SCM-34 MOLECULAR SIEVE, PREPARATION METHOD THEREFOR AND USE THEREOF

Abstract

A SCM-34 molecular sieve, preparation method therefor and use thereof are provided. The SCM-34 molecular sieve contains aluminum, phosphorus, oxygen and optionally silicon. In the XRD diffraction data of the molecular sieve, a 2θ degree of the strongest peak within the range of 5-50° is 7.59±0.2. The SCM-34 molecular sieve has a new skeleton structure and can be used to prepare a metal-containing AFI type molecular sieve or an SAPO-17 molecular sieve.

Claims

1. A SCM-34 molecular sieve, characterized in that the SCM-34 molecular sieve comprises aluminum, phosphorus, oxygen and optionally silicon; in XRD diffraction data of the molecular sieve, a 2θ degree of the strongest peak within the range of 5-50° is 7.59±0.2; an X-ray diffraction pattern of the SCM-34 molecular sieve includes X-ray diffraction peaks shown in the following table: TABLE-US-00012 relative intensity, 2θ (°) [(I/I.sub.0) × 100]  7.59 ± 0.2 100 10.81 ± 0.1 5-50 16.52 ± 0.1 5-50 17.97 ± 0.1 5-50  23.34 ± 0.05 5-50

2. The SCM-34 molecular sieve according to claim 1, characterized in that the SCM-34 molecular sieve has a schematic chemical composition as shown in the formula “Al.sub.2O.sub.3: xSiO.sub.2: yP.sub.2O”, wherein 0≤x≤0.5, 0.75≤y≤1.5; in the XRD diffraction data of the molecular sieve, the 2θ degree of the strongest peak within the range of 5-50° is 7.59±0.2; the X-ray diffraction pattern of the SCM-34 molecular sieve includes the X-ray diffraction peaks shown in the following table: TABLE-US-00013 relative intensity, 2θ (°) [(I/I.sub.0) × 100] 7.59 ± 0.2 100 10.81 ± 0.1  5-50 16.52 ± 0.1  5-50 17.97 ± 0.1  5-50 23.34 ± 0.05 5-50 34.74 ± 0.05 5-50

3. The molecular sieve according to claim 1, characterized in that the X-ray diffraction pattern of the SCM-34 molecular sieve further includes the X-ray diffraction peaks shown in the following table: TABLE-US-00014 relative intensity, 2θ (°) [(I/I.sub.0) × 100] 14.25 ± 0.1  5-50 21.01 ± 0.1  10-20  24.27 ± 0.05 5-50 26.05 ± 0.05 5-50 27.82 ± 0.05 5-50 28.15 ± 0.02 5-50 30.03 ± 0.02 5-50

4. The molecular sieve according to claim 1, characterized in that the X-ray diffraction pattern of the SCM-34 molecular sieve further includes the X-ray diffraction peaks shown in the following table: TABLE-US-00015 relative intensity, 2θ (°) [(I/I.sub.0) × 100] 10.33 ± 0.1 10-20  12.09 ± 0.1 5-50 19.77 ± 0.1 5-50  31.33 ± 0.01 5-50  38.29 ± 0.01 5-50

5. A method of preparing the SCM-34 molecular sieve according to claim 1, comprising: crystallizing a mixture containing an aluminum source, a phosphorus source, an organic template R1 and an organic template R2, a solvent S1, a solvent S2 and a solvent S3, and optionally a silicon source to obtain a SCM-34 molecular sieve; wherein the organic template R1 is selected from one or more of quaternary ammonium salts and/or quaternary ammonium bases; the organic template R2 is selected from one or more of imidazole, pyrrolidine, and derivatives thereof; the solvent S1 is selected from one or more of amide group solvents; the solvent S2 is selected from one or more of the cyclic organic solvents; the solvent S3 is selected from one or more of water and lower alcohols, wherein the organic template R1 and the organic template R2 represent different organic templates from each other, and the solvent S1, the solvent S2 and the solvent S3 represent different solvents from each other.

6. The method according to claim 5, characterized in that the organic template R1 is selected from one or more of tetraethylammonium bromide, tetraethylammonium hydroxide, tetrapropylammonium bromide, tetrapropylammonium hydroxide, tetrabutylammonium bromide, tetrabutylammonium hydroxide; the organic template R2 is selected from one or more of imidazole, 2-methylimidazole, 4-methylimidazole, 1-(3-aminopropyl) imidazole, 2-ethyl-4-methylimidazole, pyrrolidine, 1-(3-pyrrolidine) pyrrolidine, N-ethyl-2-aminomethylpyrrolidine; the solvent S1 is selected from one or more of N,N-dimethylformamide, N,N-dimethylacetamide, N,N-diethylformamide and N,N-dibutylformamide; the solvent S2 is selected from one or more of 1,4-dioxane, cyclohexane, cyclohexanone and cyclohexanol; and/or, the solvent S3 is selected from one or more of methanol, ethanol, ethylene glycol, butanol and water.

7. The method according to claim 5, characterized in that in the mixture, the molar constitution of the aluminum source based on Al.sub.2O.sub.3, the silicon source based on SiO.sub.2, the phosphorus source based on P.sub.2O.sub.5, the organic templates R1+R2, the solvents S1+S2+S3 is as follows: SiO.sub.2/Al.sub.2O.sub.3=0-1, preferably 0.1-0.75; P.sub.2O.sub.5/Al.sub.2O.sub.3=0.5-2, preferably 0.75-1.5; templates R1+R2/Al.sub.2O.sub.3=1-200, preferably 5-50; solvents S1+S2+S3/Al.sub.2O.sub.3=5-500, preferably 35-120.

8. The method according to claim 5, characterized in that the molar ratio of the organic template R1 to the organic template R2 is 0.01-1:1, preferably 0.1-0.25:1; the molar ratio of the solvent S1, the solvent S2 and the solvent S3 is 1:0.01-1:1-100, preferably 1:0.05-0.5:10-80.

9. The method according to claim 5, characterized in that the conditions for the crystallization treatment include: crystallization temperature of 120-200° C., preferably 140-180° C., more preferably 140-160° C.; crystallization time of 1-5 days, preferably 3-5 days, more preferably 4-5 days.

10. A molecular sieve composition, characterized in that it includes the molecular sieve according to claim 1, and a binder.

11. A metal containing AFI type molecular sieve or an SAPO-17 molecular sieve, comprising the molecular sieve according to claim 1.

12. A method of preparing a metal containing AFI type molecular sieve includes: using the molecular sieve according to claim 1 as reactant raw material, mixing it with a solvent SI, an organic template R, a selectively added first silicon source to prepare a precursor A, and then mixing the precursor A with a solvent SII, a metal source, a selectively added second silicon source to prepare the AFI molecular sieve.

13. A method of preparing an SAPO-17 molecular sieve, including: 1) mixing an organic template cR and a first organic solvent cS for a first heat treatment to obtain a precursor P; 2) mixing the SCM-34 molecular sieve according to claim 1, a selectively added silicon source with a second organic solvent cS for a second heat treatment to obtain a mixture material M; 3) mixing the precursor P obtained in step 1) with the mixture material M obtained in step 2) to form a mixture to be crystallized; 4) pretreating the mixture to be crystallized obtained in step 3), and then carrying out a crystallization reaction to obtain the SAPO-17 molecular sieve.

14. A method for converting methanol to hydrocarbon, comprising contacting methanol with the metal containing AFI type molecular sieve obtained by the method according to claim 12 under reaction conditions.

15. A method for converting methanol to hydrocarbon, comprising, contacting methanol with the SAPO-17 molecular sieve obtained by the method according to claim 13 under reaction conditions.

16. A method for converting syngas to hydrocarbon, comprising, contacting syngas with the SAPO-17 molecular sieve obtained by the method according to claim 13 under reaction conditions.

Description

DESCRIPTION OF DRAWINGS

[0070] FIG. 1 is the X-ray diffraction (XRD) pattern of the molecular sieve prepared in Example 1;

[0071] FIG. 2 is the SEM photo of the molecular sieve prepared in Example 1;

[0072] FIG. 3 is the XRD pattern of the AFI type molecular sieve synthesized in Example 9;

[0073] FIG. 4 and FIG. 5 are the SEM photos of the AFI type molecular sieve synthesized in Example 9;

[0074] FIG. 6 shows the TPD pattern of the AFI type molecular sieve synthesized in Example 9;

[0075] FIG. 7 is the XRD pattern of the SAPO-17 molecular sieve in Example 13;

[0076] FIG. 8 is the SEM photo of the SAPO-17 molecular sieve in Example 13;

[0077] FIG. 9 is the XRD pattern of the SAPO-17 molecular sieve in Comparative Example 1;

[0078] FIG. 10 shows the SEM photos of SAPO-17 molecular sieve in Comparative Example 1.

MODE OF CARRYING OUT THE INVENTION

[0079] 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. The end points and any values of the ranges disclosed in the present invention are not limited to the precise ranges or values, and these ranges or values should be understood to include the values close to these ranges or values.

[0080] In the present invention, the structure of the molecular sieve is determined by X-ray diffraction pattern (XRD), and the X-ray diffraction pattern (XRD) of the molecular sieve is determined by X-ray powder diffractometer, with a Cu-Kα ray source, a Kα1 wavelength λ=1.5405980 Å, a Ni filter.

[0081] In the present invention, an X'Pert PRO X-ray powder diffractometer (XRD) manufactured by PANalytical B.V. is used, with a working voltage of 40 kV, a current of mA and a scanning range of 3.5-50°. The product morphology is photographed with S-4800 Field Emission Scanning Electron Microscope (Fe-SEM) manufactured by HITACHI of Japan.

[0082] It should be noted particularly that the two or more aspects (or embodiments) disclosed in the context of the present invention 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 description, and also fall within the scope of protection in the present description.

[0083] Unless otherwise specified, all percentages, parts, ratios, etc. mentioned in the present invention are based on weight, unless taking weight as a basis is not in accordance with the conventional understanding of those skilled in the art.

[0084] The raw materials involved in the specific embodiments of the present invention are as follows: [0085] aluminum sulfate[Al.sub.2(SO.sub.4).sub.3.Math.18H.sub.2O]: an industrial product containing Al.sub.2O.sub.3, 15.7 wt. %; [0086] aluminum isopropoxide [Al(iPr).sub.3]: containing Al.sub.2O.sub.3, 24.9 wt. %; [0087] aluminum nitrate [Al(NO.sub.3).sub.3.Math.9H.sub.2O]: containing Al.sub.2O.sub.3, 27.5 wt. %; [0088] phosphoric acid (purity≥85 wt. %): containing P.sub.2O.sub.5, 72.3 wt. %, commercially available; [0089] acidic silica sol (40 wt. % aqueous solution): containing SiO.sub.2, 40 wt. %, commercially available; [0090] silica: containing SiO.sub.2, 99 wt. %; [0091] magnesium nitrate [Mg(NO.sub.3).sub.2.Math.6H.sub.2O]: containing MgO, 15.6 wt. %; [0092] cobalt nitrate [Co(NO.sub.3).sub.2.Math.6H.sub.2O]: containing CoO, 25.7 wt. %; [0093] zinc nitrate [Zn(NO.sub.3).sub.2.Math.6H.sub.2O]: containing ZnO, 27.3 wt. %.

[0094] I. Preparation of SCM-34 Molecular Sieve

Example 1

[0095] 3.8 g of aluminum nitrate [Al(NO.sub.3).sub.3.Math.9H.sub.2O] was dissolved in 4.3 mL of deionized water to form a solution C after mixing. 1.8 g of phosphoric acid (purity≥85 wt. %), 10.8 g of tetrabutylammonium hydroxide (40 wt. % aqueous solution, MkSeal) and 10.4 g of 1-(3-aminopropyl) imidazole were then added to the solution C to obtain a solution C′ after stirring for 0.5 hours, precipitating for 12 hours. Then, 0.1 g of silica (Aladdin, S104573, ≥99%), 1.4 mL of N,N-dibutylformamide and 0.4 mL of cyclohexanone were slowly added to the solution C′ to form a uniform mixture to be crystallized after stirring for 3.5 hours and then subjecting to a heat treatment at 90° C. for 8 hours, wherein the molar ratio of aluminum source based on Al.sub.2O.sub.3, silicon source based on SiO.sub.2, phosphorus source based on P.sub.2O.sub.5, total template and total solvent is: Al.sub.2O.sub.3: SiO.sub.2: P.sub.2O.sub.5: template R: solvent S=1:0.1:1.5:5:35, template R1 (tetrabutylammonium hydroxide)/template R2 (1-(3-aminopropyl) imidazole)=0.2, solvent S1 (N,N-dibutyl formamide)/solvent S2 (cyclohexanone)/solvent S3 (water)=1:0.5:78.5. The above mixture to be crystallized was placed at 140° C. for crystallization for 5 days. After filtering, washing, the product was dried at 100° C. for 8 hours to obtain a product SCM-34. The X-ray diffraction pattern data are shown in Table 1, the X-ray diffraction pattern is shown in FIG. 1, and the SEM is shown in FIG. 2.

TABLE-US-00005 TABLE 1 relative intensity, 2θ (°) [(I/I.sub.0) × 100] 7.39 100 10.24 16 10.71 35 12.01 6 14.20 5 16.44 32 17.93 35 19.71 9 21.01 18 23.31 19 24.25 15 26.03 15 27.81 11 28.13 13 30.02 10 31.33 5 34.73 7 38.28 6

Example 2

[0096] 20.4 g of aluminum isopropoxide (Al(iPr).sub.3) was dissolved in 207.2 mL of water to form a solution C after mixing. 8.6 g of phosphoric acid (purity ≥85 wt. %), 294.8 g of tetrabutylammonium hydroxide (40 wt. % aqueous solution, MkSeal) and 569.1 g of 1-(3-aminopropyl) imidazole were then added to the solution C to obtain a solution C′ after stirring for 5 hours, precipitating for 1 hour. Then, 15.0 g of acidic silica sol (Ludox HS type, 40 wt. % aqueous solution), 313.2 mL of N,N-dimethylbutylamide and 9.8 mL of cyclohexanone were slowly added to the solution C′ to form a uniform mixture to be crystallized after stirring for 2.5 hours and then subjecting to a heat treatment at 100° C. for 6 hours, wherein the molar ratio of aluminum source based on Al.sub.2O.sub.3, silicon source based on SiO.sub.2, phosphorus source based on P.sub.2O.sub.5, total template and total solvent is: Al.sub.2O.sub.3: SiO.sub.2: P.sub.2O.sub.5: template R: solvent S=1:0.5:0.75:25:120, template R1 (tetrabutylammonium hydroxide)/template R2 (1-(3-aminopropyl) imidazole)=0.1, solvent S1 (N, N-dimethylbutylamide)/solvent S2 (cyclohexanone)/solvent S3 (water)=1:0.05:11. The above mixture to be crystallized was placed at 140° C. for crystallization for 4 days. After filtering, washing, the product was dried at 120° C. for 4 hours to obtain a product SCM-34. The X-ray diffraction pattern data are shown in Table 2, and the XRD pattern is similar to FIG. 1.

TABLE-US-00006 TABLE 2 relative intensity, 2θ(°) [(I/I.sub.0) × 100] 7.65 100 10.37 17 10.89 24 12.15 43 14.29 9 16.61 24 18.01 11 19.84 16 21.11 19 23.39 21 24.30 18 26.10 7 27.86 10 28.16 9 30.05 12 31.33 17 34.75 5 38.29 11

Example 3

[0097] 1021.2 g of aluminum isopropoxide was dissolved in 1078.1 mL of water to form a solution C after mixing. 432.4 g of phosphoric acid (purity ≥85 wt. %), 24016.3 g of tetraethylammonium hydroxide (40 wt. % aqueous solution, Sigma-Aldrich) and 54426.1 g of 1-(3-aminopropyl) imidazole were then added to the solution C obtain a solution C′ after stirring for 3 hours, precipitating for 6 hours. Then, 450.0 g of silica (Aladdin, S104573, ≥99%), 4528.8 mL of N,N-dimethylbutylamine and 706.6 mL of cyclohexanone were slowly added to the solution C′ to form a uniform mixture to be crystallized after stirring for 1.5 hours and then subjecting to a heat treatment at 90° C. for 11 hours, wherein the molar ratio of aluminum source based on Al.sub.2O.sub.3, silicon source based on SiO.sub.2, phosphorus source based on P.sub.2O.sub.5, total template and total solvent is: Al.sub.2O.sub.3: SiO.sub.2: P.sub.2O.sub.5: template R: solvent S=1:0.75:0.75:50:90, template R1 (tetraethylammonium hydroxide)/template R2 (1-(3-aminopropyl) imidazole)=0.15, solvent S1 (N, N-dimethylbutylamide)/solvent S2 (cyclohexanone)/solvent S3 (water)=1:0.25:30. The above mixture to be crystallized was placed at 140° C. for crystallization for 5 days. After filtering, washing, the product was dried at 90° C. for 10 hours to obtain a product SCM-34. The X-ray diffraction pattern data are shown in Table 3, and the XRD pattern is similar to FIG. 1.

TABLE-US-00007 TABLE 3 relative intensity, 2θ (°) [(I/I.sub.0) × 100] 7.55 100 10.30 16 10.79 8 12.05 19 14.21 34 16.48 15 17.95 21 19.74 42 21.00 18 23.29 5 24.24 8 26.02 9 27.79 6 28.14 17 30.01 11 31.32 6 34.74 9 38.28 6

Example 4

[0098] 375.1 g of aluminum nitrate was dissolved in 405.1 mL of water to form a solution C after mixing. 138.4 g of phosphoric acid (purity ≥85 wt. %), 2827.6 g of tetrabutylammonium hydroxide (40 wt. % aqueous solution, MkSeal) and 3209.7 g of 1-(3-aminopropyl) imidazole were then added to the solution C to obtain a solution C′ after stirring for 2 hours, precipitating for 8 hours. Then, 36.1 g of silica (Aladdin, S104573, ≥99%), 299.1 mL of N, N-dimethylformamide and 18.7 mL of cyclohexanone were slowly added to the solution C′ to form a uniform mixture to be crystallized after stirring for 4 hours and then subjecting to a heat treatment at 110° C. for 3 hours, wherein the molar ratio of aluminum source based on Al.sub.2O.sub.3, silicon source based on SiO.sub.2, phosphorus source based on P.sub.2O.sub.5, total template and total solvent is: Al.sub.2O.sub.3: SiO.sub.2: P.sub.2O.sub.5: template R: solvent S=1:0.3:1.2:15:60, template R1 (tetrabutylammonium hydroxide)/template R2 (1-(3-aminopropyl) imidazole)=0.17, solvent S1 (N, N-dimethylbutylamide)/solvent S2 (cyclohexanone)/solvent S3 (water)=1:0.1:62. The above mixture to be crystallized was placed at 140° C. for crystallization for 5 days. After filtering, washing, the product was dried at 120° C. for 4 hours to obtain a product SCM-34. The X-ray diffraction pattern data are shown in Table 4, and the XRD pattern is similar to FIG. 1.

TABLE-US-00008 TABLE 4 relative intensity, 2θ (°) [(I/I.sub.0) × 100] 7.75 100 10.41 11 10.90 8 12.15 17 14.39 32 16.60 22 18.05 13 19.84 17 21.09 10 23.38 23 24.31 21 26.08 14 27.85 11 28.16 19 30.03 22 31.33 9 34.74 8 38.29 11

Example 5

[0099] 33.3 g of aluminum sulfate [Al.sub.2(SO.sub.4).sub.3.Math.18H.sub.2O] was dissolved in 66.3 mL of water to form a solution C after mixing. 5.2 g of phosphoric acid (purity ≥85 wt. %), 117.0 g of tetrabutylammonium hydroxide (40 wt. % aqueous solution, MkSeal) and 102.6 g of 1-(3-aminopropyl) imidazole were then added to the solution C to obtain a solution C′ after stirring for 3 hours, precipitating for 6 hours. Then, 6.1 g of acidic silica sol (Ludox HS type, 40 wt. % aqueous solution), 25.5 mL of N,N-dimethylbutylamine and 4.8 mL of cyclohexanone were slowly added to the C′ solution to form a uniform mixture to be crystallized after stirring for 4.5 hours and then subjecting to a heat treatment at 80° C. for 12 hours, wherein the molar ratio of aluminum source based on Al.sub.2O.sub.3, silicon source based on SiO.sub.2, phosphorus source based on P.sub.2O.sub.5, total template and total solvent is: Al.sub.2O.sub.3: SiO.sub.2: P.sub.2O.sub.5: total template agent R: total solvent 5=1:0.4:0.9:10:80, template agent R1 (tetrabutylammonium hydroxide)/template agent R2 (1-(3-aminopropyl) imidazole)=0.22, solvent S1 (N, N-dimethylbutylamide)/solvent S2 (cyclohexanone)/solvent S3 (water)=1:0.3:48. The above mixture to be crystallized was placed at 140° C. for crystallization for 5 days. After filtering, washing, the product was dried at 100° C. for 8 hours to obtain a product SCM-34. The X-ray diffraction pattern data are shown in Table 5, and the XRD pattern is similar to FIG. 1.

TABLE-US-00009 TABLE 5 relative intensity, 2θ (°) [(I/I.sub.0) × 100] 7.50 100 10.27 16 10.76 9 12.03 21 14.20 11 16.45 35 17.87 25 19.71 31 20.95 17 23.31 16 24.23 25 26.01 5 27.79 17 28.14 24 30.02 23 31.33 9 34.73 9 38.28 6

Example 6

[0100] 266.6 g of aluminum sulfate was dissolved in 157.5 mL of water to form a solution C after mixing. 50.7 g of phosphoric acid (purity ≥85 wt. %), 614.6 g of tetraethylammonium hydroxide (25 wt. % aqueous solution) and 801.3 g of N-ethyl-2-aminomethylpyrrolidine (purity 95%, Meryer) were then added to the solution C to form a solution C′ after stirring for 4.5 hours and precipitating for 3.5 hours. Then, 18.1 g of acidic silica sol (Ludox HS type, 40 wt. % aqueous solution), 124.9 mL of N,N-dimethylformamide and 60.2 mL of 1,4-dioxane were slowly added to the solution C′ to form a uniform mixture to be crystallized after stirring for 3.5 hours and then subjecting to a heat treatment at 80° C. for 12 hours, wherein the molar ratio of aluminum source based on Al.sub.2O.sub.3, silicon source based on SiO.sub.2, phosphorus source based on P.sub.2O.sub.5, total template and total solvent is: Al.sub.2O.sub.3: SiO.sub.2: P.sub.2O.sub.5: total template R: total solvent S=1:0.3:1.1:20:100, template R1 (tetraethylammonium hydroxide)/template R2 (N-ethyl-2-aminomethylpyrrolidine)=0.15, solvent S1 (N, N-dimethylbutylamine)/solvent S2 (1,4-dioxane)/solvent S3 (water)=1:0.4:22. The above mixture to be crystallized was placed at 140° C. for crystallization for 5 days. After filtering, washing, the product was dried at 100° C. for 8 hours to obtain a product SCM-34. The X-ray diffraction pattern data are shown in Table 6, and the XRD pattern is similar to FIG. 1.

TABLE-US-00010 TABLE 6 relative intensity, 2θ (°) [(I/I.sub.0) × 100] 7.50 100 10.27 16 10.76 17 12.03 27 14.20 13 16.45 23 17.87 14 19.71 41 20.95 15 23.31 10 24.23 33 26.01 6 27.79 7 28.14 14 30.02 28 31.33 7 34.73 8 38.28 9

[0101] II. Synthesis and Use of Metal Containing AFI Type Molecular Sieves

[0102] 1. Synthesis of Metal Containing AFI Type Molecular Sieves from SCM-34 Molecular Sieve

Example 7

[0103] At room temperature, 136.2 g of the SCM-34 molecular sieve obtained in Example 1, 34.7 g of triethylamine[TEA], 237.6 g of tetraethylammonium bromide[TEABr] and 12008.3 g of deionized water were sufficiently stirred, and then placed at 80° C. for a heat treatment for 0.5 hours to obtain a precursor A. 1.4 g of magnesium nitrate [Mg(NO.sub.3).sub.2.Math.6H.sub.2O, purity ≥98 wt. %] was dissolved in 1161.7 mL of deionized water to form a mixture B after stirring sufficiently for 1.5 hours. The precursor A was fed to the mixture B under a closed stirring condition, the stirring was continued for 3.5 hours and was further continued for 1 hour at 85° C. Then it was crystallized at 160° C. for 10 min, dried at 100° C. for 6 hours after filtering and washing, then heated to 600° C., calcined at a constant temperature for 4 hours, and thus an AFI molecular sieve (the same below) was obtained, marked as SSP5-1. Through ICP test, the SSP5-1 contains 0.18 wt. % Mg element. Its XRD pattern is similar to FIG. 3, SEM pattern is similar to FIG. 4 and FIG. 5, and the metal content and the acid distribution in the product are listed in Table 7.

Example 8

[0104] At room temperature, 20.8 g of the SCM-34 molecular sieve obtained in Example 2, 208 g of triethylamine [TEA], 4.2 g of silica [SiO.sub.2, 99 wt. %] and 685.6 g of deionized water were stirred sufficiently, and then placed at 60° C. for a heat treatment for 1 hour to obtain a precursor A. 1.1 g of cobalt nitrate [Co(NO.sub.3).sub.2.Math.4H.sub.2O, purity ≥99 wt. %], 6.3 g of silica [SiO.sub.2, 99 wt. %] were dissolved in 354.4 mL of deionized water to form a mixture B after stirring sufficiently for 2.5 hours. The precursor A was fed into the mixture B under a closed stirring condition, the stirring was continued for 0.5 hours and was further continued for 0.5 hours at 100° C. under a closed state. The above mixture after stirring was then crystallized at 110° C. for 120 min, filtered, washed, and then dried at 90° C. for 8 hours, then heated to 500° C., calcined at a constant temperature for 8 hours to obtain a product, marked as SSP5-2. After ICP test, the SSP5-2 contains 0.01 wt. % Co element. Its XRD pattern is similar to FIG. 3, SEM pattern is similar to FIG. 4 and FIG. 5, and the metal content and the acid distribution in the product are listed in Table 7.

Example 9

[0105] At room temperature, 12110.7 g of the SCM-34 molecular sieve obtained from Example 4, 8106.3 g of benzyltriethylammonium chloride [TEBAC, 99 wt. %], 4004.4 g of tetraethylammonium hydroxide [TEAOH, 50%] and 15363.4 g of acidic silica sol [SiO.sub.2, 40 wt. %] were sufficiently stirred for 1.5 hours, and then placed at 60° C. for a heat treatment for 1.5 hours to obtain a precursor A. 6055.4 g of zinc nitrate [Zn(NO.sub.3).sub.2.Math.6H.sub.2O, purity ≥99 wt. %] and 15363.4 g of acidic silica sol [SiO.sub.2, 40 wt. %] were dissolved in 4052.9 mL of deionized water to form a mixture B after stirring sufficiently for 2.5 hours. The precursor A was fed into the mixture B under a closed stirring condition, the stirring was continued for 0.5 hours, and further continued at 90° C. for 0.9 hours under a closed state. The above mixture after stirring was then crystallized at 115° C. for 86 min, filtered, washed, and then dried at 80° C. for 9 hours, then heated to 550° C., calcined at a constant temperature for 5 hours to obtain a product, marked as SSP5-3. Through ICP test, the SSP5-3 contains 1.0 wt. % Zn element. Its XRD pattern is FIG. 3, SEM pattern is FIG. 4 and FIG. 5, TPD pattern is FIG. 6, and the metal content and the acid distribution in the product are listed in Table 7.

TABLE-US-00011 TABLE 7 medium- type and weight weak acid strong acid strong acid sample content of (percentage (percentage (percentage name metal element in total acid) in total acid) in total acid) SSP5-1 Mg, 0.18% 42.8% 5.0% 52.2% SSP5-2 Co, 0.01% 34.5% 7.5% 58.0% SSP5-3 Zn, 1.0% 43.9% 19.7% 36.4%

[0106] 2. Use of Metal Containing AFI Type Molecular Sieves in the Reaction of the Methanol Conversion to Hydrocarbons

Example 10

[0107] The SSP5-1 molecular sieve synthesized in Example 7 was calcined at 550° C. for 4 hours, cooled to room temperature, then tableted, smashed and screened. 12-20 meshes of particles were selected for later use. Using methanol as raw material and a fixed bed reactor with a diameter of 15 mm, an assessment was carried out under the conditions of 505° C., a mass space velocity of 3.5 h.sup.−1 and a pressure of 1.7 MPa. The yields of ethylene, propylene and butylene were up to 96.8%. Good technical results were obtained.

Example 11

[0108] The SSP5-2 molecular sieve synthesized in Example 8 was calcined at 550° C. for 4 hours, cooled to room temperature, then tableted, smashed and screened. 12-20 meshes of particles were selected for later use. Using methanol as raw material and a fixed bed reactor with a diameter of 15 mm, an assessment was carried out under the conditions of 400° C., a mass space velocity of 0.5 h.sup.−1 and a pressure of 5.1 MPa. The yields of ethylene, propylene and butylene were up to 92.6% and good technical results were obtained.

Example 12

[0109] The SSP5-3 molecular sieve synthesized in Example 9 was calcined at 550° C. for 4 hours, cooled to room temperature, then tableted, smashed and screened. 12-20 meshes of particles were selected for later use. Using methanol as raw material and a fixed bed reactor with a diameter of 15 mm, an assessment was carried out under the conditions of 600° C., a mass space velocity of 0.1 h.sup.−1 and a pressure of 0.01 MPa. The yields of ethylene, propylene and butylene were up to 90.9% and good technical results were obtained.

[0110] III. Synthesis and Use of SAPO-17 Molecular Sieve

[0111] 1. Synthesis of SAPO-17 Molecular Sieve from SCM-34 Molecular Sieve

Example 13

[0112] At room temperature, 2.6 g of piperazine (PIP) and 8.5 g of 1,4-dioxane (DOA) were sufficiently stirred, and then placed at 90° C. for a heat treatment for 1.0 hour to obtain a precursor P.sub.1. 5.6 g of the SCM-34 molecular sieve prepared in Example 3 and 3.1 g of silica (SiO.sub.2) were mixed in 6.9 g of 1,4-dioxane solution, and subjected to a heat treatment at 40° C. for 5 hours to obtain a mixture material M.sub.1. The precursor P.sub.1 was fed into the mixture material M.sub.1 under the condition of vigorous stirring, and a mixture to be crystallized was formed after further stirring for 2.5 hours. The stirring was continued at 110° C. for 0.5 hours, and crystallization was then carried out at 140° C. for 1 hour. After filtering, washing, the product was dried at 120° C. for 4 hours, then heated to 500° C., and calcined at a constant temperature for 6 hours, and an SAPO-17 molecular sieve was obtained, marked as STE-1. See FIG. 7 for its XRD pattern and FIG. 8 for its SEM pattern.

Example 14

[0113] At room temperature, 666.7 g of 1,10-phenanthroline (1,10-PIH), 731.3 g of piperazine (PIP) and 1285.2 g of 1,2-epoxycyclopentane (CPO) were sufficiently stirred, and then placed at 40° C. for a heat treatment for 5 hours to obtain a precursor P.sub.2. 239.8 g of the SCM-34 molecular sieve prepared in Example 5 was mixed in 139.8 g of 1,2-epoxycyclopentane (CPO) solution and subjected to a heat treatment at 90° C. for 1.0 hour to obtain a mixture material M.sub.2. The precursor P.sub.2 was fed into the mixture material M.sub.2 under the condition of vigorous stirring. The stirring was continued for 4.0 hours, a closed stirring was then carried out at 80° C. for 5 hours, then crystallization was carried out at 130° C. for 2 hours. After filtering, washing, the product was dried at 100° C. for 6 hours, then heated to 600° C., and calcined at a constant temperature for 4 hours, and a product was obtained, marked as STE-2. Its XRD pattern is similar to FIG. 7, and its SEM pattern is similar to FIG. 8.

Example 15

[0114] At room temperature, 0.8 g of cyclohexylamine (HCHA), 33.7 g of piperazine (PIP), 5.5 g of 1,4-dioxane (DOA) and 5.2 g of cyclohexanone (CHO) were sufficiently stirred, and then placed at 55° C. for a heat treatment for 4.0 hours to obtain a precursor P.sub.3. 6.9 g of the SCM-34 molecular sieve prepared in Example 6 was mixed in the solution of 5.0 g of 1,4-dioxane (DOA) and 5.7 g of cyclohexanone (CHO), and a heat treatment was carried out at 70° C. for 2.0 hours to obtain a mixture material M.sub.3. The precursor P.sub.3 was fed into the mixture material M.sub.3 under the condition of vigorous stirring. The stirring was continued for 1 hour, a closed stirring was then carried out at 100° C. for 1 hour, and crystallization was then carried out at 120° C. for 5 hours. After filtering, washing, the product was dried at 80° C. for 9 hours, then heated to 400° C., and calcined at a constant temperature for 8 hours, and a product was obtained, marked as STE-3. Its XRD pattern is similar to FIG. 7, and its SEM pattern is similar to FIG. 8.

Comparative Example 1

[0115] An SAPO-17 molecular sieve was prepared according to the synthesis method of SAPO-17 molecular sieve disclosed in CN103922361A, which is specifically as follows: with aluminum isopropoxide as aluminum source, phosphoric acid as phosphorus source, silica sol as silicon source, and cyclohexylamine as template, 81 g of aluminum isopropoxide was added to 48.9 g of ultrapure water, and 45.7 g of phosphoric acid (85 wt. %) was added after stirring evenly. After stirring for 1 hour, 11.5 mL of cyclohexylamine was added to the mixed solution, and after 2 hours of stirring and aging, 11.9 g of 30 wt. % SiO.sub.2 aqueous solution was added to the system. After several hours of continuous aging, the sol was placed in a stainless steel reactor with a PTFE lining and crystallized at 200° C. for 120 hours to obtain a short and thick rod-like SAPO-17 molecular sieve. See FIG. 9 for its XRD pattern and FIG. 10 for its SEM pattern.

Comparative Example 2

[0116] According to a document (Tianjin Chemical Industry, 2016, 30 (3): 17-19.), the synthesis method of SAPO-17 molecular sieve is specifically: with aluminum isopropoxide as aluminum source, phosphoric acid as phosphorus source, silica sol as silicon source, and cyclohexylamine as template, according to a solution of a reaction ratio of 1Al.sub.2O.sub.3:1P.sub.2O.sub.5:0.3SiO.sub.2:1CHA:1HF:40H.sub.2O and a fixed amount of aluminum source of 0.015 mol, 3.06 g of aluminum isopropoxide was added to 5.4 g of deionized water, 1.7 g of phosphoric acid (85 wt. %) was added after stirring evenly, 0.7 g of cyclohexylamine was added to the mixed solution after a continued stirring of 1.5 hours, 2.25 g of silica sol (40 wt. %) was added to the reaction system after stirring and aging for 1.5 hours, the sol was placed in a stainless steel reactor with a PTFE lining and crystallized at 200° C. for 120 hours to obtain an SAPO-17 molecular sieve after further stirring for several hours.

[0117] 2. Use of SAPO-17 Molecular Sieve

[0118] (1) Use of SAPO-17 Molecular Sieve in the Reaction of Methanol-to-Hydrocarbon

Example 16

[0119] The STE-1 molecular sieve synthesized in Example 13 was calcined at 550° C. for 4 hours, cooled to room temperature, then tableted, smashed and sieved, and 12-20 meshes of particles were selected for later use. With methanol as raw material and a fixed bed reactor with a diameter of 15 mm, an assessment was conducted under the conditions of 600° C., a mass space velocity of 4.9 h.sup.−1, and a pressure of 1.0 MPa. The methanol conversion rate was 100%, the yields of ethylene, propylene in the product were up to 78.7%, and the selectivity ratio (ethylene/propylene) was 2.87. Good technical results were obtained.

Example 17

[0120] The STE-2 molecular sieve synthesized in Example 14 was used to prepare a catalyst according to the catalyst preparation method in Example 16. Using methanol as raw material and a fixed bed reactor with a diameter of 15 mm, an assessment was carried out under the conditions of 550° C., a mass space velocity of 15 h.sup.−1, and a pressure of 10 MPa. The methanol conversion rate was 100%, the yields of ethylene, propylene in the product were up to 80.8%, and the selectivity ratio (ethylene/propylene) was 2.76. Good technical results have been achieved.

Example 18

[0121] The STE-3 molecular sieve synthesized in Example 15 was used to prepare a catalyst according to the catalyst preparation method in Example 16. Using methanol as raw material and a fixed bed reactor with a diameter of 15 mm, an assessment was carried out under the conditions of 474° C., a mass space velocity of 7.1 h.sup.−1, and a pressure of 2.4 MPa. The methanol conversion rate was 100%, the yields of ethylene, propylene in the product were up to 84.5%, and the selectivity ratio (ethylene/propylene) was 2.99. Good technical results have been achieved.

Comparative Example 3

[0122] The SAPO-17 molecular sieve synthesized in Comparative Example 1 was used to prepare a catalyst according to the catalyst preparation method of Example 16. By assessing according to the manner of Example 17, the methanol conversion rate was 100%, the yields of ethylene, propylene in the product were up to 33.3%, and the selectivity ratio (ethylene/propylene) was 1.1.

Comparative Example 4

[0123] The SAPO-17 molecular sieve synthesized in Comparative Example 2 was used to prepare a catalyst according to the catalyst preparation method of Example 16. By assessing according to the manner of Example 18, the methanol conversion rate was 100%, the yields of ethylene, propylene in the product were up to 40.1%, and the selectivity ratio (ethylene/propylene) was 1.2.

[0124] (2) Use of SAPO-17 Molecular Sieve in the Reaction of Syngas-to-Hydrocarbon

Example 19

[0125] Use of SAPO-17 molecular sieve in the reaction of syngas-to-hydrocarbons

[0126] The STE-1 molecular sieve synthesized in Example 13 was calcined at 550° C. for 6 hours, then tableted, smashed, screened, and 20-40 meshes of particles were selected. A weight ratio of catalyst to filler ZnCrO.sub.x/STE=1.0 (ZnCrO.sub.x represents a mixture of zinc oxide and chromium oxide, and an oxide-molecular sieve catalyst was prepared for later use) was used. With syngas as raw material and a fixed bed reactor with a diameter of 15 mm, the process conditions are: a reaction temperature of 400° C., a pressure of 10 MPa, a space velocity of 2000 h.sup.−1, a syngas constitution H.sub.2/CO=0.5:1, a CO conversion rate of 41.9%, wherein the C.sub.2-C.sub.4 olefin selectivity was 66.9%, and the selectivity ratio (ethylene/propylene)=2.61.

Example 20

[0127] Use of SAPO-17 Molecular Sieve in the Reaction of Syngas-to-Hydrocarbon

[0128] The STE-2 molecular sieve synthesized in Example 14 was used to prepare a catalyst according to the catalyst preparation method in Example 19. The process conditions are as follows: a reaction temperature of 375° C., a pressure of 7.5 MPa, a space velocity of 1000 h.sup.−1, a syngas constitution H.sub.2/CO=0.66:1, a CO conversion rate of 45.6%, wherein the C.sub.2-C.sub.4 olefin selectivity was 75.6%, and the selectivity ratio (ethylene/propylene)=2.66.

Example 21

[0129] Use of SAPO-17 Molecular Sieve in the Reaction of Syngas-to-Hydrocarbon

[0130] The STE-3 molecular sieve synthesized in Example 15 was used to prepare a catalyst according to the catalyst preparation method in Example 19. The process conditions are: a reaction temperature of 350° C., a pressure of 1.2 MPa, a space velocity of 500 h.sup.−1, a syngas constitution H.sub.2/CO=0.75:1, a CO conversion rate 51.7%, wherein the C.sub.2-C.sub.4 olefin selectivity was 85.6%, and the selectivity ratio (ethylene/propylene)=2.98.

Comparative Example 5

[0131] Use of SAPO-17 Molecular Sieve in the Reaction of Syngas-to-Hydrocarbon

[0132] The SAPO-17 molecular sieve synthesized in Comparative Example 2 was used to prepare a catalyst according to the catalyst preparation method of Example 20. By assessing according to the manner of Example 20, the CO conversion rate was 22.3%, wherein the C.sub.2-C.sub.4 olefin selectivity was 36.8%, and the selectivity ratio (ethylene/propylene) was 1.21.

[0133] It can be seen from the above comparative tests that the SAPO-17 molecular sieves prepared in the present invention have higher ethylene and propylene yields and higher selectivity ratios (ethylene/propylene) in the reaction of the methanol conversion to hydrocarbon; the SAPO-17 molecular sieves prepared in the present invention have higher C.sub.2-C.sub.4=selectivities and also higher selectivity ratios (ethylene/propylene) in the reaction of syngas-to-hydrocarbon.