Treatment method of SAPO-34 molecular sieve forming catalyst

Abstract

The invention provides a treatment method of an SAPO-34 molecular sieve formed catalyst, which comprises the following steps: firstly carrying out acid treatment on the formed catalyst to be treated in an acid solution with the pH value of 2-4, then mixing with a template agent and a phosphorus-containing aqueous solution, carrying out crystallization treatment at the temperature of not lower than 120 DEG C, and finally drying and roasting to obtain the SAPO-34 molecular sieve formed catalyst. According to the treatment method provided by the invention, substances such as a carrier and a binder which block molecular sieve micropore channels in the forming process of the SAPO-34 molecular sieve catalyst can be effectively removed, meanwhile, the original microstructure is kept, and the treated catalyst can obtain excellent catalytic activity when being used for catalyzing a methanol-to-olefin reaction; the selectivity of diene (ethylene and propylene) is obviously improved, and the service life of the catalyst is obviously prolonged.

Description

Technical Field

[0001] The invention relates to the field of industrial catalysts, and in particular to a method for treating a SAPO-34 molecular sieve formed catalyst. Background Art

[0002] The methanol to olefins reaction usually uses a solid acid catalyst, namely an MTO catalyst. A common catalyst is a catalyst containing an active species, SAPO-34 molecular sieve. The unique CHA cage structure of the SAPO-34 molecular sieve provides a place for the methanol conversion reaction. At the same time, since the pore size of the eight-membered ring entering and exiting the cage is 0.38nm, which is close to the molecular dynamics diameter of ethylene and propylene, it exhibits high selectivity for ethylene and propylene. However, in order to improve the wear resistance of the methanol to olefins catalyst and the dispersion of the active molecular sieve, clay carriers and binders are often added during the catalyst preparation process, and catalyst microspheres are obtained by mixing and spray drying. During the mixing process, the binder or clay carrier will partially block the micropores of the molecular sieve, which can easily reduce the catalytic effect.

[0003] Chinese patent CN 102319583A provides a method for removing residual silica sol in SAPO-34 molecular sieve products, comprising the following steps: (1) dissolving and / or dispersing the solid SAPO-34 molecular sieve product in water or a mixed solvent formed by an organic solvent and water for 1 to 10 hours to obtain a slurry; (2) subjecting the slurry to solid-liquid separation; (3) drying the solid sample obtained in step (2) at 105 to 120° C. for 8 to 24 hours to obtain pure SAPO-34 molecular sieve raw powder. This patent is aimed at the purification of molecular sieves, and the hidden danger of the carrier and binder blocking the micropores of the molecular sieve during the MTO catalyst molding process cannot be eliminated.

[0004] Chinese patent CN 112062138A discloses a methanol to olefin catalyst and its preparation method and application. The preparation method includes: dispersing aluminum source into water, adding phosphorus source, silicon source and organic template, stirring evenly to form an initial gel mixture; placing the initial gel in a reactor and raising it to a set temperature for crystallization reaction; after the crystallization reaction is completed, distilling and recovering the organic template, and then adding a binder and kaolin to the molecular sieve slurry and mixing evenly; the mixed material is sprayed into balls after rubber grinding, and the balled catalyst and organic template are placed in a solid phase reactor and raised to a set temperature for secondary crystallization reaction, and the organic template is separated after the reaction is completed. In the preparation method provided by the patent, the molecular sieve synthesis mother liquor does not need to be separated. After being directly mixed with kaolin and a binder and sprayed into shape, the silicon source, aluminum source and phosphorus source that are not fully crystallized in the mother liquor are converted into molecular sieve crystals during the solid phase crystallization process, which improves the methanol conversion activity of the catalyst and greatly reduces the mother liquor discharge. However, this patent makes it difficult to ensure that all unreacted raw materials are crystallized into crystals, and the residual part will block the micropores of the original molecular sieve. In addition, during the secondary crystallization process, the proportion of local silicon source, aluminum source, and phosphorus source cannot be accurately controlled to the optimal range, and there is a possibility of crystallization into impure crystals or mixed crystals. Even if a directional molecular sieve is generated, it is difficult to ensure the stability of the physical and chemical properties.

[0005] It can be seen that the prior art pays little attention to the problem of MTO catalyst clogging the micropores of the molecular sieve during the molding process, or fails to provide an effective solution. Summary of the invention

[0006] In order to make up for the deficiencies in the prior art, an object of the present invention is to provide a method for treating a SAPO-34 molecular sieve formed catalyst, which can effectively solve the problem of blockage of the molecular sieve micropores during the catalyst forming process, thereby significantly increasing the micropore volume of the catalyst, thereby improving the catalytic effect and extending the service life of the catalyst.

[0007] Another object of the present invention is to provide a SAPO-34 molecular sieve shaped catalyst and its use.

[0008] Another object of the present invention is to provide a method for preparing olefins from methanol.

[0009] The first aspect of the present invention provides a method for treating a SAPO-34 molecular sieve formed catalyst, comprising the following steps:

[0010] S1: treating the molded catalyst to be treated with acid in an acid solution with a pH value of 2 to 4;

[0011] S2: mixing the formed catalyst treated in step S1 with a template and a phosphorus-containing aqueous solution, and performing a crystallization treatment at a temperature not lower than 120° C.; and

[0012] S3: Drying and calcining the formed catalyst after being treated in step S2.

[0013] The treatment method provided by the present invention first uses an acid solution to wash away the forming reagents blocked in the pores, such as carriers, binders, etc., and then adds a template and a phosphorus species for in-situ crystallization, thereby filling the defects caused by the acid treatment and maintaining the integrity and stability of the molecular sieve framework. The crystallization temperature is set to not less than 120°C, which can ensure that the dissolution rate of the molecular sieve framework during the crystallization process is lower than the crystallization rate, thereby achieving the goal of maintaining the original morphology of the molecular sieve.

[0014] After the above treatment process, the reagents that block the pores can be effectively removed, and the microscopic morphology of the molecular sieve is basically unchanged (such as Figure 1 and Figure 2 Compared with the untreated catalyst, the micropore volume of the catalyst treated by the treatment method of the present invention can be increased by more than 20%. When used for catalyzing the reaction of methanol to olefins, the catalytic effect can be significantly improved and the service life can be significantly extended.

[0015] In the treatment method provided by the present invention, the SAPO-34 molecular sieve shaped catalyst can be any type commonly used in the art, for example, it can be prepared by spray molding of SAPO-34 molecular sieve, a carrier and a binder, and the spray molding process can also be a common process in the art.

[0016] In the treatment method provided by the present invention, the carrier for the SAPO-34 molecular sieve shaped catalyst can be any type commonly used in the art, for example, it can be one or more of kaolin, perlite, and bentonite, and the binder can also be any type commonly used in the art, for example, it can be one or two of silica sol and alumina sol. In some preferred embodiments, the mass ratio of the SAPO-34 molecular sieve, the carrier and the binder can be 2 to 5: 1.5 to 4: 2 to 5. In some more preferred embodiments, the mass ratio of the SAPO-34 molecular sieve, the carrier and the binder can be 3.5 to 4.5: 2 to 3: 3 to 4, for example, it can be 4: 2.5: 3.5.

[0017] In the treatment method provided by the present invention, in step S1, the acid solution can be an aqueous solution of an inorganic acid and / or an organic acid commonly used in the art. In some preferred embodiments, the acid solution can be an aqueous solution formed by one or more of phosphoric acid, nitric acid, hydrochloric acid, oxalic acid, citric acid, tartaric acid, and ethylenediaminetetraacetic acid. In some preferred embodiments, the pH value of the acid solution can further be 2 to 3.

[0018] In the treatment method provided by the present invention, in the step S1, the mass ratio of the molded catalyst to be treated to the acid solution can be 1:5 to 50, for example, about 1:5, about 1:10, about 1:15, about 1:20, about 1:25, about 1:30, about 1:35, about 1:40, about 1:45, about 1:50 or any combination of mass ratio intervals. In some preferred embodiments, the mass ratio of the molded catalyst to be treated to the acid solution can be 1:10 to 30.

[0019] In the treatment method provided by the present invention, in step S1, the treatment temperature of the acid treatment can be 30-80°C, and the treatment time can be 1-10 hours. In some preferred embodiments, the treatment temperature of the acid treatment can be 50-70°C, and the treatment time can be 1-3 hours.

[0020] In the treatment method provided by the present invention, the step S1 further comprises: after the acid treatment is completed, separating the solid, washing it and drying it. In some preferred embodiments, the solid can be dried at 100-120° C. for 1-10 hours.

[0021] In the treatment method provided by the present invention, in the step S2, the mass ratio of the formed catalyst, the template and the phosphorus-containing aqueous solution after the treatment in step S1 can be 1:5-20:1-5, and the mass ratio of the template to the phosphorus-containing aqueous solution is greater than 2. By controlling the proportion of the template, it can be further ensured that the crystallization rate is greater than the dissolution rate during the crystallization process, thereby ensuring the increase in the micropore volume. In some preferred embodiments, the mass ratio of the formed catalyst, the template and the phosphorus-containing aqueous solution after the treatment in step S1 can be 1:8-12:3-5, and the mass ratio of the template to the phosphorus-containing aqueous solution is greater than 3.

[0022] In the treatment method provided by the present invention, the template agent can be an organic amine template agent commonly used in the art, such as one or more of triethylamine, diethylamine, morpholine, tetraethylammonium hydroxide, di-n-propylamine, and diisopropylamine.

[0023] In the treatment method provided by the present invention, the phosphorus-containing aqueous solution can be an aqueous solution formed by one or more of phosphoric acid, ammonium phosphate, diammonium hydrogen phosphate, and ammonium dihydrogen phosphate, wherein, in terms of P2O5, the mass ratio of P2O5 to H2O can be 1 to 4:1, for example, about 1:1, about 1.5:1, about 2:1, about 2.5:1, about 3:1, about 3.5:1, about 4:1, or any combination of mass ratio intervals. By controlling the mass ratio of P2O5 to H2O, the proportion of water can be reduced as much as possible, thereby avoiding excessive dissolution of the molecular sieve framework during the crystallization process.

[0024] In the treatment method provided by the present invention, in step S2, the treatment temperature of the crystallization treatment can be 120-150° C., and the treatment time can be 1-48 hours. In some preferred embodiments, the treatment temperature of the crystallization treatment can be 120-140° C., and the treatment time can be 5-24 hours.

[0025] In the treatment method provided by the present invention, the crystallization treatment in step S2 can be a dynamic treatment process, that is, the material inside the crystallization treatment device (such as a high-pressure crystallization kettle commonly used in the art) is in a dynamic mixing process, thereby improving the mass transfer and heat transfer efficiency of the material. The dynamic treatment method can be any common method in the art, such as connecting an online stirring device for stirring, or placing a rotating device to drive rotation.

[0026] In the treatment method provided by the present invention, the step S2 further comprises: after the crystallization treatment is completed, separating the solid and washing it.

[0027] In the treatment method provided by the present invention, in step S3, the drying temperature can be 100-130°C, the drying time can be 2-16 hours, the roasting temperature can be 500-700°C, and the roasting time can be 2-6 hours. In some preferred embodiments, the drying temperature can be 110-120°C, and the drying time can be 4-10 hours. In other preferred embodiments, the roasting temperature can be 500-600°C, and the roasting time can be 3-5 hours.

[0028] In the treatment method provided by the present invention, the desired material can be obtained through a separation step, and the separation equipment or method can be a common equipment or method in the art, including but not limited to natural sedimentation, (normal pressure or vacuum) filtration, centrifugation and other methods and their common equipment.

[0029] In the treatment method provided by the present invention, the washing step refers to washing the material with distilled water or deionized water until the surface of the material is close to or neutral, and the number of washing times can be adjusted according to actual conditions, for example, it can be 2 to 5 times, usually 3 times.

[0030] In the treatment method provided by the present invention, room temperature refers to 25±5°C.

[0031] The second aspect of the present invention provides a SAPO-34 molecular sieve formed catalyst, which is obtained by treating with the treatment method described in any one of the above technical solutions.

[0032] The third aspect of the present invention provides the use of the SAPO-34 molecular sieve shaped catalyst described in any one of the above technical solutions as a methanol to olefins catalyst (i.e., MTO catalyst).

[0033] A fourth aspect of the present invention provides a method for producing methanol to olefins, which uses the SAPO-34 molecular sieve shaped catalyst described in any one of the above technical solutions as a catalyst.

[0034] In addition to the catalyst, the method for converting methanol to olefins provided by the present invention can be a common process in the art.

[0035] The technical solution provided by the present invention has the following advantages:

[0036] (1) The treatment method of the present invention can effectively remove the carrier, binder and other substances that block the micropores of the SAPO-34 molecular sieve catalyst during the molding process, while maintaining the original microscopic morphology without destroying or changing other physical and chemical properties of the catalyst.

[0037] (2) The catalyst treated by the treatment method of the present invention can achieve excellent catalytic activity when used to catalyze the methanol to olefin reaction, the diene (ethylene + propylene) selectivity is significantly improved, and the catalyst life is also significantly extended.

[0038] (3) The treatment method of the present invention is simple in process, highly operable, and does not require expensive raw materials or reagents, thus having good industrial applicability. BRIEF DESCRIPTION OF THE DRAWINGS

[0039] Figure 1 This is a scanning electron microscope image of catalyst D1 prepared in the preparation example.

[0040] Figure 2 This is a scanning electron microscope image of catalyst S1 prepared in Example 1. DETAILED DESCRIPTION

[0041] The technical solution of the present invention is further described in detail below in conjunction with specific embodiments.

[0042] The raw materials and reagents used in the present invention are all commercially available unless otherwise specified, and the percentages used are all mass percentages unless otherwise specified.

[0043] Preparation Example

[0044] With pseudo-boehmite (70% Al2O3) as the aluminum source, phosphoric acid (85% H3PO4) as the phosphorus source, silica sol (30% SiO2) as the silicon source, triethylamine as the organic template, the aluminum source is calculated as Al2O3, the silicon source is calculated as SiO2, and the phosphorus source is calculated as P2O5. The initial mixed gel is prepared according to the molar ratio of each substance, aluminum source: phosphorus source: silicon source: organic template: water = 1:1:0.3:3.5:50. After uniform dispersion, it is transferred to a high-pressure reactor for crystallization reaction at 200°C for 24 hours. After cooling, separation, deionized water washing and drying, the SAPO-34 molecular sieve is obtained.

[0045] Molecular sieve, aluminum sol (21% Al2O3), and kaolin (85% dry basis) were uniformly mixed according to the dry basis weight percentage of 40%:25%:35%, and the mixture was spray-formed after rubber grinding to obtain methanol to olefin catalyst D1. The pore structure measured by BET is shown in Table 1, and the scanning electron microscope image is shown in Table 1. Figure 1 .

[0046] Example 1

[0047] Prepare citric acid solution with a citric acid concentration of 1.9 g / L. The pH value of the solution was measured at 20°C = 2.6. Mix 20 g of methanol to olefins catalyst D1 with 400 g of citric acid solution (solid-liquid mass ratio of 1:20). Set the temperature to 60°C, stir for 2 h, filter, wash the filter cake with deionized water 3 times, and dry at 120°C for 6 h. Mix the dried filter cake with triethylamine and phosphoric acid aqueous solution (wherein the mass ratio of P2O5: water = 1:1) in a mass ratio of 1:10:3, transfer to a high-pressure crystallization reactor, heat to 120°C, dynamically treat for 6 h, cool, filter, wash the filter cake with deionized water 3 times, dry at 120°C for 6 h, and calcine at 550°C for 4 h to obtain an improved methanol to olefins catalyst S1. The BET pore structure is shown in Table 1, and the scanning electron microscope image is shown in Table 1. Figure 2 .

[0048] pass Figure 1 and Figure 2 By comparison, it can be seen that the morphology of the catalyst before and after the process treatment of Example 1 did not change significantly.

[0049] Example 2

[0050] The difference from Example 1 is that citric acid is replaced by phosphoric acid, the phosphoric acid concentration is 0.49 g / L, the solution pH is measured at 20°C = 2.4, and the remaining steps are the same as Example 1. The obtained improved methanol to olefins catalyst is recorded as S2, and the BET measured pore structure is shown in Table 1.

[0051] Example 3

[0052] The difference from Example 1 is that triethylamine is replaced by diethylamine, and the other steps are the same as Example 1. The obtained improved methanol to olefins catalyst is recorded as S3, and the pore structure determined by BET is shown in Table 1.

[0053] Example 4

[0054] The difference from Example 1 is that the mass ratio of the dry filter cake to triethylamine and phosphoric acid aqueous solution is 1:10:5, and the remaining steps are the same as Example 1. The obtained improved methanol to olefins catalyst is recorded as S4, and the pore structure determined by BET is shown in Table 1.

[0055] Example 5

[0056] The difference from Example 1 is that in the phosphoric acid aqueous solution used, the mass ratio of P2O5:water is 3:1, and the remaining steps are the same as those in Example 1. The obtained improved methanol to olefins catalyst is recorded as S5, and the pore structure determined by BET is shown in Table 1.

[0057] Example 6

[0058] The difference from Example 1 is that the phosphoric acid aqueous solution is replaced by an ammonium phosphate aqueous solution, wherein the mass ratio of P2O5:water is 2:1, and the remaining steps are the same as those in Example 1. The obtained improved methanol to olefins catalyst is denoted as S6, and the pore structure determined by BET is shown in Table 1.

[0059] Example 7

[0060] The difference from Example 1 is that the temperature in the high-pressure crystallization reactor is raised to 140° C. and the dynamic treatment is performed for 20 h. The remaining steps are the same as those in Example 1. The obtained improved methanol to olefins catalyst is recorded as S7. The pore structure determined by BET is shown in Table 1.

[0061] Comparative Example 1

[0062] The difference from Example 1 is that after the mixture of the dried filter cake and triethylamine and phosphoric acid aqueous solution is transferred to a high-pressure crystallization kettle, the temperature is raised to 100° C. and dynamically treated for 6 hours. The remaining steps are the same as in Example 1. The obtained methanol to olefins catalyst is recorded as D2, and the pore structure determined by BET is shown in Table 1.

[0063] Comparative Example 2

[0064] The difference from Example 1 is that the mass ratio of the dry filter cake to triethylamine and phosphoric acid aqueous solution is 1:2:10, and the remaining steps are the same as Example 1. The obtained methanol to olefin catalyst is recorded as D3, and the pore structure determined by BET is shown in Table 1.

[0065] Comparative Example 3

[0066] The difference from Example 1 is that: the citric acid solution is mixed with the catalyst D1 for acid treatment, and after filtering, washing, drying and other steps, it is no longer crystallized in situ, and the dried filter cake is directly calcined at 550° C. for 4 h. The obtained methanol to olefins catalyst is recorded as D4, and the pore structure determined by BET is shown in Table 1.

[0067] Table 1 Pore structure properties of each catalyst

[0068]

[0069] It can be seen from the results of Table 1 that when the crystallization temperature is low (Comparative Example 1), the dissolution rate is greater than the crystallization rate, which causes the dissolution of the molecular sieve framework, and the micropore volume of catalyst D2 is even lower than before the treatment. Similarly, when the amount of phosphoric acid aqueous solution is large (Comparative Example 2), excessive dissolution will also cause a decrease in the micropore volume of catalyst D3. Furthermore, if only acid treatment is performed without repairing the molecular sieve framework (Comparative Example 3), even if the reagents that block the micropore channels are removed, the micropore volume is not increased, because the molecular sieve framework defects generated during the acid treatment process.

[0070] The treatment process of Examples 1-7 of the present invention can improve the pore structure properties of the molecular sieve. Compared with the untreated catalyst D1, various properties have obvious changes, especially the increase of micropore volume, which is very beneficial to the improvement of catalytic performance.

[0071] Test Example Catalyst Performance Evaluation

[0072] The catalyst performance was evaluated using a fixed fluidized bed reactor with a feed of 80% methanol aqueous solution, a reaction temperature of 480°C, and a space velocity of 1.5 h -1 , the catalyst loading amount is 10g.

[0073] Specific steps: the catalyst is loaded into a stainless steel reaction tube, the temperature is raised to 500°C for activation for 1h, the temperature is lowered to 480°C, a methanol aqueous solution is introduced, online sampling is adopted, the product is separated by condensation, and the gas phase components enter the gas chromatograph (Agilent, 7890A model) for composition analysis, equipped with HP-PLOT Al2O3 / KCl chromatographic column (50m×0.53mm×15μm) (for separation of C1-C6 hydrocarbons), HP-PLOT Q chromatographic column (30m×320μm×20μm) (for separation of alcohols and ethers), Hayesep Q column and X molecular sieve column (for separation of permanent gases such as CO, CO2, H2, N2), 2 FID detectors and 1 TCD detector.

[0074] Methanol conversion (X) and product selectivity (Si) are calculated based on the moles of carbon and carbon-based selectivity, respectively, by the following equations:

[0075]

[0076] Wherein, X is methanol conversion rate; S is product selectivity; i is species entering the reactor; o is species exiting the reactor; CxHy is olefin (x is the number of carbon atoms of hydrocarbon species, y is the number of hydrogen atoms of hydrocarbon species); m is the number of carbon atoms of the corresponding substance CxHy; n is the number of moles of the corresponding substance; MeOH is methanol; DME is dimethyl ether.

[0077] When the methanol conversion rate in the test component is lower than 99%, the catalyst is considered to be deactivated. The catalyst life is the time during which the methanol conversion rate is maintained above 99%. The test results are shown in Table 2.

[0078] Table 2 Methanol conversion reaction life and product selectivity test results

[0079]

[0080]

[0081] It can be seen from the results in Table 2 that changes in the pore structure of the catalyst can bring about changes in the catalytic performance. Compared with the untreated catalyst D1, the catalysts obtained in Examples 1-7 of the present invention can achieve significantly better catalytic activity, high diene selectivity, and significantly longer service life.

[0082] Unless otherwise defined, the terms used in the present invention have the meanings commonly understood by those skilled in the art.

[0083] The embodiments described in the present invention are for illustrative purposes only and are not intended to limit the scope of protection of the present invention. Those skilled in the art may make various other substitutions, changes and improvements within the scope of the present invention. Therefore, the present invention is not limited to the above embodiments, but is only limited by the claims.

Claims

1. A method for treating a SAPO-34 molecular sieve formed catalyst, characterized in that: The following steps are involved: S1: treating the molded catalyst to be treated with acid in an acid solution with a pH value of 2 to 4; S2: mixing the formed catalyst treated in step S1 with a template and a phosphorus-containing aqueous solution, and performing a crystallization treatment at a temperature not lower than 120° C.; and S3: Drying and calcining the formed catalyst after being treated in step S2.

2. The processing method according to claim 1, characterized in that: The SAPO-34 molecular sieve shaped catalyst is prepared by spraying the SAPO-34 molecular sieve, a carrier and a binder; Preferably, the carrier is one or more of kaolin, perlite, and bentonite, and the binder is silica sol and / or alumina sol; More preferably, the mass ratio of the SAPO-34 molecular sieve, the carrier and the binder is 2-5:1.5-4:2-5.

3. The processing method according to claim 1 or 2, characterized in that: In step S1, the acid solution is an aqueous solution formed by one or more of phosphoric acid, nitric acid, hydrochloric acid, oxalic acid, citric acid, tartaric acid, and ethylenediaminetetraacetic acid; and / or The mass ratio of the shaped catalyst to be treated to the acid solution is 1:5-50, preferably 1:10-30.

4. The processing method according to any one of claims 1 to 3, characterized in that: In the step S1, the acid treatment temperature is 30 to 80° C. and the treatment time is 1 to 10 hours; and / or After the acid treatment is complete, the solid is separated off, washed and dried.

5. The processing method according to any one of claims 1 to 4, characterized in that: In the step S2, the mass ratio of the formed catalyst, the template and the phosphorus-containing aqueous solution after the treatment in step S1 is 1:5-20:1-5, and the mass ratio of the template to the phosphorus-containing aqueous solution is greater than 2; Preferably, the template is an organic amine template, more preferably one or more of triethylamine, diethylamine, morpholine, tetraethylammonium hydroxide, di-n-propylamine, and diisopropylamine; and / or The phosphorus-containing aqueous solution is an aqueous solution formed by one or more of phosphoric acid, ammonium phosphate, diammonium hydrogen phosphate, and ammonium dihydrogen phosphate, wherein, calculated as P2O5, the mass ratio of P2O5 to H2O is 1 to 4:

1.

6. The processing method according to any one of claims 1 to 5, characterized in that: In the step S2, the crystallization treatment is performed at a temperature of 120 to 150° C. and for a time of 1 to 48 hours; and / or After the crystallization process is complete, the solid is separated and washed.

7. The processing method according to any one of claims 1 to 6, characterized in that: In step S3, the drying temperature is 100-130° C., the drying time is 2-16 hours, the roasting temperature is 500-700° C., and the roasting time is 2-6 hours.

8. A SAPO-34 molecular sieve formed catalyst, obtained by treating with the treatment method according to any one of claims 1 to 7.

9. Use of the SAPO-34 molecular sieve shaped catalyst according to claim 8 as a methanol to olefins catalyst.

10. A method for preparing olefins from methanol, characterized in that: The SAPO-34 molecular sieve shaped catalyst according to claim 8 is used as a catalyst.

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