Molecular sieve SCM-33 and method of preparation and application thereof.

Abstract

MOLECULAR SIEVE SCM-33 AND METHOD OF PREPARATION AND APPLICATION THEREOF. The present invention relates to a molecular sieve SCM-33, and to the method of preparation and application thereof. The molecular sieve SCM-33 has a schematic chemical composition as shown in the formula "SiO2·1 / x XO1.5·m MO0.5", wherein X is a trivalent structural element, the molar ratio of Si to X is x = 5, M is a structural equilibrium cation, and the molar ratio of M to Si is 0 < m ≠ 1. The method of preparation for the molecular sieve comprises: mixing a source of silicon, a source of trivalent structural element X, a source of structural equilibrium cation M, an organic molding agent Q, and water, and carrying out a crystallization reaction to obtain a molecular sieve. Molecular sieves are molecular sieves with an RTE topological structure. They have a short preparation time and low synthesis cost, and can be used as either an adsorbent or a catalyst.

Description

[001] The present invention pertains to the field of molecular sieves, in particular to an SCM-33 molecular sieve, and to the method of preparing and applying it. BACKGROUND

[002] Zeolites, or so-called molecular sieves, are a type of porous crystalline material, and have regular molecular sizes, pore structures, a relatively strong acidity, and high hydrothermal stability. They are widely used in catalysis, adsorption, ion exchange, and other fields, and play an irreplaceable role. Currently, there are up to 248 molecular sieve topologies that have been approved by the International Zeolite Association.

[003] In 1995, Marler and others first reported the synthesis of a pure silicon molecular sieve RUB-3 and elucidated its structure (Zeolites, 1995, No. 15, pp. 388-399), after which this molecular sieve received an RTE structure type code from the International Zeolite Association. Molecular sieves that have an RTE structure consist of rte units ([445462]) and cage structures [46546682], and the interconnected cages form a one-dimensional pore structure with 8-membered ring openings (Microporous and Mesoporous Materials, 1998, No. 26, pp. 49-59). The RTE molecular sieve has a pore diameter of 3.6 x 4.3 Å, which is equivalent to the diameter of many small gas molecules, allowing for greater potential applications of the molecular sieve in terms of gas adsorption and separation; on the other hand, the single-pore cage structure also makes the RTE molecular sieve suitable for application in the field of catalysis. Petition 870220103607, dated 08 / 11 / 2022, page 9 / 50 2 / 22

[004] RUB-3 is currently the only molecular sieve with RTE topology, but faces the following problems in its synthesis: 1) the organic template exo-2-aminobicyclo[2.2.1]heptane is expensive and is used in large quantities, so the cost for the synthesis of the molecular sieve is high; 2) the crystal growth rate is low and the synthesis period is 90 days or more, up to 1 year; 3) the crystal has a column shape with a size of 50 χ 50 χ 150 μm, which is very large; 4) the structure is a siliceous structure and catalytic active centers can hardly be introduced.

[005] Therefore, it is of great practical importance to develop a new molecular sieve with RTE topology and the method for its preparation. CONTENTS OF THE INVENTION

[006] The present invention relates to an SCM-33 molecular sieve and to the method of preparation and application thereof. The SCM-33 molecular sieve is a novel molecular sieve with RTE topology and requires a short preparation time, involves a low synthesis cost and has a smaller crystal size and other elements besides Si can be introduced as catalytic active centers in its structure.

[007] According to the first aspect of the present invention, an SCM-33 molecular sieve is provided. The SCM-33 molecular sieve has a schematic chemical composition as shown in the formula SiO2^1 / x XO^m MOq,5, where X is a trivalent structural element, the molar ratio of Si to X is x > 5, M is a structural equilibrium cation, and the molar ratio of M to Si is 0 < m < 1; the SCM-33 molecular sieve has an X-ray diffraction pattern shown in the following table: 2Θ (°) spacing d (A) relative intensity, (I / I0) χ 100 9.20 ± 0.3 9.61 ± 0.40 s-vs Petition 870220103607, dated 08 / 11 / 2022, page 10 / 50 3 / 22 2θ (°) spacing d (A) relative intensity, (I / I0) χ 100 14.17 ± 0.3 6.24 ± 0.30 s-vs 17.88 ± 0.3 4.96 ± 0.20 ms 19.63 ± 0.3 4.52 ± 0.15 ms 20.65 ± 0.1 4.30 ± 0.10 vs 21.72 ± 0.3 4.09 ± 0.10 ms

[008] In addition, the X-ray diffraction pattern of the SCM-33 molecular sieve has X-ray diffraction peaks shown in the following table: 2θ (°) spacing d (A) relative intensity, (I / I0) χ 100 9.20 ± 0.3 9.61 ± 0.40 s-vs 12.22 ± 0.3 7.24 ± 0.30 wm 13.00 ± 0.05 6.80 ± 0.05 ms 14.17 ± 0.3 6.24 ± 0.30 s-vs 17.88 ± 0.3 4.96 ± 0.20 ms 19.63 ± 0.3 4.52 ± 0.15 ms 20.65 ± 0.1 4.30 ± 0.10 vs 21.72 ± 0.3 4.09 ± 0.10 ms

[009] In addition, the X-ray diffraction pattern of the SCM-33 molecular sieve also includes X-ray diffraction peaks shown in the following table: 2θ (°) d-spacing (A) relative intensity, (I / I0) χ 100 15.77 ± 0.3 5.61 ± 0.25 vw 16.32 ± 0.3 5.43 ± 0.25 vw 18.39 ± 0.3 4.82 ± 0.20 w 23.60 ± 0.3 3.77 ± 0.10 vw-w 24.57 ± 0.3 3.62 ± 0.05 wm 26.04 ± 0.3 3.42 ± 0.05 ms 27.54 ± 0.3 3.24 ± 0.05 ms

[0010] Furthermore, the X-ray diffraction pattern of the mo sieve Petition 870220103607, dated 08 / 11 / 2022, page 11 / 50 4 / 22 The SCM-33 molecular pattern also includes X-ray diffraction peaks shown in the following table: 2Θ (°) spacing d (Â) relative intensity, (I / I0) x 100 12.89 ± 0.05 6.86 ± 0.05 wm 20.44 ± 0.1 4.34 ± 0.10 s-vs 25.24 ± 0.3 3.53 ± 0.05 wm 28.49 ± 0.3 3.13 ± 0.05 wm 29.22 ± 0.3 3.05 ± 0.05 ms

[0011] Furthermore, in the schematic chemical composition formula of the SCM-33 molecular sieve, the molar ratio of Si to X is preferably 10 < x < 200, more preferably 15 < x < 150, even more preferably 20 < x < 120, and / or the molar ratio of M to Si is preferably 0.01 < m < 0.85, more preferably 0.015 < m < 0.8, even more preferably 0.02 < m < 0.75.

[0012] The process for synthesizing the SCM-33 molecular sieve involves the finished state form thereof which has a schematic chemical composition as shown in the formula qQ^SiO2^1 / x XO1,5^m MOα,5·ζ H2O, wherein the molar ratio of Si to X is x > 5, preferably 10 < x < 200, more preferably 15 < x < 150 and even more preferably 20 < x < 120; the molar ratio of M to Si is 0 < m < 1, preferably 0.01 < m < 0.85, more preferably 0.015 < m < 0.8, even more preferably 0.02 < m < 0.75; The molar ratio of H2O / Si is as follows: 0.005 < z < 2, preferably 0.01 < z < 1.5, more preferably 0.015 < z < 1, even more preferably 0.02 < z < 0.5; Q is an organic mold, and the molar ratio of Q / Si is as follows: 0.01 < q < 1.0, preferably 0.02 < q < 0.5, more preferably 0.05 < q < 0.5, even more preferably 0.05 < q < 0.3.

[0013] The organic mold Q is preferably selected from a substance containing an isopropyl trimethyl ammonium cation whose Petition 870220103607, dated 08 / 11 / 2022, page 12 / 50 The structural formula for 5 / 22 is as follows:

[0014] Furthermore, the organic mold Q is more preferably a hydroxide containing an isopropyl trimethyl ammonium cation, such as isopropyl trimethyl ammonium hydroxide.

[0015] Furthermore, the trivalent element of structure X is selected from at least one of aluminum, boron, iron, gallium, indium, and chromium. Additionally, the equilibrium cation of structure M is selected from at least one of proton, ammonium cation, sodium cation, potassium cation, lithium cation, rubidium cation, cesium cation, magnesium cation, calcium cation, strontium cation, and barium cation; preferably M includes at least one potassium cation or M includes at least one potassium and one sodium cation. M, when including both potassium and sodium cations, preferably includes more potassium cations than sodium cations.

[0016] Furthermore, no more than 10% by weight of Si atoms in the SCM-33 molecular sieve are replaced by at least one non-silicon tetravalent structural element Y that is preferably selected from at least one germanium, tin, titanium, zirconium and hafnium.

[0017] Furthermore, the average crystalline particle size of the SCM-33 molecular sieve is approximately 100 ~ 200 nm.

[0018] According to the second aspect of the invention, a method is provided for preparing the aforementioned SCM-33 molecular sieve, comprising the step of mixing a silicon source, a trivalent element source of structure X, an equilibrium cation source of structure M, an organic template Q, and water for a crystallization reaction to obtain the SCM-33 molecular sieve.

[0019] In addition, the method for preparing the molecular sieve Petition 870220103607, dated 08 / 11 / 2022, page 13 / 50 6 / 22 SCM-33 may also include the step of mixing a source of non-silicon tetravalent structural element Y, a silicon source, a source of structural trivalent element X, a source of structural equilibrium cation M, an organic template Q, and water for a crystallization reaction to obtain the SCM-33 molecular sieve.

[0020] Furthermore, the organic template Q is selected from a substance containing an isopropyl trimethyl ammonium cation whose structural formula is as follows:

[0021] Furthermore, the organic mold Q is preferably a hydroxide containing an isopropyl trimethyl ammonium cation, such as isopropyl trimethyl ammonium hydroxide.

[0022] In addition, the silicon source is selected from at least one of liquid glass, silica sol, silica gel solid, silica fume, amorphous silica, diatomite, zeolite molecular sieve and tetra-alkoxysilane.

[0023] In addition, the trivalent element source of structure X is selected from at least one aluminum source, boron source, iron source, gallium source, indium source, and chromium source; the aluminum source is preferably selected from at least one aluminum sulfate, sodium aluminate, aluminum nitrate, aluminum chloride, pseudoboehmite, aluminum oxide, aluminum hydroxide, aluminosilicate zeolite, aluminum carbonate, aluminum, aluminum isopropoxide, and aluminum acetate; the boron source is preferably selected from at least one boric acid, sodium tetraborate, amorphous boron oxide, potassium borate, sodium metaborate, ammonium tetraborate, and organic boron ester; the iron source is preferably selected from at least one ferric sulfate, ferric nitrate, ferric halide (such as trichloride). Petition 870220103607, dated 08 / 11 / 2022, page 14 / 50 7 / 22 iron oxide), ferrocene and ferric citrate; the gallium source, indium source and chromium source may be selected from at least one of the conventional substances in the art, such as gallium oxide, gallium nitrate, indium oxide, indium nitrate, chromium chloride and chromium nitrate, etc.

[0024] In addition, the equilibrium cation source of structure M is selected from at least one of the following: proton source, ammonium cation source, sodium cation source, potassium cation source, lithium cation source, rubidium cation source, cesium cation source, magnesium cation source, calcium cation source, strontium cation source, and barium cation source; preferably, source M includes at least one potassium cation source or source M includes at least one potassium cation source and one sodium cation source. When using both potassium and sodium cation sources, it is preferable to use more potassium cations than sodium cations, for example, the molar ratio of potassium / sodium is 1.1 or more.The source of potassium cations is preferably selected from at least one of potassium oxide, potassium hydroxide, potassium carbonate, potassium bicarbonate, potassium chloride, potassium nitrate, potassium sulfate, and potassium fluoride; the source of sodium cations is preferably selected from at least one of sodium oxide, sodium hydroxide, sodium carbonate, sodium bicarbonate, sodium chloride, sodium nitrate, sodium sulfate, and sodium fluoride.

[0025] In addition, the source of the tetravalent non-silicon structural element Y is preferably selected from at least one germanium source, tin source, titanium source, zirconium source, and hafnium source, more preferably selected from at least one germanium oxide source, tin oxide source, titanium oxide source, zirconium oxide source, and hafnium source. Petition 870220103607, dated 08 / 11 / 2022, page 15 / 50 8 / 22 hafnium oxide.

[0026] Furthermore, the molar ratio of the organic mold Q, of the silicon source (based on SiO2), of the X source (based on X2O3), of the M source (based on M2O or MO) and of water is Q: SiO2: X2O3: M2O (or MO): H2O = 0.05 ~ 1: 1: 0 ~ 0.1: 0 ~ 0.5: 10 ~ 100, wherein the quantities of source X and source M are not 0, preferably Q: SiO2: X2O3: M2O (or MO): H2O = 0.15 ~ 0.55: 1: 0.0042 ~ 0.033: 0.01 ~ 0.375: 14 ~ 55.

[0027] Furthermore, the molar ratio of the tetravalent non-silicon structural element source Y (based on the corresponding oxide YO2) to the silicon source (based on SiO2) YO2 / SiO2 = greater than 0~0.1, preferably 0.01~0.1, more preferably 0.01 ~ 0.08.

[0028] In addition, the conditions for the crystallization reaction include: crystallization at 100-200°C for 30-400 hours, preferably crystallization at 110-190°C for 48-300 hours, more preferably crystallization at 120-180°C for 72-200 hours.

[0029] After the crystallization reaction, conventional post-treatments, such as filtration, washing and drying, are carried out to prepare a ready molecular sieve powder and then the ready powder is calcined to obtain a molecular sieve.

[0030] According to the third aspect of the present invention, a molecular sieve composite, including the SCM-33 molecular sieve according to the first aspect mentioned above or the SCM-33 molecular sieve prepared according to the method in the second aspect mentioned above, and a binder, is provided.

[0031] According to the fourth aspect of the present invention, the use of the SCM-33 molecular sieve according to the first aspect mentioned above is provided, of the SCM-33 molecular sieve prepared according to the method in the second aspect mentioned above. Petition 870220103607, dated 08 / 11 / 2022, page 16 / 50 9 / 22 or the SCM-33 molecular sieve composite according to the third aspect mentioned above as an adsorbent or catalyst.

[0032] The SCM-33 molecular sieve of the present invention, whose structure topology is RTE, is a novel non-pure silicon molecular sieve different from RUB-3, and enriches the RTE molecular sieve types.

[0033] The SCM-33 molecular sieve of the present invention has a regular molecular size, a pore structure, strong acidity, ion exchange performance, and high thermal and hydrothermal stability. The crystal size of the obtained SCM-33 zeolite molecular sieve is about 100 ~ 200 nm, which circumvents the limited mass transfer and diffusion within the pores due to the bulky crystal.

[0034] The method for preparing the SCM-33 molecular sieve provided by the present invention utilizes a lower-cost organic mold, saving on synthesis costs compared to the previous technique; the molecular sieve requires a short crystallization time, which greatly reduces the synthesis period; the method allows the introduction of various elements such as Al, Ti, Zr, and Fe into the structure to generate different catalytic active centers, which meets the needs of different catalytic reactions and has a wider application. The method of the present invention is simple to operate, highly efficient, and beneficial for industrial popularization. DESCRIPTION OF THE FIGURES

[0035] Figure 1 is the X-ray diffraction (XRD) pattern of the sample obtained in Example 1 before calcination.

[0036] Figure 2 is the X-ray diffraction (XRD) pattern of the sample obtained in Example 1 after calcination.

[0037] Figure 3 is a scanning electron microscope (SEM) photograph of the sample obtained in Example 1. Petition 870220103607, dated 08 / 11 / 2022, page 17 / 50 10 / 22 SPECIFIC MODALITIES

[0038] In order to facilitate understanding of the present invention, the following examples are listed in the present invention. However, those skilled in the art should understand that the examples serve only to assist in understanding the present invention, and should not be considered as a specific limitation of the present invention.

[0039] In the context of the present specification, among the molecular sieve XRD data, vw, w, m, s, vs indicate the intensity of the diffraction peaks, with vw referring to very weak, w referring to weak, ma medium, sa strong, vs to very strong, which is well known to those skilled in the art. In general, vw is less than 5; w is 5-20; m is 20-40; s is 40-70; vs is greater than 70.

[0040] In the context of the present specification, the molecular sieve structure is confirmed by X-ray diffraction (XRD) pattern, while the molecular sieve X-ray diffraction (XRD) pattern is determined by a powder X-ray diffractometer equipped with a Cu-Kα ray source and a Ni filter, where the wavelength of Kα1 λ = 1.5405980 Â.

[0041] In the present invention, an X'Pert PRO powder X-ray diffractometer (XRD) manufactured from PANalytical BV is used, with a working voltage of 40 kV, a current of 40 mA and a scanning range of 5-40°. The morphology of the product is measured with the S-4800 Field Emission Scanning Electron Microscope (FeSEM) manufactured by HITACHI.

[0042] It should be noted in particular that the two or more aspects (or embodiments) described in the context of this specification may be arbitrarily combined with each other, and the technical solutions (such as methods or systems) thus formed are part of the original description in this specification, and also fall within the scope of protection in this specification. Petition 870220103607, dated 08 / 11 / 2022, page 18 / 50 11 / 22

[0043] Unless otherwise specified, all percentages, parts, ratios, etc. mentioned in this specification are based on weight, unless taking weight as a basis is not in accordance with the conventional understanding of those skilled in the art. Example 1

[0044] 2.5 g of sodium meta-aluminate (AbO3 41% by weight, 58% by weight (Na2O) and 17.5 g of potassium hydroxide solution (30% by weight) were dissolved in 28 g of water. 39.4 g of isopropyl trimethyl ammonium hydroxide solution (20%) were added and stirred uniformly. Finally, 60 g of Ludox AS-40 silica sol were added slowly while stirring. After stirring for 1 hour, the mixture was placed in a crystallization kettle with a polytetrafluoroethylene lining and placed in an oven at 155°C for crystallization for 144 hours. After the reaction, the solid was filtered, washed with distilled water, and dried at 100°C to obtain a ready-to-use SCM-33 molecular sieve powder. The XRD standard is shown in Figure 1. The ready-to-use powder was placed in a muffle furnace and calcined at 550°C for 5 hours to obtain the final product. The XRD pattern is shown in Figure 2. The SEM photograph of the SCM-33 molecular sieve is shown in Figure 3.

[0045] The XRD pattern data of the final product obtained in Example 1 are shown in Table 1: Table 1 2Θ (°) spacing d (A) relative intensity, (I / I0) x 100 9.20 9.61 65.4 12.22 7.24 7.7 12.91 6.85 15.9 13.00 6.80 32.4 14.17 6.24 67.2 Petition 870220103607, dated 08 / 11 / 2022, page 19 / 50 12 / 22 2Θ (°) spacing d (A) relative intensity, (I / I0) x 100 15.82 5.60 1.2 16.35 5.42 0.1 17.88 4.96 38.4 18.39 4.82 5.2 19.63 4.52 35.8 20.53 4.32 65 20.60 4.31 100 21.72 4.09 30.4 23.24 3.82 1.5 23.60 3.77 1.6 24.57 3.62 17.9 24.94 3.57 6.3 25.24 3.53 10.7 26.04 3.42 39.5 27.54 3.24 37.6 28.49 3.13 14.8 28.92 3.08 17 29.22 3.05 31.2 30.66 2.91 19.5 Example 2

[0046] 2.5 g of sodium meta-aluminate (Al2O3 41% by weight, 58% by weight Na2O and 13.7 g of potassium hydroxide solution (30% by weight) were dissolved in 64 g of water. 39.4 g of isopropyl trimethyl ammonium hydroxide solution (20%) were added and stirred uniformly. Finally, 60 g of Ludox AS-40 silica sol were added slowly while stirring. After stirring for 1 hour, the mixture was placed in a crystallization kettle with a polytetrafluoroethylene lining and placed in an oven at 160°C for crystallization for 120 hours. After the reaction, the solid was... Petition 870220103607, dated 08 / 11 / 2022, page 20 / 50 13 / 22 filtered, washed, dried and calcined (post-treatment conditions are the same as in Example 1) to obtain an SCM-33 zeolite molecular sieve. The XRD standard is similar to Figure 2. The XRD standard data for the final product obtained in Example 2 are shown in Table 2: Table 2 2Θ (°) spacing d (Â) relative intensity, (I / I0) χ 100 9.20 9.60 76.1 12.26 7.21 8.7 12.94 6.84 23.5 13.00 6.80 38 14.18 6.24 74 15.75 5.62 0.3 16.35 5.42 0.1 17.91 4.95 37.1 18.40 4.82 5.3 19.63 4.52 37.6 20.49 4.33 61.2 20.56 4.32 100 21.70 4.09 28.3 23.27 3.82 2.5 23.60 3.77 1.8 24.57 3.62 17.4 24.88 3.58 6.5 25.27 3.52 9.7 26.04 3.42 41.1 27.55 3.24 36 28.51 3.13 13.4 28.95 3.08 15.6 Petition 870220103607, dated 08 / 11 / 2022, page 21 / 50 14 / 22 2Θ (°) spacing d (Â) relative intensity, (I / I0) x 100 29.22 3.05 28.3 30.69 2.91 18.6 Example 3

[0047] 7.5 g of sodium hydroxide solution (30% by weight), 15 g of potassium hydroxide solution (30% by weight), 40 g of H2O and 47.3 g of isopropyl trimethyl ammonium hydroxide solution (20% by weight) were stirred uniformly, 45 g of Ludox AS-40 silica sol were added slowly with stirring; after stirring for 1 hour, 6.6 g of USY molecular sieve (SiO2 / AbO3 = 12) were added; after stirring for 1.5 hours, the above mixture was loaded into a crystallization kettle with a polytetrafluoroethylene lining, and placed in an oven at 165°C for crystallization for 96 hours. After the reaction, the solid was filtered, washed, dried, and calcined (the post-treatment reaction conditions are the same as in Example 1) to obtain an SCM-33 zeolite molecular sieve, and the XRD standard is similar to Figure 2. The XRD standard data for the final product obtained in Example 3 are shown in Table 3: Table 3 2Θ (°) spacing d (Â) relative intensity, (I / I0) x 100 9.27 9.53 94 12.34 7.17 9 12.91 6.85 20.1 13.07 6.77 38.5 14.25 6.21 59.3 15.78 5.61 0.6 16.32 5.43 0.6 17.93 4.94 27.7 18.48 4.80 7 19.69 4.50 25.7 Petition 870220103607, dated 08 / 11 / 2022, page 22 / 50 15 / 22 2Θ (°) spacing d (A) relative intensity, (I / I0) x 100 20.54 4.32 57.6 20.66 4.30 100 21.83 4.07 22.4 23.07 3.85 0.2 23.54 3.78 2.1 24.67 3.61 15.1 25.34 3.51 7.3 26.15 3.41 38.5 27.65 3.22 29 28.61 3.12 13.9 29.31 3.04 30.8 30.79 2.90 12.8 Example 4

[0048] 4.2 g of aluminum sulfate octadecahydrate, 6.2 g of sodium hydroxide solution (30%) and 13.7 g of potassium hydroxide solution (30% by weight) were dissolved in 21.1 g of water, 110 g of isopropyl trimethyl ammonium hydroxide solution (20% by weight) were added and stirred uniformly, finally, 54 g of Ludox AS-40 silica gel were added slowly with stirring; after stirring for 1 hour, the above mixture was loaded into a crystallization kettle with a polytetrafluoroethylene lining and placed in an oven at 150°C for crystallization for 180 hours. After the reaction, the solid was filtered, washed, dried and calcined (the post-treatment reaction conditions are the same as in Example 1) to obtain an SCM-33 zeolite molecular sieve and the XRD standard is similar to Figure 2. Example 5

[0049] 2 g of aluminum isopropoxide were added to 40 g of isopropyl trimethyl ammonium hydroxide solution (20% by weight) and Petition 870220103607, dated 08 / 11 / 2022, page 23 / 50 16 / 22 g of potassium hydroxide solution (30% by weight); after dissolution, 75 g of water were added, 52 g of tetraethyl orthosilicate were added slowly; after complete hydrolysis, the above mixture was loaded into a crystallization kettle with a polytetrafluoroethylene lining, and placed in an oven at 175°C for crystallization for 144 hours. After the reaction, the solid was filtered, washed, dried, and calcined (the post-treatment reaction conditions are the same as in Example 1) to obtain a zeolite molecular sieve SCM-33, and the XRD pattern is similar to Figure 2. Example 6

[0050] 9.7 g of rubidium chloride and 26 g of potassium hydroxide solution (30% by weight) were dissolved in 68.5 g of water, 39.4 g of isopropyl trimethyl ammonium hydroxide solution (20% by weight) were added and stirred uniformly, 54.6 g of Ludox AS-40 silica sol were added slowly with stirring; after stirring for 1 hour, 5 g of USY molecular sieve (SiO2 / Al2O3 = 12) were added; after stirring for 1.5 hours, the above mixture was loaded into a crystallization kettle with a polytetrafluoroethylene lining, and placed in an oven at 145°C for crystallization for 192 hours. After the reaction, the solid was filtered, washed, dried, and calcined (the post-treatment reaction conditions are the same as in Example 1) to obtain an SCM-33 zeolite molecular sieve, and the XRD standard is similar to Figure 2. Example 7

[0051] 0.6 g of pseudoboehmite (AbO3 70% by weight) and 17 g of potassium hydroxide solution (30% by weight) were dissolved in 30 g of water, 49.3 g of isopropyl trimethyl ammonium hydroxide solution (20%) were added and stirred uniformly, 15 g of liquid glass (SO 27% by weight, Na2O 8.4% by weight) and 45 g of Ludox AS-40 silica sol were added slowly while stirring; after stirring Petition 870220103607, dated 08 / 11 / 2022, page 24 / 50 17 / 22 After the reaction for 1 hour, the above mixture was loaded into a crystallization kettle with a polytetrafluoroethylene lining and placed in an oven at 160°C for crystallization for 168 hours. After the reaction, the solid was filtered, washed, dried, and calcined (the post-treatment reaction conditions are the same as in Example 1) to obtain an SCM-33 zeolite molecular sieve, and the XRD pattern is similar to Figure 2. Example 8

[0052] 1.3 g of boric acid, 9 g of sodium hydroxide solution (30% by weight) and 14 g of potassium hydroxide solution (30% by weight) were dissolved in 41 g of water, 49.3 g of isopropyl trimethyl ammonium hydroxide solution (20%) were added and stirred uniformly, 75 g of Ludox AS-40 silica-sol were added slowly while stirring; after stirring for 1 hour, the above mixture was loaded into a crystallization kettle with a polytetrafluoroethylene lining and placed in an oven at 160°C for crystallization for 192 hours. After the reaction, the solid was filtered, washed, dried, and calcined (the post-treatment reaction conditions are the same as in Example 1) to obtain an SCM-33 zeolite molecular sieve, and the XRD standard is similar to Figure 2. The XRD standard data for the final product obtained in Example 8 are shown in Table 4: Table 4 2Θ (°) spacing d (A) relative intensity, (I / I0) χ 100 9.26 9.55 100 12.28 7.20 11.2 12.91 6.85 16 13.04 6.78 40.3 14.21 6.23 68.2 15.78 5.61 0.1 16.36 5.41 1.5 17.92 4.94 32.5 Petition 870220103607, dated 08 / 11 / 2022, page 25 / 50 18 / 22 2Θ (°) spacing d (A) relative intensity, (I / I0) χ 100 18.47 4.80 5.5 19.72 4.50 34.5 20.53 4.32 51.8 20.63 4.30 98.8 21.77 4.08 28.9 23.27 3.82 2.1 23.64 3.76 1 24.66 3.61 14.3 25.03 3.56 3.4 25.33 3.51 7.7 26.11 3.41 39.2 27.62 3.23 28.3 28.61 3.12 12.3 28.99 3.08 14.7 29.26 3.05 28.2 30.76 2.90 15.5 Example 9

[0053] 4.8 g of ferric nitrate nonahydrate, 9 g of sodium hydroxide solution (30% by weight) and 14 g of potassium hydroxide solution (30% by weight) were dissolved in 150 g of water, 49.3 g of isopropyl trimethyl ammonium hydroxide solution (20% by weight) were added and stirred uniformly, 75 g of Ludox AS-40 silica sol were added slowly with stirring; after stirring for 1 hour, the above mixture was loaded into a crystallization kettle with a polytetrafluoroethylene lining and placed in an oven at 150°C for crystallization for 216 hours. After the reaction, the solid was filtered, washed, dried and calcined (the post-treatment reaction conditions are the same as in Example 1) to obtain an SCM-33 zeolite molecular sieve and the XRD standard is similar to Figure 2. Petition 870220103607, dated 08 / 11 / 2022, page 26 / 50 19 / 22 Example 10

[0054] 4 g of titanium sulfate, 0.4 g of boric acid, 8 g of sodium hydroxide solution (30% by weight), 15 g of potassium hydroxide solution (30% by weight) were dissolved in 50 g of water, 49.3 g of isopropyl trimethyl ammonium hydroxide solution (20% by weight) were added and stirred uniformly, 60 g of Ludox AS-40 silica-sol were added slowly while stirring; after stirring for 1 hour, the above mixture was loaded into a crystallization kettle with a polytetrafluoroethylene lining and placed in an oven at 170°C for crystallization for 120 hours. After the reaction, the solid was filtered, washed, dried, and calcined (the post-treatment reaction conditions are the same as in Example 1) to obtain an SCM-33 zeolite molecular sieve, and the XRD standard is similar to Figure 2. The XRD standard data for the final product obtained in Example 10 are shown in Table 5: Table 5 2Θ (°) spacing d (Â) relative intensity, (I / I0) χ 100 9.23 9.57 96.9 12.30 7.19 11.9 12.92 6.85 19.8 13.04 6.78 40 14.21 6.23 84.5 15.75 5.62 0.8 16.36 5.41 1.5 17.92 4.95 39 18.48 4.80 5.1 19.69 4.50 37.3 20.52 4.33 51.4 20.63 4.30 100 21.77 4.08 37.7 Petition 870220103607, dated 08 / 11 / 2022, page 27 / 50 20 / 22 2Θ (°) spacing d (Â) relative intensity, (I / I0) x 100 23.23 3.83 1.9 23.67 3.76 1.2 24.63 3.61 16.5 25.31 3.52 8 26.14 3.41 37.3 27.61 3.23 30.2 28.58 3.12 13 29.32 3.04 28.4 30.73 2.91 16.6 Comparative Example 1

[0055] 2.5 g of sodium meta-aluminate (Al2O3 41% by weight, 58% by weight Na2O and 17.5 g of potassium hydroxide solution (30% by weight) were dissolved in 28 g of water. 30 g of tetramethyl ammonium hydroxide solution (20%) were added and stirred uniformly. Finally, 60 g of Ludox AS-40 silica sol were added slowly while stirring. After stirring for 1 hour, the mixture was placed in a crystallization kettle with a polytetrafluoroethylene lining and placed in an oven at 155°C for crystallization for 144 hours. After the reaction, the solid was filtered, washed, dried, and calcined (the post-treatment reaction conditions are the same as in Example 1) to obtain a molecular sieve, which, after XRD analysis, is a RUT molecular sieve. Its XRD pattern is obviously different from Figure 2. The XRD pattern data are shown in Table 6. Table 6 2Θ (°) spacing d (Â) relative intensity, (I / I0) x 100 7.80 11.32 5 10.09 8.76 16.3 10.82 8.17 89.1 Petition 870220103607, dated 08 / 11 / 2022, page 28 / 50 21 / 22 2Θ (°) spacing d (Â) relative intensity, (I / I0) x 100 13.68 6.47 28.3 14.43 6.13 85.8 15.82 5.60 4.6 15.82 5.60 4.6 16.65 5.32 7.7 19.32 4.59 8.7 20.07 4.42 53.1 20.64 4.30 53.7 21.57 4.12 3.2 21.78 4.08 28.6 22.09 4.02 94 22.49 3.95 100 23.09 3.85 97 23.23 3.83 44.9 23.51 3.78 6.1 24.08 3.69 16.7 25.19 3.53 38.3 25.99 3.43 4 26.99 3.30 4.5 27.38 3.26 37.7 Comparative Example 2

[0056] 2.5 g of sodium meta-aluminate (Al2O3 41% by weight, 58% by weight Na2O and 17.5 g of potassium hydroxide solution (30% by weight) were dissolved in 28 g of water. 48.7 g of tetraethyl ammonium hydroxide solution (20%) were added and stirred uniformly. Finally, 60 g of Ludox AS-40 silica sol were added slowly while stirring. After stirring for 1 hour, the mixture was placed in a crystallization kettle with a polytetrafluoroethylene lining and placed in an oven at 155°C. Petition 870220103607, dated 08 / 11 / 2022, page 29 / 50 22 / 22 for crystallization for 144 hours. After the reaction, the solid was filtered, washed, dried, and calcined (the post-treatment reaction conditions are the same as in Example 1) to obtain a molecular sieve, which, after XRD analysis, is a BEA molecular sieve. Its XRD pattern is obviously different from Figure 2. The XRD pattern data are shown in Table 7: Table 7 2Θ (°) spacing d (Â) relative intensity, (I / I0) x 100 7.23 12.22 16.7 7.59 11.65 18.4 9.66 9.15 3.5 11.61 7.62 1.5 13.29 6.66 1.2 16.51 5.36 4.3 21.43 4.14 11.2 22.46 3.95 100 25.30 3.52 6.7 26.78 3.33 15.5 28.82 3.10 3.7 29.48 3.03 15.9 30.46 2.93 3.7

Claims

1. SCM-33 molecular sieve, characterized in that the SCM-33 molecular sieve has a schematic chemical composition as shown in the formula SiO2-1 / x XO^-m MOo,5, wherein X is a trivalent structural element, the molar ratio Si / X is x > 5, M is a structural equilibrium cation, and the molar ratio M / Si is 0 < m < 1; The SCM-33 molecular sieve has an X-ray diffraction pattern shown in the following table: 2Θ (°) spacing d (A) relative intensity, (I / I0) χ 100 9.20 ± 0.3 9.61 ± 0.40 s-vs 14.17 ± 0.3 6.24 ± 0.30 s-vs 17.88 ± 0.3 4.96 ± 0.20 ms 19.63 ± 0.3 4.52 ± 0.15 ms 20.65 ± 0.1 4.30 ± 0.10 vs 21.72 ± 0.3 4.09 ± 0.10 ms 2. Molecular sieve according to claim 1, characterized in that the X-ray diffraction pattern of the SCM-33 molecular sieve has X-ray diffraction peaks shown in the following table: 2Θ (°) spacing d (A) relative intensity, (I / I0) χ 100 9.20 ± 0.3 9.61 ± 0.40 s-vs 12.22 ± 0.3 7.24 ± 0.30 wm 13.00 ± 0.05 6.80 ± 0.05 ms 14.17 ± 0.3 6.24 ± 0.30 s-vs 17.88 ± 0.3 4.96 ± 0.20 ms 19.63 ± 0.3 4.52 ± 0.15 ms Petition 870240087733, dated 10 / 14 / 2024, page 11 / 27 2 / 7 2Θ (°) spacing d (A) relative intensity, (I / I0) χ 100 20.65 ± 0.1 4.30 ± 0.10 vs 21.72 ± 0.3 4.09 ± 0.10 ms 3. Molecular sieve according to claim 2, characterized in that the X-ray diffraction pattern of the SCM-33 molecular sieve also includes X-ray diffraction peaks shown in the following table: 2Θ (°) spacing d (A) relative intensity, (I / I0) χ 100 15.77 ± 0.3 5.61 ± 0.25 vw 16.32 ± 0.3 5.43 ± 0.25 vw 18.39 ± 0.3 4.82 ± 0.20 w 23.60 ± 0.3 3.77 ± 0.10 vw-w 24.57 ± 0.3 3.62 ± 0.05 wm 26.04 ± 0.3 3.42 ± 0.05 ms 27.54 ± 0.3 3.24 ± 0.05 ms 4. Molecular sieve according to claim 3, characterized in that the X-ray diffraction pattern of the SCM-33 molecular sieve also includes X-ray diffraction peaks shown in the following table: 2Θ (°) spacing d (A) relative intensity, (I / I0) χ 100 12.90 ± 0.05 6.86 ± 0.05 wm 20.44 ± 0.1 4.34 ± 0.10 s-vs 25.24 ± 0.3 3.53 ± 0.05 wm 28.49 ± 0.3 3.13 ± 0.05 wm 29.22 ± 0.3 3.05 ± 0.05 ms 5. Molecular sieve according to any of claims 1 to 4, characterized in that, in the formula, the molar ratio of Si / X is 10 < x < 200, preferably 15 < x < 150, more preferably 20 < x < 120, and / or the molar ratio of M / Si is 0.01 < m < 0.85, preferably 0.015 < m < 0.8, more preferably 0.02 < m < 0.

75.

6. Molecular sieve according to any one of claims 1 to 5, characterized in that a ready-state form of the SCM-33 molecular sieve has a schematic chemical composition as shown in the formula qQ^SiO2^1 / x XO1.5^m MO0.5·ζ H2O, wherein the molar ratio Si / X is x > 5, preferably 10 < x < 200, more preferably 15 < x < 150, even more preferably 20 < x < 120, the molar ratio M / Si is 0 < m < 1, preferably 0.01 < m < 0.85, more preferably 0.015 < m < 0.8, even more preferably 0.02 < m < 0.75, the molar ratio H2O / Si is as follows: 0.005 < z < 2, preferably 0.01 < z < 1.5, more preferably 0.015 < z < 1, even more preferably 0.02 < z < 0.5, Q is an organic mold, the molar ratio Q / Si is as follows: 0.01 < q < 1.0, preferably 0.02 < q < 0.5, more preferably 0.05 < q < 0.5, even more preferably 0.05 < q < 0.3,where the organic mold Q is a hydroxide containing an isopropyl trimethyl ammonium cation.

7. Molecular sieve according to any one of claims 1 to 6, characterized in that the trivalent element of structure X is selected from at least one of aluminum, boron, iron, gallium, indium and chromium; the equilibrium cation of structure M is selected from at least one of proton, ammonium cation, sodium cation, potassium cation, lithium cation, rubidium cation, cesium cation, magnesium cation, calcium cation, strontium cation and barium cation, preferably M includes at least one potassium cation or M includes at least one potassium cation and one sodium cation; Petition 870240087733, 10 / 14 / 2024, p. 13 / 27 4 / 7 M, when including potassium cation and sodium cation, preferably includes more potassium cations than sodium cations.

8. Molecular sieve according to any one of claims 6 to 7, characterized in that Q is isopropyl trimethyl ammonium hydroxide.

9. Molecular sieve according to any one of claims 1 to 8, characterized in that no more than 10% by weight of Si atoms in the SCM-33 molecular sieve are replaced by at least one non-silicon tetravalent structural element Y, which is preferably selected from at least one of germanium, tin, titanium, zirconium, and hafnium.

10. Method for preparing the molecular sieve as defined in any one of claims 1 to 8, characterized in that it comprises a step of mixing a silicon source, a trivalent element source of structure X, an equilibrium cation source of structure M, an organic template Q, and water for a crystallization reaction to obtain an SCM-33 molecular sieve, wherein the organic template Q is a hydroxide containing isopropyl trimethyl ammonium cation.

11. Method for preparing the molecular sieve as defined in claim 9, characterized in that it comprises a step of mixing a source of tetravalent non-silicon structural element Y, a silicon source, a trivalent structural element X, a structural equilibrium cation M, an organic template Q, and water for a crystallization reaction to obtain an SCM-33 molecular sieve, wherein the organic template Q is a hydroxide containing isopropyl trimethyl ammonium cation.

12. Method according to claim 10 or 11, characterized in that the molar ratio of the organic mold Q, of the SO2-based silicon source, of the X2O3-based source X, of the source Petition 870240087733, dated 10 / 14 / 2024, p. 14 / 27 5 / 7 M based on M2O or MO and water is Q: SiO2: X2O3: M2O or MO: H2O=0.05 ~ 1: 1: 0 ~ 0.1: 0 ~ 0.5: 10 ~ 100, where the quantities of source X and source M are not 0, preferably Q: SiO2: X2O3: M2O: H2O=0.15 ~ 0.55: 1: 0.0042 ~ 0.033: 0.01 ~ 0.375: 14 ~ 55.

13. Method according to claim 11, characterized in that the molar ratio of the tetravalent non-silicon structural element source Y based on a corresponding oxide YO2 and the silicon source based on SiO2, i.e., YO2 / SiO2, is greater than 0 ~ 0.1, preferably 0.01 ~ 0.1, more preferably 0.01 ~ 0.

08.

14. Method according to any one of claims 10 to 13, characterized in that the crystallization conditions include: crystallization at 100 ~ 200°C for 30 ~ 400 hours, preferably at 110 ~ 190°C for 48 ~ 300 hours, more preferably at 120 ~ 180°C for 72 ~ 200 hours.

15. Method according to any one of claims 10 to 14, characterized in that: the organic mold Q is isopropyl trimethyl ammonium hydroxide; the silicon source is selected from at least one of liquid glass, silica sol, solid silica gel, silica fume, amorphous silica, diatomite, zeolite molecular sieve and tetra-alkoxysilane; the trivalent element source of structure X is selected from at least one of aluminum source, boron source, iron source, gallium source, indium source and chromium source; the aluminum source is preferably selected from at least one of aluminum sulfate, sodium aluminate, aluminum nitrate, aluminum chloride, pseudoboehmite, aluminum oxide, aluminum hydroxide, aluminosilicate molecular sieve, aluminum carbonate, aluminum, aluminum isopropoxide and aluminum acetate;The boron source is preferably selected from at least one of boric acid, sodium tetraborate, amorphous boron oxide, potassium borate, Petition 870240087733, dated 10 / 14 / 2024, page 15 / 27 6 / 7, sodium metaborate, ammonium tetraborate, and organic boron ester; the iron source is preferably selected from at least one of ferric sulfate, ferric nitrate, ferric halide (such as ferric trichloride), ferrocene, and ferric citrate; the gallium source, indium source, and chromium source may be selected from at least one of the conventional substances in the art, such as gallium oxide, gallium nitrate, indium oxide, indium nitrate, chromium chloride, and chromium nitrate;The equilibrium cation source for structure M is selected from at least one proton source, ammonium cation source, sodium cation source, potassium cation source, lithium cation source, rubidium cation source, cesium cation source, magnesium cation source, calcium cation source, strontium cation source, and barium cation source; preferably, source M includes at least one potassium cation source, or source M includes at least one potassium cation source and one sodium cation source.When using a potassium cation source and a sodium cation source, it is preferable to use more potassium cations than sodium cations, for example, the molar ratio of potassium / sodium is 1.1 or more, where the potassium cation source is preferably selected from at least one of potassium oxide, potassium hydroxide, potassium carbonate, potassium bicarbonate, potassium chloride, potassium nitrate, potassium sulfate, and potassium fluoride; the sodium cation source is preferably selected from at least one of sodium oxide, sodium hydroxide, sodium carbonate, sodium bicarbonate, sodium chloride, sodium nitrate, sodium sulfate, and sodium fluoride;and / or the source of the tetravalent non-silicon structural element Y is preferably selected from at least one germanium source, tin source, titanium source, zirconium source and hafnium source, more preferably from at least one germanium oxide source, tin oxide source, titanium oxide source, zirconium oxide source and hafnium oxide source.

16. Molecular sieve composite, characterized in that it includes the SCM-33 molecular sieve as defined in any one of claims 1 to 9, or the SCM-33 molecular sieve prepared by the method as defined in any one of claims 10 to 15, and a binder.

17. Use of the SCM-33 molecular sieve as defined in any one of claims 1 to 9, of the SCM-33 molecular sieve prepared by the method as defined in any one of claims 10 to 15, or of the composite as defined in claim 16, characterized in that it acts as an adsorbent or catalyst.

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