A eutectic molecular sieve and a preparation method thereof

Abstract

The present invention discloses a eutectic molecular sieve and a preparation method thereof. The eutectic molecular sieve is a eutectic molecular sieve of SCM-38 molecular sieve and CHA molecular sieve, and its chemical composition includes, in terms of molar ratio: SiO2:Al2O3:P2O5 = (0.08-0.80):(0.88-1.30):1. The XRD pattern of the eutectic molecular sieve contains X-ray diffraction peaks at 2θ of 7.20±0.1, 9.49±0.1, 10.81±0.1, 11.60±0.1, 15.98±0.1, 20.56±0.1, 30.55±0.1, and 31.32±0.1. The eutectic molecular sieve provided by the present invention can be applied to adsorbents or catalysts.

Description

Technical Field

[0001] The present invention belongs to the field of molecular sieves, and particularly relates to a novel eutectic molecular sieve and a preparation method thereof. Background Art

[0002] Molecular sieves are a class of porous crystalline materials and are widely used in chemical industries such as oil refining and catalysis. Different pore structures exhibit different macroscopic properties such as adsorption and catalysis, and molecular sieves with different structures have also been synthesized. Currently, more than 250 types of molecular sieves with known structures have been discovered (including those with partial disorder). Since molecular sieves have uniform and regular pores, and the pore sizes are of the same order of magnitude as organic small molecules, in chemical reactions, molecules entering the interior of the molecular sieve can be "screened" according to the spatial size of the molecules, thereby obtaining certain selective adsorption and catalytic shape-selective effects. The framework of a molecular sieve is usually composed of coordination tetrahedra (TO4) connected by sharing vertices (generally oxygen atoms). For conventional zeolite molecular sieves, the tetrahedra in the framework are mainly silicon-oxygen tetrahedra and aluminum-oxygen tetrahedra, and these two tetrahedra can also be replaced by other tetrahedra respectively, thereby forming many molecular sieves with various framework structures or various framework compositions.

[0003] In 1971, Flanigen et al. (Molecular Sieve Zeolites-I, ACS, Washingtom D.C) reported the synthesis of aluminophosphate molecular sieves, which can be understood as the replacement of silicon-oxygen tetrahedra in zeolite molecular sieves by phosphorus-oxygen tetrahedra to form molecular sieves. The framework of this type of molecular sieve is formed by AlO4 - and PO4 +It is composed of oxygen atoms connected together, and the entire molecular sieve framework exhibits electrical neutrality. Similar to zeolite molecular sieves, the aluminum-oxygen tetrahedra or phosphorus-oxygen tetrahedra in aluminophosphate molecular sieves can also be replaced by other tetrahedra. The most common ones are silicon-oxygen tetrahedra and zinc-oxygen tetrahedra. The introduction of these tetrahedra endows aluminophosphate molecular sieves with new properties. Compared with zeolite molecular sieves, the research on the artificial synthesis of aluminophosphate molecular sieves started relatively late. Under hydrothermal synthesis conditions, the oxides of aluminum, silicon, and phosphorus were mixed to obtain silicoaluminophosphate molecular sieves with the same crystal structures as analcime, chabazite, phillipsite-harmotome, L-type molecular sieve, A-type molecular sieve, B-type molecular sieve, etc., where the phosphorus content was 5% - 25% (calculated as P2O5), but no molecular sieves with structures different from known zeolite molecular sieves were found. The 1982 US Patent US 4310440 used organic amines or quaternary ammonium compounds as structure-directing agents to hydrothermally synthesize a series of aluminophosphate molecular sieves, including: AlPO4-5, AlPO4-8, AlPO4-9, AlPO4-11, AlPO4-12, AlPO4-14, AlPO4-16, AlPO4-17, AlPO4-18, AlPO4-20, AlPO4-21, AlPO4-22, AlPO4-23, AlPO4-25, AlPO4-26, AlPO4-28, AlPO4-31, etc. With the continuous deepening of the understanding of factors such as the structure, performance, synthesis method, and conditions of molecular sieves and the continuous progress of synthesis technology, new-structured molecular sieves are constantly being synthesized. For the synthesis of aluminophosphate molecular sieves, the type of organic structure-directing agent is one of the key factors determining its structure. So far, organic amines are still the most widely used structure-directing agents in the synthesis of aluminophosphate molecular sieves. Compared with silica-alumina zeolite molecular sieves, the industrial applications of aluminophosphate molecular sieves are still rare. At present, only a few molecular sieves have obtained practical industrial applications, such as SAPO-34 and SAPO-11 molecular sieves. Jiao et al. (Feng Jiao, Jinjing Li, Xiulian Pan, et al. Science, 2016, 351, 1065 - 1068) reported that SAPO molecular sieves, as part of a coupling catalyst in the reaction of syngas to olefins, achieved good catalytic effects.Su et al. (Su, J., Zhou, H., Liu, S. et al. Syngas to light olefins conversion with high olefin / paraffin ratio using ZnCrOx / AlPO-18 bifunctional catalysts. Nat Commun 10, 1297 (2019).) revealed that bifunctional catalysts prepared from aluminophosphate molecular sieves and metal oxides have excellent performance in the direct conversion of syngas to olefins with a high olefin / paraffin ratio. It can be seen from the above that aluminophosphate molecular sieves have great industrial application potential.

[0004] Since different pore structures and element compositions determine the unique physical and chemical and catalytic properties of molecular sieves, and different molecular sieves maintain their own characteristics in adsorption or reaction, the development of eutectic molecular sieves can make up for the deficiencies of the properties of single molecular sieves. Therefore, the research and development of eutectic molecular sieves is particularly important. Summary of the Invention

[0005] The technical problem to be solved by the present invention is to provide a novel eutectic molecular sieve and its preparation method not involved in the prior art.

[0006] In the first aspect of the present invention, a eutectic molecular sieve is provided. The eutectic molecular sieve is a eutectic molecular sieve of SCM-38 molecular sieve and CHA molecular sieve. Its chemical composition includes, in molar ratio: SiO2∶Al2O3∶P2O5 = (0.08 - 0.80)∶(0.88 - 1.30)∶1. The XRD pattern of the eutectic molecular sieve contains X-ray diffraction peaks at 2θ = 7.20 ± 0.1, 9.49 ± 0.1, 10.81 ± 0.1, 11.60 ± 0.1, 15.98 ± 0.1, 20.56 ± 0.1, 30.55 ± 0.1, 31.32 ± 0.1.

[0007] Furthermore, in the XRD pattern of the eutectic molecular sieve, X-ray diffraction peaks, namely the characteristic peaks of SCM-38 molecular sieve, appear at 2θ = 7.20 ± 0.1, 10.81 ± 0.1, 11.60 ± 0.1. Among them, the peak at 2θ = 7.20 ± 0.1 is the strongest peak in the characteristic peaks of SCM-38 molecular sieve. Preferably, the XRD pattern of the eutectic molecular sieve contains the X-ray diffraction peaks shown in the following table. Among them, calculated with the intensity of the strongest peak in the characteristic peaks of SCM-38 molecular sieve as 100%:

[0008] 2θ (°) <![CDATA[Relative intensity, [(I / I0)×100]]]> 7.20±0.1 100 10.81±0.1 5-80 11.60±0.1 5-80 。

[0009] Furthermore, in the XRD pattern of the eutectic molecular sieve, the characteristic peaks of SCM-38 molecular sieve further include X-ray diffraction peaks at 2θ = 14.32 ± 0.1, 21.39 ± 0.1, 21.83 ± 0.1, 27.31 ± 0.1, and 28.72 ± 0.1, that is, the characteristic peaks further included in the SCM-38 molecular sieve. Preferably, the XRD pattern of the eutectic molecular sieve contains the X-ray diffraction peaks shown in the following table, calculated with the intensity of the strongest peak among the characteristic peaks of SCM-38 molecular sieve as 100%:

[0010] 2θ (°) <![CDATA[Relative intensity, [(I / I0)×100]]]> 14.32±0.1 5-50 21.39±0.1 5-50 21.83±0.1 5-50 27.31±0.1 5-50 28.72±0.1 5-50 。

[0011] Furthermore, in the XRD pattern of the eutectic molecular sieve, X-ray diffraction peaks appear at 2θ = 9.49 ± 0.1, 15.98 ± 0.1, 20.56 ± 0.1, 30.55 ± 0.1, and 31.32 ± 0.1, which are the characteristic peaks of CHA molecular sieve. Among the characteristic peaks of CHA molecular sieve, the peak at 2θ = 9.49 ± 0.1 or 20.56 ± 0.1 is the strongest peak.

[0012] Furthermore, the XRD pattern of the eutectic molecular sieve contains the X-ray diffraction peaks shown in the following table (i.e., the diffraction peaks of CHA molecular sieve), calculated with the intensity of the strongest peak among the characteristic peaks of CHA molecular sieve as 100%:

[0013] 2θ (°) <![CDATA[Relative intensity, [(I / I0)×100]]]> 9.49±0.1 5-100 15.98±0.1 5-80 20.56±0.1 5-100 30.55±0.1 5-80 31.32±0.1 5-80 。

[0014] Furthermore, in the XRD pattern of the eutectic molecular sieve, the characteristic peaks of CHA molecular sieve further include X-ray diffraction peaks at 2θ = 12.82 ± 0.1, 14.08 ± 0.1, 18.01 ± 0.1, 25.25 ± 0.1, and 25.84 ± 0.1, that is, the characteristic peaks further included in CHA molecular sieve.

[0015] Furthermore, preferably, the XRD pattern of the eutectic molecular sieve further contains the X-ray diffraction peaks shown in the following table (i.e., the characteristic peaks further included in CHA molecular sieve), calculated with the intensity of the strongest peak among the characteristic peaks of CHA molecular sieve as 100%:

[0016] 2θ (°) <![CDATA[Relative intensity, [(I / I0)×100]]]> 12.82±0.1 1-50 14.08±0.1 1-50 18.01±0.1 1-50 25.25±0.1 1-50 25.84±0.1 1-50 。

[0017] Furthermore, the chemical composition of the eutectic molecular sieve includes, in terms of molar ratio: SiO2∶Al2O3∶P2O5 = (0.08 - 0.80)∶(0.88 - 1.30)∶1. Preferably, SiO2∶Al2O3∶P2O5 = (0.11 - 0.80)∶(0.88 - 1.30)∶1.

[0018] Further, the eutectic molecular sieve is a eutectic molecular sieve of CHA molecular sieve and SCM-38 molecular sieve. There is no particular limitation on the contents of the CHA molecular sieve and the SCM-38 molecular sieve. Further, in the eutectic molecular sieve, the CHA molecular sieve accounts for 1%-99% of the mass of the eutectic molecular sieve, further 10%-90%, and the SCM-38 molecular sieve accounts for 1%-99% of the mass of the eutectic molecular sieve, further 10%-90%.

[0019] Further, the CHA molecular sieve in the eutectic molecular sieve is preferably SAPO-34 molecular sieve.

[0020] The second aspect of the present invention provides a preparation method of the above-mentioned eutectic molecular sieve, including:

[0021] a) Mixing an aluminophosphate precursor, a silicon source, an organic base R1, an organic matter R2, a fluorine source and water, and optionally an aluminum source A to obtain a synthesis mother liquor;

[0022] b) Crystallizing the synthesis mother liquor in step a) to obtain a eutectic molecular sieve;

[0023] Among them, the organic base R1 is one or more of tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, etc.; the organic matter R2 is 6-N,N-dimethylaminohexyl-2-hydroxyethyldimethylammonium bromide, and its chemical structural formula is shown as follows:

[0024]

[0025] The aluminophosphate precursor has a chemical composition shown by the formula "Al2O3:xP2O5", where 0.8≤x≤2; the XRD pattern of the aluminophosphate precursor mainly includes the X-ray diffraction peaks shown in the following table:

[0026] 2θ (°) <![CDATA[Relative intensity, [(I / I0)×100] <!-- 3 -->]]> 7.59±0.2 100 10.81±0.1 5-50 16.52±0.1 5-50 17.97±0.1 5-50 23.34±0.05 5-50 34.74±0.05 5-50 。

[0027] Further, the XRD pattern of the aluminophosphate precursor further includes the X-ray diffraction peaks shown in the following table:

[0028]

[0029]

[0030] Further, the XRD pattern of the aluminophosphate precursor further includes the X-ray diffraction peaks shown in the following table:

[0031] 2θ (°) <![CDATA[Relative intensity, [(I / I0)×100]]]> 12.09±0.1 5-50 19.77±0.1 5-50 31.33±0.01 5-50 38.29±0.01 5-50 。

[0032] Further, in the synthetic mother liquor, the molar ratios of the respective materials are as follows: the silicon source is calculated as SiO₂, the aluminum source A is calculated as Al₂O₃, the aluminophosphate precursor is calculated as Al₂O₃ and P₂O₅, the organic base R1, the organic matter R2, the fluorine source is calculated as HF, and water is calculated as H₂O, (0.08 - 0.80)SiO₂:(0.88 - 1.3)Al₂O₃:1P₂O₅:(0.3 - 0.8)R1:(1 - 2)R2:(0.5 - 1.8)HF:(50 - 130)H₂O. The amount of the aluminum source A is determined according to the amount of Al₂O₃ in the aluminophosphate precursor, that is, when the amount of Al₂O₃ provided by the aluminophosphate precursor meets the above ratio requirements, the aluminum source A is not added; when the amount of Al₂O₃ provided by the aluminophosphate precursor cannot meet the above ratio requirements, the aluminum source A is added to meet the above ratio requirements.

[0033] Further, in the molar ratios of the respective materials in the synthetic mother liquor, SiO₂∶P₂O₅ = (0.08 - 0.80)∶1, preferably (0.11 - 0.80)∶1.

[0034] Further, the aluminum source A is selected from one or more of pseudoboehmite, aluminum isopropoxide, aluminum sol, alumina, etc.

[0035] Further, the silicon source is selected from one or more of silica sol, fumed silica, etc., preferably silica sol;

[0036] Further, the fluorine source is selected from HF aqueous solution.

[0037] Further, in step a), there is no particular limitation on the addition order of the respective materials. Preferably: first, water, optionally the aluminum source A, the silicon source, and the aluminophosphate precursor are mixed evenly, then the organic matter R2 and the organic base R1 are added in sequence and mixed evenly, and then the fluorine source is added.

[0038] Further, in step b), the crystallization conditions are as follows: the crystallization temperature is 160°C - 210°C, and the crystallization time is 8 - 100 hours. Preferably, the crystallization temperature is 170°C - 200°C, and the crystallization time is 20 - 84 hours.

[0039] Further, after the crystallization step in step b), the eutectic molecular sieve product can be separated from the obtained mixture by any conventionally known separation method, such as separation, washing, and drying. Herein, the separation, washing, and drying can be carried out in any manner conventionally known in the art. The separation methods include centrifugation or filtration, suction filtration; the drying temperature can be selected from 40 - 120°C, preferably 50 - 80°C; as the drying time, it is 8 - 48 hours, preferably 12 - 24 hours. This drying can be carried out under normal pressure or reduced pressure. For energy conservation, it is usually carried out under normal pressure.

[0040] The third aspect of the present invention provides a eutectic molecular sieve composition, comprising a eutectic molecular sieve as described in any of the foregoing aspects or a eutectic molecular sieve prepared by the preparation method of the eutectic molecular sieve as described in any of the foregoing aspects, and a binder.

[0041] The fourth aspect of the present invention provides an application of a eutectic molecular sieve, the eutectic molecular sieve as described in any of the foregoing aspects, the eutectic molecular sieve prepared by the preparation method of the eutectic molecular sieve as described in any of the foregoing aspects, or the eutectic molecular sieve composition as described in any of the foregoing aspects in an adsorbent or a catalyst.

[0042] Further, the eutectic molecular sieve or molecular sieve composition is used as an adsorbent, for example, to separate at least one component from a mixture of multiple components in a gas phase or a liquid phase. Accordingly, the at least one component can be partially or substantially completely separated from the mixture of various components. The specific manner is, for example, to bring the mixture into contact with the eutectic molecular sieve or the molecular sieve composition and selectively adsorb this component.

[0043] Further, the eutectic molecular sieve or molecular sieve composition can be used in a catalyst for organic matter conversion.

[0044] The eutectic molecular sieve of the present invention is a novel eutectic molecular sieve, specifically a eutectic molecular sieve of novel molecular sieve SCM-38 and CHA molecular sieve (especially SAPO-34 molecular sieve), which enriches the types and synthesis methods of eutectic molecular sieves. Description of the Drawings

[0045] Figure 1 XRD pattern of aluminophosphate precursor A obtained in Example 1;

[0046] Figure 2 XRD pattern of aluminophosphate precursor B obtained in Example 2;

[0047] Figure 3 XRD pattern of the eutectic molecular sieve obtained in Example 3;

[0048] Figure 4 XRD pattern of the eutectic molecular sieve obtained in Example 10;

[0049] Figure 5 XRD pattern of SCM-38 molecular sieve obtained in Comparative Example 1;

[0050] Figure 6 XRD pattern of SAPO-34 molecular sieve obtained in Comparative Example 2. Detailed Embodiments

[0051] The specific embodiments of the present invention will be described in detail below. The protection scope of the present invention is not limited by these specific embodiments.

[0052] In the present invention, the structure of the molecular sieve is determined by an X-ray diffraction pattern (XRD). The X-ray diffraction pattern (XRD) of the molecular sieve is measured by an X’Pert PRO type X-ray powder diffractometer (XRD) manufactured by PANalytical B.V. in the Netherlands, using a Cu-Kα ray source, with a Kα1 wavelength nickel filter, a working voltage of 40 kV, a current of 40 mA, and a scanning range of 3 - 50°.

[0053] In the present invention, the compositions of SiO2, Al2O3, and P2O5 in the molecular sieve are measured by an ICP method. The elemental ratios in the sample are analyzed using a Varian Analytical 725-ES type inductively coupled plasma optical emission spectrometer manufactured by Varian, Inc. in the United States.

[0054] The aluminophosphate precursor of the present invention has a schematic chemical composition as shown in the formula "Al2O3: xP2O5", where 0.8 ≤ x ≤ 2; the XRD pattern of the aluminophosphate precursor includes the X-ray diffraction peaks shown in the following table:

[0055] 2θ (°) <![CDATA[Relative intensity, [(I / I0)×100]]]> 7.59±0.2 100 10.81±0.1 5-50 16.52±0.1 5-50 17.97±0.1 5-50 23.34±0.05 5-50 34.74±0.05 5-50 。

[0056] Further, the XRD pattern of the aluminophosphate precursor also includes the X-ray diffraction peaks shown in the following table:

[0057] 2θ (°) <![CDATA[Relative intensity, [(I / I0)×100]]]> 14.25±0.1 5-50 21.01±0.1 10-20 24.27±0.05 5-50 26.05±0.05 5-50 27.82±0.05 5-50 28.15±0.02 5-50 30.03±0.02 5-50 。

[0058] Further, the XRD pattern of the aluminophosphate precursor also includes the X-ray diffraction peaks shown in the following table:

[0059] 2θ (°) <![CDATA[Relative intensity, [(I / I0)×100]]]> 12.09±0.1 5-50 19.77±0.1 5-50 31.33±0.01 5-50 38.29±0.01 5-50 。

[0060] Further, the preparation method of the aluminophosphate precursor of the present invention includes: crystallizing a mixture containing an aluminum source B, a phosphorus source, an organic templating agent R A and an organic templating agent R B , a solvent S1, a solvent S2, and a solvent S3 to obtain the aluminophosphate precursor;

[0061] wherein, the organic templating agent R A is selected from one or more of quaternary ammonium salts or quaternary ammonium bases; R BOne or more selected from imidazole or pyrrolidine derivatives; the solvent S1 is selected from one or more of amide solvents; the solvent S2 is selected from one or more of cyclic organic solvents; S3 is selected from one or more of water or lower alcohols.

[0062] Furthermore, in the preparation method of the aluminophosphate precursor, the organic template R A is selected from one or more of tetraethylammonium bromide, tetraethylammonium hydroxide, tetrapropylammonium bromide, tetrapropylammonium hydroxide, tetrabutylammonium bromide, and tetrabutylammonium hydroxide; the organic template R B is selected from one or more of imidazole, 2-methylimidazole, 4-methylimidazole, 1-(3-aminopropyl)imidazole, 2-ethyl-4-methylimidazole, pyrrolidine, 1-(3-pyrrolidino)pyrrolidine, and N-ethyl-2-aminomethylpyrrolidine; the solvent S1 is selected from one or more of N,N-dimethylformamide, N,N-dimethylacetamide, N,N-diethylformamide, and N,N-dibutylformamide; the solvent S2 is selected from one or more of 1,4-dioxane, cyclohexane, cyclohexanone; the solvent S3 is selected from one or more of methanol, ethanol, ethylene glycol, butanol, cyclohexanol, and water.

[0063] Furthermore, in the preparation method of the aluminophosphate precursor, the organic template R A is preferably one or more of tetraethylammonium bromide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, and tetrabutylammonium hydroxide; the organic template R B is preferably one or more of 1-(3-aminopropyl)imidazole, 2-ethyl-4-methylimidazole, and N-ethyl-2-aminomethylpyrrolidine; the solvent S1 is preferably one or more of N,N-dimethylacetamide and N,N-dibutylformamide; the solvent S2 is preferably one or two of 1,4-dioxane and cyclohexanone; the solvent S3 is preferably one or two of ethanol and water, and more preferably deionized water.

[0064] Furthermore, in the preparation method of the aluminophosphate precursor, in the mixture, the aluminum source B is calculated as Al2O3, the phosphorus source is calculated as P2O5, the organic template R A +R B and the solvents S1+S2+S3 have the following molar composition: P2O5 / Al2O3 = 0.75 - 2.2, preferably 1 - 2; the template R A +R B / Al2O3 = 1 - 80, preferably 5 - 50; the solvents S1+S2+S3 / Al2O3 = 5 - 500, preferably 35 - 120.

[0065] Furthermore, in the preparation method of the aluminophosphate precursor, the organic template RA with the organic template R B The molar ratio is 0.01-1:1, preferably 0.1-0.25:1.

[0066] Furthermore, in the preparation method of the aluminophosphate precursor, the molar ratio of the solvent S1, the solvent S2, and the solvent S3 is 1:0.01-1:1-100, preferably 1:0.05-0.5:10-80.

[0067] Furthermore, in the preparation method of the aluminophosphate precursor, the aluminum source B is selected from one or more of aluminum isopropoxide, aluminate, meta-aluminate, aluminum salt, aluminum hydroxide, aluminum oxide, and aluminum-containing minerals, preferably one or two of aluminate and meta-aluminate; the phosphorus source is selected from at least one of phosphoric acid, ammonium monohydrogen phosphate, and ammonium dihydrogen phosphate, preferably orthophosphoric acid.

[0068] Furthermore, in the preparation method of the aluminophosphate precursor, before the crystallization treatment, stirring and aging treatment are first carried out. The stirring time is 0.5-5 h, and the aging treatment time is 1-12 h.

[0069] Furthermore, in the preparation method of the aluminophosphate precursor, the conditions of the crystallization treatment include: the crystallization temperature is 120-200 °C, preferably 140-180 °C, more preferably 140-160 °C; the crystallization time is 1-5 d, preferably 3-5 d, more preferably 4-5 d.

[0070] Furthermore, in the preparation method of the aluminophosphate precursor, after the crystallization treatment, conventional post-treatment is carried out, such as the steps of filtering, washing, and drying to obtain the molecular sieve. The filtering, washing, and drying can be carried out in any manner conventionally known in the art, where the separation is by centrifugation or filtration, suction filtration. The drying temperature can be 40-120 °C, preferably 50-80 °C; as the drying time, it is 8-48 hours, preferably 12-24 hours. This drying can be carried out under normal pressure or under reduced pressure. For energy conservation, it is usually carried out under normal pressure.

[0071] The technical solutions of the present invention will be described in detail below in conjunction with embodiments. The following embodiments do not limit this patent.

[0072]

Example 1

[0073] Dissolve 38 g of aluminum nitrate [Al(NO3)3·9H2O] in 43 mL of deionized water. While stirring, add 25.2 g of phosphoric acid (purity ≥ 85 wt%), 151 g of tetrabutylammonium hydroxide (40 wt% aqueous solution), and 145.6 g of 1-(3-aminopropyl)imidazole. Stir for 0.5 h and age for 12 h to obtain solution A. Then, add 16 mL of N,N-dibutylformamide and 4.6 mL of cyclohexanone to solution A. Stir for 3.5 h and then heat-treat at 90 °C for 8 h to form a homogeneous crystallization mixture B. The molar ratio of the aluminum source calculated as Al2O3, the phosphorus source calculated as P2O5, the total template agent, and the total solvent is: Al2O3∶P2O5∶template agent R∶solvent S = 1∶2.1∶7∶40, where the template agent R A (tetrabutylammonium hydroxide): template agent R B (1-(3-aminopropyl)imidazole) = 0.2 (molar ratio), and solvent S1 (N,N-dibutylformamide)∶solvent S2 (cyclohexanone)∶solvent S3 (water) = 1∶0.5∶78.5 (molar ratio); Place the above crystallization mixture B in a crystallization kettle with a polytetrafluoroethylene liner and crystallize at 140 °C for 5 days. The product is filtered, washed, and dried at 80 °C for 24 h to obtain a phosphoaluminate precursor, denoted as A, for standby. Among them, in the phosphoaluminate precursor A, Al2O3∶P2O5 = 1∶2. The XRD pattern of the phosphoaluminate precursor A is shown in Figure 1 , that is, it includes the X-ray diffraction peaks shown in Table 1:

[0074] Table 1

[0075]

[0076]

[0077]

Example 2

[0078] Dissolve 33.3 g of aluminum sulfate [Al2(SO4)3·18H2O] in 66.3 mL of water. While stirring, add 5.2 g of phosphoric acid (purity ≥ 85 wt%), 117.0 g of tetrabutylammonium hydroxide (40 wt% aqueous solution), and 102.6 g of 1-(3-aminopropyl)imidazole to obtain a mixed solution. Stir for 3 h and age for 6 h to obtain solution A. Then, add 255 mL of N,N-dibutylformamide and 48 mL of cyclohexanone to the mixture A. Stir for 4.5 h and then heat-treat at 80 °C for 12 h to form a homogeneous mixture B. The molar ratio of the aluminum source calculated as Al2O3, the phosphorus source calculated as P2O5, the template agent, and the solvent is: Al2O3∶P2O5∶total template agent R∶total solvent S = 1∶0.9∶10∶80, where the template agent R A (tetrabutylammonium hydroxide): template agent R B(1-(3-aminopropyl)imidazole) = 0.22 (molar ratio), solvent S1 (N,N-dibutylformamide)∶solvent S2 (cyclohexanone)∶solvent S3 (water) = 1∶0.3∶48 (molar ratio); The above mixture B was placed in a crystallization kettle with a polytetrafluoroethylene lining and crystallized at 140 °C for 5 d. The product was filtered, washed and dried at 80 °C for 24 h to obtain an aluminum phosphate precursor, denoted as B, for standby. Among them, in the aluminum phosphate precursor B, Al2O3∶P2O5 = 1∶0.92. The XRD pattern of the aluminum phosphate precursor B is shown in Figure 2 , that is, it includes the X-ray diffraction peaks shown in Table 2 as follows:

[0079] Table 2

[0080]

[0081]

[0082]

Example 3

[0083] Weigh 24 g of water, add 3.1 g of aluminum isopropoxide and 6 g of aluminum phosphate precursor A, and stir at room temperature for 2 h; then add 4.75 g of 6-N,N-dimethylaminohexyl-2-hydroxyethyldimethylammonium bromide, continue to stir for 1 h, then add 0.6 g of 40% silica sol by mass, continue to stir for 30 min, then add 4.4 g of 25 wt% tetraethylammonium hydroxide solution, stir at room temperature for 3 h, then add 1 g of 40 wt% HF solution, stir evenly and load it into a high-pressure kettle with a polytetrafluoroethylene lining. Crystallize at 180 °C for 24 h; after cooling, centrifuge and separate, wash (the centrifugation and washing operations are repeated 2 - 3 times), and dry to obtain a eutectic zeolite. Its chemical composition, in terms of molar ratio, is SiO2∶Al2O3∶P2O5 = 0.23∶1.1∶1. This eutectic zeolite is a eutectic of SCM-38 and CHA zeolite. Among them, the mass content of SCM-38 is 42%, and the mass content of CHA zeolite is 58%. The XRD pattern of this eutectic zeolite is shown in Figure 3 , as can be seen from Figure 3 , characteristic peaks of CHA zeolite appear at 2θ = 9.49, 15.98, 20.56, 30.55, 31.35, among which the strongest peak is at 20.55. It also includes the main X-ray diffraction peaks shown in Table 3 (that is, the characteristic peaks of SCM-38. In Table 3, the intensity of the strongest peak among the characteristic peaks of SCM-38 zeolite except for the characteristic peaks of CHA zeolite is calculated as 100%), and further includes that characteristic peaks of SCM-38 also appear at 2θ = 14.33, 21.38, 21.85, 27.31, 28.72:

[0084] Table 3

[0085]

[0086]

[0087]

Example 4

[0088] Weigh 12 g of water, add 1.75 g of pseudo-boehmite and 6 g of aluminophosphate precursor A, and stir at room temperature for 2 h; then add 4.75 g of 6-N,N-dimethylaminohexyl-2-hydroxyethyldimethylammonium bromide, continue stirring for 1 h, then add 0.9 g of silica sol with a mass fraction of 40%, add 3.5 g of 25 wt% tetraethylammonium hydroxide solution after 30 min, stir at room temperature for 3 h, then add 0.43 g of 40 wt% HF solution, stir evenly and then load into a high-pressure autoclave with a Teflon liner. Crystallize at 180 °C for 24 h; after cooling, centrifuge, separate and wash (the centrifugal washing operation is repeated 2 - 3 times), and dry to obtain the eutectic molecular sieve. Its chemical composition, in terms of molar ratio, is SiO2∶Al2O3∶P2O5 = 0.11∶1∶1. This eutectic molecular sieve is a eutectic of SCM-38 and CHA structure molecular sieve. Among them, the mass content of SCM-38 is 22%, and the mass content of CHA molecular sieve is 78%. In the XRD pattern of this eutectic molecular sieve, characteristic peaks of CHA molecular sieve appear at 2θ of 9.51, 15.96, 20.56, 30.51, 31.33, among which the peak at 20.56 is the strongest peak. It also includes the main X-ray diffraction peaks shown in Table 4 (that is, the characteristic peaks of SCM-38. In Table 4, the intensity of the strongest peak among the characteristic peaks of SCM-38 molecular sieve except for the characteristic peaks of CHA molecular sieve is calculated as 100%), and further includes that characteristic peaks of SCM-38 also appear at 2θ of 14.35, 21.41, 21.82, 27.30, 28.75:

[0089] Table 4

[0090] 2θ (°) <![CDATA[Relative intensity, [(I / I0)×100]]]> 7.22 100 10.83 48 11.57 22

[0091]

Example 5

[0092] Weigh 24 g of water, add 3.7 g of aluminum isopropoxide and 6 g of aluminophosphate precursor A, and stir at room temperature for 2 h; then add 6.9 g of 6-N,N-dimethylaminohexyl-2-hydroxyethyldimethylammonium bromide, continue stirring for 1 h, then add 1.1 g of silica sol with a mass fraction of 40%, add 4.4 g of 25 wt% tetraethylammonium hydroxide solution after 30 min, stir at room temperature for 3 h, then add 1 g of 40 wt% HF solution, stir evenly and transfer to a high-pressure autoclave with a Teflon liner. Crystallize at 180 °C for 48 h; after cooling, centrifuge and separate, wash (the centrifugation and washing operations are repeated 2 - 3 times), and dry to obtain the eutectic molecular sieve. Its chemical composition, in terms of molar ratio, is SiO2∶Al2O3∶P2O5 = 0.42∶1.15∶1. This eutectic molecular sieve is a eutectic of SCM-38 and CHA structure molecular sieve. Among them, the mass content of SCM-38 is 13%, and the mass content of CHA molecular sieve is 87%. In the XRD pattern of this eutectic molecular sieve, characteristic peaks of CHA molecular sieve appear at 2θ = 9.50, 15.97, 20.55, 30.51, 31.35, among which the peak at 20.55 is the strongest peak. It also includes the main X-ray diffraction peaks shown in Table 5 (that is, the characteristic peaks of SCM-38. In Table 5, the intensity of the strongest peak among the characteristic peaks of SCM-38 except for the characteristic peaks of CHA molecular sieve is calculated as 100%), and further includes characteristic peaks of SCM-38 also appearing at 2θ = 14.30, 21.38, 21.86, 27.35, 28.70:

[0093] Table 5

[0094] 2θ (°) <![CDATA[Relative intensity, [(I / I0)×100]]]> 7.22 100 10.83 56 11.61 30

[0095]

Example 6

[0096] Weigh 28 g of water, add 4.3 g of aluminum isopropoxide and 6 g of aluminophosphate precursor A, and stir at room temperature for 2 h; then add 8.2 g of 6-N,N-dimethylaminohexyl-2-hydroxyethyldimethylammonium bromide, continue stirring for 1 h, then add 1.73 g of silica sol with a mass fraction of 40%, add 6.6 g of 25 wt% tetraethylammonium hydroxide solution after 30 min, stir at room temperature for 3 h, then add 1.3 g of 40 wt% HF solution, stir evenly and transfer to a high-pressure autoclave with a Teflon liner. Crystallize at 180 °C for 36 h; after cooling, centrifuge and separate, wash (the centrifugation and washing operations are repeated 2 - 3 times), and dry to obtain the eutectic zeolite. Its chemical composition, in terms of molar ratio, is SiO2∶Al2O3∶P2O5 = 0.63∶1.2∶1. Among them, the mass content of SCM-38 is 11%, and the mass content of CHA zeolite is 89%. In the XRD pattern of this eutectic zeolite, characteristic peaks of CHA zeolite appear at 2θ = 9.51, 15.97, 20.55, 30.52, and 31.35, where the peak at 20.55 is the strongest peak. It also includes the main X-ray diffraction peaks shown in Table 6 (i.e., the characteristic peaks of SCM-38, calculated with the intensity of the strongest peak among the characteristic peaks of SCM-38 zeolite other than the characteristic peaks of CHA zeolite in Table 6 as 100%), and further includes characteristic peaks of SCM-38 also appearing at 2θ = 14.28, 21.37, 21.84, 27.36, and 28.71:

[0097] Table 6

[0098] 2θ (°) <![CDATA[Relative intensity, [(I / I0)×100]]]> 7.23 100 10.83 55 11.61 32

[0099]

Example 7

[0100] Weigh 24 g of water, add 3.1 g of aluminum isopropoxide and 6 g of aluminophosphate precursor A, and stir at room temperature for 2 h; then add 4.75 g of 6-N,N-dimethylaminohexyl-2-hydroxyethyldimethylammonium bromide, continue stirring for 1 h, then add 0.6 g of silica sol with a mass fraction of 40%, add 2.73 g of 25 wt% tetramethylammonium hydroxide solution after 30 min, stir at room temperature for 3 h, then add 1 g of 40 wt% HF solution, stir evenly and transfer to a high-pressure autoclave with a Teflon liner. Crystallize at 180 °C for 24 h; after cooling, centrifuge and separate, wash (the centrifugation and washing operations are repeated 2 - 3 times), and dry to obtain the eutectic molecular sieve. Its chemical composition, in terms of molar ratio, is SiO2∶Al2O3∶P2O5 = 0.21∶1∶1. Among them, the mass content of SCM-38 is 45%, and the mass content of CHA molecular sieve is 55%. In the XRD pattern of this eutectic molecular sieve, characteristic peaks of the CHA molecular sieve appear at 2θ of 9.50, 15.98, 20.53, 30.51, and 31.36, among which the peak at 20.53 is the strongest peak. It also includes the main X-ray diffraction peaks shown in Table 7 (that is, the characteristic peaks of SCM-38, calculated with the intensity of the strongest peak among the characteristic peaks of SCM-38 molecular sieve other than the characteristic peaks of CHA molecular sieve in Table 7 as 100%), and further includes characteristic peaks of SCM-38 also appearing at 2θ of 14.34, 21.39, 21.84, 27.28, and 28.68:

[0101] Table 7

[0102] 2θ (°) <![CDATA[Relative intensity, [(I / I0)×100]]]> 7.25 100 10.81 53 11.60 21

[0103]

Example 8

[0104] Weigh 24 g of water, add 3.1 g of aluminum isopropoxide and 6 g of aluminophosphate precursor A, and stir at room temperature for 2 h; then add 4.75 g of 6-N,N-dimethylaminohexyl-2-hydroxyethyl dimethyl ammonium bromide, continue stirring for 1 h, then add 0.6 g of silica sol with a mass fraction of 40%, add 6.1 g of 25 wt% tetrapropylammonium hydroxide solution after 30 min, stir at room temperature for 3 h, then add 1 g of 40 wt% HF solution, stir evenly and transfer to a high-pressure autoclave with a Teflon liner. Crystallize at 180 °C for 24 h; after cooling, centrifuge, separate, wash (the centrifugation and washing operations are repeated 2 - 3 times), and dry to obtain the eutectic molecular sieve. Its chemical composition, in terms of molar ratio, is SiO2∶Al2O3∶P2O5 = 0.22∶1.1∶1. Among them, the mass content of SCM-38 is 39%, and the mass content of CHA molecular sieve is 61%. In the XRD pattern of this eutectic molecular sieve, characteristic peaks of CHA molecular sieve appear at 2θ = 9.55, 15.98, 20.60, 30.49, 31.31, among which the peak at 20.60 is the strongest peak. It also includes the main X-ray diffraction peaks shown in Table 8 (i.e., the characteristic peaks of SCM-38. In Table 8, the intensity of the strongest peak among the characteristic peaks of SCM-38 other than the characteristic peaks of CHA molecular sieve is calculated as 100%), and further includes characteristic peaks of SCM-38 also appearing at 2θ = 14.30, 21.39, 21.85, 27.34, 28.76:

[0105] Table 8

[0106]

[0107]

[0108]

Example 9

[0109] Weigh 28 g of water, add 3.28 g of pseudoboehmite and 6 g of aluminophosphate precursor A, and stir at room temperature for 2 h; then add 4.75 g of 6-N,N-dimethylaminohexyl-2-hydroxyethyldimethylammonium bromide, continue stirring for 1 h, then add 0.6 g of silica sol with a mass fraction of 40%, add 6.6 g of 25 wt% tetraethylammonium hydroxide solution after 30 min, stir at room temperature for 3 h, then add 1 g of 40 wt% HF solution, stir evenly and transfer to a high-pressure autoclave with a Teflon liner. Crystallize at 180 °C for 24 h; after cooling, centrifuge, separate and wash (the centrifugal washing operation is repeated 2 - 3 times), and dry to obtain the eutectic molecular sieve. Its chemical composition, in terms of molar ratio, is SiO2∶Al2O3∶P2O5 = 0.24∶1.2∶1. Among them, the mass content of SCM-38 is 35%, and the mass content of CHA molecular sieve is 65%. The characteristic peaks of the CHA molecular sieve appear at 2θ = 9.57, 15.99, 20.62, 30.48, 31.32 for this eutectic molecular sieve, where the peak at 20.62 is the strongest peak, and it also includes the main X-ray diffraction peaks shown in Table 9 (i.e., the characteristic peaks of SCM-38. In Table 9, the intensity of the strongest peak among the characteristic peaks of SCM-38 molecular sieve other than the characteristic peaks of CHA molecular sieve is calculated as 100%), and further includes the characteristic peaks of SCM-38 also appearing at 2θ = 14.31, 21.39, 21.85, 27.35, 28.74:

[0110] Table 9

[0111] 2θ (°) <![CDATA[Relative intensity, [(I / I0)×100]]]> 7.18 100 10.84 52 11.60 25

[0112]

Example 10

[0113] Weigh 24 g of water, 2.73 g of aluminophosphate precursor B, and stir at room temperature for 2 h; then add 4.75 g of 6-N,N-dimethylaminohexyl-2-hydroxyethyldimethylammonium bromide, continue stirring for 1 h, then add 0.6 g of silica sol with a mass fraction of 40%, add 4.4 g of 25 wt% tetraethylammonium hydroxide solution after 30 min, stir at room temperature for 3 h, then add 1 g of 40 wt% HF solution, stir evenly and transfer to a high-pressure autoclave with a Teflon liner. Crystallize at 180 °C for 24 h; after cooling, centrifuge, separate and wash (the centrifugal washing operation is repeated 2 - 3 times), and dry to obtain the eutectic molecular sieve. Its chemical composition, in terms of molar ratio, is SiO2∶Al2O3∶P2O5 = 0.21∶1.1∶1. Among them, the mass content of SCM-38 is 38%, and the mass content of CHA molecular sieve is 62%. The XRD pattern of this eutectic molecular sieve is shown in Figure 4 . From Figure 4It can be seen that characteristic peaks of CHA zeolite appear at 2θ = 9.54, 15.98, 20.53, 30.50, and 31.36, among which the peak at 20.53 is the strongest peak. It also includes the main X-ray diffraction peaks shown in Table 10 (i.e., the characteristic peaks of SCM-38. In Table 10, the intensity of the strongest peak among the characteristic peaks of SCM-38 zeolite other than the characteristic peaks of CHA zeolite is calculated as 100%), and further includes the characteristic peaks of SCM-38 also appearing at 2θ = 14.31, 21.38, 21.81, 27.30, and 28.72:

[0114] Table 10

[0115] 2θ (°) <![CDATA[Relative intensity, [(I / I0)×100]]]> 7.19 100 10.80 47 11.59 19

[0116]

Comparative Example 1

[0117] Weigh 24 g of water, add 3.1 g of aluminum isopropoxide and 6 g of aluminophosphate precursor A, and stir at room temperature for 2 h; then add 1.8 g of 4 wt% (the silica sol with 40 wt% is diluted 10 times) silica sol, stir evenly, add 4.75 g of 6-N,N-dimethylaminohexyl-2-hydroxyethyldimethylammonium bromide, and then add 4.4 g of 25 wt% aqueous solution of tetraethylammonium hydroxide. After stirring at room temperature for 4 h, add 1 g of 40 wt% HF solution, stir evenly, and transfer to a high-pressure autoclave with a Teflon liner. Crystallize at 140 °C for 66 h; then raise the temperature to 180 °C and crystallize at this temperature for 8 h; after cooling, separate, wash (the centrifugal washing operation is repeated 2 - 3 times), and dry to obtain SCM-38 zeolite. Its chemical composition, in terms of molar ratio, is SiO2∶Al2O3∶P2O5 = 0.07∶1.13∶1. The XRD pattern of this zeolite is shown in Figure 5 , that is, it includes the X-ray diffraction peaks shown in Table 11:

[0118] Table 11

[0119] 2θ (o) Relative intensity, [(I / I0)×100] 7.23 100 10.82 20 11.63 8 14.35 21 21.41 14 21.85 27 27.33 12 28.75 29

[0120] From Figure 5 and Table 11, it can be seen that the characteristic peaks of SCM-38 include 2θ = 7.20 ± 0.1, 10.81 ± 0.1, 11.60 ± 0.1, and further include the characteristic peaks appearing at 2θ = 14.32 ± 0.1, 21.39 ± 0.1, 21.83 ± 0.1, 27.31 ± 0.1, 28.72 ± 0.1.

[0121]

Comparative Example 2

[0122] Weigh 24 g of water, add 3.1 g of aluminum isopropoxide and 6 g of aluminophosphate precursor A, and stir at room temperature for 2 h; then add 2.3 g of 40 wt% silica sol, stir evenly, add 4.75 g of 6-N,N-dimethylaminohexyl-2-hydroxyethyldimethylammonium bromide, and then add 4.4 g of 25 wt% tetraethylammonium hydroxide aqueous solution. After stirring at room temperature for 4 h, add 1 g of 40 wt% HF solution, stir evenly and transfer to a high-pressure autoclave with a Teflon liner. Crystallize at 180 °C for 15 h; after cooling, separate, wash (repeat the centrifugal washing operation 2 - 3 times), and dry to obtain a zeolite with a CHA structure. Its chemical composition, in terms of molar ratio, is SiO2∶Al2O3∶P2O5 = 1.01∶1.5∶1. The XRD pattern of this zeolite is shown in Figure 6 , that is, it includes the X-ray diffraction peaks shown in Table 12:

[0123] Table 12

[0124] 2θ (°) <![CDATA[Relative intensity, [(I / I0)×100]]]> 9.49 88 12.81 14 14.07 15 15.98 42 18.00 30 20.55 100 25.23 38 25.82 23 30.53 37 31.30 27

[0125] It can be seen from Figure 6 and Table 12 that the eutectic material obtained in Comparative Example 2 does not have the characteristic peaks of SCM-38, but only has the characteristic peaks of CHA zeolite, which is different from the eutectic zeolite of the present invention.

Claims

1. A eutectic molecular sieve, characterized in that, The eutectic zeolite is a eutectic zeolite of SCM-38 zeolite and CHA zeolite, and its chemical composition includes, in terms of molar ratio: SiO2:Al2O3:P2O5 = (0.11 - 0.63):(1.0 - 1.2):

1. The XRD pattern of the eutectic zeolite contains X-ray diffraction peaks at 2θ of 7.20 ± 0.1, 9.49 ± 0.1, 10.81 ± 0.1, 11.60 ± 0.1, 15.98 ± 0.1, 20.56 ± 0.1, 30.55 ± 0.1, and 31.32 ± 0.

1.

2. The eutectic molecular sieve according to claim 1, wherein, In the XRD pattern of the eutectic zeolite, X-ray diffraction peaks at 2θ of 7.20 ± 0.1, 10.81 ± 0.1, and 11.60 ± 0.1 are the characteristic peaks of SCM-38 zeolite. Among them, the peak at 2θ of 7.20 ± 0.1 is the strongest peak among the characteristic peaks of SCM-38 zeolite.

3. The eutectic molecular sieve according to claim 2, wherein The XRD pattern of the eutectic zeolite contains the X-ray diffraction peaks shown in the following table, calculated with the intensity of the strongest peak among the characteristic peaks of SCM-38 zeolite as 100%: 。 4. The eutectic molecular sieve according to claim 1, wherein In the XRD pattern of the eutectic zeolite, the characteristic peaks of SCM-38 zeolite also include X-ray diffraction peaks at 2θ of 14.32 ± 0.1, 21.39 ± 0.1, 21.83 ± 0.1, 27.31 ± 0.1, and 28.72 ± 0.

1.

5. The eutectic molecular sieve according to claim 4, wherein The XRD pattern of the eutectic zeolite contains the X-ray diffraction peaks shown in the following table, calculated with the intensity of the strongest peak among the characteristic peaks of SCM-38 zeolite as 100%: 。 6. The eutectic molecular sieve according to any one of claims 1-5, characterized in that, In the eutectic zeolite, CHA zeolite accounts for 1% - 99% of the mass of the eutectic zeolite, and SCM-38 zeolite accounts for 1% - 99% of the mass of the eutectic zeolite.

7. The eutectic molecular sieve according to claim 6, characterized in that, In the eutectic zeolite, CHA zeolite accounts for 10% - 90% of the mass of the eutectic zeolite, and SCM-38 zeolite accounts for 10% - 90% of the mass of the eutectic zeolite.

8. The preparation method of the eutectic zeolite according to any one of claims 1 - 7, comprising: a) Mixing a phosphoaluminate precursor, a silicon source, an organic base R1, an organic compound R2, a fluorine source, water, and optionally an aluminum source A to obtain a synthesis mother liquor; b) Crystallizing the synthesis mother liquor in step a) to obtain the eutectic zeolite; wherein, the organic base R1 is one or more of tetramethylammonium hydroxide, tetraethylammonium hydroxide, and tetrapropylammonium hydroxide; the organic compound R2 is 6-N,N-dimethylaminohexyl-2-hydroxyethyldimethylammonium bromide; The phosphoaluminate precursor has a chemical composition represented by the formula "Al2O3:xP2O5", wherein 0.8 ≤ x ≤ 2; the XRD pattern of the phosphoaluminate precursor mainly includes the X-ray diffraction peaks shown in the following table: 。 9. The preparation method according to claim 8, characterized in that, In step a), the XRD pattern of the phosphoaluminate precursor further includes the X-ray diffraction peaks shown in the following table: 。 10. The preparation method according to claim 8, characterized in that, In step a), the XRD pattern of the phosphoaluminate precursor further includes the X-ray diffraction peaks shown in the following table: 。 11. The preparation method according to claim 8, wherein In the synthetic mother liquor described above, the molar ratios of each material are as follows: the aluminum source A is calculated as Al2O3, the silicon source is calculated as SiO2, the aluminophosphate precursor is calculated as Al2O3 and P2O5, the organic base R1, the organic matter R2, the fluorine source is calculated as HF, and water is calculated as H2O, (0.11-0.8)SiO2:(0.88-1.3)Al2O3:1P2O5:(0.3-0.8)R1:(1-2)R2:(0.5-1.8)HF:(50-130)H2O.

12. The preparation method according to claim 8, wherein The aluminum source A is selected from one or more of pseudoboehmite, aluminum isopropoxide, aluminum sol, and alumina; the silicon source is selected from one or more of silica sol and fumed silica; the fluorine source is selected from HF aqueous solution.

13. According to the preparation method as described in any one of claims 8-12, characterized in that, In step b), the crystallization conditions are as follows: the crystallization temperature is 160°C - 210°C, and the crystallization time is 8 - 100 hours.

14. The preparation method according to claim 13, characterized in that, In step b), the crystallization conditions are as follows: the crystallization temperature is 170°C - 200°C, and the crystallization time is 20 - 84 hours.

15. A eutectic zeolite molecular sieve composition comprising the eutectic zeolite molecular sieve according to any one of claims 1-7 or the eutectic zeolite molecular sieve prepared by the preparation method according to any one of claims 8-14, and a binder.

16. The application of the eutectic zeolite molecular sieve according to any one of claims 1-7, or the eutectic zeolite molecular sieve prepared by the preparation method according to any one of claims 8-14, or the eutectic zeolite molecular sieve composition according to claim 15 in an adsorbent or a catalyst.

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