140] Example 5

[0141] 14.34 g of deionized water, 10.55 g of methyltriethylammonium hydroxide solution (containing 40 wt% of methyltriethylammonium hydroxide), 5.355 g of pseudo-boehmite (containing Al 2 O 3 67.0 wt%), 9.33 g of phosphoric acid (containing H 3 PO 4 85 wt%) and 0.42 g of silica sol (containing SiO 2 40 wt%) were mixed evenly, and the mixture was prepared after stirring at room temperature for 3 hours. The pH value of the mixture was 6.5, and the final material ratio (molar ratio) was:

[0142] P 2 O 5 / Al 2 O 3 = 1.15

[0143] SiO 2 / Al 2 O 3 = 0.08

[0144] R / Al 2 O 3 = 0.90

[0145] H 2 O / Al 2 O 3 = 38

[0146] The mixture was loaded into a stainless steel autoclave and crystallized by rotation at 190 °C for 1.5 days. After crystallization, it was centrifuged and washed three times, and then dried in an oven at 110 °C. The XRD spectral data of the obtained sample are shown in Table 5, which is a symbiotic zeolite of SAPO-35 / SAPO-5 with LEV and AFI structures. Among them, the SAPO-5 zeolite accounts for 80 wt% in the symbiotic zeolite of SAPO-35 / SAPO-5. The phosphorus-aluminum molar ratio (P 2 O 5 / Al 2 O 3 ) of the sample measured by inductively coupled plasma atomic emission spectrometry (ICP) is 1.13, and the silicon-aluminum molar ratio (SiO 2 / Al2 O 3 ) is 0.07, and the chemical composition of the molecular sieve is (Al 0.46 P 0.52 Si 0.02 )O 2 ·0.04R.

[0147] Table 5

[0148]

[0149]

[0150] After calcination at 550 °C for 6 hours, the specific surface area of the obtained sample is 428 m 2 / g, the micropore volume is 0.11 cm 3 / g, and the total pore volume is 0.30 cm 3 / g. The total acid amount of the sample measured by NH 3 -TPD is 379 μmol / g.

[0151] Example 6

[0152] 14.69 g of deionized water, 14.77 g of methyltriethylammonium hydroxide solution (containing 40 wt% of methyltriethylammonium hydroxide), 5.192 g of pseudoboehmite (containing Al 2 O 3 67.0 wt%), 9.83 g of phosphoric acid (containing H 3 PO 4 85 wt%) and 0.51 g of silica sol (containing SiO 2 40 wt%) were mixed evenly, and the mixture was obtained after stirring at room temperature for 3 hours. The pH value of the mixture was 6.5, and the final material ratio (molar ratio) was:

[0153] P 2 O 5 / Al 2 O 3 = 1.25

[0154] SiO 2 / Al 2 O 3 = 0.10

[0155] R / Al 2 O 3 = 1.30

[0156] H 2 O / Al 2 O 3 = 44

[0157] The mixture was charged into a stainless-steel reactor and crystallized with rotation at 185 °C for 2 days. After crystallization, it was centrifuged and washed three times, and then dried in an oven at 110 °C. The XRD spectrum data of the obtained sample are shown in Table 6, which is a symbiotic zeolite of SAPO-35 / SAPO-5 with LEV and AFI structures. Among them, the SAPO-5 zeolite accounts for 85 wt% in the SAPO-35 / SAPO-5 symbiotic zeolite. The phosphorus-aluminum molar ratio (P 2 O 5 / Al 2 O 3 ) of the sample was measured by inductively coupled plasma atomic emission spectrometry (ICP) to be 1.22, and the silicon-aluminum molar ratio (SiO 2 / Al 2 O 3 ) was 0.09. The chemical composition of the zeolite was (Al 0.44 P 0.54 Si 0.02 )O 2 ·0.04R.

[0158] Table 6

[0159]

[0160] After calcination at 550 °C for 6 hours, the specific surface area of the obtained sample was 379 m 2 / g, the micropore volume was 0.11 cm 3 / g, and the total pore volume was 0.32 cm 3 / g. The total acid amount of the sample measured by NH 3 -TPD was 414 μmol / g.

[0161] Example 7

[0162] 24.31 g of deionized water, 15.49 g of methyltriethylammonium hydroxide solution (containing 40 wt% of methyltriethylammonium hydroxide), 5.661 g of pseudoboehmite (containing 67.0 wt% of Al 2 O 3 ), 8.15 g of phosphoric acid (containing 85 wt% of H 3 PO 4 ) and 1.40 g of silica sol (containing 40 wt% of SiO 2 ) were mixed evenly and stirred at room temperature for 3 hours to obtain a mixture. The pH value of the mixture was 6.5, and the final material ratio (molar ratio) was:

[0163] P 2 O 5 / Al 2 O 3 = 0.95

[0164] SiO2 / Al 2 O 3 = 0.25

[0165] R / Al 2 O 3 = 1.25

[0166] H 2 O / Al 2 O 3 = 56

[0167] The mixture was charged into a stainless steel autoclave and crystallized by rotation at 175 °C for 3 days. After crystallization, it was centrifuged and washed three times, and then dried in an oven at 110 °C. The XRD spectrum data of the obtained sample are shown in Table 7, which is a symbiotic zeolite of SAPO-35 / SAPO-5 with LEV and AFI structures. Among them, the SAPO-5 zeolite accounts for 80 wt% in the symbiotic zeolite of SAPO-35 / SAPO-5. The phosphorus-aluminum molar ratio (P 2 O 5 / Al 2 O 3 ) of the sample was measured to be 0.88 by inductively coupled plasma atomic emission spectrometry (ICP), the silicon-aluminum molar ratio (SiO 2 / Al 2 O 3 ) was 0.23, and the chemical composition of the zeolite was (Al 0.50 P 0.44 Si 0.06 )O 2 ·0.03R.

[0168] Table 7

[0169]

[0170] After calcination at 550 °C for 6 hours, the specific surface area of the obtained sample was 430 m 2 / g, the micropore volume was 0.13 cm 3 / g, and the total pore volume was 0.35 cm 3 / g. The total acid amount of the sample measured by NH 3 -TPD was 481 μmol / g.

[0171] Example 8

[0172] 33.68 g of deionized water, 15.46 g of methyltriethylammonium hydroxide solution (containing 40 wt% of methyltriethylammonium hydroxide), 6.141 g of pseudo-boehmite (containing Al 2 O 3 67.0 wt%), 7.91 g of phosphoric acid (containing H 3 PO 485 wt%) and 1.82 g of silica sol (containing SiO 2 40 wt%) were mixed evenly, and the mixture was prepared after stirring at room temperature for 3 hours. The pH value of the mixture was 6.5, and the final material ratio (molar ratio) was:

[0173] P 2 O 5 / Al 2 O 3 = 0.85

[0174] SiO 2 / Al 2 O 3 = 0.30

[0175] R / Al 2 O 3 = 1.15

[0176] H 2 O / Al 2 O 3 = 65

[0177] The mixture was loaded into a stainless-steel autoclave and crystallized by rotation at 170 °C for 3 days. After the crystallization was completed, it was centrifuged and washed three times, and then dried in an oven at 110 °C. The XRD spectrum data of the sample are shown in Table 8, which is a symbiotic zeolite of LEV and AFI-type SAPO-35 / SAPO-5. Among them, the SAPO-5 zeolite accounts for 75 wt% in the symbiotic SAPO-35 / SAPO-5 zeolite. The phosphorus-aluminum molar ratio (P 2 O 5 / Al 2 O 3 ) of the sample was measured by inductively coupled plasma atomic emission spectrometry (ICP) to be 0.85, the silicon-aluminum molar ratio (SiO 2 / Al 2 O 3 ) was 0.28, and the chemical composition of the zeolite was (Al 0.50 P 0.43 Si 0.07 )O 2 ·0.03R.

[0178] Table 8

[0179]

[0180]

[0181] After calcination at 550 °C for 6 hours, the specific surface area of the sample was 426 m 2 / g, the micropore volume was 0.11 cm 3 / g, and the total pore volume was 0.31 cm3 / g. The total acid amount of the sample measured by NH 3 -TPD is 649 μmol / g.

[0182] Example 9

[0183] Mix 40.30 g of deionized water, 13.38 g of methyltriethylammonium hydroxide solution (containing 40 wt% of methyltriethylammonium hydroxide), 5.558 g of pseudo-boehmite (containing Al 2 O 3 67.0 wt%), 8.84 g of phosphoric acid (containing H 3 PO 4 85 wt%) and 1.92 g of silica sol (containing SiO 2 40 wt%) evenly. After stirring at room temperature for 3 hours, a mixture is obtained. The pH value of the mixture is 6.5. The final material ratio (molar ratio) is:

[0184] P 2 O 5 / Al 2 O 3 = 1.05

[0185] SiO 2 / Al 2 O 3 = 0.35

[0186] R / Al 2 O 3 = 1.10

[0187] H 2 O / Al 2 O 3 = 80

[0188] Load the mixture into a stainless steel autoclave and carry out rotational crystallization at 165 °C for 4 days. After the crystallization is completed, centrifuge and wash three times, and dry in an oven at 110 °C. The XRD spectrum data of the obtained sample are shown in Table 9, which is a symbiotic zeolite of LEV and AFI type SAPO-35 / SAPO-5. Among them, the SAPO-5 zeolite accounts for 80 wt% in the symbiotic zeolite of SAPO-35 / SAPO-5. The phosphorus-aluminum molar ratio (P 2 O 5 / Al 2 O 3 ) of the sample measured by inductively coupled plasma atomic emission spectrometry (ICP) is 1.01, the silicon-aluminum molar ratio (SiO 2 / Al 2 O 3 ) is 0.32, and the chemical composition of the zeolite is (Al 0.46 P 0.47 Si0.07 )O 2 ·0.03R。

[0189] Table 9

[0190]

[0191]

[0192] The specific surface area of the sample obtained after calcination at 550 °C for 6 hours is 418 m 2 / g, the micropore volume is 0.14 cm 3 / g, and the total pore volume is 0.36 cm 3 / g. The total acid amount of the sample by NH 3 -TPD test is 692 μmol / g.

[0193] Example 10

[0194] Mix 43.13 g of deionized water, 10.74 g of methyltriethylammonium hydroxide solution (containing 40 wt% of methyltriethylammonium hydroxide), 6.133 g of pseudo-boehmite (containing Al 2 O 3 67.0 wt%), 6.97 g of phosphoric acid (containing H 3 PO 4 85 wt%) and 3.03 g of silica sol (containing SiO 2 40 wt%) uniformly, stir at room temperature for 3 hours to obtain a mixture. The pH value of the mixture is 6.5, and the final material ratio (molar ratio) is:

[0195] P 2 O 5 / Al 2 O 3 = 0.75

[0196] SiO 2 / Al 2 O 3 = 0.50

[0197] R / Al 2 O 3 = 0.80

[0198] H 2 O / Al 2 O 3 = 75

[0199] The mixture was charged into a stainless-steel reactor and crystallized by rotation at 165 °C for 4 days. After crystallization, it was centrifuged and washed three times, and then dried in an oven at 110 °C. The XRD spectral data of the sample are shown in Table 10, which is a symbiotic zeolite of SAPO-35 / SAPO-5 with LEV and AFI structures. Among them, the SAPO-5 zeolite accounts for 65 wt% in the SAPO-35 / SAPO-5 symbiotic zeolite. The phosphorus-aluminum molar ratio (P 2 O 5 / Al 2 O 3 ) of the sample was measured by inductively coupled plasma atomic emission spectrometry (ICP) to be 0.78, and the silicon-aluminum molar ratio (SiO 2 / Al 2 O 3 ) was 0.46. The chemical composition of the zeolite was (Al 0.50 P 0.39 Si 0.11 )O 2 ·0.02R.

[0200] Table 10

[0201]

[0202] After calcination at 550 °C for 6 hours, the specific surface area of the sample was 398 m 2 / g, the micropore volume was 0.12 cm 3 / g, and the total pore volume was 0.28 cm 3 / g. The total acid amount of the sample measured by NH 3 -TPD was 702 μmol / g.

[0203] Example 11

[0204] 32.89 g of deionized water, 9.35 g of methyltriethylammonium hydroxide solution (containing 40 wt% of methyltriethylammonium hydroxide), 6.103 g of pseudoboehmite (containing 67.0 wt% of Al 2 O 3 ), 9.25 g of phosphoric acid (containing 85 wt% of H 3 PO 4 ) and 2.41 g of silica sol (containing 40 wt% of SiO 2 ) were mixed evenly and stirred at room temperature for 3 hours to obtain a mixture. The pH value of the mixture was 6.5, and the final material ratio (molar ratio) was:

[0205] P 2 O 5 / Al 2 O 3 = 1.00

[0206] SiO2 / Al 2 O 3 = 0.40

[0207] R / Al 2 O 3 = 0.70

[0208] H 2 O / Al 2 O 3 = 60

[0209] The mixture was charged into a stainless-steel autoclave and crystallized with rotation at 160 °C for 5 days. After crystallization, it was centrifuged and washed three times, and then dried in an oven at 110 °C. The XRD spectrum data of the sample are shown in Table 11, which is a symbiotic zeolite of LEV and AFI-type SAPO-35 / SAPO-5. Among them, the SAPO-5 zeolite accounts for 75 wt% in the symbiotic zeolite of SAPO-35 / SAPO-5. The phosphorus-aluminum molar ratio (P 2 O 5 / Al 2 O 3 ) of the sample was measured to be 0.96 by inductively coupled plasma atomic emission spectrometry (ICP), the silicon-aluminum molar ratio (SiO 2 / Al 2 O 3 ) was 0.37, and the chemical composition of the zeolite was (Al 0.47 P 0.45 Si 0.08 )O 2 ·0.02R.

[0210] Table 11

[0211]

[0212] After calcination at 550 °C for 6 hours, the specific surface area of the sample was 383 m 2 / g, the micropore volume was 0.12 cm 3 / g, and the total pore volume was 0.35 cm 3 / g. The total acid amount of the sample measured by NH 3 -TPD was 477 μmol / g.

[0213] Examples 12 to 22

[0214] The zeolites synthesized in Examples 1 to 11 were respectively calcined at 550 °C for 6 hours to obtain H-type SAPO-35 / SAPO-5 zeolites.

[0215] Take the above-mentioned calcined H-type SAPO-35 / SAPO-5 molecular sieve powder sample, crush it, and sieve out 0.5 g of the particle size part with a mesh size of 20-40, and put it into a fixed-bed reactor for cumene cracking reaction. The reaction conditions are as follows: the reaction temperature is 300-350 °C, the reaction pressure is atmospheric pressure, and the weight hourly space velocity of cumene is 2-4 h -1 , and the specific reaction conditions of each example are shown in Table 12. A Shimadzu GC-2014 gas chromatograph was used to analyze the products, catalyst activity and product selectivity, as shown in Table 12.

[0216] Table 12 Catalyst performance results of Examples 12-22 and Comparative Example 3

[0217]

[0218] The preferred embodiments of the present invention have been described in detail above. However, the present invention is not limited thereto. Within the technical concept scope of the present invention, various simple modifications can be made to the technical solutions of the present invention, including any other suitable combination of each technical feature. These simple modifications and combinations should also be regarded as the content disclosed by the present invention and fall within the protection scope of the present invention.

Claims

1. A SAPO-35 / SAPO-5 intergrown molecular sieve, characterized in that, The SAPO-35 / SAPO-5 symbiotic molecular sieve has the following anhydrous chemical composition: (Al x P y Si z )O 2 ·mR, where R is methyltriethylammonium hydroxide, x, y, and z respectively represent the mole fractions of the sum of the moles of Al, P, and Si, x = 0.35 to 0.55, y = 0.30 to 0.55, z = 0.005 to 0.15, x + y + z = 1, m is the mole fraction of R, and m = 0.005 to 0.05; the SAPO-35 / SAPO-5 intergrown molecular sieve has an X-ray diffraction pattern including the AFI structure attributed to the SAPO-5 molecular sieve and the LEV structure attributed to the SAPO-35 molecular sieve as shown in the following table; a: ±0.30°, b: varying with 2θ.

2. The SAPO-35 / SAPO-5 intergrown molecular sieve according to claim 1, wherein, x = 0.38 - 0.52, y = 0.38 - 0.52, z = 0.01 - 0.15, x + y + z = 1, m = 0.01 - 0.

05.

3. The SAPO-35 / SAPO-5 intergrown molecular sieve according to claim 1, wherein, the peak intensity of the characteristic peak belonging to the AFI structure of the SAPO-5 molecular sieve in the SAPO-35 / SAPO-5 intergrown molecular sieve is higher than the peak intensity of the characteristic peak belonging to the LEV structure of the SAPO-35 molecular sieve.

4. The SAPO-35 / SAPO-5 intergrown molecular sieve according to claim 3, wherein, the SAPO-5 molecular sieve accounts for 55 - 90% by weight in the SAPO-35 / SAPO-5 intergrown molecular sieve.

5. A preparation method of the SAPO-35 / SAPO-5 intergrown molecular sieve according to any one of claims 1 - 4, characterized in that, this method includes the following steps: heating and crystallizing a mixture containing an aluminum source, a phosphorus source, a silicon source, methyltriethylammonium hydroxide and water, and performing post-treatment to obtain the SAPO-35 / SAPO-5 intergrown molecular sieve; Among them, the aluminum source is calculated as Al 2 O 3 ; the phosphorus source is calculated as P 2 O 5 ; the silicon source is calculated as SiO 2 ; methyltriethylammonium hydroxide R and water, with a molar ratio of Al 2 O 3 :P 2 O 5 :SiO 2 :R:H 2 O = 1:0.65~1.40:0.02~0.65:0.60~1.45:28~100.

6. The preparation method according to claim 5, wherein, the pH value of the mixture is 5.5 - 8.0; and / or The crystallization conditions of the mixture include crystallization at 150~205 o °C for 0.5~7 days; and / or the mixture does not contain seeds; the post-treatment includes: separation, washing, drying and optional calcination.

7. The preparation method according to claim 6, wherein, the crystallization conditions of the mixture include crystallizing at 155 - 200 °C for 0.5 - 6 days.

8. The preparation method according to claim 6, wherein, the crystallization conditions of the mixture include crystallizing at 160 - 195 °C for 0.75 - 5 days.

9. The preparation method according to claim 5, wherein, The aluminum source is calculated as Al 2 O 3 The phosphorus source is calculated as P 2 O 5 The silicon source is calculated as SiO 2 The methyltriethylammonium hydroxide R and water are in a molar ratio of Al 2 O 3 :P 2 O 5 :SiO 2 :R:H 2 O = 1:0.70 to 1.40:0.04 to 0.60:0.65 to 1.40:30 to 90; and / or the aluminum source is at least one selected from pseudoboehmite, alkoxyaluminum, aluminum salts, alumina and aluminum hydroxide; and / or the phosphorus source is at least one selected from phosphoric acid, ammonium hydrogen phosphate, ammonium dihydrogen phosphate and organic phosphides; and / or the silicon source is at least one selected from silica sol, silica gel and tetraethyl orthosilicate.

10. The preparation method according to claim 9, wherein, the aluminum source is pseudoboehmite; and / or the phosphorus source is phosphoric acid; and / or the silicon source is silica sol.

11. The SAPO-35 / SAPO-5 intergrown molecular sieve prepared by the preparation method according to any one of claims 5 - 10.

12. The SAPO-35 / SAPO-5 intergrown molecular sieve according to claim 11, wherein, The SAPO-35 / SAPO-5 symbiotic molecular sieve has the following anhydrous chemical composition: (Al x P y Si z )O 2 ·mR, where R is methyltriethylammonium hydroxide, x, y, and z respectively represent the mole fractions of the sum of the moles of Al, P, and Si, x = 0.35 to 0.55, y = 0.30 to 0.55, z = 0.005 to 0.15, x + y + z = 1, m is the mole fraction of R, and m = 0.005 to 0.

05.

13. The SAPO-35 / SAPO-5 intergrown molecular sieve according to claim 12, wherein, The SAPO-35 / SAPO-5 intergrown molecular sieve has an X-ray diffraction pattern including an AFI structure attributed to the SAPO-5 molecular sieve and a LEV structure attributed to the SAPO-35 molecular sieve as shown in the following table; a: ±0.30°, b: varying with 2θ.

14. The SAPO-35 / SAPO-5 intergrown molecular sieve according to claim 11, wherein, x = 0.38 - 0.52, y = 0.38 - 0.52, z = 0.01 - 0.15, x + y + z = 1, m = 0.01 - 0.05; and / or in the SAPO-35 / SAPO-5 intergrown molecular sieve, the peak intensity of the characteristic peaks belonging to the AFI structure of the SAPO-5 molecular sieve is higher than the peak intensity of the characteristic peaks belonging to the LEV structure of the SAPO-35 molecular sieve.

15. The SAPO-35 / SAPO-5 intergrown molecular sieve according to claim 14, wherein, the SAPO-5 molecular sieve accounts for 55 - 90% by weight in the SAPO-35 / SAPO-5 intergrown molecular sieve.

16. The SAPO-35 / SAPO-5 intergrown molecular sieve according to claim 11, wherein, after calcination at 300 - 800 °C for 1 - 10 hours: The specific surface area of the SAPO-35 / SAPO-5 symbiotic molecular sieve is 300-450 m 2 / g; and / or The pore volume of the SAPO-35 / SAPO-5 intergrown molecular sieve is 0.20 to 0.50 cm 3 / g; and / or The micropore volume of the SAPO-35 / SAPO-5 intergrown molecular sieve is 0.10~0.25 cm 3 / g; and / or the acid amount of the SAPO-35 / SAPO-5 intergrown molecular sieve is 200 - 1000 μmol / g.

17. The SAPO-35 / SAPO-5 intergrown molecular sieve according to claim 16, wherein, after calcination at 400 - 650 °C for 3 - 6 hours: The pore volume of the SAPO-35 / SAPO-5 symbiotic molecular sieve is 0.20~0.45 cm 3 / g; and / or The micropore volume of the SAPO-35 / SAPO-5 intergrown molecular sieve is 0.11~0.20 cm 3 / g; and / or the acid amount of the SAPO-35 / SAPO-5 intergrown molecular sieve is 300 - 900 μmol / g.

18. A molecular sieve composition comprising the SAPO-35 / SAPO-5 intergrown molecular sieve according to any one of claims 1 - 4 and 11 - 17 and a binder.

19. Use of the SAPO-35 / SAPO-5 intergrown molecular sieve according to any one of claims 1 - 4 and 11 - 17 or the molecular sieve composition according to claim 18 as a catalyst in the organic matter conversion reaction.

20. The use according to claim 19, wherein, the organic matter conversion reaction is a cracking reaction.

21. The use according to claim 19, wherein, the organic matter conversion reaction is the preparation of benzene by cumene cracking reaction.

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