ZrO x -Beta catalysts, their preparation methods, and applications

Abstract

This invention relates to the field of catalysts, and discloses ZrO x ZrO-Beta catalyst, its preparation method, and its application. The method includes: loading Zr onto a Recry-Beta molecular sieve in the presence of a settling agent, followed by drying and calcination to obtain the ZrO-. x -Beta catalyst, wherein the loading conditions include: temperature of 60-140℃ and positive pressure; wherein the amount of flocculant used is such that the pH of the material after loading is greater than 7 and less than 13. The ZrO x The -Beta catalyst contains a high content of monoclinic zirconium oxide and exhibits excellent catalytic performance in the ethanol-acetaldehyde reaction to prepare 1,3-butadiene.

Description

Technical Field

[0001] This invention relates to the field of catalysts, specifically to ZrO. x -Beta catalyst, its preparation method, and its application in hydrocarbon conversion reactions. Background Technology

[0002] Butadiene (1,3-Butadiene, BD) is an important basic raw material in petrochemicals and an intermediate monomer in synthetic rubber, playing a crucial role in industrial production, especially in rubber manufacturing and the automotive industry. With the development of naphtha cracking technology for ethylene production, approximately 97% of the world's butadiene is produced through a process that extracts 1,3-butadiene as a byproduct from C4 fractions. However, with increasingly scarce petroleum resources and rising oil prices, the petroleum-based butadiene production process is bound to be affected. Therefore, developing non-petroleum-based butadiene production processes is urgently needed. In recent years, with the continuous maturation of bioethanol production technology and the gradual increase in production scale, the ethanol-based butadiene production process represents a new alternative to the petroleum-based route. There are two processes for producing butadiene (ETB) from ethanol: the one-step process (Makshina EV, Dusselier M, Janssens W, et al. Chemical Society Reviews, 2014, 43(22):7917-7953.), namely the Lebedev process developed in the 1920s, which uses ethanol as a raw material to produce butadiene. This process has low butadiene selectivity but high acetaldehyde selectivity. Butadiene selectivity can be improved to 30-40% by recycling acetaldehyde. The two-step process (Alessandro M, Oberto C. Process for the manufacture of diolefins from alcohols and aldehydes. US2297424A. 1942.; Dunn JT, Toussaint W J. Process for making diolefins. US2421361A[P]. 1947.), namely the Ostromyslensky process developed in 1942, involves partial dehydrogenation of ethanol to produce acetaldehyde in the first reactor, and the conversion of the ethanol-acetaldehyde mixture to butadiene in the second reactor, achieving a selectivity of up to 60%. The two-step process has a more significant advantage.

[0003] Both the one-step and two-step processes include the following five reaction steps: ① ethanol dehydrogenation to acetaldehyde; ② acetaldehyde undergoes an aldol condensation reaction to generate butyrolaldehyde; ③ butyrolaldehyde is dehydrated to generate crotonaldehyde; ④ crotonaldehyde and ethanol undergo an MPV reaction to generate crotonol and acetaldehyde; ⑤ crotonol is dehydrated to generate butadiene. Among these, Ag and Cu are commonly used as catalysts for the ethanol dehydrogenation to acetaldehyde reaction, which can meet the needs of industrial production. Regarding the requirements for the second reaction in the two-step process, existing research results indicate that elements such as Ta, Zr, Zn, and Mg can enter the molecular sieve framework or pores, exhibiting L-acid centers, which are active centers in aldol condensation and MPV reduction reactions (T.-W. Kim, J.-W. Kim, C.-U. Kim, Chem. Eng. J. 2015, 278, 217-223); Si-OH on the surface of SiO2, MWW, and Beta molecular sieves exhibits weak Brønsted acid, serving as active centers for dehydration reactions (M. Gao, H. Jiang, M. Zhang, Catal. Surveys Asia 2020, 1-8; VLSushkevich, IIIvanova, E. Taarning, Green Chem. 17(4)(2015)2552–2559.; PI Kyriienko, OV Larina, SOSoloviev, SMOrdlyk, S. Dzwigaj. Catal. Commun. 77(2016)123–126.; Minhua Zhang, etc. Microporous and Mesoporous Materials 326(2021)111359). Among them, the Zr-Beta catalyst containing metallic zirconium with pure silica beta molecular sieve as support has a high butadiene selectivity, with a feed conversion rate of 43.2% and a butadiene selectivity of 73.9%. However, the catalyst has poor activity stability, is prone to carbon deposition, and only operates for a few hours. Summary of the Invention

[0004] The purpose of this invention is to overcome the shortcomings of the existing technology and provide ZrO x -Beta catalyst and its preparation method, wherein the prepared catalyst contains a high content of monoclinic zirconium oxide, and the catalyst exhibits excellent catalytic performance in the ethanol-acetaldehyde reaction to prepare 1,3-butadiene.

[0005] To achieve the above objectives, the first aspect of the present invention provides a ZrO x A method for preparing a beta catalyst, comprising:

[0006] (1) H-Beta molecular sieve was acid-washed and dealuminized to obtain Si-Beta molecular sieve;

[0007] (2) Si-Beta molecular sieve, template agent and water are mixed and then crystallized to obtain the Recry-Beta molecular sieve;

[0008] (3) In the presence of a settling agent, Zr is loaded onto Recry-Beta molecular sieves, and then dried and calcined to obtain the ZrO. x -Beta catalyst;

[0009] The particle size of the H-Beta molecular sieve is below 90 nm.

[0010] The molar ratio of the template agent to the Si-Beta molecular sieve (calculated as SiO2) is 0.08-0.25.

[0011] The conditions for the load include: a temperature of 60-140℃ and a positive pressure.

[0012] The amount of flocculant used ensures that the pH of the material after the loading is completed is greater than 7 and less than 13.

[0013] The second aspect of the present invention provides ZrO prepared by the method described above. x -Beta catalyst.

[0014] A third aspect of the present invention provides a ZrO x -Beta catalyst, the catalyst comprising a Beta molecular sieve and a zirconium-containing species supported on the Beta molecular sieve, wherein the zirconium-containing species is a monoclinic / tetragonal miscible phase;

[0015] Among them, the monoclinic phase accounts for 50%-80% of the zirconium-containing species;

[0016] The catalyst has a crystallinity of 30-60%.

[0017] The fourth aspect of the present invention provides ZrO as described above. x The application of β-Beta catalysts in hydrocarbon conversion reactions is preferably in the reaction of ethanol-acetaldehyde to prepare 1,3-butadiene.

[0018] Zirconia (ZrO₂) crystals exist in three stable crystalline phases: monoclinic (m), tetragonal (t), and cubic (c). The first two are primarily used in catalytic reactions. The Zr / O coordination environment differs significantly between the different crystalline phases: in the tetragonal phase, Zr... 4+ The ion is octetaric, O 2- The ions are tetracoordinated; in the monoclinic phase, Zr 4+ The ion is seven-coordinated, O 2-The ions are tricoordinated or tetracoordinated [Y. Zhao et al. Catalysis Communications 3(2002)239–245]. This structural difference results in different acidity and catalytic properties in the two different crystal phases of ZrO2. The m-ZrO2 structure is rich in Zr-OH-Zr structure, while the t-ZrO2 structure is dominated by Zr-O-Zr structure [Weizhen Li, Hua Huang, Hongjia Li, Wei Zhang, and Haichao Liu, Langmuir 2008, 24, 8358-8366]. The ZrO2 described in this invention... x -Beta catalysts contain a high content of m-ZrO2, which can improve butadiene selectivity and activity stability.

[0019] The ZrO of this invention x -Beta catalysts have a lower internal surface area S micro and micropore volume V micro High pore volume V meso The higher amount of weak acid can promote the interaction between Zr-OH on the monoclinic ZrO2 and Si-OH on the surface of the molecular sieve, resulting in more Zr-O-Si-OH structures, which improves the activity and selectivity of the catalyst and prolongs the catalyst's operating time.

[0020] ZrO prepared by the method of the present invention x The -Beta catalyst can be used in the reaction of ethanol-acetaldehyde to produce 1,3-butadiene, and it exhibits excellent catalytic performance, significantly improving the conversion rate of feedstock, the selectivity of 1,3-butadiene, and the stable operating time. Attached Figure Description

[0021] Figure 1 These are the XRD patterns of the catalysts prepared in Examples 1, 2 and 3 of this invention, as well as Comparative Examples 1 and 2.

[0022] Figure 2 These are zirconium oxide XRD patterns of the catalysts prepared in Examples 1, 2 and 3 of this invention and Comparative Examples 1 and 3;

[0023] Figure 3 These are XPS images of the catalysts prepared in Examples 1, 2 and 3 of the present invention and Comparative Examples 1 and 2;

[0024] Figure 4 These are UV-vis images of the catalysts prepared in Examples 1, 2 and 3 of this invention, as well as Comparative Examples 1 and 2;

[0025] Figure 5The catalysts prepared in Examples 1, 2, and 3 of this invention, as well as Comparative Examples 1 and 2, are... 29 Si MAS NMR spectrum;

[0026] Figure 6 These are NH3-TPD diagrams of the catalysts prepared in Examples 1, 2 and 3 of this invention, as well as Comparative Examples 1 and 2. Detailed Implementation

[0027] The endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0028] The technical terms used in this invention, where defined, shall be used according to their definitions, and where not defined, shall be understood according to their common meaning in the art.

[0029] The first aspect of the present invention provides a ZrO x A method for preparing a beta catalyst, comprising:

[0030] (1) H-Beta molecular sieve was acid-washed and dealuminized to obtain Si-Beta molecular sieve;

[0031] (2) Si-Beta molecular sieve, template agent and water are mixed and then crystallized to obtain the Recry-Beta molecular sieve;

[0032] (3) In the presence of a settling agent, Zr is loaded onto Recry-Beta molecular sieves, and then dried and calcined to obtain the ZrO. x -Beta catalyst;

[0033] The H-Beta molecular sieve has a particle size of less than 90 nm (for example, it can be 20, 30, 40, 50, 60, 70, 80, 90 nm or less, or any range between any two values).

[0034] The molar ratio of the template agent to the Si-Beta molecular sieve (based on SiO2) is 0.08-0.25 (for example, it can be 0.08, 0.1, 0.12, 0.14, 0.15, 0.16, 0.17, 0.18, 0.2, 0.25, or any range between any two values, preferably 0.13-0.18);

[0035] The conditions for the load include: a temperature of 60-140℃ and a positive pressure.

[0036] The amount of flocculant used ensures that the pH of the material after the loading is completed is greater than 7 and less than 13.

[0037] Preferably, the particle size of the H-Beta molecular sieve is 20-50 nm.

[0038] In this invention, the particle size of the molecular sieve and the catalyst can be determined by transmission electron microscopy.

[0039] The H-beta molecular sieve can be obtained commercially or prepared in-house. Its preparation method can be found in patent CN1324762A, which is incorporated herein by reference in its entirety.

[0040] In a preferred embodiment of the present invention, under alkaline conditions, a silicon source, an aluminum source, and a template agent are mixed and then subjected to hydrothermal crystallization, drying, ammonium exchange, and calcination to obtain H-beta molecular sieves. The order of the ammonium exchange and calcination treatments is not particularly limited.

[0041] The alkaline conditions can be provided by alkaline substances commonly used in the art, such as sodium hydroxide.

[0042] The silicon source can be a conventional silicon source in the art, such as silicon dioxide or silicone.

[0043] Preferably, the aluminum source is selected from one or more of alkali metal (metaseo)aluminates (such as sodium aluminate), hydrated alumina, aluminum hydroxide, hydrated aluminum chloride, and boehmite.

[0044] Preferably, the template agent has at least one of the structures shown in formula (1):

[0045]

[0046] R1, R2, R3 and R4 are each independently selected from alkyl groups having 1 to 4 carbon atoms. Preferably, R1, R2, R3 and R4 are each independently selected from one or more of methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl and tert-butyl, more preferably methyl or ethyl.

[0047] X - This includes hydroxide ions or halide anions.

[0048] Preferably, the template agent is tetramethylammonium hydroxide and / or tetraethylammonium hydroxide.

[0049] It should be understood that the hydrothermal crystallization is carried out under aqueous conditions.

[0050] Preferably, the amounts of each component are such that, in molar amounts, the SiO2 / Al2O3 ratio is 10-50 (e.g., it can be 10, 20, 30, 40, 50, or any range between any two values), the H2O / SiO2 ratio is 5-8 (e.g., it can be 5, 6, 7, 8, or any range between any two values), the template agent / SiO2 ratio is 0.05-0.15 (e.g., it can be 0.05, 0.08, 0.1, 0.12, 0.15, or any range between any two values), and the OH... - / SiO2 is 0.1-0.15 (for example, it can be 0.1, 0.11, 0.12, 0.13, 0.14, 0.15, or any range between any two values).

[0051] Preferably, hydrothermal crystallization is carried out at 120-200°C and under autogenous pressure for 5-120 hours, more preferably at 80-138°C (preferably 110-130°C) and under autogenous pressure for 5-72 hours (preferably 16-32 hours), and then at 140-200°C (preferably 140-160°C) and under autogenous pressure for 5-72 hours (preferably 36-56 hours).

[0052] The drying and ammonium exchange methods are conventional in the art and will not be described in detail here. The calcination conditions can be, for example, a temperature of 500-600℃ and a time of 3-5 hours.

[0053] Preferably, the acid leaching and dealuminization conditions result in a silica content of 99.5% or higher in the obtained Si-Beta molecular sieve, such as 99.5%, 99.6%, 99.7%, 99.8%, 99.9 wt% or higher, or any range between any two values, thereby reducing the impurity content of the catalyst.

[0054] Preferably, the pickling conditions include: a temperature of 60-90℃, an acid selected from one or more of nitric acid, hydrochloric acid, and sulfuric acid, and a pickling solution concentration generally of 1-15 mol / L. The number of acid exchanges and the time depend on the silica (or alumina) content in the molecular sieve during the actual operation.

[0055] The material obtained after acid washing can be further processed to obtain the Si-Beta molecular sieve. The subsequent processing operations can include filtration, washing and drying, etc., and can refer to conventional operations in the field.

[0056] Preferably, the crystallinity of the Si-Beta molecular sieve is 60-90%, for example, it can be 60, 65, 70, 75, 80, 85, 90% or any range between any two values, more preferably 70-85%.

[0057] The crystallinity was determined by XRD and calculated as the sum of the areas of the characteristic peaks at 2θ = 7-9° and 22-23°. The standard sample was the H-beta molecular sieve prepared in Preparation Example 1 of this invention.

[0058] Preferably, the BET specific surface area S of the Si-Beta molecular sieve is... BET 450-680m 2 / g, for example, can be 450, 480, 500, 550, 600, 650, 680m 2 / g and any range between any two values, more preferably 480-650m 2 / g.

[0059] Preferably, the total pore volume V of the Si-Beta molecular sieve 总 The value is 0.25-0.85cm. 3 / g, for example, can be 0.25, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.85cm 3 / g and any range between any two values, more preferably 0.45-0.7cm 3 / g.

[0060] Preferably, the packing pore volume V of the Si-Beta molecular sieve meso It is 0.2-0.55cm 3 / g, for example, can be 0.23, 0.25, 0.3, 0.4, 0.5, 0.55cm 3 / g and any range between any two values, more preferably 0.26-0.48cm 3 / g.

[0061] Specific surface area, pore volume, and pore volume can be measured using a nitrogen adsorption analyzer.

[0062] Preferably, the molar ratio of the template agent to the Si-Beta molecular sieve (based on SiO2) is 0.1-0.2 (for example, it can be 0.1, 0.12, 0.14, 0.16, 0.18, 0.2, or any range between any two values). The template agent is described in the section on template agents for preparing H-beta molecular sieves, and will not be repeated here.

[0063] Preferably, the molar ratio of water to Si-Beta molecular sieve (calculated as SiO2) is 3-10, for example, it can be 3, 4, 6, 8, 10 or any range between any two values, more preferably 5-8.

[0064] Preferably, the crystallization conditions include: a crystallization temperature of 100-300℃, more preferably 110-150℃; and a crystallization time of 12h-120h, more preferably 24h-72h. It should be understood that the pressure is autogenous pressure.

[0065] Preferably, the crystallization method is a two-step crystallization, more preferably, crystallization at 110-130℃ for 18-36 hours, and then crystallization at 130-150℃ for 18-36 hours.

[0066] Preferably, the calcination conditions include: a calcination temperature of 400-650℃, more preferably 500-600℃; and a calcination time of 2-8 hours, preferably 3-5 hours.

[0067] The method for preparing Recry-Beta molecular sieves described herein can be cited from patent 202310644040.9, which is incorporated herein by reference in its entirety.

[0068] In this invention, Zr is loaded onto Recry-Beta molecular sieves, and then dried and calcined to obtain the ZrOx-Beta catalyst.

[0069] Loading Zr onto the prepared Recry-Beta molecular sieve can be achieved through methods such as impregnation (i.e., equal-volume impregnation) or ion exchange. The preparation method involves contacting a Zr precursor solution with the Recry-Beta molecular sieve. The Zr precursor can be a water-soluble or alcohol-soluble compound, such as one or more of nitrates (e.g., ZrO(NO3)2·2H2O), chlorides, and acetates.

[0070] Furthermore, the amount of solvent in the Zr precursor solution must be sufficient to ensure both the complete dissolution of the Zr precursor in the solvent and the adequate dispersion of the molecular sieve. Preferably, compared to 1g of Recry-Beta molecular sieve, the amount of solvent in the Zr precursor solution is 5-100g, for example, it can be 5, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100g, or any range between any two values, more preferably 10-50g. The solvent can be at least one of water, ethanol, and propanol.

[0071] The conditions for the load include: a temperature of 60-140℃ (for example, it can be 60, 70, 80, 90, 100, 110, 120, 130, 140℃ and any range between any two values, more preferably 80-120℃).

[0072] In step (3), the amount of settling agent is such that the pH of the material after loading is greater than 7 and less than 13. For example, it can be 7.5, 8, 8.5, 9, 9.5, 10, 10.5, 11, 11.5, 12, 12.5, or any range between any two values, more preferably 8-12. The pH of the material after loading can be measured directly after the reaction vessel is opened after the reaction is complete.

[0073] Preferably, the settling agent is selected from at least one of urea, ammonia, and ammonium salts (such as ammonium chloride, ammonium sulfate, ammonium nitrate, ammonium bicarbonate, etc.).

[0074] The conditions for the load also include: the pressure is positive pressure, which can be self-generated pressure, that is, the load process is carried out in a closed container, or it can be external pressure applied. For example, the pressure value can be above 0.1MPa, 0.11MPa, 0.12MPa, 0.13MPa, 0.14MPa, 0.15MPa, 0.2MPa, 0.3MPa, 0.4MPa, 0.5MPa, 0.6MPa, 0.7MPa, 0.8MPa, or any range between any two values, preferably 0.2-0.8MPa.

[0075] Preferably, the load conditions further include: a time of 4-68h, for example, it can be 4, 6, 8, 10, 15, 20, 25, 30, 40, 50, 60, 68h and any range between any two values, preferably 10-50h.

[0076] There are no particular restrictions on the drying conditions, such as drying at 60-120°C, and there are no particular restrictions on the drying time, as long as the weight is kept constant.

[0077] Preferably, the calcination conditions include: a temperature of 400-600℃ and a time of 1-6 hours.

[0078] Preferably, the amount of each component is such that, based on the total weight of the catalyst, the content of Recry-Beta molecular sieve is 95-99.9 wt%, for example, it can be 95, 96, 97, 98, 99, 99.5, 99.9 wt%, or any range between any two values, more preferably 97-99.5 wt%, and the content of zirconium-containing species, calculated as Zr oxide, is 0.1-5 wt%, for example, it can be 0.1, 0.5, 1, 2, 3, 4, 5 wt%, or any range between any two values, more preferably 0.5-3 wt%.

[0079] The second aspect of the present invention provides ZrO prepared by the method described above. x -Beta catalyst.

[0080] Preferably, the zirconium-containing species in the catalyst is a monoclinic / tetragonal miscible phase, wherein the monoclinic phase accounts for more than 50% of the zirconium-containing species, for example, it can be 50, 55, 60, 65, 70, 75, 80, 90% or more, or any range between any two values, more preferably 55-80%.

[0081] The proportion of monoclinic phase in zirconium-containing species is calculated as the ratio of the monoclinic peak area to the (monoclinic + tetragonal) peak area in the zirconium oxide XRD spectrum. The monoclinic peak area is calculated as follows:

[0082] Monoclinic phase ratio

[0083] The proportions of the four sides

[0084] Here, the area refers to the peak area of ​​the peak corresponding to the value of 2θ, such as S. 2θ＝24.2 This refers to the peak area of ​​the peak when 2θ is 24.2.

[0085] Preferably, the crystallinity of the catalyst is 20-60%, for example, it can be 20, 25, 30, 35, 40, 45, 50, 60%, or any range between any two values, preferably 30-65%. The crystallinity of the catalyst is determined by XRD analysis, using the sum of the characteristic peak areas of 2θ = 7-9° / 22-23° of the H-Beta molecular sieve prepared in Preparation Example 1 of Patent 202310644040.9 as a benchmark.

[0086] Preferably, based on the total weight of the catalyst, the content of Recry-Beta molecular sieve is 95-99.9 wt%, for example, it can be 95, 96, 97, 98, 99, 99.5, 99.9 wt%, or any range between any two values, more preferably 97-99.5 wt%, and the content of zirconium-containing species, calculated as Zr oxide, is 0.1-5 wt%, for example, it can be 0.1, 0.5, 1, 2, 3, 4, 5 wt%, or any range between any two values, more preferably 0.5-3 wt%.

[0087] Preferably, the silicon-to-aluminum ratio of the catalyst is 800 or higher, for example, it can be 800, 1000, 1500, 2000, 2500 or higher, or any range between any two values, more preferably 1200-2500.

[0088] Preferably, the total acidity of the catalyst is 220-400 μmol / g, for example, it can be 220, 240, 260, 280, 300, 320, 340, 360, 380, 400 μmol / g and any range between any two values, preferably 250-350 μmol / g.

[0089] Preferably, the ratio of weak acid to moderately strong acid in the catalyst is 2-7, for example, it can be 2, 3, 4, 5, 6, 7 or any range between any two values, preferably 3.5-6.5.

[0090] Preferably, the catalyst has a BET specific surface area S BET 150-550m 2 / g, for example, can be 150, 200, 250, 300, 400, 450, 480, 500, 550m 2 / g and any range between any two values, preferably 330-510m. 2 / g.

[0091] Preferably, the total pore volume V of the catalyst 总 It is 0.45-0.7cm 3 / g, for example, can be 0.45, 0.5, 0.55, 0.6, 0.65, 0.7cm 3 / g and any range between any two values, preferably 0.55-0.67cm 3 / g.

[0092] Preferably, the packing pore volume V of the catalyst is... meso It is 0.3-0.7cm 3 / g, for example, can be 0.3, 0.4, 0.5, 0.6, 0.7cm 3 / g and any range between any two values, preferably 0.4-0.55cm 3 / g.

[0093] Preferably, the catalyst has an average particle size of 20-50 nm, more preferably 20-30 nm.

[0094] A third aspect of the present invention provides a ZrO x -Beta catalyst, the catalyst comprising a molecular sieve and a zirconium-containing species supported on the molecular sieve, wherein the zirconium-containing species is a monoclinic / tetragonal miscible phase;

[0095] Among them, the monoclinic phase accounts for more than 50% of the zirconium-containing species;

[0096] The catalyst has a crystallinity of 30-60%.

[0097] Preferably, based on the total weight of the catalyst, the content of Recry-Beta molecular sieve is 95-99.9 wt%, for example, it can be 95, 96, 97, 98, 99, 99.5, 99.9 wt%, or any range between any two values, more preferably 97-99.5 wt%, and the content of zirconium-containing species, calculated as Zr oxide, is 0.1-5 wt%, for example, it can be 0.1, 0.5, 1, 2, 3, 4, 5 wt%, or any range between any two values, more preferably 0.5-3 wt%.

[0098] Preferably, the silicon-to-aluminum ratio of the catalyst is 1200-2500;

[0099] Preferably, the total acidity of the catalyst is 250-350 μmol / g.

[0100] Preferably, the ratio of weak acid to medium-strong acid in the catalyst is 3.5-6.5.

[0101] Preferably, the catalyst has a BET specific surface area S BET 330-510m 2 / g.

[0102] Preferably, the total pore volume V of the catalyst 总 It is 0.55-0.67cm 3 / g.

[0103] Preferably, the packing pore volume V of the catalyst is... meso It is 0.45-0.55cm 3 / g.

[0104] Preferably, the catalyst has an average particle size of 20-30 nm.

[0105] The fourth aspect of the present invention provides ZrO as described above. x The application of β-Beta catalysts in hydrocarbon conversion reactions is preferably in the reaction of ethanol-acetaldehyde to prepare 1,3-butadiene.

[0106] The conditions for preparing 1,3-butadiene can be carried out with reference to existing technologies, with the aim of preparing 1,3-butadiene from ethanol-acetaldehyde.

[0107] According to the present invention, the conditions for the contact reaction of ethanol and acetaldehyde typically include reaction temperature and reaction pressure. The reaction temperature can be maintained at 250-450°C, preferably 250-400°C; the reaction pressure can be maintained at 0.1-4 MPa, preferably 0.1-1.5 MPa. The objective of the present invention can be achieved simply by using the catalyst described herein. From the perspective of further improving the catalytic activity of the catalyst, the amount of the catalyst is set based on the total amount of ethanol and acetaldehyde, so that the gas hourly space velocity (HSV) of the reactants is 0.1-9 h⁻¹. -1 (h -1 Preferably 0.1-6 hours -1 (h -1 The molar ratio of ethanol to acetaldehyde in the feed can be 1-12, preferably 1.5-5.

[0108] In the method of the present invention, the reaction for preparing 1,3-butadiene from ethanol can be carried out in various reactors conventionally used in the art, for example, including but not limited to at least one of a fixed bubble bed reactor, a fixed trickle bed reactor, and a slurry bed reactor.

[0109] The present invention will be described in detail below through embodiments.

[0110] (1) In the following examples, the crystallinity of the molecular sieve and the catalyst was analyzed by XRD, with the sum of the characteristic peak areas of 2θ = 7-9° / 22-23° of the H-Beta molecular sieve prepared in Preparation Example 1 of Patent 202310644040.9 as the benchmark.

[0111] (2) In the following examples, the zirconium oxide content in the catalyst was measured using the following analytical method: a Rigaku Electric Co., Ltd. 3013 X-ray fluorescence spectrometer was used. The testing conditions were: tungsten target, excitation voltage 40 kV, and excitation current 50 mA. Experimental procedure: The catalyst sample was pressed into a tablet and mounted on the X-ray fluorescence spectrometer. Under X-ray irradiation, fluorescence was emitted. The fluorescence wavelength λ and the atomic number Z of the element had the following relationship: λ = K(Z - S). -2 K is a constant; the element can be identified simply by measuring the wavelength λ of the fluorescence. The intensity of the characteristic spectral lines of each element is measured using a scintillation counter and a proportional counter for quantitative or semi-quantitative elemental analysis.

[0112] (3) In the following examples, the total acid content, weak acid content, and medium-strong acid content of the catalyst were measured using the following method: An AutochemⅡ2920 adsorption instrument manufactured by Micromeritic was used. A 20-40 mesh sample was placed in a sample glass tube, which was then installed in a heating chamber. Helium was used to heat the tube to remove surface impurities, followed by cooling to adsorb ammonia-helium. Helium was then switched back to heat the tube and purge until ammonia desorbed. The change in ammonia concentration was detected using a detector to obtain the NH3 adsorption-desorption curve. The total acid content was obtained by automatic integration.

[0113] (4) In the following examples, the specific surface area and pore volume of the molecular sieve and catalyst were measured according to the following analytical methods:

[0114] Equipment: Micromeritic ASAP2010 static nitrogen adsorption instrument.

[0115] Measurement conditions: Place the sample in the sample processing system and evacuate to 1.33 × 10⁻⁶ at 350°C. -2 The sample was purified by maintaining the temperature and pressure at 15 h. At liquid nitrogen temperature -196℃, the adsorption and desorption amounts of nitrogen on the purified sample under different specific pressures P / P0 were measured to obtain adsorption-desorption isotherms. The total specific surface area was then calculated using the two-parameter BET formula, and the total pore volume was calculated based on the adsorption amount at P / P0 = 0.98.

[0116] In the following examples, all reagents and raw materials are either commercially available or prepared using existing methods.

[0117] The method for preparing Recry-Beta molecular sieves described in Example 3 of patent 202310644040.9 is cited to prepare Recry-Beta molecular sieves as ZrO. x -Beta catalyst support.

[0118] Example 1

[0119] This embodiment illustrates the preparation method of the catalyst described in this invention.

[0120] 4.0 g of Recry-Beta molecular sieve was mixed with 60 mL of an aqueous solution containing 0.435 g of ZrO(NO3)2·2H2O (Acros Organic, 99.99%) at room temperature, and urea was added. The resulting solution was transferred to a sealed reactor lined with polytetrafluoroethylene and reacted at 90 °C for 20 hours. The amount of urea added was such that the pH of the reaction solution was 10 after the reaction. The reaction solution was washed three times with deionized water, and the filter cake was dried in air at 100 °C until all the water evaporated. Finally, it was calcined in flowing air at 550 °C for 2 hours to obtain the catalyst. The catalyst contained 97.6% Beta molecular sieve and 1.76 wt% zirconium dioxide.

[0121] Its XRD pattern is as follows Figure 1 As shown, the crystallinity of the catalyst is 54.8%, and the zirconium oxide XRD pattern is as follows. Figure 2 As shown in the figure, the catalyst contains a mixture of monoclinic and tetragonal zirconium oxide. (XPS image shown) Figure 3 As shown, the UV-Vis diagram is as follows: Figure 4 As shown, 29 Si MAS NMR image as follows Figure 5 As shown in the figure, it can be seen that most of the metals enter the molecular sieve framework and form Zr-O-Si and Zr-OH bonds with the framework elements. The NH3-TPD diagram is shown below. Figure 6 As shown.

[0122] The results of crystallinity, zirconium dioxide content and acidity of the product are shown in Table 1, and the results of surface area and pore volume are shown in Table 2.

[0123] Example 2

[0124] This embodiment illustrates the preparation method of the catalyst described in this invention.

[0125] 4.0 g of Recry-Beta molecular sieve was mixed with 60 mL of an aqueous solution containing 0.435 g of ZrO(NO3)2·2H2O (Acros Organic, 99.99%) at room temperature, and urea was added. The resulting solution was transferred to a sealed reactor lined with polytetrafluoroethylene and reacted at 90 °C for 48 hours. The amount of urea added was such that the pH of the reaction solution was 11 after the reaction. The reaction solution was washed three times with deionized water, and the filter cake was dried in air at 100 °C until all the water evaporated. Finally, it was calcined in flowing air at 550 °C for 2 hours to obtain the catalyst. The catalyst contained 97.2% Beta molecular sieve and 1.83 wt% zirconium dioxide.

[0126] Its XRD pattern is as follows Figure 1As shown, the crystallinity of the catalyst is 33.1%, and the zirconium oxide XRD pattern is as follows. Figure 2 As shown in the figure, the catalyst contains a mixture of monoclinic and tetragonal zirconium oxide. (XPS image shown) Figure 3 As shown, the UV-Vis diagram is as follows: Figure 4 As shown, 29 Si MAS NMR image as follows Figure 5 As shown in the figure, it can be seen that most of the metals enter the molecular sieve framework and form Zr-O-Si and Zr-OH bonds with the framework elements. The NH3-TPD diagram is shown below. Figure 6 As shown.

[0127] The results of crystallinity, zirconium dioxide content and acidity of the product are shown in Table 1, and the results of surface area and pore volume are shown in Table 2.

[0128] Example 3

[0129] This embodiment illustrates the preparation method of the catalyst described in this invention.

[0130] 4.0 g of Recry-Beta molecular sieve was mixed with 60 mL of an aqueous solution containing 0.435 g of ZrO(NO3)2·2H2O (Acros Organic, 99.99%) at room temperature, and urea was added. The resulting solution was transferred to a reaction vessel lined with polytetrafluoroethylene and sealed. The reaction was carried out at 90 °C for 6 hours. The amount of urea added was such that the pH of the reaction solution was 9 after the reaction. The reaction solution was washed three times with deionized water, and the filter cake was dried in air at 100 °C until all the water evaporated. Finally, it was calcined in flowing air at 550 °C for 2 hours to obtain the catalyst. The catalyst contained 97.8% Beta molecular sieve and 1.54 wt% zirconium dioxide.

[0131] Its XRD pattern is as follows Figure 1 As shown, the crystallinity of the catalyst is 58.9%, and the zirconium oxide XRD pattern is as follows. Figure 2 As shown in the figure, the catalyst contains pure-phase monoclinic zirconium oxide. (XPS image follows.) Figure 3 As shown, the UV-Vis diagram is as follows: Figure 4 As shown, 29 SiMAS NMR image as follows Figure 5 As shown in the figure, it can be seen that most of the metals enter the molecular sieve framework and form Zr-O-Si and Zr-OH bonds with the framework elements. The NH3-TPD diagram is shown below. Figure 6 As shown.

[0132] The results of crystallinity, zirconium dioxide content and acidity of the product are shown in Table 1, and the results of surface area and pore volume are shown in Table 2.

[0133] Example 4

[0134] This embodiment illustrates the preparation method of the catalyst described in this invention.

[0135] 4.0 g of Recry-Beta molecular sieve was mixed with 60 mL of an aqueous solution containing 0.435 g of ZrO(NO3)2·2H2O (Acros Organic, 99.99%) at room temperature, and urea was added. The resulting solution was transferred to a sealed reactor lined with polytetrafluoroethylene and reacted at 90 °C for 72 hours. The amount of urea added was such that the pH of the reaction solution was 12 after the reaction. The reaction solution was washed three times with deionized water, and the filter cake was dried in air at 100 °C until all the water evaporated. Finally, it was calcined in flowing air at 550 °C for 2 hours to obtain the catalyst. XRD results showed that the crystallinity of the catalyst was 23.5%.

[0136] Example 5

[0137] This embodiment illustrates the preparation method of the catalyst described in this invention.

[0138] 4.0 g of Recry-Beta molecular sieve was mixed with 60 mL of an aqueous solution containing 0.435 g of ZrO(NO3)2·2H2O (Acros Organic, 99.99%) at room temperature, and urea was added. The resulting solution was transferred to a sealed reactor lined with polytetrafluoroethylene and reacted at 120 °C for 20 hours. The amount of urea added was such that the pH of the reaction solution was 11 after the reaction. The reaction solution was washed three times with deionized water, and the filter cake was dried in air at 100 °C until all the water evaporated. Finally, it was calcined in flowing air at 550 °C for 2 hours to obtain the catalyst. XRD results showed that the crystallinity of the catalyst was 50.1%.

[0139] Example 6

[0140] This embodiment illustrates the preparation method of the catalyst described in this invention.

[0141] 4.0 g of Recry-Beta molecular sieve was mixed with 60 mL of an aqueous solution containing 0.435 g of ZrO(NO3)2·2H2O (Acros Organic, 99.99%) at room temperature, and urea was added. The resulting solution was transferred to a polytetrafluoroethylene-lined reactor and sealed. The reaction was carried out at 90 °C for 20 hours. The amount of urea added was such that the pH of the reaction solution was 9 after the reaction. The reaction solution was washed three times with deionized water, and the filter cake was dried in air at 100 °C until all the water evaporated. Finally, it was calcined in flowing air at 550 °C for 2 hours to obtain the catalyst. The catalyst had a crystallinity of 56.4%.

[0142] Example 7

[0143] This embodiment illustrates the preparation method of the catalyst described in this invention.

[0144] 4.0 g of Recry-Beta molecular sieve was mixed with 60 mL of an aqueous solution containing 0.435 g of ZrO(NO3)2·2H2O (Acros Organic, 99.99%) at room temperature, and urea was added. The resulting solution was transferred to a sealed reactor lined with polytetrafluoroethylene and reacted at 90 °C for 20 hours. The amount of urea added was such that the pH of the reaction solution was 8 after the reaction. The reaction solution was washed three times with deionized water, and the filter cake was dried in air at 100 °C until all the water evaporated. Finally, it was calcined in flowing air at 550 °C for 2 hours to obtain the catalyst. The catalyst had a crystallinity of 58.3%.

[0145] Example 8

[0146] This embodiment illustrates the preparation method of the catalyst described in this invention.

[0147] 4.0 g of Recry-Beta molecular sieve was mixed with 60 mL of an aqueous solution containing 0.435 g of ZrO(NO3)2·2H2O (Acros Organic, 99.99%) at room temperature, and urea was added. The resulting solution was transferred to a sealed reactor lined with polytetrafluoroethylene and reacted at 90 °C for 20 hours. The amount of urea added was such that the pH of the reaction solution was 12 after the reaction. The reaction solution was washed three times with deionized water, and the filter cake was dried in air at 100 °C until all the water evaporated. Finally, it was calcined in flowing air at 550 °C for 2 hours to obtain the catalyst. The catalyst had a crystallinity of 35.6%.

[0148] Example 9

[0149] This embodiment illustrates the preparation method of the catalyst described in this invention.

[0150] 4.0 g of Recry-Beta molecular sieve was mixed with 120 mL of ethanol containing 0.435 g of ZrO(NO3)2·2H2O (Acros Organic, 99.99%) at room temperature, and ammonia was added. The resulting solution was transferred to a PTFE-lined reactor and sealed. The reaction was carried out at 80 °C for 3 hours. The amount of ammonia added was adjusted so that the pH of the reaction solution was 8 after the reaction. The reaction solution was washed three times with deionized water, and the suspension was dried in air at 100 °C until all the water evaporated. Finally, it was calcined in flowing air at 550 °C for 2 hours to obtain the catalyst. The catalyst had a crystallinity of 60.3%.

[0151] Comparative Example 1

[0152] This comparative example is used to illustrate the preparation method of the reference catalyst.

[0153] 4.0 g of Recry-Beta molecular sieve was mixed with 120 mL of an aqueous solution containing 0.435 g of ZrO(NO3)2·2H2O (Acros Organic, 99.99%) at room temperature, and urea was added. The mixture was stirred continuously for 6 hours at 90 °C in a three-necked flask until the reaction was complete. The amount of urea added was such that the pH of the reaction solution after the reaction was completed was 7. The suspension was dried in air at 100 °C until all the water evaporated, and finally calcined in flowing air at 550 °C for 5 hours to obtain the catalyst. The catalyst contained 97.9% Beta molecular sieve and 1.47 wt% zirconium dioxide.

[0154] Its XRD pattern is as follows Figure 1 As shown, the crystallinity of the catalyst is 60.9%, and the zirconium oxide XRD pattern is as follows. Figure 2 As shown in the figure, the catalyst contains a mixture of monoclinic and tetragonal zirconium oxide. (XPS image shown) Figure 3 As shown, the UV-Vis diagram is as follows: Figure 4 As shown, 29 Si MAS NMR image as follows Figure 5 As shown in the figure, it can be seen that most of the metals enter the molecular sieve framework and form Zr-O-Si and Zr-OH bonds with the framework elements. The NH3-TPD diagram is shown below. Figure 6 As shown.

[0155] The results of crystallinity, zirconium dioxide content and acidity of the product are shown in Table 1, and the results of surface area and pore volume are shown in Table 2.

[0156] Comparative Example 2

[0157] This comparative example is used to illustrate the preparation method of the reference catalyst.

[0158] 4.0 g of Recry-Beta molecular sieve was mixed with 60 mL of an aqueous solution containing 0.435 g of ZrO(NO3)2·2H2O (Acros Organic, 99.99%) at room temperature, and urea was added. The resulting solution was transferred to a sealed reactor lined with polytetrafluoroethylene and reacted at 150 °C for 20 hours. The amount of urea added was such that the pH of the reaction solution was 13 after the reaction. The reaction solution was washed three times with deionized water, and the filter cake was dried in air at 100 °C until all the water evaporated. Finally, it was calcined in flowing air at 550 °C for 2 hours to obtain the catalyst. The catalyst contained 97.0% Beta molecular sieve and 1.89 wt% zirconium dioxide.

[0159] Its XRD pattern is as follows Figure 1 As shown, the catalyst is amorphous, as illustrated in the XPS image. Figure 3 As shown, the UV-Vis diagram is as follows: Figure 4 As shown, 29 Si MAS NMR image as follows Figure 5 As shown in the figure, it can be seen that most of the metals enter the molecular sieve framework and form Zr-O-Si and Zr-OH bonds with the framework elements. The NH3-TPD diagram is shown below. Figure 6 As shown.

[0160] The results of crystallinity, zirconium dioxide content and acidity of the product are shown in Table 1, and the results of surface area and pore volume are shown in Table 2.

[0161] Comparative Example 3

[0162] This comparative example is used to illustrate the preparation of the catalyst for comparison.

[0163] 4.0 g of Recry-Beta molecular sieve was mixed with 120 mL of ethanol solution containing 0.435 g of ZrO(NO3)2·2H2O (Acros Organic, 99.99%) at room temperature. The mixture was stirred continuously at 80 °C for 3 hours. After the reaction, the pH of the reaction solution was 7. The suspension was dried in air at 100 °C until all the ethanol evaporated, and finally calcined in flowing air at 550 °C for 2 hours to obtain the catalyst. The crystallinity of the Beta molecular sieve in the catalyst was 73.8%. The XRD pattern of zirconia is shown below. Figure 2 As shown in the figure, the catalyst contains pure-phase tetragonal zirconium oxide.

[0164] The results of crystallinity, zirconium dioxide content and acidity of the product are shown in Table 1, and the results of surface area and pore volume are shown in Table 2.

[0165] Comparative Example 4

[0166] This comparative example is used to illustrate the preparation of the catalyst for comparison.

[0167] 4.0 g of Recry-Beta molecular sieve was mixed with 60 mL of an aqueous solution containing 0.435 g of ZrO(NO3)2·2H2O (Acros Organic, 99.99%) at room temperature, and urea was added. The resulting solution was transferred to a sealed reactor lined with polytetrafluoroethylene and reacted at 90 °C for 20 hours. The amount of urea added was such that the pH of the reaction solution was 13 after the reaction. The reaction solution was washed three times with deionized water, and the filter cake was dried in air at 100 °C until all the water evaporated. Finally, it was calcined in flowing air at 550 °C for 2 hours to obtain the catalyst. XRD results showed that the catalyst was amorphous.

[0168] Table 1

[0169]

[0170] As can be seen from the results in Table 1, with the increase of preparation temperature and time, the amount of monoclinic zirconium oxide in the catalyst further increases, the crystallinity gradually decreases, the zirconium oxide content gradually increases, and the amount and proportion of weak acid gradually increase, indicating that monoclinic zirconium oxide is more able to interact with the Beta molecular sieve support.

[0171] Table 2

[0172]

[0173]

[0174] The results in Table 2 show that, compared to Recry-Beta molecular sieves, the catalyst has a higher BET specific surface area S0. BET and micropore volume V micro All decreased, and the accumulated pore volume V meso The increase is present; except for catalyst 1, the packing pore volume V of the catalyst has increased. meso The increase indicates that zirconium species have entered the molecular sieve channels or onto the framework.

[0175] Test Example 1

[0176] The process of preparing 1,3-butadiene from ethanol was carried out using a fixed-bed reactor. The reactor was a stainless steel tubular isothermal reactor with an inner diameter of 12 mm and a catalyst loading of 4 g. Ethanol and acetaldehyde (40 wt% aqueous solution of acetaldehyde) were introduced from the top of the reactor. Material balance was performed on the apparatus, and the liquid recovery was over 95%.

[0177] The evaluation conditions were: based on a mixture of ethanol and acetaldehyde as reactants, and a gas hourly space velocity of 2 h⁻¹. -1Carrier gas flow rate: 450 ml / min, reaction temperature: 350℃, reaction pressure: 0.44 MPa, catalyst loading: 2.0 g. Ethanol and acetaldehyde solution were used as raw materials, with an ethanol:acetaldehyde ratio of 1:1 (molar ratio).

[0178] For ease of expression, the following substances are abbreviated as: ethanol (EtOH), acetaldehyde (AA), unreacted ethanol (unreacted-EtOH), and unreacted acetaldehyde (unreacted-AA).

[0179] The ethanol conversion and 1,3-butadiene selectivity are calculated using the following formulas:

[0180]

[0181]

[0182] Where n is the mass percentage of each component in the product, and i is butadiene or other components in the product.

[0183] The catalysts prepared by the examples and comparative examples were applied to the reaction of ethanol-acetaldehyde to prepare 1,3-butadiene. The catalytic performance results are shown in Table 3 (sampling results at a reaction time of 2 h, and the operating time is the time when the butadiene selectivity is greater than 60%).

[0184] Table 3

[0185]

[0186] As can be seen from the results in Table 3, the ZrO prepared by the method of the present invention... x When the -Beta catalyst is applied to the reaction of ethanol to produce 1,3-butadiene, the conversion rate of ethanol to acetaldehyde is high, and the butadiene selectivity, yield, and run-time are significantly better than those of the comparative example. This demonstrates that the catalyst provided by the present invention has excellent catalytic performance.

[0187] from Figure 2-6 The results show that, compared with Comparative Examples 1 and 2, the catalysts prepared in Examples 1 and 2 contain a high content of monoclinic zirconium oxide as the active component, allowing most of the metal to enter the molecular sieve framework and form bonds with the framework elements. This improves the activity and selectivity of the catalyst and effectively extends the stable operating time (it can run continuously for at least 91 hours when the ethanol-acetaldehyde conversion rate is above 40% and the butadiene selectivity is ≥60%). The catalysts prepared in Comparative Examples 1 and 2 can only run continuously for less than 30 hours when the butadiene selectivity is ≥60%, and the repeatability is poor with rapid degradation.

[0188] Following the method described above, the catalyst described in Example 1 of this invention was used to prepare 1,3-butadiene under an alcohol-aldehyde ratio of 2:1. The results showed that the ethanol-acetaldehyde conversion rate was above 60%, and the butadiene selectivity was ≥60%, with continuous operation for at least 153 hours.

[0189] The preferred embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combinations of various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.

Claims

1. A ZrO x The method for preparing a -Beta catalyst is characterized by, The method includes: (1) H-Beta molecular sieve was acid-washed and dealuminized to obtain Si-Beta molecular sieve; (2) Si-Beta molecular sieve, template agent and water are mixed and then crystallized to obtain Recry-Beta molecular sieve; (3) In the presence of a settling agent, Zr is loaded onto Recry-Beta molecular sieve, and then dried and calcined to obtain ZrO. x -Beta catalyst; The particle size of the H-Beta molecular sieve is below 90 nm. The molar ratio of the template agent to the Si-Beta molecular sieve (calculated as SiO2) is 0.08-0.

25. The conditions for the load include: a temperature of 60-140℃ and a positive pressure. The amount of flocculant used resulted in a pH of 8-12 for the material after the loading was completed. The zirconium-containing species in the catalyst are a monoclinic / tetragonal miscible phase, wherein the monoclinic phase accounts for 55-80% of the zirconium-containing species; In step (1), the acid leaching and dealuminization conditions ensure that the silica content in the obtained Si-Beta molecular sieve is above 99.5 wt%. The BET specific surface area of ​​the Si-Beta molecular sieve S BET 450-680 m 2 / g; The total pore volume of the Si-Beta molecular sieve V 总 It is 0.25-0.85 cm. 3 / g; The packing pore volume V of the Si-Beta molecular sieve meso It is 0.2-0.55 cm. 3 / g; The template agent has at least one of the structures shown in formula (1): Equation (1); Among them, R1, R2, R3, and R4 are each independently selected from alkyl groups having 1-4 carbon atoms, X - Including hydroxide ions or halide anions; The crystallization conditions include: a crystallization temperature of 100-300℃ and a crystallization time of 12h-120h.

2. The method according to claim 1, wherein, The H-Beta molecular sieve has a particle size of 20-50 nm.

3. The method according to claim 1 or 2, wherein, The Si-Beta molecular sieve has a crystallinity of 60-90%.

4. The method according to claim 3, wherein, The Si-Beta molecular sieve has a crystallinity of 70-85%.

5. The method according to claim 1 or 2, wherein, The BET specific surface area of ​​the Si-Beta molecular sieve S BET 480-650m 2 / g.

6. The method according to claim 1 or 2, wherein, The total pore volume of the Si-Beta molecular sieve V 总 It is 0.45-0.7cm 3 / g.

7. The method according to claim 1 or 2, wherein, The packing pore volume V of the Si-Beta molecular sieve meso The value is 0.26-0.48cm. 3 / g.

8. The method according to claim 1 or 2, wherein, R1, R2, R3 and R4 are each independently selected from one or more of methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl and tert-butyl.

9. The method according to claim 8, wherein, R1, R2, R3 and R4 are each independently methyl or ethyl.

10. The method according to claim 9, wherein, The template agent is tetramethylammonium hydroxide and / or tetraethylammonium hydroxide.

11. The method according to claim 1 or 2, wherein, The molar ratio of the template agent to the Si-Beta molecular sieve (calculated as SiO2) is 0.1-0.

2.

12. The method according to claim 1 or 2, wherein, The molar ratio of water to Si-Beta molecular sieve (calculated as SiO2) is 3-10.

13. The method according to claim 12, wherein, The molar ratio of water to Si-Beta molecular sieve (calculated as SiO2) is 5-8.

14. The method according to claim 1 or 2, wherein, In step (2), the crystallization conditions include: a crystallization temperature of 110-150℃ and a crystallization time of 24h-72h.

15. The method according to claim 1 or 2, wherein, The method further includes calcining the crystallized product to obtain the Recry-Beta molecular sieve.

16. The method according to claim 15, wherein, The conditions for the calcination treatment include: a calcination temperature of 400-650℃ and a calcination time of 2-8 hours.

17. The method according to claim 16, wherein, The conditions for the roasting treatment include: a roasting temperature of 500-600℃ and a roasting time of 3-5 hours.

18. The method according to claim 1 or 2, wherein, In step (3), the loading method includes: impregnating Recry-Beta molecular sieves with a Zr precursor solution.

19. The method according to claim 18, wherein, The amounts of each component are such that, based on the total weight of the catalyst, the content of Recry-Beta molecular sieve is 95-99.9 wt%, and the content of zirconium-containing species, calculated as Zr oxide, is 0.1-5 wt%.

20. The method according to claim 19, wherein, The amounts of each component are such that, based on the total weight of the catalyst, the content of Recry-Beta molecular sieve is 97-99.5 wt%, and the content of zirconium-containing species, calculated as Zr oxide, is 0.5-3 wt%.

21. The method according to claim 1 or 2, wherein, In step (3), the conditions of the load include: a temperature of 80-120℃; a pressure of 0.2 MPa - 0.8 MPa; and / or The load duration is 4-68 hours; and / or The roasting conditions include a temperature of 400-600℃ and a time of 1-6 hours.

22. The method according to claim 21, wherein, In step (3), The load duration is 10-50 hours.

23. The method according to claim 1 or 2, wherein, The settling agent is selected from at least one of urea, ammonia, and ammonium salts.

24. ZrO prepared by the method according to any one of claims 1-23 x -Beta catalyst.

25. The ZrO according to claim 24 x -Beta catalyst, where The catalyst has a silicon-to-aluminum ratio of 800 or higher; and / or The total acidity of the catalyst is 220-400 μmol / g; and / or In the catalyst, the ratio of weak acid to moderately strong acid is 2-7; and / or The catalyst's BET specific surface area S BET 150-550 m 2 / g; and / or The total pore volume of the catalyst V 总 It is 0.45-0.7 cm. 3 / g; and / or The packing pore volume V of the catalyst meso It is 0.3-0.7 cm. 3 / g; and / or The catalyst has an average particle size of 20-50 nm.

26. The ZrO according to claim 25 x -Beta catalyst, where The catalyst has a silicon-to-aluminum ratio of 1200-2500.

27. The ZrO according to claim 25 x -Beta catalyst, where The total acidity of the catalyst is 250-350 μmol / g.

28. The ZrO according to claim 25 x -Beta catalyst, where In the catalyst, the ratio of weak acid to moderately strong acid is 3.5-6.

5.

29. The ZrO according to claim 25 x -Beta catalyst, where The catalyst's BET specific surface area S BET 330-510m 2 / g.

30. The ZrO according to claim 25 x -Beta catalyst, where The total pore volume of the catalyst V 总 It is 0.55-0.67cm 3 / g.

31. The ZrO according to claim 25 x -Beta catalyst, where The packing pore volume V of the catalyst meso It is 0.4-0.55cm 3 / g.

32. The ZrO according to claim 25 x -Beta catalyst, where The catalyst has an average particle size of 20-30 nm.

33. The catalyst according to claim 25, wherein, Based on the total weight of the catalyst, the Recry-Beta molecular sieve content is 95-99.9 wt%, and the zirconium-containing species content, calculated as Zr oxide, is 0.1-5 wt%.

34. The catalyst according to claim 33, wherein, Based on the total weight of the catalyst, the Recry-Beta molecular sieve content is 97-99.5 wt%, and the zirconium-containing species content, calculated as Zr oxide, is 0.5-3 wt%.

35. A ZrO x -Beta catalyst, characterized in that The catalyst comprises a Beta molecular sieve and a zirconium-containing species supported on the Beta molecular sieve, wherein the zirconium-containing species is a monoclinic / tetragonal miscible phase. Among them, the monoclinic phase accounts for 55%-80% of the zirconium-containing species; The crystallinity of the catalyst is 30-60%. The catalyst has a silicon-to-aluminum ratio of 1200-2500; The total acidity of the catalyst is 250-350 μmol / g; In the catalyst, the ratio of weak acid to moderately strong acid is 3.5-6.5; The catalyst's BET specific surface area S BET 330-510m 2 / g; The total pore volume of the catalyst V 总 It is 0.55-0.67cm 3 / g; The packing pore volume V of the catalyst meso It is 0.45-0.55cm 3 / g; The catalyst has an average particle size of 20-30 nm.

36. The ZrO according to claim 35 x -Beta catalyst, where Based on the total weight of the catalyst, the Recry-Beta molecular sieve content is 95-99.9 wt%, and the zirconium-containing species content, calculated as Zr oxide, is 0.1-5 wt%.

37. The ZrO according to claim 36 x -Beta catalyst, where Based on the total weight of the catalyst, the Recry-Beta molecular sieve content is 97-99.5 wt%, and the zirconium-containing species content, calculated as Zr oxide, is 0.5-3 wt%.

38. The ZrO according to any one of claims 24-37 x - Application of Beta catalysts in hydrocarbon conversion reactions.

39. The application according to claim 38, wherein, The hydrocarbon conversion reaction is the reaction of preparing 1,3-butadiene from ethanol and acetaldehyde.

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