Micro-mesoporous molecular sieve composite material as well as preparation method and application thereof

Abstract

The invention discloses a micro-mesoporous molecular sieve composite material and a preparation method and application thereof, the preparation method comprises the following steps: step 1, mixing a KIT-6 molecular sieve, a rare earth-containing compound, a titanium-containing compound, a hydrogenation active metal precursor, a first template agent and water, crystallizing and roasting to obtain a composite material; and 2, mixing the composite material, a Y molecular sieve guiding agent, an aluminum source, an alkali source, a silicon source and water, crystallizing, and roasting to obtain the micro-mesoporous molecular sieve composite material. As an acidic carrier material, the micro-mesoporous molecular sieve composite material can be widely applied to hydrofining catalysts and hydrocracking catalysts.

Description

Technical Field

[0001] This invention belongs to the field of hydrocracking, specifically relating to a micro-mesoporous molecular sieve composite material, its preparation method, and its application. Background Technology

[0002] Molecular sieves, due to their unique pore structure, are widely used in adsorption, separation, and catalysis, especially in the petrochemical industry. With the continuous expansion of molecular sieve catalytic applications, single-channel molecular sieves can no longer meet the diverse needs of catalyst preparation. Microporous molecular sieves excel in heterogeneous catalysis applications primarily due to their strong acidity and high structural stability. However, because microporous molecular sieves generally have small pore sizes and long, narrow channels, it is difficult for large molecules in reactants, such as heavy oil, to diffuse into the pores. This reduces the utilization rate of acidic sites within the microporous molecular sieve channels. Simultaneously, the narrow, long channels result in significant diffusion resistance, hindering the rapid diffusion and overflow of reaction product molecules, potentially leading to deep cracking and coking. While mesoporous molecular sieves can compensate for the diffusion limitations of microporous molecular sieves within reactants and products, their structural stability is often poor, further limiting their catalytic applications. Microporous-mesoporous composite molecular sieve materials can produce good synergistic effects and catalytic performance by combining the strengths and weaknesses of several individual materials, making their overall performance superior to that of the original constituent materials. This type of molecular sieve with multiple structures and superimposed functions can avoid the defects of single pore structures. The multi-level pore system can provide pores of different sizes at the same time, which will be of great help in solving problems such as mass transfer of macromolecules.

[0003] CN106311319A discloses a hydrocracking catalyst containing a micro-mesoporous composite molecular sieve and its application. The catalyst includes a catalyst support and active components. By weight percentage, the catalyst support comprises 5-50 wt% micro-mesoporous composite molecular sieve, 5-30 wt% γ-microporous molecular sieve, 10-50 wt% alumina, 20-55 wt% amorphous silica-alumina, 5-25 wt% binder, and 1-5 wt% extrusion aid. By weight percentage, the active components comprise 10%-40% group VIB metal oxides, 1%-20% group VIII metal oxides, and / or 0.1%-10% group VA oxides. Although the catalyst contains 5-50 wt% Beta / KIT-6 micro-mesoporous composite molecular sieve, both are relatively weak in acid strength because Beta molecular sieve is a microporous molecular sieve with isomerization and KIT-6 mesoporous molecular sieve is an all-silica molecular sieve. Therefore, the hydrocracking catalytic effect needs to be enhanced.

[0004] Therefore, further research is needed in this field on hydrocracking catalysts. Summary of the Invention

[0005] The main objective of this invention is to provide a micro-mesoporous molecular sieve composite material, its preparation method, and its application, so as to overcome the defects of poor cracking effect of hydrocracking catalysts in the prior art.

[0006] To achieve the above objectives, the present invention provides a method for preparing micro-mesoporous molecular sieve composite materials, comprising the following steps:

[0007] Step 1: KIT-6 molecular sieve, rare earth compound, titanium compound, hydrogenated active metal precursor, first template agent and water are mixed, crystallized and calcined to obtain composite material;

[0008] Step 2: Mix the composite material, Y molecular sieve directing agent, aluminum source, alkali source, silicon source and water, crystallize and calcine to obtain micro-mesoporous molecular sieve composite material.

[0009] The method for preparing the micro-mesoporous molecular sieve composite material of the present invention includes, in step 1, firstly mixing KIT-6 molecular sieve, rare earth compound, titanium compound and water, crystallizing to obtain a first crystallized product, then mixing the first crystallized product, hydrogenated active metal precursor, first template agent and water, crystallizing, calcining to obtain the composite material.

[0010] The preparation method of the micro-mesoporous molecular sieve composite material of the present invention, wherein the KIT-6 molecular sieve, rare earth compound, titanium compound and water are mixed by atomizing the rare earth compound, titanium compound and water, so that the KIT-6 molecular sieve adsorbs the atomized droplets.

[0011] The preparation method of the micro-mesoporous molecular sieve composite material of the present invention, wherein the KIT-6 molecular sieve, rare earth compound, titanium compound and water are mixed in the following manner: first, the mixture of rare earth compound and water is atomized, and the KIT-6 molecular sieve adsorbs the atomized droplets formed by rare earth compound and water; then, the mixture of titanium compound and water is atomized, and the KIT-6 molecular sieve adsorbs the atomized droplets formed by rare earth compound and water.

[0012] The method for preparing micro-mesoporous molecular sieve composite materials according to the present invention, wherein in step 1, the rare earth-containing compound is a rare earth salt, the titanium-containing compound is titanium oxynitrate or titanium sulfate, the hydrogenated active metal precursor is a Group VIB metal precursor and / or a Group VIII metal precursor, and the first template agent is at least one of PVP, urea, and hexadecyltrimethylammonium bromide.

[0013] The method for preparing the micro-mesoporous molecular sieve composite material of the present invention, wherein, in step 1, the rare earth compound is calculated as rare earth oxide, the titanium compound is calculated as titanium dioxide, the hydrogenated active metal precursor is calculated as hydrogenated active metal oxide, and the mass ratio of KIT-6 molecular sieve: rare earth oxide: titanium dioxide: metal oxide: first template agent: water is 1:(0.01-0.12):(0.01-0.15):(0.10-0.30):(0.01-0.03):(0.50-1.5).

[0014] The preparation method of the micro-mesoporous molecular sieve composite material of the present invention includes, after crystallization in step 2, an ammonium ion exchange step, followed by calcination; after calcination in step 2, a steam treatment step is also included.

[0015] The preparation method of the micro-mesoporous molecular sieve composite material of the present invention, wherein in step 2, the aluminum source is calculated as Al2O3, the alkali source is calculated as Na2O, and the silicon source is calculated as SiO2, and the mass ratio of each substance is: (0.5-1.5) composite material : (0.06-1.7) Y molecular sieve directing agent : 1 Al2O3 : (0.06-1.2) Na2O : (2.0-3.5) SiO2 : (10-50) H2O.

[0016] The preparation method of the micro-mesoporous molecular sieve composite material of the present invention includes a crystallization temperature of 100-190℃ and a pressure of 1-13MPa in step 1; and a crystallization temperature of 90-100℃ in step 2.

[0017] To achieve the above objectives, the present invention also provides a micro-mesoporous molecular sieve composite material, comprising KIT-6 molecular sieve, rare earth oxides, titanium oxides, hydrogenated active metal oxides, and Y molecular sieve, wherein the specific surface area of ​​the micro-mesoporous molecular sieve composite material is 730-820 m². 2 / g, total pore volume is 0.8-0.13mL / g, pore size distribution is 4-50nm, Brønsted acid content is 0.25-2.1mmol / g, L-acid content is 0.3-0.45mmol / g.

[0018] To achieve the above objectives, the present invention further provides the application of the micro-mesoporous molecular sieve composite material obtained by the above preparation method as an acidic support material in hydrorefining catalysts and hydrocracking catalysts.

[0019] The beneficial effects of this invention are:

[0020] This invention simultaneously introduces rare earth oxides and TiO2 into the pores of KIT-6 pure silica mesoporous molecular sieves, forming a large number of new acidic centers. These centers exhibit good pre-cracking capabilities for organic macromolecules and can serve as a hydrocracking support component. Building upon this, some metal oxides with hydrogenation capabilities are introduced into the KIT-6 pure silica mesoporous molecular sieves and crystallized to form a lamellar structure. This enhances the hydrogenation function in addition to the existing acidic cracking capabilities. Furthermore, the lamellar structure facilitates contact with large organic molecules, reduces steric hindrance of active centers, improves hydrogenation reaction performance, and inhibits carbon deposition. Therefore, the micro-mesoporous molecular sieve composite material of this invention can be widely used as an acidic support material in hydrorefining catalysts and hydrocracking catalysts. Attached Figure Description

[0021] Figure 1 The image shows a scanning electron microscope (SEM) image of the rare earth oxide / TiO2 / metal oxide / KIT-6 mesoporous molecular sieve composite material B prepared in Example 1 of this invention. Detailed Implementation

[0022] The technical solution of the present invention will be described in detail below. The following embodiments are implemented under the premise of the technical solution of the present invention and a detailed implementation process is given. However, the protection scope of the present invention is not limited to the following embodiments. Structures or experimental methods that do not specify specific conditions in the following embodiments are generally performed under conventional conditions.

[0023] This invention provides a method for preparing micro-mesoporous molecular sieve composite materials, comprising the following steps:

[0024] Step 1: KIT-6 molecular sieve, rare earth compound, titanium compound, hydrogenated active metal precursor, first template agent and water are mixed, crystallized and calcined to obtain composite material;

[0025] Step 2: Mix the composite material, Y molecular sieve directing agent, aluminum source, alkali source, silicon source and water, crystallize and calcine to obtain micro-mesoporous molecular sieve composite material.

[0026] In one embodiment, the crystallization temperature in step 1 is 100–190°C, the pressure is 1–13 MPa, and the time is 2–10 h.

[0027] In one embodiment, in step 1, KIT-6 molecular sieve, rare earth compound, titanium compound and water are first mixed and crystallized to obtain a first crystallized product. Then the first crystallized product, hydrogenated active metal precursor, first template agent and water are mixed, crystallized and calcined to obtain the composite material.

[0028] In another embodiment, the KIT-6 molecular sieve, rare earth compound, titanium compound, and water are mixed by atomizing the mixture, allowing the KIT-6 molecular sieve to adsorb the atomized droplets. In yet another embodiment, the mixture of rare earth compound and water is first atomized, and the KIT-6 molecular sieve adsorbs the atomized droplets; then the mixture of titanium compound and water is atomized, and the KIT-6 molecular sieve continues to adsorb the atomized droplets. Next, crystallization is performed to obtain a first crystallized product. The crystallization temperature is, for example, 100–150°C, the pressure is 1–5 MPa, and the time is 2–10 h.

[0029] In one embodiment, a first crystallizer, a hydrogenated active metal precursor, a first template agent, and water are mixed and crystallized at a temperature of 120–190°C and a pressure of 2–13 MPa for 2–10 hours, and calcined at a temperature of 500–550°C in an air atmosphere to obtain the composite material. This composite material has a lamellar structure.

[0030] This invention does not specifically limit the source and preparation method of KIT-6 molecular sieve; it can be a commercially available product or prepared according to existing technical methods.

[0031] In one embodiment, the rare earth compound is a rare earth salt, specifically a water-soluble rare earth salt. The rare earth element is preferably cerium, lanthanum, or praseodymium. The rare earth salt can be one or more of cerium nitrate, lanthanum nitrate, and praseodymium nitrate.

[0032] In one embodiment, the titanium-containing compound is titanium oxynitrate or titanium sulfate.

[0033] In one embodiment, the hydrogenating active metal in the hydrogenating active metal precursor is a Group VIB metal and / or a Group VIII metal, preferably molybdenum, tungsten, nickel, or cobalt. The hydrogenating active metal precursor can be a hydrogenating active metal salt, such as a nitrate, or a salt formed by the hydrogenating active metal as an anion, preferably ammonium heptamolybdate, ammonium metatungstate, nickel nitrate, or cobalt nitrate.

[0034] In one embodiment, the first template agent is at least one of PVP, urea, and hexadecyltrimethylammonium bromide.

[0035] In one embodiment, the rare earth compound is calculated as rare earth oxide, the titanium compound is calculated as titanium dioxide, the hydrogenated active metal precursor is calculated as hydrogenated active metal oxide, and the mass ratio of KIT-6 molecular sieve: rare earth oxide: titanium dioxide: metal oxide: first template agent: water is 1:(0.01-0.12):(0.01-0.15):(0.10-0.30):(0.01-0.03):(0.50-1.5), preferably 1:(0.03-0.10):(0.05-0.10):(0.20-0.30):(0.015-0.02):(0.7-1.0).

[0036] Step 2 of this invention is as follows: the above-prepared composite material, Y molecular sieve directing agent, aluminum source, alkali source, silicon source and water are mixed, crystallized and calcined to obtain micro-mesoporous molecular sieve composite material.

[0037] In one embodiment, the crystallization temperature in step 2 is 90-100°C, and the crystallization time is 24-48 hours. After crystallization, an ammonium ion exchange step is included, followed by calcination, and then a steam treatment step. Specifically, after crystallization, the mixture is filtered, then subjected to ion exchange in a 1-2 mol / L ammonium sulfate aqueous solution, dried, calcined, and steam treated to obtain a micro-mesoporous molecular sieve composite material. In one embodiment, the steam treatment temperature is 550-650°C, preferably 580-620°C.

[0038] In one embodiment, the aluminum source is calculated as Al2O3, the alkali source as Na2O, and the silicon source as SiO2. The mass ratio of each substance in step 2 is: (0.5-1.5) composite material : (0.06-1.7) Y molecular sieve directing agent : 1 Al2O3 : (0.06-1.2) Na2O : (2.0-3.5) SiO2 : (10-50) H2O. The aluminum source can be at least one of aluminum sulfate and sodium aluminate, the alkali source can be at least one of sodium aluminate and potassium hydroxide, and the silicon source can be at least one of water glass and silica sol.

[0039] In one embodiment, the Y-zeolite directing agent of the present invention can be prepared by the following method:

[0040] The alkali source, aluminum source, silicon source and water are mixed and aged to obtain Y molecular sieve directing agent.

[0041] The alkali source can be at least one of sodium aluminate and potassium hydroxide, the aluminum source can be at least one of aluminum sulfate and sodium aluminate, and the silicon source can be at least one of water glass and silica sol. The molar ratio of the alkali source, aluminum source, silicon source, and water can be (6-8.5)Na₂O:1Al₂O₃:(7-13)SiO₂:(200-350)H₂O (the alkali source is calculated as Na₂O, the aluminum source as Al₂O₃, and the silicon source as SiO₂), preferably (6.5-7.5)Na₂O:1Al₂O₃:(9-11)SiO₂:(220-300)H₂O. The aging temperature is 20-60℃, preferably 25-40℃.

[0042] The micro-mesoporous molecular sieve composite material obtained by the method of this invention has a specific surface area of ​​730-790 m². 2 / g, total pore volume is 0.8-0.12mL / g, pore size distribution is 4-50nm, Brønsted acid content is 1.7-2.1mmol / g, L-acid content is 0.3-0.4mmol / g.

[0043] The micro-mesoporous molecular sieve composite material of this invention can be used as an acidic support material and is widely used in hydrorefining catalysts and hydrocracking catalysts.

[0044] In one embodiment, the micro-mesoporous molecular sieve composite material of the present invention can be used as a component of a catalytic cracking catalyst support. The preparation method of the catalytic cracking catalyst support includes, for example, the following steps:

[0045] Microporous-mesoporous molecular sieve composite material, amorphous silica-alumina, macroporous alumina, metatitanic acid, cellulose and phosphoalumina sol are mixed, shaped and calcined to obtain a hydrocracking catalyst support.

[0046] In one embodiment, the present invention involves uniformly mixing a solid material micro-mesoporous molecular sieve composite, amorphous silica-alumina, macroporous alumina, metatitanic acid, and cellulose to obtain a mixture. Phosphorus aluminum sol is then atomized into micron-sized droplets. The mixture is then subjected to the adsorption of these micron-sized droplets, followed by shaping and calcination to obtain a catalyst support. Specifically, the atomization of phosphorus aluminum sol into micron-sized droplets can be achieved by pressurizing and spraying the phosphorus aluminum sol, and then using gas to impact the phosphorus aluminum sol in a perpendicular spray direction, thereby atomizing it into micron-sized droplets.

[0047] In one embodiment, the mass ratio of the micro-mesoporous molecular sieve composite material, amorphous silica-alumina, macroporous alumina, metatitanic acid, cellulose and phosphoaluminate sol is (40-70): (10-30): (10-30): (1-5): (1-5): (14-20).

[0048] In one embodiment, a method for preparing a catalyst from a hydrocracking catalyst support includes: loading an active component onto the catalyst support to obtain a hydrocracking catalyst.

[0049] In one embodiment, the active component is loaded onto the catalyst support by: forming an active component solution with a second template agent; adsorbing the active component solution onto the catalyst support; crystallizing; and calcining to obtain a hydrocracking catalyst. The crystallization temperature is 120–190°C, the pressure is 2–13 MPa, and the crystallization time is 2–10 h. The calcination temperature is 500–550°C.

[0050] In one embodiment, the active component is a precursor of a Group VIB metal and / or a Group VIII metal, preferably molybdenum, tungsten, nickel, or cobalt. The precursor can be a metal salt, such as a nitrate, or a salt formed by the metal as an anion, preferably ammonium heptamolybdate, ammonium metatungstate, nickel nitrate, or cobalt nitrate. In another embodiment, the active component in the hydrocracking catalyst has a mass content of 20–25 wt% based on oxides.

[0051] In one embodiment, the second template agent is at least one selected from PVP, urea, and hexadecyltrimethylammonium bromide, and the content of the second template agent in the active component solution is 0.1 to 0.5 wt%.

[0052] The hydrocracking catalyst obtained by the method of this invention has a specific surface area of ​​320–370 m². 2 With a pore volume of 0.6–0.8 mL / g and suitable acidity, it is used as an acidic support material in hydrorefining catalysts and hydrocracking catalysts.

[0053] The technical solution of the present invention will be further described in detail below through specific embodiments.

[0054] Example 1

[0055] Microporous-mesoporous molecular sieve composites were prepared by the following method:

[0056] (1) 87g of sodium aluminate solution (Al2O3 content is 4wt%, Na2O content is 20wt%) and 130g of water glass solution (SiO2 content is 20wt%) were added sequentially to 35g of deionized water (i.e. 8.5Na2O:1Al2O3:11.8SiO2:322H2O) and aged at 20℃ for 24h to obtain Y molecular sieve directing agent.

[0057] (2) According to the mass ratio of KIT-6 molecular sieve: rare earth oxide: TiO2: metal oxide: template agent: water = 1:0.01:0.01:0.1:0.01:0.5, KIT-6 molecular sieve was atomized and adsorbed with cerium nitrate and titanium oxynitrate aqueous solution. It was crystallized for 10 h at 100℃ and 1 MPa to obtain mixture A. Mixture A was mixed evenly with ammonium heptamolybdate, nickel nitrate and PVP. It was crystallized for 10 h at 120℃ and 2 MPa. After calcination at 550℃, rare earth oxide / TiO2 / metal oxide / KIT-6 mesoporous molecular sieve composite material B with plate-like structure was obtained.

[0058] (3) Add 5g of mesoporous molecular sieve composite material B, 5g of Y molecular sieve directing agent, 80g of aluminum sulfate solution (Al2O3 content is 2wt%), and 80g of sodium aluminate solution (Al2O3 content is 5wt%, Na2O content is 5wt%) to 90g of water glass solution (SiO2 content is 20wt%). Stir evenly and then add 5g of deionized water to make mixture C. Crystallize mixture C at 100℃ for 24h to obtain a slurry of Y / rare earth oxide / TiO2 / metal oxide / KIT-6 micro-mesoporous molecular sieve composite material. After filtration, ion exchange in 1mol / L ammonium sulfate aqueous solution for 1 hour, dry at 100℃ for 1 hour, calcine at 550℃ for 3 hours, and steam treat at 650℃ for 1 hour to obtain Y / rare earth oxide / TiO2 / metal oxide / KIT-6 micro-mesoporous molecular sieve composite material.

[0059] Example 2

[0060] Microporous-mesoporous molecular sieve composites were prepared by the following method:

[0061] (1) 77g of sodium aluminate solution (Al2O3 content of 4wt%, Na2O content of 20wt%) and 105g of water glass solution (SiO2 content of 20wt%) were added sequentially to 67g of deionized water (i.e. 6.82Na2O:1Al2O3:11.81SiO2:323H2O), and aged at 20℃ for 24h to obtain Y molecular sieve directing agent.

[0062] (2) According to the mass ratio of KIT-6 molecular sieve: rare earth oxide: TiO2: metal oxide: template agent: water = 1:0.06:0.075:0.15:0.015:1, KIT-6 molecular sieve was atomized and adsorbed with cerium nitrate and titanium oxynitrate aqueous solution. It was crystallized for 5h at 125℃ and 2.5MPa to obtain mixture A. Mixture A was mixed evenly with ammonium metatungstate, nickel nitrate and urea. It was crystallized for 5h at 140℃ and 8MPa. After calcination at 500℃, rare earth oxide / TiO2 / metal oxide / KIT-6 mesoporous molecular sieve composite material B with plate-like structure was obtained.

[0063] (3) 10g of mesoporous molecular sieve composite material B, 10g of Y molecular sieve directing agent, 65g of aluminum sulfate solution (Al2O3 content of 2wt%), and 65g of sodium aluminate solution (Al2O3 content of 5wt% and Na2O content of 5wt%) were added to 75g of water glass solution (SiO2 content of 20wt%). After stirring evenly, 50g of deionized water was added to prepare mixture C. Mixture C was crystallized at 90℃ for 48h to obtain a slurry of Y / rare earth oxide / TiO2 / metal oxide / KIT-6 micro-mesoporous molecular sieve composite material. After filtration, it was ion exchanged in 1.5mol / L ammonium sulfate aqueous solution for 1 hour, dried at 100℃ for 1 hour, calcined at 550℃ for 3 hours, and treated with steam at 600℃ for 1 hour to obtain Y / rare earth oxide / TiO2 / metal oxide / KIT-6 micro-mesoporous molecular sieve composite material.

[0064] Example 3

[0065] Microporous-mesoporous molecular sieve composites were prepared by the following method:

[0066] (1) 65g of sodium aluminate solution (Al2O3 content is 4wt%, Na2O content is 20wt%) and 82g of water glass solution (SiO2 content is 20wt%) were added sequentially to 100g of deionized water (i.e. 6.2Na2O:1Al2O3:10.7SiO2:206H2O) and aged at 40℃ for 24h to obtain Y molecular sieve directing agent.

[0067] (2) According to the mass ratio of KIT-6 molecular sieve: rare earth oxide: TiO2: metal oxide: template agent: water = 1:0.12:0.15:0.3:0.03:1.5, KIT-6 molecular sieve was atomized and adsorbed with cerium nitrate and titanium sulfate aqueous solution, respectively. It was crystallized for 2 hours at 150℃ and 5MPa to obtain mixture A. Mixture A was mixed evenly with ammonium molybdate, cobalt nitrate and hexadecyltrimethylammonium bromide. It was crystallized for 2 hours at 190℃ and 13MPa. After calcination at 525℃, rare earth oxide / TiO2 / metal oxide / KIT-6 mesoporous molecular sieve composite material B with plate-like structure was obtained.

[0068] (3) 15g of mesoporous molecular sieve composite material B, 15g of Y molecular sieve directing agent, 70g of aluminum sulfate solution (Al2O3 content of 2wt%), and 40g of sodium aluminate solution (Al2O3 content of 5wt% and Na2O content of 5wt%) were added to 63g of water glass solution (SiO2 content of 20wt%). After stirring evenly, 82g of deionized water was added to prepare mixture C. Mixture C was crystallized at 95℃ for 36h to obtain a slurry of Y / rare earth oxide / TiO2 / metal oxide / KIT-6 micro-mesoporous molecular sieve composite material. After filtration, it was ion exchanged in 2mol / L ammonium sulfate aqueous solution for 0.5h, dried at 100℃ for 1h, calcined at 525℃ for 4h, and treated with steam at 550℃ for 1h to obtain Y / rare earth oxide / TiO2 / metal oxide / KIT-6 micro-mesoporous molecular sieve composite material.

[0069] Example 4

[0070] Microporous-mesoporous molecular sieve composites were prepared by the following method:

[0071] (1) 65g of sodium aluminate solution (Al2O3 content is 4wt%, Na2O content is 20wt%) and 82g of water glass solution (SiO2 content is 20wt%) were added sequentially to 100g of deionized water (i.e. 6.2Na2O:1Al2O3:10.7SiO2:206H2O) and aged at 40℃ for 24h to obtain Y molecular sieve directing agent.

[0072] (2) According to the mass ratio of KIT-6 molecular sieve: rare earth oxide: TiO2: metal oxide: template agent: water = 1:0.12:0.15:0.3:0.03:1.5, KIT-6 molecular sieve was atomized and adsorbed with cerium nitrate and titanium sulfate aqueous solution, respectively. It was crystallized for 2 hours at 150℃ and 5MPa to obtain mixture A. Mixture A was mixed evenly with ammonium molybdate, cobalt nitrate and hexadecyltrimethylammonium bromide. It was crystallized for 2 hours at 190℃ and 13MPa. After calcination at 525℃, rare earth oxide / TiO2 / metal oxide / KIT-6 mesoporous molecular sieve composite material B with plate-like structure was obtained.

[0073] (3) 30g of mesoporous molecular sieve composite material B, 10g of Y molecular sieve directing agent, 75g of aluminum sulfate solution (Al2O3 content of 2wt%), and 45g of sodium aluminate solution (Al2O3 content of 5wt% and Na2O content of 5wt%) were added to 78g of water glass solution (SiO2 content of 20wt%). After stirring evenly, 85g of deionized water was added to prepare mixture C. Mixture C was crystallized at 95℃ for 36h to obtain a slurry of Y / rare earth oxide / TiO2 / metal oxide / KIT-6 micro-mesoporous molecular sieve composite material. After filtration, it was ion exchanged in 1mol / L ammonium sulfate aqueous solution for 0.5h, dried at 100℃ for 1h, and calcined at 500℃ for 4h to obtain Y / rare earth oxide / TiO2 / metal oxide / KIT-6 micro-mesoporous molecular sieve composite material.

[0074] The specific surface area, pore volume, pore size distribution, and infrared acid content of the micro-mesoporous molecular sieve composite materials of Examples 1-4 were tested respectively, and the results are shown in Table 1.

[0075] Table 1 Properties of micro-mesoporous molecular sieve composites

[0076]

[0077] According to the mass ratio of micro-mesoporous molecular sieve composite material: amorphous silica-alumina: macroporous alumina: metatitanic acid: organic macromolecular cellulose: aluminum phosphate sol (70%): (4%): (5%): (1%): (5%): (15%), the solid materials were mixed evenly, and then 15wt% of aluminum phosphate sol was pressurized to 2MPa and sprayed out, and then passed through a flow rate of 10m perpendicular to the spray direction. 3A high-speed gas stream of [speed value] / min is ejected and impacts the solid mixture, creating a wet atmosphere for the binder. This ensures thorough and uniform adsorption, followed by rolling, molding, and calcination to obtain the support. An aqueous solution of a metal salt (20 wt% ammonium metatungstate, 5 wt% nickel nitrate, and 0.5 wt% hexadecyltrimethylammonium bromide) was prepared and mixed with the support for adsorption. The mixture was then crystallized at 190°C and 13 MPa for 2 hours, followed by calcination at 550°C to obtain the hydrocracking catalyst. The properties of this catalyst are shown in Table 2. The catalysts prepared in Examples 1-4 were used in the hydrogenation reaction of high-aromatic distillate oil. The properties of the high-aromatic distillate oil are shown in Table 3, and the reaction conditions and evaluation results are shown in Table 4.

[0078] Table 2 Properties of the catalyst

[0079]

[0080] Table 3 Properties of High Aromatic Distillate Oils

[0081]

[0082] Table 4 Reaction conditions and evaluation results

[0083]

[0084] As shown in Tables 2-4, the hydrocracking catalyst prepared by the method of this invention possesses both microporous and mesoporous structures and is suitable for acidity. When this hydrocracking catalyst is used in oil hydrocracking reactions, the yield of light oil is high, while the yield of tail oil is low, enabling the simultaneous production of chemical feedstocks and aviation kerosene. The hydrorefining catalyst prepared by the method of this invention exhibits excellent deep denitrification performance.

[0085] Of course, the present invention may have other various embodiments. Without departing from the spirit and essence of the present invention, those skilled in the art can make various corresponding changes and modifications according to the present invention, but these corresponding changes and modifications should all fall within the protection scope of the claims of the present invention.

Claims

1. A method for preparing a micro-mesoporous molecular sieve composite material, characterized in that, Includes the following steps: Step 1: KIT-6 molecular sieve, rare earth compound, titanium compound, hydrogenated active metal precursor, first template agent and water are mixed, crystallized and calcined to obtain composite material; Step 2: Mix the composite material, Y molecular sieve directing agent, aluminum source, alkali source, silicon source and water, crystallize and calcine to obtain micro-mesoporous molecular sieve composite material.

2. The method for preparing the micro-mesoporous molecular sieve composite material according to claim 1, characterized in that, In step 1, KIT-6 molecular sieve, rare earth compound, titanium compound and water are first mixed and crystallized to obtain a first crystallized product. Then the first crystallized product, hydrogenated active metal precursor, first template agent and water are mixed, crystallized and calcined to obtain the composite material.

3. The method for preparing the micro-mesoporous molecular sieve composite material according to claim 1, characterized in that, The KIT-6 molecular sieve, rare earth compound, titanium compound and water are mixed by atomizing the rare earth compound, titanium compound and water, so that the KIT-6 molecular sieve adsorbs the atomized droplets.

4. The method for preparing the micro-mesoporous molecular sieve composite material according to claim 3, characterized in that, The mixing method of KIT-6 molecular sieve, rare earth compound, titanium compound and water is as follows: First, the mixture of rare earth compound and water is atomized, and KIT-6 molecular sieve adsorbs the atomized droplets formed by rare earth compound and water; then the mixture of titanium compound and water is atomized, and KIT-6 molecular sieve adsorbs the atomized droplets formed by rare earth compound and water.

5. The method for preparing the micro-mesoporous molecular sieve composite material according to claim 1, characterized in that, In step 1, the rare earth-containing compound is a rare earth salt, the titanium-containing compound is titanium oxynitrate or titanium sulfate, the hydrogenated active metal precursor is a Group VIB metal precursor and / or a Group VIII metal precursor, and the first template agent is at least one of PVP, urea, and hexadecyltrimethylammonium bromide.

6. The method for preparing the micro-mesoporous molecular sieve composite material according to claim 1, characterized in that, In step 1, the rare earth compound is calculated as rare earth oxide, the titanium compound is calculated as titanium dioxide, the hydrogenated active metal precursor is calculated as hydrogenated active metal oxide, and the mass ratio of KIT-6 molecular sieve: rare earth oxide: titanium dioxide: metal oxide: first template agent: water is 1:(0.01-0.12):(0.01-0.15):(0.10-0.30):(0.01-0.03):(0.50-1.5).

7. The method for preparing the micro-mesoporous molecular sieve composite material according to claim 1, characterized in that, In step 2, the aluminum source is calculated as Al2O3, the alkali source as Na2O, and the silicon source as SiO2. The mass ratio of each substance is as follows: (0.5-1.5) composite material: (0.06-1.7) Y molecular sieve directing agent: 1 Al2O3: (0.06-1.2) Na2O: (2.0-3.5) SiO2: (10-50) H2O.

8. The method for preparing the micro-mesoporous molecular sieve composite material according to claim 1, characterized in that, The crystallization temperature in step 1 is 100-190℃, and the crystallization pressure is 1-13MPa; the crystallization temperature in step 2 is 90-100℃.

9. A micro-mesoporous molecular sieve composite material, characterized in that, The composite material includes KIT-6 molecular sieve, rare earth oxides, titanium oxides, hydrogenated active metal oxides, and Y molecular sieve, and has a specific surface area of ​​730-820 m². 2 / g, total pore volume is 0.8-0.13mL / g, pore size distribution is 4-50nm, Brønsted acid content is 0.25-2.1mmol / g, L-acid content is 0.3-0.45mmol / g.

10. The application of the micro-mesoporous molecular sieve composite material obtained by the preparation method according to any one of claims 1-8 as an acidic support material in hydrorefining catalysts and hydrocracking catalysts.

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