Al2O3-hierarchical pore high-silicon molecular sieve loaded Mo type catalytic material as well as preparation method and application of Al2O3-hierarchical pore high-silicon molecular sieve loaded Mo type catalytic material

Abstract

The invention discloses an Al2O3-hierarchical pore high-silicon molecular sieve loaded Mo type catalytic material as well as a preparation method and application thereof. The Al2O3-hierarchical pore high-silicon molecular sieve loaded Mo type catalytic material comprises a carrier and an active component, the active component comprises an active element Mo; the carrier is an Al2O3-hierarchical pore high-silicon molecular sieve; the hierarchical pore high-silicon molecular sieve has micropores and mesopores; the silica-alumina ratio of the hierarchical pore high-silica molecular sieve is 280 to 300; the specific surface area of the micropores is 160-240 m < 2 > / g, and the volume of the micropores is 0.05-0.25 cm < 3 > / g; the specific surface area of the mesopores is 230-280 m < 2 > / g, the volume of the mesopores is 0.15-0.75 cm < 3 > / g, and the pore diameter of the mesopores is 3-12 nm. The method provided by the invention has high conversion rate and high selectivity; the stability, the controllability and the reproducibility are good; steps and equipment are simple, raw materials and reagents are common and easy to obtain, production cost is low, and large-scale industrialization is facilitated.

Description

Technical Field

[0001] The present application relates to an Al2O3 - hierarchical porous high - silica molecular sieve supported Mo - type catalytic material, its preparation method and application in the method for producing propylene by olefin disproportionation, belonging to the field of catalyst materials. Background Art

[0002] Propylene is an important basic organic raw material. Due to the rapid growth of the demand for propylene, the supply of propylene from traditional production methods such as steam cracking and FCC by - products has been difficult to fully meet the market demand. Steam cracking and FCC by - products are currently the two main production methods of propylene, but with the limitation of production capacity, the supply of these methods has gradually been unable to meet the market demand. Therefore, people have begun to seek new methods to produce propylene, such as the biotechnological production of propylene, the coal - to - ethylene process, etc. Technologies that specifically produce propylene, such as methanol - to - olefins, propane dehydrogenation, and olefin disproportionation, will develop rapidly. Therefore, the process research and application of ethylene - butene disproportionation to produce propylene have received increasing attention.

[0003] The key point and difficulty in the reaction of olefin disproportionation to produce propylene are catalyst preparation. The catalysts widely used in industrial olefin disproportionation reactions are usually based on transition metals. According to the type of transition metal, they are mainly divided into three categories: Re - based, W - based, and Mo - based. The supported Mo - based catalyst is one of the options. Mo - based catalysts are widely used in the disproportionation reaction to produce propylene, and their catalytic activity and selectivity have been quite recognized. Such catalysts mainly load the oxides of Mo on some appropriate carriers, such as Al2O3, SiO2, SiO2 - Al2O3, etc.

[0004] Preparing high - performance supported Mo - based catalysts requires in - depth research and optimization of the catalyst formulation, physical properties, and preparation process. Various factors during the preparation process, including the selection of raw materials, control of composition, dispersion of the catalyst, properties of the carrier, etc., will all affect the final performance of the catalyst. Therefore, during the research and preparation of high - performance catalysts, in - depth physical and chemical analysis is required to understand the influence of various factors on catalytic activity and selectivity, and to improve the performance of the catalyst by optimizing process conditions and formulations. This requires systematic and in - depth research and continuous experimental verification in catalyst preparation, characterization, and application.

[0005] Currently, in the research on using various high-silica zeolites as carriers to prepare Mo-based Al2O3-high-silica zeolite catalysts for disproportionation reactions, microporous high-silica zeolites are mostly used. The pore size of microporous high-silica zeolites is relatively small, which limits the contact between reactant molecules and catalytic active sites, thus reducing the reaction rate and selectivity. In addition, the diffusion rate of macromolecules in micropores is relatively slow, which may lead to carbon deposition, reduce the activity of the catalyst, and ultimately affect its service life and product selectivity.

[0006] To solve these problems, researchers have carried out various methods. One of them is to change the pore size through surfactants. Methods such as preparing high-silica zeolites containing mesopores or macropores can improve the performance of the catalyst, enhance the activity stability and anti-carbon deposition ability. Treating high-silica zeolites with surfactants can change their molecular sieve pore size, and alkali treatment can change the silicon-aluminum ratio of high-silica zeolites and stabilize the high-silica zeolite framework. By surfactant and alkali treatment, hierarchical pore high-silica zeolites can be prepared, which have the advantages of fast reaction rate and high pore formation efficiency. The method of comprehensively using alkali treatment to synthesize hierarchical pore high-silica zeolites is simple and feasible, and can effectively improve the performance of the catalyst.

[0007] CN117065785A discloses a high-silica zeolite catalyst and its preparation method. The preparation method of the high-silica zeolite catalyst includes: 1) a step of mixing high-silica zeolite, silica sol, and sesbania powder, and then adding inorganic base for kneading; 2) a step of extruding, curing, first drying, and first calcining the kneaded and formed material in step 1); 3) a step of performing ammonium exchange, washing, second drying, and second calcining on the first calcined product. CN202010153541.3 discloses an active material, its preparation method and application. The active material is a metal-tungsten ammonium salt, and the chemical formula of the metal-tungsten ammonium salt is (NH4)4[MW 12 O 44 , where M is a metal element, and the metal element is selected from any one of Fe, Co, Ni, Cu, Ru, Rh, Ga, Mo, Al; the carrier includes modified silica; the modified silica contains modified elements, and the modified elements include at least one of alkali metal elements, alkaline earth metal elements, and rare earth metal elements. Through the optimized design of the tungsten metal component, taking it as the active material component of the olefin disproportionation catalyst and using the metal-modified silica as the carrier, a new olefin disproportionation catalyst is obtained. The above catalyst can, to a certain extent, solve the problems of low catalyst activity and fast deactivation in the process of lower olefin disproportionation in the existing process. However, at present, the synthesis process of this type of catalyst is relatively complex, and there are problems such as difficult process control, poor repeatability, high cost, low conversion rate, and poor product selectivity, which limit its industrial application. Summary of the Invention

[0008] In one aspect of the present application, an Mo-type catalyst supported on Al2O3-mesoporous high-silica molecular sieve is provided. The Mo-type catalyst supported on Al2O3-mesoporous high-silica molecular sieve comprises a support and an active component;

[0009] The active component comprises the active element Mo;

[0010] The support is an Al2O3-mesoporous high-silica molecular sieve;

[0011] The mesoporous high-silica molecular sieve has micropores and mesopores;

[0012] The silica-alumina ratio of the mesoporous high-silica molecular sieve is 280-300;

[0013] The specific surface area of the micropores is 160-240 m 2 / g, and the volume of the micropores is 0.05-0.25 cm 3 / g;

[0014] The specific surface area of the mesopores is 230-280 m 2 / g, the volume of the mesopores is 0.15-0.75 cm 3 / g, and the pore diameter of the mesopores is 3-12 nm.

[0015] Optionally, in the support, the weight ratio of Al2O3 to the mesoporous high-silica molecular sieve is 30:10-30:70.

[0016] Optionally, the content of the active component is 3-5 wt% of the mass of the support.

[0017] In another aspect of the present application, a preparation method of the above-mentioned Mo-type catalyst supported on Al2O3-mesoporous high-silica molecular sieve is provided. This method has good stability, controllability and reproducibility. In addition, the raw materials are common, easily available and inexpensive, which is conducive to large-scale industrial application.

[0018] Optionally, the preparation method of the Mo-type catalyst supported on Al2O3-mesoporous high-silica molecular sieve comprises:

[0019] (1) Adding a molecular sieve into a solution I containing an inorganic base and a surfactant for alkali treatment, drying I and calcining I to obtain a support precursor; subjecting the support precursor to ammonium exchange and mixing it with Al2O3 to obtain an Al2O3-mesoporous high-silica molecular sieve;

[0020] (2) Impregnating the Al2O3-mesoporous high-silica molecular sieve obtained in step (1) in a molybdate solution, stirring, drying II and calcining II to obtain the Mo-type catalyst supported on Al2O3-mesoporous high-silica molecular sieve.

[0021] As a specific embodiment, the preparation method includes:

[0022] Performing surfactant treatment, alkali treatment and ammonium exchange on the high-silica molecular sieve, and then mixing it with Al2O3 to obtain an Al2O3-mesoporous high-silica molecular sieve material;

[0023] Impregnating the Al2O3-mesoporous high-silica molecular sieve material in a molybdate solution to obtain an Al2O3-mesoporous high-silica molecular sieve supported Mo-type catalytic material.

[0024] Optionally, the surfactant is tetrapropylammonium hydroxide.

[0025] Optionally, in the solution I, the concentration of the surfactant is 0.05 - 0.25 mol / L.

[0026] Optionally, the concentration of the surfactant is independently selected from any value of 0.05 mol / L, 0.1 mol / L, 0.15 mol / L, 0.2 mol / L, 0.25 mol / L or any range value between any two of the above.

[0027] Optionally, the inorganic base is NaOH;

[0028] In the solution I, the concentration of the inorganic base is 0.05 - 0.2 mol / L.

[0029] Optionally, the concentration of the inorganic base is independently selected from any value of 0.05 mol / L, 0.1 mol / L, 0.15 mol / L, 0.2 mol / L or any range value between any two of the above.

[0030] Optionally, the solid-liquid ratio of the molecular sieve to the solution I is 1:10 - 1:50.

[0031] Optionally, the solid-liquid ratio of the molecular sieve to the solution I is independently selected from any value of 1:10, 1:20, 1:30, 1:40, 1:50 or any range value between any two of the above.

[0032] Optionally, the temperature of the alkali treatment is 50 - 70 °C, and the time of the alkali treatment is 0.5 - 2 h.

[0033] Optionally, the temperature of the alkali treatment is independently selected from any value of 50 °C, 60 °C, 65 °C, 70 °C or any range value between any two of the above.

[0034] Optionally, the time of the alkali treatment is independently selected from any value of 0.5 h, 1 h, 2 h or any range value between any two of the above.

[0035] Optionally, the temperature of the first drying is 90 to 130 °C, and the time of the first drying is 12 to 24 h.

[0036] Optionally, the temperature of the first drying is independently selected from any value of 90 °C, 100 °C, 110 °C, 120 °C, 130 °C or any range value between any two of the above.

[0037] Optionally, the time of the first drying is independently selected from any value of 12 h, 16 h, 20 h, 24 h or any range value between any two of the above.

[0038] Optionally, the temperature of the first calcination is 550 to 750 °C, and the time of the first calcination is 3 to 6 h.

[0039] Optionally, the temperature of the first calcination is independently selected from any value of 550 °C, 650 °C, 750 °C or any range value between any two of the above.

[0040] Optionally, the time of the first calcination is independently selected from any value of 3 h, 4 h, 5 h, 6 h or any range value between any two of the above.

[0041] Optionally, the ammonium exchange includes the following steps:

[0042] Treat the carrier precursor with an aqueous ammonium chloride solution, followed by drying III and calcination III.

[0043] Optionally, in the aqueous ammonium chloride solution, the concentration of NH4Cl is 0.8 to 1.2 mol / L.

[0044] Optionally, the concentration of NH4Cl is independently selected from any value of 0.8 mol / L, 1 mol / L, 1.2 mol / L or any range value between any two of the above.

[0045] Optionally, the solid-liquid ratio of the carrier precursor to the aqueous ammonium chloride solution is 1:10 to 1:30.

[0046] Optionally, the solid-liquid ratio of the carrier precursor to the aqueous ammonium chloride solution is independently selected from any value of 1:10, 1:20, 1:30 or any range value between any two of the above.

[0047] Optionally, the temperature of the treatment with the aqueous ammonium chloride solution is 70 to 90 °C, and the time of the treatment with the aqueous ammonium chloride solution is 6 to 8 h.

[0048] Optionally, the temperature of the treatment with the aqueous ammonium chloride solution is independently selected from any value of 70 °C, 80 °C, 90 °C or any range value between any two of the above.

[0049] Optionally, the treatment time of the ammonium chloride aqueous solution is independently selected from any value among 6 h, 7 h, and 8 h or any range value between any two of the above.

[0050] Optionally, the temperature of the third drying is 90 - 130 °C, and the time of the third drying is 12 - 24 h.

[0051] Optionally, the temperature of the third drying is independently selected from any value among 90 °C, 100 °C, 110 °C, 120 °C, and 130 °C or any range value between any two of the above.

[0052] Optionally, the time of the third drying is independently selected from any value among 12 h, 16 h, 20 h, and 24 h or any range value between any two of the above.

[0053] Optionally, the temperature of the third calcination is 550 - 750 °C, and the time of the third calcination is 3 - 6 h.

[0054] Optionally, the temperature of the third calcination is independently selected from any value among 550 °C, 650 °C, and 750 °C or any range value between any two of the above.

[0055] Optionally, the time of the third calcination is independently selected from any value among 3 h, 4 h, 5 h, and 6 h or any range value between any two of the above.

[0056] Optionally, the mixing with Al2O3 includes the following steps:

[0057] Mixing and shaping the ammonium-exchanged molecular sieve with Al2O3, performing the fourth calcination, and crushing and sieving.

[0058] Optionally, the weight ratio of Al2O3 to the ammonium-exchanged molecular sieve is 1:10 - 1:50.

[0059] Optionally, the weight ratio of Al2O3 to the ammonium-exchanged molecular sieve is independently selected from any value among 1:10, 1:20, 1:30, 1:40, and 1:50 or any range value between any two of the above.

[0060] Optionally, the mixing and shaping method is selected from at least one of rolling into balls, extruding into strips, and tabletting.

[0061] Optionally, the temperature of the fourth calcination is 500 - 700 °C, and the time of the fourth calcination is 3 - 6 h.

[0062] Optionally, the temperature of the fourth calcination is independently selected from any value among 500 °C, 600 °C, and 700 °C or any range value between any two of the above.

[0063] Optionally, the time of the fourth calcination is independently selected from any value among 3 h, 4 h, 5 h, and 6 h or any range value between any two of the above.

[0064] Optionally, the crushing and sieving is carried out to 20 - 40 mesh;

[0065] Optionally, the crushing and sieving is independently selected from any value among 20 mesh, 22 mesh, 24 mesh, 26 mesh, 28 mesh, 30 mesh, 32 mesh, 34 mesh, 36 mesh, 38 mesh, and 40 mesh or any range value between any two of the above.

[0066] Optionally, in the step (2), the molybdenum salt includes ammonium molybdate.

[0067] Optionally, the molybdenum salt is ammonium heptamolybdate;

[0068] In the molybdenum salt solution, the concentration of the molybdenum salt is 3 - 5 wt%.

[0069] Optionally, the concentration of the molybdenum salt is independently selected from any value among 3 wt%, 4 wt%, and 5 wt% or any range value between any two of the above.

[0070] Optionally, the solid - liquid ratio of the Al2O3 - hierarchical porous high - silica molecular sieve to the molybdenum salt solution is 1:0.6 - 1:1.

[0071] Optionally, the solid - liquid ratio of the Al2O3 - hierarchical porous high - silica molecular sieve to the molybdenum salt solution is independently selected from any value among 1:0.6, 1:0.8, and 1:1 or any range value between any two of the above.

[0072] Optionally, the stirring time is 5 - 15 min.

[0073] Optionally, the stirring time is independently selected from any value among 5 min, 8 min, 10 min, 12 min, and 15 min or any range value between any two of the above.

[0074] Optionally, the temperature of the second drying is 90 - 130 °C, and the time of the second drying is 12 - 24 h.

[0075] Optionally, the temperature of the second drying is independently selected from any value among 90 °C, 100 °C, 110 °C, 120 °C, and 130 °C or any range value between any two of the above.

[0076] Optionally, the time of the second drying is independently selected from any value among 12 h, 14 h, 16 h, 18 h, 20 h, 22 h, and 24 h or any range value between any two of the above.

[0077] Optionally, the temperature of the second calcination is 550 to 750 °C, and the time of the second calcination is 3 to 6 h.

[0078] As a specific embodiment, the preparation method of the Al2O3-mesoporous high-silica molecular sieve supported Mo-type catalytic material specifically comprises the following steps:

[0079] 1) Treat the high-silica molecular sieve material with tetrapropylammonium hydroxide and NaOH solution, wash until neutral, dry, and calcine to obtain a sodium ion-containing mesoporous high-silica molecular sieve material;

[0080] 2) Treat the sodium ion-containing mesoporous high-silica molecular sieve material with NH4Cl solution, wash, dry, and calcine to obtain a mesoporous high-silica molecular sieve material;

[0081] 3) Uniformly mix and mold the mesoporous high-silica molecular sieve material and Al2O3, calcine, crush and screen to obtain the Al2O3-mesoporous high-silica molecular sieve material;

[0082] 4) Immerse the Al2O3-mesoporous high-silica molecular sieve material in an ammonium molybdate solution, stir, dry, and calcine to obtain the Al2O3-mesoporous high-silica molecular sieve supported Mo-type catalytic material.

[0083] Among them, the numerical ranges of the various conditions involved in steps 1) to 4) are as described above.

[0084] Another aspect of the present application provides a method for producing propylene by ethylene-butene disproportionation. This method uses the Al2O3-mesoporous high-silica molecular sieve supported Mo-type catalytic material, which has a high conversion rate of raw material ethylene / butene and a high selectivity of the product propylene.

[0085] The method includes: contacting a raw material containing ethylene and butene with a pretreated catalyst, reacting to obtain propylene;

[0086] Among them, the catalyst is the above-mentioned Al2O3-mesoporous high-silica molecular sieve supported Mo-type catalyst.

[0087] Optionally, the temperature of the reaction is 80 to 160 °C; the time of the reaction is 1 to 6 h;

[0088] The mass space velocity of the raw material is 0.1 to 2.5 h -1 ;

[0089] In the raw material, the molar ratio of ethylene to butene is 0.5:1 to 2.0:1.

[0090] Optionally, the temperature of the reaction is independently selected from any value among 80°C, 90°C, 100°C, 110°C, 120°C, 130°C, 140°C, 150°C, 160°C or any range value between any two of the above.

[0091] Optionally, the time of the reaction is independently selected from any value among 1 h, 1.5 h, 2 h, 2.5 h, 3 h, 3.5 h, 4 h, 4.5 h, 5 h, 5.5 h, 6 h or any range value between any two of the above.

[0092] Optionally, the mass space velocity of the raw material is independently selected from -1 0.1 h -1 0.3 h -1 0.5 h -1 0.7 h -1 0.9 h -1 1.1 h -1 1.3 h -1 1.5 h -1 1.7 h -1 1.9 h -1 2.1 h -1 2.3 h -1 any value among the above or any range value between any two of the above.

[0093] Optionally, in the raw material, the molar ratio of ethylene to butene is independently selected from any value among 0.5:1, 0.6:1, 0.7:1, 0.8:1, 0.9:1, 1.0:1, 1.1:1, 1.2:1, 1.3:1, 1.4:1, 1.5:1, 1.6:1, 1.7:1, 1.8:1, 1.9:1, 2:1 or any range value between any two of the above.

[0094] Optionally, in the raw material, butene is a mixture of 1-butene and 2-butene.

[0095] Optionally, the pretreatment is that the Al2O3-mesoporous high-silica molecular sieve supported Mo catalyst is activated in an activation atmosphere;

[0096] wherein, the activation atmosphere is N 2；

[0097] The activation temperature is 100 - 180°C, and the activation temperature time is 1 - 6 h.

[0098] In the context of the present application, unless otherwise specified, the term "silica-alumina ratio" or "Si / Al" means the molar ratio of silicon element to aluminum element in the high-silica molecular sieve.

[0099] The beneficial effects that the present application can produce include:

[0100] 1) The present application provides a method for synthesizing an Al2O3 - hierarchical pore high - silica molecular sieve supported molybdenum - based catalyst with good stability, controllability, and repeatability. Moreover, the process and production equipment are simple, and the raw materials and reagents used are relatively easy to obtain and inexpensive, which is very beneficial for large - scale industrial use.

[0101] 2) The present application proposes a new method for preparing propylene by ethylene - butene disproportionation using an Al2O3 - hierarchical pore high - silica molecular sieve supported molybdenum catalyst, achieving efficient conversion of ethylene / butene and high selectivity for propylene.

[0102] 3) The method described in the present application has high conversion rate and high selectivity; good stability, controllability, and reproducibility; simple steps and equipment, common and easily available raw materials and reagents, and low production cost, which is conducive to large - scale industrialization. Description of the Drawings

[0103] Figure 1 It is the nitrogen physical adsorption - desorption curve of the raw high - silica molecular sieve (Si / Al = 300) in the examples of the present application.

[0104] Figure 2 It is the nitrogen physical adsorption - desorption curve of Catalyst 1 in Example 1 of the present application.

[0105] Figure 3 It is the pore size distribution curve of the raw high - silica molecular sieve (Si / Al = 300) in the examples of the present application.

[0106] Figure 4 It is the pore size distribution curve of Catalyst 1 in Example 1 of the present application. Detailed Description of the Embodiments

[0107] As described above, the present application relates to the preparation of an Al2O3 - hierarchical pore high - silica molecular sieve supported Mo - type catalytic material by alkali treatment and its application in the ethylene - butene disproportionation reaction. The hierarchical pore high - silica molecular sieve is obtained by alkali treatment and ammonium exchange, etc., and the main active components of the catalytic material are Al2O3 and Mo ions. In addition, the present application also relates to a method for the ethylene - butene disproportionation to propylene reaction using the said catalyst. The said catalytic material improves the conversion rate and selectivity in the ethylene - butene disproportionation reaction.

[0108] The following describes the present application in detail with reference to the embodiments, but the present application is not limited to these embodiments.

[0109] Unless otherwise specified, the raw materials and reagents in the examples of the present application are purchased through commercial channels, and the high - silica molecular sieve (Si / Al = 300) is produced by Jiangsu Huangma Co., Ltd.

[0110] The analysis method in the embodiments of this application is as follows:

[0111] Use a Quantachrome QuadraSorb SI4 physical adsorption analyzer for specific surface area and pore size distribution characterization.

[0112] Use a WDXRF (Magix 600) X-ray fluorescence spectrometer to determine the silica-alumina ratio of the high-silica molecular sieve.

[0113] Use a GC-7900 gas chromatograph (FID detector, HP-PLOT Q capillary column) from Tianmei to analyze the composition of the ethylene-butene disproportionation reaction products.

[0114] The calculation of conversion rate and selectivity in the embodiments of this application is as follows (using butene conversion rate as the evaluation index):

[0115]

[0116]

[0117] Where XEthene represents the ethylene conversion rate; SPropene represents the propylene selectivity; represents the molar number of raw material ethylene; represents the molar number of olefins with carbon number m in the reaction products.

[0118] Preparation of the catalyst in Example 1

[0119] Treat 12 g of the high-silica molecular sieve material with 7.32 g of tetrapropylammonium hydroxide with a concentration of 0.15 mol / L and 240 mL of 0.2 mol / L NaOH solution at 65 °C for 0.5 hours, wash until neutral, dry at 100 °C for 12 hours, and calcine at 550 °C for 3 hours to obtain a sodium-ion-containing hierarchical porous high-silica molecular sieve material; keep the solution temperature at 80 °C, treat 12 g of the sodium-ion-containing hierarchical porous high-silica molecular sieve material with 240 mL of 0.8 mol / L NH4Cl solution for 7 hours, wash and then dry at 110 °C for 12 hours, and calcine at 550 °C for 3 hours to obtain a hierarchical porous high-silica molecular sieve material; uniformly mix Al2O3 and the hierarchical porous high-silica molecular sieve material with a mass ratio of 30:70 by extrusion into strips, calcine at 500 °C for 3 hours and then crush and screen to obtain a 20-mesh material to prepare an Al2O3-hierarchical porous high-silica molecular sieve material; immerse 10 g of the Al2O3-hierarchical porous high-silica molecular sieve material in 6 mL of ammonium molybdate solution with a concentration of 3 wt%, stir for 10 min and then dry at 120 °C for 12 hours, and calcine at 500 °C for 3 hours to finally obtain an Al2O3-hierarchical porous high-silica molecular sieve supported Mo-type catalytic material, denoted as Catalyst 1.

[0120] The specific surface area and pore size distribution of the raw material high-silica molecular sieve and catalyst 1 were tested, and the test results are shown in Figures 1 to 4 , as can be seen from the figure, the pore size of the molecular sieve treated with tetrapropylammonium hydroxide increases, and the adsorption capacity is enhanced.

[0121] Preparation of the catalyst in Example 2

[0122] 12 g of the high-silica molecular sieve material was treated with 10.98 g of tetrapropylammonium hydroxide with a concentration of 0.05 mol / L and 360 mL of 0.2 mol / L NaOH solution at 65 °C for 0.5 h, dried at 90 °C for 12 h, and calcined at 550 °C for 2 h to obtain a sodium-ion-containing hierarchical pore high-silica molecular sieve material; keeping the solution temperature at 90 °C, 12 g of the sodium-ion-containing hierarchical pore high-silica molecular sieve material was treated with 360 mL of 0.8 mol / L NH4Cl solution for 7 h, washed and dried at 120 °C for 12 h, and calcined at 550 °C for 2 h to obtain a hierarchical pore high-silica molecular sieve material; Al2O3 and the hierarchical pore high-silica molecular sieve material with a mass ratio of 30:50 were uniformly mixed by tableting, calcined at 550 °C for 3 h and then crushed and sieved into 24-mesh material to obtain an Al2O3-hierarchical pore high-silica molecular sieve material; 10 g of the Al2O3-hierarchical pore high-silica molecular sieve material was impregnated in 7 mL of 3 wt% ammonium molybdate solution, stirred for 10 min and then dried at 120 °C for 12 h, and calcined at 500 °C for 3 h to finally obtain an Al2O3-hierarchical pore high-silica molecular sieve supported Mo-type catalytic material, denoted as catalyst 2.

[0123] Preparation of the catalyst in Example 3

[0124] 12 g of the high-silica molecular sieve material was treated with 14.64 g of tetrapropylammonium hydroxide with a concentration of 0.10 mol / L and 240 mL of 0.2 mol / L NaOH solution at 65 °C for 0.5 h, dried at 90 °C for 16 h, and calcined at 550 °C for 3 h to obtain a sodium-ion-containing hierarchical pore high-silica molecular sieve material; keeping the solution temperature at 85 °C, 12 g of the sodium-ion-containing hierarchical pore high-silica molecular sieve material was treated with 480 mL of 0.8 mol / L NH4Cl solution for 8 h, washed and dried at 130 °C for 16 h, and calcined at 550 °C for 3 h to obtain a hierarchical pore high-silica molecular sieve material; Al2O3 and the hierarchical pore high-silica molecular sieve material with a mass ratio of 30:70 were uniformly mixed by rolling, calcined at 550 °C for 3 h and then crushed and sieved into 28-mesh material to obtain an Al2O3-hierarchical pore high-silica molecular sieve material; 10 g of the Al2O3-hierarchical pore high-silica molecular sieve material was impregnated in 8 mL of 3 wt% ammonium molybdate solution, stirred for 10 min and then dried at 120 °C for 16 h, and calcined at 500 °C for 3 h to finally obtain an Al2O3-hierarchical pore high-silica molecular sieve supported Mo-type catalytic material, denoted as catalyst 3.

[0125] Preparation of the catalyst in Example 4

[0126] 12 g of high-silica molecular sieve material was treated with 21.96 g of tetrapropylammonium hydroxide with a concentration of 0.15 mol / L and 240 mL of 0.15 mol / L NaOH solution at 65 °C for 0.5 h, dried at 110 °C for 20 h, and calcined at 550 °C for 3 h to obtain a sodium-ion-containing hierarchical pore high-silica molecular sieve material; keeping the solution temperature at 85 °C, 12 g of the sodium-ion-containing hierarchical pore high-silica molecular sieve material was treated with 360 mL of NH4Cl solution with a concentration of 0.8 mol / L for 8 h, washed and dried at 110 °C for 20 h, and calcined at 550 °C for 3 h to obtain a hierarchical pore high-silica molecular sieve material; Al2O3 and the hierarchical pore high-silica molecular sieve material with a mass ratio of 30:10 were uniformly mixed by rolling balls, calcined at 550 °C for 3 h and then crushed and sieved into 20-mesh material to obtain an Al2O3-hierarchical pore high-silica molecular sieve material; 10 g of the Al2O3-hierarchical pore high-silica molecular sieve material was impregnated in 9 mL of ammonium molybdate solution with a concentration of 3 wt%, stirred for 10 min, dried at 120 °C for 12 h, and calcined at 500 °C for 3 h to finally obtain an Al2O3-hierarchical pore high-silica molecular sieve supported Mo-type catalytic material, denoted as catalyst 4.

[0127] Preparation of the catalyst in Example 5

[0128] 12 g of high-silica molecular sieve material was treated with 29.28 g of tetrapropylammonium hydroxide with a concentration of 0.2 mol / L and 240 mL of 0.1 mol / L NaOH solution at 65 °C for 0.5 h, dried at 130 °C for 12 h, and calcined at 550 °C for 3 h to obtain a sodium-ion-containing hierarchical pore high-silica molecular sieve material; keeping the solution temperature at 90 °C, 12 g of the sodium-ion-containing hierarchical pore high-silica molecular sieve material was treated with 360 mL of NH4Cl solution with a concentration of 0.8 mol / L for 7 h, washed and dried at 130 °C for 12 h, and calcined at 550 °C for 3 h to obtain a hierarchical pore high-silica molecular sieve material; Al2O3 and the hierarchical pore high-silica molecular sieve material with a mass ratio of 30:70 were uniformly mixed by extrusion into strips, calcined at 500 °C for 3 h and then crushed and sieved into 32-mesh material to obtain an Al2O3-hierarchical pore high-silica molecular sieve material; 10 g of the Al2O3-hierarchical pore high-silica molecular sieve material was impregnated in 10 mL of ammonium molybdate solution with a concentration of 3 wt%, stirred for 10 min, dried at 130 °C for 12 h, and calcined at 550 °C for 3 h to finally obtain an Al2O3-hierarchical pore high-silica molecular sieve supported Mo-type catalytic material, denoted as catalyst 5.

[0129] Preparation of the catalyst in Example 6

[0130] 12 g of high-silica molecular sieve material was treated with 36.6 g of tetrapropylammonium hydroxide with a concentration of 0.25 mol / L and 240 mL of 0.2 mol / L NaOH solution at 65 °C for 0.5 h, dried at 100 °C for 24 h, and calcined at 550 °C for 3 h to obtain a sodium-ion-containing hierarchical pore high-silica molecular sieve material; maintaining the solution temperature at 85 °C, 12 g of the sodium-ion-containing hierarchical pore high-silica molecular sieve material was treated with 480 mL of 0.8 mol / L NH4Cl solution for 8 h, washed and dried at 110 °C for 24 h, and calcined at 550 °C for 3 h to obtain a hierarchical pore high-silica molecular sieve material; Al2O3 and the hierarchical pore high-silica molecular sieve material with a mass ratio of 30:70 were uniformly mixed by extrusion into strips, calcined at 500 °C for 3 h, crushed and sieved into 20-mesh material to obtain an Al2O3 - hierarchical pore high-silica molecular sieve material; 10 g of the Al2O3 - hierarchical pore high-silica molecular sieve material was impregnated in 6 mL of ammonium molybdate solution with a concentration of 3 wt%, stirred for 10 min, dried at 120 °C for 20 h, and calcined at 550 °C for 3 h to finally obtain an Al2O3 - hierarchical pore high-silica molecular sieve supported Mo-type catalytic material, denoted as catalyst 6.

[0131] Preparation of the catalyst in Example 7

[0132] 12 g of high-silica molecular sieve material was treated with 36.6 g of tetrapropylammonium hydroxide with a concentration of 0.25 mol / L and 240 mL of 0.1 mol / L NaOH solution at 65 °C for 0.5 h, dried at 100 °C for 16 h, and calcined at 550 °C for 3 h to obtain a sodium-ion-containing hierarchical pore high-silica molecular sieve material; maintaining the solution temperature at 80 °C, 12 g of the sodium-ion-containing hierarchical pore high-silica molecular sieve material was treated with 360 mL of 0.8 mol / L NH4Cl solution for 7 h, washed and dried at 130 °C for 20 h, and calcined at 550 °C for 3 h to obtain a hierarchical pore high-silica molecular sieve material; Al2O3 and the hierarchical pore high-silica molecular sieve material with a mass ratio of 30:50 were uniformly mixed by extrusion into strips, calcined at 500 °C for 3 h, crushed and sieved into 24-mesh material to obtain an Al2O3 - hierarchical pore high-silica molecular sieve material; 10 g of the Al2O3 - hierarchical pore high-silica molecular sieve material was impregnated in 8 mL of ammonium molybdate solution with a concentration of 3 wt%, stirred for 10 min, dried at 130 °C for 24 h, and calcined at 550 °C for 3 h to finally obtain an Al2O3 - hierarchical pore high-silica molecular sieve supported Mo-type catalytic material, denoted as catalyst 7.

[0133] Preparation of the catalyst in Example 8

[0134] 12 g of high-silica molecular sieve material was treated with 7.32 mL of tetrapropylammonium hydroxide with a concentration of 0.05 mol / L and 240 mL of 0.05 mol / L NaOH solution at 65 °C for 0.5 h, dried at 90 °C for 16 h, and calcined at 550 °C for 3 h to obtain a sodium-ion-containing hierarchical porous high-silica molecular sieve material; maintaining the solution temperature at 80 °C, 12 g of the sodium-ion-containing hierarchical porous high-silica molecular sieve material was treated with 480 mL of NH4Cl solution with a concentration of 0.8 mol / L for 8 h, washed, dried at 130 °C for 20 h, and calcined at 550 °C for 3 h to obtain a hierarchical porous high-silica molecular sieve material; Al2O3 and the hierarchical porous high-silica molecular sieve material with a mass ratio of 30:50 were uniformly mixed by extrusion into strips, calcined at 500 °C for 3 h, then crushed and sieved into 24-mesh material to obtain an Al2O3 - hierarchical porous high-silica molecular sieve material; 10 g of the Al2O3 - hierarchical porous high-silica molecular sieve material was impregnated in 9 mL of ammonium molybdate solution with a concentration of 3 wt%, stirred for 3 h, dried at 130 °C for 16 h, and calcined at 550 °C for 3 h to finally obtain an Al2O3 - hierarchical porous high-silica molecular sieve supported Mo-type catalytic material, denoted as Catalyst 8.

[0135] Preparation of the catalyst in Example 9

[0136] 12 g of high-silica molecular sieve material was treated with 36.6 g of tetrapropylammonium hydroxide with a concentration of 0.25 mol / L and 240 mL of 0.15 mol / L NaOH solution at 65 °C for 0.5 h, dried at 110 °C for 20 h, and calcined at 550 °C for 3 h to obtain a sodium-ion-containing hierarchical porous high-silica molecular sieve material; maintaining the solution temperature at 80 °C, 12 g of the sodium-ion-containing hierarchical porous high-silica molecular sieve material was treated with 240 mL of NH4Cl solution with a concentration of 0.8 mol / L for 4 h, washed, dried at 130 °C for 16 h, and calcined at 550 °C for 3 h to obtain a hierarchical porous high-silica molecular sieve material; Al2O3 and the hierarchical porous high-silica molecular sieve material with a mass ratio of 30:70 were uniformly mixed by tableting, calcined at 500 °C for 3 h, then crushed and sieved into 28-mesh material to obtain an Al2O3 - hierarchical porous high-silica molecular sieve material; 10 g of the Al2O3 - hierarchical porous high-silica molecular sieve material was impregnated in 0.6 mL of ammonium molybdate solution with a concentration of 3 wt%, stirred for 2 h 10 min, dried at 120 °C for 20 h, and calcined at 550 °C for 3 h to finally obtain an Al2O3 - hierarchical porous high-silica molecular sieve supported Mo-type catalytic material, denoted as Catalyst 9.

[0137] Preparation of the catalyst in Example 10

[0138] 12 g of high-silica molecular sieve material was treated with 7.32 g of tetrapropylammonium hydroxide with a concentration of 0.10 mol / L and 120 mL of 0.15 mol / L NaOH solution at 65 °C for 0.5 h, dried at 110 °C for 16 h, and calcined at 550 °C for 3 h to obtain a sodium-ion-containing hierarchical pore high-silica molecular sieve material; while maintaining the solution temperature at 90 °C, 12 g of the sodium-ion-containing hierarchical pore high-silica molecular sieve material was treated with 120 mL of 0.8 mol / L NH4Cl solution for 8 h, washed, dried at 130 °C for 12 h, and calcined at 550 °C for 3 h to obtain a hierarchical pore high-silica molecular sieve material; Al2O3 and the hierarchical pore high-silica molecular sieve material with a mass ratio of 30:70 were uniformly mixed by extrusion into strips, calcined at 500 °C for 3 h, and then crushed and sieved into 32-mesh materials to obtain an Al2O3 - hierarchical pore high-silica molecular sieve material; 10 g of the Al2O3 - hierarchical pore high-silica molecular sieve material was impregnated in 6 mL of ammonium molybdate solution with a concentration of 3 wt%, stirred for 10 min, dried at 120 °C for 16 h, and calcined at 550 °C for 3 h to finally obtain an Al2O3 - hierarchical pore high-silica molecular sieve supported Mo-type catalytic material, denoted as catalyst 10.

[0139] Test Example 1

[0140] The catalysts 1 - 10 obtained in Examples 1 - 10 were respectively activated under a N2 atmosphere, and the activation temperature and time are shown in Table 1.

[0141] The raw materials containing ethylene and butene were contacted with the activated catalysts of Examples 1 - 10 for reaction to prepare propylene. The specific reaction parameters are shown in Table 1.

[0142] The composition of the product was analyzed using a GC-7900 gas chromatograph (FID detector, HP-PLOT Q capillary column) from Tianmei Company, and the results are shown in Table 1.

[0143] Table 1 Process conditions and results of catalysts 1 - 10 for the disproportionation of ethylene - butene to propylene

[0144]

[0145]

[0146] As described above, only several embodiments of the present application are presented, and no any form of limitation is imposed on the present application. Although the present application is disclosed with preferred embodiments as above, it is not intended to limit the present application. Any person skilled in the relevant art can make some changes or modifications within the scope of the technical solution of the present application by using the disclosed technical content, which are equivalent to equivalent embodiments and all fall within the scope of the technical solution.

Claims

1. Application of an Al2O3 - hierarchical porous high - silica molecular sieve supported Mo - type catalyst in olefin disproportionation, characterized in that, The Al2O3 - hierarchical porous high - silica molecular sieve supported Mo - type catalyst includes a support and an active component; The active component includes the active element Mo; The support is Al2O3 - hierarchical porous high - silica molecular sieve; The hierarchical porous high - silica molecular sieve has micropores and mesopores; The silica - to - alumina ratio of the hierarchical porous high - silica molecular sieve is 280 - 300; The specific surface area of ​​the micropores is 160 to 240 m 2 / g, the volume of micropores is 0.05~0.25cm 3 / g; The specific surface area of the mesopores is 230 to 280 m 2 / g, the volume of the mesopores is 0.15 to 0.75 cm 3 / g, and the pore diameter of the mesopores is 3 to 12 nm.

2. The Al2O3 - hierarchical porous high - silica molecular sieve supported Mo - type catalyst according to claim 1, characterized in that, In the support, the weight ratio of Al2O3 to the hierarchical porous high - silica molecular sieve is 30:10 - 30:70; The content of the active component is 3 - 5 wt% of the mass of the support.

3. A preparation method of the Al2O3 - hierarchical porous high - silica molecular sieve supported Mo - type catalyst according to any one of claims 1 to 2, characterized in that, The preparation method includes: (1) Adding the molecular sieve into solution I containing an inorganic base and a surfactant for alkali treatment, drying I, and calcining I to obtain a support precursor; subjecting the support precursor to ammonium exchange and mixing it with Al2O3 to obtain Al2O3 - hierarchical porous high - silica molecular sieve; (2) Impregnating the Al2O3 - hierarchical porous high - silica molecular sieve obtained in step (1) in a molybdate solution, stirring, drying II, and calcining II to obtain the Al2O3 - hierarchical porous high - silica molecular sieve supported Mo - type catalyst.

4. The method according to claim 3, characterized in that, The surfactant is tetrapropylammonium hydroxide; Preferably, in solution I, the concentration of the surfactant is 0.05 - 0.25 mol / L; Preferably, the inorganic base is NaOH; In solution I, the concentration of the inorganic base is 0.05 - 0.2 mol / L; Preferably, the solid - to - liquid ratio of the molecular sieve to solution I is 1:10 - 1:50; Preferably, the temperature of the alkali treatment is 50 - 70 °C, and the time of the alkali treatment is 0.5 - 2 h; Preferably, the temperature of drying I is 90 - 130 °C, and the time of drying I is 12 - 24 h; Preferably, the temperature of calcining I is 550 - 750 °C, and the time of calcining I is 3 - 6 h.

5. The method according to claim 3, characterized in that, The ammonium exchange includes the following steps: Treating the support precursor with an ammonium chloride aqueous solution, drying III, and calcining III; Preferably, the concentration of the ammonium chloride aqueous solution is 0.8 - 1.2 mol / L; Preferably, the solid - to - liquid ratio of the support precursor to the ammonium chloride aqueous solution is 1:10 - 1:30; Preferably, the temperature of the treatment with the ammonium chloride aqueous solution is 70 - 90 °C, and the time is 6 - 8 h; Preferably, the temperature of drying III is 90 - 130 °C, and the time of drying III is 12 - 24 h; Preferably, the temperature of calcining III is 550 - 750 °C, and the time of calcining III is 3 - 6 h.

6. The method according to claim 3, characterized in that, The mixing with Al2O3 includes the following steps: Mixing the ammonium - exchanged molecular sieve with Al2O3 for shaping, calcining IV, and crushing and sieving; Preferably, the weight ratio of Al2O3 to the ammonium - exchanged molecular sieve is 1:10 - 1:50; Preferably, the shaping method is selected from at least one of rolling into balls, extruding into strips, and tabletting; Preferably, the temperature of calcining IV is 500 - 700 °C, and the time of calcining IV is 3 - 6 h; Preferably, the crushing and sieving is carried out to 20 - 40 mesh.

7. The method according to claim 3, characterized in that, In step (2), the molybdate is ammonium heptamolybdate; In the molybdate solution, the concentration of the molybdate is 3-5 wt%. Preferably, the solid-liquid ratio of the Al2O3 - hierarchical porous high-silica molecular sieve to the molybdate solution is 1:0.6 - 1:

1. Preferably, the stirring time is 5 - 15 min. Preferably, the temperature of the second drying is 90 - 130 °C, and the time of the second drying is 12 - 24 h. Preferably, the temperature of the second calcination is 550 - 750 °C, and the time of the second calcination is 3 - 6 h.

8. A method for producing propylene by ethylene-butene disproportionation, characterized in that, Contact the raw material containing ethylene and butene with the pretreated catalyst, and react to obtain propylene. Among them, the catalyst is selected from the Al2O3 - hierarchical porous high-silica molecular sieve supported Mo-type catalyst according to any one of claims 1 - 2.

9. The method according to claim 8, characterized in that, The temperature of the reaction is 80 - 160 °C. The mass hourly space velocity of the raw material is 0.1 to 2.5 h -1 ; In the raw material, the molar ratio of ethylene to butene is 0.5:1 - 2.0:

1.

10. The method according to claim 1, characterized in that, The pretreatment is that the Al2O3 - hierarchical porous high-silica molecular sieve supported Mo-type catalyst is activated in an activation atmosphere. Among them, the activation atmosphere is N2. The temperature of the activation is 100 - 180 °C, and the time of the activation temperature is 1 - 6 h.

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