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CN112517058B - AEI type molecular sieve and preparation method and application thereof - Google Patents

AEI type molecular sieve and preparation method and application thereof Download PDF

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CN112517058B
CN112517058B CN201910879538.7A CN201910879538A CN112517058B CN 112517058 B CN112517058 B CN 112517058B CN 201910879538 A CN201910879538 A CN 201910879538A CN 112517058 B CN112517058 B CN 112517058B
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molecular sieve
catalyst
type molecular
aei
water
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CN112517058A (en
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赵昱
陆贤
刘红星
申学峰
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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Sinopec Shanghai Research Institute of Petrochemical Technology
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Abstract

The invention discloses an AEI type molecular sieve and a preparation method thereof. The AEI type molecular sieve crystal is flaky crystal with the length of 0.2-1.0 mu m, the width of 0.2-1.0 mu m and the thickness of 20-100 nm, and is prepared by firstly preparing dry glue, and then adding an organic template agent, an organic solvent and water for crystallization. The invention also discloses a process method for preparing the low-carbon olefin by using the oxygen-containing compound, wherein the AEI type molecular sieve provided by the invention is used as a catalyst, and the low-carbon olefin has high selectivity and catalytic activity and good reaction stability.

Description

AEI type molecular sieve and preparation method and application thereof
Technical Field
The invention relates to an AEI type molecular sieve and a preparation method thereof, which are particularly suitable for being used as a catalyst for converting oxygen-containing compounds into low-carbon olefin.
Background
With the rapid development of economy, new energy sources and valuable industrial products are necessary to be searched, and the problem of new energy source supply is particularly important. Low-carbon olefin, C 2 -C 4 Olefins are very important chemical raw materials. Ethylene production is a sign of the state of the art. At present, the prominent problems faced by the production of ethylene and propylene in China are low consumption self-supply rate and prominent contradiction between supply and demand.
The method for preparing the low-carbon olefin mainly comprises a petroleum route and a non-petroleum route. Because of the factors of exhaustion of petroleum resources, serious environmental pollution and the like, petroleum routes are greatly limited, and for China lacking oil and rich in coal, it is imperative to produce low-carbon olefin by a non-petroleum route to replace the original production process. As an important oxygenate to olefins process, the methanol to olefins route has attracted considerable attention as a route to replace the traditional petroleum-based olefin production route because its feedstock is available in large quantities, inexpensively, and conveniently from synthesis gas, which is widely available from coal, biomass, and natural gas. Thus, the preparation of the light olefins from the methanol and the synthesis gas is the most feasible process for preparing the light olefins instead of the petroleum route.
Molecular sieves having an AEI structure were originally synthesized by Wendelbo et al and structurally characterized by Chen et al, and have a structural composition very similar to SAPO-34 molecular sieves having a CHA framework, with the basic structural units being double six-membered rings (D6R). But the AEI and CHA structure molecular sieves are arranged in a distinct manner in a double six-membered ring: the double six-membered rings of two adjacent layers of the CHA molecular sieve are distributed in parallel in the same direction, and the arrangement can lead the whole structure to have skeleton expansion in a certain direction. The two six-membered rings of two adjacent layers of the AEI molecular sieve are distributed in a crossed manner, and the structure leads to strict control of pore size and tighter structure, so that the AEI molecular sieve has higher catalytic activity and stability in the reaction.
Figure BDA0002205458880000021
CN200810043287.0 discloses a catalyst for converting oxygen-containing compound into low-carbon olefin, whose main component is SAPO-34 molecular sieve, and is a flaky crystal, one crystal face has an aspect ratio of less than 4.0, and the other two crystal faces have aspect ratios of more than 4.0. The catalyst is used in the reaction of preparing olefin from methanol, and has high diene selectivity.
CN201510489687.4 discloses a synthesis method and application of AEI structure type molecular sieve. The molecular sieve is prepared by controlling the heating rate to the crystallization temperature, alone or in combination with H 2 O：Al 2 O 3 The molar ratio of the synthesis mixture is such as to increase the yield of the desired molecular sieve product, and can be used in methanol-to-olefins reactions. As can be seen from the test results, the SAPO-18 catalyst prepared more C than the SAPO-34 catalyst 2 -C 4 Olefins and lower selectivity to coke and light saturated compounds.
Zhang Yan (oil and gas chemical industries 2017, 46 (5), 41-46) adopts N, N-diisopropylethylamine as a template agent, synthesizes the SAPO-18 molecular sieve by a hydrothermal method, has a small cube structure with the particle size of 1-2 mu m, is used in MTO reaction, and has a diene selectivity of 76% and a service life of 140min when the silicon-aluminum ratio is 0.2.
For the reaction of converting oxygen-containing compounds into low-carbon olefins, how to further improve the low-carbon olefin selectivity of the catalyst and prolong the service life of the catalyst is an aim in the field.
Disclosure of Invention
Aiming at the problems of poor reaction stability and low-carbon olefin selectivity in the process of preparing low-carbon olefin from an oxygen-containing compound by using a catalyst in the prior art, the invention provides an AEI type molecular sieve, a preparation method thereof and application of the molecular sieve in a process of converting the oxygen-containing compound into the low-carbon olefin. The AEI type molecular sieve is a flaky crystal, and has high low-carbon olefin selectivity and catalytic activity and good reaction stability when being used for preparing low-carbon olefin from oxygen-containing compounds.
The first aspect of the invention provides an AEI type molecular sieve, the crystal morphology of the AEI type molecular sieve is lamellar crystal, the length is 0.2-1.0 mu m, the width is 0.2-1.0 mu m, and the thickness is 20-100 nm.
In a second aspect the invention provides a catalyst for the conversion of oxygenates to lower olefins, said catalyst comprising an AEI type molecular sieve as described above.
In the technical scheme, the AEI type molecular sieve content in the catalyst is 40-100 wt%. The catalyst can also contain alumina and silicon dioxide, wherein the content of the alumina is 0-35 wt percent, the content of the silicon dioxide is 0-25 wt percent, and the content of each component is calculated by taking the weight of the catalyst as the reference.
The third aspect of the invention provides a method for preparing an AEI type molecular sieve, comprising the steps of:
(a) Preparation of the dry adhesive: drying the crystallization liquid comprising a phosphorus source, an aluminum source, water and optionally a silicon source to obtain a dry gel;
(b) Crystallization: grinding the dry gel into powder, and then contacting with an organic template agent, an organic solvent and water to obtain a mixture; crystallizing the mixture to obtain an AEI type molecular sieve; the organic solvent is at least one selected from methanol, ethanol, acetonitrile, ethylene glycol and glycerol.
In the above technical scheme, the drying in the step (a) can be performed by a conventional method, and the drying temperature can be 80-100 ℃.
In the above technical scheme, in the step (a), the phosphorus source is P 2 O 5 Metering Al as Al source 2 O 3 Meter, silicon source with SiO 2 Metering the amount of water, al 2 O 3 ：SiO 2 ：P 2 O 5 ：H 2 The molar ratio of O is 1.0: (0-1.0): (0.8-1.2): (10-50).
In the above technical scheme, the organic template agent is at least two selected from tetraethylammonium hydroxide, triethylamine, N-diisopropylethylamine and morpholine, preferably N, N-diisopropylethylamine and tetraethylammonium hydroxide, or tetraethylammonium hydroxide and morpholine.
In the above technical scheme, the aluminum source in the step (a) is calculated by moleThe molar addition amount is taken as a reference, and in the mixed solution of the organic template agent, the organic solvent and the water in the step (b), the organic template agent, the organic solvent and the water are mixed with Al 2 O 3 The molar ratio of (1.2-2.5): (5-30): (10-50): 1.
in the technical scheme, in the step (b), the obtained dry glue is ground into powder, and the granularity is 20-200 meshes.
In the above technical solution, the crystallization conditions in the step (b) are as follows: crystallizing at 140-210 deg.c for 8-96 hr under autogenous pressure.
In the above technical scheme, after crystallization is finished, the crystallization can be further processed by washing, drying, roasting and other conventional post-treatment methods, for example, the washing can be performed by distilled water, the washing is generally performed until the crystallization is nearly neutral, and the drying conditions are as follows: drying for 4-24 h at 80-100 ℃, wherein the roasting conditions are as follows: roasting for 4-10 h at 550-650 ℃.
In the above technical scheme, a binder may be added to the AEI-type molecular sieve, and the catalyst may be obtained by spray-forming and then calcining. The binder may be at least one of kaolin, aluminum sol and silica sol. Wherein the firing can be performed by a conventional method, and the firing conditions are as follows: roasting for 4-10 h at 550-650 ℃.
The fourth aspect of the invention provides an application of the catalyst in a process for converting an oxygen-containing compound into a low-carbon olefin, which comprises the following steps: and (3) contacting the oxygen-containing compound raw material with the catalyst to react to obtain the low-carbon olefin.
In the above technical scheme, the reactor can adopt a fixed bed reactor or a fluidized bed reactor. The reaction conditions are preferably as follows: the reaction temperature is 350-500 ℃, the reaction pressure is 0-1 MPa, and the weight airspeed is 1-6 h -1 . Wherein the oxygen-containing compound can be at least one of methanol, formaldehyde, ethanol and dimethyl ether, preferably methanol, and the oxygen-containing compound raw material can be pure oxygen-containing compound, crude oxygen-containing compound containing water or oxygen-containing compound containing inert gas.
The AEI type molecular sieve of the invention is used as a catalyst in the reaction of converting oxygen-containing compounds into low-carbon olefin, especially in the reaction of converting methanol into light hydrocarbon, the methanol conversion rate can reach 100%, the low-carbon olefin yield can reach more than 89%, and the service life of the catalyst can reach more than 130 min.
The preparation method of the AEI type molecular sieve of the invention adopts the dry glue of firstly synthesizing aluminum (silicon) phosphate, and then the dry glue is crystallized in the water solution of various templates and organic solvents, and the crystallization process can effectively control the growth mode and direction of crystals, thereby preparing nano flaky crystals.
Drawings
FIG. 1 is an XRD pattern of the AEI structure molecular sieve obtained in example 1;
FIG. 2 is an XRD pattern of the AEI structure molecular sieve obtained in example 2;
FIG. 3 is an XRD pattern of the AEI structure molecular sieve obtained in example 3;
FIG. 4 is an XRD pattern of the AEI structure molecular sieve obtained in comparative example 1;
FIG. 5 is an XRD pattern of the AEI structure molecular sieve obtained in comparative example 2;
FIG. 6 is an XRD pattern of the AEI structure molecular sieve obtained in comparative example 3;
FIG. 7 is an XRD pattern of the AEI structure molecular sieve obtained in comparative example 4;
FIG. 8 is an XRD pattern of the AEI structure molecular sieve obtained in comparative example 5;
FIG. 9 is an XRD pattern of the AEI structure molecular sieve obtained in comparative example 6;
FIG. 10 is a scanning electron microscope image of the AEI structure molecular sieve obtained in example 1;
FIG. 11 is a scanning electron microscope image of the AEI structure molecular sieve obtained in example 2;
FIG. 12 is a scanning electron microscope image of the AEI structure molecular sieve obtained in example 3;
FIG. 13 is a scanning electron microscope image of the AEI structure molecular sieve obtained in comparative example 1;
FIG. 14 is a scanning electron microscope image of the AEI structure molecular sieve obtained in comparative example 2;
FIG. 15 is a scanning electron microscope image of the AEI structure molecular sieve obtained in comparative example 3;
FIG. 16 is a scanning electron microscope image of the AEI structure molecular sieve obtained in comparative example 4;
FIG. 17 is a scanning electron microscope image of the AEI structure molecular sieve obtained in comparative example 5;
FIG. 18 is a scanning electron micrograph of the AEI structure molecular sieve obtained in comparative example 6.
Detailed Description
The present invention is further illustrated by the following examples, but the scope of the present invention is not limited to the examples.
In the context of this specification, the morphology of the catalyst is determined by Scanning Electron Microscopy (SEM). The Scanning Electron Microscope (SEM) of the catalyst is determined by a Nova NanoSEM 450 type scanning electron microscope, a catalyst sample is firstly ground to powder of 200-400 meshes, and the catalyst sample is fixed by double-sided conductive adhesive and then tested in a high vacuum state. The emission voltage of the microscope was 200kV, and the sample size was calculated by manually counting 250-300 particles on the picture.
In the context of this specification, XRD is determined by Bruker D8 polycrystalline X-ray powder diffractometer, using a Cu-K alpha radiation source, K alpha 1 wavelength
Figure BDA0002205458880000061
The voltage is 40kV, the current is 100mA, the scanning angle 2 theta is 5-50 degrees, and the scanning speed is 1 degree/min.
[ comparative example 1 ]
Aluminum isopropoxide, phosphoric acid and N, N-diisopropylethylamine and tetraethylammonium hydroxide are respectively used as an aluminum source, a phosphorus source and a template agent, and the molar ratio of the aluminum isopropoxide to the phosphoric acid to the N, N-diisopropylethylamine is 1.0N: 0.8TEAOH:1.0Al 2 O 3 ：1.0P 2 O 5 ：50H 2 O weighing ingredients, uniformly mixing, loading the reaction mixture into a crystallization kettle with a polytetrafluoroethylene lining, crystallizing for 48 hours at the autogenous pressure of 180 ℃, washing the crystallized product to be neutral by deionized water, separating to obtain a solid, drying in a 100 ℃ oven, and roasting for 6 hours at 550 ℃ in a muffle furnace to obtain the cubic AEI structure molecular sieve, wherein the number is marked as A1. From the XRD of FIG. 4 and the scanning electron microscope of FIG. 13, it can be seen that A1 is a cubic AEI structure molecular sieve.
[ comparative example 2 ]
With alumina, phosphoric acid, silica sol, NThe diisopropylethylamine and tetraethylammonium hydroxide are respectively an aluminum source, a phosphorus source and a template agent, and the molar ratio of the diisopropylethylamine to the tetraethylammonium hydroxide is 0.5N, N-diisopropylethylamine: 1.5TEAOH:1.0Al 2 O 3 ：0.1SiO 2 ：1.0P 2 O 5 ：45H 2 O weighing ingredients, uniformly mixing, loading the reaction mixture into a crystallization kettle with a polytetrafluoroethylene lining, crystallizing for 8 hours at 195 ℃ under autogenous pressure, washing the crystallized product to be neutral by deionized water, separating to obtain a solid, drying in a 100 ℃ oven, and roasting in a muffle furnace at 550 ℃ for 6 hours to obtain the cubic AEI structure molecular sieve, wherein the number is marked as A2. From the XRD of FIG. 5 and the scanning electron microscope of FIG. 14, it can be seen that A2 is a cubic AEI structure molecular sieve.
[ comparative example 3 ]
Pseudo-boehmite, phosphoric acid, tetraethylammonium hydroxide, morpholine and tetraethyl orthosilicate are respectively used as an aluminum source, a phosphorus source and a template agent, and a silicon source is used as a template agent according to the molar ratio of 1.2TEAOH:0.6 morph: 1.0Al 2 O 3 ：1.1P 2 O 5 ：30H 2 O：0.25SiO 2 After being uniformly mixed, the reaction mixture is put into a crystallization kettle with a polytetrafluoroethylene lining, crystallized for 24 hours under the autogenous pressure at 185 ℃, the crystallized product is washed to be neutral by deionized water, the solid is obtained after separation and dried in a drying oven at 100 ℃, and the solid is baked for 6 hours at 550 ℃ in a muffle furnace, so that the cubic AEI structure molecular sieve with the number of A3 is obtained. From the XRD of FIG. 6 and the scanning electron microscope of FIG. 15, it can be seen that A3 is a cubic AEI structure molecular sieve.
[ example 1 ]
Aluminum isopropoxide and phosphoric acid are respectively used as aluminum source and phosphorus source, and the mole ratio is 1.0Al 2 O 3 ：1.0P 2 O 5 ：25H 2 Weighing the ingredients, stirring for 4 hours, drying at 100 ℃ to obtain dry glue, and grinding the dry glue into 100-200 meshes of powder for later use; at a molar ratio of 1.0Al 2 O 3 :1.0N, N-diisopropylethylamine: 0.8TEAOH:25H (25H) 2 O：10CH 3 CH 2 Weighing ingredients N, N-diisopropylethylamine, TEAOH and H by OH 2 O and CH 3 CH 2 OH, stirring uniformly, adding aluminum phosphate dry gel, stirring uniformly, and loading the reaction mixture into a reactor with polymerCrystallizing in a crystallization kettle with a tetrafluoroethylene bushing for 48 hours at a self-generated pressure of 180 ℃, washing a crystallized product to be neutral by deionized water, separating to obtain a solid, drying in a drying oven at 100 ℃, and roasting in a muffle furnace at 550 ℃ for 6 hours to obtain the nano flaky AEI structure molecular sieve, wherein the number is marked as B1. From the XRD of FIG. 1 and the scanning electron microscope of FIG. 10, B1 is a nano-platelet AEI structure molecular sieve.
[ example 2 ]
Alumina, phosphoric acid and silica sol are respectively used as an aluminum source, a phosphorus source and a silicon source, and the molar ratio is 1.0Al 2 O 3 ：0.1SiO 2 ：1.0P 2 O 5 ：25H 2 Weighing the ingredients, stirring for 4 hours, drying at 100 ℃ to obtain dry glue, and grinding the dry glue into 100-200 mesh powder for later use; at a molar ratio of 1.0Al 2 O 3 :0.5N, N-diisopropylethylamine: 1.5TEAOH:20H (H) 2 O：5CH 3 CN weighing ingredients N, N-diisopropylethylamine, TEAOH and H 2 O and CH 3 CN, stirring uniformly, adding aluminum silicophosphate dry gel into the mixture, stirring uniformly, loading the reaction mixture into a crystallization kettle with a polytetrafluoroethylene lining, crystallizing for 8 hours at 195 ℃ under autogenous pressure, washing the crystallized product to be neutral by deionized water, separating to obtain a solid, drying in a 100 ℃ oven, and roasting in a muffle furnace at 550 ℃ for 6 hours to obtain the nano flaky AEI structure molecular sieve with the number of B2. From the XRD of FIG. 2 and the scanning electron microscope of FIG. 11, B2 is a nano-platelet AEI structure molecular sieve.
[ example 3 ]
Pseudo-boehmite, phosphoric acid and tetraethyl orthosilicate are respectively used as an aluminum source, a phosphorus source and a silicon source, and the molar ratio is 1.0Al 2 O 3 ：1.1P 2 O 5 ：20H 2 O：0.25SiO 2 Weighing the ingredients, stirring for 4 hours, drying at 100 ℃ to obtain dry glue, and grinding the dry glue into 100-200 mesh powder for later use; at a molar ratio of 1.0Al 2 O 3 ：1.2TEAOH：0.6Morpholine：10H 2 O：10CH 3 OH weighting ingredients TEAOH, morpholine, H 2 O and CH 3 OH, adding the silicon aluminum phosphate dry gel into the mixture after the mixture is uniformly mixed, stirring the mixture uniformly, and filling the reaction mixture into a polytetrafluoroethylene liningCrystallizing in a crystallization kettle for 24 hours under the autogenous pressure at 185 ℃, washing the crystallized product to be neutral by deionized water, separating to obtain solid, drying in a drying oven at 100 ℃, and roasting in a muffle furnace at 550 ℃ for 6 hours to obtain the nano flaky AEI structure molecular sieve, wherein the number is marked as B3. From the XRD of FIG. 3 and the scanning electron microscope of FIG. 12, B3 is a nano-platelet AEI structure molecular sieve.
[ comparative example 4 ]
In comparison with example 1, no CH is added 3 CH 2 OH to give an AEI structure molecular sieve, designated A4. From the XRD of FIG. 7 and the scanning electron microscope of FIG. 16, it can be seen that A4 is a cubic AEI structure molecular sieve.
[ comparative example 5 ]
In comparison with example 2, no CH is added 3 CN, the molecular sieve with AEI structure is obtained, and the number is marked as A5. From the XRD of FIG. 8 and the scanning electron microscope of FIG. 17, it can be seen that A5 is a cubic AEI structure molecular sieve.
[ comparative example 6 ]
In comparison with example 3, no CH is added 3 OH to give an AEI structure molecular sieve, designated A6. From the XRD of FIG. 9 and the scanning electron microscope of FIG. 18, it can be seen that A6 is a cubic AEI structure molecular sieve.
[ example 4 ]
Catalyst evaluation experiment
The samples obtained in comparative examples 1 to 6 and examples 1 to 3 were designated as A1 to A6 and B1 to B3, respectively, and the particle size fractions of 20 to 40 mesh were obtained by tabletting and crushing the samples. And (3) adopting a fixed bed catalytic reaction device to respectively carry out catalyst evaluation experiments. The experimental conditions are as follows: the catalyst loading is 2.0g, the reaction temperature is 460 ℃, the reaction pressure is 0.1MPa, the weight space velocity of the pure methanol is 4h, and the raw material of the reaction is -1 . The results are shown in Table 1, and compared with A1-A6, the catalyst provided by the invention has higher reaction stability, and the reaction stability and the low-carbon olefin selectivity of B1-B3 are higher than those of A1-A6.
TABLE 1 reaction results of methanol conversion to lower olefins
Figure BDA0002205458880000101
[ example 5 ]
Taking samples A1-A6 and B1-B3 as molecular sieves, alumina as a binder and kaolin as a carrier material, wherein the molecular sieves are 40% by weight: 5% aluminum sol: 20% kaolin: the ingredients were weighed with 35% deionized water and mixed well and then sheared at high speed for 90 minutes in a high speed shear to obtain a suspension prior to spray drying. And (3) spray drying to obtain a catalyst, and roasting at 550 ℃ for 6 hours to obtain a catalyst finished product, wherein the catalyst finished product is respectively named as PA1 to PA6 and PB1 to PB3. And (3) respectively performing catalyst evaluation experiments by adopting a fluidized bed reaction device. The experimental conditions are as follows: the catalyst loading is 40.0g, the reaction temperature is 485 ℃ and the normal pressure, the reaction raw material is pure methanol, and the weight space velocity is 5h -1 . The results are shown in Table 2, and compared with PA1-PA6, the catalyst provided by the invention has higher reaction stability, and the reaction stability and the low-carbon olefin selectivity of PB1-PB3 are higher than those of PA1-PA6.
TABLE 2 reaction results of methanol conversion to lower olefins
Figure BDA0002205458880000111

Claims (11)

1. An AEI type molecular sieve, wherein the crystal morphology of the AEI type molecular sieve is lamellar crystals, the length is 0.2-1.0 mu m, the width is 0.2-1.0 mu m, and the thickness is 20-100 nm;
the preparation method of the molecular sieve comprises the following steps:
(a) Preparation of the dry adhesive: drying the crystallization liquid comprising a phosphorus source, an aluminum source, water and optionally a silicon source to obtain a dry gel;
(b) Crystallization: grinding the dry gel into powder, and then contacting with an organic template agent, an organic solvent and water to obtain a mixture; crystallizing the mixture to obtain an AEI type molecular sieve; the organic solvent is at least one selected from methanol, ethanol, acetonitrile, ethylene glycol and glycerol.
2. A catalyst for the conversion of oxygenates to lower olefins, characterized in that: the catalyst comprising the AEI-type molecular sieve of claim 1; the AEI type molecular sieve is 40-100 wt% of the catalyst, the catalyst contains alumina and silica, wherein the alumina content is 0-35 wt% and the silica content is 0-25 wt%, and the contents of the components are calculated by taking the weight of the catalyst as a reference.
3. The method for preparing the molecular sieve according to claim 1, comprising the steps of:
(a) Preparation of the dry adhesive: drying the crystallization liquid comprising a phosphorus source, an aluminum source, water and optionally a silicon source to obtain a dry gel;
(b) Crystallization: grinding the dry gel into powder, and then contacting with an organic template agent, an organic solvent and water to obtain a mixture; crystallizing the mixture to obtain an AEI type molecular sieve; the organic solvent is at least one selected from methanol, ethanol, acetonitrile, ethylene glycol and glycerol.
4. A method according to claim 3, characterized in that: the organic template agent is at least two selected from tetraethylammonium hydroxide, triethylamine, N-diisopropylethylamine and morpholine.
5. A method according to claim 3, characterized in that: the organic template agent is N, N-diisopropylethylamine and tetraethylammonium hydroxide or tetraethylammonium hydroxide and morpholine.
6. A method according to claim 3 or 4, characterized in that: in step (a), the phosphorus source is P 2 O 5 Metering Al as Al source 2 O 3 Meter, silicon source with SiO 2 Metering the amount of water, al 2 O 3 ：SiO 2 ：P 2 O 5 ：H 2 The molar ratio of O is 1.0: (0-1.0): (0.8-1.2): (10-50); in the mixed solution of the organic template agent, the organic solvent and the water in the step (b), the organic template agent, the organic solvent and the water are used as the basis of the molar addition amount of the aluminum source in the step (a)Al 2 O 3 The molar ratio of (1.2-2.5): (5-30): (10-50): 1.
7. a method according to claim 3, characterized in that: in the step (b), the obtained dry gel is ground into powder with the granularity of 20-200 meshes.
8. A method according to claim 3, characterized in that: the crystallization conditions described in step (b) are as follows: crystallizing for 8-96 h at 140-210 ℃ under autogenous pressure.
9. Use of the catalyst of claim 2 in a process for converting an oxygenate to a lower olefin, the process comprising: and (3) contacting the oxygen-containing compound raw material with the catalyst to react to obtain the low-carbon olefin.
10. The use according to claim 9, characterized in that: a fixed bed reactor or a fluidized bed reactor is adopted, and the reaction conditions are as follows: the reaction temperature is 350-500 ℃, the reaction pressure is 0-1 MPa, and the weight airspeed is 1-6 h -1 The method comprises the steps of carrying out a first treatment on the surface of the Wherein the oxygen-containing compound is at least one of methanol, formaldehyde, ethanol and dimethyl ether.
11. The use according to claim 10, characterized in that: the oxygen-containing compound is methanol.
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