Metal aluminum phosphate molecular sieve and synthesis method thereof

Abstract

The invention discloses a metal aluminum phosphate molecular sieve and a synthesis method thereof. The molecular sieve has the following chemical composition in molar ratio: Al2O3: xSiO2: yP2O5: zMeO, Me is a group VIII metal element, x is more than or equal to 0 and less than or equal to 0.5, y is more than or equal to 0.5 and less than or equal to 2, z is more than or equal to 0.1 and less than or equal to 1, and the molecular sieve has special XRD diffraction data and is a novel molecular sieve. The metal aluminophosphate molecular sieve can be used as an adsorbent or a catalyst component.

Description

Technical Field

[0001] The invention belongs to the field of catalysts, and in particular relates to a metal aluminum phosphate molecular sieve and a synthesis method thereof. Background Art

[0002] Since the discovery of molecular sieve crystal materials in the 18th century, after several centuries of research and development, this type of material has achieved extraordinary technical results in the fields of adsorption separation, heterogeneous catalysis, carriers of various guest molecules and ion exchange, and has produced a wide range of application bases. Especially with the rapid development of petrochemicals in the 20th century, molecular sieve catalytic materials have become the cornerstone of human production and life. According to the definition of the International Union of Pure and Applied Chemistry (IUPAC), traditional zeolite molecular sieves are a crystalline silicate material, generally composed of silicon-oxygen tetrahedrons [SiO4] 4- and aluminum oxide tetrahedron [AlO4] 5- They are connected by shared oxygen atoms and are collectively called TO4 tetrahedrons (primary structural units). The silicon element can also be replaced by other elements, especially some trivalent or tetravalent elements such as Al, B, Ga, Ge, Ti, etc. A key factor in determining the application performance of molecular sieves is their pore or cage characteristics. The pore diameter of this type of material is generally less than 2nm, and it is classified as microporous materials. In physical and chemical reactions, the substances entering the molecular sieve can be "screened" according to their molecular intrinsic spatial size, so as to carry out corresponding selective adsorption and catalytic shape-selective applications. "Molecular sieve" is named after this. Furthermore, obtaining molecular sieves with new crystal structures is of great significance for the development of molecular sieve applications.

[0003] In 1982, materials scientists ST Wilson and EMFlanigen (US 4310440) of Union Carbide Corporation (UCC) of the United States successfully developed a new family of molecular sieves - aluminum phosphate molecular sieve AlPO4-n using aluminum source, phosphorus source and organic template, where n represents the model (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.). The framework of this type of molecular sieve is composed of AlO4 - and PO4 +The molecular sieve framework is electrically neutral as a whole. Similar to traditional zeolite molecular sieves, the aluminum-oxygen tetrahedron or phosphorus-oxygen tetrahedron in aluminum phosphate molecular sieves can also be replaced by other tetrahedrons. Therefore, based on AlPO4-n, UCC used Si atoms to partially replace the Al atoms and P atoms in the aluminum phosphate molecular sieve framework in 1984, and successfully prepared another series of silicon-aluminum phosphate molecular sieves: SAPO-n, where n represents the model (US4440871, US4499327). After the Si atoms in the structure replace the P and Al atoms in the original AlPO, a non-neutral molecular sieve framework composed of SiO4, AlO4 and PO4 tetrahedrons is formed. Among the SAPO-n molecular sieves, it is worth mentioning that the SAPO-34 molecular sieve whose topological structure is CHA, contains a three-dimensional cross structure of an ellipsoidal supercage and an 8-membered ring channel in its skeleton structure. The pore diameter of the 8-membered ring channel is about 0.38 nm, and the pore diameter of the supercage is maintained between 0.43 and 0.50 nm. Because of its excellent selectivity for low-carbon olefins such as ethylene and propylene due to its pore structure, and the appropriate amount of skeleton silicon atoms makes its structure have suitable proton acidity, good thermal stability and good hydrothermal stability. Thanks to this, the SAPO-34 molecular sieve has been successfully commercialized as a catalyst for methanol to low-carbon olefins (MTO) ("Recent Progress in Methanol-to-Olefins (MTO) Catalysts", M. Yang, D. Fan, YX. Wei, P. Tian, ​​ZM. Liu, Adv. Mater. 2019, 1902181).

[0004] Up to now, according to the website of the International Molecular Sieve Association (http: / / www.iza-structure.org), including the newly obtained AlPO-91 molecular sieve with ANO topological structure ("Crystalline metallophosphates, their method of preparation, and use", Yuhas, BD, Wilson, KN, Sylejmani-Rekaliu, M., Mowat, JPS, Sinkler, W., US Patent 10,336,622B1 (2019)), there are a total of 248 molecular sieves with different complete and stable topological structures. Although many different crystalline molecular sieves have been obtained, there is still a need for new molecular sieves with desired properties for gas separation and drying, hydrocarbon conversion reactions and other applications. Summary of the invention

[0005] In order to solve the above problems in the prior art, the present invention provides a novel metal aluminum phosphate molecular sieve and a synthesis method thereof.

[0006] In a first aspect, the present invention provides a metal aluminum phosphate molecular sieve having a chemical composition in the following molar ratio: Al2O3:xSiO2:yP2O5:zMeO, wherein Me is a metal element of Group VIII, 0≤x≤0.5, 0.5≤y≤2, 0.1≤z≤1; the molecular sieve comprises the XRD diffraction data shown in the following table:

[0007] 2θ(°) <![CDATA[Relative intensity, [(I / I0)×100]]]> 5.88±0.2 100 10.67±0.1 5-50 17.85±0.1 5-50 23.12±0.05 5-50 28.08±0.02 5-50 34.71±0.01 5-50

[0008] Among them, the incident ray of X-ray diffraction is Cu Kα1.

[0009] Furthermore, the molecular sieve also includes XRD diffraction data as shown in the following table:

[0010] 2θ(°) <![CDATA[Relative intensity, [(I / I0)×100]]]> 7.56±0.1 20-80 13.72±0.1 5-50 19.68±0.1 5-50 25.92±0.05 5-50 31.22±0.02 5-50

[0011] Among them, the incident ray of X-ray diffraction is Cu Kα1.

[0012] Furthermore, the molecular sieve further comprises XRD diffraction data shown in the following table:

[0013] 2θ(°) <![CDATA[Relative intensity, [(I / I0)×100]]]> 16.46±0.1 5-50 20.90±0.1 5-50 24.50±0.05 5-50 27.66±0.05 5-50 32.91±0.01 5-50 38.21±0.01 5-50

[0014] Among them, the incident ray of X-ray diffraction is Cu Kα1.

[0015] Furthermore, in the metal aluminum phosphate molecular sieve, the Me is at least one of Fe, Co, and Ni.

[0016] Furthermore, the molecular sieve has a rod-like morphology with a length of 2.5 to 5.5 μm and a width of 0.5 to 1.0 μm.

[0017] The second aspect of the present invention provides a method for preparing the above-mentioned metal aluminum phosphate molecular sieve, comprising mixing an aluminum source, a metal source, a phosphorus source, an organic template, a solvent and optionally a silicon source to obtain a crystallized mixture and subjecting it to crystallization treatment to obtain the metal aluminum phosphate molecular sieve.

[0018] Furthermore, in the method for preparing the molecular sieve, the optional silicon source means that the silicon source may or may not be added.

[0019] Furthermore, in the crystallization mixture, the molar compositions of the aluminum source calculated as Al2O3, the metal source calculated as MeO, the silicon source calculated as SiO2, the phosphorus source calculated as P2O5, the organic template and the solvent are as follows: SiO2 / Al2O3=0~1, preferably 0.05~0.5; and / or, MeO / Al2O3=0.1~1, preferably 0.25~0.75; and / or, P2O5 / Al2O3=0.5~2, preferably 0.75~1.5; and / or, organic template / Al2O3=1~1000, preferably 15~150; and / or, solvent / Al2O3=20~1000, preferably 50~200.

[0020] Furthermore, the organic template includes template R1 and template R2, and the molar ratio of template R1 to template R2 is (0.1-1):1, preferably (0.2-0.5):1.

[0021] Further, the aluminum source is selected from at least one of aluminum isopropoxide, aluminates, metaaluminates, aluminum hydroxides, aluminum oxides and aluminum-containing minerals; and / or, the metal source is selected from at least one of sulfates, nitrates, acetates, halides, oxides, hydroxides and minerals of the corresponding metals; and / or, the silicon source is selected from at least one of organosilicon, solid silicon oxide, silica sol, diatomaceous earth and water glass; and / or, the phosphorus source is selected from at least one of phosphoric acid, monoammonium hydrogen phosphate and diammonium phosphate.

[0022] Further, preferably, the aluminum source is selected from one of aluminum isopropoxide, aluminum sulfate, and aluminum nitrate; and / or, the metal source is selected from one of the acetates of the corresponding metals; and / or, the silicon source is selected from one of silica sol and solid silicon oxide; and / or, the phosphorus source is selected from phosphoric acid.

[0023] Further, the template agent R1 is selected from one of tetraethylammonium bromide, tetraethylammonium hydroxide, tetrapropylammonium bromide, tetrapropylammonium hydroxide, tetrabutylammonium bromide, and tetrabutylammonium hydroxide; and / or, the template agent R2 is selected from one of imidazole, 2-methylimidazole, 4-methylimidazole, 1-(3-aminopropyl)imidazole, 1-isopropylimidazole, N-n-butylimidazole, 2-ethyl-4-methylimidazole, and 1,3-bis(1-adamantyl)imidazole hydroxide; in some embodiments, the template agent R1 is selected from tetraethylammonium hydroxide, tetrapropylammonium hydroxide, and tetrabutylammonium hydroxide; and / or, the template agent R2 is selected from 1-(3-aminopropyl)imidazole, 1-isopropylimidazole, and 2-ethyl-4-methylimidazole. In some preferred embodiments, the template agent R1 is selected from tetraethylammonium hydroxide; and / or, the template agent R2 is selected from 1-(3-aminopropyl)imidazole.

[0024] Further, the solvent is selected from one or more of N,N-dimethylformamide, N,N-dimethylacetamide, N,N-diethylformamide, N,N-dibutylformamide, ethanol, ethylene glycol, butanol and water. In some preferred embodiments, the solvent is selected from deionized water.

[0025] In some embodiments, in the preparation method, the aluminum source, metal source, phosphorus source, organic template, solvent and optionally silicon source are stirred and mixed, and the stirring time is 1 to 12 hours.

[0026] Furthermore, in the preparation method, stirring and precipitation treatments are performed before crystallization treatment.

[0027] Furthermore, in the preparation method, the aluminum source, metal source, phosphorus source, organic template, and solvent are preferably mixed and precipitated, and then an optional silicon source is added, stirred and mixed to obtain a crystallized mixture for crystallization treatment to obtain a metal aluminum phosphate molecular sieve.

[0028] In some embodiments, in the preparation method, the precipitation is static precipitation, and the precipitation treatment time is 1 to 12 hours.

[0029] Furthermore, before obtaining the crystallized mixture, a step is performed, namely precipitation, and then an optional silicon source is added, stirred and mixed, and then heat-treated to obtain a heat-treated crystallized mixture. Furthermore, the heat treatment temperature is 80° C. to 120° C., and the time is 1 to 12 hours.

[0030] Furthermore, the conditions of the crystallization treatment include: a crystallization temperature of 140 to 200° C., preferably 140 to 180° C., more preferably 140 to 160° C.; and / or a crystallization time of 1 to 5 days, preferably 2 to 5 days, more preferably 3 to 5 days.

[0031] Furthermore, the method further comprises conventional post-treatment steps, such as filtering, washing and drying the crystallized product to obtain a metal aluminum phosphate molecular sieve. Preferably, the drying temperature is 90 to 120° C. and the drying time is 0.5 to 10 hours. And optionally, a step of calcining the obtained molecular sieve.

[0032] The metal aluminum phosphate molecular sieve provided by the present invention may sometimes contain a certain amount of water after synthesis, but there is no need to limit the amount of water in the present invention, and the presence or absence of the water does not substantially affect the XRD spectrum of the molecular sieve.

[0033] The metal aluminum phosphate molecular sieve provided by the present invention can be used in any physical form, such as powder, granule or molded product (such as strip, clover, etc.). These physical forms can be obtained in any conventional manner known in the art without particular limitation.

[0034] The present invention also provides a molecular sieve composition in the third aspect, comprising the above-mentioned metal aluminum phosphate molecular sieve or the metal aluminum phosphate molecular sieve prepared according to the preparation method of the metal aluminum phosphate molecular sieve, and a binder. The other materials contained in the molecular sieve composition can be active materials and inactive materials. As the active material, it can be other molecular sieves, and as the inactive material (generally referred to as a binder), it can be clay, alumina, silica gel, etc. These other materials can be used alone, or a plurality of them can be used in combination in any proportion. As the amount of the other materials, the conventional amount used in the art can be referred to, and there is no particular restriction.

[0035] The fourth aspect of the present invention provides the above-mentioned metal aluminum phosphate molecular sieve, the metal aluminum phosphate molecular sieve prepared by the preparation method of the metal aluminum phosphate molecular sieve, or the above-mentioned molecular sieve composition, which can be used as an adsorbent or a catalyst.

[0036] The metal aluminum phosphate molecular sieve or molecular sieve composition of the present invention can be used as an adsorbent, for example, to separate at least one component from a mixture of multiple components in 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, for example, by contacting the mixture with the metal aluminum phosphate molecular sieve or the molecular sieve composition to selectively adsorb the component.

[0037] According to one aspect of the present invention, the metal aluminum phosphate molecular sieve or the molecular sieve composition can also be used as a catalyst (or as its catalytically active component) directly or after necessary treatment or conversion (such as ion exchange, etc.) conventionally performed on the molecular sieve in the art. To this end, according to one aspect of the present invention, for example, reactants (such as hydrocarbons) can be subjected to a predetermined reaction in the presence of the catalyst, and the target product can be obtained thereby. Among them, the predetermined reaction can be exemplified as follows: methanol conversion, synthesis gas to hydrocarbons, olefin cracking, olefin disproportionation and isopropylbenzene cracking and other reactions.

[0038] Compared with the prior art, the present invention can produce the following beneficial effects:

[0039] The metal aluminum phosphate molecular sieve of the present invention is a new type of molecular sieve never obtained before in the art and has a special X-ray diffraction spectrum. BRIEF DESCRIPTION OF THE DRAWINGS

[0040] Figure 1 The XRD diffraction spectrum of the molecular sieve prepared in Example 3;

[0041] Figure 2 This is a SEM photograph of the molecular sieve prepared in Example 3. DETAILED DESCRIPTION

[0042] The following examples will further illustrate the technical solutions provided by the present invention, but the protection scope of the present invention is not limited by these examples.

[0043] In the present invention, the structure of the molecular sieve is determined by an X-ray diffraction spectrum (XRD), and the X-ray diffraction spectrum (XRD) of the molecular sieve is measured by an X-ray powder diffractometer using a Cu-Kα ray source, with a Kα1 wavelength of λ = 1.5405980 angstroms. Nickel filter. The X'Pert PRO X-ray powder diffraction (XRD) instrument used was from PANalytical of the Netherlands, with an operating voltage of 40 kV, a current of 40 mA, and a scanning range of 3.0 to 50°.

[0044] In the present invention, the morphology of the molecular sieve is photographed using a S-4800 field emission scanning electron microscope (Fe-SEM) produced by Japan HITACHI Corporation.

[0045] Unless otherwise specified, the operations and processing methods involved in the present invention are conventional methods in the art.

[0046] Unless otherwise specified, the instruments used in the present invention are conventional instruments in the art.

[0047] The raw materials involved in the specific implementation of the present invention are as follows:

[0048] Aluminum sulfate [Al2(SO4)3·18H2O]: contains Al2O3, 15.7% by weight, industrial product;

[0049] Aluminum isopropoxide [Al(iPr)3]: contains Al2O3, 24.9 wt%;

[0050] Aluminum nitrate [Al2(NO3)3·9H2O]: contains Al2O3, 27.5 wt%;

[0051] Cobalt nitrate [Co(NO3)2·6H2O]: contains CoO, 25.7 wt%;

[0052] Cobalt sulfate [CoSO4·7H2O]: contains CoO, 26.7 wt%;

[0053] Cobalt acetate [Co(CO2CH3)2·4H2O]: contains CoO, 30.1 wt%;

[0054] Nickel nitrate [Ni(NO3)2·6H2O]: contains NiO, 25.7 wt%;

[0055] Nickel sulfate [NiSO4·6H2O]: contains NiO, 28.4 wt%;

[0056] Nickel acetate [Ni(CO2CH3)2·4H2O]: containing NiO, 30.0 wt%;

[0057] Ferrous nitrate [Fe(NO3)2·6H2O]: contains FeO, 25.0 wt%;

[0058] Ferrous sulfate [FeSO4·7H2O]: contains FeO, 25.8% by weight;

[0059] Ferrous acetate [Fe(CO2CH3)2]: contains FeO, 41.3% by weight

[0060] Phosphoric acid (purity ≥ 85wt.%): containing P2O5, 72.3% by weight, commercially available;

[0061] Acidic silica sol (40wt.% aqueous solution): containing SiO2, 40wt%, commercially available;

[0062] White carbon black: contains SiO2, 99% by weight.

[0063] [Example 1]

[0064] 10.2 g of aluminum isopropoxide was dissolved in 68.3 mL of deionized water and mixed to form a solution S. Then, 4.3 g of ferrous acetate, 8.3 g of phosphoric acid (purity ≥ 85 wt.%), 147.3 g of tetraethylammonium hydroxide (25 wt.% aqueous solution) and 62.6 g of 1-(3-aminopropyl)imidazole (≥ 98%) were added to the solution S. The mixture was stirred for 1 h and precipitated for 12 h to obtain a solution S'. Then, 0.8 g of white carbon black (≥ 99%) was slowly added to the S' solution. After stirring for 10 h, the mixture was heat treated at 100 ° C for 8 h to form a uniform crystallized mixture. The molar ratio of aluminum source calculated as Al2O3, iron source calculated as FeO, silicon source calculated as SiO2, phosphorus source calculated as P2O5, template and solvent is: Al2O3:FeO:SiO2:P2O5:template R:solvent S=1:1:0.5:1:15:200, template R1 (tetraethylammonium hydroxide) / template R2 (1-(3-aminopropyl)imidazole)=0.5:1, the above crystallization mixture is placed at 140°C for crystallization for 5d, the product is filtered, washed and dried at 120°C for 5h to obtain the product metal aluminum phosphate molecular sieve, its X-ray diffraction spectrum is shown in Table 1, Figure 1 As shown. The components of the molecular sieve after drying the sample were measured by inductively coupled plasma atomic emission spectroscopy (ICP) and the molar ratio was Al2O3:0.5SiO2:1.0P2O5:1.0FeO. The morphology of the obtained metal aluminum phosphate molecular sieve is similar to Figure 2 Similarly, it is a rod-shaped crystal, about 2.5μm long and about 0.5μm wide.

[0065] Table 1

[0066]

[0067]

[0068] [Example 2]

[0069] 13.3 g of aluminum sulfate was dissolved in 97.3 mL of water and mixed to form a solution S. Then, 1.2 g of cobalt acetate, 2.5 g of phosphoric acid (purity ≥ 85 wt.%), 203.4 g of tetrapropylammonium hydroxide (50 wt.% aqueous solution) and 312.9 g of 1-(3-aminopropyl)imidazole (≥ 98%) were added to the solution S. The solution was stirred for 12 h and precipitated for 1 h to obtain a solution S'. Then, 0.16 g of acidic silica sol (40 wt.% aqueous solution) was slowly added to the S' solution. After stirring for 8 h, the solution was heat treated at 110 ° C for 6 h to form a uniform crystallized mixture, wherein Al The molar ratio of aluminum source calculated as Al2O3, cobalt source calculated as CoO, silicon source calculated as SiO2, phosphorus source calculated as P2O5, template and solvent is: Al2O3: CoO: SiO2: P2O5: template R: solvent S = 1: 0.25: 0.05: 1.5: 150: 150, template R1 (tetrapropylammonium hydroxide) / template R2 (1-(3-aminopropyl)imidazole) = 0.2: 1, the above crystallization mixture is placed at 140 ° C for crystallization for 5 days, the product is filtered, washed and dried at 90 ° C for 10 hours to obtain the product metal aluminum phosphate molecular sieve, and its X-ray diffraction line is shown in Table 2. Figure 1 As shown. The components of the molecular sieve after drying the sample were measured by inductively coupled plasma atomic emission spectroscopy (ICP) and the molar ratio was Al2O3:0.05SiO2:1.49P2O5:0.27CoO. The morphology of the obtained metal aluminum phosphate molecular sieve is similar to Figure 2 Similarly, it is a rod-shaped crystal, about 5.5μm long and about 1.0μm wide.

[0070] Table 2

[0071]

[0072]

[0073] [Example 3]

[0074] 750.2 g of aluminum nitrate was dissolved in 1150.3 mL of water and mixed to form solution S. Then, 124.5 g of cobalt acetate, 161.4 g of phosphoric acid (purity ≥ 85 wt.%), 2104.6 g of tetraethylammonium hydroxide (50 wt.% aqueous solution) and 2234.8 g of 1-(3-aminopropyl)imidazole were added to solution S. After stirring for 8 h and settling for 6 h, solution S' was obtained. Then, 32.0 g of acidic silica sol (40 wt.% aqueous solution) was slowly added to the S' solution. After stirring for 3.5 h, the mixture was heat treated at 80 ° C for 12 h to form a uniform crystallized mixture. The molar ratio of the aluminum source calculated as Al2O3, the cobalt source calculated as CoO, the silicon source calculated as SiO2, the phosphorus source calculated as P2O5, the template and the solvent is: Al2O3: CoO: SiO2: P2O5: template R: solvent S = 1: 0.5: 0.2: 1.4: 25: 121, template R1 (tetraethylammonium hydroxide) / template R2 (1-(3-aminopropyl) imidazole) = 0.4. The above crystallization mixture is placed at 140°C for crystallization for 5 days. The product is filtered, washed and dried at 110°C for 6 hours to obtain the product metal aluminum phosphate molecular sieve, and its X-ray diffraction lines are shown in Table 4. Figure 1 As shown. The components of the molecular sieve after drying the sample were measured by inductively coupled plasma atomic emission spectroscopy (ICP) and the molar ratio was Al2O3:0.18SiO2:1.37P2O5:0.48CoO. The morphology of the obtained metal aluminum phosphate molecular sieve is shown in Figure 2 ,pass Figure 2 It can be seen that it is a rod-shaped crystal with a length of about 3.5 μm and a width of about 0.7 μm.

[0075] Table 3

[0076]

[0077]

[0078] [Example 4]

[0079] 40.8 g of aluminum isopropoxide was dissolved in 1013.8 mL of water and mixed to form a solution S. Then, 24.8 g of nickel acetate, 19.6 g of phosphoric acid (purity ≥ 85 wt.%), 339.9 g of tetraethylammonium hydroxide (50 wt.% aqueous solution) and 423.7 g of 2-ethyl-4-methylimidazole (≥ 96%) were added to the solution S. After stirring for 4 h and settling for 9 h, a solution S' was obtained. Then, 0.6 g of white carbon black (≥ 99%) was slowly added to the S' solution. After stirring for 6 h, the mixture was heat treated at 90 ° C for 10 h to form a uniform crystallized mixture, wherein Al The molar ratio of aluminum source calculated as Al2O3, nickel source calculated as NiO, silicon source calculated as SiO2, phosphorus source calculated as P2O5, template and solvent is: Al2O3: NiO: SiO2: P2O5: template R: solvent S = 1: 0.75: 0.1: 0.85: 50: 99, template R1 (tetraethylammonium hydroxide) / template R2 (2-ethyl-4-methylimidazole) = 0.3, the above crystallization mixture is placed at 160 ° C for crystallization for 4 days, the product is filtered, washed and dried at 100 ° C for 8 hours to obtain the product metal aluminum phosphate molecular sieve, and its X-ray diffraction lines are shown in Table 3. Figure 1 As shown. The components of the molecular sieve after drying the sample were measured by inductively coupled plasma atomic emission spectroscopy (ICP) and the molar ratio was Al2O3:0.11SiO2:0.87P2O5:0.72NiO. The morphology of the obtained metal aluminum phosphate molecular sieve is similar to Figure 2 Similarly, it is a rod-shaped crystal with a length of about 4.5 μm and a width of about 0.8 μm.

[0080] Table 4

[0081] 2θ(°) <![CDATA[Relative intensity, [(I / I0)×100]]]> 5.99 100 7.65 55 10.69 36 13.81 8 16.49 15 17.88 27 19.77 43 20.96 22 23.16 36 24.53 8 25.98 10 27.69 11 28.09 13 31.22 5 32.92 8 34.71 18 38.22 7

[0082] [Example 5]

[0083] 204.2 g of aluminum isopropoxide was dissolved in 110.0 mL of water and mixed to form a solution S. Then, 49.8 g of nickel acetate, 138.4 g of phosphoric acid (purity ≥ 85 wt.%), 599.7 g of tetraethylammonium hydroxide (50 wt.% aqueous solution) and 1201.9 g of 1-(3-aminopropyl)imidazole were added to the solution S. The solution was stirred for 4 h and precipitated for 10 h to obtain a solution S'. Then, 32.0 g of acidic silica sol (40 wt.% aqueous solution) was slowly added to the S' solution. After stirring for 4.5 h, the solution was heat treated at 110 ° C for 6 h to form a uniform crystallized mixture. The molar ratio of the aluminum source calculated as Al2O3, the nickel source calculated as NiO, the silicon source calculated as SiO2, the phosphorus source calculated as P2O5, the template and the solvent is: Al2O3: NiO: SiO2: P2O5: template R: solvent S = 1: 0.4: 0.4: 1.2: 19: 50, template R1 (tetraethylammonium hydroxide) / template R2 (1-(3-aminopropyl)imidazole) = 0.25, the above crystallization mixture is placed at 140°C for crystallization for 5 days, the product is filtered, washed and dried at 100°C for 8 hours to obtain the product metal aluminum phosphate molecular sieve, and its X-ray diffraction lines are shown in Table 5. Figure 1 As shown. The components of the molecular sieve after drying the sample were measured by inductively coupled plasma atomic emission spectroscopy (ICP) and the molar ratio was Al2O3:0.39SiO2:1.18P2O5:0.39NiO. The morphology of the obtained metal aluminum phosphate molecular sieve is similar to Figure 2 Similarly, it is a rod-shaped crystal with a length of about 3.0 μm and a width of about 1.0 μm.

[0084] Table 5

[0085] 2θ(°) <![CDATA[Relative intensity, [(I / I0)×100]]]> 5.88 100 7.57 61 10.68 33 13.74 15 16.48 25 17.89 5 19.70 22 20.93 19 23.15 7 24.53 26 25.96 24 27.68 5 28.09 19 31.24 15 32.91 20 34.72 12 38.21 9

[0086] [Example 6]

[0087] 37.5 g of aluminum nitrate was dissolved in 18.6 mL of water and mixed to form a solution S. Then, 5.2 g of ferrous acetate, 5.2 g of phosphoric acid (purity ≥ 85 wt.%), 69.2 g of tetraethylammonium hydroxide (50 wt.% aqueous solution) and 195.1 g of 1-(3-aminopropyl)imidazole were added to the solution S. The mixture was stirred for 8 h and precipitated for 8 h to obtain a solution S'. Then, 1.0 g of white carbon black (≥ 99%) was slowly added to the S' solution. After stirring for 6.5 h, the mixture was heat treated at 100 ° C for 8 h to form a uniform crystallized mixture, wherein the mixture was crystalline and the content of the mixture was crystalline. The molar ratio of aluminum source calculated as FeO, iron source calculated as SiO2, phosphorus source calculated as P2O5, template and solvent is: Al2O3:FeO:SiO2:P2O5:template R:solvent S=1:0.6:0.3:0.9:36:60, template R1 (tetraethylammonium hydroxide) / template R2 (1-(3-aminopropyl)imidazole)=0.15, the above crystallization mixture is placed at 140°C for crystallization for 5d, the product is filtered, washed and dried at 110°C for 6h to obtain the product metal aluminum phosphate molecular sieve, and its X-ray diffraction lines are shown in Table 6. Figure 1 As shown. The components of the molecular sieve after drying the sample were measured by inductively coupled plasma atomic emission spectroscopy (ICP) and the molar ratio was Al2O3:0.32SiO2:0.94P2O5:0.62FeO. The morphology of the obtained metal aluminum phosphate molecular sieve is similar to Figure 2 Similarly, it is a rod-shaped crystal with a length of about 5.0 μm and a width of about 0.7 μm.

[0088] Table 6

[0089] 2θ(°) <![CDATA[Relative intensity, [(I / I0)×100]]]> 5.79 100 7.61 77 10.75 23 13.81 20 16.50 15 17.93 10 19.75 12 21.00 33 23.15 27 24.53 6 25.95 22 27.70 15 28.09 8 31.24 13 32.91 11 34.71 6 38.21 7

[0090] [Example 7]

[0091] 10212.0 g of aluminum isopropoxide was dissolved in 84487.5 mL of water and mixed to form a solution S. Then, 1866.3 g of nickel acetate, 5764.7 g of phosphoric acid (purity ≥ 85 wt.%), 34720.7 g of tetraethylammonium hydroxide (50 wt.% aqueous solution) and 44703.2 g of 1-(3-aminopropyl)imidazole were added to the solution S. The solution was stirred for 6 h and precipitated for 9 h to obtain a solution S'. Then, 375.0 g of white carbon black (≥ 99%) was slowly added to the S' solution. After stirring for 3.5 h, the mixture was heat treated at 90 ° C for 11 h to form a uniform crystallized mixture. The molar ratio of the aluminum source calculated as Al2O3, the nickel source calculated as NiO, the silicon source calculated as SiO2, the phosphorus source calculated as P2O5, the template and the solvent is: Al2O3: NiO: SiO2: P2O5: template R: solvent S = 1: 0.3: 0.25: 0.75: 19: 190, template R1 (tetraethylammonium hydroxide) / template R2 (1-(3-aminopropyl)imidazole) = 0.33, the above crystallization mixture is placed at 140°C for crystallization for 5 days, the product is filtered, washed and dried at 90°C for 10 hours to obtain the product metal aluminum phosphate molecular sieve, and its X-ray diffraction lines are shown in Table 7. Figure 1 As shown. The components of the molecular sieve after drying the sample were measured by inductively coupled plasma atomic emission spectroscopy (ICP) and the molar ratio was Al2O3:0.27SiO2:0.78P2O5:0.33NiO. The morphology of the obtained metal aluminum phosphate molecular sieve is similar to Figure 2 Similarly, it is a rod-shaped crystal with a length of about 4.5 μm and a width of about 0.6 μm.

[0092] Table 7

[0093] 2θ(°) <![CDATA[Relative intensity, [(I / I0)×100]]]> 5.77 100 7.50 73 10.58 23 13.63 5 16.39 33 17.80 28 19.61 11 20.81 22 23.07 9 24.46 16 25.90 34 27.62 25 28.06 8 31.20 20 32.90 10 34.71 11 38.20 6

[0094] It should be noted that the embodiments described above are only used to explain the present invention and do not constitute any limitation to the present invention. The present invention has been described with reference to typical embodiments, but it should be understood that the words used therein are descriptive and explanatory words, rather than restrictive words. The present invention may be modified as specified within the scope of the claims of the present invention, and the present invention may be revised without departing from the scope and spirit of the present invention. Although the present invention described therein relates to specific methods, materials and embodiments, it does not mean that the present invention is limited to the specific examples disclosed therein, on the contrary, the present invention can be extended to all other methods and applications with the same functions.

Claims

1. A metal aluminum phosphate molecular sieve having a chemical composition in the following molar ratio: Al2O3:xSiO2:yP2O5:zMeO, wherein: Me is a metal element of Group VIII, 0≤x≤0.5, 0.5≤y≤2, 0.1≤z≤1; the molecular sieve comprises XRD diffraction data as shown in the following table: Among them, the incident ray of X-ray diffraction is Cu Kα1.

2. The molecular sieve according to claim 1, characterized in that The molecular sieve also includes XRD diffraction data as shown in the following table: Among them, the incident ray of X-ray diffraction is Cu Kα1.

3. The molecular sieve according to claim 1, characterized in that The molecular sieve has XRD diffraction data as shown in the following table: Among them, the incident ray of X-ray diffraction is Cu Kα1.

4. The molecular sieve according to any one of claims 1 to 3, characterized in that The Me is at least one of Fe, Co and Ni.

5. The molecular sieve according to claim 1, characterized in that The molecular sieve has a rod-like crystal morphology.

6. The molecular sieve according to claim 5, characterized in that In the rod-shaped crystal form, the length is 2.5 to 5.5 μm and the width is 0.5 to 1.0 μm.

7. A method for preparing the metal aluminum phosphate molecular sieve as described in any one of claims 1 to 6, comprising mixing a mixture containing an aluminum source, a Me metal source, a phosphorus source, an organic template, a solvent and optionally a silicon source to obtain a crystallized mixture and subjecting it to crystallization treatment to obtain the metal aluminum phosphate molecular sieve.

8. The preparation method according to claim 7, characterized in that: In the crystallization mixture, the molar compositions of the aluminum source calculated as Al2O3, the metal source calculated as MeO, the silicon source calculated as SiO2, the phosphorus source calculated as P2O5, the organic template and the solvent are as follows: SiO2 / Al2O3=0~1, preferably 0.05~0.5; and / or, MeO / Al2O3=0.1~1, preferably 0.25~0.75; and / or, P2O5 / Al2O3=0.5~2, preferably 0.75~1.5; and / or, organic template / Al2O3=1~1000, preferably 15~150; and / or, solvent / Al2O3=20~1000, preferably 50~200.

9. The preparation method according to claim 7, characterized in that: The organic template includes template R1 and template R2, and the molar ratio of template R1 to template R2 is (0.1-1):1, preferably (0.2-0.5):

1.

10. The preparation method according to claim 7, characterized in that: The aluminum source is selected from at least one of aluminum isopropoxide, aluminates, metaaluminates, aluminum hydroxides, aluminum oxides and aluminum-containing minerals; and / or, the metal source is selected from at least one of corresponding metal sulfates, nitrates, acetates, corresponding metal halides, oxides, hydroxides and corresponding metal minerals; and / or, the silicon source is selected from at least one of organic silicon, solid silicon oxide, silica sol, diatomaceous earth and water glass; and / or, the phosphorus source is selected from at least one of phosphoric acid, monoammonium hydrogen phosphate and diammonium phosphate.

11. The preparation method according to claim 9, characterized in that: The template agent R1 is selected from one of tetraethylammonium bromide, tetraethylammonium hydroxide, tetrapropylammonium bromide, tetrapropylammonium hydroxide, tetrabutylammonium bromide, and tetrabutylammonium hydroxide; and / or, the template agent R2 is selected from one of imidazole, 2-methylimidazole, 4-methylimidazole, 1-(3-aminopropyl)imidazole, 1-isopropylimidazole, N-n-butylimidazole, 2-ethyl-4-methylimidazole, and 1,3-bis(1-adamantyl)imidazole hydroxide; and / or, the solvent is selected from one of N,N-dimethylformamide, N,N-dimethylacetamide, N,N-diethylformamide, N,N-dibutylformamide, ethanol, ethylene glycol, butanol, and water.

12. The preparation method according to claim 7, characterized in that: The conditions of the crystallization treatment include: a crystallization temperature of 140 to 200° C., preferably 140 to 180° C., more preferably 140 to 160° C.; and / or a crystallization time of 1 to 5 days, preferably 2 to 5 days, more preferably 3 to 5 days.

13. A molecular sieve composition, characterized in that: The invention comprises the molecular sieve according to any one of claims 1 to 6 or the molecular sieve prepared according to any one of claims 7 to 12, and a binder.

14. Use of the metal aluminum phosphate molecular sieve according to any one of claims 1 to 6, or the metal aluminum phosphate molecular sieve prepared by the preparation method according to any one of claims 7 to 12, or the molecular sieve composition according to claim 13 in an adsorbent or catalyst.

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