SCM-33 MOLECULAR SIEVE, PREPARATION METHOD THEREFOR AND APPLICATION THEREOF

Abstract

A SCM-33 molecular sieve has a schematic chemical composition as shown in the formula “SiO.sub.2.Math.1/x XO.sub.1.5.Math.m MO.sub.0.5”, wherein X is a framework trivalent element, the Si/X molar ratio x is ≥5, M is a framework equilibrium cation, and the M/Si molar ratio is 0 <m≤1. The molecular sieve is a novel molecular sieve with RTE topology and the molecular sieve requires short preparation time, involves a low synthesis cost and can be used as adsorbent or catalyst.

Claims

1. A SCM-33 molecular sieve, characterized in that the SCM-33 molecular sieve has a schematic chemical composition as shown in the formula “SiO.sub.2.Math.1/x XO.sub.1.5.Math.MO.sub.0.5”, wherein X is a framework trivalent element, the Si/X molar ratio x is ≥5, M is a framework equilibrium cation, and the M/Si molar ratio is 0<m≤1; the SCM-33 molecular sieve has an X-ray diffraction pattern shown in the following table: TABLE-US-00012 2θ (°) d-spacing (Å) relative intensity, (I/I.sub.0) × 100  9.20 ± 0.3 9.61 ± 0.40  .sup. s-vs 14.17 ± 0.3 6.24 ± 0.30  .sup. s-vs 17.88 ± 0.3 4.96 ± 0.20 m-s 19.63 ± 0.3 4.52 ± 0.15 m-s 20.65 ± 0.1 4.30 ± 0.10 vs 21.72 ± 0.3 4.09 ± 0.10  m-s.

2. The 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: TABLE-US-00013 2θ (°) d-spacing (Å) relative intensity, (I/I.sub.0) × 100  9.20 ± 0.3 9.61 ± 0.40  .sup. s-vs 12.22 ± 0.3 7.24 ± 0.30  w-m  13.00 ± 0.05 6.80 ± 0.05 m-s 14.17 ± 0.3 6.24 ± 0.30  .sup. s-vs 17.88 ± 0.3 4.96 ± 0.20 m-s 19.63 ± 0.3 4.52 ± 0.15 m-s 20.65 ± 0.1 4.30 ± 0.10 vs 21.72 ± 0.3 4.09 ± 0.10  m-s.

3. The 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: TABLE-US-00014 2θ (°) d-spacing (Å) relative intensity, (I/I.sub.0) × 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.sup.  24.57 ± 0.3 3.62 ± 0.05 .sup. w-m 26.04 ± 0.3 3.42 ± 0.05 m-s  27.54 ± 0.3 3.24 ± 0.05 m-s.

4. The 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: TABLE-US-00015 2θ (°) d-spacing (Å) relative intensity, (I/I.sub.0) × 100  12.90 ± 0.05 6.86 ± 0.05 w-m 20.44 ± 0.1 4.34 ± 0.10  s-vs 25.24 ± 0.3 3.53 ± 0.05 w-m 28.49 ± 0.3 3.13 ± 0.05 w-m 29.22 ± 0.3 3.05 ± 0.05 m-s..sup. 

5. The molecular sieve according to claim 1, characterized 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. The molecular sieve according to claim 1, a form of an as-made state of the SCM-33 molecular sieve has a schematic chemical composition as shown in the formula “qQ.Math.SiO.sub.2.Math.1/x XO.sub.1.5.Math.MO.sub.0.5.Math.z H.sub.2O”, wherein the Si/X molar ratio x is ≥5, preferably 10≤x≤200, more preferably 15≤x≤150, even more preferably 20≤x≤120, the M/Si molar ratio 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 H.sub.2O/Si molar ratio 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 template, the Q/Si molar ratio 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.

7. The molecular sieve according to claim 1, characterized in that the framework trivalent element X is selected from at least one of aluminum, boron, iron, gallium, indium and chromium; the framework equilibrium cation 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 at least includes potassium cation or M at least includes potassium cation and sodium cation; M, when including potassium cation and sodium cation, preferably includes more potassium cations than sodium cations.

8. The molecular sieve according to claim 6, characterized in that the Q is an organic template, preferably selected from a substance containing isopropyl trimethylammonium cation, and the structural formula of the isopropyl trimethylammonium cation is as follows: ##STR00003## more preferably a hydroxide containing isopropyl trimethylammonium cation, such as isopropyl trimethylammonium hydroxide.

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

10. A method for preparing the molecular sieve according to claim 1, comprising a step of mixing a silicon source, a framework trivalent element X source, a framework equilibrium cation M source, an organic template Q and water for a crystallization reaction to obtain a SCM-33 molecular sieve.

11. A method for preparing the molecular sieve according to claim 9, comprising a step of mixing a non-silicon tetravalent framework element Y source, a silicon source, a framework trivalent element X source, a framework equilibrium cation M source, an organic template Q and water for a crystallization reaction to obtain a SCM-33 molecular sieve.

12. The method according to claim 10, characterized in that the molar ratio of the organic template Q, the silicon source based on SiO.sub.2, the X source based on X.sub.2O.sub.3, the M source based on M.sub.2O or MO and water is Q: SiO.sub.2: X.sub.2O.sub.3: M.sub.2O or MO: H.sub.2O=0.05˜1: 1: 0˜0.1: 0˜0.5: 10˜100, wherein the amounts of X source and M source are not 0, preferably Q: SiO.sub.2: X.sub.2O.sub.3: M.sub.2O: H.sub.2O=0.15˜0.55: 1: 0.0042˜0.033: 0.01˜0.375: 14˜55.

13. The method according to claim 11, characterized in that the molar ratio of the non-silicon tetravalent framework element Y source based on a corresponding oxide YO.sub.2 and the silicon source based on SiO.sub.2, i.e. YO.sub.2/SiO.sub.2, is greater than 0˜0.1, preferably 0.01˜0.1, more preferably 0.01˜0.08.

14. The method according to claim 10, 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. The method according to claim 10, characterized in that: the organic template Q is selected from a substance containing isopropyl trimethylammonium cation, and the structural formula of the isopropyl trimethylammonium cation is as follows: ##STR00004## the organic template Q is preferably a hydroxide containing isopropyl trimethylammonium cation, such as isopropyl trimethylammonium hydroxide; the silicon source is selected from at least one of water glass, silica sol, solid silica gel, fumed silica, amorphous silica, diatomite, zeolitemolecular sieve and tetraalkoxysilane; the framework trivalent element X source 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, pseudo boehmite, 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, 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 can 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 framework equilibrium cation M source is selected from at least one of 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, the M source at least includes a potassium cation source or the M source at least includes a potassium cation source and a sodium cation source; when using the potassium cation source and the 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, wherein 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 non-silicon tetravalent framework element Y source is preferably selected from at least one of germanium source, tin source, titanium source, zirconium source and hafnium source, more preferably from at least one of germanium oxide source, tin oxide source, titanium oxide source, zirconium oxide source and hafnium oxide source.

16. A molecular sieve composite, comprising the SCM-33 molecular sieve according to claim 1, and a binder.

17. A catalyst comprising the SCM-33 molecular sieve according to claim 1.

18. A molecular sieve composite, comprising the SCM-33 molecular sieve prepared by the method according to claim 10 and a binder.

19. An absorbent comprising the SCM-33 molecular sieve according to claim 1.

Description

DESCRIPTION OF DRAWINGS

[0034] FIG. 1 is the X-ray diffraction (XRD) pattern of the sample obtained in Example 1 before calcination;

[0035] FIG. 2 is the X-ray diffraction (XRD) pattern of the sample obtained in Example 1 after calcination;

[0036] FIG. 3 is a scanning electron microscope (SEM) photograph of the sample obtained in Example 1.

SPECIFIC EMBODIMENTS

[0037] In order to facilitate the 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 only serve to assist the understanding of the present invention, and should not be regarded as a specific limitation to the present invention.

[0038] In the context of the present specification, among the XRD data of the molecular sieve, vw, w, m, s, vs indicate the intensity of diffraction peaks, with vw referring to very weak, w referring to weak, m to medium, s to strong, vs to very strong, which has been 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.

[0039] In the context of the present specification, the structure of the molecular sieve is confirmed by the X-ray diffraction (XRD) pattern, while the X-ray diffraction (XRD) pattern of the molecular sieve is determined by X-ray powder diffractometer equipped with a Cu-Ka ray source and a Ni filter , where the Kα1 wavelength k=1.5405980 Å.

[0040] In the present invention, an X′ Pert PRO X-ray powder diffractometer (XRD) manufactured from PANalytical B.V. is used, with a working voltage of 40 kV, a current of 40 mA and a scanning range of 5-40° . The product morphology is measured with S-4800 Field Emission Scanning Electron Microscope (Fe-SEM) manufactured from HITACHI.

[0041] It should be noted particularly that the two or more aspects (or embodiments) disclosed in the context of the present specification can be arbitrarily combined with each other, and the technical solutions (such as methods or systems) thus formed are a part of the original disclosure in the present specification, and also fall within the scope of protection in the present specification.

[0042] Unless otherwise specified, all percentages, parts, ratios, etc. mentioned in the present 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

[0043] 2.5 g of sodium metaaluminate (Al.sub.2O.sub.341 wt %, Na.sub.2O 58 wt %) and 17.5 g of potassium hydroxide solution (30 wt %) were dissolved in 28 g of water, 39.4 g of isopropyl trimethylammonium hydroxide solution (20 wt %) was added and stirred evenly, finally 60 g of Ludox AS-40 silica sol was added slowly under stirring; after stirring for 1 hour, the above mixture was charged into 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 an as-made powder of SCM-33 molecular sieve. The XRD pattern is shown in FIG. 1. The as-made powder solid was placed in a muffle furnace and calcined at 550° C. for 5 hours to obtain the final product.

[0044] The XRD pattern is shown in FIG. 2. The SEM photograph of the SCM-33 molecular sieve is shown in FIG. 3.

[0045] Therein, the XRD pattern data of the final product obtained in Example 1 are shown in Table 1:

TABLE-US-00005 TABLE 1 2θ (°) d-spacing (Å) relative intensity, (I/I.sub.0) × 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 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 metaaluminate (Al.sub.2O.sub.341 wt %, Na.sub.2O 58 wt %) and 13.7 g of potassium hydroxide solution (30 wt %) were dissolved in 64 g of water, 39.4 g of isopropyl trimethylammonium hydroxide solution (20 wt %) was added and stirred evenly, finally 60 g of Ludox AS-40 silica sol was added slowly under stirring; after stirring for 1 hour, the above mixture was charged into 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 filtered, washed, dried and calcined (the post-treatment conditions are the same as those in Example 1) to obtain a SCM-33 zeolite molecular sieve. The XRD pattern is similar to FIG. 2. Therein, the XRD pattern data of the final product obtained in Example 2 are shown in Table 2:

TABLE-US-00006 TABLE 2 2θ (°) d-spacing (Å) relative intensity, (I/I.sub.0) × 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 29.22 3.05 28.3 30.69 2.91 18.6.

EXAMPLE 3

[0047] 7.5 g of sodium hydroxide solution (30 wt %), 15 g of potassium hydroxide solution (30 wt %), 40 g of H.sub.2O and 47.3 g of isopropyl trimethylammonium hydroxide solution (20 wt %) were stirred evenly, 45 g of Ludox AS-40 silica sol was added slowly under stirring; after stirring for 1 hour, 6.6 g of USY molecular sieve (SiO.sub.2/Al.sub.2O.sub.3=12) was added; after stirring for 1.5 hours, the above mixture was charged 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 a SCM-33 zeolite molecular sieve, and the XRD pattern is similar to FIG. 2. Therein, the XRD pattern data of the final product obtained in Example 3 are shown in Table 3:

TABLE-US-00007 TABLE 3 2θ (°) d-spacing (Å) relative intensity, (I/I.sub.0) × 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 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 wt %) and 13.7 g of potassium hydroxide solution (30 wt %) were dissolved in 21.1 g of water, 110 g of isopropyl trimethylammonium hydroxide solution (20 wt %) was added and stirred evenly, finally, 54 g of Ludox AS-40 silica gel was added slowly under stirring; after stirring for 1 hour, the above mixture was charged 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 a SCM-33 zeolite molecular sieve, and the XRD pattern is similar to FIG. 2.

EXAMPLE 5

[0049] 2 g of aluminum isopropoxide was added into 40 g of isopropyl trimethylammonium hydroxide solution (20 wt %) and 12 g of potassium hydroxide solution (30 wt %); after dissolution, 75 g of water was added, 52 g of tetraethyl orthosilicate was added slowly; after a complete hydrolysis, the above mixture was charged 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 SCM-33 zeolite molecular sieve, and the XRD pattern is similar to FIG. 2.

EXAMPLE 6

[0050] 9.7 g of rubidium chloride and 26 g of potassium hydroxide solution (30 wt %) were dissolved in 68.5 g of water, 39.4 g of isopropyl trimethylammonium hydroxide solution (20 wt %) was added and stirred evenly, 54.6 g of Ludox AS-40 silica sol was slowly added under stirring; after stirring for 1 hour, 5 g of USY molecular sieve (SiO.sub.2/Al.sub.2O.sub.3=12) was added; after stirring for 1.5 hours, the above mixture was charged 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 a SCM-33 zeolite molecular sieve, and the XRD pattern is similar to FIG. 2.

EXAMPLE 7

[0051] 0.6 g of pseudo boehmite (Al.sub.2O.sub.3 70 wt %) and 17 g of potassium hydroxide solution (30 wt %) were dissolved in 30 g of water, 49.3 g of isopropyl trimethylammonium hydroxide solution (20 wt %) was added and stirred evenly, 15 g of water glass (SiO.sub.2 27 wt %, Na.sub.2O 8.4 wt %) and 45 g of Ludox AS-40 silica sol were added slowly under stirring; after stirring for 1 hour, the above mixture was charged 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 a SCM-33 zeolite molecular sieve, and the XRD pattern is similar to FIG. 2.

EXAMPLE 8

[0052] 1.3 g of boric acid, 9 g of sodium hydroxide solution (30 wt %) and 14 g of potassium hydroxide solution (30 wt %) were dissolved in 41 g of water, 49.3 g of isopropyl trimethylammonium hydroxide solution (20 wt %) was added and stirred evenly, 75 g of Ludox AS-40 silica sol was added slowly under stirring; after stirring for 1 hour, the above mixture was charged 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 a SCM-33 zeolite molecular sieve, and the XRD pattern is similar to FIG. 2. Therein, the XRD pattern data of the final product obtained in Example 8 are shown in Table 4:

TABLE-US-00008 TABLE 4 2θ (°) d-spacing (Å) relative intensity, (I/I.sub.0) × 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 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 wt %) and 14 g of potassium hydroxide solution (30 wt %) were dissolved in 150 g of water, 49.3 g of isopropyl trimethylammonium hydroxide solution (20 wt %) was added and stirred evenly, 75 g of Ludox AS-40 silica sol was added slowly under stirring; after stirring for 1 hour, the above mixture was charged 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 a SCM-33 zeolite molecular sieve, and the XRD pattern is similar to FIG. 2.

EXAMPLE 10

[0054] 4 g of titanium sulfate, 0.4 g of boric acid, 8 g of sodium hydroxide solution (30 wt %), 15 g of potassium hydroxide solution (30 wt %) were dissolved in 50 g of water, 49.3 g of isopropyl trimethylammonium hydroxide solution (20 wt %) was added and stirred evenly, 60 g of Ludox AS-40 silica sol was added slowly under stirring; after stirring for 1 hour, the above mixture was charged 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 a SCM-33 zeolite molecular sieve, and the XRD pattern is similar to FIG. 2. Therein, the XRD pattern data of the final product obtained in Example 10 are shown in Table 5.

TABLE-US-00009 TABLE 5 2θ (°) d-spacing (Å) relative intensity, (I/I.sub.0) × 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 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 metaaluminate (Al.sub.2O.sub.3 41 wt %, Na.sub.2O 58 wt %) and 17.5 g of potassium hydroxide solution (30 wt %) were dissolved in 28 g of water, 30 g of tetramethyl ammonium hydroxide solution (20 wt %) was added and stirred evenly, finally 60 g of Ludox AS-40 silica sol was slowly added under stirring; after stirring for 1 hour, the above mixture was charged into 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 FIG. 2. The XRD pattern data are shown in Table 6:

TABLE-US-00010 TABLE 6 2θ (°) d-spacing (Å) relative intensity, (I/I.sub.0) × 100 7.80 11.32 5 10.09 8.76 16.3 10.82 8.17 89.1 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 metaaluminate (Al.sub.2O.sub.3 41 wt %, Na.sub.2O 58 wt %) and 17.5 g of potassium hydroxide solution (30 wt %) were dissolved in 28 g of water, 48.7 g of tetraethyl ammonium hydroxide solution (20 wt %) was added and stirred evenly, finally 60 g of Ludox AS-40 silica sol was slowly added under stirring; after stirring for 1 hour, the above mixture was charged into 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 BEA molecular sieve. Its XRD pattern is obviously different from FIG. 2. The XRD pattern data are shown in Table 7:

TABLE-US-00011 TABLE 7 2θ (°) d-spacing (Å) relative intensity, (I/I.sub.0) × 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