GeAlPO-34 molecular sieve as well as preparation method and application thereof

Abstract

The invention relates to a novel GeAlPO-34 molecular sieve and a preparation method thereof. The method comprises the following steps: performing first heat treatment on a germanium source and a first template agent in the presence of a first solvent to obtain a first crystallized precursor; s2, performing second heat treatment on the SCM-34 molecular sieve and a second template agent in the presence of a second solvent to obtain a second crystallized precursor; and S3, carrying out a crystallization reaction on a mixture containing the first crystallization precursor and the second crystallization precursor to obtain the GeAlPO-34 molecular sieve. When the GeAlPO-34 molecular sieve prepared by the method is used for industrial production of methanol downstream products, industrial production of synthesis gas downstream products and hydrocarbon cracking, the GeAlPO-34 molecular sieve has excellent performance.

Description

Technical Field

[0001] The present invention relates to the field of molecular sieves, and in particular to a GeAlPO-34 molecular sieve and a preparation method and application 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 [SiO 4 ] 4- and aluminum oxide tetrahedron [AlO 4 ] 5- They are connected by shared oxygen atoms and are collectively referred to as TO 4 Tetrahedron (primary structural unit), in which 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 the characteristics of their pores or cages. The pore diameter of this type of material is generally less than 2nm, and it is classified as a microporous material. 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 AlPO using aluminum source, phosphorus source and organic template. 4 -n, n represents the model (including: AlPO 4 -5. AlPO 4 -8. AlPO 4 -9. AlPO 4 -11. AlPO 4 -12. AlPO 4 -14. AlPO 4 -16. AlPO 4 -17. AlPO 4 -18. AlPO 4 -20, AlPO 4-21.AlPO 4 -22. AlPO 4 -23. AlPO 4 -25.AlPO 4 -26.AlPO 4 -28.AlPO 4 -31, etc.), the framework of this type of molecular sieve is made of AlO 4 - and PO 4 + The molecular sieve framework is electrically neutral. 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, UCC has 4 -n, in 1984, Si atoms were used to partially replace Al atoms and P atoms in the aluminum phosphate molecular sieve framework to successfully prepare another series of silicon aluminum phosphate molecular sieves: SAPO-n, where n represents the model (US4440871, US4499327). After the Si atoms in the structure replaced the P and Al atoms in the original AlPO, a SiO 4 、AlO 4 and PO 4 A non-neutral molecular sieve framework composed of tetrahedrons. Among the SAPO-n molecular sieves, it is worth mentioning that the topological structure of the SAPO-34 molecular sieve is CHA. The molecular sieve framework structure contains a three-dimensional cross structure of an ellipsoidal supercage and an 8-membered ring channel. The pore size of the 8-membered ring channel is about 0.38nm, and the pore diameter of the supercage is maintained between 0.43-0.50nm. Because of its excellent selectivity for low-carbon olefins such as ethylene and propylene due to its pore structure, and the appropriate amount of framework 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).

[0004] So far, most of the known topologically linked aluminum phosphate molecular sieves are prepared by hydrothermal or solvent thermal synthesis. The main steps of a typical hydrothermal or solvent thermal synthesis method are to first mix the reactants such as metal source, non-metal source, organic template, solvent, etc. to obtain an initial crystallization mixture, and then place the crystallization mixture in a reactor lined with polytetrafluoroethylene and stainless steel as the outer wall. After sealing, the crystallization reaction is carried out at a certain temperature and autogenous pressure, imitating the process of mineralization and rock formation on the earth, that is, the process of molecular sieve crystals precipitating from the crystallization mixture. Specifically, taking the synthesis of SAPO-34 molecular sieve as an example, the reaction mixture contains a skeleton reactant (such as silica sol, phosphoric acid and alumina) and a structure directing agent (SDA) and water, and is evenly mixed and placed in a fixed temperature oven (140-220°C) for several days for crystallization reaction. When the crystallization reaction is completed, the solid product containing SAPO-34 molecular sieve is filtered out and dried for use. It is worth mentioning that for the synthesis of aluminum phosphate molecular sieves, the type of organic template is one of the key factors that determine its structure, and the presence of organic amine salts is still the most widely used template in the synthesis of aluminum phosphate molecular sieves.

[0005] 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 255 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.

[0006] The research and development of a synthetic method for preparing GeAlPO-34 molecular sieve has always been a research topic in this field. Summary of the invention

[0007] In view of the shortcomings of the prior art, the present invention provides a new method for preparing GeAlPO-34 molecular sieve. The GeAlPO-34 molecular sieve synthesized by the method has Al 2 O 3 :xP 2 O 5 :yGeO 2The composition is 0.8≤x≤1.4, 0.01≤y≤0.2, and it has excellent performance when used in the industrial production of methanol downstream products, the industrial production of synthesis gas downstream products and hydrocarbon cracking.

[0008] In a first aspect, the present invention provides a GeAlPO-34 molecular sieve, wherein the X-ray diffraction spectrum of the GeAlPO-34 molecular sieve comprises the X-ray diffraction peaks shown in the following table:

[0009]

[0010]

[0011] In some embodiments, the GeAlPO-34 molecular sieve comprises Al 2 O 3 , P 2 O 5 and GeO 2 .

[0012] In some embodiments, the Al 2 O 3 With P 2 O 5 The molar ratio of Al is 1:(0.8-1.4). 2 O 3 With P 2 O 5 The molar ratio can be 1:0.8, 1:1.0, 1:1.2, 1:1.4 or any value therebetween.

[0013] In some embodiments, the Al 2 O 3 With GeO 2 The molar ratio of Al is 1:(0.01-0.2). 2 O 3 With GeO 2 The molar ratio is 1:0.01, 1:0.05, 1:0.1, 1:0.15, 1:0.2 or any value therebetween.

[0014] In a second aspect, the present invention provides a method for preparing GeAlPO-34 molecular sieve, comprising the following steps:

[0015] S1: subjecting a germanium source and a first template to a first heat treatment in the presence of a first solvent to obtain a first crystallization precursor;

[0016] S2: subjecting the SCM-34 molecular sieve and the second template to a second heat treatment in the presence of a second solvent to obtain a second crystallization precursor;

[0017] S3: subjecting the mixture containing the first crystallization precursor and the second crystallization precursor to a crystallization reaction to obtain a GeAlPO-34 molecular sieve.

[0018] In the present invention, due to its special structure, SCM-34 molecular sieve can be used as a reaction raw material for crystal-to-crystal conversion to obtain the corresponding GeAlPO-34 molecular sieve under different conditions. Compared with preparing GeAlPO compounds by co-crystallization of raw materials, the preparation method of the present invention takes a short time, and the Ge element in the obtained product exists as a framework element, and the framework Ge content is higher.

[0019] In some embodiments, the SCM-34 molecular sieve has the formula "Al 2 O 3 :zP 2 O 5 ” is a schematic chemical composition shown in FIG. 1 , wherein 0.75≤z≤1.5. In some specific embodiments, z can be 0.75, 0.9, 1.0, 1.2, 1.4, 1.5 or any value therebetween.

[0020] In some embodiments, in the X-ray diffraction pattern data of the SCM-34 molecular sieve, the 2θ angle of the strongest peak in the range of 2θ angle of 5-50° is 7.59±0.2.

[0021] In some embodiments, the X-ray diffraction pattern of the SCM-34 molecular sieve includes the X-ray diffraction peaks shown in the following table:

[0022] 2θ(°) <![CDATA[Relative intensity, [(I / I 0 )×100]]]> 7.59±0.2 50-100 10.81±0.1 10-20 16.52±0.1 5-50 17.97±0.1 5-50 23.34±0.05 5-50 34.74±0.05 5-50 .

[0023] Furthermore, the X-ray diffraction spectrum of the SCM-34 molecular sieve includes the X-ray diffraction peaks shown in the following table:

[0024] 2θ(°) <![CDATA[Relative intensity, [(I / I 0 )×100]]]> 7.59±0.2 50-100 10.81±0.1 10-20 14.25±0.1 5-50 16.52±0.1 5-50 17.97±0.1 5-50 21.01±0.1 10-20 23.34±0.05 5-50 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 34.74±0.02 5-50 .

[0025] Furthermore, the X-ray diffraction spectrum of the SCM-34 molecular sieve includes the X-ray diffraction peaks shown in the following table:

[0026]

[0027]

[0028] Among them, the incident ray of X-ray diffraction is Cu Kα1.

[0029] In some embodiments, the preparation method of the SCM-34 molecular sieve includes: crystallizing a mixture containing an aluminum source, a phosphorus source, an organic template R1 and an organic template R2, a solvent S1, a solvent S2 and a solvent S3 to obtain the SCM-34 molecular sieve.

[0030] In some embodiments, the organic template R1 is selected from at least one of a quaternary ammonium salt or a quaternary ammonium base, and the organic template R2 is selected from at least one of an imidazole or a pyrrolidine derivative.

[0031] In some preferred embodiments, the organic template R1 is selected from at least one of tetraethylammonium bromide, tetraethylammonium hydroxide, tetrapropylammonium bromide, tetrapropylammonium hydroxide, tetrabutylammonium bromide, and tetrabutylammonium hydroxide; the organic template R2 is selected from at least one of imidazole, 2-methylimidazole, 4-methylimidazole, 1-(3-aminopropyl)imidazole, 2-ethyl-4-methylimidazole, pyrrolidine, 1-(3-pyrrolidine)pyrrolidine, and N-ethyl-2-aminomethylpyrrolidine.

[0032] In some embodiments, the solvent S1 is selected from at least one of amide-based solvents, the solvent S2 is selected from at least one of cyclic organic solvents, and the solvent S3 is selected from at least one of water or low-carbon alcohols.

[0033] In some preferred embodiments, the solvent S1 is selected from at least one of N,N-dimethylformamide, N,N-dimethylacetamide, N,N-diethylformamide and N,N-dibutylformamide; the solvent S2 is selected from at least one of 1,4-dioxane, cyclohexane, cyclohexanone and cyclohexanol; and the solvent S3 is selected from one or more of methanol, ethanol, ethylene glycol, butanol and water.

[0034] In some embodiments, the organic template R1 is preferably at least one of tetraethylammonium bromide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide and tetrabutylammonium hydroxide; the organic template R2 is preferably at least one of 1-(3-aminopropyl)imidazole, 2-ethyl-4-methylimidazole, and N-ethyl-2-aminomethylpyrrolidine; the solvent S1 is preferably one or both of N,N-dimethylacetamide and N,N-dibutylformamide; the solvent S2 is preferably one or both of 1,4-dioxane and cyclohexanone; the solvent S3 is preferably one or both of ethanol and water, wherein the water is preferably deionized water.

[0035] In some embodiments, in the mixture, the aluminum source is Al 2 O 3 Phosphorus source is P 2 O 5 The molar composition of organic template R1+R2 and solvent S1+S2+S3 is as follows:2 O 5 / Al 2 O 3 =0.5-2, preferably 0.75-1.5; Template (R1+R2)

[0036] / Al 2 O 3 =1-200, preferably 5-50; solvent (S1+S2+S3) / Al 2 O 3 =5-500, preferably 35-120.

[0037] In some embodiments, the molar ratio of the organic template R1 to the organic template R2 is (0.01-1):1, preferably (0.1-0.25):1.

[0038] In some embodiments, 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.

[0039] In some embodiments, the aluminum source is selected from at least one of aluminum isopropoxide, aluminates, metaaluminates, aluminum salts, aluminum hydroxides, aluminum oxides, and aluminum-containing minerals, preferably one or both of aluminates and metaaluminates.

[0040] In some embodiments, the phosphorus source is selected from at least one of phosphoric acid, ammonium monohydrogen phosphate and ammonium dihydrogen phosphate, preferably orthophosphoric acid.

[0041] In some embodiments, in the preparation method of the SCM-34 molecular sieve, stirring and settling treatments are first performed before crystallization treatment. The stirring time is 0.5-5 hours, and the settling time is 1-12 hours.

[0042] In some embodiments, in the preparation method of the SCM-34 molecular sieve, the conditions for the crystallization treatment include: the crystallization temperature is 120-200°C, preferably 140-180°C, and more preferably 140-160°C; the crystallization time is 1-5d, preferably 3-5d, and more preferably 4-5d.

[0043] In some embodiments, in the method for preparing the SCM-34 molecular sieve, conventional post-treatment is performed after the crystallization treatment, such as filtering, washing, and drying to obtain the SCM-34 molecular sieve; and optionally, the obtained SCM-34 molecular sieve is calcined.

[0044] In some embodiments, the first template includes at least one of 1,3-dimethylimidazolium chloride, n-butylamine, triethylamine, diethylamine, ethylamine, piperidine, or morpholine.

[0045] In some embodiments, the second template comprises a quaternary ammonium base cationic template, preferably, the second template comprises at least one of tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, tetramethylammonium bromide, tetraethylammonium bromide, tetrapropylammonium bromide or tetrabutylammonium bromide.

[0046] In some embodiments, the first solvent and / or the second solvent are each independently selected from at least one of methanol, ethanol, ethylene glycol, pentanol, butanol, octanol, acetone, pyridine, 1,4-dioxane, or dimethylformamide.

[0047] In some embodiments, the germanium source includes at least one of germanium oxide, germanium methoxide, and germanium ethoxide.

[0048] In some embodiments, the ratio of the mass of the SCM-34 molecular sieve to the mass sum of the first template and the second template is 1:(10-500), for example, 1:10, 1:50, 1:100, 1:200, 1:300, 1:400, 1:500 or any value therebetween.

[0049] In some embodiments, the ratio of the mass of the SCM-34 molecular sieve to the sum of the masses of the first solvent and the second solvent is 1:(50-10000), for example, 1:50, 1:100, 1:200, 1:500, 1:800, 1:1000, 1:2000, 1:5000, 1:8000, 1:10000 or any value therebetween.

[0050] In some embodiments, the mass ratio of the SCM-34 molecular sieve to the germanium source is 1:(0.1-10), preferably 1:(0.1-5). In some specific embodiments, the mass ratio of the SCM-34 molecular sieve to the germanium source can be 1:0.1, 1:0.5, 1:1, 1:2, 1:4, 1:6, 1:8, 1:10 or any value therebetween.

[0051] In some embodiments, the mass ratio of the first template to the second template is 1:(0.01-100), preferably 1:(0.1-10). In some specific embodiments, the mass ratio of the first template to the second template is 1:0.01, 1:0.05, 1:1, 1:5, 1:10, 1:20, 1:50, 1:80, 1:100 or any value therebetween.

[0052] In some embodiments, the mass ratio of the first solvent to the second solvent is 1:(0.01-100), preferably 1:(0.1-10). In some specific embodiments, the mass ratio of the first solvent to the second solvent is 1:0.01, 1:0.05, 1:1, 1:5, 1:10, 1:20, 1:50, 1:80, 1:100 or any value therebetween.

[0053] In some embodiments, the temperature of the first heat treatment is 50-100°C, and the time is 1-12h; preferably, the temperature of the first heat treatment is 70-85°C, and the time is 2-8h. In some specific embodiments, the temperature of the first heat treatment can be 50°C, 60°C, 70°C, 80°C, 90°C, 100°C, or any value therebetween. In some specific embodiments, the time of the first heat treatment can be 1h, 2h, 4h, 6h, 8h, 10h, 12h, or any value therebetween.

[0054] In some embodiments, the temperature of the second heat treatment is 90-140°C, and the time is 1-12h; preferably, the temperature of the second heat treatment is 100-120°C, and the time is 3-6h. In some specific embodiments, the temperature of the second heat treatment can be 90°C, 100°C, 110°C, 120°C, 130°C, 140°C, or any value therebetween. In some specific embodiments, the time of the first heat treatment can be 1h, 2h, 4h, 6h, 8h, 10h, 12h, or any value therebetween.

[0055] In some embodiments, the temperature of the crystallization reaction is 140-200°C and the time is 12-120h; preferably, the temperature of the crystallization reaction is 140-200°C and the time is 12-120h. In some specific embodiments, the temperature of the crystallization reaction can be 140°C, 150°C, 160°C, 170°C, 180°C, 190°C, 200°C or any value therebetween. In some specific embodiments, the time of the first heat treatment can be 12h, 20h, 40h, 60h, 80h, 100h, 120h or any value therebetween.

[0056] In some embodiments, the method further includes pre-treating the mixture of the first crystallization precursor and the second crystallization precursor before the crystallization reaction.

[0057] In some embodiments, the pretreatment comprises stirring at 100-120° C. for 1-10 h, and then settling at 100-120° C. for 12-24 h.

[0058] In some embodiments, the mixture of the first crystallization precursor and the second crystallization precursor is prepared by adding the first crystallization precursor to the second crystallization precursor under stirring to form a crystallization mixture. Preferably, the stirring time is 0.5-10 hours, preferably 1.5-5 hours.

[0059] In some embodiments, the method further comprises washing, drying and calcining the product of the crystallization reaction.

[0060] In some embodiments, the calcination temperature is 400-600°C and the time is 2-12h. In some specific embodiments, the calcination temperature can be 400°C, 450°C, 500°C, 550°C, 600°C or any value therebetween. In some specific embodiments, the first heat treatment time can be 2h, 4h, 6h, 8h, 10h, 12h or any value therebetween.

[0061] In a third aspect, the present invention provides a catalyst, which comprises the GeAlPO-34 molecular sieve described in the first aspect or a calcined product of the GeAlPO-34 molecular sieve obtained according to the preparation method described in the second aspect.

[0062] In some embodiments, the calcination temperature is 400-600°C and the time is 2-12h. In some specific embodiments, the calcination temperature can be 400°C, 450°C, 500°C, 550°C, 600°C or any value therebetween. In some specific embodiments, the first heat treatment time can be 2h, 4h, 6h, 8h, 10h, 12h or any value therebetween.

[0063] In a fourth aspect, the present invention provides the use of the GeAlPO-34 molecular sieve described in the first aspect, the GeAlPO-34 molecular sieve obtained by the preparation method described in the second aspect, or the catalyst described in the third aspect in a hydrocarbon production reaction.

[0064] In some embodiments, the hydrocarbon production reaction includes a methanol-to-hydrocarbons reaction or a syngas-to-hydrocarbons reaction.

[0065] In some embodiments, the conditions of the methanol-to-hydrocarbon reaction include: using methanol as a raw material, a reaction temperature of 400-600°C, a reaction pressure of 0.01-10 MPa, and a methanol weight space velocity of 0.1-15 h -1 .

[0066] In some embodiments, the syngas includes H 2 and CO.

[0067] In some embodiments, the conditions for the synthesis gas to olefins reaction include: using synthesis gas as raw material H 2 / CO=(0.5-2.5):1, reaction temperature is 300-500℃, reaction pressure is 0.1-10MPa, synthesis gas weight space velocity is 20-2000h -1 .

[0068] Compared with the prior art, the present invention has the following advantages:

[0069] The present invention adopts the self-developed SCM-34 molecular sieve combined with inorganic or organic germanium source for the first time to prepare GeAlPO-34 molecular sieve by crystal-to-crystal conversion, which significantly improves the performance of GeAlPO-34 molecular sieve. The GeAlPO-34 molecular sieve synthesized by this method shows excellent performance when used in the industrial production of methanol downstream products, the industrial production of synthesis gas downstream products and hydrocarbon cracking. For example, in the methanol conversion reaction to hydrocarbons, the selectivity of ethylene and propylene is high and the total yield is high; in the synthesis gas to hydrocarbons reaction, the selectivity of C2-C4 olefins is high and the total yield is high. BRIEF DESCRIPTION OF THE DRAWINGS

[0070] Figure 1 This is the XRD spectrum of the GeAlPO-34 molecular sieve of Example 1.

[0071] Figure 2 This is the SEM photograph of the GeAlPO-34 molecular sieve of Example 1.

[0072] Figure 3 This is the XRD pattern of the SAPO-34 molecular sieve of Comparative Example 1.

[0073] Figure 4 This is the SEM photograph of the SAPO-34 molecular sieve of Comparative Example 1.

[0074] Figure 5 This is the XRD pattern of the SCM-34 molecular sieve of Example 1. DETAILED DESCRIPTION

[0075] In order to make the present invention more easily understood, the present invention will be described in detail below in conjunction with embodiments. These embodiments are only for illustration and are not intended to limit the application scope of the present invention.

[0076] Unless otherwise specified, the operations and processing methods involved in the present invention are conventional methods in the art.

[0077] Unless otherwise specified, the instruments used in the present invention are conventional instruments in the art.

[0078] In the present invention, the crystal phase of the product is measured by an X'Pert PRO X-ray powder diffraction (XRD) instrument of PANalytical Company of the Netherlands, with an operating voltage of 40 kV, a current of 40 mA, and a scanning range of 5-50°. The morphology of the product is photographed by an S-4800 field emission scanning electron microscope (Fe-SEM) of HITACHI Company of Japan.

[0079] Example 1

[0080] (I) Synthesis of SCM-34 molecular sieve

[0081] 187.6 g of aluminum nitrate was dissolved in 630.6 mL of water and mixed to form solution C. Then, 74.9 g of phosphoric acid (purity ≥ 85 wt.%), 1885.1 g of tetrabutylammonium hydroxide (40 wt.% aqueous solution, MkSeal) and 2319.8 g of 1-(3-aminopropyl)imidazole were added to solution C. After stirring for 2 h and settling for 8 h, solution C' was obtained. Then, 99.9 mL of N,N-dimethylformamide and 13.4 mL of cyclohexanone were slowly added to solution C'. After stirring for 4 h, the mixture was heat treated at 110 ° C for 3 h to form a uniform crystallized mixture, wherein Al 2 O 3 Aluminum source, P 2 O 5 The molar ratio of phosphorus source, template and solvent is: Al 2 O 3 :P 2 O 5 :Template R:Solvent S=1:1.3:20:100,Template R1(tetrabutylammonium hydroxide) / Template R2(1-(3-aminopropyl)imidazole)=0.17,Solvent S1(N,N-dimethylbutyramide) / Solvent S2(water) / Solvent S3(cyclohexanone)=1:72:0.1;The above crystallization mixture was placed at 140℃ for crystallization for 5 days, and the product was filtered, washed and dried at 120℃ for 4 hours to obtain the product SCM-34(I). According to ICP test, the composition of the obtained SCM-34(I) molecular sieve is Al 2 O 3 :1.28P 2 O 5 Its X-ray diffraction pattern is shown in Figure 5 The X-ray diffraction pattern of the obtained SCM-34(I) molecular sieve includes the X-ray diffraction peaks shown in Table 1 below:

[0082] Table 1

[0083] 2θ(°) <![CDATA[Relative intensity, [(I / I 0 )×100]]]> 7.59 100 10.34 8 10.80 19 12.12 5 14.23 5 16.45 35 23.31 26 24.27 11 26.10 10 27.80 5 28.14 11 30.05 9 31.33 7 34.74 5 38.28 5

[0084] Among them, the incident ray of X-ray diffraction is Cu Kα1.

[0085] (II) Synthesis of GeAlPO-34 Molecular Sieve

[0086] At room temperature, 16.5 g of germanium oxide (GeO 2 ), 450 g of triethylamine (PIP) was dissolved in 2044.3 g of 1,4-dioxane (DOA), stirred thoroughly and then heat treated at 85 °C for 2.0 h to obtain a crystallized precursor CP 1 .

[0087] 3.3 g of the SCM-34 molecular sieve prepared in step (I) and 1200.0 g of tetramethylammonium hydroxide (25% aqueous solution) were weighed and mixed in 1256.7 g of ethanol, and then heat-treated at 100° C. for 6 h to obtain a crystallized precursor CP 2 .

[0088] The precursor CP 1 Add the crystallization precursor CP under strong stirring 2 After 1.5 hours of strong stirring, a crystallized mixture CM was formed. The mixture was placed at 100°C for 10 hours of stirring, and then precipitated for 24 hours. The mixture was then placed at 140°C for 120 hours of crystallization. The product was filtered, washed, dried at 100°C for 8 hours, and then heated to 550°C and calcined at a constant temperature for 5 hours to obtain GeAlPO-34 molecular sieve, which was designated as STG-1. Its XRD spectrum is shown in Figure 1 , its SEM image is shown in Figure 2 , and its composition is Al 2 O 3 :1.33P 2 O 5 :0.16GeO 2 The X-ray diffraction pattern of the obtained GeAlPO-34 molecular sieve includes the X-ray diffraction peaks shown in Table 2 below:

[0089] Table 2

[0090] 2θ(°) <![CDATA[Relative intensity, [(I / I 0 )×100]]]> 9.56 100 13.01 9.3 19.16 5.2 20.82 16.7 23.26 3.0 25.08 4.0 26.23 9.3 28.32 2.4 30.98 16.6 31.28 13.9 44.37 7.2

[0091] Example 2

[0092] (I) Synthesis of SCM-34 molecular sieve

[0093] 10.2 g of aluminum isopropoxide (Al(iPr) 3) was dissolved in 27.8 mL of water and mixed to form solution C. Then, 4.3 g of phosphoric acid (purity ≥ 85 wt.%), 147.6 g of tetrabutylammonium hydroxide (40 wt.% aqueous solution, MkSeal) and 284.5 g of 1-(3-aminopropyl)imidazole were added to solution C. After stirring for 5 h and settling for 1 h, solution C' was obtained. Then, 45.7 mL of N,N-dimethylbutanamide and 1.4 mL of cyclohexanone were slowly added to solution C'. After stirring for 2.5 h, the mixture was heat treated at 100 ° C for 6 h to form a uniform crystallized mixture, wherein Al 2 O 3 Aluminum source, P 2 O 5 The molar ratio of phosphorus source, template and solvent is: Al 2 O 3 :P 2 O 5 :Template R:Solvent S=1:0.5:0.75:25:67.5,Template R1(tetraethylammonium hydroxide) / Template R2(1-(3-aminopropyl)imidazole)=0.1,Solvent S1(N,N-dimethylbutyramide) / Solvent S2(water) / Solvent S3(cyclohexanone)=1:11:0.05;The above crystallization mixture was placed at 140℃ for 4d, and the product was filtered, washed and dried at 120℃ for 4h to obtain the product SCM-34(II). According to ICP test, the composition of the obtained SCM-34(II) molecular sieve is Al 2 O 3 :0.75P 2 O 5 , and its X-ray diffraction pattern is similar to that of SCM-34(I).

[0094] (II) Synthesis of GeAlPO-34 Molecular Sieve

[0095] At room temperature, 11.2 g of methoxygermanium, 263.4 g of morpholine and 131.5 g of piperazine were dissolved in 1285.2 g of dimethylformamide, stirred thoroughly and then heat treated at 70 ° C for 8.0 h to obtain a crystallization precursor CP 1 .

[0096] 112.3 g of the SCM-34 molecular sieve prepared in step (I) and 728.1 g of tetrapropylammonium hydroxide (40% aqueous solution) were weighed and mixed in 1139.8 g of acetone, and heat treated at 140° C. for 1.0 h to obtain a crystallized precursor CP 2 .

[0097] The crystallization precursor CP 1 Add the crystallization precursor CP under strong stirring 2After 5.0 hours of strong stirring, a crystallized mixture CM was formed, which was placed at 120°C for 1.0 hour of stirring, and then continued to settle for 24 hours, and then placed at 200°C for 12 hours of crystallization. The product was filtered, washed, dried at 100°C for 10 hours, and then heated to 600°C and calcined at a constant temperature for 4 hours to obtain the product, which was recorded as STG-2. Its XRD spectrum is similar to Figure 1 Similar, its SEM image and Figure 2 Similarly, ICP analysis revealed that its composition is Al 2 O 3 :0.8P 2 O 5 :0.02GeO 2 .

[0098] Example 3

[0099] (I) Synthesis of SCM-34 molecular sieve

[0100] Take 9.4 g of aluminum nitrate [Al(NO 3 ) 3 9H 2 O] was dissolved in 33.0 mL of deionized water and mixed to form solution C. Then, 8.6 g of phosphoric acid (purity ≥ 85 wt.%), 27 g of tetrabutylammonium hydroxide (40 wt.% aqueous solution, MkSeal) and 20.4 g of 1-(3-aminopropyl)imidazole were added to solution C. After stirring for 0.5 h and settling for 12 h, solution C' was obtained. Then, 13.8 mL of N,N-dibutylformamide and 4.3 mL of cyclohexanone were slowly added to solution C'. After stirring for 3.5 h, the mixture was heat treated at 90 ° C for 8 h to form a uniform crystallized mixture, wherein Al 2 O 3 Aluminum source, P 2 O 5 The molar ratio of phosphorus source, template and solvent is: Al 2 O 3 :P 2 O 5 :Template R:Solvent S=1:1.5:5:57.3,Template R1(tetrabutylammonium hydroxide) / Template R2(1-(3-aminopropyl)imidazole)=0.2,Solvent S1(N,N-dibutylformamide) / Solvent S2(water) / Solvent S3(cyclohexanone)=1:31.7:0.5;The above crystallization mixture was placed at 140℃ for crystallization for 5 days, and the product was filtered, washed and dried at 100℃ for 8 hours to obtain the product SCM-34(III). According to ICP test, the composition of the obtained SCM-34(III) molecular sieve is Al 2 O 3 :1.46P 2 O 5, and its X-ray diffraction pattern is similar to that of SCM-34(I).

[0101] (II) Synthesis of GeAlPO-34 Molecular Sieve

[0102] At room temperature, 26.1 g of germanium oxide, 1322.5 g of triethylamine and 2333.7 g of diethylamine were dissolved in 32025.5 g of water, stirred thoroughly, and then heat treated at 50 ° C for 12.0 h to obtain a crystallization precursor CP 1 .

[0103] Weigh 52.2 g of the SCM-34 molecular sieve prepared in step (I) and 1563.8 g of tetraethylammonium hydroxide (25% aqueous solution) in 21233.4 g of ethanol, and heat treat at 90° C. for 12.0 h to obtain a crystallized precursor CP 2 .

[0104] The crystallization precursor CP 1 Add the crystallization precursor CP under strong stirring 2 After 0.5 h of strong stirring, a crystallized mixture CM was formed, which was placed at 110 ° C for 2.0 h and then precipitated for 14 h. The mixture was then placed at 170 ° C for 72 h of crystallization. The product was filtered, washed, dried at 80 ° C for 9 h, and then heated to 450 ° C and calcined at a constant temperature for 7 h to obtain the product, which was recorded as STG-3. Figure 1 Similar, its SEM image and Figure 2 Similarly, ICP analysis revealed that its composition is Al 2 O 3 :1.5P 2 O 5 :0.05GeO 2 .

[0105] Example 4

[0106] (I) Synthesis of SCM-34 molecular sieve

[0107] Take 13.3 g of aluminum sulfate [Al 2 (SO 4 ) 3 18H 2 O] was dissolved in 19.1 mL of water and mixed to form solution C. Then, 2.1 g of phosphoric acid (purity ≥ 85 wt.%), 14.2 g of tetrabutylammonium hydroxide (40 wt.% aqueous solution, MkSeal) and 16.1 g of 1-(3-aminopropyl)imidazole were added to solution C. After stirring for 3 h and settling for 6 h, solution C' was obtained. Then, 5.1 mL of N,N-dimethylformamide and 0.9 mL of cyclohexanone were slowly added to solution C'. After stirring for 4.5 h, the mixture was heat treated at 80 ° C for 12 h to form a uniform crystallized mixture, wherein Al2 O 3 Aluminum source, P 2 O 5 The molar ratio of phosphorus source, template and solvent is: Al 2 O 3 :P 2 O 5 :Template R:Solvent S=1:0.9:10:80,Template R1(tetrabutylammonium hydroxide) / Template R2(1-(3-aminopropyl)imidazole)=0.22,Solvent S1(N,N-dimethylbutyramide) / Solvent S2(water) / Solvent S3(cyclohexanone)=1:48:0.3;The above crystallization mixture was placed at 140℃ for crystallization for 5 days, and the product was filtered, washed and dried at 100℃ for 8 hours to obtain the product SCM-34(IV). The composition of the obtained SCM-34(IV) molecular sieve is Al 2 O 3 :0.96P 2 O 5 , and its X-ray diffraction pattern is similar to that of SCM-34(I).

[0108] (II) Synthesis of GeAlPO-34 Molecular Sieve

[0109] At room temperature, 12.3 g of ethoxygermanium, 134.6 g of 1,3-dimethylimidazolium chloride, 252.3 g of pyridine and 2165.9 g of ethylene glycol were fully stirred, and then heat-treated at 75 ° C for 6.0 h to obtain a crystallization precursor CP 1 4.1 g of the SCM-34 molecular sieve prepared in step (I) and 388.2 g of tetraethylammonium bromide were weighed and mixed with 1666.9 g of water, and then heat-treated at 110° C. for 4.5 h to obtain a crystallized precursor CP. 2 . The crystallization precursor CP 1 Add the crystallization precursor CP under strong stirring 2 After 4.5 hours of strong stirring, a crystallized mixture CM was formed, which was placed at 105°C for 6.0 hours of stirring, and then continued to settle for 16 hours, and then placed at 195°C for 24 hours of crystallization. The product was filtered, washed, dried at 80°C for 8 hours, and then heated to 550°C and calcined at a constant temperature for 6 hours to obtain the product, which was recorded as STG-4. Its XRD spectrum is similar to Figure 1 Similar, its SEM image and Figure 2 Similarly, ICP analysis revealed that its composition is Al 2 O 3 :1.03P 2 O 5 :0.11GeO 2 .

[0110] Example 5

[0111] (I) Synthesis of SCM-34 molecular sieve

[0112] 408.5 g of aluminum isopropoxide was dissolved in 1010.5 mL of water and mixed to form solution C. Then, 253.6 g of phosphoric acid (purity ≥ 85 wt.%), 16920.7 g of tetrabutylammonium hydroxide (40 wt.% aqueous solution, MkSeal) and 21770.4 g of 1-(3-aminopropyl)imidazole were added to solution C. After stirring for 3 h and settling for 6 h, solution C' was obtained. Then, 1811.5 mL of N, N-dimethylbutanamide and 282.6 mL of cyclohexanone were slowly added to solution C'. After stirring for 1.5 h, the mixture was heat treated at 90 ° C for 11 h to form a uniform crystallized mixture, wherein Al 2 O 3 Aluminum source, P 2 O 5 The molar ratio of phosphorus source, template and solvent is: Al 2 O 3 :P 2 O 5 :Template R:Solvent S=1:1.1:50:158.6,Template R1(tetrabutylammonium hydroxide) / Template R2(1-(3-aminopropyl)imidazole)=0.15,Solvent S1(N,N-dimethylbutyramide) / Solvent S2(water) / Solvent S3(cyclohexanone)=1:53.9:0.22;Put the above crystallization mixture at 140℃ for 5d, and the product was filtered, washed and dried at 90℃ for 10h to obtain the product SCM-34(V). According to ICP test, the composition of the obtained SCM-34(V) molecular sieve is Al 2 O 3 :1.16P 2 O 5 , and its X-ray diffraction pattern is similar to that of SCM-34(I).

[0113] (II) Synthesis of GeAlPO-34 Molecular Sieve

[0114] At room temperature, 2.0 g of methoxygermanium, 12.3 g of piperidine, 13.4 g of ethylamine and 236.4 g of water were fully stirred, and then heat-treated at 80 ° C for 3.0 h to obtain a crystallization precursor CP 1 .

[0115] Weigh 0.5 g of the SCM-34 molecular sieve prepared in step (I) and 90.8 g of tetrabutylammonium hydroxide (40% aqueous solution) and mix them in 398.6 g of dimethylformamide, and heat treat at 115° C. for 3.5 h to obtain a crystallized precursor CP. 2 .

[0116] The crystallization precursor CP1 Add the crystallization precursor CP under strong stirring 1 After stirring for 2.5 hours, a crystallized mixture CM was formed, which was placed at 105°C and stirred for 10.5 hours; then placed at 150°C for crystallization for 108 hours. The product was filtered, washed, dried at 110°C for 5 hours, and then heated to 450°C and calcined at a constant temperature for 7 hours to obtain the product, which was recorded as STG-5. Its XRD spectrum is similar to Figure 1 Similar, its SEM image and Figure 2 Similarly, ICP analysis revealed that its composition is Al 2 O 3 :1.21P 2 O 5 :0.13GeO 2 .

[0117] Examples 6-10

[0118] According to the method for preparing SCM-34 and the method for preparing GeAlPO-34 molecular sieve in Example 1, the raw materials used are shown in Table 3, and the reaction material selection ratios and conditions (see Table 4) are controlled to synthesize GeAlPO-34 molecular sieves respectively.

[0119] Table 3

[0120]

[0121]

[0122] Table 4

[0123]

[0124] Comparative Example 1

[0125] According to the synthesis method of SAPO-34 molecular sieve described in the literature (Shandong Chemical Industry, 2023, 52(10):76-79.), the specific method is as follows: using pseudo-boehmite (65wt.%) as an aluminum source, phosphoric acid (85wt.%) as a phosphorus source, white carbon black (99wt.%) as a silicon source, and diethylamine as a template agent, according to the reaction ratio of 1Al 2 O 3 ∶1P 2 O 5 ∶0.6SiO 2 ∶2DEA∶40H 2O, a scheme in which the amount of aluminum source is fixed at 0.1 mol, 15.6 g of pseudo-boehmite is added to 70.3 g of deionized water, and after stirring evenly, 11.5 g of phosphoric acid is added, and stirring is continued for 1.5 h. Then, 14.6 g of diethylamine is added to the mixed solution, and after stirring and aging for 1.5 h, 3.6 g of white carbon black is added to the reaction system, and stirring is continued for several hours. After that, the sol is placed in a stainless steel reactor lined with polytetrafluoroethylene and crystallized at 200 ° C for 24 h to obtain SAPO-34 molecular sieve, and its XRD spectrum is shown in Figure 3 , its SEM picture is shown in Figure 4 .

[0126] Comparative Example 2

[0127] According to the literature (Chinese patent: CN104276580A), according to the reaction ratio GeO 2 :Al 2 O 3 :P 2 O 5 :R:NH 3 :H 2 O=1.15:1.00:1.00:0.80:3.2:135.5 Weigh each material, mix germanium oxide, boehmite, phosphoric acid, tetraethylammonium bromide, ammonia and water, stir for 20 minutes, put into a reactor, and crystallize at 150°C for 240 hours. The crystallized product is filtered, washed with water until the pH value is 8, and dried at 120°C for 12 hours to obtain GeAPO zeolite with CHA topological structure for use.

[0128] Application Example 1 Application of GeAlPO-34 molecular sieve in methanol to hydrocarbon reaction

[0129] The STG-1 molecular sieve synthesized in Example 1 was calcined at 550°C for 4 hours, and after cooling to room temperature, it was tableted, crushed, and sieved. The particles of 12-20 mesh were taken as catalyst for later use. Methanol was used as the raw material, and a fixed bed reactor with a diameter of 15 mm was used at 600°C and a mass space velocity of 15 h -1 Under the conditions of 10MPa and pressure, the yield of ethylene and propylene reached 70.8%, achieving good technical results.

[0130] Application Example 2: Application of GeAlPO-34 molecular sieve in methanol to hydrocarbon reaction

[0131] The STG-4 molecular sieve synthesized in Example 4 was used to prepare a catalyst in the same manner as in Application Example 1. Methanol was used as a raw material and a fixed bed reactor with a diameter of 15 mm was used at 550°C and a mass space velocity of 0.1 h -1 Under the conditions of 0.01MPa and pressure, the yield of ethylene and propylene reached 73.5%, achieving good technical results.

[0132] Application Example 3: Application of GeAlPO-34 molecular sieve in methanol conversion to hydrocarbons

[0133] The STG-6 molecular sieve synthesized in Example 6 was used to prepare a catalyst in the same manner as in Application Example 1. Methanol was used as the raw material. A fixed bed reactor with a diameter of 15 mm was used at 462°C and a mass space velocity of 2.2 h -1 Under the conditions of 1.4MPa and pressure, the yield of ethylene and propylene reached 87.7%, achieving good technical results.

[0134] Application Example 4: Application of GeAlPO-34 molecular sieve in methanol conversion to hydrocarbons

[0135] The STG-7 molecular sieve synthesized in Example 7 was used to prepare a catalyst in the same manner as in Application Example 1. Methanol was used as a raw material and a fixed bed reactor with a diameter of 15 mm was used at 400°C and a mass space velocity of 10.9 h / min. -1 Under the conditions of 5.7MPa and pressure, the yield of ethylene and propylene reached 80.6%, achieving good technical results.

[0136] Application Example 5: Application of GeAlPO-34 molecular sieve in methanol conversion to hydrocarbons

[0137] The STG-10 molecular sieve synthesized in Example 10 was used to prepare a catalyst in the same manner as in Application Example 1. Methanol was used as a raw material. A fixed bed reactor with a diameter of 15 mm was used at 430°C and a mass space velocity of 8.1 h -1 Under the conditions of 0.1MPa pressure, the ethylene and propylene yields reached 85.1%, achieving good technical results.

[0138] Application Example 6 Application of SAPO-34 molecular sieve in methanol conversion to hydrocarbons

[0139] The SAPO-34 molecular sieve synthesized in Comparative Example 1 was selected, and a catalyst was prepared by the same method as in Application Example 1. The catalyst was evaluated in the manner of Application Example 4, and the yields of ethylene and propylene reached 58.6%.

[0140] Application Example 7 Application of GeAPO zeolite with CHA topology in methanol conversion to hydrocarbons

[0141] The GeAPO zeolite with CHA topological structure synthesized in Comparative Example 2 was selected, and the catalyst was prepared by the same method as in Application Example 1. The catalyst was evaluated in the manner of Application Example 4, and the yield of ethylene and propylene reached 50.1%.

[0142] Application Example 8 Application of GeAlPO-34 molecular sieve in the reaction of synthesis gas to hydrocarbons

[0143] The STG-2 molecular sieve synthesized in Example 2 was calcined at 550°C for 6 h, then tableted, crushed, and sieved to obtain particles of 20-40 mesh. x / STG=2.0(ZnCrO x Represents a mixture of zinc oxide and chromium oxide) to obtain an oxide-molecular sieve catalyst for use. Using synthesis gas as raw material, a fixed bed reactor with a diameter of 15 mm was used. The process conditions were: reaction temperature 450°C, pressure 6.1 MPa, space velocity 1200 h -1 , the synthesis gas consists of H 2 / CO=2.5:1, the conversion rate of CO is 78.5%, of which C 2＝ -C 4＝ The selectivity was 91.7%.

[0144] Application Example 9: Application of GeAlPO-34 molecular sieve in the reaction of synthesis gas to hydrocarbons

[0145] The STG-3 molecular sieve synthesized in Example 3 was used to prepare a catalyst in the same manner as in Application Example 8. The process conditions were: reaction temperature 300°C, pressure 10 MPa, space velocity 2000 h -1 , the synthesis gas consists of H 2 / CO=0.5:1, the conversion rate of CO is 61.2%, of which C 2 ＝ -C 4 ＝ The selectivity was 79.8%.

[0146] Application Example 10 Application of GeAlPO-34 molecular sieve in the reaction of synthesis gas to hydrocarbons

[0147] The STG-5 molecular sieve synthesized in Example 5 was used to prepare a catalyst in the same manner as in Application Example 8. The process conditions were: reaction temperature 500°C, pressure 0.1 MPa, space velocity 20 h -1 , the synthesis gas consists of H 2 / CO=1:1, the conversion rate of CO is 70.8%, of which C 2＝ -C 4＝ The selectivity was 83.6%.

[0148] Application Example 11 Application of GeAlPO-34 molecular sieve in the reaction of synthesis gas to hydrocarbons

[0149] The STG-8 molecular sieve synthesized in Example 8 was used to prepare a catalyst using the same method as in Application Example 8. The process conditions were: reaction temperature 400°C, pressure 1 MPa, space velocity 100 h -1 , the synthesis gas consists of H 2 / CO=1.75:1, the conversion rate of CO is 71.9%, of which C 2＝ -C 4＝ The selectivity was 81.6%.

[0150] Application Example 12 Application of SAPO-34 molecular sieve in the reaction of synthesis gas to hydrocarbons

[0151] The SAPO-34 molecular sieve synthesized in Comparative Example 1 was selected, and the catalyst was prepared by the same method as in Application Example 8. The catalyst was evaluated in the same manner as in Application Example 9. The CO conversion rate was 32.4%, of which C 2＝ -C 4＝ The selectivity was 61.6%.

[0152] Application Example 13 Application of GeAPO zeolite with CHA topology in the reaction of synthesis gas to hydrocarbons

[0153] The GeAPO zeolite with CHA topology synthesized in Comparative Example 2 was selected, and the catalyst was prepared by the same method as in Application Example 8. The catalyst was evaluated in the same manner as in Application Example 11, and the CO conversion rate was 35.3%, of which C 2＝ -C 4＝ The selectivity was 55.5%.

[0154] 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 GeAlPO-34 molecular sieve, the X-ray diffraction spectrum of the GeAlPO-34 molecular sieve includes the X-ray diffraction peaks shown in the following table: 。 2. The GeAlPO-34 molecular sieve according to claim 1, characterized in that The GeAlPO-34 molecular sieve comprises Al2O3, P2O5 and GeO2. Preferably, the molar ratio of Al2O3 to P2O5 is 1:(0.8-1.4), and the molar ratio of Al2O3 to GeO2 is 1:(0.01-0.2).

3. A method for preparing GeAlPO-34 molecular sieve, comprising the following steps: S1: subjecting a germanium source and a first template to a first heat treatment in the presence of a first solvent to obtain a first crystallization precursor; S2: subjecting the SCM-34 molecular sieve and the second template to a second heat treatment in the presence of a second solvent to obtain a second crystallization precursor; S3: subjecting the mixture containing the first crystallization precursor and the second crystallization precursor to a crystallization reaction to obtain a GeAlPO-34 molecular sieve.

4. The preparation method according to claim 3, characterized in that: The SCM-34 molecular sieve has a schematic chemical composition as shown in the formula "Al2O3:zP2O5", wherein 0.75≤z≤1.5; Preferably, in the X-ray diffraction spectrum data of the SCM-34 molecular sieve, the 2θ angle of the strongest peak in the range of 2θ angle 5-50° is 7.59±0.2; More preferably, the X-ray diffraction spectrum of the SCM-34 molecular sieve includes the X-ray diffraction peaks shown in the following table: 。 5. The preparation method according to claim 3 or 4, characterized in that: The first template comprises at least one of 1,3-dimethylimidazolium chloride, n-butylamine, triethylamine, diethylamine, ethylamine, piperidine or morpholine; and / or The second template comprises a quaternary ammonium base cationic template, preferably, the second template comprises at least one of tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, tetramethylammonium bromide, tetraethylammonium bromide, tetrapropylammonium bromide or tetrabutylammonium bromide; and / or The first solvent and / or the second solvent are each independently selected from at least one of methanol, ethanol, ethylene glycol, pentanol, butanol, octanol, acetone, pyridine, 1,4-dioxane or dimethylformamide; and / or The germanium source comprises at least one of germanium oxide, methoxy germanium and ethoxy germanium; and / or The ratio of the mass of the SCM-34 molecular sieve to the mass sum of the first template and the second template is 1:(10-500); and / or The ratio of the mass of the SCM-34 molecular sieve to the mass sum of the first solvent and the second solvent is 1:(50-10000); and / or The mass ratio of the SCM-34 molecular sieve to the germanium source is 1:(0.1-10), preferably 1:(0.1-5); and / or The mass ratio of the first template to the second template is 1:(0.01-100), preferably 1:(0.1-10); and / or The mass ratio of the first solvent to the second solvent is 1:(0.01-100), preferably 1:(0.1-10).

6. The preparation method according to any one of claims 3 to 5, characterized in that: The temperature of the first heat treatment is 50-100°C and the time is 1-12h; preferably, the temperature of the first heat treatment is 70-85°C and the time is 2-8h; and / or The temperature of the second heat treatment is 90-140°C and the time is 1-12h; preferably, the temperature of the second heat treatment is 100-120°C and the time is 3-6h; and / or The temperature of the crystallization reaction is 140-200° C., and the time is 12-120 h; preferably, the temperature of the crystallization reaction is 140-200° C., and the time is 12-120 h.

7. The preparation method according to any one of claims 3 to 6, characterized in that: The method further includes pre-treating the mixture of the first crystallization precursor and the second crystallization precursor before the crystallization reaction; Preferably, the pretreatment comprises stirring at 100-120°C for 1-10 hours, and then settling at 100-120°C for 12-24 hours.

8. The preparation method according to any one of claims 3 to 7, characterized in that: The method further comprises washing, drying and calcining the product of the crystallization reaction; Preferably, the calcination temperature is 400-600° C. and the calcination time is 2-12 hours.

9. A catalyst, comprising the GeAlPO-34 molecular sieve according to claim 1 or a calcined product of the GeAlPO-34 molecular sieve obtained by the preparation method according to any one of claims 2 to 8, Preferably, the calcination temperature is 400-600° C. and the calcination time is 2-12 hours.

10. Use of the GeAlPO-34 molecular sieve according to claim 1, the GeAlPO-34 molecular sieve obtained by the preparation method according to any one of claims 2 to 8, or the catalyst according to claim 9 in hydrocarbon production reactions, Preferably, the hydrocarbon production reaction includes a methanol-to-hydrocarbons reaction or a synthesis gas-to-olefins reaction.

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