A eutectic phosphoaluminate material and a preparation method thereof

Abstract

The present invention discloses a eutectic aluminophosphate material and a preparation method thereof. The chemical composition of the eutectic aluminophosphate material, in terms of molar ratio, is SiO2:Al2O3:P2O5 = 0 - 0.10:0.88 - 1.30:1. The XRD pattern of the eutectic aluminophosphate material contains a broad peak appearing between 2θ of 4.60 ± 0.05 and 5.70 ± 0.05, and X-ray diffraction peaks appearing at 2θ of 7.20 ± 0.1, 10.81 ± 0.1, 11.60 ± 0.1, 14.32 ± 0.1, 21.39 ± 0.1, 21.83 ± 0.1, 27.31 ± 0.1, 28.72 ± 0.1, where the peak at 2θ of 7.20 ± 0.1 is the strongest peak. The eutectic aluminophosphate material provided by the present invention is a novel eutectic material and can be applied in adsorbents or catalysts.

Description

Technical Field

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

[0002] Molecular sieves are a class of porous crystalline materials, which are widely used in chemical industries such as oil refining and catalysis. Different pore structures reflect 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, thus obtaining certain selective adsorption and catalytic shape selectivity effects. The framework of molecular sieves 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, thus 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 is electrically neutral. 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 is relatively late. Under hydrothermal synthesis conditions, a mixture of aluminum, silicon, and phosphorus oxides was used to obtain silicoaluminophosphate molecular sieves with the same crystal structures as analcime, chabazite, phillipsite-harmotome, L-type molecular sieve, A-type molecular sieve, and B-type molecular sieve, etc. The phosphorus content is 5% - 25% (calculated as P2O5), but no molecular sieve with a structure different from the known zeolite molecular sieves was found. The 1982 US Patent US 4310440 used organic amines or quaternary ammonium compounds as template 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 structure molecular sieves are constantly being synthesized. For the synthesis of aluminophosphate molecular sieves, the type of organic template agent is one of the key factors determining its structure. So far, organic amines are still the most widely used template 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 the 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 / A1PO-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. From the above, it can be seen that molecular sieves have great industrial application potential.

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

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

[0006] In the first aspect of the present invention, a eutectic aluminophosphate material is provided. In terms of molar ratio, its chemical composition is SiO2∶Al2O3∶P2O5 = 0 - 0.10∶0.88 - 1.30∶1. The XRD pattern of the eutectic aluminophosphate material contains a broad peak appearing between 2θ of 4.60 ± 0.05 and 5.70 ± 0.05; X-ray diffraction peaks appear at 2θ of 7.20 ± 0.1, 10.81 ± 0.1, 11.60 ± 0.1, 14.32 ± 0.1, 21.39 ± 0.1, 21.83 ± 0.1, 27.31 ± 0.1, and 28.72 ± 0.1, where the peak at 2θ of 7.20 ± 0.1 is the strongest peak.

[0007] Furthermore, in the XRD pattern of the eutectic aluminophosphate material, X-ray diffraction peaks appear at 2θ of 7.20 ± 0.1, 10.81 ± 0.1, 11.60 ± 0.1, 14.32 ± 0.1, 21.39 ± 0.1, 21.83 ± 0.1, 27.31 ± 0.1, and 28.72 ± 0.1, which are the characteristic peaks of SCM-38 molecular sieve. Among them, the peak at 2θ of 7.20 ± 0.1 is the strongest peak in the characteristic peaks of SCM-38 molecular sieve, and SCM-38 molecular sieve is a new type of molecular sieve; a broad peak appearing between 2θ of 4.60 ± 0.05 and 5.70 ± 0.05 is the characteristic peak of another new crystal material, namely crystal material B.

[0008] Further, the XRD pattern of the eutectic aluminophosphate material contains the X-ray diffraction peaks as shown in the following table:

[0009]

[0010]

[0011] Further, for the eutectic aluminophosphate material, in terms of molar ratio, its chemical composition is SiO2∶Al2O3∶P2O5 = 0 - 0.10: 0.88 - 1.30∶1. Preferably, SiO2∶Al2O3∶P2O5 = 0 - 0.09∶0.88 - 1.30∶1.

[0012] Further, the eutectic aluminophosphate material is a eutectic material of SCM-38 molecular sieve and crystal material B, where the SCM-38 molecular sieve accounts for 70% - 99% of the mass of the eutectic aluminophosphate material, further 75% - 96%, and the crystal material B accounts for 1% - 30% of the mass of the eutectic aluminophosphate material, further 4% - 25%.

[0013] The second aspect of the present invention provides a preparation method of the above-mentioned eutectic aluminophosphate material, including:

[0014] a) Mixing an aluminophosphate precursor, an organic base R1, an organic matter R2, a fluorine source, water, and optionally an aluminum source A and an optionally silicon source to obtain a synthesis mother liquor;

[0015] b) Crystallizing the synthesis mother liquor in step a) to obtain the eutectic aluminophosphate material.

[0016] Further, the aluminophosphate precursor has a chemical composition as shown in the formula "Al2O3: xP2O5", where 0.8 ≤ x ≤ 2; the XRD pattern of the aluminophosphate precursor mainly includes the X-ray diffraction peaks as shown in the following table:

[0017] 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

[0018] Further, the XRD pattern of the aluminophosphate precursor further includes the X-ray diffraction peaks as shown in the following table:

[0019]

[0020]

[0021] Further, the XRD pattern of the aluminophosphate precursor further includes the X-ray diffraction peaks as shown in the following table:

[0022] 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

[0023] 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 - 0.10)SiO2∶(0.88 - 1.30)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.

[0024] Further, in the molar ratios of the respective materials in the synthetic mother liquor, SiO2∶P2O5 = (0 - 0.10)∶1, preferably (0 - 0.09)∶1.

[0025] Further, the aluminum source A is selected from one or more of pseudoboehmite, aluminum isopropoxide, aluminum sol, alumina, etc.

[0026] Further, the silicon source is selected from one or more of silica sol, fumed silica, etc.

[0027] Further, the organic base R1 is one or more of tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, etc.

[0028] Further, the organic matter R2 is one or more of 6-N,N-dimethylaminohexyl-2-hydroxyethyldimethylammonium bromide, N,N,N',N'-tetramethylhexanediamine, triethylamine, or cyclohexylamine. Among them, the chemical structural formula of 6-N,N-dimethylaminohexyl-2-hydroxyethyldimethylammonium bromide is shown as follows:

[0029]

[0030] Further, the fluorine source is selected from aqueous HF solution.

[0031] Further, in step a), there is no particular limitation on the addition order of the respective materials. Preferably: first, water, optional aluminum source A, aluminophosphate precursor, and optional silicon source are mixed evenly, then organic matter R2 and organic base R1 are added in sequence and mixed evenly, and then the fluorine source is added.

[0032] Further, in step b), the crystallization conditions are as follows: the crystallization temperature is 170°C - 210°C, the crystallization time is 12 - 100 hours. Preferably, the crystallization temperature is 180°C - 200°C, and the crystallization time is 20 - 80 hours.

[0033] Furthermore, after the crystallization step in step b), the eutectic aluminophosphate 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, where the separation is such as centrifugation or filtration, suction filtration; the drying temperature can be optionally 40 - 120°C, preferably 50 - 80°C; as the drying time, 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 often selected to be carried out under normal pressure.

[0034] The third aspect of the present invention provides a eutectic aluminophosphate material composition, comprising the aluminophosphate eutectic material according to any of the foregoing aspects or the aluminophosphate eutectic material prepared by the preparation method of the aluminophosphate eutectic material according to any of the foregoing aspects, and a binder.

[0035] The fourth aspect of the present invention provides an application of a eutectic aluminophosphate material, which is the application of the aluminophosphate eutectic material according to any of the foregoing aspects, or the aluminophosphate eutectic material prepared by the preparation method of the aluminophosphate eutectic material according to any of the foregoing aspects, or the aluminophosphate eutectic material composition according to any of the foregoing aspects in an adsorbent or a catalyst.

[0036] Furthermore, the aluminophosphate eutectic material or its composition is 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. The specific manner is, for example, to bring the mixture into contact with the aluminophosphate eutectic material or the aluminophosphate eutectic material composition and selectively adsorb this component.

[0037] Furthermore, the eutectic aluminophosphate material or the aluminophosphate eutectic material composition can be used in a catalyst for the conversion of organic substances.

[0038] The eutectic aluminophosphate material of the present invention has a unique XRD diffraction pattern and is a eutectic material of two novel crystal materials, enriching the types of eutectic aluminophosphate materials. Description of the Drawings

[0039] Figure 1 XRD pattern of the aluminophosphate precursor obtained in Example 1;

[0040] Figure 2 XRD pattern of the aluminophosphate precursor obtained in Example 2;

[0041] Figure 3 XRD pattern of the eutectic aluminophosphate material obtained in Example 3;

[0042] Figure 4 XRD pattern of the eutectic aluminophosphate material obtained in Example 10;

[0043] Figure 5 XRD pattern of the eutectic aluminophosphate material obtained in Example 13;

[0044] Figure 6 XRD pattern of the eutectic aluminophosphate material obtained in Example 14;

[0045] Figure 7 XRD pattern of the eutectic aluminophosphate material obtained in Example 15;

[0046] Figure 8 XRD pattern of the product obtained in Comparative Example 1;

[0047] Figure 9 XRD pattern of the product obtained in Comparative Example 2;

[0048] Figure 10 XRD pattern of the product obtained in Comparative Example 3. Detailed Description of the Invention

[0049] The following provides a detailed description of the specific embodiments of the present invention. The protection scope of the present invention is not limited by these specific embodiments.

[0050] In the present invention, the structure of the molecular sieve is determined by the 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) produced by PANalytical B.V. in the Netherlands, using a Cu-Kα ray source, with the Kα1 wavelength λ = 1.5405980 Å A nickel filter is used, with a working voltage of 40 kV, a current of 40 mA, and a scanning range of 3 - 50°.

[0051] In the present invention, the compositions of SiO2, Al2O3, and P2O5 in the molecular sieve are measured by the ICP method. An inductively coupled plasma emission spectrometer of the Varian Analytical 725-ES type produced by Varian, Inc. in the United States is used to analyze the element ratios in the sample.

[0052] 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 following X-ray diffraction peaks shown in the table below:

[0053] 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

[0054] Further, the XRD pattern of the aluminophosphate precursor further includes the X-ray diffraction peaks shown in the following table:

[0055]

[0056]

[0057] Further, the XRD pattern of the aluminophosphate precursor further includes the X-ray diffraction peaks shown in the following table:

[0058] 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

[0059] Further, the method for preparing the aluminophosphate precursor of the present invention includes: crystallizing a mixture containing aluminum source B, phosphorus source, organic template R A and organic template R B , solvent S1, solvent S2 and solvent S3 to obtain the aluminophosphate precursor;

[0060] Wherein, the organic template R A is selected from one or more of quaternary ammonium salts or quaternary ammonium hydroxides; R B is selected from one or more of imidazole or pyrrolidine derivatives; solvent S1 is selected from one or more of amide solvents; solvent S2 is selected from one or more of cyclic organic solvents; S3 is selected from one or more of water or lower alcohols.

[0061] Further, in the method for preparing 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, 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, 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.

[0062] Further, in the method for preparing the aluminophosphate precursor, the organic template R A is preferably selected from one or more of tetraethylammonium bromide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide and tetrabutylammonium hydroxide; the organic template R BPreferably, it is 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.

[0063] Further, in the method for preparing the aluminophosphate precursor, in the mixture, the aluminum source B is calculated as Al2O3, the phosphorus source is calculated as P2O5, and the organic template R A +R B 、the molar composition of the solvent S1 + S2 + S3 is as follows: P2O5 / Al2O3 = 0.75 - 2.2, preferably 1 - 2; the template R A +R B / Al2O3 = 1 - 80, preferably 5 - 50; the solvent S1 + S2 + S3 / Al2O3 = 5 - 500, preferably 35 - 120.

[0064] Further, in the method for preparing the aluminophosphate precursor, the organic template R A and the organic template R B have a molar ratio of 0.01 - 1:1, preferably 0.1 - 0.25:1.

[0065] Further, in the method for preparing 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.

[0066] Further, in the method for preparing 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.

[0067] Further, in the method for preparing 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.

[0068] Further, in the method for preparing 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.

[0069] Further, in the preparation method of the aluminophosphate precursor, after the crystallization treatment, conventional post-treatment is carried out, such as 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 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 at normal pressure or under reduced pressure. To save energy, it is usually carried out at normal pressure.

[0070] The technical solutions of the present invention will be described in detail below with reference to the embodiments.

[0071]

Example 1

[0072] 38 g of aluminum nitrate [Al(NO3)3·9H2O] was dissolved in 43 mL of deionized water. Under stirring, 25.2 g of phosphoric acid (purity ≥ 85 wt%) and 151 g of tetrabutylammonium hydroxide (40 wt% aqueous solution) and 145.6 g of 1-(3-aminopropyl)imidazole were added. After stirring for 0.5 h and aging for 12 h, solution A was obtained. Then, 16 mL of N,N-dibutylformamide and 4.6 mL of cyclohexanone were added to solution A. After stirring for 3.5 h, it was placed in a heat treatment at 90°C for 8 h to form a uniform 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 was: Al2O3:P2O5:template agent R:solvent S = 1:2.1:7:40, and the template agent R A (tetrabutylammonium hydroxide):template agent R B (1-(3-aminopropyl)imidazole) = 0.2 (molar ratio), solvent S1 (N,N-dibutylformamide):solvent S2 (cyclohexanone):solvent S3 (water) = 1:0.5:78.5 (molar ratio); The above crystallization mixture B was placed in a crystallization kettle with a polytetrafluoroethylene inner liner and crystallized at 140°C for 5 days. The product was filtered, washed, and then dried at 80°C for 24 h to obtain the aluminophosphate precursor, denoted as A, for standby. Among them, in the aluminophosphate precursor A, Al2O3:P2O5 = 1:2. The XRD pattern of the aluminophosphate precursor A is shown in Figure 1 , that is, it includes the X-ray diffraction peaks shown in Table 1:

[0073] Table 1

[0074] 2θ (°) <![CDATA[Relative intensity, [(I / I0)×100]]]> 7.41 100 10.71 25 12.00 6 14.21 5 16.45 32 17.94 36 19.73 9 21.00 10 23.33 22 24.27 18 26.03 18 27.80 11 28.15 13 30.01 10 31.34 5 34.71 7 38.28 6

[0075]

Example 2

[0076] Take 33.3 g of aluminum sulfate [Al2(SO4)3·18H2O] and dissolve it 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 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, and the template agent R A (tetrabutylammonium hydroxide): template agent R B (1-(3-aminopropyl)imidazole) = 0.22 (molar ratio), and the molar ratio of solvent S1 (N,N-dibutylformamide)∶solvent S2 (cyclohexanone)∶solvent S3 (water) = 1∶0.3∶48; place the above mixture B in a crystallization kettle with a Teflon liner and crystallize at 140 °C for 5 d. After the product is filtered, washed, and dried at 80 °C for 24 h, an aluminophosphate precursor is obtained, denoted as B, for standby. Among them, in the aluminophosphate precursor B, Al2O3∶P2O5 = 1∶0.92. The XRD pattern of the aluminophosphate precursor B is shown in Figure 2 , that is, it includes the X-ray diffraction peaks shown in Table 2:

[0077] Table 2

[0078] 2θ (°) <![CDATA[Relative intensity, [(I / I0)×100]]]> 7.49 100 10.77 35 12.01 5 14.18 15 16.43 38 17.87 40 19.70 8 20.96 12 23.32 30 24.22 26 26.03 23 27.80 17 28.15 20 30.01 18 31.32 8 34.74 8 38.28 5

[0079]

Example 3

[0080] 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, and 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. After stirring evenly, load it into a high-pressure kettle with a Teflon liner and crystallize at 180 °C for 48 h; after cooling, centrifuge and separate, wash (the centrifugal washing operation is repeated 2 - 3 times), and dry to obtain a eutectic aluminophosphate material. Its chemical composition, calculated as a molar ratio, is Al2O3:P2O5 = 1.2∶1, where the mass content of SCM-38 is about 95%, and the mass content of crystal material B is about 5%. The XRD pattern of this eutectic aluminophosphate material is shown in Figure 3 , where a broad peak appears between 2θ of 4.62 and 5.70, and it also includes the main X-ray diffraction peaks shown in Table 3:

[0081] Table 3

[0082] 2θ (°) <![CDATA[Relative intensity, [(I / I0)×100]]]> 7.20 100 10.81 68 11.60 29 14.32 37 21.39 65 21.83 35 27.31 27 28.72 29

[0083]

Example 4

[0084] Weigh 24 g of water, add 1.24 g of pseudoboehmite and 6 g of aluminophosphate precursor A, and stir at room temperature for 1 h; then add 4.75 g of 6-N,N-dimethylaminohexyl-2-hydroxyethyldimethylammonium bromide, and then add 4.4 g of 25 wt% tetraethylammonium hydroxide solution. After stirring at room temperature for 3 h, add 1 g of 40 wt% HF solution. After stirring evenly, transfer it to a high-pressure autoclave with a Teflon liner and crystallize at 180 °C for 36 h; after cooling, centrifuge and separate, wash (the centrifugal washing operation is repeated 2-3 times), and dry to obtain a eutectic aluminophosphate material. Its chemical composition, in terms of molar ratio, is A12O3:P2O5 = 0.99:1, where the mass content of SCM-38 is about 92%, and the mass content of crystal material B is about 8%. In the XRD pattern of this eutectic aluminophosphate material, a broad peak appears between 2θ of 4.65 and 5.65, and it also includes the main X-ray diffraction peaks shown in Table 4:

[0085] Table 4

[0086]

[0087]

[0088]

Example 5

[0089] Weigh 24 g of water, 3.1 g of aluminum isopropoxide and 6 g of aluminophosphate precursor A, and stir at room temperature for 3 h; then add 7.12 g of 6-N,N-dimethylaminohexyl-2-hydroxyethyldimethylammonium bromide, and then add 4.4 g of 25 wt% tetraethylammonium hydroxide solution. After stirring at room temperature for 3 h, add 1 g of 40 wt% HF solution. After stirring evenly, transfer it to a high-pressure autoclave with a Teflon liner and crystallize at 180 °C for 36 h; after cooling, separate and wash (the centrifugal washing operation is repeated 2-3 times), and dry to obtain a eutectic aluminophosphate material. Its chemical composition, in terms of molar ratio, is Al2O3:P2O5 = 1.12:1, where the mass content of SCM-38 is about 96%, and the mass content of crystal material B is about 4%. In the XRD pattern of this eutectic aluminophosphate material, a broad peak appears between 2θ of 4.65 and 5.65, and it also includes the main X-ray diffraction peaks shown in Table 5:

[0090] Table 5

[0091] 2θ (°) <![CDATA[Relative intensity, [(I / I0)×100]]]> 7.22 100 10.79 63 11.58 25 14.33 34 21.40 60 21.82 32 27.33 28 28.69 29

[0092]

Example 6

[0093] Weigh 24 g of water, 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, and then add 4.4 g of 25 wt% tetraethylammonium hydroxide solution. After stirring at room temperature for 3 h, add 0.5 g of 40 wt% HF solution. After stirring evenly, transfer it to a Teflon-lined autoclave and crystallize at 190 °C for 24 h; after cooling, separate and wash (repeat the centrifugal washing operation 2 - 3 times), and dry to obtain a eutectic aluminophosphate material. Its chemical composition, in terms of molar ratio, is Al2O3∶P2O5 = 1.05∶1, where the mass content of SCM-38 is about 89%, and the mass content of crystal material B is about 11%. In the XRD pattern of this eutectic aluminophosphate material, a broad peak appears between 2θ of 4.65 and 5.70, and it also includes the main X-ray diffraction peaks shown in Table 6:

[0094] Table 6

[0095] 2θ (°) <![CDATA[Relative intensity, [(I / I0)×100]]]> 7.21 100 10.80 67 11.60 29 14.32 37 21.39 65 21.83 35 27.31 27 28.72 29

[0096]

Example 7

[0097] Weigh 24 g of water, 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, and then add 6.2 g of 25 wt% tetraethylammonium hydroxide solution. After stirring at room temperature for 3 h, add 1.3 g of 40 wt% HF solution. After stirring evenly, transfer it to a Teflon-lined autoclave and crystallize at 180 °C for 36 h; after cooling, separate and wash (repeat the centrifugal washing operation 2 - 3 times), and dry to obtain a eutectic aluminophosphate material. Its chemical composition, in terms of molar ratio, is Al2O3∶P2O5 = 0.9∶1, where the mass content of SCM-38 is about 94%, and the mass content of crystal material B is about 6%. In the XRD pattern of this eutectic aluminophosphate material, a broad peak appears between 2θ of 4.65 and 5.69, and it also includes the main X-ray diffraction peaks shown in Table 7:

[0098] Table 7

[0099]

[0100]

[0101]

Example 8

[0102] Weigh 24 g of water, 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, and then add 2.73 g of 25 wt% tetramethylammonium hydroxide solution. After stirring at room temperature for 3 h, add 1 g of 40 wt% HF solution. After stirring evenly, transfer it to a high-pressure autoclave with a Teflon liner. Crystallize at 180 °C for 36 h; after cooling, separate, wash (repeat the centrifugal washing operation 2 - 3 times), and dry to obtain a eutectic aluminophosphate material. Its chemical composition, in terms of molar ratio, is Al2O3∶P2O5 = 1.1∶1, where the mass content of SCM-38 is about 90%, and the mass content of crystal material B is about 10%; in the XRD pattern of this eutectic aluminophosphate material, a broad peak appears between 2θ of 4.65 and 5.68, and it also includes the X-ray diffraction peaks shown in Table 8:

[0103] Table 8

[0104] 2θ (°) <![CDATA[Relative intensity, [(I / I0)×100]]]> 7.19 100 10.83 53 11.62 30 14.35 35 21.37 61 21.84 28 27.30 21 28.73 28

[0105]

Example 9

[0106] Weigh 24 g of water, 3.1 g of aluminum isopropoxide, and 6 g of aluminophosphate precursor A, and stir at room temperature for 3 h; then add 4.75 g of 6-N,N-dimethylaminohexyl-2-hydroxyethyldimethylammonium bromide, and then add 6.1 g of 25 wt% tetrapropylammonium hydroxide solution. After stirring at room temperature for 3 h, add 1 g of 40 wt% HF solution. After stirring evenly, transfer it to a high-pressure autoclave with a Teflon liner. Crystallize at 180 °C for 48 h; after cooling, centrifuge to separate, wash and dry to obtain a eutectic aluminophosphate material. Its chemical composition, in terms of molar ratio, is Al2O3:P2O5 = 1.13∶1, where the mass content of SCM-38 is about 65%, and the mass content of crystal material B is about 35%. In the XRD pattern of this eutectic aluminophosphate material, a broad peak appears between 2θ of 4.65 and 5.71, and it also includes the main X-ray diffraction peaks shown in Table 9:

[0107] Table 9

[0108] 2θ (°) <![CDATA[Relative intensity, [(I / I0)×100]]]> 7.23 100 10.79 44 11.58 29 14.28 35 21.44 51 21.81 28 27.33 22 28.76 25

[0109]

Example 10

[0110] 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% 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, put it into a high-pressure autoclave with a Teflon liner, and crystallize at 180 °C for 48 h; after cooling, separate and wash (repeat the centrifugal washing operation 2-3 times), dry to obtain the eutectic aluminophosphate material. Its chemical composition, in terms of molar ratio, is SiO2∶Al2O3∶P2O5 = 0.07:1.18∶1, where the mass content of SCM-38 is about 93%, and the mass content of crystal material B is about 7%; the XRD pattern of this eutectic aluminophosphate material is shown in Figure 4 , in which a broad peak appears between 2θ of 4.65 and 5.66, and also includes the main X-ray diffraction peaks shown in Table 10:

[0111] Table 10

[0112]

[0113]

[0114]

Example 11

[0115] Weigh 24 g of water, add 2.45 g of aluminum isopropoxide, then add 6 g of aluminophosphate precursor A, and stir at room temperature for 3 h; then 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 3 h, add 1 g of 40 wt% HF solution, stir evenly, put it into a high-pressure autoclave with a Teflon liner, and crystallize at 180 °C for 36 h; after cooling, separate and wash (repeat the centrifugal washing operation 2-3 times), dry to obtain the eutectic aluminophosphate material. Its chemical composition, in terms of molar ratio, is Al2O3∶P2O5 = 0.90:1, where the mass content of SCM-38 is about 88%, and the mass content of crystal material B is about 12%; in its XRD pattern, a broad peak appears between 2θ of 4.65 and 5.65, and also includes the main X-ray diffraction peaks shown in Table 11:

[0116] Table 11

[0117] 2θ (°) <![CDATA[Relative intensity, [(1 / I0)×100]]]> 7.21 100 10.82 63 11.63 31 14.35 35 21.40 64 21.81 38 27.32 29 28.70 35

[0118]

Example 12

[0119] Weigh 24 g of water, add 3.72 g of aluminum isopropoxide, then add 6 g of aluminophosphate precursor A, and stir at room temperature for 3 h; then add 4.75 g of 6-N,N-dimethylaminohexyl-2-hydroxyethyldimethylammonium bromide, and then add 5.28 g of 25 wt% tetraethylammonium hydroxide aqueous solution. After stirring at room temperature for 3 h, add 1 g of 40 wt% HF solution. After stirring evenly, transfer it to a high-pressure autoclave with a Teflon liner and crystallize at 180 °C for 36 h; after cooling, separate and wash (repeat the centrifugal washing operation 2-3 times), and dry to obtain a eutectic aluminophosphate material. Its chemical composition, in terms of molar ratio, is Al2O3∶P2O5 = 1.2∶1, where the mass content of SCM-38 is about 80%, and the mass content of crystal material B is about 20%; in its XRD pattern, a broad peak appears between 2θ of 4.65 and 5.69, and it also includes the main X-ray diffraction peaks shown in Table 12:

[0120] Table 12

[0121] 2θ (°) <![CDATA[Relative intensity, [(I / I0)×100]]]> 7.20 100 10.83 58 11.64 35 14.33 40 21.37 62 21.79 33 27.34 28 28.69 33

[0122]

Example 13

[0123] Weigh 27 g of water, add 4.3 g of aluminum isopropoxide and 6 g of aluminophosphate precursor A, and stir at room temperature for 3 h; then add 1.6 g of triethylamine, and then add 6.2 g of 25 wt% tetraethylammonium hydroxide solution. After stirring at room temperature for 3 h, add 1 g of 40 wt% HF solution. After stirring evenly, transfer it to a high-pressure autoclave with a Teflon liner. Crystallize at 180 °C for 24 h; after cooling, centrifuge and separate, wash (repeat the centrifugal washing operation 2-3 times), and dry to obtain a eutectic aluminophosphate material. Its chemical composition, in terms of molar ratio, is Al2O3:P2O5 = 1.24∶1, where the mass content of SCM-38 is about 83%, and the mass content of crystal material B is about 17%; the XRD pattern of this eutectic zeolite is shown in Figure 5 , where a broad peak appears between 2θ of 4.65 and 5.68, and it also includes the main X-ray diffraction peaks shown in Table 13:

[0124] Table 13

[0125]

[0126]

[0127]

Example 14

[0128] Weigh 27 g of water, add 3.1 g of aluminum isopropoxide and 6 g of aluminophosphate precursor A, and stir at room temperature for 3 h; then add 2.72 g of N,N,N',N'-tetramethylhexanediamine, and then add 4.4 g of 25 wt% tetraethylammonium hydroxide aqueous solution. After stirring at room temperature for 3 h, add 1 g of 40 wt% HF solution. After stirring evenly, transfer it to a high-pressure autoclave with a Teflon liner and crystallize at 180 °C for 24 h; after cooling, separate and wash (the centrifugal washing operation is repeated 2 - 3 times), and dry to obtain a eutectic aluminophosphate material. Its chemical composition, in terms of molar ratio, is Al2O3:P2O5 = 1.19:1, where the mass content of SCM-38 is about 77%, and the mass content of crystal material B is about 23%. The XRD pattern of this eutectic zeolite is shown in Figure 6 , where a broad peak appears between 2θ of 4.57 and 5.68, and it also includes the main X-ray diffraction peaks shown in Table 14:

[0129] Table 14

[0130] 2θ (°) <![CDATA[Relative intensity, [(I / I0)×100]]]> 7.22 100 10.80 52 11.59 40 14.33 31 21.36 51 21.82 27 27.31 40 28.78 31

[0131]

Example 15

[0132] Weigh 24 g of water, add 2.73 g of aluminophosphate precursor B, and stir at room temperature for 3 h; then add 4.75 g of 6-N,N-dimethylaminohexyl-2-hydroxyethyldimethylammonium bromide, and then add 0.5 g of 25 wt% tetraethylammonium hydroxide aqueous solution. After stirring at room temperature for 3 h, add 1 g of 40 wt% HF solution. After stirring evenly, transfer it to a high-pressure autoclave with a Teflon liner and crystallize at 180 °C for 48 h; after cooling, separate and wash (the centrifugal washing operation is repeated 2 - 3 times), and dry to obtain a eutectic aluminophosphate material. Its chemical composition, in terms of molar ratio, is Al2O3:P2O5 = 1.19:1, where the mass content of SCM-38 is about 85%, and the mass content of crystal material B is about 15%. The XRD pattern of this eutectic aluminophosphate material is shown in Figure 7 , where a broad peak appears between 2θ of 4.58 and 5.66, and it also includes the main X-ray diffraction peaks shown in Table 15:

[0133] Table 15

[0134] 2θ (°) <![CDATA[Relative intensity, [(I / I0)×100]]]> 7.22 100 10.81 41 11.60 21 14.32 25 21.39 35 21.81 20 27.36 20 28.79 22

[0135]

Comparative Example 1

[0136] Weigh 24 g of water, add 9.3 g of aluminum isopropoxide, stir at room temperature for 2 h, then add 5.27 g of phosphoric acid, and stir at room temperature for 3 h; 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 3 h, add 1 g of 40 wt% HF solution. After stirring evenly, transfer it to a high-pressure autoclave with a Teflon liner. Crystallize at 180 °C for 48 h; after cooling, centrifuge, wash and dry. The obtained product is not a eutectic molecular sieve containing SCM-38 molecular sieve, and its XRD diffraction pattern is as shown in Figure 8 shown.

[0137]

Comparative Example 2

[0138] Weigh 24 g of water, add a mixture A of 3.1 g of aluminum isopropoxide and 6 g of aluminophosphate precursor, stir at room temperature for 3 h; add 4.75 g of 6-N,N-dimethylaminohexyl-2-hydroxyethyldimethylammonium bromide, and after stirring at room temperature for 3 h, add 1 g of 40 wt% HF solution. After stirring evenly, transfer it to a high-pressure autoclave with a Teflon liner. Crystallize at 180 °C for 48 h; after cooling, centrifuge, wash and dry. The obtained product does not have the characteristic peaks of the eutectic molecular sieve of the present invention, and its XRD diffraction pattern is as shown in Figure 9 shown.

[0139]

Comparative Example 3

[0140] Weigh 24 g of water, add a mixture A of 3.1 g of aluminum isopropoxide and 6 g of aluminophosphate precursor, stir at room temperature for 3 h; 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 3 h, transfer it to a high-pressure autoclave with a Teflon liner. Crystallize at 180 °C for 48 h; after cooling, separate, wash (the centrifugal washing operation is repeated 2-3 times), and dry. The obtained product does not have the characteristic peaks of the eutectic molecular sieve of the present invention, and its XRD diffraction pattern is as shown in Figure 10 shown.

Claims

1. A eutectic phosphoaluminate material, characterized in that, The chemical composition of the eutectic aluminophosphate material is, in terms of molar ratio, SiO2:Al2O3:P2O5 = 0 - 0.10:0.88 - 1.30:

1. The XRD pattern of the eutectic aluminophosphate material contains a broad peak appearing between 2θ of 4.60 ± 0.05 and 5.70 ± 0.05; X-ray diffraction peaks appear at 2θ of 7.20 ± 0.1, 10.81 ± 0.1, 11.60 ± 0.1, 14.32 ± 0.1, 21.39 ± 0.1, 21.83 ± 0.1, 27.31 ± 0.1, 28.72 ± 0.1, and the peak at 2θ of 7.20 ± 0.1 is the strongest peak.

2. The eutectic aluminophosphate material according to claim 1, characterized in that, The chemical composition of the eutectic aluminophosphate material includes, in terms of molar ratio: SiO2:Al2O3:P2O5 = 0 - 0.09:0.88 - 1.30:

1.

3. The eutectic aluminophosphate material according to claim 1, wherein The XRD pattern of the eutectic aluminophosphate material contains the X-ray diffraction peaks shown in the following table: 。 4. The eutectic aluminophosphate material according to any one of claims 1-3, characterized in that The eutectic aluminophosphate material is a eutectic material of SCM-38 zeolite and crystal material B, where SCM-38 zeolite accounts for 70% - 99% of the mass of the eutectic aluminophosphate material, and crystal material B accounts for 1% - 30% of the mass of the eutectic aluminophosphate material.

5. The eutectic aluminophosphate material according to any one of claims 1-3, characterized in that, The eutectic aluminophosphate material is a eutectic material of SCM-38 zeolite and crystal material B, where SCM-38 zeolite accounts for 75% - 96% of the mass of the eutectic aluminophosphate material, and crystal material B accounts for 4% - 25% of the mass of the eutectic aluminophosphate material.

6. The preparation method of the eutectic aluminophosphate material according to any one of claims 1 - 5, comprising: a) Mixing an aluminophosphate precursor, an organic base R1, an organic compound R2, a fluorine source, water, and optionally an aluminum source A and an optionally silicon source to obtain a synthesis mother liquor; b) Crystallizing the synthesis mother liquor obtained in step a) to obtain the eutectic aluminophosphate material; wherein, the organic base R1 is one or more of tetramethylammonium hydroxide, tetraethylammonium hydroxide, and tetrapropylammonium hydroxide; the organic compound R2 is one or more of 6-N,N-dimethylaminohexyl-2-hydroxyethyldimethylammonium bromide, N,N,N,’N’-tetramethylhexanediamine, triethylamine, or cyclohexylamine; 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: 。 7. The preparation method according to claim 6, characterized in that, In step a), the XRD pattern of the aluminophosphate precursor further includes the X-ray diffraction peaks shown in the following table: 。 8. The preparation method according to claim 6, characterized in that, In step a), the XRD pattern of the aluminophosphate precursor further includes the X-ray diffraction peaks shown in the following table: 。 9. The preparation method according to claim 6, characterized in that, In the synthetic mother liquor described above, the molar ratios of each material 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 - 0.1)SiO2: (0.88 - 1.3)Al2O3: 1P2O5: (0.3 - 0.8)R1: (1 - 2)R2: (0.5 - 1.8)HF: (50 - 130)H2O.

10. The preparation method according to claim 6, characterized in that, The silicon source is selected from one or more of silica sol and fumed silica; the aluminum source A is selected from one or more of pseudo-boehmite, aluminum isopropoxide, aluminum sol, and alumina; the fluorine source is selected from HF aqueous solution.

11. According to the preparation method described in any one of claims 6-10, characterized in that, In step b), the crystallization conditions are as follows: the crystallization temperature is 170°C - 210°C, and the crystallization time is 12 - 100 hours.

12. The preparation method according to claim 11, wherein, In step b), the crystallization conditions are as follows: the crystallization temperature is 180°C - 200°C, and the crystallization time is 20 - 80 hours.

13. A eutectic aluminophosphate composition, comprising the eutectic aluminophosphate according to any one of claims 1 - 5 or the eutectic aluminophosphate prepared by the preparation method according to any one of claims 6 - 12, and a binder.

14. The application of the eutectic aluminophosphate according to any one of claims 1 - 5, or the eutectic aluminophosphate prepared by the preparation method according to any one of claims 6 - 12, or the eutectic aluminophosphate composition according to claim 13 in an adsorbent or a catalyst.

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