CN109833904B - Acid-base bifunctional catalyst, preparation method thereof and application thereof in ethanol conversion reaction - Google Patents
Acid-base bifunctional catalyst, preparation method thereof and application thereof in ethanol conversion reaction Download PDFInfo
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
The application discloses an acid-base bifunctional catalyst, a preparation method thereof and application of the acid-base bifunctional catalyst in a reaction for preparing olefin by ethylene conversion. The acid-base bifunctional catalyst is characterized by comprising a tin-doped beta molecular sieve and magnesium oxide; wherein the mass content of the tin-doped beta molecular sieve in the acid-base bifunctional catalyst is 10-90%; the mass content of the magnesium oxide in the acid-base bifunctional catalyst is 10-90%. The catalyst is prepared by a deposition precipitation method by compounding a tin-doped beta molecular sieve and magnesium oxide according to a certain proportion. The acid-base bifunctional catalyst can realize acid-base synergistic action by component modulation, overcomes the problem that the acidity and the basicity of the catalyst in the field are difficult to regulate in the prior art, efficiently catalyzes ethanol conversion, selectively generates chemicals such as 1, 3-butadiene, ethylene, 1-butene and the like, has simple preparation process and strong operability, and can be used for large-scale industrial production.
Description
Technical Field
The application relates to an acid-base bifunctional catalyst and a preparation method thereof, which can be used for catalyzing ethanol dehydration, dehydrogenation and condensation reactions to selectively generate chemicals such as 1, 3-butadiene, 1-butene, ethylene and the like, and belongs to the field of catalytic synthesis.
Background
1, 3-butadiene, 1-butene and ethylene are important organic chemical raw materials and have very wide application, and the production of the raw materials mainly depends on petroleum refining process. With the increasing depletion of petroleum resources and the increase of carbon emission pressure, it is of great importance to find other raw material resources or develop new production paths.
Ethanol can be converted to these olefin products over a suitable catalyst (chem.soc.rev.,2014,43, 7917; ACS catal.2017,7,3703). However, the traditional industrial production mode of ethanol is mainly based on a biological fermentation process, so that the preparation of olefin by ethanol conversion is limited by various aspects such as cost, grain yield and the like. Recently, with the successful development of coal-to-ethanol technology, the production cost of ethanol will be further reduced greatly. Therefore, the method has practical significance for producing high-value olefin by using ethanol conversion instead of the traditional route.
The traditional catalysts for preparing olefin by ethanol conversion mainly comprise composite metal oxide, magnesia/silica and sepiolite (J.appl.chem.,1962,105; Catal.Sci.Technol.,2017,7, 168; Catal.Lett.,1995,34,359), wherein the magnesia/silica catalyst has better activity and selectivity and is used for early industrial production, but the regulation of the acidity and alkalinity of the catalyst is always a difficult point. The reaction process of preparing olefin by converting ethanol requires acid-base concerted catalysis, so whether the acidity and the alkalinity of the catalyst can be optimally regulated or controlled is a key consideration factor for developing a new catalyst in the reaction process.
Disclosure of Invention
According to one aspect of the application, the acid-base bifunctional catalyst is provided, the acid-base synergistic effect can be realized by modulating the components, the problem that the acidity and the alkalinity of the catalyst in the field are difficult to regulate in the prior art is solved, ethanol conversion is efficiently catalyzed, high-value olefins such as 1, 3-butadiene, ethylene, 1-butene and the like are selectively generated, the preparation process is simple, the operability is high, and large-scale industrial production can be carried out.
The acid-base bifunctional catalyst is characterized by comprising a tin-doped beta molecular sieve and magnesium oxide; wherein the mass content of the tin-doped beta molecular sieve in the acid-base bifunctional catalyst is 10-90%; the mass content of the magnesium oxide in the acid-base bifunctional catalyst is 10-90%.
Preferably, the mass content of the tin-doped beta molecular sieve in the acid-base bifunctional catalyst is 30-90%.
Preferably, the acid-base bifunctional catalyst is prepared by compounding a tin-doped beta molecular sieve and magnesium oxide.
Preferably, in the tin-doped beta molecular sieve, the molar ratio of silicon element to tin element is 40-200: 1.
according to another aspect of the present application, a method for preparing the above acid-base bifunctional catalyst is provided. The method has simple process, and the prepared catalyst has stable product performance and can realize large-scale industrial production.
The method for preparing the acid-base bifunctional catalyst at least comprises the following steps:
a) obtaining a tin-doped beta molecular sieve;
b) putting the tin-doped beta molecular sieve into a solution containing magnesium ions, and adding an alkali solution to adjust the pH value;
c) and drying and roasting the solid obtained by separation and washing to obtain the acid-base bifunctional catalyst.
The tin doped beta molecular sieve may be obtained from commercial sources, prepared according to the description in the prior art, or prepared according to the methods described in the present application.
As a preferred mode, the tin-doped beta molecular sieve is prepared by a preparation method at least comprising the following steps:
(1) dealuminizing the H-beta molecular sieve;
(2) and mixing and grinding the dealuminized H-beta molecular sieve and a tin precursor, and roasting to obtain the tin-doped beta molecular sieve.
The source of the H-beta molecular sieve can be selected by those skilled in the art as the case may be, and can be obtained commercially or prepared according to the description in the prior art.
Preferably, the H- β molecular sieve has a silica to alumina molar ratio of SiO2/Al2O312.5 to 50, further preferably, the H- β molecular sieve has a molar ratio of Si to Al to SiO2/Al2O3＝20～30。
In one embodiment, the dealumination treatment is to put the H-beta molecular sieve into a nitric acid solution with a concentration of 10-14mol/L, and keep the H-beta molecular sieve at a temperature of not less than 50-90 ℃ for not less than 7-30 hours.
Preferably, the dealuminization treatment is to place the H-beta molecular sieve in a nitric acid solution with the mass concentration of 65-68% and keep the H-beta molecular sieve at the temperature of not less than 75-85 ℃ for not less than 8-20 hours.
In one embodiment, in the dealumination treatment, the solid-to-liquid ratio of the H-beta molecular sieve to the nitric acid solution is 1 g: 15-100 mL. Preferably, in the dealumination treatment, the solid-to-liquid ratio of the H-beta molecular sieve to the nitric acid solution is 1 g: 20-40 mL.
In one embodiment, the solution containing magnesium ions is obtained by dissolving magnesium salts in water. Preferably, the magnesium salt is magnesium nitrate and/or magnesium acetate.
The concentration of the magnesium ion-containing solution and the ratio of the magnesium ion-containing solution to the tin-doped beta molecular sieve can be selected by one skilled in the art according to specific needs. As a specific embodiment, in the step b), the ratio of the mole number of the magnesium element in the solution containing magnesium ions to the mass of the tin-doped beta molecular sieve is 0.25 to 6 mmol: 1g of the total weight of the composition.
The kind of the tin precursor can be selected by those skilled in the art according to the actual needs. Preferably, the tin precursor is at least one of crystalline stannic chloride, dimethylstannic chloride, stannous chloride or stannous oxalate.
In one embodiment, the molar ratio of the silicon element in the H- β molecular sieve after the dealumination treatment to the tin element in the tin precursor is:
Si：Sn＝40～200：1；
as an embodiment, the mass ratio of the dealuminated H- β molecular sieve to the tin precursor is 2: 0.05 to 0.3. Preferably, the mass ratio of the dealuminated H-beta molecular sieve to the tin precursor is 2: 0.058 to 0.29.
Preferably, the step of adding the alkali solution to adjust the pH value is to add the alkali solution to adjust the pH value of the system to 10-12.
Preferably, the alkali solution is selected from ammonia and/or sodium hydroxide solution. Further preferably, the concentration of the ammonia water and/or the sodium hydroxide solution is 1 mol/L.
As a specific embodiment, the method for preparing the acid-base bifunctional catalyst comprises the following steps: and (2) placing the tin-doped beta molecular sieve into a magnesium precursor water solution, adding an alkali solution to adjust the pH value to 10-12, filtering, washing and drying the obtained solid product, and roasting the solid product in the air at 500 ℃ for 4 hours to obtain the tin-doped beta molecular sieve.
As a specific embodiment, the preparation method of the tin-doped beta molecular sieve comprises the following steps:
(1) dealuminizing an H-beta molecular sieve (the molar ratio of silicon to aluminum is 12.5-50) by using 10-14mol/L nitric acid, and washing and drying an obtained product;
(2) and mixing and grinding the dealuminized beta molecular sieve and a tin precursor, and roasting at 550 ℃ to obtain the tin-doped beta molecular sieve.
According to a further aspect of the present application, there is provided the use of the above-mentioned acid-base bifunctional catalyst, and the acid-base bifunctional catalyst prepared according to any of the above-mentioned methods, as a catalyst in a reaction process for producing olefins by ethanol conversion.
The ethanol conversion comprises one of ethanol dehydration, ethanol dehydrogenation and ethanol condensation.
Preferably, the reaction for preparing olefin by ethanol conversion is at least one of the reaction for preparing 1, 3-butadiene by ethanol conversion, the reaction for preparing ethylene by ethanol conversion and the reaction for preparing 1-butene by ethanol conversion.
Benefits of the present application include, but are not limited to:
(1) the application provides an acid-base bifunctional catalyst which can realize an acid-base synergistic effect by component modulation, and efficiently catalyze ethanol to selectively generate high-value olefins such as 1, 3-butadiene, ethylene, 1-butene and the like.
(2) The application provides a preparation method of the acid-base bifunctional catalyst, which is simple in preparation process, strong in operability and capable of carrying out large-scale industrial production.
Detailed Description
The present application will be described in detail with reference to examples, but the present application is not limited to these examples.
The raw materials used in the present application are commercially available without specific description and are used without specific treatment.
In this application, the H-beta molecular sieves employed are purchased from catalyst works of southern Kai university.
EXAMPLE 1 preparation of the catalyst
Taking 5g H- β molecular Sieve (SiO)2/Al2O325) is dispersed into 100mL nitric acid solution with the concentration of 14mol/L, stirred for 8h at 80 ℃, filtered, washed and dried to obtain a dealuminized β molecular sieve, 2g of dealuminized β molecular sieve is mixed with 0.29g of crystallized tin tetrachloride and ground for 10min, and the obtained powder is roasted for 4h at 550 ℃ in air atmosphere to obtain the tin-doped β molecular sieve.
Dissolving 1.42g of magnesium nitrate hexahydrate in 80mL of deionized water, adding 2g of tin-doped β molecular sieve, dropwise adding 1mol/L sodium hydroxide aqueous solution into the solution until the pH value of the system is equal to 12, continuously stirring for 6h at room temperature, filtering, washing until the filtrate is neutral, drying the product at 100 ℃, roasting for 4h at 500 ℃ to obtain the Sn- β/MgO catalyst, and marking as a sample 1#。
EXAMPLE 2 preparation of the catalyst
Taking 5g H- β molecular Sieve (SiO)2/Al2O325) is dispersed in 100mL nitric acid solution with the concentration of 14mol/L, the mixture is stirred for 8 hours at the temperature of 80 ℃, filtration, washing and drying are carried out, thus obtaining the dealuminized β molecular sieve, 2g dealuminized β molecular sieve is taken and mixed with 0.29g crystallized tin tetrachloride and ground for 10 minutes, and the obtained powder is roasted for 4 hours at the temperature of 550 ℃ in air atmosphere, thus obtaining the tin-doped β molecular sieve.
Dissolving 2.88g of magnesium nitrate hexahydrate in 80mL of deionized water, adding 0.5g of tin-doped β molecular sieve, dropwise adding 1mol/L ammonia water solution into the solution until the pH value of the system is equal to 12, continuously stirring for 6h at room temperature, filtering, washing until the filtrate is neutral, drying the product at 100 ℃, roasting for 4h at 500 ℃ to obtain a Sn- β/MgO catalyst, and marking as a sample 2#。
EXAMPLE 3 preparation of the catalyst
Taking 5g H- β molecular Sieve (SiO)2/Al2O36.25) is dispersed in 100mL nitric acid solution with the concentration of 10mol/L, stirred for 8h at 80 ℃, filtered, washed and dried to obtain dealuminized β molecular sieve, 2g dealuminized β molecular sieve is taken and mixed with 0.058g crystallized stannic chloride and ground for 10min to obtain powderAnd finally roasting the mixture for 4 hours at 550 ℃ in an air atmosphere to obtain the tin-doped β molecular sieve.
Dissolving 1.42g of magnesium nitrate hexahydrate in 80mL of deionized water, adding 2g of tin-doped β molecular sieve, dropwise adding 1mol/L of sodium hydroxide aqueous solution into the solution until the pH value of the system is equal to 10, continuously stirring for 6 hours at room temperature, filtering, washing until the filtrate is neutral, drying the product at 100 ℃, roasting for 4 hours at 500 ℃ to obtain the Sn- β/MgO catalyst, and marking as a sample 3#。
EXAMPLE 4 preparation of the catalyst
Taking 5g H- β molecular Sieve (SiO)2/Al2O315) is dispersed in 100mL nitric acid solution with the concentration of 12mol/L, the mixture is stirred for 8 hours at 80 ℃, and is filtered, washed and dried to obtain a dealuminized β molecular sieve, 2g of dealuminized β molecular sieve is mixed with 0.29g of crystallized tin tetrachloride and is ground for 10 minutes, and the obtained powder is roasted for 4 hours at 550 ℃ in air atmosphere to obtain the tin-doped β molecular sieve.
Dissolving 0.22g of magnesium nitrate hexahydrate in 80mL of deionized water, adding 2g of tin-doped β molecular sieve, dropwise adding 1mol/L ammonia water solution into the solution until the pH value of the system is equal to 10, continuously stirring for 6 hours at room temperature, filtering, washing until the filtrate is neutral, drying the product at 100 ℃, roasting for 4 hours at 500 ℃ to obtain a Sn- β/MgO catalyst, and marking as a sample 4#。
EXAMPLE 5 preparation of the catalyst
Taking 5g H- β molecular Sieve (SiO)2/Al2O320) is dispersed into 100mL nitric acid solution with the concentration of 14mol/L, the mixture is stirred for 8 hours at the temperature of 80 ℃, filtration, washing and drying are carried out, thus obtaining the dealuminized β molecular sieve, 2g dealuminized β molecular sieve is taken and mixed with 0.29g crystallized tin tetrachloride and ground for 10 minutes, and the obtained powder is roasted for 4 hours at the temperature of 550 ℃ in air atmosphere, thus obtaining the tin-doped β molecular sieve.
Dissolving 5.36g of magnesium acetate tetrahydrate in 80mL of deionized water, adding 2g of tin-doped β molecular sieve, dropwise adding 1mol/L sodium hydroxide aqueous solution into the solution until the pH value of the system is equal to 12, continuously stirring for 6h at room temperature, filtering, washing until the filtrate is neutral, drying the product at 100 ℃, roasting for 4h at 500 ℃ to obtain the Sn- β/MgO catalyst, and marking as a sample 5#。
EXAMPLE 6 preparation of the catalyst
Taking 5g H- β molecular Sieve (SiO)2/Al2O325) is dispersed in 100mL nitric acid solution with the concentration of 14mol/L, the mixture is stirred for 8 hours at the temperature of 80 ℃, filtration, washing and drying are carried out, thus obtaining dealuminized β molecular sieve, 2g dealuminized β molecular sieve is taken and mixed with 0.18g dimethyltin dichloride and ground for 10 minutes, and the obtained powder is roasted for 4 hours at the temperature of 550 ℃ in air atmosphere, thus obtaining the tin-doped β molecular sieve.
Dissolving 1.42g of magnesium nitrate hexahydrate in 80mL of deionized water, adding 2g of tin-doped β molecular sieve, dropwise adding 1mol/L sodium hydroxide aqueous solution into the solution until the pH value of the system is equal to 12, continuously stirring for 6 hours at room temperature, filtering, washing until the filtrate is neutral, drying the product at 100 ℃, roasting for 4 hours at 500 ℃ to obtain the Sn- β/MgO catalyst, and marking as a sample 6#。
EXAMPLE 7 preparation of the catalyst
Taking 5g H- β molecular Sieve (SiO)2/Al2O325) is dispersed in 100mL nitric acid solution with the concentration of 14mol/L, the mixture is stirred for 8 hours at the temperature of 80 ℃, filtration, washing and drying are carried out, thus obtaining dealuminized β molecular sieve, 2g dealuminized β molecular sieve is taken and mixed with 0.18g dimethyltin dichloride and ground for 10 minutes, and the obtained powder is roasted for 4 hours at the temperature of 550 ℃ in air atmosphere, thus obtaining the tin-doped β molecular sieve.
Dissolving 1.42g of magnesium nitrate hexahydrate in 80mL of deionized water, adding 2g of tin-doped β molecular sieve, dropwise adding 1mol/L ammonia water solution into the solution until the pH value of the system is equal to 11, continuously stirring for 6 hours at room temperature, filtering, washing until the filtrate is neutral, drying the product at 100 ℃, roasting at 500 ℃ for 4 hours to obtain a Sn- β/MgO catalyst, and marking as a sample 7#。
EXAMPLE 8 preparation of the catalyst
Taking 5g H- β molecular Sieve (SiO)2/Al2O325) is dispersed into 100mL nitric acid solution with the concentration of 14mol/L, the mixture is stirred for 8 hours at the temperature of 80 ℃, filtration, washing and drying are carried out, thus obtaining dealuminized β molecular sieve, 2g dealuminized β molecular sieve is mixed with 0.16g stannous chloride and ground for 10 minutes, and the obtained powder is roasted for 4 hours at the temperature of 550 ℃ in air atmosphere, thus obtaining the tin-doped β molecular sieve.
Dissolving 1.42g of magnesium nitrate hexahydrate in 80mL of deionized water, adding 2g of tin-doped β molecular sieve, dropwise adding 1mol/L sodium hydroxide aqueous solution into the solution until the pH value of the system is equal to 12, continuously stirring for 6h at room temperature, filtering, washing until the filtrate is neutral, drying the product at 100 ℃, roasting for 4h at 500 ℃ to obtain a Sn- β/MgO catalyst, and marking as a sample 8#。
EXAMPLE 9 preparation of the catalyst
Taking 5g H- β molecular Sieve (SiO)2/Al2O325) is dispersed into 100mL nitric acid solution with the concentration of 14mol/L, the mixture is stirred for 8 hours at the temperature of 80 ℃, filtration, washing and drying are carried out, thus obtaining the dealuminized β molecular sieve, 2g of the dealuminized β molecular sieve is mixed with 0.17g of stannous oxalate and ground for 10 minutes, and the obtained powder is roasted for 4 hours at the temperature of 550 ℃ in air atmosphere, thus obtaining the tin-doped β molecular sieve.
Dissolving 1.42g of magnesium nitrate hexahydrate in 80mL of deionized water, adding 2g of tin-doped β molecular sieve, dropwise adding 1mol/L sodium hydroxide aqueous solution into the solution until the pH value of the system is equal to 12, continuously stirring for 6h at room temperature, filtering, washing until the filtrate is neutral, drying the product at 100 ℃, roasting for 4h at 500 ℃ to obtain the Sn- β/MgO catalyst, and marking as a sample 9#。
EXAMPLE 10 use of the catalyst
0.5g of Sn- β/MgO catalyst sample 1 which is subjected to tabletting and screening by a 40-60-mesh sieve is respectively taken#Sample 2#Sample 3#Sample 6#Sample 7#Sample No. 8#Sample 9#(the mass content of the molecular sieve is 50 percent), the mixture is put into a fixed bed reactor, the pretreatment is carried out for 30min at 450 ℃ in nitrogen atmosphere, then the temperature is reduced to 425 ℃, the raw material ethanol is introduced to start the reaction, the flow rate of the ethanol is 0.017mL/min, the flow rate of the nitrogen is 50mL/min, and the analysis is carried out after the reaction is carried out for 30 min.
Product analysis was performed on-line using Tianmei gas chromatography 7900, FID detector, HP-PLOT Q capillary column.
The results show that sample 1#Sample 2#Sample 3#Sample 6#Sample 7#Sample No. 8#Sample (ii) and a method for producing the same9#The results are similar, and both have higher selectivity of 1, 3-butadiene and selectivity of ethylene.
With sample 1#As a representative, the reaction results: the ethanol conversion rate was 77%, the 1, 3-butadiene selectivity was 50%, and the ethylene selectivity was 34%.
EXAMPLE 11 use of the catalyst
0.5g of Sn- β/MgO catalyst sample 4 which is pressed into tablets and sieved by a 40-60 mesh sieve is taken#(the mass content of the molecular sieve is 90 percent), the mixture is put into a fixed bed reactor, the pretreatment is carried out for 30min at 450 ℃ in nitrogen atmosphere, then the temperature is reduced to 425 ℃, the raw material ethanol is introduced to start the reaction, the flow rate of the ethanol is 0.017mL/min, the flow rate of the nitrogen is 50mL/min, and the analysis is carried out after the reaction is carried out for 30 min.
Product analysis was performed on-line using Tianmei gas chromatography 7900, FID detector, HP-PLOT Q capillary column.
And (3) reaction results: ethanol conversion 90%, 1, 3-butadiene selectivity 5%, ethylene selectivity 90%.
EXAMPLE 12 use of the catalyst
0.5g of Sn- β/MgO catalyst sample 5 which is pressed into tablets and sieved by a 40-60 mesh sieve is taken#(the mass content of the molecular sieve is 30 percent), the mixture is put into a fixed bed reactor, the pretreatment is carried out for 30min at 450 ℃ in nitrogen atmosphere, then the temperature is reduced to 425 ℃, the raw material ethanol is introduced to start the reaction, the flow rate of the ethanol is 0.017mL/min, the flow rate of the nitrogen is 50mL/min, and the analysis is carried out after the reaction is carried out for 30 min.
Product analysis was performed on-line using Tianmei gas chromatography 7900, FID detector, HP-PLOT Q capillary column.
And (3) reaction results: the ethanol conversion rate is 80%, the 1, 3-butadiene selectivity is 60%, and the ethylene selectivity is 8%.
Although the present application has been described with reference to a few embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the application as defined by the appended claims.
Claims (11)
1. An acid-base bifunctional catalyst for the reaction of preparing olefin by ethanol conversion is characterized by consisting of a tin-doped beta molecular sieve and magnesium oxide;
wherein the mass content of the tin-doped beta molecular sieve in the acid-base bifunctional catalyst is 10-90%;
the mass content of the magnesium oxide in the acid-base bifunctional catalyst is 10-90%;
in the tin-doped beta molecular sieve, the molar ratio of silicon element to tin element is 40-200: 1;
the preparation method of the acid-base bifunctional catalyst for the reaction of preparing the olefin by converting the ethanol at least comprises the following steps:
a) obtaining a tin-doped beta molecular sieve;
b) putting the tin-doped beta molecular sieve into a solution containing magnesium ions, and adding an alkali solution to adjust the pH value;
c) separating and washing the obtained solid, drying and roasting to obtain the acid-base bifunctional catalyst.
2. A method for preparing the acid-base bifunctional catalyst for the reaction of preparing olefin by converting ethanol according to claim 1, which comprises at least the following steps:
a) obtaining a tin-doped beta molecular sieve;
b) putting the tin-doped beta molecular sieve into a solution containing magnesium ions, and adding an alkali solution to adjust the pH value;
c) separating and washing the obtained solid, drying and roasting to obtain the acid-base bifunctional catalyst.
3. The method of claim 2, wherein the tin-doped beta molecular sieve is prepared by a preparation method comprising at least the following steps:
(1) dealuminizing the H-beta molecular sieve;
(2) and mixing and grinding the dealuminized H-beta molecular sieve and a tin precursor, and roasting to obtain the tin-doped beta molecular sieve.
4. The method of claim 3, wherein the H- β molecular sieve has a silica to alumina molar ratio (SiO)2/Al2O3＝12.5～50。
5. The method according to claim 3, wherein the dealumination treatment comprises placing the H-beta molecular sieve in a nitric acid solution with the concentration of 10-14mol/L, and keeping the H-beta molecular sieve at the temperature of not less than 50 ℃ for not less than 7 hours.
6. The method of claim 3, wherein the dealumination treatment comprises placing the H-beta molecular sieve in a nitric acid solution with a mass concentration of 65-68%, and keeping the H-beta molecular sieve at a temperature of not less than 75 ℃ for not less than 8 hours.
7. The method of claim 3, wherein the tin precursor is at least one of crystalline tin tetrachloride, dimethyl tin dichloride, stannous chloride, or stannous oxalate.
8. The method according to claim 3, wherein the molar ratio of the mole number of the silicon element in the dealuminated H-beta molecular sieve to the mole number of the tin element in the tin precursor is Si: Sn ═ 40 to 200: 1.
9. The method according to claim 3, wherein the mass ratio of the dealuminated H-beta molecular sieve to the tin precursor is 2: 0.05 to 0.3.
10. The method according to claim 2, wherein the adding of the alkali solution to adjust the pH value is to adjust the pH value of the system to 10-12 by adding the alkali solution.
11. Use of the acid-base bifunctional catalyst for ethanol conversion to olefins according to claim 1 or the acid-base bifunctional catalyst prepared by the method according to any one of claims 2 to 10 as a catalyst for ethanol conversion to olefins.
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