Me-SCM-34 molecular sieve and its preparation and application

Abstract

The present invention discloses a Me-SCM-34 molecular sieve, a method for preparing the same, and applications thereof. The Me-SCM-34 molecular sieve comprises the following components, measured by weight: (1) 0.1 to 20 parts of the metal element Me; and (2) 80 to 99.9 parts of an SCM-34 molecular sieve. The molecular sieve has a novel framework structure and is inexpensive to prepare. It exhibits high activity and stability when used in methanol-to-olefins and hydrogenation reactions.

Description

Technical Field

[0001] The present invention relates to the field of molecular sieves, and in particular to a Me-SCM-34 molecular sieve and a preparation method and application thereof, wherein Me is a metal heteroatom. Background Art

[0002] Porous materials are a class of solid compounds with regular pore structures. According to the definition of the International Union of Pure and Applied Chemistry (IUPAC), porous materials with pore diameters less than 2nm are classified as microporous materials; those with pore diameters greater than 2nm are classified as mesopore materials or macropore materials (pore diameters greater than 50nm). Molecular sieve materials generally have pore diameters less than 2nm, making them microporous materials. They are a class of porous materials characterized by selective adsorption. Their unique pore system enables them to sieve small molecules of varying sizes, hence the name "molecular sieve." These materials, with their wide range of pore size distribution and rich and diverse topological structures, are widely used in fields such as adsorption separation, heterogeneous catalysis, as carriers for various guest molecules, and ion exchange, achieving excellent technical results.

[0003] Traditional zeolite molecular sieve is a crystalline silicate material, generally composed of silicon oxygen tetrahedron [SiO4] 4- and aluminum oxide tetrahedron [AlO4] 5- They are connected by shared oxygen atoms and are collectively referred to as TO4 tetrahedrons (primary structural units). The silicon element can also be partially isomorphously replaced by other elements, especially some trivalent or tetravalent elements such as Al, B, Ga, Ge, Ti, etc. Due to the peculiarities of their structure and chemical properties, zeolite molecular sieves are widely used in catalysis, adsorption, and ion exchange. A key factor in determining the application performance of molecular sieves is their pore or cage characteristics, which are determined by the intrinsic crystal structure of the molecular sieve. Therefore, obtaining molecular sieves with new crystal structures is of great significance for expanding the application of molecular sieves.

[0004] In 1982, scientists ST Wilson and EMF Lanigen of Union Carbide Corporation (UCC) in the United States successfully synthesized and developed a new family of molecular sieves using aluminum sources, phosphorus sources and organic templates - aluminum phosphate molecular sieve AlPO4-n, where n represents the model. Two years later, based on AlPO4-n, UCC used Si atoms to partially replace the Al atoms and P atoms in the AlPO framework, and successfully prepared another series of silicoaluminophosphate molecular sieves: SAPO-n, where n represents the model. In the structure of SAPO-n, Si atoms replace the P or Al atoms in the original AlPO to form a non-neutral molecular sieve framework composed of SiO4, AlO4 and PO4 tetrahedrons. In the framework of this type of molecular sieve, silicon exists in two ways: (1) one Si atom replaces one P atom; (2) two silicon atoms replace a pair of aluminum atoms and phosphorus atoms respectively. The most representative SAPO-n molecular sieve is the SAPO-34 molecular sieve with a topological structure of CHA. The molecular sieve has a framework structure similar to chabazite and belongs to the cubic crystal system. The structural unit is AlO2 - , SiO2 and PO2 + It is composed of tetrahedra, and its skeleton contains a three-dimensional cross structure of ellipsoidal supercages and 8-membered ring channels. The pore diameter of the 8-membered ring channels is about 0.38nm, and the pore diameter of the supercage is maintained between 0.43 and 0.50nm. Due to its suitable proton acidity, large specific surface area, good adsorption performance, good thermal stability, good hydrothermal stability and excellent shape selectivity for light olefins in the pore structure, SAPO-34 molecular sieve has been successfully commercialized as a catalyst for methanol to light olefins (MTO), and has demonstrated good catalytic activity and selectivity.

[0005] Currently, most of the known topologically linked molecular sieves are prepared by hydrothermal or solvent thermal synthesis methods. The main steps of a typical hydrothermal or solvent thermal synthesis method are to first evenly mix the reactants such as metal source, non-metal source, organic template, solvent, etc. to obtain an initial sol, i.e., a crystallization mixture, and then place the crystallization mixture in a reactor lined with polytetrafluoroethylene and stainless steel as the outer wall. After sealing, the reaction mixture is crystallized at a certain temperature and autogenous pressure, i.e., the process in which the molecular sieve crystals precipitate from the crystallization mixture. Specifically, taking the synthesis of silicon-phosphorus-aluminum 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, which are evenly mixed and placed statically or dynamically in a fixed temperature oven (160-220°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 later use.

[0006] According to the website of the International Molecular Sieve Association, there are a total of 255 molecular sieves with different topological structures, including the newly obtained AlPO-91 molecular sieve with ANO topology ("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)). Although many different crystalline molecular sieves have been obtained, new molecular sieves with desired properties for gas separation and drying, hydrocarbon conversion reactions and other applications are still needed. Summary of the Invention

[0007] The present invention provides a metal heteroatom-containing SCM-34 molecular sieve, namely Me-SCM-34 molecular sieve, and its preparation method and application. The molecular sieve has a novel skeleton structure and is low in production cost. It exhibits high activity and stability when used in methanol-to-olefins and hydrogenation reactions.

[0008] The first aspect of the present invention provides a Me-SCM-34 molecular sieve comprising the following components in parts by weight:

[0009] (1) 0.1 to 20 parts, preferably 0.6 to 16 parts, of the metal element Me;

[0010] (2) 80 to 99.9 parts, preferably 84 to 99.4 parts, of SCM-34 molecular sieve.

[0011] Furthermore, in the Me-SCM-34 molecular sieve, Me is at least one of Co, Ni, and Cu, preferably Co.

[0012] Furthermore, the Me-SCM-34 molecular sieve is synthesized in situ.

[0013] Furthermore, the SCM-34 molecular sieve has a schematic chemical composition as shown in the formula "Al2O3:xSiO2:yP2O", wherein 0≤x≤0.5, 0.75≤y≤1.5.

[0014] Furthermore, in the XRD diffraction data of the Me-SCM-34 molecular sieve, the 2θ angle of the strongest peak in the range of 5-50° is 7.59±0.2; the X-ray diffraction pattern of the Me-SCM-34 molecular sieve includes the X-ray diffraction peaks shown in the following table:

[0015] 2θ(°) <![CDATA[Relative intensity, [(I / I0)×100]]]> 7.59±0.2 100 10.81±0.1 5-70 16.52±0.1 5-70 17.97±0.1 5-70 23.34±0.05 5-50 34.74±0.05 5-50

[0016] Furthermore, the X-ray diffraction pattern of the Me-SCM-34 molecular sieve also includes the X-ray diffraction peaks shown in the following table:

[0017] 2θ(°) <![CDATA[Relative intensity, [(I / I0)×100]]]> 14.25±0.1 5-50 21.01±0.1 10-20 24.27±0.05 5-70 26.05±0.05 5-50 27.82±0.05 5-50 28.15±0.02 5-50 30.03±0.02 5-50

[0018] Furthermore, the X-ray diffraction pattern of the Me-SCM-34 molecular sieve also includes the X-ray diffraction peaks shown in the following table:

[0019]

[0020]

[0021] The incident ray of X-ray diffraction is Cu Kα1.

[0022] The second aspect of the present invention provides a method for preparing Me-SCM-34 molecular sieve, comprising: synthesizing Me-SCM-34 molecular sieve using an amine chelate of metal Me (hereinafter referred to as Me amine chelate) as a template.

[0023] Furthermore, the method includes: preparing a mixed solution containing Me amine chelate and an aluminum source, then mixing it with a phosphorus source and an optionally added silicon source to obtain a crystallized mixture, and then performing a crystallization reaction to obtain a Me-SCM-34 molecular sieve.

[0024] Preferably, the preparation method of the Me-SCM-34 molecular sieve comprises the following steps:

[0025] a. Mixing an aluminum source and a solvent to form solution A;

[0026] b. adding the Me amine chelate source to solution A and stirring to form a mixture A1;

[0027] c. mixing a phosphorus source and an optionally added silicon source with the mixture A1 to form a crystallized mixture A2;

[0028] d. subjecting the crystallization mixture A2 to a crystallization reaction to obtain Me-SCM-34 molecular sieve;

[0029] The aluminum source is calculated as Al2O3, the silicon source is calculated as SiO2, the phosphorus source is calculated as P2O5, the Me amine chelate source is calculated as Me amine chelate, and the molar ratio of the solvent is 1:0~1:0.5~2:0.5~50:5~500.

[0030] Furthermore, the molar ratio of the aluminum source used is calculated as Al2O3, the silicon source is calculated as SiO2, the phosphorus source is calculated as P2O5, the Me amine chelate source is calculated as Me amine chelate, and the solvent is 1:0.1~0.75:0.75~1.5:5~35:25~300.

[0031] Furthermore, in step a, the solvent is preferably water.

[0032] Furthermore, the Me amine chelate source can be a Me salt and a chelating agent, or an amine chelate prepared from a Me salt and a chelating agent. The Me salt is selected from at least one of Me sulfates, nitrates, carbonates, and acetates. If Me is Co, the cobalt salt is selected from at least one of cobalt sulfate, cobalt nitrate, cobalt carbonate, and cobalt acetate. The chelating agent is selected from at least one of ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, 1,10-phenanthroline, 2,2-bipyridine, or 4,4-bipyridine; preferably, selected from at least one of diethylenetriamine, triethylenetetramine, and tetraethylenepentamine.

[0033] Furthermore, the aluminum source is selected from at least one of aluminum isopropoxide, aluminum salts, aluminum hydroxides, aluminum oxides and aluminum-containing minerals; and / or the silicon source is selected from at least one of organosilicon, silica sol, solid silicon oxide and diatomaceous earth; and / or the phosphorus source is selected from at least one of phosphoric acid, ammonium monohydrogen phosphate and ammonium dihydrogen phosphate; preferably, the aluminum source is selected from aluminum isopropoxide; and / or the silicon source is selected from at least one of silica sol and solid silicon oxide; and / or the phosphorus source is selected from phosphoric acid.

[0034] Furthermore, in step d, the crystallization conditions include: a crystallization temperature of 120 to 200° C., preferably 140 to 180° C., more preferably 140 to 160° C.; and / or a crystallization time of 1 to 7 days, preferably 2 to 5 days, more preferably 3 to 5 days.

[0035] Furthermore, in step d, after the crystallization reaction, conventional post-treatment is performed, such as filtering, washing, and drying to obtain the molecular sieve; and optionally, the molecular sieve obtained is calcined. The washing can be performed using conventional methods in the art, such as using a conventional solvent such as ethanol, acetone, or deionized water for thorough washing. The drying conditions are drying at 60-100°C for 4-24 hours. The calcination conditions are calcining at 400-600°C for 2-15 hours.

[0036] The third aspect of the present invention provides the use of the Me-SCM-34 molecular sieve and the Me-SCM-34 molecular sieve prepared according to any of the aforementioned methods.

[0037] Furthermore, the application is the use of the Me-SCM-34 molecular sieve in methanol to olefins or hydrogenation reactions.

[0038] Furthermore, the reaction conditions of methanol to olefins are: using methanol as raw material, reaction temperature is 400-600°C, reaction pressure is 0.1-10 MPa, methanol weight space velocity is 0.1-15h -1 .

[0039] Furthermore, the conditions for the hydrogenation reaction are: the application of the Me-SCM-34 molecular sieve in the hydrogenation reaction of unsaturated compounds or polymers with unsaturated bonds; more preferably, the Me-SCM-34 molecular sieve is suitable for the hydrogenation process of unsaturated components in the cracking of carbon nine and above hydrocarbon fractions. The reaction conditions are: reaction temperature of 30-100 ° C, reaction pressure of 2.0-3.5 MPa, and volume space velocity of 1.0-2.5 hours per hour. -1 , the hydrogen / oil volume ratio is 100-600:1.

[0040] Furthermore, the application can also be to prepare Me-AFI molecular sieve or Me-SAPO-17 molecular sieve by crystallization of the Me-SCM-34 molecular sieve.

[0041] The method for preparing Me-AFI molecular sieve from Me-SCM-34 molecular sieve comprises: mixing the Me-SCM-34 molecular sieve with water and heat-treating it to obtain a precursor; mixing a template with water to obtain a mixture; mixing the precursor with the mixture, pretreating it, and then performing a crystallization reaction to obtain the Me-AFI molecular sieve. The template is at least one of triethylamine, n-butylamine, di-n-propylamine, diisopropylamine, ethylenediamine, and ethylamine. The mass ratio of the Me-SCM-34 molecular sieve solid, water, and template is 1:1-15:0.1-10. The heat treatment, pretreatment, and crystallization reaction conditions for preparing the Me-AFI molecular sieve can be carried out according to conventional methods in the art.

[0042] The method for preparing Me-SAPO-17 molecular sieve from Me-SCM-34 molecular sieve comprises: mixing the Me-SCM-34 molecular sieve with a template and water, heat-treating the mixture to obtain a precursor; then subjecting the mixture to pretreatment and crystallization to obtain the Me-SAPO-17 molecular sieve. The template is at least one of cyclohexylamine, piperazine, and pyridine; and the mass ratio of the Me-SCM-34 molecular sieve solid to water and the template is 1:1 to 20:0.5 to 5. The heat treatment, pretreatment, and crystallization conditions for preparing the Me-SAPO-17 molecular sieve can be performed according to conventional methods in the art.

[0043] Compared with the prior art, the present invention has the following advantages:

[0044] (1) The Me-SCM-34 molecular sieve of the present invention is a new type of molecular sieve with a novel framework structure, which enriches the types of molecular sieves;

[0045] (2) The Me-SCM-34 molecular sieve of the present invention is used in methanol to olefins or hydrogenation reactions and has high activity, wherein the methanol conversion rate is 100% and the single-pass selectivity of ethylene and propylene is high;

[0046] (3) The Me-SCM-34 molecular sieve of the present invention can be crystallized to prepare Me-AFI molecular sieve and Me-SAPO-17 molecular sieve, which enriches the preparation methods of AFI molecular sieve and SAPO-17 molecular sieve. BRIEF DESCRIPTION OF THE DRAWINGS

[0047] Figure 1 is the XRD diffraction pattern of Co-SCM-34, the product of Example 3;

[0048] Figure 2 is a SEM photograph of the product Co-SCM-34 of Example 3;

[0049] Figure 3 is the XRD diffraction pattern of Cu-SCM-34, the product of Example 10;

[0050] Figure 4 is a SEM photograph of Cu-SCM-34, the product of Example 10;

[0051] Figure 5 is the XRD diffraction pattern of Ni-SCM-34, the product of Example 14;

[0052] Figure 6 is a SEM photograph of Ni-SCM-34, the product of Example 14;

[0053] Figure 7 is the XRD diffraction pattern of Co-AFI, the product of Example 21;

[0054] Figure 8 is a SEM photograph of the product Co-AFI of Example 21;

[0055] Figure 9 is the XRD diffraction pattern of Co-SAPO-17, the product of Example 22;

[0056] Figure 10 This is a SEM photograph of Co-SAPO-17, the product of Example 22. DETAILED DESCRIPTION

[0057] For ease of understanding of the present invention, the present invention enumerates the following examples. However, it should be understood by those skilled in the art that the examples are merely helpful in understanding the present invention and should not be considered as specific limitations of the present invention. The endpoints of the ranges disclosed in the present invention and any values ​​are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. In the present invention, unless otherwise expressly stated, percentages and percentage compositions are all by mass.

[0058] Unless otherwise specified, the instruments used in the present invention are conventional instruments in the art.

[0059] In the present invention, the crystalline phase of the molecular sieve product was determined using an X'Pert PRO X-ray powder diffraction (XRD) instrument from PANalytical (Netherlands), operating at 40 kV, 40 mA, and a scanning range of 5 to 50°. The product morphology was photographed using an S-4800 field emission scanning electron microscope (Fe-SEM) from HITACHI (Japan).

[0060] In the present invention, the metal element content in the molecular sieve product is determined on a plasma Perkin-Elmer 3300DVICP analyzer. The specific operation method is as follows: the sample is placed in a 100°C oven to dry for 2 hours. Then, 0.2-0.5g of the dried sample is weighed into a crucible, 10 drops of sulfuric acid solution with a volume ratio of 1:1 and 8mL of hydrofluoric acid are added, and the sample is heated and shaken frequently to accelerate the decomposition. After the solution in the crucible is clear, the solution is evaporated until white smoke disappears, removed and cooled, and 5mL of 1:1 hydrochloric acid and an appropriate amount of water are added. The residue is heated to dissolve, and then transferred to a 100mL volumetric flask. The crucible is rinsed with water, diluted to the scale, and shaken to mix well. The prepared solution is introduced into an ICP spectrometer for analysis, and the percentage content is recorded.

[0061] The raw materials involved in the specific implementation of the present invention are as follows:

[0062] Aluminum sulfate [Al2(SO4)3·18H2O]: contains Al2O3, 15.7% by weight, industrial product;

[0063] Aluminum isopropoxide [Al(iPr)3]: contains Al2O3, 24.9 wt%;

[0064] Aluminum nitrate [Al2(NO3)3·9H2O]: contains Al2O3, 27.5 wt%;

[0065] Cobalt sulfate [CoSO4·6H2O]: contains CoO, 26.7 wt%;

[0066] Cobalt acetate [Co(OAc)2·4H2O]: contains CoO, 30.1 wt%;

[0067] Cobalt chloride [CoCl2·6H2O]: contains CoO, 31.5 wt%;

[0068] Copper nitrate [Cu(NO3)2·6H2O]: CuO, 27.1 wt%;

[0069] Nickel nitrate [Ni(NO3)2·6H2O]: contains NiO, 25.6 wt%;

[0070] Phosphoric acid (purity ≥ 85 wt.%): containing P2O5, 72.3 wt.%, commercially available;

[0071] Acidic silica sol (40 wt.% aqueous solution): containing SiO2, 40 wt%, commercially available;

[0072] White carbon black: contains SiO2, 99% by weight.

[0073] [Example 1]

[0074] Synthesis of Co-SCM-34 Molecular Sieve Materials Using Cobaltamine Chelates as Templates

[0075] 13.02 g of aluminum isopropoxide solid [Al(iPr)3] was weighed and dissolved in 213.7 mL of deionized water. After stirring evenly, 168.7 g of cobalt sulfate solid (CoSO4·6H2O) and 61.9 g of diethylenetriamine solution (DETA, 99 wt%) were added and stirred thoroughly. 8.3 g of phosphoric acid (H3PO4, purity ≥85 wt.%) and 1.8 g of silica sol (SiO2, 40 wt.%) were added under stirring. The mixture was sealed and vigorously stirred until uniformly mixed. After complete mixing, the crystallized mixture was placed in a polytetrafluoroethylene-lined pressure vessel and crystallized at 120°C for 7 days. The product was filtered and washed, and then dried at 90°C for 6 h. Then the temperature was raised to 600°C and calcined at a constant temperature for 6 h to obtain the product, which was recorded as CS-1 and characterized by XRD as Me-SCM-34 molecular sieve. The stoichiometric ratios of the reactants in this system—the aluminum source (calculated as Al2O3), the silicon source (calculated as SiO2), the phosphorus source (calculated as P2O5), the metal chelate template, and the solvent—were in a molar ratio of Al2O3:SiO2:P2O5:cobalamine chelate:solvent = 1:0.2:1.2:10:200. ICP analysis revealed that the product contained 6 parts by weight of Co and 94 parts by weight of SCM-34 molecular sieve. The XRD peak intensities of the product CS-1 are shown in Table 1.

[0076] Table 1

[0077] 2θ(°) <![CDATA[Relative intensity, [(I / I0)×100]]]> 7.70 100 10.40 9 10.90 50 12.18 5 14.35 8 16.53 52 17.99 27 19.69 12 21.11 14 23.38 26 24.31 42 26.10 30 27.85 5 28.16 20 30.05 22 31.33 8 34.74 20 38.30 16

[0078] [Example 2]

[0079] Synthesis of Co-SCM-34 Molecular Sieve Materials Using Cobaltamine Chelates as Templates

[0080] Weigh 2221.66g of aluminum isopropoxide [Al(iPr)3] and dissolve it in 9622.7mL of water. Stir well and add 67749.7g of cobalt acetate solid [Co(OAc)2·4H2O=C4H6O4·Co·4H2O, 249.08] and 39777.3g of triethylenetetramine solution (TETA, 99%) and stir well. Add 1129.0g of phosphoric acid (H3PO4, purity ≥85wt.%) and 391.7g of white carbon black (SiO2, 99wt%) under stirring. Stir vigorously in a closed container until the mixture is evenly mixed. After homogenization, the crystallization mixture was placed in a polytetrafluoroethylene-lined pressure vessel and crystallized at 200°C for 1 day. The product was filtered, washed, and dried at 80°C for 12 hours. The product was then heated to 550°C and calcined at this temperature for 10 hours to obtain the product, designated CS-2. XRD characterization confirmed it to be Me-SCM-34 molecular sieve. The stoichiometric ratios of the reactants in this system (aluminum source calculated as Al2O3, silicon source calculated as SiO2, phosphorus source calculated as P2O5, metal chelate template, and solvent) were 1:0.6:0.9:25:50. ICP analysis revealed that the product contained 10 parts by weight of Co and 90 parts by weight of SCM-34 molecular sieve. The XRD peak intensities corresponding to the X-ray diffraction peaks of the product CS-2 are shown in Table 2.

[0081] Table 2

[0082] 2θ(°) <![CDATA[Relative intensity, [(I / I0)×100]]]> 7.50 100 10.30 15 10.90 52 12.02 18 14.20 10 16.46 66 17.95 58 19.78 25 21.03 15 23.28 32 24.26 44 25.99 36 27.73 16 28.14 18 29.98 10 31.33 19 34.72 6 38.28 22

[0083] [Example 3]

[0084] Synthesis of Co-SCM-34 Molecular Sieve Materials Using Cobaltamine Chelates as Templates

[0085] Weigh 375.1 g of aluminum nitrate [Al(NO3)3·9H2O] and dissolve it in 1755.7 mL of deionized water. Stir well and then add 2431.5 g of Co-DETA chelate (prepared by cobalt salt and diethylenetriamine, n Co :n DETA=1:1), after thorough stirring, 115.3 g of phosphoric acid (H3PO4, purity ≥85 wt%) and 45.0 g of silica sol (SiO2, 40 wt%) were added, and the mixture was sealed and vigorously stirred until uniformly mixed. After complete mixing, the crystallization mixture was placed in a polytetrafluoroethylene-lined pressure vessel and crystallized at 140°C for 5 days. The product was filtered and washed, and then dried at 100°C for 10 hours after washing. Then, the temperature was raised to 600°C and constant temperature calcined for 6 hours to obtain the product, which was recorded as CS-3. The stoichiometric ratio of the reactants in this system, the molar ratio of the aluminum source calculated as Al2O3, the silicon source calculated as SiO2, the phosphorus source calculated as P2O5, the metal chelate template and the solvent was Al2O3:SiO2:P2O5:cobalamine chelate:solvent = 1:0.3:1.0:15:100. ICP test shows that the content of Co in the product is 8 parts by weight and the content of SCM-34 molecular sieve is 92 parts by weight. The XRD diffraction pattern of the product CS-3 is shown in Figure 1 The corresponding X-ray diffraction peak intensities are shown in Table 3, and the SEM photos are shown in Figure 2 .

[0086] Table 3

[0087]

[0088]

[0089] [Example 4]

[0090] Synthesis of Co-SCM-34 Molecular Sieve Materials Using Cobaltamine Chelates as Templates

[0091] 151.1 g of aluminum sulfate solid [Al2(SO4)3·18H2O, purity ≥98 wt.%] was weighed and dissolved in 2065.9 mL of deionized water. After stirring, 32.3 g of cobalt sulfate (CoSO4·7H2O) and 6.9 g of ethylenediamine (DEA) were added. 13.3 g of phosphoric acid (H3PO4, purity ≥85 wt.%) and 3.5 g of silica sol (SiO2, 40 wt%) were added under stirring. The mixture was sealed and vigorously stirred until uniformly mixed. After complete mixing, the crystallized mixture was placed in a polytetrafluoroethylene-lined pressure-resistant container and crystallized at 160 ° C for 3 days. The product was filtered and washed, and then dried at 110 ° C for 8 h. Then the temperature was raised to 550 ° C and calcined at a constant temperature for 9 h to obtain the product, which was recorded as CS-4. XRD characterization showed that it was Me-SCM-34 molecular sieve. The XRD pattern was consistent with that of the product. Figure 1The stoichiometric ratios of the reactants in this system—the aluminum source calculated as Al2O3, the silicon source calculated as SiO2, the phosphorus source calculated as P2O5, the metal chelate template, and the solvent—are in a molar ratio of Al2O3:SiO2:P2O5:cobalamine chelate:solvent = 1:1:0.5:0.5:500. ICP testing indicates that the product contains 1 part Co and 99 parts SCM-34 molecular sieve by weight.

[0092] [Example 5]

[0093] Synthesis of Co-SCM-34 Molecular Sieve Materials Using Cobaltamine Chelates as Templates

[0094] Weigh 18.8g of aluminum nitrate solid [Al(NO3)3·9H2O] and dissolve it in 270mL of water. After stirring evenly, add 416.4g of cobalt chloride solid (CoCl2·6H2O) and 331.3g of tetraethylenepentamine solution (TEPA). Under stirring, add 8.7g of phosphoric acid (purity ≥85wt.%) and 0.3g of white carbon black (SiO2, 99wt.%). Stir vigorously in a closed manner until the mixture is uniformly mixed. After complete mixing, place the crystallized mixture in a polytetrafluoroethylene-lined pressure-resistant container and crystallize at 180°C for 2d. The product is filtered and washed, and then dried at 100°C for 9h after washing. Then, the temperature is raised to 450°C and calcined at a constant temperature for 12h to obtain the product, which is recorded as CS-5. It is characterized by XRD as Me-SCM-34 molecular sieve. The XRD pattern is the same as that of CS-5. Figure 1 The stoichiometric ratios of the reactants in this system—the aluminum source calculated as Al2O3, the silicon source calculated as SiO2, the phosphorus source calculated as P2O5, the metal chelate template, and the solvent—are in a molar ratio of Al2O3:SiO2:P2O5:cobalamine chelate:solvent = 1:0.1:1.5:35:300. ICP testing indicates that the product contains 14 parts by weight of Co and 86 parts of SCM-34 molecular sieve.

[0095] [Examples 6 to 20]

[0096] According to the method of Example 5, the raw materials used are shown in Table 4, and the reaction materials are controlled to select different ratios (Table 5) to synthesize Me-SCM-34 molecular sieve materials.

[0097] Table 4

[0098]

[0099] Table 5

[0100]

[0101]

[0102] [Example 21]

[0103] Preparation of Co-AFI molecular sieve using Co-SCM-34 molecular sieve as raw material

[0104] At room temperature, 3.3g of CS-5 molecular sieve and 6.6g of deionized water were fully mixed and then placed at 60℃ for heat treatment for 2h to obtain precursor A. 1.1g of triethylamine liquid (TEA) was weighed and mixed with 4.4mL of deionized water, and stirred for 0.5h to form mixture B. Precursor A was added to mixture B under closed stirring, and after continuing to stir for 0.5h, it was placed at 110℃ and stirred for 15h; the above stirred mixture was then placed at 140℃ for crystallization for 1d, filtered and washed, and dried at 90℃ for 8h, then heated to 500℃ and calcined at a constant temperature for 8h to obtain Co-AFI molecular sieve. According to ICP testing, the product contains 11 parts of Co element and 89 parts of AFI molecular sieve in parts by weight. Its XRD diffraction pattern is shown in Figure 2. Figure 7 , SEM photos see Figure 8 .

[0105] [Example 22]

[0106] Preparation of Co-SAPO-17 molecular sieve using Co-SCM-34 molecular sieve as raw material

[0107] At room temperature, 0.6 g of CS-6 molecular sieve, 1.2 g of cyclohexylamine liquid (CHA) and 3.2 g of water were weighed and mixed, and heat-treated at 80°C for 1.5 h to obtain precursor A. Precursor A was placed at 110°C and vigorously stirred for 0.5 h to form a crystallized mixture; then placed at 160°C for crystallization for 1.5 days. The product was filtered, washed, and dried at 120°C for 4 h, then heated to 500°C and calcined at constant temperature for 6 h to obtain Co-SAPO-17 molecular sieve, whose XRD diffraction pattern is shown in FIG. Figure 9 , SEM photos see Figure 10 .

[0108] [Example 23]

[0109] Application of Me-SCM-34 catalyst in methanol conversion to hydrocarbons.

[0110] Take the CS-11 molecular sieve synthesized in Example 11, press, crush and sieve, and take 20-40 mesh particles for use. Use methanol as raw material, use a fixed bed reactor with a diameter of 15 mm, at 400 ° C and a mass space velocity of 1.0 h -1 Under the conditions of 1.0MPa and pressure, the yield of ethylene and propylene can reach 83.2%, achieving good technical results.

[0111] [Example 24]

[0112] Application of Me-SCM-34 catalyst in methanol conversion to hydrocarbons.

[0113] The CS-20 molecular sieve synthesized in Example 20 was used to prepare a catalyst using the catalyst preparation method of Example 23. Methanol was used as the raw material and a fixed bed reactor with a diameter of 15 mm was used at 350°C and a mass space velocity of 1.2 h -1 Under the conditions of 3.3MPa and pressure, the yield of ethylene and propylene can reach 82.1%, achieving good technical results.

[0114] [Example 25]

[0115] Application of Me-SCM-34 catalyst in methanol conversion to hydrocarbons.

[0116] The CS-14 molecular sieve synthesized in Example 14 was used to prepare a catalyst using the catalyst preparation method of Example 23. Methanol was used as the raw material and a fixed bed reactor with a diameter of 15 mm was used at 500°C and a mass space velocity of 10.0 h -1 Under the conditions of 4.10MPa and pressure, the yield of ethylene and propylene can reach 84.0%, achieving good technical results.

[0117] [Example 26]

[0118] Application of Me-SCM-34 catalyst in methanol conversion to hydrocarbons.

[0119] The CS-3 molecular sieve synthesized in Example 3 was used to prepare a catalyst using the catalyst preparation method of Example 23. Methanol was used as the raw material and a fixed bed reactor with a diameter of 15 mm was used at 490°C and a mass space velocity of 1.75 h -1 Under the conditions of 1.50MPa and pressure, the yield of ethylene and propylene can reach 87.8%, achieving good technical results.

[0120] [Example 27]

[0121] Application of Me-SCM-34 catalyst in methanol conversion to hydrocarbons.

[0122] The CS-19 molecular sieve synthesized in Example 19 was used to prepare a catalyst using the catalyst preparation method of Example 23. 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 0.1 h -1 Under the conditions of 0.1MPa and pressure, the yield of ethylene and propylene can reach 83.6%, achieving good technical results.

[0123] [Comparative Example 1]

[0124] A ZSM-5 molecular sieve having a SiO2 / Al2O3 molar ratio of 43 was used to prepare a catalyst using the catalyst preparation method of Example 23. The catalyst was evaluated according to the method and reaction conditions of Example 24, and the yield of ethylene and propylene could reach 33.3%.

[0125] [Comparative Example 2]

[0126] A SAPO-34 molecular sieve having a SiO2 / Al2O3 molar ratio of 3.2 was used to prepare a catalyst using the catalyst preparation method of Example 23. The catalyst was evaluated according to the method of Example 24. The reaction conditions showed that the yield of ethylene and propylene could reach 70.1%.

[0127] [Comparative Example 3]

[0128] Take SCM-34 molecular sieve with a SiO2 / Al2O3 molar ratio of 2.5, and use the catalyst preparation method of Example 23 to prepare a catalyst. According to the method and reaction conditions of Example 24, the yield of ethylene and propylene can reach 69.6%.

[0129] [Example 28]

[0130] Application of Me-SCM-34 catalyst in hydrogenation reaction.

[0131] Take the CS-16 molecular sieve synthesized in Example 16, and use the catalyst preparation method of Example 23 to prepare a catalyst. The catalyst is reduced at 500°C for 12 hours in a 1.5L / min pure hydrogen flow to obtain a metallic Co-SCM-34 catalyst. Since aromatic hydrocarbons account for 65% to 80% of the cracked carbon nine and above hydrocarbon fractions, and also contain a large amount of polymerizable unsaturated components, this example uses a raw material prepared by cracking carbon nine and above hydrocarbons and saturated hydrogenated oil in a certain ratio (see Table 6 for specific components) to test the hydrogenation activity of the catalyst of the present invention. The process conditions are: inlet temperature 65°C, pressure 2.2MPa, volume space velocity of fresh oil = 2.2h -1 , hydrogen oil volume ratio H2 / feedstock oil = 525:1, experimental results are shown in Table 7.

[0132] Table 6

[0133]

[0134] [Comparative Example 4]

[0135] A homemade Co / Al2O3-SiO2 catalyst (prepared by an excess impregnation method, a certain amount of Co(NO3)2·6H2O solid was dissolved in a certain volume of distilled water and impregnated on an Al2O3 / SiO2 carrier. The sample was then placed in a rotary evaporator and dried at 80°C for 3 h under vacuum conditions. Finally, it was calcined in a muffle furnace at 450°C for 6 h to obtain the catalyst. ICP testing showed that the Co mass content in the catalyst was 12%) was tested for hydrogenation activity according to the conditions of Example 28. The results are shown in Table 7.

[0136] Table 7

[0137]

[0138] It should be noted that the embodiments described above are only used to explain the present invention and do not constitute any limitation of 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 function.

Claims

1. A Me-SCM-34 molecular sieve comprising the following components in parts by weight: (1) 0.1~20 parts of metal element Me; (2) 80-99.9 parts of SCM-34 molecular sieve; The SCM-34 molecular sieve has a schematic chemical composition as shown in the formula "Al2O3:xSiO2:yP2O", wherein: 0≤x≤0.5, 0.75≤y≤1.5; The X-ray diffraction pattern of the Me-SCM-34 molecular sieve includes X-ray diffraction peaks as shown in the following table, wherein the 2θ angle of the strongest peak in the range of 5-50° is 7.59±0.2: 。 2. The Me-SCM-34 molecular sieve according to claim 1, characterized in that Calculated by weight, it includes the following components: (1) 0.6~16 parts of metal element Me; (2) 84~99.4 parts of SCM-34 molecular sieve.

3. The Me-SCM-34 molecular sieve according to claim 1, characterized in that Me is at least one of Co, Ni, and Cu.

4. The Me-SCM-34 molecular sieve according to claim 1, characterized in that The X-ray diffraction pattern of the Me-SCM-34 molecular sieve also includes the X-ray diffraction peaks shown in the following table: 。 5. The Me-SCM-34 molecular sieve according to claim 1 or 4, characterized in that: The X-ray diffraction pattern of the Me-SCM-34 molecular sieve also includes the X-ray diffraction peaks shown in the following table: 。 6. The method for preparing the Me-SCM-34 molecular sieve according to any one of claims 1 to 5, comprising: Me-SCM-34 molecular sieve was synthesized using amine chelates of metal Me as templates; The aluminum source is calculated as Al2O3, the silicon source is calculated as SiO2, the phosphorus source is calculated as P2O5, the Me amine chelate source is calculated as Me amine chelate, and the molar ratio of the solvent is 1:0~1:0.5~2:0.5~50:5~500; The Me amine chelate source is a Me salt and a chelating agent and / or an amine chelate prepared from a Me salt and a chelating agent, wherein the chelating agent is selected from at least one of ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, 1,10-phenanthroline, 2,2-bipyridine or 4,4-bipyridine.

7. The preparation method according to claim 6, characterized in that: The preparation method comprises the following steps: a. Mixing an aluminum source and a solvent to form solution A; b. adding the Me amine chelate source to solution A and stirring to form a mixture A1; c. mixing a phosphorus source and an optionally added silicon source with the mixture A1 to form a crystallized mixture A2; d. The crystallization mixture A2 is subjected to a crystallization reaction to obtain Me-SCM-34 molecular sieve.

8. The preparation method according to claim 7, characterized in that: The aluminum source is calculated as Al2O3, the silicon source is calculated as SiO2, the phosphorus source is calculated as P2O5, the Me amine chelate source is calculated as Me amine chelate, and the solvent has a molar ratio of 1:0.1~0.75:0.75~1.5:5~35:25~300.

9. The preparation method according to claim 7, characterized in that: The Me salt is selected from at least one of Me sulfate, nitrate, carbonate and acetate.

10. The preparation method according to claim 7, characterized in that: In step d, the conditions of the crystallization reaction include: a crystallization temperature of 120-200° C., and / or a crystallization time of 1-7 days.

11. The preparation method according to claim 10, characterized in that: In step d, the conditions of the crystallization reaction include: a crystallization temperature of 140-180° C., and / or a crystallization time of 2-5 days.

12. The preparation method according to claim 10, characterized in that: In step d, the conditions of the crystallization reaction include: a crystallization temperature of 140-160° C., and / or a crystallization time of 3-5 days.

13. Use of the Me-SCM-34 molecular sieve according to any one of claims 1 to 5 or the Me-SCM-34 molecular sieve prepared by the method according to any one of claims 6 to 12 in a methanol to olefins reaction.

14. Use of the Me-SCM-34 molecular sieve according to any one of claims 1 to 5 or the Me-SCM-34 molecular sieve prepared by the method according to any one of claims 6 to 12 in the hydrogenation reaction of unsaturated compounds.

15. Use of the Me-SCM-34 molecular sieve according to any one of claims 1 to 5 or the Me-SCM-34 molecular sieve prepared by the method according to any one of claims 6 to 12 in the hydrogenation reaction of polymers having unsaturated bonds.

16. Use of the Me-SCM-34 molecular sieve according to any one of claims 1 to 5 or the Me-SCM-34 molecular sieve prepared according to any one of claims 6 to 12 in the preparation of Me-AFI molecular sieve or Me-SAPO-17 molecular sieve.

17. Use of the Me-SCM-34 molecular sieve according to any one of claims 1 to 5 or the Me-SCM-34 molecular sieve prepared according to any one of claims 6 to 12 in the preparation of Me-AFI molecular sieve or Me-SAPO-17 molecular sieve by crystallization.

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