MAPO-17 molecular sieve as well as preparation method and application thereof

Abstract

The invention discloses an MAPO-17 molecular sieve as well as a preparation method and application thereof. M in the molecular sieve is at least one of Co, Mg, Ni and Zn; in Fourier transform infrared characterization before and after CO adsorption, the surface OH stretching vibration peak of the MAPO-17 molecular sieve has an obvious red shift phenomenon before and after CO molecular adsorption, and the red shift range is 280-350 cm <-1 >. When the MAPO-17 molecular sieve provided by the invention is used for industrial production of methanol downstream products and industrial production of synthesis gas downstream products, the MAPO-17 molecular sieve has relatively high activity and stability, a relatively good technical effect is achieved, and the problems of high MTO reaction energy consumption and low conversion rate and low light olefin yield when the reaction temperature is relatively low in the prior art are particularly solved.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of molecular sieves, in particular to a kind of MAPO-17 molecular sieve and preparation method and application thereof. BACKGROUND

[0002] Since the molecular sieve crystal material was discovered in the eighteenth century, after several centuries of research and development, the material has achieved extraordinary influential technical effects in the fields of adsorption separation, heterogeneous catalysis, carriers of various guest molecules and ion exchange, and has produced extensive application basis, especially with the rapid development of petroleum chemical industry in the twentieth century, molecular sieve catalytic materials have become the cornerstone of human social production and life.According to the definition of International Union of Pure and Applied Chemistry (IUPAC), traditional zeolite molecular sieve is a kind of crystalline silicate material, which is generally composed of silicon oxygen tetrahedron [SiO4] 4- And aluminum oxygen tetrahedron [AlO4] 5- Connected by sharing oxygen atoms, collectively known as TO4 tetrahedron (primary structural unit), in which the silicon element can also be isomorphously replaced by other elements, especially some trivalent or tetravalent elements such as Al, B, Ga, Ge, Ti, etc.A key factor determining the application performance of molecular sieve is its pore or cage characteristics, the pore diameter of such materials is generally less than 2nm, belonging to microporous materials, which can "screen" the substances entering the interior of the molecular sieve according to their molecular intrinsic spatial size in physical and chemical reactions, so as to carry out corresponding selective adsorption and catalytic shape selection applications, "molecular sieve" is named after this, further, the molecular sieve with new crystal structure has very important significance for developing the application of molecular sieve.

[0003] In 1982, S.T.Wilson and E.M.Flanigen et al. (US 4310440) of United Carbon Corporation (UCC) successfully developed a new family of molecular sieves-Aluminum phosphate molecular sieve AlPO4-n, n represents the model (including: AlPO4-5, AlPO4-8, AlPO4-9, AlPO4-11, AlPO4-12, AlPO4-14, AlPO4-16, AlPO4-17, AlPO4-18, AlPO4-20, AlPO4-21, AlPO4-22, AlPO4-23, AlPO4-25, AlPO4-26, AlPO4-28, AlPO4-31, etc.), the framework of the molecular sieve is connected by AlO4 - And PO4 +The molecular sieve is connected by common oxygen atoms, and the whole molecular sieve framework is electrically neutral. The AlPO-17 molecular sieve has a structure code ERI assigned by the International Zeolite Association (IZA) and a chemical formula of Al 18 P 18 O 72 , belongs to a triclinic system, has a space group of P 63 / mmc (#194), and has a unit cell parameter of α = β = 90° and γ = 120°, has a cage structure with a three-dimensional eight-membered ring (pore size of ), belongs to a small-pore molecular sieve, and the size of the ERI cage structure, which is a representative structural feature, is about Similar to traditional silicon-aluminum zeolite molecular sieves, the aluminum oxide tetrahedron or the phosphorus oxide tetrahedron in the aluminum phosphate molecular sieve can be replaced by other oxygen-containing tetrahedrons. Therefore, in 1984, the UCC company successfully prepared another series of silicon aluminum phosphate molecular sieves: SAPO-n, n represents the model (US4440871, US4499327), by using silicon atoms to partially replace the aluminum atoms and the phosphorus atoms in the framework of the aluminum phosphate molecular sieve. In the structure of the SAPO-n, the Si atom replaces the P or Al atom 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) 2 silicon atoms replace a pair of aluminum atoms and phosphorus atoms, respectively, and exhibits certain acidity, oxidation, etc., greatly improving the catalytic activity, and having a wide application prospect in the petroleum and chemical industry.

[0004] At present, all the molecular sieves with known topological results are prepared by hydrothermal or solvothermal synthesis. A typical hydrothermal or solvothermal synthesis method mainly comprises the following steps: first, uniformly mixing metal sources, non-metal sources, organic template agents, solvents and other reactants to obtain an initial sol, i.e., a crystallization mixture, then placing the crystallization mixture in a reaction kettle with polytetrafluoroethylene as the inner liner and stainless steel as the outer wall, and then performing a crystallization reaction under certain temperature and autogenous pressure, like the process of earth rock formation, i.e., the process of precipitation of molecular sieve crystals from the crystallization mixture. Taking the synthesis of a silicon phosphorus aluminum ERI (SAPO-17) molecular sieve as an example, the reaction mixture comprises a framework reactant (for example, silica sol, phosphoric acid and aluminum oxide), a structure directing agent (SDA) and water, and is uniformly mixed and placed in a fixed-temperature oven (190-220°C) for several days to perform a crystallization reaction. When the crystallization reaction is completed, the solid product containing the ERI molecular sieve is filtered out and dried for use.

[0005] It is worth mentioning that in the process of synthesizing SAPO-17 molecular sieve, small amine substances are generally used as templates, and then substances such as quinuclidine (Intrazeolite Chemistry, 1983, Vol 218, P79, piperidine (Acta Crystallographica Section C Crystal Structure Communications, 1986, Vol 42, P283) and cyclohexylamine (Solid State Nuclear Magnetic Resonance, 1992, Vol 1, P137) are applied to the synthesis system of SAPO-17. In addition, Liu et al. (ChemSusChem, 2011, Vol 4, P91) synthesized needle-shaped AlPO-17 crystals with neopentylamine as a structure directing agent. Tuel et al. (Comptes Rendus Chimie, 2005, Vol 8, P531) prepared a large single crystal AlPO-17 of about 100 μm with N,N,N',N'-tetramethyl-1,6-hexanediamine as a template. Gao et al. (Chemical Communication, 1994, P1465) synthesized disc-shaped AlPO-17 crystals with methylamine as a template in a water-free system. US 4778780 first reported the use of 1,6-hexanediamine and its derivatives as organic templates to synthesize SAPO-17, CN 103922361A used T-type zeolite or SSZ-13 zeolite or Y-type zeolite or A-type zeolite or MOR-type zeolite crystalline silicon as a silicon source, and a seed crystal transformation method was used to prepare SAPO-17 molecular sieve in a high-temperature hydrothermal system. CN109574034A discloses a method for ultrasonic-assisted synthesis of ultra-fine ERI-type molecular sieve, which can obtain ERI-type molecular sieve (T-type molecular sieve, silicon-aluminum ratio 3-4) with a crystal size of 300-400 nm by means of ultrasonic treatment under the reaction conditions of 2-48 h and 100-200°C. In addition, due to the micro-topological structure of ERI (SAPO-17) molecular sieve and the moderate Bronsted acid center (Catalysis, 1992, Vol 9, p1), researchers use it as a MTO (methanol to olefin) catalyst, US 4499327 discloses using water as a diluent, and the weight hourly space velocity is not more than 1h -1Under the same conversion conditions, SAPO-17 has a higher ratio of ethylene and propylene than SAPO-34 and SAPO-56.

New Chemical Materials, 2015, 43, 166

Studies in Surface Science and Catalysis, 1994, 81, 393

[0006] So far, according to the International Molecular Sieve Association website (http: / / www.iza-structure.org), a total of 256 different molecular sieves with complete stable topological structures have been obtained, including the latest AlPO-91 molecular sieve with ANO topological structure ("Crystalline metallophosphates, their method of preparation, and use", Yuhas, B. D., Wilson, K. N., Sylejmani-Rekaliu, M., Mowat, J. P. S., Sinkler, W., US Patent 10,336,622B1 (2019)). 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. Therefore, the development of MAPO-17 zeolite molecular sieves is a valuable research topic in the field. SUMMARY

[0007] In view of the deficiencies of the prior art, the present application provides a MAPO-17 molecular sieve, a preparation method and applications thereof. The MAPO-17 molecular sieve has high activity and stability when used in the industrial production of methanol downstream products and the industrial production of syngas downstream products, and good technical effects are achieved. In particular, the problems of high energy consumption and low conversion rate and low yield of low-carbon olefins at a low reaction temperature in the MTO reaction of the prior art are solved.

[0008] The first aspect of the present application provides a MAPO-17 molecular sieve, wherein M in the molecular sieve is at least one of Co, Mg, Ni and Zn.

[0009] In the Fourier transform infrared characterization before and after CO adsorption, the surface OH stretching vibration peak of the MAPO-17 molecular sieve before and after CO molecule adsorption shows obvious red shift phenomenon, and the red shift range is 280-350 cm -1 .

[0010] Further, in the MAPO-17 molecular sieve, the mass content of M is 0.1% to 20%, and the mass content of AlPO-17 molecular sieve is 80% to 99.9%, based on the mass of the MAPO-17 molecular sieve.

[0011] Further, in the Fourier transform infrared spectroscopy CO adsorption, the red shift range is preferably 300 to 340 cm -1 .

[0012] Further, the AlPO-17 in the molecular sieve has a schematic chemical composition as shown in the formula "Al2O3·xP2O", wherein 0.75≤x≤1.5.

[0013] Further, the crystal in the molecular sieve is a flat columnar morphology with a hexagonal bottom surface, wherein the average thickness of the crystal is 200 to 600 nm.

[0014] The second aspect of the present application provides a preparation method of the above-mentioned MAPO-17 molecular sieve, comprising the following steps:

[0015] (1) mixing a solvent S, ERI molecular sieve seed crystal, a cyclic organic complexing agent C, and a metal M salt solution, and heat treating to obtain a crystallization precursor A;

[0016] (2) mixing an aluminum source and a phosphorus source with a solvent S', and heat treating to obtain a mixture B;

[0017] (3) mixing the crystallization precursor A and the mixture B, and performing crystallization to obtain the molecular sieve.

[0018] Further, in step (1), the solvent S includes at least one of N,N-dimethylformamide, N,N-dimethylacetamide, ethanol, ethylene glycol, and water, and is preferably at least one of N,N-dimethylformamide and water; the ERI molecular sieve seed crystal is an AlPO-17 molecular sieve; the cyclic organic complexing agent C is selected from at least one of 1,10-phenanthroline, 2,2-bipyridine, 4,4-bipyridine, piperazine, aminopropylimidazole, and cyclohexylamine, and is preferably at least one of piperazine, aminopropylimidazole, and cyclohexylamine; the metal M salt solution is selected from at least one of a sulfate, a nitrate, a carbonate, and an acetate of the corresponding metal; and M is at least one of Co, Mg, Ni, and Zn.

[0019] Further, in step (1), the heat treatment is performed at 50 to 100°C for 0.1 to 2 h.

[0020] Further, in steps (1) and (2), the molar ratio of the cyclic organic complexing agent C, the metal M salt solution in terms of metal, the phosphorus source in terms of P, the aluminum source in terms of Al, and the solvent (S+S') is (1-500):(0.001-1.0):(0.5-3.0):1:(10-1000), preferably (2.5-150):(0.005-0.6):(0.5-2.0):1:(25-750).

[0021] Further, the mass ratio of the solvent S' in step (2) to the solvent S in step (1) is 1:0.1-10.

[0022] Further, in step (1), the AlPO-17 molecular sieve seed accounts for 0.1%-5.0% of the total mass of solid feed (i.e., the sum of the total mass of solid reactants in steps (1) and (2)).

[0023] Further, in step (2), the aluminum source is at least one selected from the group consisting of aluminum salts, aluminate salts, aluminum hydroxides, aluminum oxides, and aluminum-containing minerals, preferably at least one selected from the group consisting of aluminum nitrate, aluminum sulfate, and aluminum isopropylate; the phosphorus source is at least one selected from the group consisting of orthophosphoric acid, ammonium monohydrogen phosphate, and ammonium dihydrogen phosphate, preferably orthophosphoric acid; and the solvent S' includes at least one selected from the group consisting of N,N-dimethylformamide, N,N-dimethylacetamide, ethanol, ethylene glycol, and water, preferably at least one selected from the group consisting of N,N-dimethylformamide and water.

[0024] Further, in step (2), the heat treatment is performed at 50-100°C for 0.1-2h.

[0025] Further, in step (3), the crystallization precursor A is added to the mixture B under stirring, and the stirring speed is not particularly limited, as long as the mixture is uniformly mixed.

[0026] Further, in step (3), the molar ratio of the crystallization precursor A in terms of the cyclic organic complexing agent C added to the mixture B in terms of the aluminum source is (1-500):1, preferably (2.5-150):1.

[0027] Further, in step (3), the crystallization is not temperature-switching crystallization, i.e., the crystallization is one-stage constant-temperature crystallization.

[0028] Further, in step (3), the crystallization temperature is 140-250°C, preferably 150-230°C, more preferably 160-220°C, and the crystallization time is 0.1-2h, preferably 0.15-1.8h, more preferably 0.2-1.5h.

[0029] Further, the product obtained from the mixture obtained after the crystallization step is completed can be treated by any separation method conventionally known. As the separation method, for example, a method in which the obtained mixture is filtered, washed, and dried can be mentioned. Here, the filtration, washing, and drying can be performed in any manner conventionally known in the art. Specifically, for example, as the filtration, the obtained product mixture can be simply suction-filtered. As the washing, for example, washing using deionized water and / or ethanol can be mentioned. As the drying temperature, for example, 40 to 250°C, preferably 60 to 150°C can be mentioned, and as the time for drying, for example, 8 to 30 hours, preferably 10 to 20 hours can be mentioned. The drying can be performed under normal pressure or under reduced pressure.

[0030] Further, the molecular sieve obtained after the crystallization step is completed can be treated by calcination to obtain a calcined MAPO-17 molecular sieve, and the calcination can be performed in any manner conventionally known in the art, for example, the calcination temperature is generally 300 to 800°C, preferably 400 to 650°C, and the calcination time is generally 1 to 10 hours, preferably 3 to 6 hours. In addition, the calcination is generally performed in an atmosphere containing oxygen, for example, in an air or oxygen atmosphere.

[0031] The third aspect of the present application also provides the use of the molecular sieve according to any one of the aforementioned first aspect, or the molecular sieve prepared according to any one of the aforementioned second aspect as a catalyst for the conversion of organic compounds.

[0032] Further, the use of the MAPO-17 molecular sieve as a catalyst in a methanol-to-olefins reaction.

[0033] Further, the reaction conditions for the methanol-to-olefins reaction are as follows: using methanol as a raw material, at a reaction temperature of 200 to 400°C, a reaction pressure of 0.01 to 10 MPa, a methanol weight hourly space velocity of 0.1 to 15 h -1 .

[0034] Further, the use of the MAPO-17 molecular sieve as a catalyst in a synthesis gas-to-hydrocarbons reaction.

[0035] Further, the reaction conditions for the synthesis gas-to-hydrocarbons reaction are as follows: using synthesis gas as a raw material, H2 / CO = 0.5 to 1, at a reaction temperature of 200 to 400°C, a reaction pressure of 0.1 to 10 MPa, a synthesis gas weight hourly space velocity of 20 to 2000 h -1 .

[0036] The MAPO-17 molecular sieve provided by the application is used in a reaction process of methanol conversion into olefins, and the yield of ethylene and propylene is 74-87% in a set evaluation condition range, and good technical effects are achieved

[0037] The MAPO-17 molecular sieve provided by the application is used in a reaction process of synthesis gas into olefins, and the yield of C 2＝ -C 4＝ is 77-90%, and good technical effects are achieved.

[0038] Compared with the prior art, the application has the following advantages:

[0039] 1. The application provides a MAPO-17 molecular sieve, which has a unique composition, and in Fourier transform infrared spectrum characterization before and after CO adsorption, the surface OH stretching vibration peak of the MAPO-17 molecular sieve before and after CO molecule adsorption has obvious red shift phenomenon, and the red shift range is 280-350 cm -1 , which is beneficial to improving the catalytic performance.

[0040] 2. To solve the problems of long synthesis time and low crystallization efficiency of the MAPO-17 molecular sieve in the prior art, the preparation method provided by the application prepares the MAPO-17 molecular sieve in a short time by adopting the mode of selecting a molecular sieve seed with an ERI structure and combining a cyclic organic template agent to complex a divalent metal cation to prepare a crystallization precursor, and compared with the traditional method, the method greatly improves the crystallization rate of the molecular sieve, and the obtained product has good crystallinity, uniform crystal grain size distribution and low preparation cost.

[0041] 3. The MAPO-17 molecular sieve provided by the application has high activity, yield and stability when used in industrial production of methanol downstream products and industrial production of synthesis gas downstream products, good technical effects are achieved, and the problems of high energy consumption, low conversion rate and low yield of low-carbon olefins at a low reaction temperature in the MTO reaction in the prior art are solved. BRIEF DESCRIPTION OF DRAWINGS

[0042] Figure 1 It is an XRD diffraction spectrum of the product of Example 1;

[0043] Figure 2 It is a high-magnification SEM image of the product of Example 1;

[0044] Figure 3 It is a low-magnification SEM image of the product of Example 1;

[0045] Figure 4 It is Fourier transform infrared spectra of the product of Example 1 before and after CO adsorption;

[0046] Figure 5SEM image of the product of Comparative Example 1;

[0047] Figure 6 SEM image of the product of Comparative Example 3. DETAILED DESCRIPTION

[0048] The technical solutions of the present application are further illustrated by the following examples. The examples are implemented on the premise of the technical solutions of the present application, and detailed implementation modes and specific operation processes are given, but the protection scope of the present application is not limited to the following examples.

[0049] Unless otherwise specified, the instruments used in the present application are conventional instruments in the art.

[0050] In the present application, the crystal phase of the molecular sieve product is determined by using an X'Pert PRO type X-ray powder diffractometer (XRD) of the Netherlands Panalytical Company, the working voltage is 40 kV, the current is 40 mA, and the scanning range is 5-50°. The product morphology is photographed by using an S-4800 type field emission scanning electron microscope (Fe-SEM) of the Japan HITACHI Company.

[0051] In the present application, the content of metal elements in the molecular sieve product is determined by using a plasma Perkin-Elmer 3300D VICP analyzer, and the specific operation method is as follows: the sample is placed in a 100℃ oven and dried for 2 hours, then 0.2-0.5 g of the dried sample is taken in a crucible, 10 drops of a sulfuric acid solution with a volume ratio of 1:1 and 8 mL of hydrofluoric acid are added, heating is performed, the sample is decomposed by frequent shaking, after the solution in the crucible is clear, the solution is evaporated to white smoke, taken out and cooled, 5 mL of 1:1 hydrochloric acid and appropriate amount of water are added. Heating and dissolving the residue, then transferring into a 100 mL volumetric flask, washing the crucible with water and diluting to the mark and shaking well, introducing the prepared solution into the ICP spectrometer for analysis, and recording the percentage content.

[0052] In the present application, the scanning electron microscope (SEM) of the molecular sieve is S-4800II type field emission scanning electron microscope. The measurement method of the thickness of the sheet-shaped crystal is: using a scanning electron microscope to observe the molecular sieve under a magnification, randomly selecting an observation field, measuring the thickness of all the crystals in the observation field, repeating the operation 20 times, and taking the average value of 20 times as the average thickness of the crystal.

[0053] In the present application, the CO adsorption in-situ infrared is carried out on a self-built ultra-high vacuum in-situ infrared system, which is composed of a Bruker Vertex 70V vacuum infrared spectrometer, an ultra-high vacuum in-situ cell and an external MCT detector. The vacuum spectrometer and the in-situ cell are connected through a vacuum cavity and a pipeline, all light paths are in the vacuum system, and the detector is an external high-sensitivity MCT detector placed in the vacuum cavity, so that the system can avoid the interference of water and carbon dioxide in the air on the background signal, and obtain excellent signal-to-noise ratio. The CO adsorption in-situ infrared research process is as follows: after the MAPO-17 molecular sieve sample is fixed on the sample holder, vacuum dehydration is carried out at 350-400℃ for more than 2 hours, the in-situ cell is vacuumed to an in-situ cell background pressure of <2.0x10 -8 mbar, liquid nitrogen is added in the liquid nitrogen storage tank outside the vacuum of the sample holder to reduce the temperature to below -140℃, the blank tungsten net is taken as the background, the infrared spectrum of the molecular sieve is collected, and then the CO gas with a pressure of 1x10 -3 mbar, 1x10 -2 mbar, 0.1mbar, 0.5mbar, 1.0mbar is gradually introduced, and then the corresponding infrared spectrum is collected. The red shift refers to the movement of the infrared absorption band of the OH bond on the surface of the molecular sieve to the low wave number direction.

[0054] In the present application, the solid reactants in step (1) and step (2) of the preparation method specifically refer to ERI molecular sieve seeds, metal M salt, aluminum source and phosphorus source.

[0055] In the present application, the inorganic salt of the raw material can be a hydrated salt, for example, aluminum sulfate is Al2(SO4)3·18H2O, aluminum nitrate is Al2(NO3)3·9H2O, magnesium acetate is Mg(OAc)2·4H2O, etc.

[0056] Example 1

[0057] Synthesis of MAPO-17 molecular sieve

[0058] Under normal temperature, 112.1 g of AlPO-17 molecular sieve seed crystal (0.15% of the total mass of all solid reactants in preparation), 9664.9 g of cyclic organic complexing agent piperazine [PIP, 112.2 mol] and 1219.4 g of zinc acetate (5.6 mol) were dissolved in 99324.7 mL of deionized water (5518.0 mol) and stirred well, and then placed in a heat treatment at 90°C for 0.3 h to obtain a crystallization precursor A1. 74039.3 g of aluminum sulfate (111.1 mol) and 19213.8 g of phosphoric acid (166.6 mol) were dissolved in 155656.8 mL of deionized water (8647.6 mol) and stirred well, and then placed in a heat treatment at 100°C for 0.1 h to obtain a mixture B1. The crystallization precursor A1 was added to the mixture B1 under stirring, and after stirring well, a crystallization mixture was formed, and then placed in a crystallization at 160°C for 1.5 h. The product was filtered, washed, dried at 80°C for 8 h, then the temperature was increased to 550°C, and calcined at a constant temperature for 6 h to obtain the product, which is denoted as MA-1.

[0059] ICP test showed that the weight percentage of Zn in the product was 0.8%, the weight percentage of AlPO-17 was 99.2%, and the molar ratio of Al2O3:P2O5 in AlPO-17 was 1:0.75. The XRD diffraction pattern is shown in Figure 1 , wherein 2θ = 7.68, 9.82, 19.62, 20.49, 21.39° are the characteristic diffraction peaks of the molecular sieve AlPO-17, the low-magnification SEM image is shown in Figure 2 , and the high-magnification SEM image is shown in Figure 3 . The molecular sieve crystal has a hexagonal flat columnar morphology, and the average thickness of the crystal is 600 nm. The Fourier transform infrared characterization before and after CO adsorption is shown in Figure 4 , and the shift of the OH stretching vibration peak is 316 cm -1 .

[0060]

Example 2

[0061] Synthesis of MAPO-17 molecular sieve

[0062] Under normal temperature, 0.53 g of AlPO-17 molecular sieve seed crystal (2.2% of the total mass of all solid reactants in preparation), 249.8 g of cyclic organic complexing agent piperazine [PIP, 2.9 mol] and 5.1 g of cobalt acetate (0.02 mol) were dissolved in 510.56 mL of deionized water (28.4 mol) and 173.4 mL of N, N-dimethylformamide (2.5 mol) and stirred well, and then placed in a heat treatment at 100°C for 0.1 h to obtain a crystallization precursor A2. 10.2 g of isopropyl alcohol aluminum (0.05 mol) and 9.2 g of ammonium dihydrogen phosphate (0.08 mol) were dissolved in 96.88 mL of deionized water (5.4 mol) and stirred well, and then placed in a heat treatment at 60°C for 1.5 h to obtain a mixture B2. The crystallization precursor A2 was added to the mixture B2 under stirring, and after stirring well, a crystallization mixture was formed, and then placed in a crystallization at 150°C for 1.8 h. The product was filtered, washed, dried at 110°C for 6 h, then heated to 600°C, and calcined at 600°C for 4 h to obtain the product, which is denoted as MA-2.

[0063] ICP test showed that the weight percentage of Co in the product was 12%, the weight percentage of AlPO-17 molecular sieve was 88%, the molar ratio of Al2O3 to P2O5 in the AlPO-17 was 1:1.05, the XRD was similar to Figure 1 , the SEM image was similar to Figure 2 , the molecular sieve crystal was hexagonal flat columnar morphology, the average thickness of the crystal was 200 nm, and the Fourier transform infrared characterization before and after CO adsorption was similar Figure 4 , the displacement of the OH stretching vibration peak was 310 cm -1 .

[0064]

Example 3

[0065] Synthesis of MAPO-17 molecular sieve

[0066] Under normal temperature, 2.13 g of AlPO-17 molecular sieve seed crystal (0.17% of the total mass of all solid reactants in preparation), 816.35 g of cyclic organic complexing agent cyclohexylamine [HCHA, 99 wt.%, 123.08 mol], 456.5 g of piperazine [PIP, 5.3 mol] and 5.2 g of nickel acetate (0.02 mol) were dissolved in 524.7 mL of deionized water (29.2 mol) and stirred well, and then placed in a heat treatment at 80°C for 0.5 h to obtain a crystallization precursor A3. 787.8 g of aluminum nitrate (2.1 mol) and 181.6 g of phosphoric acid (1.6 mol) were dissolved in 534.8 mL of deionized water (29.7 mol) and stirred well, and then placed in a heat treatment at 80°C for 0.5 h to obtain a mixture B3. The crystallization precursor A3 was added to the mixture B3 under stirring, and after stirring well, a crystallization mixture was formed, and then placed in a crystallization at 220°C for 0.15 h. The product was filtered, washed and dried at 80°C for 9 h, and then heated to 550°C and calcined at a constant temperature for 5 h to obtain the product, which is denoted as MA-3.

[0067] ICP test showed that the weight percentage of Ni in the product was 0.1%, the weight percentage of AlPO-17 molecular sieve was 99.9%, the molar ratio of Al2O3 to P2O5 in AlPO-17 was 1:0.85, the XRD spectrum was similar to Figure 1 , the SEM image was similar to Figure 2 , the molecular sieve crystal was hexagonal flat columnar morphology, the average thickness of the crystal was 400 nm, and the Fourier transform infrared characterization before and after CO adsorption was similar Figure 4 , the displacement of the OH stretching vibration peak was 300 cm -1 .

[0068]

Example 4

[0069] Synthesis of MAPO-17 molecular sieve

[0070] Under normal temperature, 12.89 g of AlPO-17 molecular sieve seed crystal (0.31% of total mass of all solid reactants in preparation), 1008.69 g of cyclic organic complexing agent cyclohexylamine [HCHA, 99 wt.%, 10.2 mol] and 922.3 g of magnesium acetate (4.3 mol) were dissolved in 12055.42 mL of deionized water (669.7 mol) and stirred thoroughly, and then heated at 50°C for 2 h to form a crystallization precursor A4; 3202.5 g of aluminum nitrate (8.5 mol) and 1948.5 g of phosphoric acid (16.9 mol) were dissolved in 18145.58 mL of deionized water (1008.1 mol) and stirred thoroughly, and then heated at 55°C for 1.8 h to obtain a mixture B4. The precursor A4 was added to the mixture B4 under stirring, and then stirred thoroughly to form a crystallization mixture, which was then placed in a closed system and crystallized at 220°C for 0.2 h. The product was filtered, washed, dried at 100°C for 7.5 h, then heated to 500°C and calcined at 500°C for 8 h to obtain the MAPO-17 molecular sieve (the same below), which was recorded as MA-4.

[0071] ICP test showed that the product contained 15% of Mg and 85% of AlPO-17 molecular sieve by weight percentage, and the molar ratio of Al2O3:P2O5 was 1:1.25, and the XRD pattern was similar to Figure 1 , the SEM image was similar to Figure 2 , the molecular sieve crystal was hexagonal flat columnar morphology, the average thickness of the crystal was 500 nm, and the Fourier transform infrared characterization before and after CO adsorption was similar to Figure 4 , the shift of OH stretching vibration peak was 340 cm -1 .

[0072]

Example 5

[0073] Synthesis of MAPO-17 molecular sieve

[0074] Under normal temperature, 25.5 g of AlPO-17 molecular sieve seed crystal (0.1% of the total mass of all solid reactants in preparation), 33 026.9 g of cyclic organic complexing agent cyclohexylamine [HCHA, 332.9 mol] and 5 122.9 g of magnesium nitrate (20.0 mol) were dissolved in 88 324.26 mL of deionized water (4 906.9 mol) and stirred thoroughly, and then placed in a heat treatment at 70°C for 0.8 h to obtain a crystallization precursor A5. 13 602.4 g of isopropyl alcohol aluminum [Al(iPr)3, purity ≥ 99 wt.%, 66.6 mol] and 6 598.4 g of ammonium dihydrogen phosphate [(NH4)2HPO4, 49.9 mol] were dissolved in 69 321.55 mL of deionized water (3 851.2 mol) and stirred thoroughly, and then placed in a heat treatment at 70°C for 0.8 h to obtain a mixture B5. The crystallization precursor A5 was added to the mixture B5 under stirring, and after stirring thoroughly, a crystallization mixture was formed, and then placed in a crystallization at 200°C for 0.5 h. After the product was filtered, washed and dried at 110°C for 5 h, and then the temperature was increased to 400°C, and the product was obtained after heat treatment at constant temperature for 12 h, and was recorded as MA-5.

[0075] ICP test showed that the weight percentage of Mg in the product was 8%, and the weight percentage of AlPO-17 molecular sieve was 92%, the molar ratio of Al2O3: P2O5 was 1: 1.5, the XRD was similar to Figure 1 , the SEM image was similar to Figure 2 , the molecular sieve crystal was hexagonal flat columnar morphology, the average thickness of the crystal was 300 nm, and the Fourier transform infrared characterization before and after CO adsorption was similar to Figure 4 , the displacement of OH stretching vibration peak was 336 cm -1 .

[0076]

Examples 6-20

[0077] According to the method of Example 5, the raw materials used are shown in Table 1, and the different ratios of raw materials and conditions (Table 2) are controlled, and MAPO-17 molecular sieves are synthesized respectively.

[0078] Table 1 Raw materials used in preparation of examples

[0079]

[0080]

[0081] Table 2 Raw material ratio and preparation conditions in each example

[0082]

[0083]

[0084]

[0085] Example 21

[0086] Application of MAPO-17 molecular sieve in methanol conversion to olefins reaction.

[0087] MA-1 molecular sieve synthesized in Example 1 was calcined at 550℃ for 4h, and after cooling to room temperature, it was pressed into tablets, knocked into pieces, and sieved to obtain 12-20 mesh particles for use. Methanol was used as raw material, and a fixed bed reactor with a diameter of 15mm was used to evaluate the catalyst prepared in Example 21 under the conditions of 400℃, mass space velocity 0.1h -1 , and pressure 0.01MPa. The yield of ethylene and propylene reached 80.7%, and good technical effects were achieved.

[0088] Example 22

[0089] Application of MAPO-17 molecular sieve in methanol conversion to olefins reaction.

[0090] MA-3 molecular sieve synthesized in Example 3 was used to prepare the catalyst according to the catalyst preparation method in Example 21, and methanol was used as raw material. A fixed bed reactor with a diameter of 15mm was used to evaluate the catalyst under the conditions of 349℃, mass space velocity 2.2h -1 , and pressure 1.44MPa. The yield of ethylene and propylene reached 86.9%, and good technical effects were achieved.

[0091] Example 23

[0092] Application of MAPO-17 molecular sieve in methanol conversion to olefins reaction.

[0093] MA-4 molecular sieve synthesized in Example 4 was used to prepare the catalyst according to the catalyst preparation method in Example 21, and methanol was used as raw material. A fixed bed reactor with a diameter of 15mm was used to evaluate the catalyst under the conditions of 200℃, mass space velocity 10h -1 , and pressure 10MPa. The yield of ethylene and propylene reached 74.8%, and good technical effects were achieved.

[0094] Example 24

[0095] Application of MAPO-17 molecular sieve in methanol conversion to olefins reaction.

[0096] MA-11 molecular sieve synthesized in Example 11 was used to prepare the catalyst according to the catalyst preparation method in Example 21, and methanol was used as raw material. A fixed bed reactor with a diameter of 15mm was used to evaluate the catalyst under the conditions of 250℃, mass space velocity 8.5h -1, the pressure is 1.1 MPa, the ethylene and propylene yield reaches 78.4%, and good technical effects are achieved.

[0097]

Example 25

[0098] Application of MAPO-17 molecular sieve in methanol conversion to olefins reaction.

[0099] MA-18 molecular sieve synthesized in Example 18 is taken, the catalyst preparation method in Example 21 is used to prepare the catalyst, methanol is used as the raw material, a fixed bed reactor with a diameter of 15 mm is used, the process conditions are 300℃, a mass space velocity of 2.6h -1 , the pressure is 1.1 MPa, the ethylene and propylene yield reaches 81.6%, and good technical effects are achieved.

[0100]

Example 26

[0101] Application of MAPO-17 molecular sieve in synthesis gas to olefins reaction.

[0102] MA-2 molecular sieve synthesized in Example 2 is taken, calcination is carried out at 550℃ for 4h, then tabletting, knocking, sieving, 20-40 mesh particles are taken, and the catalyst preparation method in Example 26 is used to prepare the catalyst. The catalyst preparation method in Example 26 is used to prepare the catalyst, methanol is used as the raw material, a fixed bed reactor with a diameter of 15 mm is used, the process conditions are 300℃, a mass space velocity of 2.6h x , the pressure is 1.1 MPa, the ethylene and propylene yield reaches 81.6%, and good technical effects are achieved. x , the pressure is 1.1 MPa, the ethylene and propylene yield reaches 81.6%, and good technical effects are achieved. -1 , the pressure is 1.1 MPa, the ethylene and propylene yield reaches 81.6%, and good technical effects are achieved. 2＝ , the pressure is 1.1 MPa, the ethylene and propylene yield reaches 81.6%, and good technical effects are achieved. 4＝ , the pressure is 1.1 MPa, the ethylene and propylene yield reaches 81.6%, and good technical effects are achieved.

[0103]

Example 27

[0104] Application of MAPO-17 molecular sieve in synthesis gas to olefins reaction.

[0105] MA-6 molecular sieve synthesized in Example 6 is taken, the catalyst preparation method in Example 26 is used to prepare the catalyst. The process conditions are: the reaction temperature is 200℃, the pressure is 0.10 MPa, the space velocity is 2000h -1 , the pressure is 1.1 MPa, the ethylene and propylene yield reaches 81.6%, and good technical effects are achieved. 2＝ , the pressure is 1.1 MPa, the ethylene and propylene yield reaches 81.6%, and good technical effects are achieved. 4＝ , the pressure is 1.1 MPa, the ethylene and propylene yield reaches 81.6%, and good technical effects are achieved.

[0106]

Example 28

[0107] Application of MAPO-17 molecular sieve in synthesis gas to olefin reaction.

[0108] MA-15 molecular sieve synthesized in Example 15 was taken, and the catalyst was prepared by the catalyst preparation method of Example 26. The process conditions were: reaction temperature 249℃, pressure 6.38MPa, space velocity 1865h -1 , the composition of the synthesis gas was H2 / CO=0.75:1, the conversion rate of CO was 35.8%, and the selectivity of C2 ＝ -C4 ＝ The selectivity was 79.2%, and good technical effects were achieved.

[0109]

Example 29

[0110] Application of MAPO-17 molecular sieve in synthesis gas to olefin reaction.

[0111] MA-20 molecular sieve synthesized in Example 20 was taken, and the catalyst was prepared by the catalyst preparation method of Example 26. The process conditions were: reaction temperature 350℃, pressure 13.8MPa, space velocity 874h -1 , the composition of the synthesis gas was H2 / CO=0.88:1, the conversion rate of CO was 48.8%, and the selectivity of C2 2＝ -C 4＝ The selectivity was 89.7%, and good technical effects were achieved.

[0112]

Comparative Example 1

[0113] Synthesis of AlPO-17 molecular sieve

[0114] According to the synthesis conditions of Example 4, no magnesium source was added in the reactants, and the others were the same:

[0115] At room temperature, 12.89g of AlPO-17 molecular sieve seed, 1008.69g of cyclic organic complexing agent cyclohexylamine [HCHA, 99wt.%, 10.2mol] were dissolved in 12055.42mL of deionized water (669.7mol) and stirred thoroughly, and then heated at 50℃ for 2h to form a crystallization precursor A; 3202.5g of aluminum nitrate (8.5mol) and 1948.5g of phosphoric acid (16.9mol) were dissolved in 18145.58mL of deionized water (1008.1mol) and stirred thoroughly, and then heated at 55℃ for 1.8h to obtain a mixture B. The precursor A was added into the mixture B under stirring, and then stirred thoroughly to form a crystallization mixture, which was then placed in a sealed system and crystallized at 220℃ for 0.2h. The product was filtered, washed, dried at 100℃ for 7.5h, and then heated to 500℃ for constant temperature calcination for 8h to obtain the AlPO-17 molecular sieve. The SEM picture of the AlPO-17 molecular sieve is shown in Figure 1. Figure 5As shown, the morphology is long rod, which is different from the morphology of the molecular sieve of the application.

[0116] Since the framework of the AlPO-17 molecular sieve is electrically neutral and has no proton defect site, it does not have the property of adsorbing CO, i.e., the test results before and after adsorbing CO are consistent, and the hydroxyl displacement is 0 cm -1 .

[0117]

Comparative Example 2

[0118] According to the synthesis conditions of Example 5, no cyclic organic complexing agent is added in the reactants, and the others are the same:

[0119] Under normal temperature conditions, 25.5 g of AlPO-17 molecular sieve seed crystals (0.1% of the total mass of solids) and 5122.9 g of magnesium nitrate (20.0 mol) were dissolved in 88324.26 mL of deionized water (4906.9 mol) and stirred well, and then placed in a 70°C heat treatment for 0.8 h to obtain a crystallization precursor A. 13602.4 g of aluminum isopropoxide [Al(iPr)3, purity ≥ 99 wt.%, 66.6 mol] and 6598.4 g of ammonium dihydrogen phosphate [(NH4)2HPO4, 49.9 mol] were dissolved in 69321.55 mL of deionized water (3851.2 mol) and stirred well, and then placed in a 70°C heat treatment for 0.8 h to obtain a mixture B. The crystallization precursor A was added to the mixture B under stirring, and after stirring well, a crystallization mixture was formed, and then placed in a 200°C crystallization for 0.5 h. The product was filtered, washed, and then dried at 110°C for 5 h, and then the temperature was increased to 400°C, and the product was calcined at a constant temperature for 12 h to obtain the product, which was amorphous (not crystallized) as shown by XRD.

[0120]

Comparative Example 3

[0121] According to the synthesis conditions of Example 2, the cobalt acetate in the reactants is replaced by the same molar number of copper acetate, and the others are the same:

[0122] Under normal temperature, 0.53 g of AlPO-17 molecular sieve seed crystal (2.2% of the total mass of all solid reactants in preparation), 249.8 g of cyclic organic complexing agent piperazine [PIP, 2.9 mol] and 4.0 g of copper acetate (0.02 mol) were dissolved in 510.56 mL of deionized water (28.4 mol) and 173.4 mL of N,N-dimethylformamide (2.5 mol) and stirred thoroughly, and then placed in a heat treatment at 100°C for 0.1 h to obtain a crystallization precursor A2. 10.2 g of isopropyl alcohol aluminum (0.05 mol) and 9.2 g of ammonium dihydrogen phosphate (0.08 mol) were dissolved in 96.88 mL of deionized water (5.4 mol) and stirred thoroughly, and then placed in a heat treatment at 60°C for 1.5 h to obtain a mixture B2. The crystallization precursor A2 was added to the mixture B2 under stirring, and after stirring thoroughly, a crystallization mixture was formed, and then placed in a crystallization at 150°C for 1.8 h. The product was filtered, washed, dried at 110°C for 6 h, and then heated to 600°C, and calcined at constant temperature for 4 h to obtain the product. The SEM photograph of the product is shown in Figure 6 The CO FTIR test result shows that the hydroxyl displacement is 0 cm -1 This indicates that the Cu element does not participate in the product synthesis and does not appear in the proton defect site, i.e. the Cu does not enter the molecular sieve framework, and the product is an electrically neutral AlPO-17 molecular sieve, so it cannot produce hydroxyl displacement.

[0123]

Comparative Example 4

[0124] The product AlPO-17 molecular sieve of Comparative Example 1 was used to prepare and evaluate the catalyst according to the preparation method and reaction conditions of Example 21, and the ethylene and propylene yield was 10.7%;

[0125] It should be noted that the above-described examples are only used to explain the present application and do not constitute any limitation on the present application. The present application is described by referring to typical examples, but it should be understood that the words used therein are descriptive and explanatory words, rather than limiting words. The present application can be modified as specified within the scope of the claims of the present application, and the present application can be revised without departing from the scope and spirit of the present application. Although the present application described therein relates to specific methods, materials and examples, it does not mean that the present application is limited to the specific examples disclosed therein, on the contrary, the present application can be extended to all other methods and applications having the same function.

Claims

1. A MAPO-17 molecular sieve, wherein M in the molecular sieve is at least one of Co, Mg, Ni, Zn; In the Fourier transform infrared characterization before and after CO adsorption, the surface OH stretching vibration peak of MAPO-17 molecular sieve before and after CO molecule adsorption has obvious red shift phenomenon, and the red shift range is 280-350 cm -1 .

2. The MAPO-17 molecular sieve of claim 1, wherein, The mass content of M in the MAPO-17 molecular sieve is 0.1% to 20% based on the mass of the MAPO-17 molecular sieve, and the mass content of the AlPO-17 molecular sieve is 80% to 99.9%.

3. The MAPO-17 molecular sieve of claim 1, wherein, The AlPO-17 in the molecular sieve has a schematic chemical composition as shown in the formula "Al2O3-xP2O", wherein 0.75≤x≤1.

5.

4. The MAPO-17 molecular sieve of claim 1, wherein, The average thickness of the crystals in the molecular sieve is 200 to 600 nm.

5. A method for preparing the MAPO-17 molecular sieve according to any one of claims 1 to 4, comprising the following steps: (1) mixing a solvent S, ERI molecular sieve seeds, a cyclic organic complexing agent C, and a metal M salt solution, and heat-treating to obtain a crystallization precursor A; (2) mixing an aluminum source, a phosphorus source, and a solvent S', and heat-treating to obtain a mixture B; (3) mixing the crystallization precursor A and the mixture B, and crystallizing to obtain the molecular sieve.

6. The preparation method according to claim 5, characterized in that, In step (1), the solvent S comprises at least one of N,N-dimethylformamide, N,N-dimethylacetamide, ethanol, ethylene glycol, and water; the ERI molecular sieve seeds are AlPO-17 molecular sieve; the cyclic organic complexing agent C is at least one selected from 1,10-phenanthroline, 2,2-bipyridine, 4,4-bipyridine, piperazine, aminopropylimidazole, and cyclohexylamine; and the metal M salt solution is at least one selected from the corresponding metal sulfate, nitrate, carbonate, and acetate.

7. The preparation method according to claim 5, characterized in that, In step (1), the heat-treatment is performed at 50 to 100°C for 0.1 to 2 h. In step (1), the ERI molecular sieve seeds account for 0.1% to 5.0% of the total mass of the solid feed.

8. The preparation method according to claim 5, characterized in that, In steps (1) and (2), the molar ratio of the cyclic organic complexing agent C, the metal M salt solution (calculated based on the metal), the phosphorus source (calculated based on P), the aluminum source (calculated based on Al), and the solvent (S+S') is (1-500):(0.001-1.0):(0.5-3.0):1:(10-1000). In step (2), the mass ratio of the solvent S' to the solvent S in step (1) is 1:0.1-10.

9. The preparation method according to claim 5, characterized in that, In step (2), the aluminum source is at least one selected from aluminum salt, aluminate, aluminum hydroxide, aluminum oxide, and aluminum-containing minerals; the phosphorus source is at least one selected from orthophosphoric acid, monoammonium phosphate, and dihydrogen ammonium phosphate; and the solvent S' comprises at least one of N,N-dimethylformamide, N,N-dimethylacetamide, ethanol, ethylene glycol, and water. In step (2), the heat-treatment is performed at 50 to 100°C for 0.1 to 2 h.

10. The method of claim 5, wherein, In step (3), the crystallization temperature is 140 to 250°C, and the crystallization time is 0.1 to 2 h.

11. Use of the MAPO-17 molecular sieve according to any one of claims 1 to 4 or the MAPO-17 molecular sieve prepared by the method according to any one of claims 5 to 10 in a methanol-to-olefins reaction.

12. Use according to claim 11, characterized in that, The reaction conditions of the reaction of converting methanol into hydrocarbons are as follows: using methanol as raw material, the reaction temperature is 200-400℃, the reaction pressure is 0.01-10MPa, the weight space velocity of methanol is 0.1-15h -1 .

13. Use of the MAPO-17 molecular sieve according to any one of claims 1 to 4 or of the MAPO-17 molecular sieve prepared according to the method of any one of claims 5 to 10 in a synthesis gas to hydrocarbons reaction.

14. Use according to claim 13, characterized in that, The reaction conditions of the hydrocarbon synthesis reaction from the synthesis gas are as follows: H2 / CO = 0.5-1, reaction temperature = 200-400°C, reaction pressure = 0.1-10 MPa, and synthesis gas weight space velocity = 20-2000 h -1 .

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