SCM-36 molecular sieve, method for manufacturing the same, and use thereof

Abstract

The present invention discloses an SCM-36 molecular sieve, a method for manufacturing the same, and uses thereof. The molecular sieve has a schematic chemical composition of "mSiO2·nAl2O3", where m / n ≥ 5. The molecular sieve has unique XRD diffraction data and is a novel molecular sieve, which can be used as an adsorbent or a catalyst for the conversion of organic compounds.

Description

Technical Field

[0001] The present invention relates to an SCM-36 molecular sieve, a method for manufacturing the same, and uses thereof. Background Art

[0002] In industry, molecular sieve materials are widely used in fields such as catalysis, ion exchange, adsorption, and separation due to their open structures and large surface areas. Subtle differences in these material structures indicate differences in various observable properties used to characterize them, such as their morphologies, specific surface areas, pore sizes, and the variability of these sizes. At the same time, it also means that there are significant differences in the catalytic and adsorption properties of the materials themselves.

[0003] The basic framework structure of crystalline microporous zeolites is based on a rigid three-dimensional TO4 (SiO4, AlO4, etc.) unit structure; in this structure, TO4 shares oxygen atoms in a tetrahedral manner, and the charge balance of the framework tetrahedra such as AlO4 is maintained by the presence of surface cations such as Na + , H + . Thus, it can be seen that the framework properties of zeolites can be changed by cation exchange. At the same time, there is a rich pore system with a certain pore size in the zeolite structure. These pores intersect to form a three-dimensional network structure, and the framework can still stably exist after the water or organic matter in the pores is removed (US 4439409). It is precisely based on the above structure that zeolites not only have good catalytic activity for a variety of organic reactions, excellent shape selectivity, but also can achieve good selectivity through modification (US 6162416, US 4954325, US 5362697).

[0004] The specific structure of molecular sieves is determined by X-ray diffraction patterns (XRD). X-ray diffraction patterns (XRD) are measured by an X-ray powder diffractometer using a Cu-Kα ray source and a nickel filter. Different zeolite molecular sieves have different XRD pattern characteristics. Existing molecular sieves, such as A-type zeolite, Y-type zeolite, MCM-22 molecular sieve, etc., all have XRD patterns with their own characteristics.

[0005] At the same time, molecular sieves with the same XRD pattern characteristics but different framework element types are also different molecular sieves. For example, TS-1 molecular sieve (US4410501) and ZSM-5 molecular sieve (US3702886) have the same XRD pattern characteristics, but different framework elements. Specifically, the framework elements of TS-1 molecular sieve are Si and Ti, with catalytic oxidation function, while the framework elements of ZSM-5 molecular sieve are Si and Al, with acid catalytic function.

[0006] In addition, molecular sieves with the same XRD pattern characteristics and the same types of framework elements but different relative contents of framework elements belong to different molecular sieves. For example, zeolite X (US2882244) and zeolite Y (US3130007) have the same XRD pattern characteristics, and their framework elements are both Si and Al, but the relative contents of Si and Al are different. Specifically, the Si / Al molar ratio of zeolite X is less than 1.5, while that of zeolite Y is greater than 1.5. SUMMARY OF THE INVENTION

[0007] Based on the prior art, the present inventors have conducted intensive research and discovered a novel SCM-36 molecular sieve, and further discovered its beneficial properties. Specifically, the present invention provides an SCM-36 molecular sieve, a method for manufacturing the same, and its uses.

[0008] In a first aspect of the present invention, there is provided an SCM-36 molecular sieve having a schematic chemical composition of "mSiO2·nAl2O3", where m / n ≥ 5, and the molecular sieve has an X-ray diffraction pattern as shown in the following table,

[0009]

[0010] a: ±0.30°, b: varying with 2θ.

[0011] In the above technical solution, the molecular sieve may further have at least one diffraction peak in the X-ray diffraction pattern as shown in the following table,

[0012]

[0013] a: ±0.30°, b: varying with 2θ.

[0014] In the above technical solution, the molecular sieve has a schematic chemical composition of "mSiO2·nAl2O3", where m / n ≥ 5, preferably m / n = 5 to 80, more preferably m / n = 10 to 65. Here, m / n is the SiO2 / Al2O3 molar ratio.

[0015] In the above technical solution, the specific surface area of the molecular sieve is 300 to 700 m 2 / g, preferably 300 to 600 m 2 / g, preferably 350 to 500 m 2 / g; the external specific surface area is 50 to 300 m 2 / g, preferably 80 to 250 m 2 / g.

[0016] In the above technical solution, the total pore volume of the molecular sieve is 0.20 to 1.50 cm 3 / g, preferably 0.40 - 1.20 cm 3 / g; the micropore volume is 0.05 - 0.35 cm 3 / g, preferably 0.08 - 0.30 cm 3 / g.

[0017] In the above technical solution, the molecular sieve has a nano - sheet morphology, the thickness of the crystal < 30 nm, preferably 5 - 25 nm, more preferably 7 - 20 nm.

[0018] In the above technical solution, the micropore diameter of the molecular sieve is 0.20 - 0.75 nm, preferably 0.30 - 0.70 nm.

[0019] In the above technical solution, the chemical composition of the molecular sieve further includes elements other than silicon and aluminum, selected from at least one of titanium, boron, zirconium, tin, and iron.

[0020] In the above technical solution, in the schematic chemical composition of the molecular sieve, based on the total molar number of oxides, the content of the oxides of elements other than silicon and aluminum does not exceed 3% in mole fraction.

[0021] The second aspect of the present invention provides a method for manufacturing an SCM - 36 molecular sieve, including the step of crystallizing a mixture containing 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 including 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 its quaternary ammonium salt form; the organic structure - directing agent (B) is selected from at least one of quaternary ammonium salts or quaternary ammonium bases of alkylpyridines with 10 - 16 carbon atoms or n - octyltrimethyl compounds.

[0022] In the above technical solution, the molar ratio of the silicon source (calculated as SiO2), the aluminum source (calculated as Al2O3), the organic structure - directing agent (A), the organic structure - directing agent (B), the alkali source, and water is 1:(0.01 - 0.20):(0.05 - 0.80):(0.05 - 0.80):(0.05 - 0.50):(8 - 80), preferably 1:(0.01 - 0.10):(0.08 - 0.65):(0.08 - 0.65):(0.08 - 0.45):(10 - 70), more preferably 1:(0.02 - 0.07):(0.10 - 0.50):(0.10 - 0.50):(0.10 - 0.40):(12 - 60).

[0023] In the above technical solution, the crystallization temperature of the mixture is 120 to 200 °C, and the crystallization time is 1 to 15 days. Preferably, the crystallization temperature is 130 to 190 °C, and the crystallization time is 2 to 12 days. More preferably, the crystallization temperature is 140 to 180 °C, and the crystallization time is 3 to 9 days.

[0024] In the above technical solution, preferably, after crystallization, filtration, washing, and drying are carried out; the drying temperature for the drying is 40 to 150 °C, preferably 50 to 120 °C, and the drying time is 1 to 30 hours, preferably 2 to 24 hours.

[0025] In the above technical solution, the calcination temperature for the calcination is 300 to 800 °C, preferably 400 to 650 °C, the calcination time is 1 to 12 hours, preferably 2 to 10 hours, and the calcination atmosphere is air or an oxygen atmosphere.

[0026] In the above technical solution, the silicon source is selected from at least one of silicic acid, silica gel, silica sol, tetraethyl orthosilicate, and water glass; the aluminum source is selected from at least one of aluminum hydroxide, alumina, aluminate, aluminum salt, and tetraalkoxyaluminum.

[0027] In the above technical solution, the base source is selected from at least one of inorganic bases with alkali metals or alkaline earth metals as cations.

[0028] In the above technical solution, the organic structure-directing agent (A) is selected from at least one of tetramethylammonium hydroxide, tetramethylammonium chloride, tetramethylammonium bromide, or tetramethylammonium iodide.

[0029] In the above technical solution, the organic structure-directing agent (B) is preferably selected from at least one of cetylpyridinium bromide, tetradecylpyridinium bromide, dodecylpyridinium bromide, decylpyridinium bromide, cetylpyridinium chloride, tetradecylpyridinium chloride, cetylpyridinium 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.

[0030] 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 selected from at least one of a titanium source, a boron source, a zirconium source, a tin source, and an iron source.

[0031] In the above technical solution, the titanium source is selected from at least one of organometallic titanium complexes, tetraalkoxytitanium, titanium dioxide, and titanium nitrate; the boron source is selected from at least one of boric acid, borate, borax, and boron trioxide; the zirconium source is selected from at least one of organometallic zirconium complexes, zirconium salts, zirconium hydroxide, zirconium alkoxide, and zirconium dioxide; the tin source is selected from at least one of organometallic tin complexes, tin salts, and tin dioxide; the iron source is selected from at least one of organometallic iron complexes, iron nitrate, iron chloride, and iron oxide.

[0032] In the above technical solution, the molar ratio of the silicon source (calculated as SiO2) to the non-silicon and non-aluminum sources (calculated as the corresponding oxides) is 1:(0.002 - 0.10), preferably 1:(0.005 - 0.05).

[0033] The third aspect of the present invention provides a molecular sieve composition, comprising the SCM-36 molecular sieve according to any one of the foregoing aspects or the SCM-36 molecular sieve manufactured by the manufacturing method according to any one of the foregoing aspects, and a binder.

[0034] The fourth aspect of the present invention provides an application of the SCM-36 molecular sieve or the SCM-36 molecular sieve composition according to any one of the foregoing aspects, or the SCM-36 molecular sieve manufactured by the manufacturing method according to any one of the foregoing aspects as an adsorbent or a catalyst for the conversion of organic compounds.

[0035] According to the present invention, the SCM-36 molecular sieve involved has a framework structure and chemical composition that have never been obtained in the prior art. BRIEF DESCRIPTION OF THE DRAWINGS

[0036] Figure 1 It is the X-ray diffraction pattern (XRD) of the molecular sieve obtained in Example 1;

[0037] Figure 2 It is the scanning electron micrograph (SEM) of the molecular sieve obtained in Example 1;

[0038] Figure 3 It is the transmission electron micrograph (TEM) of the molecular sieve obtained in Example 1;

[0039] Figure 4 It is the X-ray diffraction pattern (XRD) of the molecular sieve obtained in Example 2;

[0040] Figure 5 It is the scanning electron micrograph (SEM) of the molecular sieve obtained in Example 3;

[0041] Figure 6 It is the X-ray diffraction pattern (XRD) of the sample obtained in Comparative Example 1;

[0042] Figure 7 XRD pattern of the sample obtained in Comparative Example 3;

[0043] Figure 8 XRD pattern of the sample obtained in Comparative Example 4. Detailed Description of the Invention

[0044] The following provides a detailed description of the specific embodiments of the present invention. It should be noted, however, that the scope of protection of the present invention is not limited by these specific embodiments, but is determined by the appended claims.

[0045] 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.

[0046] When this specification uses prefixes such as "well-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 of filing this application, but also include those that are not commonly used at present but will become commonly recognized in the art as suitable for similar purposes.

[0047] In the context of this specification, unless otherwise explicitly stated, any matters or things not mentioned 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 solutions or technical ideas are regarded as part of the original disclosure or original record of the present invention, and should not be regarded as new content not disclosed or anticipated herein, unless those skilled in the art consider such combination to be obviously unreasonable.

[0048] In the context of this specification, for a molecular sieve, before other substances (such as organic template molecules, etc.) filled in the pores during the synthesis of the molecular sieve, except for water and metal ions, are removed from its pores, it is called a "precursor".

[0049] In the context of this specification, in the XRD data of a 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 is 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.

[0050] 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 only one kind of crystal is contained 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.

[0051] In the context of this specification, the so-called specific surface area refers to the total area per unit mass of the sample, including the internal surface area and the external surface area. Non-porous samples only have an external surface area, such as Portland cement, some clay mineral powders, etc.; porous and multi-porous samples have an external surface area and an internal surface area, such as asbestos fibers, diatomite, and molecular sieves. For porous and multi-porous samples, the surface area of pores with a pore diameter less than 2 nm is the internal surface area, and the surface area after deducting the internal surface area is called the external surface area. The external specific surface area is the external surface area per unit mass of the sample.

[0052] In the context of this specification, the so-called pore volume refers to the volume of pores per unit mass of the porous material. The so-called total pore volume is the volume of all pores (generally only pores with a pore diameter less than 50 nm are counted) per unit mass of the molecular sieve. The so-called micropore volume is the volume of all micropores (generally pores with a pore diameter less than 2 nm) per unit mass of the molecular sieve. The 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 the nitrogen physical adsorption and desorption isotherm of the molecular sieve with a physical adsorption instrument (such as the TriStar 3000 physical adsorption instrument of Micromeritics Instrument Corporation of the United States), and then calculating by the BET method and the t-plot method. The experimental conditions for nitrogen physical adsorption and desorption are: the measurement temperature is -169 °C, and the molecular sieve is pretreated in vacuum at 300 °C for 10 hours before measurement.

[0053] In the context of this specification, the so-called thickness of the crystal refers to observing the molecular sieve with a transmission electron microscope at a magnification of 100,000 times, randomly selecting an observation field of view, and calculating the average value of the sum of the thicknesses of all flaky crystals in the observation field of view. Repeat this operation a total of 10 times. The average value of the sum of the 10 average values is used as the crystal thickness.

[0054] The present invention relates to a SCM-36 molecular sieve. The framework structure and chemical composition of the SCM-36 molecular sieve have never been obtained in the art before.

[0055] According to the present invention, the SCM-36 molecular sieve may exist in an uncalcined state (as-synthesized state) or in a calcined state. When in the as-synthesized state, the SCM-36 molecular sieve generally has a schematic chemical composition represented by the formula "mSiO2·nAl2O3·organic structure-directing agent·water". When in the calcined state or in the as-synthesized state, the SCM-36 molecular sieve generally may also have a schematic chemical composition represented by the formula "mSiO2·nAl2O3". In the latter case, it is known that the molecular sieve sometimes (especially just after synthesis) contains a certain amount of water, but the present invention believes that it is not necessary to specify the amount of this water because the presence or absence of this water does not substantially affect the XRD pattern of the molecular sieve. In view of this, this schematic chemical composition actually represents the anhydrous chemical composition of the molecular sieve. Moreover, obviously, this schematic chemical composition represents the framework chemical composition of the SCM-36 molecular sieve.

[0056] According to the present invention, the molecular sieve in its calcined form has an X-ray diffraction pattern including as shown in the following table

[0057]

[0058] a: ±0.30°, b: varying with 2θ.

[0059] According to the present invention, the molecular sieve may also have at least one diffraction peak in the X-ray diffraction pattern including as shown in the following table

[0060]

[0061] a: ±0.30°, b: varying with 2θ.

[0062] According to the present invention, the SCM-36 molecular sieve has a schematic chemical composition of mSiO2·nAl2O3, where the silica-alumina ratio m / n ≥ 5, preferably m / n = 5 - 80, more preferably m / n = 10 - 65.

[0063] According to the present invention, the specific surface area (BET method) of the molecular sieve is 300 - 700 m 2 / g, preferably 300 - 600 m 2 / g, preferably 350 - 500 m 2 / g; the external specific surface area is 50 - 300 m 2 / g, preferably 80 - 250 m 2 / g.

[0064] According to the present invention, the total pore volume of the molecular sieve is 0.20 - 1.50 cm 3 / g, preferably 0.40 - 1.20 cm 3 / g; the micropore volume (t-plot method) is 0.05 - 0.35 cm 3 / g, preferably 0.08 - 0.30 cm 3 / g.

[0065] According to the present invention, the molecular sieve has a nano-sheet morphology, and the thickness of the crystal is < 30 nm, preferably 5 - 25 nm, more preferably 7 - 20 nm.

[0066] According to the present invention, the micropore diameter of the molecular sieve measured by argon adsorption is 0.20 - 0.75 nm, preferably 0.30 - 0.70 nm.

[0067] According to the present invention, the molecular sieve contains elements other than silicon and aluminum with a molar fraction not exceeding 3%. The elements other than silicon and aluminum are selected from at least one of titanium, boron, zirconium, tin, and iron.

[0068] According to the present invention, the SCM-36 molecular sieve can be prepared by the following preparation method. In view of this, the present invention also relates to a method for preparing an SCM-36 molecular sieve, which includes a step of crystallizing a mixture containing a silicon source, an aluminum source, an organic structure-directing agent (A), an organic structure-directing agent (B), an alkali source, and water (hereinafter simply referred to as the mixture) under crystallization conditions to obtain the molecular sieve (hereinafter referred to as the crystallization step); and optionally, further includes a step of calcining the obtained molecular sieve.

[0069] According to the present 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 selected from at least one of quaternary ammonium salts or quaternary ammonium bases of alkylpyridines with 10 to 16 carbon atoms or n-octyltrimethyl compounds.

[0070] According to the present invention, in the method for preparing the molecular sieve, the organic structure-directing agent (A) is preferably selected from at least one of tetramethylammonium hydroxide, tetramethylammonium chloride, tetramethylammonium bromide, or tetramethylammonium iodide. The organic structure-directing agent (B) is preferably selected from at least one of cetylpyridinium bromide, tetradecylpyridinium bromide, dodecylpyridinium bromide, decylpyridinium bromide, cetylpyridinium chloride, tetradecylpyridinium chloride, cetylpyridinium hydroxide, n-octyltrimethylammonium chloride, n-octyltrimethylammonium bromide, or n-octyltrimethylammonium hydroxide, and more preferably at least one of cetylpyridinium bromide, tetradecylpyridinium bromide, dodecylpyridinium bromide, cetylpyridinium chloride, cetylpyridinium hydroxide, n-octyltrimethylammonium chloride, or n-octyltrimethylammonium bromide.

[0071] According to the present invention, in the method for manufacturing the molecular sieve, the molar ratios of the silicon source (calculated as SiO2), the aluminum source (calculated as Al2O3), the organic structure-directing agent (A), the organic structure-directing agent (B), the alkali source, and water are 1:(0.01 - 0.20):(0.05 - 0.80):(0.05 - 0.80):(0.05 - 0.50):(8 - 80), preferably 1:(0.01 - 0.10):(0.08 - 0.65):(0.08 - 0.65):(0.08 - 0.45):(10 - 70), and more preferably 1:(0.02 - 0.07):(0.10 - 0.50):(0.10 - 0.50):(0.10 - 0.40):(12 - 60).

[0072] According to the present invention, in the method for manufacturing the molecular sieve, the crystallization temperature of the mixture is 120 - 200 °C, and the crystallization time is 1 - 15 days. Preferably, the crystallization temperature is 130 - 190 °C, and the crystallization time is 2 - 12 days. More preferably, the crystallization temperature is 140 - 180 °C, and the crystallization time is 3 - 9 days.

[0073] According to the present invention, in the method for manufacturing the molecular sieve, the crystallization step can be carried out in any manner conventionally known in the art. For example, a method can be cited in which the silicon source, the silicon source, the organic structure-directing agent, the alkali source, and water are mixed in a predetermined ratio, and the obtained mixture is hydrothermally crystallized under crystallization conditions.

[0074] According to the present invention, in the method for manufacturing the molecular sieve, the silicon source is selected from at least one of silicic acid, silica gel, silica sol, tetraethyl orthosilicate, and water glass; the aluminum source is selected from at least one of aluminum hydroxide, alumina, aluminate, aluminum salt, and tetraalkoxyaluminum.

[0075] According to the present invention, in the method for manufacturing the molecular sieve, the alkali source is selected from at least one of inorganic bases with alkali metals or alkaline earth metals as cations, such as at least one of sodium hydroxide and potassium hydroxide.

[0076] According to the present invention, in the method for manufacturing the molecular sieve, the mixture further includes a non-silicon and non-aluminum source, and the non-silicon and aluminum source is selected from at least one of a titanium source, a boron source, a zirconium source, a tin source, and an iron source.

[0077] According to the present invention, in the method for manufacturing the molecular sieve, the titanium source is selected from at least one of titanium-containing organometallic complexes, tetraalkoxytitanium, titanium dioxide, and titanium nitrate; the boron source is selected from at least one of boric acid, borate, borax, and boron trioxide; the zirconium source is selected from at least one of zirconium-containing organometallic complexes, zirconium salts, zirconium hydroxide, zirconium alkoxide, and zirconium dioxide; the tin source is selected from at least one of tin-containing organometallic complexes, tin salts, and tin dioxide; and the iron source is selected from at least one of iron-containing organometallic complexes, iron nitrate, iron chloride, and iron oxide.

[0078] According to the present invention, the molar ratio of the silicon source (calculated as SiO2) to the non-silicon and non-aluminum sources (calculated as the corresponding oxides) is 1:(0.002 - 0.10), preferably 1:(0.005 - 0.05).

[0079] According to the present invention, in the method for manufacturing the molecular sieve, after the crystallization step is completed, the molecular sieve can be separated from the obtained product mixture as a product by any conventionally known separation method, thereby obtaining the SCM-36 molecular sieve of the present invention. As the separation method, for example, methods such as filtering, washing, and drying the obtained product mixture can be cited. Here, the filtering, washing, and drying can be carried out in any manner conventionally known in the art. Specifically, for example, as the filtering, the obtained product mixture can be simply suction-filtered. As the washing, for example, washing with deionized water can be cited. As the drying temperature, for example, 40 - 150°C can be cited, preferably 50 - 120°C, and as the drying time, for example, 1 - 30 hours can be cited, preferably 2 - 24 hours. This drying can be carried out under normal pressure or under reduced pressure.

[0080] According to the present invention, if necessary, the molecular sieve manufactured according to the aforementioned method for manufacturing the molecular sieve can also be calcined to remove the organic template agent and possible moisture, etc., thereby obtaining the calcined molecular sieve (which also belongs to the SCM-36 molecular sieve of the present invention). The calcination can be carried out in any manner conventionally known in the art. For example, the calcination temperature is generally 300 - 800°C, preferably 400 - 650°C, and the calcination time is generally 1 - 12 hours, preferably 2 - 10 hours. In addition, the calcination is generally carried out in an oxygen-containing atmosphere, such as in an air or oxygen atmosphere.

[0081] According to the present invention, the various obtained SCM-36 molecular sieves can be applied in any physical form, such as powder form, granular form, or molded form (such as strip form, clover form, etc.). These physical forms can be obtained in any manner conventionally known in the art, and there is no particular limitation.

[0082] According to the present invention, the SCM-36 molecular sieve can be used in combination with other materials to obtain a molecular sieve composition. As these other materials, for example, active materials and inactive materials can be cited. As the active materials, for example, synthetic zeolites, natural zeolites or other types of molecular sieves, etc. can be cited. As the inactive materials (generally referred to as binders), for example, clay, clay, silica gel and alumina, etc. can be cited. These other materials can be used alone or in combination of multiple kinds in any proportion. As the dosage of these other materials, the conventional dosage in the art can be directly referred to, and there is no particular limitation.

[0083] The SCM-36 molecular sieve or molecular sieve composition of the present invention can be used as an adsorbent, for example, to separate at least one component from a mixture of multiple components in the gas phase or liquid phase. Accordingly, the at least one component can be partially or substantially completely separated from the mixture of various components, specifically, for example, by bringing the mixture into contact with the SCM-36 molecular sieve or the molecular sieve composition and selectively adsorbing this component.

[0084] According to one aspect of the present invention, the molecular sieve SCM-36 or the molecular sieve composition can also be used as a catalyst (or as its catalytically active component) directly or after necessary treatments or conversions (such as ion exchange, etc.) conventionally carried out on molecular sieves in the art. For this purpose, according to one aspect of the present invention, for example, reactants (such as hydrocarbons) can be subjected to a predetermined reaction in the presence of the catalyst, and thereby a target product can be obtained. Among them, the predetermined reaction can be exemplified as follows: cumene cracking, methanol conversion reaction to produce olefins or aromatics, etc.

[0085] In the context of this specification, including in the following examples and comparative examples, when the catalyst is applied to the cumene cracking reaction:

[0086] The cumene cracking reaction uses cumene as a raw material and cracks into products such as propylene and benzene under the action of a catalyst.

[0087] Conversion percentage of cumene = (molar amount of cumene in feed - molar amount of cumene in product) / (molar amount of cumene in feed) × 100%.

[0088] Selectivity percentage of benzene = (molar amount of benzene in product) / (total molar amount of aromatics in product) × 100%;

[0089] Among them, the aromatics in the product do not include the raw material cumene.

[0090] In the context of this specification, including in the following examples and comparative examples, when the catalyst is applied to the methanol conversion reaction:

[0091] The methanol conversion reaction uses methanol as a raw material and is converted into hydrocarbons such as olefins and aromatics under the action of a catalyst.

[0092] The conversion rate of methanol % = (the molar amount of feed methanol - the molar amount of methanol in the product - 2 × the molar amount of dimethyl ether in the product) / (the molar amount of feed methanol) × 100%;

[0093] The selectivity of C2-C4 olefins % = (2 × the molar amount of C2 olefins in the product + 3 × the molar amount of C3 olefins in the product + 4 × the molar amount of C4 olefins in the product) / (the molar amount of feed methanol - the molar amount of methanol in the product - 2 × the molar amount of dimethyl ether in the product) × 100%.

[0094] The selectivity of aromatics % = (6 × the molar amount of benzene in the product + 7 × the molar amount of toluene in the product + 8 × the molar amount of xylene in the product) / (the molar amount of feed methanol - the molar amount of methanol in the product - 2 × the molar amount of dimethyl ether in the product) × 100%.

[0095] The technical solution of the present invention will be further described in detail below through examples, but the protection scope of the present invention is not limited to these examples.

[0096] Example 1

[0097] Mix 24.73 grams of deionized water, 6.89 grams of sodium hydroxide solution (containing 10% by weight of NaOH), 5.35 grams of organic structure directing agent (A) tetramethylammonium hydroxide (containing 25% by weight of TMAOH), 3.05 grams of organic structure directing agent (B) n-octyltrimethylammonium chloride, 1.234 grams of sodium aluminate (containing 40.5% by weight of Al2O3 and 30.6% by weight of Na2O), and 14.72 grams of silica sol (containing 40% by weight of SiO2) evenly to obtain a mixture. The material ratio (molar ratio) of the reactants is:

[0098] Al2O3 / SiO2 = 0.05

[0099] Tetramethylammonium hydroxide (A) / SiO2 = 0.15

[0100] N-octyltrimethylammonium chloride (B) / SiO2 = 0.15

[0101] NaOH / SiO2 = 0.30

[0102] H2O / SiO2 = 25;

[0103] After mixing evenly, load it into a stainless steel autoclave and crystallize at 160 °C for 6 days. After crystallization, filter and wash, dry in an oven at 110 °C for 12 hours, and calcine in air at 550 °C for 6 hours to obtain molecular sieve.

[0104] The XRD spectrum data of the dried sample are shown in Table 1 and Figure 1 as shown. The SEM image of the sample is as shown in Figure 2 and the TEM image is as shown in Figure 3 .

[0105] Table 1

[0106]

[0107]

[0108] The specific surface area of the obtained calcined product is 380 m 2 / g, the external specific surface area is 170 m 2 / g, the total pore volume is 0.92 cm 3 / g, the micropore volume is 0.10 cm 3 / g, and the micropore size distribution of the sample is 0.59 nm and 0.67 nm. The sample has a nano-sheet morphology, and the thickness of the crystal is about 15 nm.

[0109] The SiO2 / Al2O3 of the calcined sample measured by inductively coupled plasma atomic emission spectrometry (ICP) is 21.6 (molar ratio).

[0110] Example 2

[0111] Same as Example 1, except that:

[0112] Al2O3 / SiO2 = 0.067

[0113] Tetramethylammonium hydroxide (A) / SiO2 = 0.15

[0114] n-Octyltrimethylammonium chloride (B) / SiO2 = 0.20

[0115] NaOH / SiO2 = 0.30

[0116] H2O / SiO2 = 20;

[0117] After mixing evenly, it is loaded into a stainless steel autoclave and crystallized at 160 °C for 5 days. After crystallization, it is filtered, washed, dried in an oven at 100 °C for 16 hours, and calcined in air at 550 °C for 8 hours to obtain the molecular sieve.

[0118] The XRD spectrum data of the dried sample are shown in Table 2 and Figure 4 as shown. The SEM image of the sample is similar to Figure 2 that;

[0119] Table 2

[0120]

[0121]

[0122] The specific surface area of the obtained calcined product is 392 m 2 / g, the external specific surface area is 166 m 2 / g, the total pore volume is 0.73 cm 3 / g, the micropore volume is 0.10 cm 3 / g, and the micropore size distribution of the sample is 0.59 nm and 0.67 nm. The sample has a nano-sheet morphology, and the thickness of the crystal is about 12 nm.

[0123] The SiO2 / Al2O3 of the calcined sample measured by inductively coupled plasma atomic emission spectrometry (ICP) is 15.6 (molar ratio).

[0124] Example 3

[0125] Same as Example 1, except that:

[0126] Al2O3 / SiO2 = 0.04

[0127] Tetramethylammonium chloride (A) / SiO2 = 0.20

[0128] n-Octyltrimethylammonium chloride (B) / SiO2 = 0.15

[0129] NaOH / SiO2 = 0.25

[0130] H2O / SiO2 = 35;

[0131] After mixing evenly, it is loaded into a stainless steel autoclave and crystallized at 155 °C for 7 days. After crystallization, it is filtered, washed, dried in an oven at 80 °C for 16 hours, and calcined in air at 500 °C for 10 hours to obtain molecular sieve.

[0132] The XRD spectrum data of the dried sample is shown in Table 3, and the SEM image of the sample is as Figure 5 shown.

[0133] Table 3

[0134]

[0135]

[0136] The specific surface area of the obtained calcined product is 388 m 2 / g, the external specific surface area is 162 m 2 / g, the total pore volume is 0.75 cm 3 / g, the micropore volume is 0.10 cm 3 / g, and the micropore size distribution of the sample is 0.58 nm and 0.66 nm. The sample has a nano-sheet morphology, and the thickness of the crystal is about 13 nm.

[0137] The SiO2 / Al2O3 of the calcined sample was measured to be 26.1 (molar ratio) by inductively coupled plasma atomic emission spectrometry (ICP).

[0138] Example 4

[0139] Same as Example 1, except that:

[0140] Al2O3 / SiO2 = 0.045

[0141] Tetramethylammonium hydroxide (A) / SiO2 = 0.25

[0142] n-Octyltrimethylammonium chloride (B) / SiO2 = 0.15

[0143] NaOH / SiO2 = 0.20

[0144] H2O / SiO2 = 45;

[0145] After mixing evenly, it was loaded into a stainless steel autoclave and crystallized at 165 °C for 4 days. After crystallization, it was filtered, washed, dried in an oven at 60 °C for 24 hours, and calcined in air at 600 °C for 4 hours to obtain molecular sieve.

[0146] The XRD spectrum data of the dried sample is shown in Table 4, and the SEM image of the sample is similar to Figure 2 that.

[0147] Table 4

[0148]

[0149]

[0150] The specific surface area of the obtained calcined product is 377 m 2 / g, the external specific surface area is 158 m 2 / g, the total pore volume is 0.74 cm 3 / g, the micropore volume is 0.11 cm 3 / g, and the micropore pore size distribution of the sample is 0.59 nm and 0.67 nm. The sample has a nano-sheet morphology, and the thickness of the crystal is about 11 nm.

[0151] The SiO2 / Al2O3 of the calcined sample was measured to be 22.3 (molar ratio) by inductively coupled plasma atomic emission spectrometry (ICP).

[0152] Example 5

[0153] Same as Example 1, except that:

[0154] Al2O3 / SiO2 = 0.017

[0155] Tetramethylammonium hydroxide (A) / SiO2 = 0.20

[0156] n-Octyltrimethylammonium chloride (B) / SiO2 = 0.25

[0157] NaOH / SiO2 = 0.20

[0158] H2O / SiO2 = 30;

[0159] After mixing evenly, it was loaded into a stainless steel autoclave and crystallized at 155 °C for 8 days. After crystallization, it was filtered and washed, dried in an oven at 120 °C for 6 hours, and calcined in air at 550 °C for 8 hours to obtain molecular sieve.

[0160] The XRD spectrum data of the dried sample is shown in Table 5, and the SEM image of the sample is similar to Figure 2 that.

[0161] Table 5

[0162]

[0163] The specific surface area of the obtained calcined product is 372 m 2 / g, the external specific surface area is 149 m 2 / g, the total pore volume is 0.74 cm 3 / g, the micropore volume is 0.09 cm 3 / g, and the micropore pore size distribution of the sample is 0.60 nm and 0.67 nm. The sample has a nano-sheet morphology, and the thickness of the crystal is about 12 nm.

[0164] The SiO2 / Al2O3 = 61.5 (molar ratio) of the calcined sample was measured by inductively coupled plasma atomic emission spectrometry (ICP).

[0165] Example 6

[0166] Same as Example 1, except that:

[0167] Al2O3 / SiO2 = 0.03

[0168] Tetramethylammonium iodide (A) / SiO2 = 0.20

[0169] n-Octyltrimethylammonium chloride (B) / SiO2 = 0.20

[0170] NaOH / SiO2 = 0.25

[0171] H2O / SiO2 = 35;

[0172] After mixing evenly, it was loaded into a stainless-steel reactor and crystallized at 170 °C for 5 days. After crystallization, it was filtered, washed, dried in an oven at 100 °C for 12 hours, and calcined in air at 500 °C for 10 hours to obtain molecular sieve.

[0173] The XRD spectrum data of the dried sample are shown in Table 6, and the SEM image of the sample is similar to Figure 2 that.

[0174] Table 6

[0175]

[0176] The specific surface area of the obtained calcined product is 362 m 2 / g, the external specific surface area is 149 m 2 / g, the total pore volume is 0.67 cm 3 / g, the micropore volume is 0.10 cm 3 / g, and the micropore size distribution of the sample is 0.59 nm and 0.67 nm. The sample has a nano-sheet morphology, and the thickness of the crystal is about 12 nm.

[0177] The SiO2 / Al2O3 of the calcined sample was measured by inductively coupled plasma atomic emission spectrometry (ICP) to be 34.5 (molar ratio).

[0178] Example 7

[0179] Same as Example 1, except that tetrabutylammonium bromide was used as the organic structure-directing agent (B), and the material ratio (molar ratio) of the reactants was:

[0180] Al2O3 / SiO2 = 0.05

[0181] Tetramethylammonium hydroxide (A) / SiO2 = 0.15

[0182] Tetradecylpyridinium bromide (B) / SiO2 = 0.15

[0183] NaOH / SiO2 = 0.30

[0184] H2O / SiO2 = 35;

[0185] After mixing evenly, it was loaded into a stainless-steel reactor and crystallized at 160 °C for 7 days. After crystallization, it was filtered, washed, dried in an oven at 110 °C for 6 hours, and calcined in air at 550 °C for 6 hours to obtain molecular sieve.

[0186] The XRD spectrum data of the dried sample are shown in Table 7, and the SEM image of the sample is similar to Figure 2 that.

[0187] Table 7

[0188]

[0189] The specific surface area of the obtained calcined product is 378 m 2 / g, the external specific surface area is 156 m 2 / g, the total pore volume is 0.77 cm 3 / g, the micropore volume is 0.11 cm 3 / g, and the micropore size distribution of the sample is 0.59 nm and 0.66 nm. The sample has a nano-sheet morphology, and the thickness of the crystal is about 13 nm.

[0190] The SiO2 / Al2O3 of the calcined sample was measured by inductively coupled plasma atomic emission spectrometry (ICP) to be 21.1 (molar ratio).

[0191] Example 8

[0192] Same as Example 1, except that cetylpyridinium bromide was used as the organic structure-directing agent (B), and the material ratio (molar ratio) of the reactants was:

[0193] Al2O3 / SiO2 = 0.045

[0194] Tetramethylammonium hydroxide (A) / SiO2 = 0.15

[0195] Cetylpyridinium bromide (B) / SiO2 = 0.20

[0196] NaOH / SiO2 = 0.25

[0197] H2O / SiO2 = 30;

[0198] After mixing evenly, it was loaded into a stainless steel autoclave and crystallized at 160 °C for 6 days. After crystallization, it was filtered, washed, dried in an oven at 90 °C for 12 hours, and calcined in air at 550 °C for 6 hours to obtain the molecular sieve.

[0199] The XRD spectrum data of the dried sample is shown in Table 8, and the SEM image of the sample is Figure 2 similar.

[0200] Table 8

[0201]

[0202] The specific surface area of the obtained calcined product is 394 m 2 / g, the external specific surface area is 171 m 2 / g, the total pore volume is 0.68 cm 3 / g, the micropore volume is 0.12 cm 3 / g, and the micropore size distribution of the sample is 0.59 nm and 0.67 nm. The sample has a nano-sheet morphology, and the thickness of the crystal is about 12 nm.

[0203] The SiO2 / Al2O3 of the calcined sample was measured by inductively coupled plasma atomic emission spectrometry (ICP) to be 22.8 (molar ratio).

[0204] Example 9

[0205] Same as Example 8, except that:

[0206] Al2O3 / SiO2 = 0.068

[0207] Tetramethylammonium hydroxide (A) / SiO2 = 0.20

[0208] Cetylpyridinium bromide (B) / SiO2 = 0.15

[0209] NaOH / SiO2 = 0.30

[0210] H2O / SiO2 = 40;

[0211] After mixing evenly, it was loaded into a stainless steel autoclave and crystallized at 160 °C for 6 days. After crystallization, it was filtered, washed, dried in an oven at 80 °C for 16 hours, and calcined in air at 550 °C for 6 hours to obtain molecular sieve.

[0212] The XRD spectrum data of the dried sample are shown in Table 9, and the SEM image of the sample is similar to Figure 2 that.

[0213] Table 9

[0214]

[0215] The specific surface area of the obtained calcined product was 372 m 2 / g, the external specific surface area was 144 m 2 / g, the total pore volume was 0.65 cm 3 / g, the micropore volume was 0.11 cm 3 / g, and the micropore size distribution of the sample was 0.59 nm and 0.67 nm. The sample had a nano-sheet morphology, and the thickness of the crystal was about 15 nm.

[0216] The SiO2 / Al2O3 of the calcined sample was measured by inductively coupled plasma atomic emission spectrometry (ICP) to be 14.5 (molar ratio).

[0217] Example 10

[0218] Same as Example 1, except that:

[0219] Al2O3 / SiO2 = 0.05

[0220] TiO2 / SiO2 = 0.01

[0221] Tetramethylammonium hydroxide (A) / SiO2 = 0.15

[0222] n-Octyltrimethylammonium chloride (B) / SiO2 = 0.20

[0223] NaOH / SiO2 = 0.25

[0224] H2O / SiO2 = 35;

[0225] After mixing evenly, it was loaded into a stainless-steel autoclave and crystallized at 160 °C for 7 days. After crystallization, it was filtered, washed, dried in an oven at 100 °C for 10 hours, and calcined in oxygen at 550 °C for 6 hours to obtain molecular sieve.

[0226] The XRD spectrum data of the dried sample are shown in Table 10, and the SEM image of the sample is similar to Figure 2 that.

[0227] Table 10

[0228]

[0229] The specific surface area of the obtained calcined product is 364 m 2 / g, the external specific surface area is 146 m 2 / g, the total pore volume is 0.71 cm 3 / g, the micropore volume is 0.12 cm 3 / g, and the micropore pore size distribution of the sample is 0.59 nm and 0.67 nm. The sample has a nano-sheet morphology, and the thickness of the crystal is about 18 nm.

[0230] The SiO2 / Al2O3 = 21.2 (molar ratio) and SiO2 / TiO2 = 106.2 (molar ratio) of the calcined sample were measured by inductively coupled plasma atomic emission spectrometry (ICP).

[0231] Example 11

[0232] Same as Example 1, except that:

[0233] Al2O3 / SiO2 = 0.065

[0234] B2O3 / SiO2 = 0.012

[0235] Tetramethylammonium hydroxide (A) / SiO2 = 0.20

[0236] n-Octyltrimethylammonium chloride (B) / SiO2 = 0.15

[0237] NaOH / SiO2 = 0.30

[0238] H2O / SiO2 = 40;

[0239] After mixing evenly, it was loaded into a stainless-steel reactor and crystallized at 155 °C for 7 days. After crystallization, it was filtered, washed, dried in an oven at 80 °C for 8 hours, and calcined in air at 550 °C for 6 hours to obtain molecular sieve.

[0240] The XRD spectrum data of the dried sample are shown in Table 11, and the SEM image of the sample is similar to Figure 2 that;

[0241] Table 11

[0242]

[0243] The specific surface area of the obtained calcined product is 385 m 2 / g, the external specific surface area is 152 m 2 / g, the total pore volume is 0.63 cm 3 / g, the micropore volume is 0.09 cm 3 / g, and the micropore aperture of the sample is mainly distributed in the range of 0.59 - 0.67 nm. The sample has a nano-sheet morphology, and the thickness of the crystal is about 20 nm.

[0244] The SiO2 / Al2O3 = 15.9 (molar ratio) and SiO2 / B2O3 = 96.3 (molar ratio) of the calcined sample were measured by inductively coupled plasma atomic emission spectrometry (ICP).

[0245] Example 12

[0246] Same as Example 7, only:

[0247] Al2O3 / SiO2 = 0.035

[0248] ZrO2 / SiO2 = 0.008

[0249] Tetramethylammonium hydroxide (A) / SiO2 = 0.20

[0250] Dodecylpyridinium bromide (B) / SiO2 = 0.20

[0251] NaOH / SiO2 = 0.25

[0252] H2O / SiO2 = 30;

[0253] After mixing evenly, it was loaded into a stainless-steel reactor and crystallized at 165 °C for 6 days. After crystallization, it was filtered, washed, dried in an oven at 110 °C for 12 hours, and calcined in air at 550 °C for 5 hours to obtain molecular sieve.

[0254] The XRD spectrum data of the dried sample are shown in Table 12, and the SEM image of the sample is similar to Figure 2 that;

[0255] Table 12

[0256]

[0257] The specific surface area of the obtained calcined product is 373 m 2 / g, the external specific surface area is 148 m 2 / g, the total pore volume is 0.75 cm 3 / g, the micropore volume is 0.09 cm 3 / g, and the micropore size distribution of the sample is 0.59 nm and 0.67 nm. The sample has a nano-sheet morphology, and the thickness of the crystal is about 16 nm.

[0258] The SiO2 / Al2O3 = 30.6 (molar ratio) and SiO2 / ZrO2 = 131.2 (molar ratio) of the calcined sample were measured by inductively coupled plasma atomic emission spectrometry (ICP).

[0259] Example 13

[0260] Same as Example 1, except that:

[0261] Al2O3 / SiO2 = 0.05

[0262] SnO2 / SiO2 = 0.008

[0263] Tetramethylammonium bromide (A) / SiO2 = 0.15

[0264] n-Octyltrimethylammonium bromide (B) / SiO2 = 0.20

[0265] NaOH / SiO2 = 0.30

[0266] H2O / SiO2 = 25;

[0267] After mixing evenly, it was loaded into a stainless steel autoclave and crystallized at 160 °C for 7 days. After crystallization, it was filtered, washed, dried in an oven at 110 °C for 12 hours, and calcined in air at 550 °C for 6 hours to obtain the molecular sieve.

[0268] The XRD spectrum data of the dried sample is shown in Table 13, and the SEM image of the sample is similar to Figure 2 that;

[0269] Table 13

[0270]

[0271] The specific surface area of the obtained calcined product is 386 m 2 / g, the external specific surface area is 154 m 2 / g, the total pore volume is 0.73 cm3 / g, the micropore volume is 0.10 cm 3 / g, the micropore size distribution of the sample is 0.59 nm and 0.66 nm. The sample has a nano-sheet morphology, and the thickness of the crystal is about 15 nm.

[0272] The SiO2 / Al2O3 = 21.5 (molar ratio) and SiO2 / SnO2 = 126.4 (molar ratio) of the calcined sample were measured by inductively coupled plasma atomic emission spectrometry (ICP).

[0273] Example 14

[0274] Same as Example 8, except that:

[0275] Al2O3 / SiO2 = 0.04

[0276] Fe2O3 / SiO2 = 0.005

[0277] Tetramethylammonium chloride (A) / SiO2 = 0.15

[0278] Cetylpyridinium hydroxide (B) / SiO2 = 0.25

[0279] NaOH / SiO2 = 0.20

[0280] H2O / SiO2 = 30;

[0281] After mixing evenly, it was loaded into a stainless steel autoclave and crystallized at 165 °C for 7 days. After crystallization, it was filtered, washed, dried in an oven at 110 °C for 12 hours, and calcined in air at 550 °C for 6 hours to obtain molecular sieve.

[0282] The XRD spectrum data of the dried sample is shown in Table 14, and the SEM image of the sample is similar to Figure 2 similar;

[0283] Table 14

[0284]

[0285] The specific surface area of the obtained calcined product is 383 m 2 / g, the external specific surface area is 155 m 2 / g, the total pore volume is 0.75 cm 3 / g, the micropore volume is 0.10 cm 3 / g, the micropore size distribution of the sample is 0.60 nm and 0.66 nm. The sample has a nano-sheet morphology, and the thickness of the crystal is about 17 nm.

[0286] The SiO2 / Al2O3 of the calcined sample was measured by inductively coupled plasma atomic emission spectrometry (ICP) to be 26.5 (molar ratio), and SiO2 / Fe2O3 was 188.4 (molar ratio).

[0287] Example 15

[0288] Same as Example 1, except that:

[0289] Al2O3 / SiO2 = 0.045

[0290] Tetramethylammonium hydroxide (A) / SiO2 = 0.45

[0291] Dodecylpyridinium bromide (B) / SiO2 = 0.20

[0292] NaOH / SiO2 = 0.25

[0293] H2O / SiO2 = 25;

[0294] After mixing evenly, it was loaded into a stainless steel autoclave and crystallized at 160 °C for 6 days. After crystallization, it was filtered, washed, dried in an oven at 110 °C for 12 hours, and calcined in air at 550 °C for 6 hours to obtain molecular sieve.

[0295] The XRD spectrum data of the dried sample is shown in Table 15, and the SEM image of the sample is similar to Figure 2 similar;

[0296] Table 15

[0297]

[0298] The specific surface area of the obtained calcined product was 368 m 2 / g, the external specific surface area was 145 m 2 / g, the total pore volume was 0.72 cm 3 / g, the micropore volume was 0.09 cm 3 / g, and the micropore size distribution of the sample was 0.58 nm and 0.66 nm. The sample had a nano-sheet morphology, and the thickness of the crystal was about 17 nm.

[0299] The SiO2 / Al2O3 of the calcined sample was measured by inductively coupled plasma atomic emission spectrometry (ICP) to be 22.8 (molar ratio).

[0300] Example 16

[0301] Same as Example 7, except that:

[0302] Al2O3 / SiO2 = 0.040

[0303] Tetramethylammonium chloride (A) / SiO2 = 0.15

[0304] Dodecylpyridinium bromide (B) / SiO2 = 0.45

[0305] NaOH / SiO2 = 0.15

[0306] H2O / SiO2 = 30;

[0307] After mixing evenly, it was loaded into a stainless steel autoclave and crystallized at 160 °C for 8 days. After crystallization, it was filtered and washed, dried in an oven at 110 °C for 12 hours, and calcined in air at 550 °C for 6 hours to obtain molecular sieve.

[0308] The XRD spectrum data of the dried sample are shown in Table 16, and the SEM image of the sample is similar to Figure 2 that;

[0309] Table 16

[0310]

[0311] The specific surface area of the obtained calcined product is 388 m 2 / g, the external specific surface area is 159 m 2 / g, the total pore volume is 0.71 cm 3 / g, the micropore volume is 0.10 cm 3 / g, and the micropore pore size distribution of the sample is 0.59 nm and 0.66 nm. The sample has a nano-sheet morphology, and the thickness of the crystal is about 17 nm.

[0312] The SiO2 / Al2O3 = 26.1 (molar ratio) of the calcined sample was measured by inductively coupled plasma atomic emission spectrometry (ICP).

[0313] Example 17

[0314] Same as Example 1, except that:

[0315] Al2O3 / SiO2 = 0.05

[0316] Tetramethylammonium hydroxide (A) / SiO2 = 0.20

[0317] Cetylpyridinium chloride (B) / SiO2 = 0.25

[0318] NaOH / SiO2 = 0.15

[0319] H2O / SiO2 = 20;

[0320] After mixing evenly, it was loaded into a stainless steel autoclave and crystallized at 160 °C for 7 days. After crystallization, it was filtered and washed, dried in an oven at 110 °C for 12 hours, and calcined in air at 550 °C for 6 hours to obtain molecular sieve.

[0321] The XRD spectral data of the dried sample are shown in Table 17, and the SEM image of the sample is similar to Figure 2 that;

[0322] Table 17

[0323]

[0324] The specific surface area of the obtained calcined product is 392 m 2 / g, the external specific surface area is 159 m 2 / g, the total pore volume is 0.72 cm 3 / g, the micropore volume is 0.09 cm 3 / g, and the micropore size distribution of the sample is 0.60 nm and 0.66 nm. The sample has a nano-sheet morphology, and the thickness of the crystal is about 15 nm.

[0325] The SiO2 / Al2O3 of the calcined sample was measured by inductively coupled plasma atomic emission spectrometry (ICP) to be 21.6 (molar ratio).

[0326] Comparative Example 1

[0327] Same as Example 1, except that:

[0328] Al2O3 / SiO2 = 0.22

[0329] Tetramethylammonium hydroxide (A) / SiO2 = 0.15

[0330] n-Octyltrimethylammonium chloride (B) / SiO2 = 0.15

[0331] NaOH / SiO2 = 0.30

[0332] H2O / SiO2 = 25;

[0333] After mixing evenly, it was loaded into a stainless steel autoclave and crystallized at 160 °C for 6 days. After crystallization, it was filtered, washed, dried in an oven at 110 °C for 12 hours, and calcined in air at 550 °C for 6 hours to obtain the sample.

[0334] The XRD spectral data of the dried sample are as Figure 6 shown, which is an amorphous substance and not SCM-36 molecular sieve.

[0335] Comparative Example 2

[0336] Same as Example 1, except that:

[0337] Al2O3 / SiO2 = 0.05

[0338] Tetramethylammonium hydroxide (A) / SiO2 = 0.15

[0339] n-Octyltrimethylammonium chloride (B) / SiO2 = 0.15

[0340] NaOH / SiO2 = 0.55

[0341] H2O / SiO2 = 25;

[0342] After mixing evenly, it was loaded into a stainless steel autoclave and crystallized at 160 °C for 6 days. After crystallization, it was filtered, washed, dried in an oven at 110 °C for 12 hours, and calcined in air at 550 °C for 6 hours to obtain the sample.

[0343] The XRD spectrum data of the dried sample is the same as Figure 6 similar, being amorphous and not being SCM-36 zeolite.

[0344] Comparative Example 3

[0345] Same as Example 1, except that octylamine was used as the organic structure-directing agent (B):

[0346] Al2O3 / SiO2 = 0.05

[0347] Tetramethylammonium hydroxide (A) / SiO2 = 0.15

[0348] Octylamine (B) / SiO2 = 0.15

[0349] NaOH / SiO2 = 0.30

[0350] H2O / SiO2 = 25;

[0351] After mixing evenly, it was loaded into a stainless steel autoclave and crystallized at 160 °C for 6 days. After crystallization, it was filtered, washed, dried in an oven at 110 °C for 12 hours, and calcined in air at 550 °C for 6 hours to obtain the sample.

[0352] The XRD spectrum data of the dried sample is as Figure 7 shown, being a mixture of MOR and other structure zeolites and not being SCM-36 zeolite.

[0353] Comparative Example 4

[0354] Same as Example 1, except that only tetramethylammonium hydroxide was used as the organic structure-directing agent:

[0355] Al2O3 / SiO2 = 0.05

[0356] Tetramethylammonium hydroxide / SiO2 = 0.15

[0357] NaOH / SiO2 = 0.30

[0358] H2O / SiO2 = 25;

[0359] After mixing evenly, it was loaded into a stainless-steel reactor and crystallized at 160 °C for 6 days. After crystallization, it was filtered and washed, dried in an oven at 110 °C for 12 hours, and calcined in air at 550 °C for 6 hours to obtain the sample.

[0360] The XRD spectrum data of the dried sample is as Figure 8 shown, which is a mixture of SOD and other structured molecular sieves and is not SCM-36 molecular sieve.

[0361] Example 18

[0362] The molecular sieve synthesized in Example 5 was ion-exchanged with 0.5 mol / L NH4Cl solution (the mass ratio of the molecular sieve to the ammonium chloride solution was 1:20) at 70 °C for 2 hours, then centrifuged and washed. The sample obtained after two ion-exchanges was dried at 100 °C for 12 hours and calcined at 550 °C for 6 hours to obtain H-type SCM-36 molecular sieve.

[0363] Take the above-mentioned calcined H-type SCM-36 molecular sieve powder sample, crush it and screen out the particle size part of 20-40 mesh and put it into a fixed-bed reactor for cumene cracking reaction. The reaction conditions are: the reaction temperature is 320 °C, the reaction pressure is atmospheric pressure, and the weight hourly space velocity of cumene is 2 h -1 . The products were analyzed by a Shimadzu GC-2014 gas chromatograph. After 1 hour of reaction, the conversion rate of cumene was 25.2%, and the selectivity of benzene in the products was 94.1%.

[0364] Example 19

[0365] The molecular sieve synthesized in Example 5 was ion-exchanged with 0.5 mol / L NH4Cl solution (the mass ratio of the molecular sieve to the ammonium chloride solution was 1:20) at 70 °C for 2 hours, then centrifuged and washed. The sample obtained after two ion-exchanges was dried at 100 °C for 12 hours and calcined at 550 °C for 6 hours to obtain H-type SCM-36 molecular sieve.

[0366] Take the above-mentioned calcined H-type SCM-36 molecular sieve powder sample, crush it and screen out the particle size part of 20-40 mesh and put it into a fixed-bed reactor for methanol conversion reaction. The reaction conditions are: the reaction temperature is 460 °C, the reaction pressure is 0.1 MPa, and the weight hourly space velocity of raw material methanol is 1 h -1 . The products were analyzed by a Shimadzu GC-2014 gas chromatograph. After 45 minutes of reaction, the conversion rate of methanol was 99.0%, the selectivity of C2-C4 olefins in the products was 58.6%, and the selectivity of aromatics was 4.2%.

[0367] The specific implementation manners of the present invention have been described in detail above. However, the present invention is not limited thereto. Within the scope of the technical concept of the present invention, various simple modifications can be made to the technical solution 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 SCM-36 molecular sieve, the molecular sieve having a schematic chemical composition of "mSiO2·nAl2O3", where m / n ≥ 5; the molecular sieve having an X-ray diffraction pattern as shown in the following table, a: ±0.30°, b: varying with 2θ.

2. The molecular sieve according to claim 1, characterized in that, m / n = 5 - 80.

3. The molecular sieve according to claim 1, characterized in that, m / n = 10 - 65.

4. The molecular sieve according to claim 1, characterized in that, The molecular sieve further has at least one diffraction peak in the X-ray diffraction pattern as shown in the following table, a: ±0.30°, b: varying with 2θ.

5. The molecular sieve according to claim 1, characterized in that, The specific surface area of the molecular sieve is 300 to 700 m 2 / g; the external specific surface area is 50 to 300 m 2 / g; and / or, the total pore volume of the molecular sieve is 0.20 to 1.50 cm 3 / g; the micropore volume is 0.05 to 0.35 cm 3 / g; And / or, the micropore aperture of the molecular sieve is 0.20 - 0.75 nm.

6. The molecular sieve according to claim 5, characterized in that, The specific surface area of the molecular sieve is 300 to 600 m 2 / g; the external specific surface area is 80 to 250 m 2 / g; and / or, the total pore volume of the molecular sieve is 0.40 to 1.20 cm 3 / g; the micropore volume is 0.08 to 0.30 cm 3 / g; And / or, the micropore aperture of the molecular sieve is 0.30 - 0.70 nm.

7. The molecular sieve according to claim 5, characterized in that, The specific surface area of the molecular sieve is 350 to 500 m 2 / g.

8. The molecular sieve according to claim 1, characterized in that, The molecular sieve has a nano-sheet morphology, and the thickness of the crystal < 30 nm.

9. The molecular sieve according to claim 8, wherein In the molecular sieve, the thickness of the crystal is 5 - 25 nm.

10. The molecular sieve according to claim 8, wherein, In the molecular sieve, the thickness of the crystal is 7 - 20 nm.

11. The molecular sieve according to any one of claims 1-10, characterized in that, The chemical composition of the molecular sieve further includes elements other than silicon and aluminum, selected from at least one of titanium, boron, zirconium, tin, and iron.

12. The molecular sieve according to claim 11, wherein In the schematic chemical composition of the molecular sieve, based on the total molar number of oxides, it contains elemental oxides of elements other than silicon and aluminum with a molar fraction not exceeding 3%.

13. A method for manufacturing the molecular sieve according to any one of claims 1 - 10, including the step of crystallizing a mixture containing 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 including the step of calcining the obtained molecular sieve; Among them, The organic structure-directing agent A is selected from at least one of tetramethylammonium hydroxide or its quaternary ammonium salts; the organic structure-directing agent B is selected from at least one of quaternary ammonium salts or quaternary ammonium bases of alkylpyridines with 10 to 16 carbon atoms or n-octyltrimethyl compounds; The molar ratio of the silicon source calculated as SiO2, the aluminum source calculated as Al2O3, the organic structure-directing agent A, the organic structure-directing agent B, the alkali source, and water is 1: (0.01 - 0.20): (0.05 - 0.80): (0.05 - 0.80): (0.05 - 0.50): (8 - 80).

14. The manufacturing method according to claim 13, characterized in that, The molar ratio of the silicon source calculated as SiO2, the aluminum source calculated as Al2O3, the organic structure-directing agent A, the organic structure-directing agent B, the alkali source, and water is 1: (0.02 - 0.07): (0.10 - 0.50): (0.10 - 0.50): (0.10 - 0.40): (12 - 60).

15. The manufacturing method according to claim 13, characterized in that, The crystallization temperature of the mixture crystallization is 120 - 200 °C, and the crystallization time is 1 - 15 days.

16. The manufacturing method according to claim 15, characterized in that, The crystallization temperature of the mixture crystallization is 130 - 190 °C, and the crystallization time is 2 - 12 days.

17. The manufacturing method according to claim 15, characterized in that, The crystallization temperature of the mixture crystallization is 140 - 180 °C, and the crystallization time is 3 - 9 days.

18. The manufacturing method according to claim 13, characterized in that, The organic structure-directing agent A is selected from at least one of tetramethylammonium hydroxide, tetramethylammonium chloride, tetramethylammonium bromide, or tetramethylammonium iodide; And / or, the organic structure-directing agent B is selected from at least one of cetylpyridinium bromide, tetradecylpyridinium bromide, dodecylpyridinium bromide, decylpyridinium bromide, cetylpyridinium chloride, tetradecylpyridinium chloride, cetylpyridinium hydroxide, n-octyltrimethylammonium chloride, n-octyltrimethylammonium bromide, or n-octyltrimethylammonium hydroxide.

19. The manufacturing method according to claim 18, characterized in that, 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.

20. The manufacturing method according to claim 13, characterized in that, The silicon source is selected from at least one of silicic acid, silica gel, silica sol, tetraethyl orthosilicate, and water glass; And / or, the aluminum source is selected from at least one of aluminum hydroxide, aluminum oxide, aluminate, aluminum salt, and tetraalkoxyaluminum; And / or, the base source is selected from at least one of inorganic bases with alkali metals or alkaline earth metals as cations.

21. The manufacturing method according to any one of claims 13-20, characterized in that, The mixture further includes a non-silicon and non-aluminum source, and the non-silicon and non-aluminum source is selected from at least one of a titanium source, a boron source, a zirconium source, a tin source, and an iron source.

22. The manufacturing method according to claim 21, wherein, The molar ratio of the silicon source calculated as SiO2 to the non-silicon and non-aluminum source calculated as the corresponding oxide is 1: (0.002 - 0.10).

23. The manufacturing method according to claim 21, wherein, The molar ratio of the silicon source calculated as SiO2 to the non-silicon and non-aluminum source calculated as the corresponding oxide is 1: (0.005 - 0.05).

24. A molecular sieve composition comprising the SCM-36 molecular sieve according to any one of claims 1-12 or the SCM-36 molecular sieve manufactured by the manufacturing method according to any one of claims 13-23, and a binder.

25. Use of the SCM-36 molecular sieve according to any one of claims 1-12 or the molecular sieve composition according to claim 24, or the SCM-36 molecular sieve manufactured by the manufacturing method according to any one of claims 13-23 as an adsorbent or a catalyst for organic compound conversion.

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