CN115959681A - SCM-36 molecular sieves, methods of making, and uses thereof - Google Patents

Abstract

The invention discloses an SCM-36 molecular sieve, a preparation method and application thereof. The molecular sieve has a schematic chemical composition of "mSiO ₂ ·nAl ₂ O ₃ ", wherein m/n.gtoreq.5. The molecular sieve has unique XRD diffraction data, is a novel molecular sieve, and can be used as an adsorbent or a catalyst for organic compound conversion.

Description

SCM-36 molecular sieves, methods of making, and uses thereof

Technical Field

The invention relates to an SCM-36 molecular sieve, a manufacturing method and application thereof.

Background

In industry, molecular sieve materials are widely used in the fields of catalysis, ion exchange, adsorption, and separation due to their open structure and large surface area. The structural nuances of these materials are indicative of the differences in the various observable properties that characterize them, such as their morphology, specific surface area, void size and variability of these dimensions, and also mean that they themselves are significantly different in terms of catalytic and adsorptive properties of the materials.

The basic framework structure of crystalline microporous zeolites is based on a rigid, three-dimensional TO ₄ (SiO ₄ ，AlO ₄ Etc.) a cell structure; in this structure TO ₄ Sharing oxygen atoms in a tetrahedral fashion, skeletal tetrahedrons such as AlO ₄ Is balanced by surface cations such as Na ⁺ 、H ⁺ The presence of (c) remains. It follows that the framework properties of zeolites can be altered by means of cation exchange. Meanwhile, a rich pore channel system with a certain pore diameter exists in the structure of the zeolite, the pore channels are mutually staggered to form a three-dimensional net structure, and the framework of the pore channel can still exist stably after water or organic matters in the pore channels are removed (US 4439409). Based on the above structure, zeolite has not only good catalytic activity for various organic reactions, excellent shape selectivity, but also good selectivity by modification (US 6162416, US 4954325, US 5362697).

The specific structure of the molecular sieve is determined by X-ray diffraction pattern (XRD) measured by X-ray powder diffractometer using Cu-K alpha ray source and nickel filter. The XRD spectrogram characteristics of different zeolite molecular sieves are different. The existing molecular sieves, such as A-type zeolite, Y-type zeolite, MCM-22 molecular sieve and the like, have XRD spectrums with respective characteristics.

Meanwhile, the molecular sieve has the same XRD spectrogram characteristics, but different types of framework elements and different molecular sieves. Such as TS-1 molecular sieve (US 4410501) and ZSM-5 molecular sieve (US 3702886), which both have the same XRD spectrum characteristics but different framework elements. Specifically, the TS-1 molecular sieve has a catalytic oxidation function due to the framework elements of Si and Ti, and the ZSM-5 molecular sieve has an acid catalytic function due to the framework elements of Si and Al.

In addition, the molecular sieve has the same XRD spectrogram characteristics, the types of the framework elements are also the same, but the relative contents of the framework elements are different, and the molecular sieve belongs to different molecular sieves. Such as X zeolite (US 2882244) and Y zeolite (US 3130007), both having the same XRD spectrum characteristics, with both framework elements Si and Al, but with different relative contents of Si and Al. In particular, the Si/Al molar ratio of the X zeolite is lower than 1.5, while the Si/Al molar ratio of the Y zeolite is higher than 1.5.

Disclosure of Invention

Based on the prior art, the inventors have assiduously studied to discover a novel SCM-36 molecular sieve, and further discover that the molecular sieve has beneficial properties. In particular, the invention provides an SCM-36 molecular sieve, a manufacturing method and application thereof.

In a first aspect, the present invention provides an SCM-36 molecular sieve having the exemplary chemical composition "mSiO ₂ ·nAl ₂ O ₃ ", wherein m/n.gtoreq.5, said molecular sieve having an X-ray diffraction pattern including that shown in the following table,

a: ± 0.30 °, b: as a function of 2 theta.

In the above technical solution, the molecular sieve may further have at least one diffraction peak in an X-ray diffraction pattern as shown in the following table,

a: ± 0.30 °, b: as a function of 2 theta.

In the above technical scheme, the molecular sieve has a schematic chemical composition of "mSiO ₂ ·nAl ₂ O ₃ ", wherein m/n.gtoreq.5, preferably m/n =5 to 80, more preferably m/n =10 to 65. Wherein m/n is SiO ₂ /Al ₂ O ₃ The molar ratio.

In the technical scheme, the specific surface area of the molecular sieve is 300-700 m ² Per gram, preferably 300 to 600 meters ² Per gram, preferably 350 to 500 m ² Per gram; the external specific surface area is 50 to 300 meters ² Per gram, preferably 80 to 250 m ² Per gram.

In the technical scheme, the total pore volume of the molecular sieve is 0.20-1.50 cm ³ Per gram, preferably 0.40 to 1.20 cm ³ Per gram; the micropore volume is 0.05-0.35 cm ³ Per gram, preferably 0.08 to 0.30 cm ³ Per gram.

In the technical scheme, the molecular sieve is in a nano-sheet shape, and the thickness of the crystal is less than 30 nanometers, preferably 5 to 25 nanometers, and more preferably 7 to 20 nanometers.

In the technical scheme, the pore diameter of the micropores of the molecular sieve is 0.20-0.75 nm, preferably 0.30-0.70 nm.

In the above technical solution, the chemical composition of the molecular sieve further includes non-silicon and non-aluminum elements, and the elements are selected from at least one of titanium, boron, zirconium, tin and iron.

In the above technical solution, the molecular sieve has a schematic chemical composition that contains, based on the total number of moles of oxides, oxides of elements other than silicon and aluminum in a mole fraction of not more than 3%.

In a second aspect, the present invention provides a method for manufacturing an SCM-36 molecular sieve, comprising the steps of crystallizing a mixture comprising a silicon source, an aluminum source, an organic structure directing agent (a), an organic structure directing agent (B), an alkali source and water to obtain said molecular sieve; and optionally, further comprising the step of calcining the obtained molecular sieve; wherein the organic structure directing agent (a) is selected from at least one of tetramethylammonium hydroxide or a quaternary ammonium salt form thereof; the organic structure directing agent (B) is at least one selected from quaternary ammonium salts of C ten to C sixteen alkylpyridine or n-octyl trimethyl compound or quaternary ammonium bases thereof.

In the above technical scheme, the silicon source is SiO ₂ Calculated as Al), an aluminum source (calculated as Al) ₂ O ₃ In terms of the weight percentage, the molar ratio of the organic structure directing agent (A), the organic structure directing agent (B), the alkali source and the water is 1 (0.01-0.20), (0.05-0.80), (0.05-0.50), (8-80), preferably 1 (0.01-0.10), (0.08-0.65), (0.08-0.45), (10-70), more preferably 1 (0.02-0.07), (0.10-0.50), (0.10-0.40) and (12-60).

In the technical scheme, the crystallization temperature of the mixture is 120-200 ℃, the crystallization time is 1-15 days, the preferred crystallization temperature is 130-190 ℃, the crystallization time is 2-12 days, the more preferred crystallization temperature is 140-180 ℃, and the crystallization time is 3-9 days.

In the above technical solution, preferably, after the crystallization is finished, filtering, washing and drying are performed; the drying temperature is 40-150 ℃, preferably 50-120 ℃, and the drying time is 1-30 hours, preferably 2-24 hours.

In the above technical scheme, the roasting temperature is 300-800 ℃, preferably 400-650 ℃, the roasting time is 1-12 hours, preferably 2-10 hours, and the roasting atmosphere is air or oxygen atmosphere.

In the above technical scheme, the silicon source is selected from at least one of silicic acid, silica gel, silica sol, tetraethyl silicate and water glass; the aluminum source is at least one selected from the group consisting of aluminum hydroxide, aluminum oxide, aluminates, aluminum salts, and tetraalkoxyaluminum.

In the above technical solution, the alkali source is at least one selected from inorganic bases in which alkali metal and alkaline earth metal are cations.

In the above technical solution, the organic structure directing agent (a) is at least one selected from tetramethylammonium hydroxide, tetramethylammonium chloride, tetramethylammonium bromide or tetramethylammonium iodide.

In the above technical solution, the organic structure directing agent (B) is preferably at least one selected from cetylpyridinium bromide, tetradecylpyridinium bromide, dodecylpyridinium bromide, cetylpyridinium chloride, tetradecylpyridinium chloride, hexadecylpyridinium hydroxide, n-octyltrimethylammonium chloride, n-octyltrimethylammonium bromide or n-octyltrimethylammonium hydroxide. The organic structure directing agent (B) is further preferably at least one of cetylpyridinium bromide, tetradecylpyridinium bromide, dodecylpyridinium bromide, cetylpyridinium chloride, cetylpyridinium hydroxide, n-octyltrimethylammonium chloride or n-octyltrimethylammonium bromide.

In the above technical solution, the mixture further includes a non-silicon and non-aluminum source, and the non-silicon and non-aluminum source is at least one selected from a titanium source, a boron source, a zirconium source, a tin source, and an iron source.

In the above technical solution, the titanium source is selected from at least one of titanium-containing organic metal complex, titanium tetraalkoxide, titanium dioxide and titanium nitrate; the boron source is at least one of boric acid, borate, borax and boron trioxide; the zirconium source is selected from at least one of zirconium-containing organic metal complex, zirconium salt, zirconium hydroxide, zirconium alcohol and zirconium dioxide; the tin source is at least one of tin-containing organic metal complex, tin salt and tin dioxide; the iron source is selected from at least one of iron-containing organometallic complexes, ferric nitrate, ferric chloride, and ferric oxide.

In the above technical scheme, the silicon source is SiO ₂ Calculated) to the non-silicon and non-aluminium sources (calculated as the corresponding oxides) is 1 (0.002-0.10), preferably 1 (0.005-0.05).

In a third aspect, the present invention provides a molecular sieve composition comprising an SCM-36 molecular sieve according to any of the preceding aspects or an SCM-36 molecular sieve produced according to the production process of any of the preceding aspects, and a binder.

In a fourth aspect, the present invention provides the use of an SCM-36 molecular sieve or SCM-36 molecular sieve composition according to any of the preceding aspects, or an SCM-36 molecular sieve produced according to the method of manufacture of any of the preceding aspects, as an adsorbent or as a catalyst for the conversion of organic compounds.

The SCM-36 molecular sieve, according to the present invention, has a framework structure and chemical composition that have not been previously available in the art.

Drawings

FIG. 1 is an X-ray diffraction pattern (XRD) of the molecular sieve obtained in example 1;

FIG. 2 is a Scanning Electron Micrograph (SEM) of the molecular sieve obtained in example 1;

FIG. 3 is a Transmission Electron Micrograph (TEM) of the molecular sieve obtained in example 1;

FIG. 4 is an X-ray diffraction pattern (XRD) of the molecular sieve obtained in example 2;

FIG. 5 is a Scanning Electron Micrograph (SEM) of the molecular sieve obtained in example 3;

FIG. 6 is an X-ray diffraction pattern (XRD) of the sample obtained in comparative example 1;

FIG. 7 is an X-ray diffraction pattern (XRD) of the sample obtained in comparative example 3;

fig. 8 is an X-ray diffraction pattern (XRD) of the sample obtained in comparative example 4.

Detailed Description

The following detailed description of the embodiments of the present invention is provided, but it should be noted that the scope of the present invention is not limited by the embodiments, but is defined by the appended claims.

All publications, patent applications, patents, and other references mentioned in this specification are herein incorporated by reference in their entirety. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. In case of conflict, the present specification, including definitions, will control.

When the specification concludes with the claims defining the existence of materials, methods, procedures, means, or components, or the like, that are regarded as being "known to one of ordinary skill in the art", "prior art", or the like, it is intended that the subject matter so derived encompass those materials, methods, procedures, means, or components which have been conventionally used in the art at the time of filing this application, but which may not be so commonly used at the present time, but will become known in the art as being suitable for a similar purpose.

In the context of the present specification, anything or things which are not mentioned, except where explicitly stated, are directly applicable to those known in the art without any changes. Moreover, any embodiment described herein may be freely combined with one or more other embodiments described herein, and the technical solutions or concepts resulting therefrom are considered part of the original disclosure or original disclosure of the invention, and should not be considered as new matters not disclosed or contemplated herein, unless a person skilled in the art would consider such a combination to be clearly unreasonable.

In the context of the present specification, a molecular sieve is referred to as a "precursor" before substances (such as organic templating agent molecules and the like) filling the channels of the molecular sieve are not removed during synthesis of the molecular sieve except water and metal ions in the channels.

In the context of the present specification, in the XRD data of molecular sieves, w, m, s, vs represent diffraction peak intensities, w is weak, m is medium, s is strong, and vs is very strong, as is well known to those skilled in the art. Generally, w is less than 20; m is 20 to 40; s is 40 to 70; vs is greater than 70.

In the context of the present specification, the structure of a molecular sieve is determined by X-ray diffraction pattern (XRD), which is determined by X-ray powder diffractometry using a Cu-ka radiation source, a nickel filter. Before the sample is tested, a Scanning Electron Microscope (SEM) is adopted to observe the crystallization condition of the molecular sieve sample, the sample is confirmed to contain only one crystal, namely the molecular sieve sample is a pure phase, and then XRD test is carried out on the basis, so that no interference peak of other crystals exists in a diffraction peak in an XRD spectrogram.

In the context of the present specification, the specific surface area refers to the total area of a unit mass of a sample, including the inner surface area and the outer surface area. Non-porous samples have only an outer surface area, such as portland cement, some clay mineral particles, etc.; porous and porous samples have an external and an internal surface area, such as asbestos fibers, diatomaceous earth, molecular sieves, and the like. The surface area of pores with a pore diameter of less than 2 nm in the porous and multiporous samples is the internal surface area, the surface area minus the internal surface area is called the external surface area, and the external surface area per unit mass of the sample is the external specific surface area.

In the context of the present specification, the pore volume refers to the volume of pores per unit mass of the porous material. The total pore volume refers to the volume of all pores (generally only pores with pore diameters of less than 50 nm) per unit mass of the molecular sieve. The micropore volume means the volume of all micropores (generally, pores having a pore diameter of less than 2 nm) per unit mass of the molecular sieve. Pore structure parameters of the material, such as: the total pore volume, micropore volume, total specific surface area and external specific surface area are obtained by measuring nitrogen physical adsorption and desorption isotherms of the molecular sieve by a physical adsorption instrument (such as TriStar 3000 physical adsorption instrument of Mac instruments, USA), and calculating by a BET method and a t-plot method. The experimental conditions of the physical adsorption and desorption of nitrogen are as follows: the temperature was measured at-169 ℃ and the molecular sieves were pre-treated in vacuo at 300 ℃ for 10 hours before measurement.

In the context of this specification, by thickness of crystals is meant that the molecular sieve is observed using a transmission electron microscope at a magnification of 10 ten thousand times, an observation field is randomly selected, and the average of the sum of the thicknesses of all plate-like crystals in the observation field is calculated. This operation was repeated a total of 10 times. The average value of the sum of the average values of 10 times was taken as the crystal thickness.

The invention relates to an SCM-36 molecular sieve. The framework structure and chemical composition of the SCM-36 molecular sieve have not been previously available in the art.

According to the present invention, the SCM-36 molecular sieve may be present in the uncalcined state (as synthesized) or in the calcined state. When present in the as-synthesized state, the SCM-36 molecular sieve typically has the formula "mSiO ₂ ·nAl ₂ O ₃ The SCM-36 molecular sieve may also generally have the formula "mSiO", when present in the calcined state or in the synthesized state ₂ ·nAl ₂ O ₃ "schematic chemical composition of. In the latter case, it is known that molecular sieves sometimes (especially immediately after synthesis) contain some amount of moisture, but it is not considered necessary to specify this amount of moisture in the present invention because the presence or absence of this moisture does not substantially affect the XRD pattern of the molecular sieve. In view of this, the schematic chemical composition represents, in effect, the anhydrous chemical composition of the molecular sieve. Moreover, it is apparent that the schematic chemical composition represents the framework chemical composition of the SCM-36 molecular sieve.

According to the invention, the molecular sieve has, in its calcined form, an X-ray diffraction pattern including the following table,

a: ± 0.30 °, b: as a function of 2 theta.

According to the present invention, the molecular sieve may also have at least one diffraction peak comprising an X-ray diffraction pattern as shown in the following table,

a: ± 0.30 °, b: as a function of 2 theta.

According to the invention, the SCM-36 molecular sieve has a schematic chemical composition mSiO ₂ ·nAl ₂ O ₃ Wherein the ratio of silicon to aluminum m/n is not less than 5, preferably m/n =5 to 80, more preferably m/n =10 to 65.

According to the invention, the molecular sieve has a specific surface area (BET method) of 300 to 700 m ² Per gram, preferably 300 to 600 meters ² Per gram, preferably 350 to 500 m ² Per gram; the external specific surface area is 50 to 300 meters ² Per gram, preferably 80 to 250 m ² And (c) grams.

According to the invention, the total pore volume of the molecular sieve is 0.20-1.50 cm ³ Per gram, preferably 0.40 to 1.20 cm ³ Per gram; the pore volume of the micropore (t-plot method) is 0.05-0.35 cm ³ Per gram, preferably 0.08 to 0.30 cm ³ Per gram.

According to the invention, the molecular sieve is in a nano-sheet shape, and the thickness of the crystal is less than 30 nanometers, preferably 5 to 25 nanometers, and more preferably 7 to 20 nanometers.

According to the invention, the molecular sieve has a pore size of 0.20 to 0.75 nm, preferably 0.30 to 0.70 nm, measured by argon adsorption.

According to the invention, the molecular sieve contains elements other than silicon and other than aluminum in a mass fraction of not more than 3%. The non-silicon and non-aluminum elements are selected from at least one of titanium, boron, zirconium, tin, and iron.

According to the present invention, the SCM-36 molecular sieve may be produced by the following production method. In view of this, the present invention also relates to a method for manufacturing an SCM-36 molecular sieve, comprising a step of crystallizing a mixture (hereinafter referred to simply as a mixture) comprising a silicon source, an aluminum source, an organic structure directing agent (a), an organic structure directing agent (B), an alkali source and water under crystallization conditions to obtain the molecular sieve (hereinafter referred to as a crystallization step); and optionally, further comprising the step of calcining the obtained molecular sieve.

According to the invention, the organic structure directing agent (a) is selected from at least one of tetramethylammonium hydroxide or its quaternary ammonium salt form; the organic structure directing agent (B) is at least one selected from quaternary ammonium salts of C ten to C sixteen alkylpyridine or n-octyl trimethyl compound or quaternary ammonium bases thereof.

According to the present invention, in the method for producing a molecular sieve, the organic structure directing agent (a) is preferably at least one selected from tetramethylammonium hydroxide, tetramethylammonium chloride, tetramethylammonium bromide, or tetramethylammonium iodide. The organic structure directing agent (B) is preferably at least one selected from cetylpyridinium bromide, tetradecylpyridinium bromide, dodecylpyridinium bromide, cetylpyridinium chloride, tetradecylpyridinium chloride, cetylpyridinium hydroxide, n-octyltrimethylammonium chloride, n-octyltrimethylammonium bromide or n-octyltrimethylammonium hydroxide, and more preferably at least one selected from cetylpyridinium bromide, tetradecylpyridinium bromide, dodecylpyridinium bromide, cetylpyridinium chloride, hexadecylpyridinium hydroxide, n-octyltrimethylammonium chloride or n-octyltrimethylammonium bromide.

According to the invention, in the method for manufacturing the molecular sieve, the silicon source is (in SiO) ₂ Calculated as Al), an aluminum source (calculated as Al) ₂ O ₃ The molar ratio of the alkali source to the water is 1 (0.01-0.20), (0.05-0.80), (0.05-0.50), (8-80), preferably 1 (0.01-0.10), (0.08-0.65), (0.08-0.45), (10-70), more preferably 1 (0.02-0.07), (0.10-0.50), (0.10-0.40) and (12-60).

According to the invention, in the method for manufacturing the molecular sieve, the crystallization temperature of the mixture is 120-200 ℃, the crystallization time is 1-15 days, preferably the crystallization temperature is 130-190 ℃, the crystallization time is 2-12 days, more preferably the crystallization temperature is 140-180 ℃, and the crystallization time is 3-9 days.

In the method for manufacturing the molecular sieve according to the present invention, the crystallization step may be performed in any manner conventionally known in the art, for example, a method of mixing the silicon source, the organic structure directing agent, an alkali source and water in a predetermined ratio and hydrothermally crystallizing the obtained mixture under crystallization conditions may be illustrated.

According to the present invention, in the method for producing a molecular sieve, the silicon source is at least one selected from the group consisting of silicic acid, silica gel, silica sol, tetraethyl silicate, and water glass; the aluminum source is at least one selected from the group consisting of aluminum hydroxide, aluminum oxide, aluminates, aluminum salts, and tetraalkoxyaluminum.

According to the present invention, in the method for producing a molecular sieve, the alkali source is selected from at least one of inorganic bases in which an alkali metal and an alkaline earth metal are cations, such as at least one of sodium hydroxide and potassium hydroxide.

According to the present invention, in the method for producing a molecular sieve, the mixture further includes a non-silicon and non-aluminum source selected from at least one of a titanium source, a boron source, a zirconium source, a tin source, and an iron source.

According to the present invention, in the method for producing a molecular sieve, the titanium source is at least one selected from the group consisting of a titanium-containing organometallic complex, a titanium tetraalkoxide, a titanium oxide and a titanium nitrate; the boron source is at least one of boric acid, borate, borax and boron trioxide; the zirconium source is selected from at least one of a zirconium-containing organic metal complex, a zirconium salt, zirconium hydroxide, zirconium alcohol and zirconium dioxide; the tin source is at least one of organic metal complex containing tin, tin salt and tin dioxide; the iron source is selected from at least one of iron-containing organometallic complexes, ferric nitrate, ferric chloride, and ferric oxide.

According to the invention, the silicon source is made of SiO ₂ For example) to the non-silicon and non-aluminum sources (based on the corresponding oxides) in a molar ratio of 1 (0.002 to 0.10), preferably 1 (0.005 to 0.05).

According to the present invention, in the method for producing the molecular sieve, after the crystallization step is finished, the molecular sieve may be separated from the obtained product mixture as a product by any separation means conventionally known, thereby obtaining the SCM-36 molecular sieve of the present invention. The separation method includes, for example, a method of filtering, washing and drying the obtained product mixture. Here, the filtering, washing and drying may be performed in any manner conventionally known in the art. As a specific example, as the filtration, for example, the obtained product mixture may be simply filtered with suction. Examples of the washing include washing with deionized water. The drying temperature is, for example, 40 to 150 ℃, preferably 50 to 120 ℃, and the drying time is, for example, 1 to 30 hours, preferably 2 to 24 hours. The drying may be performed under normal pressure or under reduced pressure.

According to the present invention, the molecular sieve produced by the foregoing molecular sieve production method may be calcined as necessary to remove the organic template and water and the like that may be present, thereby obtaining a calcined molecular sieve (SCM-36 molecular sieve also pertaining to the present invention). The calcination may be carried out in any manner conventionally known in the art, for example, the calcination temperature is generally 300 to 800 ℃, preferably 400 to 650 ℃, and the calcination time is generally 1 to 12 hours, preferably 2 to 10 hours. In addition, the calcination is generally carried out in an oxygen-containing atmosphere, such as air or an oxygen atmosphere.

The various SCM-36 molecular sieves obtained as described above may be used in any physical form according to the present invention, such as a powder, granules or molded article (e.g., a bar, a clover, etc.). These physical forms can be obtained in any manner conventionally known in the art and are not particularly limited.

According to the present invention, the SCM-36 molecular sieve may be used in combination with other materials to obtain a molecular sieve composition. Examples of the other materials include active materials and inactive materials. Examples of the active material include synthetic zeolite, natural zeolite, and other types of molecular sieves, and examples of the inactive material (generally referred to as a binder) include clay, silica gel, and alumina. These other materials may be used singly or in combination of two or more in any ratio. As the amount of the other materials, those conventionally used in the art can be directly referred to, and there is no particular limitation.

The SCM-36 molecular sieve or molecular sieve composition of the present invention may be used as an adsorbent, for example, to separate at least one component from a mixture of components in the gas or liquid phase. Accordingly, the at least one component may be partially or substantially completely separated from the mixture of components, such as by contacting the mixture with the SCM-36 molecular sieve or the molecular sieve composition to selectively adsorb such a component.

According to one aspect of the invention, the molecular sieve SCM-36 or the molecular sieve composition may also be used as a catalyst (or as a catalytically active component thereof) either directly or after having been subjected to the necessary treatments or conversions (such as ion exchange, etc.) conventionally performed in the art for molecular sieves. To this end, according to one aspect of the present invention, it is possible to, for example, subject a reactant (such as a hydrocarbon) to a predetermined reaction in the presence of the catalyst, and thereby obtain a target product. Among them, the predetermined reaction can be exemplified by the following: cracking cumene, and converting methanol to generate olefin or arene.

In the context of the present description, including in the following examples and comparative examples, the catalyst is applied in cumene cracking reactions:

the cumene is used as a raw material in the cumene cracking reaction and is cracked into products such as propylene, benzene and the like under the action of a catalyst.

Conversion of cumene% = (molar amount of cumene fed-molar amount of cumene in product)/(molar amount of cumene fed) × 100%.

Benzene selectivity% = (molar amount of benzene in product)/(total molar amount of aromatic hydrocarbons in product) × 100%;

wherein the aromatics in the product do not comprise the raw material cumene.

In the context of the present specification, including in the following examples and comparative examples, the catalyst is used in methanol conversion reactions:

the methanol conversion reaction takes methanol as a raw material and converts the methanol into hydrocarbon such as olefin, aromatic hydrocarbon and the like under the action of a catalyst.

Percent conversion of methanol = (molar amount of methanol feed-molar amount of methanol in product-2 x molar amount of dimethyl ether in product)/(molar amount of methanol feed) × 100%;

percent selectivity for C2 to C4 olefins = (2 x molar amount of C2 olefins in product +3 x molar amount of C3 olefins in product +4 x molar amount of C4 olefins in product)/(molar amount of feed methanol-molar amount of methanol in product-2 x molar amount of dimethyl ether in product) × 100%.

% selectivity for aromatics = (6 × molar amount of benzene in product +7 × molar amount of toluene in product +8 × molar amount of xylene in product)/(molar amount of methanol fed-molar amount of methanol in product-2 × molar amount of dimethyl ether in product) × 100%.

The technical solutions of the present invention will be described in further detail below with reference to examples, but the scope of the present invention is not limited to these examples.

Example 1

Dissolving 24.73 g of deionized water and 6.89 g of sodium hydroxideLiquid (containing 10 weight percent of NaOH), 5.35 g of organic structure directing agent (A), tetramethylammonium hydroxide (containing 25 weight percent of TMAOH), 3.05 g of organic structure directing agent (B), n-octyltrimethylammonium chloride and 1.234 g of sodium metaaluminate (containing Al) ₂ O ₃ 40.5 wt.% Na ₂ 30.6% by weight of O), 14.72 g of silica sol (containing SiO) ₂ 40 percent by weight) to prepare a mixture, wherein the material ratio (mol ratio) of reactants is as follows:

Al ₂ O ₃ /SiO ₂ ＝0.05

tetramethylammonium hydroxide (A)/SiO ₂ ＝0.15

N-octyl trimethyl ammonium chloride (B)/SiO ₂ ＝0.15

NaOH/SiO ₂ ＝0.30

H ₂ O/SiO ₂ ＝25；

After being mixed evenly, the mixture is put into a stainless steel reaction kettle and crystallized for 6 days at 160 ℃. Filtering, washing, drying in a 110 deg.C oven for 12 hr, and calcining in 550 deg.C air for 6 hr to obtain the molecular sieve.

The XRD spectrum data of the dried sample are shown in table 1 and fig. 1, the SEM image of the sample is shown in fig. 2, and the TEM image is shown in fig. 3.

TABLE 1

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The specific surface area of the obtained calcined product was 380 m ² Per gram, external specific surface area 170 m ² G, total pore volume 0.92 cm ³ Per gram, micropore volume of 0.10 cm ³ The micropore size distribution of the sample was 0.59 nm and 0.67 nm per gram. The sample has a nano-sheet shape, and the thickness of the crystal is about 15 nanometers.

Measuring SiO of the roasted sample by inductively coupled plasma atomic emission spectrometry (ICP) ₂ /Al ₂ O ₃ =21.6 (molar ratio).

Example 2

As in example 1, except that:

Al ₂ O ₃ /SiO ₂ ＝0.067

tetramethyl ammonium hydroxide (A)/SiO ₂ ＝0.15

N-octyl trimethyl ammonium chloride (B)/SiO ₂ ＝0.20

NaOH/SiO ₂ ＝0.30

H ₂ O/SiO ₂ ＝20；

After being mixed evenly, the mixture is put into a stainless steel reaction kettle and crystallized for 5 days at 160 ℃. Filtering, washing, drying in 100 deg.C oven for 16 hr, and calcining in 550 deg.C air for 8 hr to obtain molecular sieve.

The XRD spectrum data of the dried sample is shown in table 2 and fig. 4, and the SEM image of the sample is similar to fig. 2;

TABLE 2

The specific surface area of the resulting calcined product was 392 m ² Per gram, external specific surface area 166 m ² G, total pore volume 0.73 cm ³ Per gram, micropore volume of 0.10 cm ³ The micropore size distribution of the sample was 0.59 nm and 0.67 nm per gram. The sample is in a nano-sheet shape, and the thickness of the crystal is about 12 nanometers.

Measuring SiO of the roasted sample by inductively coupled plasma atomic emission spectrometry (ICP) ₂ /Al ₂ O ₃ =15.6 (molar ratio).

Example 3

As in example 1, except that:

Al ₂ O ₃ /SiO ₂ ＝0.04

tetramethylammonium chloride (A)/SiO ₂ ＝0.20

N-octyl trimethyl ammonium chloride (B)/SiO ₂ ＝0.15

NaOH/SiO ₂ ＝0.25

H ₂ O/SiO ₂ ＝35；

After being mixed evenly, the mixture is put into a stainless steel reaction kettle and crystallized for 7 days at the temperature of 155 ℃. Filtering, washing, drying in 80 deg.C oven for 16 hr, and calcining in 500 deg.C air for 10 hr to obtain molecular sieve.

The XRD spectrum data of the dried sample is shown in table 3, and the SEM image of the sample is shown in fig. 5.

TABLE 3

The specific surface area of the obtained calcined product was 388 m ² Per gram, external specific surface area of 162 m ² G, total pore volume 0.75 cm ³ Per gram, micropore volume of 0.10 cm ³ The micropore size distribution of the sample was 0.58 nm and 0.66 nm per gram. The sample has a nano-sheet shape, and the thickness of the crystal is about 13 nm.

Measuring SiO of the roasted sample by inductively coupled plasma atomic emission spectrometry (ICP) ₂ /Al ₂ O ₃ =26.1 (molar ratio).

Example 4

As in example 1, except that:

Al ₂ O ₃ /SiO ₂ ＝0.045

tetramethyl ammonium hydroxide (A)/SiO ₂ ＝0.25

N-octyl trimethyl ammonium chloride (B)/SiO ₂ ＝0.15

NaOH/SiO ₂ ＝0.20

H ₂ O/SiO ₂ ＝45；

After being mixed evenly, the mixture is put into a stainless steel reaction kettle and crystallized for 4 days at 165 ℃. Filtering, washing, drying in 60 deg.C oven for 24 hr, and calcining in 600 deg.C air for 4 hr to obtain molecular sieve.

The XRD spectrum data for the dried samples are shown in table 4, and the SEM images of the samples are similar to fig. 2.

TABLE 4

The specific surface area of the obtained calcined product was 377 m ² Per gram, external specific surface area of 158 m ² G, total pore volume 0.74 cm ³ G, micropore volume of 0.11 cm ³ The micropore size distribution of the sample was 0.59 nm and 0.67 nm per gram. The sample is in a nano-sheet shape, and the thickness of the crystal is about 11 nanometers.

Measuring SiO of the roasted sample by inductively coupled plasma atomic emission spectrometry (ICP) ₂ /Al ₂ O ₃ =22.3 (molar ratio).

Example 5

The same as example 1, except that:

Al ₂ O ₃ /SiO ₂ ＝0.017

tetramethylammonium hydroxide (A)/SiO ₂ ＝0.20

N-octyl trimethyl ammonium chloride (B)/SiO ₂ ＝0.25

NaOH/SiO ₂ ＝0.20

H ₂ O/SiO ₂ ＝30；

After being mixed evenly, the mixture is put into a stainless steel reaction kettle and crystallized for 8 days at the temperature of 155 ℃. Filtering, washing, drying in 120 deg.C oven for 6 hr, and calcining in 550 deg.C air for 8 hr to obtain molecular sieve.

The XRD spectrum data for the dried samples are shown in table 5, and the SEM images of the samples are similar to fig. 2.

TABLE 5

The specific surface area of the obtained calcined product was 372 m ² Per gram, external specific surface area 149 m ² G, total pore volume 0.74 cm ³ Per gram, micropore volume of 0.09 cm ³ In grams, the micropore size distribution of the sample was 0.60 nm and 0.67 nm. The sample is in a nano-sheet shape, and the thickness of the crystal is about 12 nanometers.

Measuring SiO of the roasted sample by inductively coupled plasma atomic emission spectrometry (ICP) ₂ /Al ₂ O ₃ =61.5 (molar ratio).

Example 6

The same as example 1, except that:

Al ₂ O ₃ /SiO ₂ ＝0.03

tetramethyl ammonium iodide (A)/SiO ₂ ＝0.20

N-octyl trimethyl ammonium chloride (B)/SiO ₂ ＝0.20

NaOH/SiO ₂ ＝0.25

H ₂ O/SiO ₂ ＝35；

After being mixed evenly, the mixture is put into a stainless steel reaction kettle and crystallized for 5 days at the temperature of 170 ℃. Filtering, washing, drying in 100 deg.C oven for 12 hr, and calcining in 500 deg.C air for 10 hr to obtain molecular sieve.

The XRD spectrum data for the dried samples are shown in table 6, and the SEM images of the samples are similar to fig. 2.

TABLE 6

The specific surface area of the obtained calcined product was 362 m ² Per gram, external specific surface area 149 m ² G, total pore volume 0.67 cm ³ Per gram, micropore volume of 0.10 cm ³ The micropore size distribution of the sample was 0.59 nm and 0.67 nm per gram. The sample has a nano-sheet shape, and the thickness of the crystal is about 12 nanometers.

Measuring SiO of the roasted sample by inductively coupled plasma atomic emission spectrometry (ICP) ₂ /Al ₂ O ₃ =34.5 (molar ratio).

Example 7

In the same way as example 1, except that tetrabutylammonium bromide is used as the organic structure directing agent (B), the material ratio (molar ratio) of the reactants is as follows:

Al ₂ O ₃ /SiO ₂ ＝0.05

tetramethyl ammonium hydroxide (A)/SiO ₂ ＝0.15

Tetradecylpyridine bromide (B)/SiO ₂ ＝0.15

NaOH/SiO ₂ ＝0.30

H ₂ O/SiO ₂ ＝35；

After being mixed evenly, the mixture is put into a stainless steel reaction kettle and crystallized for 7 days at 160 ℃. Filtering, washing, drying in 110 deg.C oven for 6 hr, and calcining in 550 deg.C air for 6 hr to obtain molecular sieve.

The XRD spectrum data for the dried samples are shown in table 7, and the SEM images of the samples are similar to fig. 2.

TABLE 7

The specific surface area of the obtained calcined product was 378 m ² Per gram, external specific surface area of 156 m ² G, total pore volume 0.77 cm ³ Per gram, micropore volume of 0.11 cm ³ The micropore size distribution of the sample was 0.59 nm and 0.66 nm per gram. The sample is in a nano-sheet shape, and the thickness of the crystal is about 13 nm.

Measuring SiO of the roasted sample by inductively coupled plasma atomic emission spectrometry (ICP) ₂ /Al ₂ O ₃ =21.1 (molar ratio).

Example 8

The same as example 1, except that cetylpyridinium bromide is used as the organic structure directing agent (B), and the material ratio (mol ratio) of the reactants is:

Al ₂ O ₃ /SiO ₂ ＝0.045

tetramethyl ammonium hydroxide (A)/SiO ₂ ＝0.15

Cetyl pyridine (B)/SiO bromide ₂ ＝0.20

NaOH/SiO ₂ ＝0.25

H ₂ O/SiO ₂ ＝30；

After being mixed evenly, the mixture is put into a stainless steel reaction kettle and crystallized for 6 days at 160 ℃. Filtering, washing, drying in a 90 deg.C oven for 12 hr, and calcining in 550 deg.C air for 6 hr to obtain the molecular sieve.

The XRD spectrum data for the dried samples are shown in table 8, and the SEM images of the samples are similar to fig. 2.

TABLE 8

The specific surface area of the resulting calcined product was 394 m ² Per gram, external specific surface area 171 m ² G, total pore volume 0.68 cm ³ G, micropore volume of 0.12 cm ³ The micropore size distribution of the sample was 0.59 nm and 0.67 nm per gram. The sample has a nano-sheet shape, and the thickness of the crystal is about 12 nanometers.

Measuring SiO of the roasted sample by inductively coupled plasma atomic emission spectrometry (ICP) ₂ /Al ₂ O ₃ =22.8 (molar ratio).

Example 9

Same as example 8, except that:

Al ₂ O ₃ /SiO ₂ ＝0.068

tetramethylammonium hydroxide (A)/SiO ₂ ＝0.20

Cetylpyridinium bromide (B)/SiO ₂ ＝0.15

NaOH/SiO ₂ ＝0.30

H ₂ O/SiO ₂ ＝40；

After being mixed evenly, the mixture is put into a stainless steel reaction kettle and crystallized for 6 days at 160 ℃. Filtering, washing, drying in 80 deg.C oven for 16 hr, and calcining in 550 deg.C air for 6 hr to obtain molecular sieve.

The XRD spectrum data for the dried samples are shown in table 9, and the SEM images of the samples are similar to fig. 2.

TABLE 9

The specific surface area of the obtained calcined product was 372 m ² Per gram, external specific surface area 144 m ² G, total pore volume 0.65 cm ³ Per gram, micropore volume of 0.11 cm ³ The micropore size distribution of the sample was 0.59 nm and 0.67 nm per gram. The sample has a nano-sheet shape, and the thickness of the crystal is about 15 nanometers.

Measuring SiO of the roasted sample by inductively coupled plasma atomic emission spectrometry (ICP) ₂ /Al ₂ O ₃ =14.5 (molar ratio).

Example 10

As in example 1, except that:

Al ₂ O ₃ /SiO ₂ ＝0.05

TiO ₂ /SiO ₂ ＝0.01

tetramethyl ammonium hydroxide (A)/SiO ₂ ＝0.15

N-octyl trimethyl ammonium chloride (B)/SiO ₂ ＝0.20

NaOH/SiO ₂ ＝0.25

H ₂ O/SiO ₂ ＝35；

After being mixed evenly, the mixture is put into a stainless steel reaction kettle and crystallized for 7 days at 160 ℃. Filtering, washing, drying in 100 deg.C oven for 10 hr, and calcining in 550 deg.C oxygen for 6 hr to obtain molecular sieve.

The XRD spectrum data of the dried sample is shown in table 10, and the SEM image of the sample is similar to that of fig. 2.

Watch 10

The specific surface area of the obtained calcined product was 364 m ² Per gram, external specific surface area 146 m ² G, total pore volume 0.71 cm ³ Per gram, micropore volume of 0.12 cm ³ The micropore size distribution of the sample was 0.59 nm and 0.67 nm per gram. The sample has a nano-sheet shape, and the thickness of the crystal is about 18 nanometers.

Measuring SiO of the roasted sample by inductively coupled plasma atomic emission spectrometry (ICP) ₂ /Al ₂ O ₃ =21.2 (molar ratio), siO ₂ /TiO ₂ =106.2 (molar ratio).

Example 11

The same as example 1, except that:

Al ₂ O ₃ /SiO ₂ ＝0.065

B ₂ O ₃ /SiO ₂ ＝0.012

tetramethylammonium hydroxide (A)/SiO ₂ ＝0.20

N-octyl trimethyl ammonium chloride (B)/SiO ₂ ＝0.15

NaOH/SiO ₂ ＝0.30

H ₂ O/SiO ₂ ＝40；

After being mixed evenly, the mixture is put into a stainless steel reaction kettle and crystallized for 7 days at the temperature of 155 ℃. Filtering, washing, drying in 80 deg.C oven for 8 hr, and calcining in 550 deg.C air for 6 hr to obtain molecular sieve.

The XRD spectrum data of the dried sample is shown in table 11, and the SEM image of the sample is similar to fig. 2;

TABLE 11

The specific surface area of the obtained calcined product was 385 m ² Per gram, external specific surface area of 152 m ² G, total pore volume 0.63 cm ³ Per gram, micropore volume of 0.09 cm ³ The micropore size of the sample is mainly distributed between 0.59 and 0.67 nm. The sample has a nano-sheet shape, and the thickness of the crystal is about 20 nm.

Measuring SiO of the roasted sample by inductively coupled plasma atomic emission spectrometry (ICP) ₂ /Al ₂ O ₃ =15.9 (molar ratio), siO ₂ /B ₂ O ₃ =96.3 (molar ratio).

Example 12

Same as example 7, except that:

Al ₂ O ₃ /SiO ₂ ＝0.035

ZrO ₂ /SiO ₂ ＝0.008

tetramethylammonium hydroxide (A)/SiO ₂ ＝0.20

Brominated dodecyl pyridine (B)/SiO ₂ ＝0.20

NaOH/SiO ₂ ＝0.25

H ₂ O/SiO ₂ ＝30；

After being mixed evenly, the mixture is put into a stainless steel reaction kettle and crystallized for 6 days at 165 ℃. Filtering, washing, drying in a 110 deg.C oven for 12 hr, and calcining in 550 deg.C air for 5 hr to obtain the molecular sieve.

The XRD spectrum data for the dried samples are shown in table 12, with SEM images of the samples similar to fig. 2;

TABLE 12

The specific surface area of the obtained calcined product was 373 m ² Per gram, external specific surface area of 148 m ² G, total pore volume 0.75 cm ³ Per gram, micropore volume of 0.09 cm ³ The micropore size distribution of the sample was 0.59 nm and 0.67 nm per gram. The sample has a nano-sheet shape, and the thickness of the crystal is about 16 nanometers.

Measuring SiO of the roasted sample by inductively coupled plasma atomic emission spectrometry (ICP) ₂ /Al ₂ O ₃ =30.6 (molar ratio), siO ₂ /ZrO ₂ =131.2 (molar ratio).

Example 13

As in example 1, except that:

Al ₂ O ₃ /SiO ₂ ＝0.05

SnO ₂ /SiO ₂ ＝0.008

tetramethyl ammonium bromide (A)/SiO ₂ ＝0.15

N-octyl trimethyl ammonium bromide (B)/SiO ₂ ＝0.20

NaOH/SiO ₂ ＝0.30

H ₂ O/SiO ₂ ＝25；

After being mixed evenly, the mixture is put into a stainless steel reaction kettle and crystallized for 7 days at 160 ℃. Filtering, washing, drying in a 110 deg.C oven for 12 hr, and calcining in 550 deg.C air for 6 hr to obtain the molecular sieve.

The XRD spectrum data for the dried samples are shown in table 13, with SEM images of the samples similar to fig. 2;

watch 13

The specific surface area of the obtained calcined product is 386 m ² Per gram, external specific surface area 154 m ² G, total pore volume 0.73 cm ³ Per gram, micropore volume of 0.10 cm ³ The micropore size distribution of the sample was 0.59 nm and 0.66 nm per gram. The sample has a nano-sheet shape, and the thickness of the crystal is about 15 nanometers.

Measuring SiO of the roasted sample by inductively coupled plasma atomic emission spectrometry (ICP) ₂ /Al ₂ O ₃ =21.5 (molar ratio), siO ₂ /SnO ₂ =126.4 (molar ratio).

Example 14

Same as example 8, except that:

Al ₂ O ₃ /SiO ₂ ＝0.04

Fe ₂ O ₃ /SiO ₂ ＝0.005

tetramethylammonium chloride (A)/SiO ₂ ＝0.15

Hexadecylpyridine (B) hydroxide/SiO ₂ ＝0.25

NaOH/SiO ₂ ＝0.20

H ₂ O/SiO ₂ ＝30；

After being mixed evenly, the mixture is put into a stainless steel reaction kettle and crystallized for 7 days at 165 ℃. Filtering, washing, drying in a 110 deg.C oven for 12 hr, and calcining in 550 deg.C air for 6 hr to obtain the molecular sieve.

The XRD spectrum data for the dried samples are shown in table 14, with SEM images of the samples similar to fig. 2;

TABLE 14

The specific surface area of the obtained calcined product was 383 m ² Per gram, external specific surface area of 155 m ² G, total pore volume 0.75 cm ³ G, micropore volume of 0.10 cm ³ In grams, the micropore size distribution of the sample was 0.60 nm and 0.66 nm. The sample has a nano-sheet shape, and the thickness of the crystal is about 17 nanometers.

Measuring SiO of the roasted sample by inductively coupled plasma atomic emission spectrometry (ICP) ₂ /Al ₂ O ₃ =26.5 (molar ratio), siO ₂ /Fe ₂ O ₃ =188.4 (molar ratio).

Example 15

The same as example 1, except that:

Al ₂ O ₃ /SiO ₂ ＝0.045

tetramethyl ammonium hydroxide (A)/SiO ₂ ＝0.45

Brominated dodecyl pyridine (B)/SiO ₂ ＝0.20

NaOH/SiO ₂ ＝0.25

H ₂ O/SiO ₂ ＝25；

After being mixed evenly, the mixture is put into a stainless steel reaction kettle and crystallized for 6 days at 160 ℃. Filtering, washing, drying in a 110 deg.C oven for 12 hr, and calcining in 550 deg.C air for 6 hr to obtain the molecular sieve.

The XRD spectrum data of the dried sample is shown in table 15, and the SEM image of the sample is similar to fig. 2;

watch 15

The specific surface area of the obtained calcined product was 368 m ² Per gram, external specific surface area of 145 m ² G, total pore volume 0.72 cm ³ Per gram, micropore volume of 0.09 cm ³ The micropore size distribution of the sample was 0.58 nm and 0.66 nm per gram. The sample has a nano-sheet shape, and the thickness of the crystal is about 17 nanometers.

Measuring SiO of the roasted sample by inductively coupled plasma atomic emission spectrometry (ICP) ₂ /Al ₂ O ₃ =22.8 (molar ratio).

Example 16

Same as example 7, except that:

Al ₂ O ₃ /SiO ₂ ＝0.040

tetramethylammonium chloride (A)/SiO ₂ ＝0.15

Brominated dodecyl pyridine (B)/SiO ₂ ＝0.45

NaOH/SiO ₂ ＝0.15

H ₂ O/SiO ₂ ＝30；

After being mixed evenly, the mixture is put into a stainless steel reaction kettle and crystallized for 8 days at 160 ℃. Filtering, washing, drying in a 110 deg.C oven for 12 hr, and calcining in 550 deg.C air for 6 hr to obtain the molecular sieve.

The XRD spectrum data for the dried samples are shown in table 16, with SEM images of the samples similar to fig. 2;

TABLE 16

The specific surface area of the obtained calcined product was 388 m ² Per gram, external specific surface area of 159 m ² G, total pore volume 0.71 cm ³ G, micropore volume of 0.10 cm ³ The micropore size distribution of the sample was 0.59 nm and 0.66 nm per gram. The sample has a nano-sheet shape, and the thickness of the crystal is about 17 nanometers.

Measuring SiO of the roasted sample by inductively coupled plasma atomic emission spectrometry (ICP) ₂ /Al ₂ O ₃ =26.1 (molar ratio).

Example 17

The same as example 1, except that:

Al ₂ O ₃ /SiO ₂ ＝0.05

tetramethylammonium hydroxide (A)/SiO ₂ ＝0.20

Cetylpyridinium chloride (B)/SiO ₂ ＝0.25

NaOH/SiO ₂ ＝0.15

H ₂ O/SiO ₂ ＝20；

After being mixed evenly, the mixture is put into a stainless steel reaction kettle and crystallized for 7 days at 160 ℃. Filtering, washing, drying in a 110 deg.C oven for 12 hr, and calcining in 550 deg.C air for 6 hr to obtain the molecular sieve.

The XRD spectrum data for the dried samples are shown in table 17, with SEM images of the samples similar to fig. 2;

TABLE 17

The specific surface area of the resulting calcined product was 392 m ² Per gram, external specific surface area of 159 m ² G, total pore volume 0.72 cm ³ Per gram, micropore volume of 0.09 cm ³ Per gram, the micropore size distribution of the sample is 0.60 nm and 0.66 nm. The sample is in a nano-sheet shape, and the thickness of the crystal is about 15 nanometers.

Measuring SiO of the roasted sample by inductively coupled plasma atomic emission spectrometry (ICP) ₂ /Al ₂ O ₃ =21.6 (molar ratio).

Comparative example 1

The same as example 1, except that:

Al ₂ O ₃ /SiO ₂ ＝0.22

tetramethyl ammonium hydroxide (A)/SiO ₂ ＝0.15

N-octyl trimethyl ammonium chloride (B)/SiO ₂ ＝0.15

NaOH/SiO ₂ ＝0.30

H ₂ O/SiO ₂ ＝25；

After being mixed evenly, the mixture is put into a stainless steel reaction kettle and crystallized for 6 days at 160 ℃. After crystallization, filtering, washing, drying in a 110 ℃ oven for 12 hours, and roasting in 550 ℃ air for 6 hours to obtain a sample.

The XRD spectrum data of the dried sample is shown in figure 6 as amorphous and not SCM-36 molecular sieve.

Comparative example 2

The same as example 1, except that:

Al ₂ O ₃ /SiO ₂ ＝0.05

tetramethylammonium hydroxide (A)/SiO ₂ ＝0.15

N-octyl trimethyl ammonium chloride (B)/SiO ₂ ＝0.15

NaOH/SiO ₂ ＝0.55

H ₂ O/SiO ₂ ＝25；

After being mixed evenly, the mixture is put into a stainless steel reaction kettle and crystallized for 6 days at 160 ℃. Filtering and washing after crystallization, drying in a 110 ℃ oven for 12 hours, and roasting in air at 550 ℃ for 6 hours to obtain a sample.

The XRD spectrum data for the dried sample was similar to that of fig. 6, being amorphous and not SCM-36 molecular sieve.

Comparative example 3

Same as example 1, except that octylamine was used as organic structure directing agent (B):

Al ₂ O ₃ /SiO ₂ ＝0.05

tetramethylammonium hydroxide (A)/SiO ₂ ＝0.15

Octylamine (B)/SiO ₂ ＝0.15

NaOH/SiO ₂ ＝0.30

H ₂ O/SiO ₂ ＝25；

After being mixed evenly, the mixture is put into a stainless steel reaction kettle and crystallized for 6 days at 160 ℃. Filtering and washing after crystallization, drying in a 110 ℃ oven for 12 hours, and roasting in air at 550 ℃ for 6 hours to obtain a sample.

The XRD pattern data of the dried sample is shown in FIG. 7 as a mixture of MOR and other structural molecular sieves, not SCM-36 molecular sieve.

Comparative example 4

As in example 1, except that only tetramethylammonium hydroxide was used as the organic structure directing agent:

Al ₂ O ₃ /SiO ₂ ＝0.05

tetramethyl ammonium hydroxide/SiO ₂ ＝0.15

NaOH/SiO ₂ ＝0.30

H ₂ O/SiO ₂ ＝25；

After being mixed evenly, the mixture is put into a stainless steel reaction kettle and crystallized for 6 days at 160 ℃. After crystallization, filtering, washing, drying in a 110 ℃ oven for 12 hours, and roasting in 550 ℃ air for 6 hours to obtain a sample.

The XRD spectrum data of the dried sample is shown in figure 8 and is a mixture of SOD and molecular sieves with other structures, not SCM-36 molecular sieve.

Example 18

The molecular sieve synthesized in example 5 was mixed with 0.5mol/L NH ₄ And (3) carrying out ion exchange on the Cl solution (the mass ratio of the molecular sieve to the ammonium chloride solution is 1: 20) at 70 ℃ for 2 hours, then carrying out centrifugal washing, drying a sample obtained after twice ion exchange at 100 ℃ for 12 hours, and roasting at 550 ℃ for 6 hours to obtain the H-type SCM-36 molecular sieve.

Taking the baked H-type SCM-36 molecular sieve powder sample, after crushing, sieving a part with the granularity of 20-40 meshes, putting the part into a fixed bed reactor, and performing cumene cracking reaction under the reaction conditions of: the reaction temperature is 320 ℃, the reaction pressure is normal pressure, and the weight space velocity of the isopropyl benzene is 2h ^-1 . The product was analyzed by shimadzu GC-2014 gas chromatography, the cumene conversion rate after 1 hour of reaction was 25.2%, and the benzene selectivity in the product was 94.1%.

Example 19

The molecular sieve synthesized in example 5 was mixed with 0.5mol/L NH ₄ And (3) carrying out ion exchange on a Cl solution (the mass ratio of the molecular sieve to the ammonium chloride solution is 1: 20) at 70 ℃ for 2 hours, then carrying out centrifugal washing, drying a sample obtained after twice ion exchange at 100 ℃ for 12 hours, and roasting at 550 ℃ for 6 hours to obtain the H-type SCM-36 molecular sieve.

Taking the roasted H-type SCM-36 molecular sieve powder sample, crushing, sieving to obtain a 20-40 mesh part, and putting the part into a fixed bed reactor for methanol conversion reaction. The reaction conditions are as follows: the reaction temperature is 460 ℃, the reaction pressure is 0.1MPa, and the weight space velocity of the raw material methanol is 1h ^-1 . The product was analyzed by shimadzu GC-2014 gas chromatograph, and after 45 minutes of reaction, the conversion of methanol was 99.0%, the selectivity of C2-C4 olefins in the product was 58.6%, and the selectivity of aromatics was 4.2%.

The specific embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.

Claims (13)

1. An SCM-36 molecular sieve having a schematic chemical composition "mSiO ₂ ·nAl ₂ O ₃ ", wherein m/n is not less than 5, preferably m/n =5 to 80, more preferably m/n =10 to 65; the molecular sieve has an X-ray diffraction pattern including that shown in the following table,

a: ± 0.30 °, b: as a function of 2 theta.

2. The molecular sieve of claim 1, further comprising at least one diffraction peak comprising an X-ray diffraction pattern as shown in the following Table,

a: ± 0.30 °, b: as a function of 2 theta.

3. The molecular sieve of claim 1, having a specific surface area of 300 to 700 meters ² Per gram, preferably 300 to 600 m ² Per gram, preferably 350 to 500 m ² Per gram; the external specific surface area is 50 to 300 meters ² Per gram, preferably 80 to 250 m ² Per gram;

and/or the total pore volume of the molecular sieve is 0.20-1.50 cm ³ Per gram, preferably 0.40 to 1.20 cm ³ Per gram; the micropore volume is 0.05-0.35 cm ³ Per gram, preferably 0.08 to 0.30 cm ³ Per gram;

and/or the pore diameter of the micropores of the molecular sieve is 0.20-0.75 nm, preferably 0.30-0.70 nm.

4. The molecular sieve of claim 1, wherein the molecular sieve has a nano-platelet morphology, and the thickness of the crystals is less than 30 nm, preferably 5 to 25 nm, and more preferably 7 to 20 nm.

5. The molecular sieve of any of claims 1-4, wherein the molecular sieve further comprises elements other than silicon and aluminum in its chemical composition, selected from the group consisting of at least one of titanium, boron, zirconium, tin, and iron;

preferably, the molecular sieve has a schematic chemical composition that contains no more than 3 mole percent, based on the total moles of oxides, of elemental oxides other than silicon and aluminum.

6. A method for producing the molecular sieve of any one of claims 1 to 4, comprising the step of crystallizing a mixture comprising a silicon source, an aluminum source, an organic structure-directing agent (A), an organic structure-directing agent (B), an alkali source and water to obtain the molecular sieve; and optionally, further comprising the step of calcining the obtained molecular sieve;

wherein the organic structure directing agent (A) is at least one selected from tetramethylammonium hydroxide or a quaternary ammonium salt thereof; the organic structure directing agent (B) is at least one selected from quaternary ammonium salts of C ten to C sixteen alkylpyridine or n-octyl trimethyl compound or quaternary ammonium bases thereof.

7. The method of claim 6, wherein the silicon source is SiO ₂ Calculated by Al, the aluminum source ₂ O ₃ The molar ratio of the organic structure directing agent (A), the organic structure directing agent (B), the alkali source and the water is 1 (0.01-0.20), (0.05-0.80), (0.05-0.50), (8-80), preferably 1 (0.01-0.10), (0.08-0.65), (0.08-0.45), (10-70), more preferably 1 (0.02-0.07), (0.10-0.50), (0.10-0.40) and (12-60).

8. The method according to claim 6, wherein the mixture is crystallized at a crystallization temperature of 120 to 200 ℃ for 1 to 15 days, preferably at a crystallization temperature of 130 to 190 ℃ for 2 to 12 days, more preferably at a crystallization temperature of 140 to 180 ℃ for 3 to 9 days.

9. The production method according to claim 6, wherein the organic structure directing agent (A) is at least one selected from the group consisting of tetramethylammonium hydroxide, tetramethylammonium chloride, tetramethylammonium bromide and tetramethylammonium iodide;

and/or the organic structure directing agent (B) is selected from at least one of cetylpyridinium bromide, tetradecylpyridinium bromide, dodecylpyridinium bromide, cetylpyridinium chloride, tetradecylpyridinium chloride, hexadecylpyridinium hydroxide, n-octyltrimethylammonium chloride, n-octyltrimethylammonium bromide or n-octyltrimethylammonium hydroxide; preferably, the organic structure directing agent (B) is selected from at least one of cetylpyridinium bromide, tetradecylpyridinium bromide, dodecylpyridinium bromide, cetylpyridinium chloride, cetylpyridinium hydroxide, n-octyltrimethylammonium chloride or n-octyltrimethylammonium bromide.

10. The method according to claim 6, wherein the silicon source is at least one selected from the group consisting of silicic acid, silica gel, silica sol, tetraethyl silicate, and water glass;

and/or the aluminum source is selected from at least one of aluminum hydroxide, aluminum oxide, aluminate, aluminum salt and tetraalkoxy aluminum;

and/or the alkali source is at least one of inorganic alkali taking alkali metal and alkaline earth metal as cations.

11. The production method according to any one of claims 6 to 10, characterized in that the mixture further comprises a non-silicon and non-aluminum source selected from at least one of a titanium source, a boron source, a zirconium source, a tin source, and an iron source;

preferably, the silicon source is SiO ₂ The molar ratio of the non-silicon and non-aluminum sources to the corresponding oxides is 1 (0.002-0.10), preferably 1 (0.005-0.05).

12. A molecular sieve composition comprising the SCM-36 molecular sieve according to any of claims 1 to 5 or the SCM-36 molecular sieve produced according to the production process of any of claims 6 to 11, and a binder.

13. Use of a SCM-36 molecular sieve as defined in any of claims 1 to 5 or a SCM-36 molecular sieve composition as defined in claim 12 or a SCM-36 molecular sieve produced according to the production process of any of claims 6 to 11 as an adsorbent or catalyst for conversion of organic compounds.

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