A phosphate-aluminate material and its preparation method

Abstract

The present invention discloses a phosphoaluminate material and a preparation method thereof. For the phosphoaluminate material, in terms of molar ratio, Al2O3:P2O5 = (0.5 - 1.1):1. The XRD pattern of the phosphoaluminate material contains X-ray diffraction peaks at 2θ of 9.55±0.1, 15.17±0.1, 15.99±0.1, 17.69±0.1, 18.09±0.1, 20.10±0.1, 21.13±0.1, 21.78±0.1, 25.72±0.1, and the peak at 2θ of 9.55±0.1 is the strongest peak. The phosphoaluminate material provided by the present invention is a novel crystal 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 an aluminophosphate material and a preparation method thereof. Background Art

[0002] Molecular sieves are a class of porous crystalline materials that 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 sizes of the molecules, thereby obtaining certain selective adsorption and catalytic shape selectivity 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, thus forming many molecular sieves with various framework structures or various framework compositions.

[0003] In 1971, Flanigen et al. reported the synthesis of aluminophosphate molecular sieves (Molecular Sieve Zeolites-I, ACS, Washingtom D.C), which can be understood as the silicon-oxygen tetrahedra in zeolite molecular sieves being replaced 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 shows 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, a mixture of aluminum, silicon, and phosphorus oxides was used to obtain silicoaluminophosphate molecular sieves with the same crystal structures as analcime, chabazite, phil1ipsite-harmotome, L-type molecular sieve, A-type molecular sieve, B-type molecular sieve, etc., where 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 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 in-depth 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 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 / 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 potential for industrial applications.

[0004] Since different pore structures and elemental compositions determine the unique physical, chemical, and catalytic properties of molecular sieves, the development of aluminophosphate materials with special structures, including, is particularly important. Summary of the Invention

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

[0006] In the first aspect of the present invention, an aluminophosphate material is provided. In terms of molar ratio, its chemical composition is Al2O3∶P2O5 = (0.5 - 1.1)∶1. The XRD pattern of the aluminophosphate material contains X-ray diffraction peaks at 2θ = 9.55 ± 0.1, 15.17 ± 0.1, 15.99 ± 0.1, 17.69 ± 0.1, 18.09 ± 0.1, 20.10 ± 0.1, 21.13 ± 0.1, 21.78 ± 0.1, 25.72 ± 0.1, where the peak at 2θ = 9.55 ± 0.1 is the strongest peak.

[0007] Further, the XRD pattern of the aluminophosphate material contains the X-ray diffraction peaks shown in the following table:

[0008] 2θ (°) <![CDATA[Relative intensity, [(I / I0)×100]]]> 9.55±0.1 100 15.17±0.1 5-80 15.99±0.1 5-80 17.69±0.1 5-80 18.09±0.1 5-80 20.10±0.1 5-80 21.13±0.1 5-80 21.78±0.1 5-80 25.72±0.1 5-80 .

[0009] Further, the XRD pattern of the aluminophosphate material further includes X-ray diffraction peaks at 2θ = 13.78 ± 0.1, 24.87 ± 0.1, 29.95 ± 0.1, 31.29 ± 0.1, 32.59 ± 0.1, 32.83 ± 0.1.

[0010] Further, the XRD pattern of the aluminophosphate material further includes the X-ray diffraction peaks shown in the following table:

[0011] 2θ (°) <![CDATA[Relative intensity, [(I / I0)×100]]]> 13.78±0.1 3-50 24.87±0.1 3-50 29.95±0.1 3-50 31.29±0.1 3-50 32.59±0.1 3-50 32.83±0.1 3-50 .

[0012] The second aspect of the present invention provides a method for preparing the above aluminophosphate material, comprising:

[0013] a) Mixing an aluminophosphate precursor, an organic base R1, an organic compound R2, a fluorine source, water, and optionally an aluminum source A or a phosphorus source A to obtain a synthesis mother liquor;

[0014] b) Crystallizing the synthesis mother liquor obtained in step a), drying it without calcination to obtain the aluminophosphate material.

[0015] The aluminophosphate precursor has a chemical composition represented 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:

[0016] 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 。

[0017] Further, the XRD pattern of the aluminophosphate precursor further includes the X-ray diffraction peaks shown in the following table:

[0018]

[0019]

[0020] Further, the XRD pattern of the aluminophosphate precursor further includes the X-ray diffraction peaks shown in the following table:

[0021] 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 。

[0022] Further, in the synthesis mother liquor, the molar ratios of the respective materials are as follows: the aluminum source A is calculated as Al2O3, the phosphorus source A is calculated as P2O5, the aluminophosphate precursor is calculated as Al2O3 and P2O5, the organic base R1, the organic compound R2, the fluorine source is calculated as HF, and water is calculated as H2O, (0.5 - 0.88)Al2O3∶1P2O5∶(0.3 - 0.8)R1∶(1 - 2)R2∶(0.5 - 1.8)HF∶(50 - 130)H2O. Preferably, (0.5 - 0.85)Al2O3∶1P2O5∶(0.3 - 0.8)R1∶(1 - 2)R2∶(0.5 - 1.8)HF∶(50 - 130)H2O. Among them, the dosage of the optional aluminum source A or phosphorus source A is determined according to the amounts of Al2O3 and P2O5 in the aluminophosphate precursor, that is, when the amounts of Al2O3 and P2O5 provided by the aluminophosphate precursor meet the above ratio requirements, the aluminum source A and the phosphorus source A are not added. When the amount of Al2O3 or P2O5 provided by the aluminophosphate precursor cannot meet the above ratio requirements, the aluminum source A or the phosphorus source A is added to meet the above ratio requirements.

[0023] Further, the phosphorus source A is selected from at least one of phosphoric acid, ammonium monohydrogen phosphate, ammonium dihydrogen phosphate, etc.

[0024] Further, the aluminum source A is selected from one or more of pseudoboehmite, aluminum isopropoxide, aluminum sol, alumina, etc.

[0025] Further, the organic base R1 is one or more of tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, etc.

[0026] Further, the organic compound R2 is 6-N,N-dimethylaminohexyl-2-hydroxyethyldimethylammonium bromide, and its chemical structural formula is as follows:

[0027]

[0028] Further, the fluorine source is selected from HF aqueous solution.

[0029] Further, in step a), there is no particular limitation on the addition order of each material. Preferably, water, aluminum source A and the aluminophosphate precursor are first mixed evenly, then the organic compound R2 and the organic base R1 are added in sequence and mixed evenly, and then the fluorine source is added.

[0030] Further, in step b), the crystallization conditions are as follows: the crystallization temperature is 120°C - 200°C, and the crystallization time is 8 - 100 hours. Preferably, the crystallization temperature is 130°C - 190°C, and the crystallization time is 12 - 80 hours; or the segmented crystallization method is adopted. The first-stage crystallization temperature is 130°C - 190°C, and the crystallization time is 48 - 72 hours. Preferably, the crystallization temperature is 130°C - 160°C, and the crystallization time is 24 - 72 hours; the second-stage crystallization temperature is 160°C - 200°C, and the crystallization time is 4 - 24 hours. Preferably, the crystallization temperature is 170°C - 200°C, and the optimized crystallization time is 5 - 18 hours. Among them, the second-stage crystallization temperature is at least 10°C higher than the first-stage crystallization temperature, preferably at least 20°C higher.

[0031] Further, after the crystallization step in step b), an aluminophosphate material product can be separated from the obtained mixture by any conventional known separation method, such as separation and washing. Here, the separation and washing can be carried out in any conventional known manner in the art, and the separation is such as centrifugation or filtration, suction filtration.

[0032] Further, the drying conditions in step b) are as follows: the drying temperature is 40 - 120°C, preferably 50 - 80°C, and the drying time is 8 - 48 hours, preferably 12 - 36 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.

[0033] Further, the aluminophosphate material is obtained after drying in step b), wherein there is no calcination step after crystallization, that is, no calcination step above 300 °C.

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

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

[0036] Further, the aluminophosphate material or the aluminophosphate material 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 aluminophosphate material or the aluminophosphate material composition, and selectively adsorb this component.

[0037] Further, the aluminophosphate material or the aluminophosphate material composition can be used in a catalyst for organic matter conversion.

[0038] An aluminophosphate material of the present invention is a novel molecular sieve material, having special XRD diffraction peaks, which enriches the types of aluminophosphate materials. Description of the Drawings

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

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

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

[0042] Figure 4 SEM image of the aluminophosphate material obtained in Example 3;

[0043] Figure 5 XRD pattern of the aluminophosphate material obtained in Example 11;

[0044] Figure 6 SEM image of the aluminophosphate material obtained in Example 11;

[0045] Figure 7XRD pattern of the product obtained in Comparative Example 1;

[0046] Figure 8 XRD pattern of the product obtained in Comparative Example 2. Specific Embodiments

[0047] 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.

[0048] 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) produced by PANalytical B.V. in the Netherlands, using a Cu-Kα ray source with a Ka1 wavelength λ = 1.5405980 Å A nickel filter, with a working voltage of 40 kV, a current of 40 mA, and a scanning range of 3 - 50°.

[0049] In the present invention, the compositions of SiO2, Al2O3, and P2O5 in the molecular sieve are measured by an 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 elemental ratios in the sample.

[0050] The aluminophosphate precursor of the present invention has a schematic chemical composition as shown by 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:

[0051] 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

[0052] Furthermore, the XRD pattern of the aluminophosphate precursor further includes the X-ray diffraction peaks shown in the following table:

[0053] 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

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

[0055] 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

[0056] Furthermore, the preparation method of the aluminophosphate precursor of the present invention includes: subjecting a mixture containing an aluminum source B, a phosphorus source B, an organic template R A and an organic template R B , a solvent S1, a solvent S2, and a solvent S3 to a crystallization treatment to obtain the aluminophosphate precursor;

[0057] wherein, the organic template R AOne or more selected from quaternary ammonium salts or quaternary ammonium hydroxides; R B One or more selected from imidazoles 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.

[0058] Furthermore, 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, 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-pyrrolidinyl)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.

[0059] Furthermore, in the method for preparing 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.

[0060] Furthermore, in the method for preparing the aluminophosphate precursor, in the mixture, the aluminum source B is calculated as Al2O3, the phosphorus source B is calculated as P2O5, the organic template R A +R B 、solvent S1+52+S3 have the following molar composition: P2O5 / Al2O3 = 0.75 - 2.2, preferably 1 - 2; template R A +R B / Al2O3 = 1 - 80, preferably 5 - 50; solvent S1+S2+S3 / Al2O3 = 5 - 500, preferably 35 - 120.

[0061] Further, in the preparation method of 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.

[0062] Further, in the preparation method of the aluminophosphate precursor, the molar ratio of the solvent S1, solvent S2, and solvent S3 is 1:0.01 - 1:1 - 100, preferably 1:0.05 - 0.5:10 - 80.

[0063] Further, 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 B is selected from at least one of phosphoric acid, ammonium monohydrogen phosphate, and ammonium dihydrogen phosphate, preferably orthophosphoric acid.

[0064] Further, in the preparation method of the aluminophosphate precursor, before the crystallization treatment, stirring and aging treatments are first carried out. The stirring time is 0.5 - 5 h, and the aging treatment time is 1 - 12 h.

[0065] Further, 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.

[0066] Further, in the preparation method of the aluminophosphate precursor, after the crystallization treatment, conventional post - treatments are 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 at normal pressure or under reduced pressure. For energy conservation, it is usually carried out at normal pressure.

[0067] The technical solutions of the present invention will be described in detail below with reference to the embodiments.

[0068]

Example 1

[0069] 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 the molar ratio of solvent S1 (N,N-dibutylformamide)∶solvent S2 (cyclohexanone)∶solvent S3 (water) = 1∶0.5∶78.5; Place the above crystallization mixture B in a crystallization kettle with a polytetrafluoroethylene liner and crystallize at 140 °C for 5 d. After the product is filtered and washed, dry it 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:

[0070] Table 1

[0071] 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

[0072]

Example 2

[0073] 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:

[0074] Table 2

[0075] 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

[0076]

Example 3

[0077] Weigh 24 g of water, add 2.17 g of aluminum isopropoxide and 6 g of the aluminum phosphate 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. After stirring at room temperature for 3 h, add 1 g of 40 wt% HF solution. After stirring evenly, it was loaded into a high-pressure kettle with a polytetrafluoroethylene lining. Crystallize at 140 °C for 66 h; crystallize at 180 °C for 8 h. After cooling, centrifuge and separate, wash (the centrifugal washing operation is repeated 2 - 3 times), and dry at 60 °C for 32 h to obtain the aluminum phosphate material. Its chemical composition, in terms of molar ratio, is Al2O3∶P2O5 = 1∶1. The SEM image of this aluminum phosphate material is shown in Figure 4 , its morphology is an inclined cuboid. The XRD pattern of this aluminum phosphate material is shown in Figure 3 , that is, it includes the main X-ray diffraction peaks shown in Table 3 as follows:

[0078] Table 3

[0079] 2θ (°) <![CDATA[Relative intensity, [(I / I0)×100]]]> 9.55 100 15.17 21 15.99 19 17.69 27 18.09 22 20.10 20 21.13 25 21.78 32 25.72 22

[0080] It can be seen from Figure 3 that obvious X-ray diffraction peaks can also be seen at 2θ of 13.78, 24.87, 29.95, 31.29, 32.59, and 32.83, which are the characteristic peaks of the aluminum phosphate material of the present invention.

[0081]

Example 4

[0082] Weigh 24 g of water, add 1.55 g of pseudo-boehmite 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. Crystallize at 140 °C for 66 h; crystallize at 180 °C for 8 h. After cooling, centrifuge and separate, wash (the centrifugation and washing operations are repeated 2 - 3 times), and dry at 80 °C for 16 h to obtain the aluminophosphate material. Its chemical composition, in terms of molar ratio, is Al2O3∶P2O5 = 1∶1. The morphology of this aluminophosphate is similar to Figure 4 and presents an inclined cuboid morphology; the XRD pattern of this aluminophosphate material includes the main X-ray diffraction peaks shown in Table 4:

[0083] Table 4

[0084]

[0085]

[0086]

Example 5

[0087] Weigh 24 g of water, 0.93 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 3.3 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 140 °C for 66 h; crystallize at 180 °C for 8 h. After cooling, centrifuge and separate, wash (the centrifugation and washing operations are repeated 2 - 3 times), and dry at 80 °C for 18 h to obtain the aluminophosphate material. Its chemical composition, in terms of molar ratio, is Al2O3∶P2O5 = 0.9∶1. The morphology of this aluminophosphate is similar to Figure 4 and presents an inclined cuboid morphology; the XRD pattern of this aluminophosphate material includes the main X-ray diffraction peaks shown in Table 5:

[0088] Table 5

[0089]

[0090]

[0091]

Example 6

[0092] Weigh 24 g of water, 0.62 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 3.3 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 high-pressure autoclave with a Teflon liner. Crystallize at 140 °C for 66 h; crystallize at 180 °C for 8 h. After cooling, centrifuge and wash (the centrifugation and washing operations are repeated 2 - 3 times), and dry at 70 °C for 24 h to obtain the aluminophosphate material. Its chemical composition, in terms of molar ratio, is Al2O3∶P2O5 = 0.9∶1. The morphology of this aluminophosphate is similar to Figure 4 and presents an inclined cuboid morphology; the XRD pattern of this aluminophosphate material includes the main X-ray diffraction peaks shown in Table 6:

[0093] Table 6

[0094]

[0095]

[0096]

Example 7

[0097] Weigh 24 g of water, add 0.31 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 3.3 g of 25 wt% tetraethylammonium hydroxide solution. After stirring at room temperature for 3 h, add 0.43 g of 40 wt% HF solution. After stirring evenly, transfer it to a high-pressure autoclave with a Teflon liner. Crystallize at 140 °C for 66 h; crystallize at 180 °C for 8 h. After cooling, centrifuge and wash (the centrifugation and washing operations are repeated 2 - 3 times), and dry at 50 °C for 36 h to obtain the aluminophosphate material. Its chemical composition, in terms of molar ratio, is Al2O3∶P2O5 = 0.8∶1. The morphology of this aluminophosphate is similar to Figure 4 and presents an inclined cuboid morphology; the XRD pattern of this aluminophosphate material 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, 2.17 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 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 Teflon-lined autoclave. Crystallize at 140 °C for 66 h; crystallize at 180 °C for 8 h. After cooling, centrifuge and wash (the centrifugation and washing operations are repeated 2 - 3 times), and dry at 80 °C for 16 h to obtain the aluminophosphate material. Its chemical composition, in terms of molar ratio, is Al2O3∶P2O5 = 1∶1. The morphology of this aluminophosphate is similar to that of Figure 4 and shows an inclined cuboid morphology; the XRD pattern of this aluminophosphate material includes the main X-ray diffraction peaks shown in Table 8:

[0103] Table 8

[0104] 2θ (°) <![CDATA[Relative intensity, [(I / I0)×100]]]> 9.54 100 13.88 10 15.17 19 15.97 17 17.68 26 18.06 20 20.12 19 21.10 24 21.78 31 24.87 8 25.71 23 29.96 5 31.30 4 32.61 8 32.78 9

[0105]

Example 9

[0106] Weigh 24 g of water, 2.17 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 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 Teflon-lined autoclave. Crystallize at 140 °C for 66 h; crystallize at 180 °C for 8 h. After cooling, centrifuge and wash (the centrifugation and washing operations are repeated 2 - 3 times), and dry at 80 °C for 18 h to obtain the aluminophosphate material. Its chemical composition, in terms of molar ratio, is Al2O3∶P2O5 = 1∶1. The morphology of this aluminophosphate is similar to that of Figure 4 and shows an inclined cuboid morphology; the XRD pattern of this aluminophosphate material includes the main X-ray diffraction peaks shown in Table 9:

[0107] Table 9

[0108] 2θ (°) <![CDATA[Relative intensity, [(I / I0)×100]]]> 9.56 100 13.89 9 15.18 22 15.96 16 17.67 28 18.08 21 20.11 17 21.14 26 21.77 30 24.89 9 25.70 22 29.96 6 31.28 5 32.59 7 32.84 9

[0109]

Example 10

[0110] Weigh 24 g of water, add 2.17 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 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 24 h; after cooling, separate and wash (the centrifugal washing operation is repeated 2 - 3 times), and dry at 70 °C for 24 h to obtain the aluminophosphate material. Its chemical composition, in terms of molar ratio, is Al2O3∶P2O5 = 1∶1. The morphology of this aluminophosphate is similar to Figure 4 and shows an inclined cuboid morphology; the XRD pattern of this aluminophosphate material includes the main X-ray diffraction peaks shown in Table 10:

[0111] Table 10

[0112] 2θ (°) <![CDATA[Relative intensity, [(I / I0)×100]]]> 9.51 100 13.78 10 15.12 21 15.94 18 17.63 26 18.04 21 20.11 17 21.14 23 21.79 30 24.88 7 25.69 19 29.31 5 31.28 4 32.61 6 32.85 8

[0113]

Example 11

[0114] Weigh 24 g of water, add 2 g of diammonium hydrogen phosphate, dissolve it, and then add 2.73 g of aluminophosphate precursor B. 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. After stirring evenly, transfer it 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 and wash (the centrifugal washing operation is repeated 2 - 3 times), and dry at 70 °C for 24 h to obtain the aluminophosphate material. Its chemical composition, in terms of molar ratio, is Al2O3∶P2O5 = 0.95∶1. The morphology of this aluminophosphate is shown in Figure 6 and shows an inclined cuboid morphology; the XRD pattern of this aluminophosphate material is shown in Figure 5 and includes the main X-ray diffraction peaks shown in Table 11:

[0115] Table 11

[0116] 2θ (°) <![CDATA[Relative intensity, [(I / I0)×100]]]> 9.50 100 15.09 23 15.91 19 17.62 28 18.06 22 20.10 15 21.16 26 21.80 32 25.70 21

[0117] It can be seen from Figure 5 that obvious X-ray diffraction peaks can also be seen at 2θ of 13.79, 24.89, 29.94, 31.28, 32.56, and 32.81, which are the characteristic peaks of the aluminophosphate material described in the present invention.

[0118]

Example 12

[0119] Weigh 28 g of water, add 2.17 g of aluminum isopropoxide and 6 g of aluminophosphate precursor A, and stir at room temperature for 2 h; then add 7.8 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 1.3 g of 40 wt% HF solution. After stirring evenly, transfer it to a high-pressure autoclave with a Teflon liner. Crystallize at 160 °C for 36 h; crystallize at 200 °C for 5 h. After cooling, centrifuge and separate, wash (the centrifugation and washing operations are repeated 2 - 3 times), and dry at 70 °C for 24 h to obtain the aluminophosphate material. Its chemical composition, in terms of molar ratio, is Al2O3∶P2O5 = 1.1∶1. The morphology of this aluminophosphate is similar to that of Figure 4 and presents an inclined cuboid morphology; the XRD pattern of this aluminophosphate material includes the main X-ray diffraction peaks shown in Table 12:

[0120] Table 12

[0121]

[0122]

[0123]

Example 13

[0124] Weigh 28 g of water, add 2.17 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 g of 40 wt% HF solution. After stirring evenly, transfer it to a high-pressure autoclave with a Teflon liner. Crystallize at 130 °C for 72 h; crystallize at 190 °C for 8 h. After cooling, centrifuge and separate, wash (the centrifugation and washing operations are repeated 2 - 3 times), and dry at 70 °C for 24 h to obtain the aluminophosphate material. Its chemical composition, in terms of molar ratio, is Al2O3∶P2O5 = 0.98∶1. The morphology of this aluminophosphate is similar to that of Figure 4 and presents an inclined cuboid morphology; the XRD pattern of this aluminophosphate material includes the main X-ray diffraction peaks shown in Table 13:

[0125] Table 13

[0126]

[0127]

[0128]

Comparative Example 1

[0129] Weigh 24 g of water, add 5.4 g of aluminum isopropoxide, stir at room temperature for 1 h, then add 3.51 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 140 °C for 66 h; crystallize at 180 °C for 8 h. After cooling, centrifuge and wash (the centrifugation and washing operations are repeated 2 - 3 times), and dry at 60 °C for 32 h. The obtained product is not the aluminophosphate material described in the present invention, and its XRD pattern is shown in Figure 7 。

[0130]

Comparative Example 2

[0131] Weigh 24 g of water, add 2.17 g of aluminum isopropoxide and 6 g of aluminophosphate precursor A, 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. Stir at room temperature for 3 h, and then transfer it to a high-pressure autoclave with a Teflon liner. Crystallize at 140 °C for 66 h; crystallize at 180 °C for 8 h. After cooling, centrifuge and wash (the centrifugation and washing operations are repeated 2 - 3 times), and dry at 60 °C for 32 h. The obtained product is not the aluminophosphate material described in the present invention, and its XRD pattern is shown in Figure 8 。

Claims

1. A preparation method of a phosphoaluminate material, wherein, The chemical composition of the aluminophosphate material includes Al2O3:P2O5 = (0.5 - 1.1):

1. The XRD pattern of the aluminophosphate material contains X-ray diffraction peaks at 2θ = 9.55±0.1, 15.17±0.1, 15.99±0.1, 17.69±0.1, 18.09±0.1, 20.10±0.1, 21.13±0.1, 21.78±0.1, 25.72±0.1, where the peak at 2θ = 9.55±0.1 is the strongest peak; The preparation method of the aluminophosphate material described above includes: a) Mixing an aluminophosphate precursor, an organic base R1, an organic compound R2, a fluorine source, water, and optionally an aluminum source A or a phosphorus source A to obtain a synthesis mother liquor; 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; b) Crystallizing the synthesis mother liquor obtained in step a), drying it without calcination to obtain the aluminophosphate material described above; Among them, 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 shown in the following table: 。 2. The preparation method according to claim 1, wherein In step a), the XRD pattern of the aluminophosphate precursor further includes the X-ray diffraction peaks shown in the following table: 。 3. The preparation method according to claim 1, 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: 。 4. The preparation method according to claim 1, characterized in that, In the synthesis mother liquor described above, the molar ratios of each material are as follows: the aluminum source A is calculated as Al2O3, the phosphorus source A is calculated as P2O5, the aluminophosphate precursor is calculated as Al2O3, P2O5, the organic base R1, the organic compound R2, the fluorine source is calculated as HF, and water is calculated as H2O: (0.5 - 0.88)Al2O3:1P2O5:(0.3 - 0.8)R1:(1 - 2)R2:(0.5 - 1.8)HF:(50 - 130)H2O.

5. The preparation method according to claim 1, characterized in that, In the synthesis mother liquor described above, the molar ratios of each material are as follows: the aluminum source A is calculated as Al2O3, the phosphorus source A is calculated as P2O5, the aluminophosphate precursor is calculated as Al2O3, P2O5, the organic base R1, the organic compound R2, the fluorine source is calculated as HF, and water is calculated as H2O: (0.5 - 0.85)Al2O3:1P2O5:(0.3 - 0.8)R1:(1 - 2)R2:(0.5 - 1.8)HF:(50 - 130)H2O.

6. The preparation method according to claim 1, characterized in that The phosphorus source A is selected from at least one of phosphoric acid, ammonium monohydrogen phosphate, and ammonium dihydrogen phosphate; 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.

7. According to the preparation method described in any one of claims 1-6, characterized in that, In step b), the crystallization conditions are as follows: the crystallization temperature is 120°C - 200°C, and the crystallization time is 8 - 100 hours.

8. The preparation method according to claim 7, characterized in that In step b), the crystallization conditions are as follows: the crystallization temperature is 130°C - 190°C, and the crystallization time is 12 - 80 hours.

9. The preparation method according to any one of claims 1-6, characterized in that, In step b), the crystallization is carried out by a segmented crystallization method. The crystallization temperature in the first stage is 130°C - 190°C, and the crystallization time is 48 - 72 hours; the crystallization temperature in the second stage is 160°C - 200°C, and the crystallization time is 4 - 24 hours; wherein, the crystallization temperature in the second stage is at least 10°C higher than that in the first stage.

10. The preparation method according to claim 9, characterized in that, In step b), the crystallization is carried out by a segmented crystallization method. The crystallization temperature in the first stage is 130°C - 160°C; the crystallization temperature in the second stage is 170°C - 200°C, and the crystallization time is 5 - 18 hours; wherein, the crystallization temperature in the second stage is at least 20°C higher than that in the first stage.

11. According to the preparation method described in claim 1, characterized in that, The drying conditions in step b) are as follows: the drying temperature is 40 - 120°C, and the drying time is 8 - 48 hours.

12. The preparation method according to claim 11, wherein The drying conditions in step b) are as follows: the drying temperature is 50 - 80°C, and the drying time is 12 - 36 hours.

13. The preparation method according to claim 1, characterized in that, The XRD pattern of the aluminophosphate material contains the X-ray diffraction peaks shown in the following table: 。 14. The preparation method according to claim 13, characterized in that, The XRD pattern of the aluminophosphate material further includes X-ray diffraction peaks at 2θ of 13.78 ± 0.1, 24.87 ± 0.1, 29.95 ± 0.1, 31.29 ± 0.1, 32.59 ± 0.1, and 32.83 ± 0.

1.

15. The preparation method according to claim 14, characterized in that, The XRD pattern of the aluminophosphate material further includes the following X-ray diffraction peaks: 。 16. The aluminophosphate material prepared by the method according to any one of claims 1 - 15.

17. An aluminophosphate material composition comprising the aluminophosphate material according to claim 16 and a binder.

18. The application of the aluminophosphate material according to claim 16 or the aluminophosphate material composition according to claim 17 in an adsorbent or a catalyst.

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