SAPO-34 molecular sieve and method for preparing the same

Abstract

The present invention concerns a SAPO-34 molecular sieve and method for preparing the same, whose chemical composition in the anhydrous state is expressed as: mDIPA.(Si.sub.xAl.sub.yP.sub.z)O.sub.2, wherein, DIPA is diisopropylamine existing in cages and pore channels of said molecular sieve, wherein m is the molar number of diisopropylamine per one mole of (SixAlyPz)O.sub.2, and m is from 0.03 to 0.25; x, y, z respectively represents the molar number of Si, Al, P, and x is from 0.01 to 0.30, and y is from 0.40 to 0.60, and z is from 0.25 to 0.49, and x+y+z=1. The SAPO-34 molecular sieve can be used as catalysts for acid-catalyzed reaction or oxygenate to olefins reaction.

Claims

1. A SAPO-34 molecular sieve with a chemical composition in the anhydrous state is expressed as:
mDIPA.(Si.sub.xAl.sub.yP.sub.z)O.sub.2; wherein, DIPA is diisopropylamine existing in cages and pore channels of the molecular sieve; m is the molar number of diisopropylamine per one mole of (SixAlyPz)O.sub.2, and m is from 0.03 to 0.25; x, y, z respectively represents the molar number of Si, Al, P, and x is from 0.01 to 0.30, and y is from 0.40 to 0.60, and z is from 0.25 to 0.49, and x+y+z=1; wherein the molecular sieve is a molecular sieve crystal and there is a slight Si surface enrichment phenomenon on the molecular sieve crystal, and the ratio of the surface Si content to the bulk Si content of the crystal ranges from 1.48 to 1.01; wherein the Si content is calculated by the molar ratio of Si/(Si+Al+P).

2. The SAPO-34 molecular sieve according to claim 1, wherein in X-ray diffraction spectrogram of the SAPO-34 molecular sieve, the diffraction peaks are included as follows: TABLE-US-00005 No. 2 1 9.5177 2 12.7987 3 14.1388 4 15.9829 5 18.1242 6 20.5413 7 22.278 8 23.0981 9 25.3853 10 25.7835 11 27.5448 12 28.5382 13 29.5454 14 30.4947 15 31.3812 16 34.3501 17 36.4789 18 39.6546 19 43.4168 20 47.4822 21 49.1405 22 50.4542 23 51.1735 24 53.0514 25 53.9912 26 54.7895 27 55.7846 28 56.4017 29 59.6235 30 60.8263.

3. The SAPO-34 molecular sieve according to claim 1, wherein the ratio of the surface Si content to the bulk Si content of the crystal ranges from 1.42 to 1.02.

4. The SAPO-34 molecular sieve according to claim 1, wherein the ratio of the surface Si content to the bulk Si content of the crystal ranges from 1.36 to 1.03.

5. The SAPO-34 molecular sieve according to claim 1, wherein the ratio of the surface Si content to the bulk Si content of the crystal ranges from 1.33 to 1.03.

6. A method for preparing the SAPO-34 molecular sieve according to claim 1, including the steps as follows: (a) mixing a silicon source, an aluminum source, a phosphorus source, a surfactant BM, deionized water and structural-directing agent DIPA, and obtaining an initial gel mixture having the following molar ratio: SiO.sub.2/Al.sub.2O.sub.3 is from 0.05 to 1.5; P.sub.2O.sub.5/Al.sub.2O.sub.3 is from 0.5 to 1.5; H.sub.2O/Al.sub.2O.sub.3 is from 16 to 150; DIPA/Al.sub.2O.sub.3 is from 2.0 to 5.9; BM/Al.sub.2O.sub.3 is from 0.001 to 0.05; (b) transferring the initial gel mixture into a synthetic kettle, then sealing and heating to crystallization temperature range from 150 C. to 220 C., crystallizing for crystallization time range from 0.5 h to 72 h under an autogenous pressure; and (c) after finishing the crystallization, separating the solid product, followed by washing and drying to obtain the SAPO-34 molecular sieve; wherein, the structural-directing agent DIPA is diisopropylamine; said surfactant BM is alkyl ammonium halide.

7. The method according to claim 6, wherein the silicon source is one or more selected from silica sol, active silica, orthosilicate esters and metakaolin; the aluminum source is one or more selected from aluminum salts, activated alumina, aluminum alkoxide and metakaolin; and the phosphorus source is one or more selected from phosphoric acid, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, organophosphorous compounds and phosphorus oxides.

8. The method according to claim 6, wherein in the initial gel mixture, the surfactant BM is one or more selected from dodecyl trimethylammonium chloride, tetradecyl trimethylammonium chloride, cetyl trimethylammonium chloride, octadecyl trimethylammonium chloride, dodecyl trimethylammonium bromide, tetradecyl trimethylammonium bromide, cetyl trimethylammonium bromide, and octadecyl trimethylammonium bromide.

9. The method according to claim 6, wherein in the initial gel mixture, the molar ratio of H.sub.2O/Al.sub.2O.sub.3 is from 26 to 120.

10. The method according to claim 6, wherein in the initial gel mixture, the molar ratio of DIPA/Al.sub.2O.sub.3 is from 3.0 to 5.0.

11. The method according to claim 6, wherein in the initial gel mixture, the molar ratio of BM/Al.sub.2O.sub.3 is from 0.001 to 0.03.

12. The method according to claim 6, wherein the crystallization temperature ranges from 180 C. to 210 C.; the crystallization time ranges from 1 h to 24 h.

13. The method according to claim 6, wherein in the initial gel mixture the molar ratio of H.sub.2O/Al.sub.2O.sub.3 is from 31 to 100.

14. The method according to claim 6, wherein the crystallization temperature ranges from 190 C. to 210 C.

15. The method according to claim 6, wherein the crystallization time ranges from 1 h to 24 h.

16. The method according to claim 15, wherein the crystallization time ranges from 1 h to 12 h.

17. A process for producing ethylene from ethanol using a catalyst, wherein said catalyst is obtained by calcining at least one of the SAPO-34 molecular sieves according to claim 1, at a temperature from 400 to 700 C. in air.

18. A process for producing olefins from an oxygenate using a catalyst, wherein the catalyst is obtained by calcining at least one of the SAPO-34 molecular sieves according to claim 1 at a temperature from 400 to 700 C. in air.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 is a scanning electron microscope image of the sample prepared in Example 1.

SPECIFIC EMBODIMENTS OF THE INVENTION

(2) The present invention will be described in details by Examples, but the present invention is not limited to these Examples.

(3) In Examples, abbreviations are used as follows:

(4) Diisopropylamine is abbreviated as DIPA; dodecyl trimethylammonium bromide is abbreviated as DTAB; tetradecyl trimethylammonium bromide is abbreviated as TTAB; cetyl trimethylammonium bromide is abbreviated as CTAB; octadecyl trimethylammonium bromide is abbreviated as OTAB; dodecyl trimethylammonium chloride is abbreviated as DTAC; tetradecyl trimethylammonium chloride is abbreviated as TTAC; cetyl trimethylammonium chloride is abbreviated as CTAC; octadecyl trimethylammonium chloride is abbreviated as OTAC.

(5) The elemental analysis of the bulk composition was determined with X-ray Fluorescence (XRF) at PANalytical X'Pert PRO X-ray diffractometer with Cu target (=0.15418 nm), operated at 40 KV and 100 mA.

(6) The elemental analysis of the surface composition was determined with X-ray photoelectron spectroscopy at Thermo ESCALAB 250Xi X-Ray Photoelectron Spectrometer (Mono AlK X-ray source) using Al2p=74.7 eV of Al.sub.2O.sub.3 in sample surface as internal standard to calibrate charge of sample surface.

EXAMPLE 1

(7) The amount of ingredients and the crystallization condition were shown in Table 1. The synthesis process was as follows: 14.06 g of pseudoboehmite (with Al.sub.2O.sub.3 mass percent of 72.5%) and 90 g of deionized water mixing homogeneously by stirring, and then 23.0 g of phosphoric acid (with H.sub.3PO.sub.4 mass percent of 85%) was added by droplets and stirred to smooth, and then 6.4 g of silica sol (with SiO.sub.2 mass percent of 30%) and 1.09 g cetyl trimethyl ammonium bromide (CTAB) were added, and then 30.4 g of diisopropylamine (abbreviated as DIPA, with a mass percent of 99%) was added into the mixture to obtain an initial gel mixture with the molar ratio of 3.0DIPA: 0.30SiO.sub.2:1Al.sub.2O.sub.3:1P.sub.2O.sub.5:0.03CTAB:50H.sub.2O. The initial gel mixture was transferred into a stainless steel synthetic kettle.

(8) The synthetic kettle was heated to 200 C., dynamically crystallized for 24 h. After finishing the crystallization, the solid product was centrifugal separated, washed and dried at 100 C. in air to obtain 27.6 g of raw powder sample. The sample was detected with XRD and XRD data were shown in Table 2, indicating that the sample prepared was SAPO-34 molecular sieve. The scanning electron microscope image of the sample was illustrated in FIG. 1.

(9) The elemental analysis of the surface composition and the bulk composition of the sample were detected with XPS and XRF, respectively. The ratio of the surface Si content to the bulk Si content was shown in Table 1. The bulk composition of the sample obtained in Example 1 was Al.sub.0.49P.sub.0.43Si.sub.0.08.

(10) The organic content of the sample obtained in Example 1 was detected with CHN analyzer, indicating the molar ratio of C/N was 6.01. The chemical compositions of the raw powder of molecular sieve were obtained by normalization of CHN and XRF results, which was 0.08DIPA.(Si.sub.0.08Al.sub.0.49P.sub.0.40)O.sub.2.

(11) The raw powder sample was detected with .sup.13C MAS NMR analysis, and the result showed that only the characteristic .sup.13C resonance of DIPA was observed without any characteristic .sup.13C resonance of CTAB observed, indicating CTAB didn't enter into the final product.

(12) TABLE-US-00001 TABLE 1 The list of amount of ingredients and crystallization conditions of the molecular sieves* Silicon Phosphorus source and Aluminum source and molar BM and Molar source and molar amount of molar Crystal- amount molar amount of amount of SiO.sub.2 amount Crystallization lization Si.sub.surface/ Example of DIPA Al.sub.2O.sub.3 thereof P.sub.2O.sub.5 thereof thereof H.sub.2O thereof Temperature Time Si.sub.bulk 1 0.3 mol pseudoboehmite phosphoric silica sol 5.0 mol CTAB 200 C. 24 h 1.06 0.1 mol acid 0.10 mol 0.03 mol 0.003 mol 2 0.59 mol aluminium phosphoric silica sol 1.6 mol DTAB 150 C. 48 h 1.01 isopropoxide acid 0.10 mol 0.005 mol 0.0001 mol 0.1 mol 3 0.12 mol kaolinite 0.1 mol phosphoric silica sol 15 mol OTAB 180 C. 24 h 1.29 acid 0.10 mol 0.15 mol 0.001 mol 4 0.18 mol -alumina 0.1 mol phosphoric silica sol 8.3 mol TTAB 200 C. 24 h 1.48 acid 0.10 mol 0.12 mol 0.005 mol 5 0.5 mol aluminum sulfate phosphoric active silica 2.6 mol CTAC 190 C. 12 h 1.42 0.1 mol acid 0.05 mol 0.03 mol 0.002 mol 6 0.3 mol aluminium phosphoric ethyl 12 mol DTAC 200 C. 24 h 1.25 chloride 0.1 mol acid 0.12 mol orthosilicate 0.003 mol 0.08 mol 7 0.033 mol pseudoboehmite phosphoric silica sol 3.1 mol OTAC 200 C. 24 h 1.33 0.1 mol acid 0.09 mol 0.03 mol 0.004 mol 8 0.08 mol metakaolin phosphoric silica sol 10 mol TTAC 200 C. 24 h 1.36 0.1 mol acid 0.15 mol 0.05 mol 0.002 mol 9 0.26 mol pseudoboehmite ammonium silica sol 6.6 mol OTAC 220 C. 0.5 h 1.03 0.1 mol dihydrogen 0.06 mol 0.001 mol phosphate 0.10 mol 10 0.2 mol pseudoboehmite diammonium metakaolin 5.2 mol CTAC 200 C. 24 h 1.12 0.1 mol hydrogen 0.06 mol 0.0009 mol phosphate 0.10 mol 11 0.2 mol aluminum sulfate diammonium silica sol 8.8 mol DTAC 200 C. 18 h 1.18 0.1 mol hydrogen 0.07 mol 0.002 mol phosphate 0.15 mol 12 0.3 mol pseudoboehmite diammonium silica sol 6.5 mol CTAB 180 C. 24 h 1.27 0.1 mol hydrogen 0.12 mol 0.002 mol phosphate 0.12 mol 13 0.4 mol pseudoboehmite phosphoric metakaolin 12 mol DTAB 210 C. 1 h 1.22 0.1 mol anhydride 0.03 mol 0.003 mol 0.13 mol 14 0.39 mol pseudoboehmite phosphoric silica sol 4.5 mol OTAB 190 C. 12 h 1.45 0.1 mol acid 0.10 mol 0.03 mol 0.004 mol 15 0.39 mol aluminum nitrate phosphoric tetramethyl 6.5 mol TTAB 150 C. 72 h 1.40 0.1 mol acid 0.10 mol orthosilicate 0.003 mol 0.03 mol 16 0.30 mol pseudoboehmite trimethyl silica sol 6.5 mol CTAB 210 C. 5 h 1.33 0.1 mol phosphine 0.03 mol 0.003 mol 0.10 mol 17 0.35 mol pseudoboehmite triethyl silica sol 6.5 mol DTAB 170 C. 60 h 1.12 0.1 mol phosphine 0.03 mol 0.003 mol 0.10 mol 18 0.24 mol pseudoboehmite phosphoric silica sol 5.0 mol CTAB 200 C. 24 h 1.10 0.1 mol acid 0.10 mol 0.03 mol 0.002 mol + OTAB 0.001 mol 19 0.25 mol pseudoboehmite phosphoric silica sol 5.0 mol CTAB 200 C. 24 h 1.08 0.1 mol acid 0.10 mol 0.03 mol 0.001 mol + CTAC 0.001 mol + DTAB 0.001 mol

(13) TABLE-US-00002 TABLE 2 XRD result of the sample obtained in Example 1 No. 2 d() 100 I/I.sub.0 1 9.5177 9.29267 100 2 12.7987 6.91689 19.92 3 14.1388 6.26416 13.11 4 15.9829 5.5453 50.04 5 18.1242 4.89469 22.4 6 20.5413 4.32386 84.84 7 22.278 3.99057 6.09 8 23.0981 3.85071 4.97 9 25.3853 3.50871 23.15 10 25.7835 3.45542 18.75 11 27.5448 3.23834 3.71 12 28.5382 3.12783 2.09 13 29.5454 3.02346 5.07 14 30.4947 2.93147 25.16 15 31.3812 2.85065 18.51 16 34.3501 2.61076 6.33 17 36.4789 2.46314 2.67 18 39.6546 2.2729 3.18 19 43.4168 2.08427 5.1 20 47.4822 1.91487 2.79 21 49.1405 1.85407 5.48 22 50.4542 1.80883 3.22 23 51.1735 1.78508 3.43 24 53.0514 1.72624 2.25 25 53.9912 1.69839 1.01 26 54.7895 1.67552 1.62 27 55.7846 1.64797 2.24 28 56.4017 1.63139 1.57 29 59.6235 1.55071 0.97 30 60.8263 1.52163 1.28

EXAMPLES 2 to 17

(14) The amount of ingredients and the crystallization conditions were shown in Table 1, and the synthesis processes were the same as Example 1.

(15) The samples were detected with XRD. XRD data of samples were similar to Table 2, which showed that each corresponding peak had the same peak position and the 10% difference of peak intensity, indicating the samples prepared were SAPO-34 molecular sieves.

(16) The elemental analysis of the surface composition and the bulk composition of the sample were detected with XPS and XRF, and the ratios of the surface Si content to the bulk Si content were shown in Table 1.

(17) The raw powder samples obtained in Examples 2 to 17 were detected with CHN elemental analysis respectively, and the results showed that the ratios of C/N fluctuated at a range of 6.00.05. The chemical compositions of the raw powders of molecular sieves were obtained by normalization of CHN and XRF results, which were 0.25DIPA.(Si.sub.0.01Al.sub.0.50P.sub.0.49)O.sub.2, 0.04DIPA.(Si.sub.0.30Al.sub.0.45P.sub.0.25)O.sub.2, 0.06DIPA.(Si.sub.0.25Al.sub.0.40P.sub.0.35)O.sub.2, 0.20DIPA.(Si.sub.0.09Al.sub.0.47P.sub.0.44)O.sub.2, 0.10DIPA.(Si.sub.0.15Al.sub.0.45P.sub.0.40)O.sub.2, 0.03DIPA.(Si.sub.0.10Al.sub.0.48P.sub.0.42)O.sub.2, 0.05DIPA.(Si.sub.0.13Al.sub.0.45P.sub.0.42)O.sub.2, 0.07DIPA.(Si.sub.0.10Al.sub.0.49P.sub.0.41)O.sub.2, 0.07DIPA.(Si.sub.0.15Al.sub.0.50P.sub.0.35)O.sub.2, 0.08DIPA.(Si.sub.0.07Al.sub.0.06P.sub.0.33)O.sub.2, 0.08DIPA.(Si.sub.0.08Al.sub.0.49P.sub.0.43)O.sub.2, 0.12DIPA.(Si.sub.0.09Al.sub.0.49P.sub.0.42)O.sub.2, 0.09DIPA.(Si.sub.0.09Al.sub.0.47P.sub.0.44)O.sub.2 and 0.10DIPA.(Si.sub.0.10Al.sub.0.50P.sub.0.40)O.sub.2, respectively.

(18) The raw powder samples obtained in Examples 2 to 17 were detected with .sup.13C MAS NMR analysis respectively, only the characteristic .sup.13C resonance of DIPA was observed without any characteristic .sup.13C resonance of surfactant BM which had been added observed, indicating surfactant BM which had been added didn't enter into the final products.

EXAMPLE 18

(19) The amount of ingredients and the crystallization conditions were shown in Table 1, and the synthesis process was the same as Example 1, except that the crystallization is carried out statically and the surfactant BM was changed to a mixture of CTAB and OTAB. The sample was detected with XRD.

(20) XRD data of sample were similar to Table 2, which showed that each corresponding peak had the same peak position and the 10% difference of peak intensity, indicating the sample prepared was SAPO-34 molecular sieve.

(21) The elemental analysis of the surface composition and the bulk composition of the sample were detected with XPS and XRF, and the ratios of the surface Si content to the bulk Si content were shown in Table 1.

(22) The raw powder sample obtained in Example 18 was detected with CHN elemental analysis respectively, and the result showed that the ratio of C/N was 5.95. The chemical compositions of the raw powders of molecular sieves were obtained by normalization of CHN and XRF results, which was 0.0 8DIPA.(Si.sub.0.08Al.sub.0.49P.sub.0.43)O.sub.2.

(23) The raw powder sample obtained in Example 18 was detected with .sup.13C MAS NMR analysis respectively, only the characteristic .sup.13C resonance of DIPA was observed without any characteristic .sup.13C resonances of CTAB or OTAB observed, indicating CTAB or OTAB didn't enter into the final product.

EXAMPLE 19

(24) The amount of ingredients and the crystallization conditions were shown in Table 1, and the synthesis process was the same as Example 1, except that the crystallization is carried out statically and the surfactant was changed to a mixture of CTAB, CTAC and DTAB. The sample was detected with XRD. XRD data of sample were similar to Table 2, which showed that each corresponding peak had the same peak position and the 10% difference of peak intensity, indicating the sample prepared was SAPO-34 molecular sieve.

(25) The raw powder sample obtained in Example 19 was detected with CHN elemental analysis respectively, and the result showed that the ratio of C/N was 5.99. The chemical compositions of the raw powders of molecular sieves were obtained by normalization of CHN and XRF results, which was 0.09DIPA.(Si.sub.0.08Al.sub.0.50P.sub.0.42)O.sub.2.

(26) The raw powder sample obtained in Example 19 was detected with .sup.13C MAS NMR analysis respectively, only the characteristic .sup.13C resonance of DIPA was observed without any characteristic .sup.13C resonances of CTAB, CTAC or DTAB observed, indicating CTAB, CTAC or DTAB didn't enter into the final product.

EXAMPLE 20

(27) 3 g of the samples obtained in Examples 1 to 19 respectively, were put into plastic beaker, adding 3 ml of 40% hydrofluoric acid to dissolve the framework of molecular sieve under ice-bath condition, and then adding 15 ml of tetrachloromethane to dissolve the organic compounds. The organic compounds were analyzed with GC-MS. The results indicated that the organic compound in the samples obtained in Examples 1 to 19 all was diisopropylamine.

EXAMPLE 21

(28) The sample obtained in Example 1 was immobilized using epoxy resin and polished at a glazing machine. The composition analysis from the core to the shell was detected with SEM-EDX linear scanning of the crystal section near the crystal core. The result indicated that the atomic ratio of Si/Al near the core area of the crystal was about 0.14 and the atomic ratio of Si/Al near the surface area of the crystal was about 0.17.

(29) The sample obtained in Example 11 (with the morphology of rhombic octahedron and the crystal size from 1 m to 5 m according to the SEM photo) was immobilized using epoxy resin and polished at a glazing machine. The composition analysis from the core to the shell was detected with SEM-EDX linear scanning of the crystal section near the crystal core. The result indicated that the atomic ratio of Si/Al near the core area of the crystal was about 0.16 and the atomic ratio of Si/Al near the surface area of the crystal was about 0.22.

COMPARATIVE EXAMPLE 1

Without Addition of a Surfactant

(30) The amount of ingredients, the synthesis process and the crystallization conditions were the same as Example 1, except without addition of CTAB in the initial gel mixture. The sample was detected with XRD. XRD data of sample were similar to Table 2, which showed that each corresponding peak had the same peak position and the 10% difference of peak intensity, indicating the sample prepared was SAPO-34 molecular sieve. The relative crystallinity of the sample obtained in Comparative Example 1 was 90% of the sample obtained in Example 1 (defining the crystallinity of the sample obtained in Example 1 as 100%).

(31) Relative crystallinity=(I.sub.1+I.sub.2+I.sub.3) 100%/(I.sub.1+I.sub.2+I.sub.3), wherein I.sub.1, I.sub.2 and I.sub.3 are the intensities of the three strongest diffraction peaks in X-ray diffraction spectrogram of the sample obtained in Comparative Example 1; I.sub.1, I.sub.2 and I.sub.3 are the intensities of the three strongest diffraction peaks in X-ray diffraction spectrogram of the sample obtained in Example 1.

(32) The elemental analysis of the surface composition and the bulk composition of the sample were detected with XPS and XRF, respectively, showing that the ratio of the surface Si content to the bulk Si content Si.sub.surface/Si.sub.bulk was 2.2.

EXAMPLE 22

(33) The sample obtained in Example 1 was calcined at 600 C. for 4 hours in air, then pressed, crushed and sieved to 20-40 mesh. 5.0 g of the sample was added into a batch reactor loaded 30 mL of ethanol to carry out an ethanol dehydration evaluation. The reaction was carried out at 150 C. under stirring. The result showed that ethanol conversion reached 90% and the selectivity for ether in products was 90%.

EXAMPLE 23

(34) The sample obtained in Example 1 was calcined at 600 C. for 4 hours in air, then pressed, crushed and sieved to 20-40 mesh. 1.0 g of a sample was weighted and loaded into a fixed bed reactor to carry out a methanol to olefins reaction evaluation. The sample was activated at 550 C. for 1 hour in nitrogen gas and reduced to 450 C. to perform a reaction. Methanol was carried by nitrogen gas with a flow rate of 40 mL/min and the Weight Hour Space Velocity of the methanol was 2.0 h.sup.1. The reaction products were analyzed by an on-line gas chromatograph (Varian3800, FID detector, capillary column was PoraPLOT Q-HT). The results were shown in Table 3.

(35) TABLE-US-00003 TABLE 3 The result of methanol to olefins on the sample Selectivity (mass %)* Sample Life (min) CH.sub.4 C.sub.2H.sub.4 C.sub.2H.sub.6 C.sub.3H.sub.6 C.sub.3H.sub.8 C.sub.4.sup.+ C.sub.5.sup.+ C.sub.2H.sub.4 + C.sub.3H.sub.6 Example 1 206 1.2 51.0 0.64 37.2 0.64 7.3 1.2 88.2 *The highest (ethylene + propylene) selectivity when methanol conversion was 100%.

COMPARATIVE EXAMPLE 2

(36) The sample obtained in Comparative Example 1 was calcined at 600 C. for 4 hours in air, then pressed, crushed and sieved to 20-40 mesh. 1.0 g of a sample was weighted and loaded into a fixed bed reactor to carry out a methanol to olefins reaction evaluation. The sample was activated at 550 C. for 1 hour in nitrogen gas and reduced to 450 C. to perform a reaction. Methanol was carried by nitrogen gas with a flow rate of 40 mL/min and the Weight Hour Space Velocity of the methanol was 2.0 h.sup.1. The reaction products were analyzed by an on-line gas chromatograph (Varian3800, FID detector, capillary column was PoraPLOT Q-HT). The results were shown in Table 4.

(37) TABLE-US-00004 TABLE 4 The result of methanol to olefins on the sample Selectivity (mass %)* Sample Life (min) CH.sub.4 C.sub.2H.sub.4 C.sub.2H.sub.6 C.sub.3H.sub.6 C.sub.3H.sub.8 C.sub.4.sup.+ C.sub.5.sup.+ C.sub.2H.sub.4 + C.sub.3H.sub.6 Comparative 106 1.37 41.14 0.50 38.60 1.23 12.07 3.97 80.6 Example 1 *The highest (ethylene + propylene) selectivity when methanol conversion was 100%.