Hydrocracking Catalysts, Their Preparation and Application

Abstract

This invention discloses a hydrocracking catalyst, comprising a support and rare earth metal and heteropolyacid metal active components supported on the support, wherein the catalyst has a specific surface area of ​​337-355 m². 2 ·g ‑1 The pore size is 0.40-0.46 cm. 3 ·g ‑1 This invention also discloses its preparation method and applications. The supported carbon aerogel Y / ZSM-35 / NU-87 composite molecular sieve used in this invention accelerates the breaking and formation of Si-O-Si bonds during the initial framework formation process using hydroxyl radicals. This facilitates the introduction of carbonates into the molecular sieve framework, achieving in-situ generation of mesopores and promoting the interaction between the support and the active component. The impregnation solution prepared using a heteropolyacid containing an active metal and a complexing agent can effectively regulate the active phase structure, forming highly dispersed type II phase hydrogenation active centers, significantly improving catalyst activity.

Description

Technical Field

[0001] This invention relates to a hydrocracking catalyst, its preparation, and its application. Background Technology

[0002] With the continuous expansion of the lubricant consumption market, the demand for high-quality lubricant base oils is growing rapidly. In the lubricant production process, the crude oil resources suitable for lubricant production are becoming increasingly scarce, with 85% being traditional base oils. Traditional base oils have low viscosity indices, making it difficult to produce higher-grade lubricant base oils. Therefore, lubricant base oil production must deal with relatively inferior raw materials, which poses a challenge for traditional solvent refining processes.

[0003] In recent years, hydrocracking technology has become one of the main technical routes for producing high-grade lubricating oil base oils, producing lubricating oils with high viscosity indices. Typically, hydrocracking tail oil is produced using hydrocracking dewaxing processes, including Mobil's MLDW process and BP's BP process. Hydrocracking tail oil is rich in alkanes and cycloalkanes, and low in aromatics, making it a high-quality feedstock for lubricating oil base oils. After isomerization and dewaxing, it can produce high-quality lubricating oil base oils. Therefore, exploring hydrocracking technology processes for producing lubricating oil base oils is essential. Summary of the Invention

[0004] This invention aims to provide a hydrocracking catalyst and its preparation and application. It utilizes the characteristics of hydrocracking tail oil, which is rich in alkanes and cycloalkanes and has a low content of aromatics, to serve as a high-quality raw material for lubricating oil base oil. After isomerization and dewaxing, it can produce high-quality lubricating oil base oil, thereby solving the problems of low viscosity index of base oil in traditional processes, which makes it difficult to produce higher grade lubricating oil base oil.

[0005] As one aspect of the present invention, a hydrocracking catalyst is disclosed, comprising a support and rare earth metal and heteropolyacid metal active components supported on the support, wherein the catalyst has a specific surface area of ​​337-355 m². 2 ·g -1 The pore size is 0.40-0.46cm. 3 ·g -1 .

[0006] In a specific embodiment, the carrier is prepared by calcining 15-25 wt% macroporous alumina material, 20-30 wt% amorphous silica-alumina and 20-50 wt% supported carbon aerogel Y / ZSM-35 / NU-87 composite molecular sieve with binder and extrusion aid.

[0007] In a specific embodiment, the supported carbon aerogel Y / ZSM-35 / NU-87 composite molecular sieve is prepared by the following method:

[0008] (1) Sodium hydroxide, sodium aluminate and water glass are mixed and then statically aged at 25-80℃ for 12-36h to obtain Y-type molecular sieve nanocrystal precursor, which contains (5-30) Na2O, 1Al2O3, and (5-40) SiO2; further, it also contains (200-800) molar H2O;

[0009] (2) According to the mass ratio of 7.2~10:1:1~1.5:2.0~3.5, ZSM-35 molecular sieve, NU-87 molecular sieve, carbon aerogel and Y-type molecular sieve nanocrystal precursor are added to a microwave vibrating container and organic alcohol is added. Microwave irradiation is carried out for 20-40 minutes under microwave power of 400-600W to obtain A mixed slurry.

[0010] (3) Mix the silicon source, aluminum source, alkaline solution, strong oxidant and carbonate evenly, then add A mixed slurry to fully react and form a gel solution. The components and their molar amounts are (2-80) Na2O, 1Al2O3, (5-200) SiO2, and further, it also contains (10-800) molar amounts of H2O. Crystallize at 90-150℃ for 12-24h, and calcine to obtain the supported carbon aerogel Y / ZSM-35 / NU-87 composite molecular sieve. The alkaline solution can be prepared as follows: dissolve sodium aluminate in hot (e.g., 95℃) sodium hydroxide solution, wherein the molar amounts of Na2O and Al2O3 are (10-15) Na2O:1Al2O3.

[0011] In a specific embodiment, the organic alcohol is selected from one or more of ethanol, isopropanol, ethylene glycol, propylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, trimethylene glycol, and triethylene glycol. The amount added is such that the mass ratio of the Y-type molecular sieve nanocrystal precursor suspension to the organic alcohol is 1:1.5-2.5. The organic alcohol acts as a dispersant, and those skilled in the art can adjust the dosage appropriately according to process requirements.

[0012] In a specific embodiment, the silicon source is one or more of water glass, tetraethyl orthosilicate, and silicon powder; the aluminum source is one or more of aluminum sulfate octadecylhydrate, aluminum oxide, aluminum chloride, and aluminum isopropoxide.

[0013] In a specific embodiment, the carbonate is one or more of sodium carbonate, potassium carbonate, and ammonium carbonate. The amount of carbonate added is 1-15% of the amount of SiO2 added to the gel.

[0014] In a specific embodiment, the strong oxidant is sodium persulfate, and the amount of strong oxidant added is 1-5% of the amount of SiO2 added to the gel.

[0015] As another aspect of the present invention, a method for preparing the above-mentioned hydrocracking catalyst is provided, comprising:

[0016] Rare earth metal salts, heteropoly acids C4H6O4Ni·4H2O, and H3[PW] 12 O 40 ]·XH2O and H3[PMo 12 O 40 ]·XH2O was added to ethyl propyl ether, and a complexing agent was added while stirring. The pH was adjusted to 2-3 to prepare a complexed heteropolyacid impregnation solution, wherein rare earth metal salts, heteropolyacids C4H6O4Ni·4H2O, and H3[PW 12 O 40 ]·XH2O、H3[PMo 12 O 40 The molar ratio of XH2O to complexing agent is 0.5~2:11~24:1:2~5:0.2~0.5, with ethylpropyl ether as the dispersant.

[0017] The complexing agent is one or more selected from citric acid, tartaric acid, malic acid, succinic acid, salicylic acid, 1,2,3,4-butanetetracarboxylic acid, and 2-phosphonobutane-1,2,4-tricarboxylic acid. The rare earth metal salt is at least one selected from lanthanum chloride, cerium chloride, lanthanum nitrate, and cerium nitrate.

[0018] In a specific embodiment, the method further includes: impregnating the carrier in a complexed heteropoly acid impregnation solution of equal volume and then drying it.

[0019] As another aspect of the present invention, it relates to the application of the above-mentioned hydrocracking catalyst in the hydrocracking production of lubricating oil base oil.

[0020] A mixture of reduced-pressure secondary and reduced-pressure tertiary ketone-benzene dewaxing oils was used as raw material. The reaction was carried out at a temperature of 360–410℃, a pressure of 12.0–17.0 MPa, and a space velocity of 1.5–2.0 h⁻¹. -1 Hydrocracking evaluation was conducted under a hydrogen-to-oil ratio of 700–1500:1, which can effectively achieve high tail oil production, with a tail oil yield exceeding 40% ω, a viscosity index of around 135, and a tail oil BMCI value of 9.6.

[0021] The supported carbon aerogel Y / ZSM-35 / NU-87 composite molecular sieve used in this invention accelerates the breaking and formation of Si-O-Si bonds during the initial framework formation process using hydroxyl radicals. This facilitates the introduction of carbonates into the molecular sieve framework, enabling in-situ generation of mesopores and promoting the interaction between the support and the active component. The impregnation solution prepared using a heteropolyacid containing an active metal and a complexing agent effectively regulates the active phase structure, forming highly dispersed type II phase hydrogenation active centers, significantly improving catalyst activity. Attached Figure Description

[0022] Appendix Figure 1XRD pattern of the carrier in Example 1. Detailed Implementation

[0023] The inventors conducted experiments according to CN114433205 A, CN114437796 A, CN 111448293 A, and CN107286980A, but the results did not meet the inventors' expectations. After further research and development, the inventors arrived at this invention.

[0024] The specific embodiments of the present invention will be further described in detail below with reference to the accompanying drawings, so as to make the technical solution of the present invention easier to understand and master. However, the present invention is not limited thereto. Unless otherwise specified, the experimental methods in the following embodiments are conventional methods; unless otherwise specified, the reagents and materials are all commercially available. Among them, sodium hydroxide (Beijing Chemical Plant, analytical grade), sodium aluminate (Shandong Aluminum Industry Research Institute, industrial grade), water glass (Beijing Hongxing Sodium Silicate Plant, SiO2 content 27.81wt%, Na2O content 8.74wt%), ZSM-35 molecular sieve (brand: innochem, silicon-to-aluminum ratio 19), carbon aerogel (Nanjing Bingzhou New Material Technology Co., Ltd.), NU-87 (prepared according to CN 102211780 A), phosphotungstic acid hydrate (brand: innochem, purity 99%), phosphomolybdic acid hydrate (brand: innochem, purity 98%), nickel acetate tetrahydrate (brand: innochem, purity 99%), lanthanum nitrate (brand: innochem, purity AR, ≥44.0%), tartaric acid (brand: innochem, purity ≥99%), and citric acid (brand: innochem, purity 99%).

[0025] Example 1

[0026] 1. Preparation of carbon-supported aerogel Y / ZSM-35 / NU-87 composite molecular sieve

[0027] (1) Add 8g of sodium hydroxide to 20.9g of water and stir until the sodium hydroxide is completely dissolved. Then add 1.7g of sodium aluminate and stir until the sodium aluminate is completely dissolved to obtain a sodium aluminate mixed solution. Take 61.8g of the sodium aluminate mixed solution and 31.4g of water glass and pour them into 26.2g of deionized water. After stirring evenly, let it stand at 60℃ for 16h to obtain a Y-type molecular sieve nanocrystal precursor slurry containing 5Na2O, 1Al2O3, and 5SiO2 in molar fractions.

[0028] (2) Add 14.3g of ZSM-35 molecular sieve, 1.6g of NU-87 molecular sieve, and 1.98g of carbon aerogel to a microwave vibrating container containing 3.5g of Y-type molecular sieve nanocrystal precursor slurry, with a mass ratio of 9:1:1.2:2.2, and add 8.75g of isopropanol. Microwave irradiate for 30min under a microwave power of 400W to obtain the A mixed slurry.

[0029] (3) Alkali solution 1: Dissolve 16g of sodium hydroxide in 15.6g of water, then add 3.3g of sodium aluminate and stir until completely dissolved. The molar ratio of alkali solution is 10Na2O:1Al2O3.

[0030] (4) After mixing 20.83g of tetraethyl orthosilicate and 1.15g of ammonium carbonate evenly, a solution of 1.33g of aluminum chloride and 36g of water, and 12g of alkali solution 1 were added and mixed evenly. Then, 0.238g of sodium persulfate was added, and finally, mixed slurry A was added to form a gel solution with the following composition and molar ratio: 30Na2O:1Al2O3:20SiO2. The solution was stirred at 37℃ for 3h. The gel was then transferred to a polytetrafluoroethylene liner and crystallized at 120℃ for 24h. After filtration, washing, and drying, the solution was calcined at 600℃ for 10h to obtain the supported carbon aerogel Y / ZSM-35 / NU-87 composite molecular sieve.

[0031] 2. Mix 12g of macroporous alumina material, 15g of amorphous silica-alumina, 23g of supported carbon aerogel Y / ZSM-35 / NU-87 composite molecular sieve, and 5.0g of guar gum powder evenly, then dropwise add the mixture to an aqueous solution containing 4.5g of concentrated nitric acid (96wt%), extrude it into strips, dry the above-mentioned material, and calcine it at 450℃ for 6h to prepare a carrier.

[0032] 3. Prepare a solution by mixing 37.5g lanthanum nitrate, 158g nickel acetate (tetrahydrate), 167g phosphotungstic acid pentahydrate, and 217g phosphomolybdic acid. Add the solution to 20ml ethyl propyl ether and stir at 65℃ for 60min. After cooling to room temperature while stirring, add 1.74g tartaric acid to adjust the pH to 2 and continue stirring for 60min. (Note: The last sentence appears to be incomplete and possibly contains errors. It likely refers to a solution containing rare earth metal salts and heteropoly acids.) 12 O 40 ]·XH2O,H3[PMo 12 O 40 The complexing agent is prepared by mixing XH2O with a molar ratio of 2:11:1:2:0.2, resulting in a complexed heteropolyacid impregnation solution.

[0033] 4. Take 42.5 ml of heteropoly acid to prepare an impregnation solution, add 50 g of support, impregnate the prepared support with an equal volume for 2 h, dry at 120 °C for 4 h, calcine at 500 °C in air atmosphere for 4 h, and add hydrocracking catalyst.

[0034] Example 2

[0035] 1. Preparation method of carbon-supported aerogel Y / ZSM-35 / NU-87 composite molecular sieve

[0036] (1) Add 25g of sodium hydroxide to 33.4g of water and stir until the sodium hydroxide is completely dissolved. Then add 5.2g of sodium aluminate and stir until the sodium aluminate is completely dissolved to obtain a sodium aluminate mixed solution. Take 42g of the sodium aluminate mixed solution and 94.2g of water glass and pour them into 57.5g of deionized water. After stirring evenly, let it stand at 35℃ for 16h to obtain a Y-type molecular sieve nanocrystal precursor slurry containing 16Na2O, 1Al2O3, and 15SiO2 in molar fractions.

[0037] (2) 20.6g of ZSM-35 molecular sieve, 2.29g of NU-87 molecular sieve, and 2.86g of carbon aerogel were added to a microwave vibrating container containing 7.4g of Y-type molecular sieve nanocrystal precursor slurry, with a mass ratio of 10:1:1.2:3.2. 18.5g of isopropanol was also added. The mixture was microwave irradiated for 30min at a microwave power of 400W to obtain the A mixed slurry.

[0038] (3) Alkali solution 1: Dissolve 16g of sodium hydroxide in 15.6g of water, then add 3.3g of sodium aluminate and stir until completely dissolved. The molar ratio of alkali solution is 10Na2O:1Al2O3.

[0039] (4) After mixing 46.75g of water glass and 4g of sodium carbonate evenly, add 10.5g of aluminum sulfate octadecylhydrate and 23.75g of water solution, 10.64g of alkali solution 1, and mix evenly. Then add 0.98g of sodium persulfate, and finally add the A mixed slurry to form a gel solution with the following composition and molar ratio: 2.85Na2O:Al2O3:8.4SiO2. Stir at 35℃ for 3h. Transfer the above gel to a polytetrafluoroethylene liner and crystallize at 96℃ for 12h. After filtration, washing, drying, and calcination at 550℃ for 10h, obtain the supported carbon aerogel Y / ZSM-35 / NU-87 composite molecular sieve.

[0040] 2. Mix 12g of macroporous alumina material, 15g of amorphous silica-alumina, 23g of supported carbon aerogel Y / ZSM-35 / NU-87 composite molecular sieve, and 5.0g of guar gum powder evenly, then dropwise add the mixture to an aqueous solution containing 4.5g of concentrated nitric acid (96wt%), extrude it into strips, dry the above-mentioned material, and calcine it at 400-600℃ for 6-10h to prepare a carrier.

[0041] 3. Prepare a solution by mixing 37.5g lanthanum nitrate, 158g nickel acetate (tetrahydrate), 167g phosphotungstic acid pentahydrate, and 217g phosphomolybdic acid. Add the solution to 20ml ethyl propyl ether and stir at 65℃ for 60min. After cooling to room temperature while stirring, add 2.23g citric acid to adjust the pH to 2 and continue stirring for 60min. The solution contains rare earth metal salts and heteropoly acids C4H6O4Ni·4H2O, H3[PW 12 O 40 ]·XH2O,H3[PMo 12 O 40 The complexing agent is prepared by mixing XH2O with a molar ratio of 2:11:1:2:0.2, resulting in a complexed heteropolyacid impregnation solution.

[0042] 4. Take 42.5 ml of heteropoly acid to prepare an impregnation solution, add 50 g of support, impregnate the prepared support with an equal volume for 2 h, dry at 120 °C for 4 h, calcine at 500 °C in air atmosphere for 4 h, and add hydrocracking catalyst.

[0043] Example 3

[0044] 1. Preparation method of carbon-supported aerogel Y / ZSM-35 / NU-87 composite molecular sieve

[0045] (1) Add 25g of sodium hydroxide to 33.4g of water and stir until the sodium hydroxide is completely dissolved. Then add 5.2g of sodium aluminate and stir until the sodium aluminate is completely dissolved to obtain a sodium aluminate mixed solution. Take 42g of the sodium aluminate mixed solution and 94.2g of water glass and pour them into 57.5g of deionized water. After stirring evenly, let it stand at 35℃ for 16h to obtain a Y-type molecular sieve nanocrystal precursor slurry containing 16Na2O, 1Al2O3, and 15SiO2 in molar fractions.

[0046] (2) Add 2.88g of ZSM-35 molecular sieve, 0.4g of NU-87 molecular sieve, and 0.6g of carbon aerogel to a microwave vibrating container containing 0.79g of Y-type molecular sieve nanocrystal precursor slurry, with a mass ratio of 7.2:1:1.5:2.0, and add 2.0g of isopropanol. Microwave irradiate for 30min under a microwave power of 400W to obtain the A mixed slurry.

[0047] (3) Alkali solution 1: Dissolve 16g of sodium hydroxide in 15.6g of water, then add 3.3g of sodium aluminate and stir until completely dissolved. The molar ratio of alkali solution is 10Na2O:1Al2O3.

[0048] (4) Mix 4.16g of tetraethyl orthosilicate with 0.048g of potassium carbonate and stir until homogeneous. Then add a solution of 1.02g of alumina, 9g of water, and 1.6g of alkali solution 1 and stir until homogeneous. Then add 0.24g of sodium persulfate and finally add the A mixture slurry to form a gel solution with the following composition and molar ratio: 2Na2O:Al2O3:2SiO2. Stir at 25℃ for 3h. Transfer the above gel to a polytetrafluoroethylene liner and crystallize at 95℃ for 15h. After filtration, washing, drying, and calcination at 400℃ for 6h, obtain the supported carbon aerogel Y / ZSM-35 / NU-87 composite molecular sieve.

[0049] 2. Mix 12g of macroporous alumina material, 15g of amorphous silica-alumina, 23g of supported carbon aerogel Y / ZSM-35 / NU-87 composite molecular sieve, and 5.0g of guar gum powder evenly, then dropwise add the mixture to an aqueous solution containing 4.5g of concentrated nitric acid (96wt%), extrude it into strips, dry the above-mentioned material, and calcine it at 400-600℃ for 6-10h to prepare a carrier.

[0050] 3. Prepare a solution by mixing 37.5g lanthanum nitrate, 158g nickel acetate (tetrahydrate), 167g phosphotungstic acid pentahydrate, and 217g phosphomolybdic acid. Add the solution to 20ml ethyl propyl ether and stir at 65℃ for 60min. After cooling to room temperature while stirring, add 2.23g citric acid to adjust the pH to 2 and continue stirring for 60min. The solution contains rare earth metal salts and heteropoly acids C4H6O4Ni·4H2O, H3[PW 12 O 40 ]·XH2O,H3[PMo 12 O 40 The complexing agent is prepared by mixing XH2O with a molar ratio of 2:11:1:2:0.2, resulting in a complexed heteropolyacid impregnation solution.

[0051] 4. Take 42.5 ml of heteropoly acid to prepare an impregnation solution, add 50 g of support, impregnate the prepared support with an equal volume for 2 h, dry at 120 °C for 4 h, calcine at 500 °C in air atmosphere for 4 h, and add hydrocracking catalyst.

[0052] Example 4

[0053] 1. Preparation method of carbon-supported aerogel Y / ZSM-35 / NU-87 composite molecular sieve

[0054] (1) Add 32.1g of sodium hydroxide to 45.9g of water and stir until the sodium hydroxide is completely dissolved. Then add 6.5g of sodium aluminate and stir until the sodium aluminate is completely dissolved to obtain a sodium aluminate mixed solution. Take 45.1g of the sodium aluminate mixed solution and 125.6g of water glass and pour them into 79g of deionized water. After stirring evenly, let it stand at 45℃ for 12h to obtain a Y-type molecular sieve nanocrystal precursor slurry containing 20Na2O, 1Al2O3, and 20SiO2 in molar fractions.

[0055] (2) Add 9.75g of ZSM-35 molecular sieve, 1.08g of NU-87 molecular sieve, and 1.35g of carbon aerogel to a microwave vibrating container containing 2.34g of Y-type molecular sieve nanocrystal precursor slurry, with a mass ratio of 9:1:1.2:2.0, and add 5.85g of isopropanol. Microwave irradiate for 30min under a microwave power of 400W to obtain the A mixed slurry.

[0056] (3) Alkali solution 2: Dissolve 24g of sodium hydroxide in 20.8g of water, then add 5g of sodium aluminate and stir until completely dissolved. The molar ratio of alkali solution is 15Na2O:Al2O3.

[0057] (4) Mix 5.04g of silica powder with 1.34g of sodium carbonate until homogeneous, then add 4.08g of aluminum isopropoxide, 36g of water solution, and 1.6g of alkali solution 2 and mix until homogeneous. Then add 0.4g of sodium persulfate, and finally add mixture A to form a gel solution containing 2Na2O, Al2O3, and 8.4SiO2 in molar proportions. Stir at 35℃ for 3h. Transfer the gel to a polytetrafluoroethylene liner and crystallize at 150℃ for 20h. After filtration, washing, and drying, calcine at 500℃ for 8h to obtain the supported carbon aerogel Y / ZSM-35 / NU-87 composite molecular sieve.

[0058] 2. Mix 12g of macroporous alumina material, 15g of amorphous silica-alumina, 23g of supported carbon aerogel Y / ZSM-35 / NU-87 composite molecular sieve, and 5.0g of guar gum powder evenly, then dropwise add the mixture to an aqueous solution containing 4.5g of concentrated nitric acid (96wt%), extrude it into strips, dry the above-mentioned material, and calcine it at 400-600℃ for 6-10h to prepare a carrier.

[0059] 3. Prepare a solution by mixing 37.5g lanthanum nitrate, 158g nickel acetate (tetrahydrate), 167g phosphotungstic acid pentahydrate, and 217g phosphomolybdic acid. Add the solution to 20ml ethyl propyl ether and stir at 65℃ for 60min. After cooling to room temperature while stirring, add 2.23g citric acid to adjust the pH to 2 and continue stirring for 60min. The solution contains rare earth metal salts and heteropoly acids C4H6O4Ni·4H2O, H3[PW 12 O40 ]·XH2O,H3[PMo 12 O 40 The complexing agent is prepared by mixing XH2O with a molar ratio of 2:11:1:2:0.2, resulting in a complexed heteropolyacid impregnation solution.

[0060] 4. Take 42.5 ml of heteropoly acid to prepare an impregnation solution, add 50 g of support, impregnate the prepared support with an equal volume for 2 h, dry at 120 °C for 4 h, calcine at 500 °C in air atmosphere for 4 h, and add hydrocracking catalyst.

[0061] Example 5

[0062] 1. Preparation method of carbon-supported aerogel Y / ZSM-35 / NU-87 composite molecular sieve

[0063] (1) Add 8g of sodium hydroxide to 20.9g of water and stir until the sodium hydroxide is completely dissolved. Then add 1.7g of sodium aluminate and stir until the sodium aluminate is completely dissolved to obtain a sodium aluminate mixed solution. Take 61.8g of the sodium aluminate mixed solution and 31.4g of water glass and pour them into 26.2g of deionized water. After stirring evenly, let it stand at 60℃ for 16h to obtain a Y-type molecular sieve nanocrystal precursor slurry containing 5Na2O, 1Al2O3, and 5SiO2 in molar fractions.

[0064] (2) 19.6g of ZSM-35 molecular sieve, 2.2g of NU-87 molecular sieve, and 2.72g of carbon aerogel were added to a microwave vibrating container containing 7.7g of Y-type molecular sieve nanocrystal precursor slurry in a mass ratio of 9:1:1.2:3.5, and 18.5g of isopropanol was added. The mixture was microwave irradiated for 30min at a microwave power of 400W to obtain the A mixed slurry.

[0065] (3) Preparation of alkali solution 2: Dissolve 24g of sodium hydroxide in 20.8g of water, then add 5g of sodium aluminate and stir until completely dissolved. The molar ratio of alkali solution is 15Na2O:Al2O3.

[0066] (4) After stirring 46.75g of water glass and 4g of sodium carbonate evenly, add 10.5g of aluminum sulfate octadecylhydrate, 23.75g of aqueous solution, and 10.64g of alkali solution 2 and mix evenly. Then add 0.98g of sodium persulfate, and finally add the A mixed slurry to form a gel solution containing 2.85Na2O, Al2O3, and 8.4SiO2 in molar fractions. Stir at 35℃ for 3h. Transfer the above gel to a polytetrafluoroethylene liner and crystallize at 150℃ for 24h. After filtration, washing, drying, and calcination at 550℃ for 7h, obtain the supported carbon aerogel Y / ZSM-35 / NU-87 composite molecular sieve.

[0067] 2. Mix 12g of macroporous alumina material, 15g of amorphous silica-alumina, 23g of supported carbon aerogel Y / ZSM-35 / NU-87 composite molecular sieve, and 5.0g of guar gum powder evenly, then dropwise add the mixture to an aqueous solution containing 4.5g of concentrated nitric acid (96wt%), extrude it into strips, dry the above-mentioned material, and calcine it at 400-600℃ for 6-10h to prepare a carrier.

[0068] 3. Prepare a solution by mixing 37.5g lanthanum nitrate, 158g nickel acetate (tetrahydrate), 167g phosphotungstic acid pentahydrate, and 217g phosphomolybdic acid. Add the solution to 20ml ethyl propyl ether and stir at 65℃ for 60min. After cooling to room temperature while stirring, add 1.74g tartaric acid to adjust the pH to 2 and continue stirring for 60min. (Note: The last sentence appears to be incomplete and possibly contains errors. It likely refers to a solution containing rare earth metal salts and heteropoly acids.) 12 O 40 ]·XH2O,H3[PMo 12 O 40 The complexing agent is prepared by mixing XH2O with a molar ratio of 2:11:1:2:0.2, resulting in a complexed heteropolyacid impregnation solution.

[0069] 4. Take 42.5 ml of heteropoly acid to prepare an impregnation solution, add 50 g of support, impregnate the prepared support with an equal volume for 2 h, dry at 120 °C for 4 h, calcine at 500 °C in air atmosphere for 4 h, and add hydrocracking catalyst.

[0070] Example 6

[0071] 1. Preparation method of carbon-supported aerogel Y / ZSM-35 / NU-87 composite molecular sieve

[0072] (1) Add 8g of sodium hydroxide to 20.9g of water and stir until the sodium hydroxide is completely dissolved. Then add 1.7g of sodium aluminate and stir until the sodium aluminate is completely dissolved to obtain a sodium aluminate mixed solution. Take 61.8g of the sodium aluminate mixed solution and 31.4g of water glass and pour them into 26.2g of deionized water. After stirring evenly, let it stand at 60℃ for 16h to obtain a Y-type molecular sieve nanocrystal precursor slurry containing 5Na2O, 1Al2O3, and 5SiO2 in molar fractions.

[0073] (2) Add 14.3g of ZSM-35 molecular sieve, 1.6g of NU-87 molecular sieve, and 1.98g of carbon aerogel to a microwave vibrating container containing 3.5g of Y-type molecular sieve nanocrystal precursor slurry, with a mass ratio of 9:1:1.2:2.2, and add 8.75g of isopropanol. Microwave irradiate for 30min under a microwave power of 400W to obtain the A mixed slurry.

[0074] (3) Alkali solution 1: Dissolve 16g of sodium hydroxide in 15.6g of water, then add 3.3g of sodium aluminate and stir until completely dissolved. The molar ratio of alkali solution is 10Na2O:1Al2O3.

[0075] (4) After mixing 20.83g of tetraethyl orthosilicate and 1.15g of ammonium carbonate evenly, a solution of 1.33g of aluminum chloride and 36g of water, and 12g of alkali solution 1 were added and mixed evenly. Then, 0.238g of sodium persulfate was added, and finally, mixed slurry A was added to form a gel solution containing 30Na2O, 1Al2O3, and 20SiO2 in molar fractions. The solution was stirred at 37℃ for 3h. The gel was then transferred to a polytetrafluoroethylene liner and crystallized at 120℃ for 24h. After filtration, washing, and drying, the gel was calcined at 600℃ for 10h to obtain the supported carbon aerogel Y / ZSM-35 / NU-87 composite molecular sieve.

[0076] 2. Mix 12g of macroporous alumina material, 15g of amorphous silica-alumina, 23g of supported carbon aerogel Y / ZSM-35 / NU-87 composite molecular sieve, and 5.0g of guar gum powder evenly, then dropwise add the mixture to an aqueous solution containing 4.5g of concentrated nitric acid (96wt%), extrude it into strips, dry the above-mentioned material, and calcine it at 450℃ for 6h to prepare a carrier.

[0077] 3. Prepare a solution by mixing 9.4g lanthanum nitrate, 345g nickel acetate (tetrahydrate), 167g phosphotungstic acid pentahydrate, and 529g phosphomolybdic acid. Add this solution to 20ml ethyl propyl ether and stir at 65℃ for 60min. After cooling to room temperature while stirring, add 4.35g tartaric acid to adjust the pH to 2 and continue stirring for 60min. (Note: The last sentence appears to be incomplete and possibly contains errors. It likely refers to a solution containing rare earth metal salts and heteropoly acids.) 12 O 40 ]·XH2O,H3[PMo 12 O 40 The complexing agent contains 0.5:24:1:5:0.5 molar fractions of XH2O, resulting in a complexed heteropoly acid impregnation solution.

[0078] 4. Take 42.5 ml of heteropoly acid to prepare an impregnation solution, add 50 g of support, impregnate the prepared support with an equal volume for 2 h, dry at 120 °C for 4 h, calcine at 500 °C in air atmosphere for 4 h, and add hydrocracking catalyst.

[0079] Example 7

[0080] 1. Preparation method of carbon-supported aerogel Y / ZSM-35 / NU-87 composite molecular sieve

[0081] (1) Add 8g of sodium hydroxide to 20.9g of water and stir until the sodium hydroxide is completely dissolved. Then add 1.7g of sodium aluminate and stir until the sodium aluminate is completely dissolved to obtain a sodium aluminate mixed solution. Take 61.8g of the sodium aluminate mixed solution and 31.4g of water glass and pour them into 26.2g of deionized water. After stirring evenly, let it stand at 60℃ for 16h to obtain a Y-type molecular sieve nanocrystal precursor slurry containing 5Na2O, 1Al2O3, and 5SiO2 in molar fractions.

[0082] (2) Add 14.3g of ZSM-35 molecular sieve, 1.6g of NU-87 molecular sieve, and 1.98g of carbon aerogel to a microwave vibrating container containing 3.5g of Y-type molecular sieve nanocrystal precursor slurry, with a mass ratio of 9:1:1.2:2.2, and add 8.75g of isopropanol. Microwave irradiate for 30min under a microwave power of 400W to obtain the A mixed slurry.

[0083] (3) Alkali solution 1: Dissolve 16g of sodium hydroxide in 15.6g of water, then add 3.3g of sodium aluminate and stir until completely dissolved. The molar ratio of alkali solution is 10Na2O:1Al2O3.

[0084] (4) After mixing 20.83g of tetraethyl orthosilicate and 1.15g of ammonium carbonate evenly, a solution of 1.33g of aluminum chloride and 36g of water, and 12g of alkali solution 1 were added and mixed evenly. Then, 0.238g of sodium persulfate was added, and finally, mixed slurry A was added to form a gel solution with the following composition and molar ratio: 30Na2O:1Al2O3:20SiO2. The solution was stirred at 37℃ for 3h. The gel was then transferred to a polytetrafluoroethylene liner and crystallized at 120℃ for 24h. After filtration, washing, and drying, the solution was calcined at 600℃ for 10h to obtain the supported carbon aerogel Y / ZSM-35 / NU-87 composite molecular sieve.

[0085] 2. Mix 12g of macroporous alumina material, 15g of amorphous silica-alumina, 23g of supported carbon aerogel Y / ZSM-35 / NU-87 composite molecular sieve, and 5.0g of guar gum powder evenly, then dropwise add the mixture to an aqueous solution containing 4.5g of concentrated nitric acid (96wt%), extrude it into strips, dry the above-mentioned material, and calcine it at 450℃ for 6h to prepare a carrier.

[0086] 3. Prepare a solution by mixing 27.4g lanthanum nitrate, 258g nickel acetate (tetrahydrate), 167g phosphotungstic acid pentahydrate, and 357g phosphomolybdic acid. Add the solution to 20ml ethyl propyl ether and stir at 65℃ for 60min. After cooling to room temperature while stirring, add 4.35g tartaric acid to adjust the pH to 2 and continue stirring for 60min. (Note: The last sentence appears to be incomplete and possibly contains errors. It likely refers to a solution containing rare earth metal salts and heteropoly acids.) 12 O40 ]·XH2O,H3[PMo 12 O 40 The complexing agent contains 1.5:18:1:3.4:0.5 molar ratios of XH2O, resulting in a complexed heteropolyacid impregnation solution.

[0087] 4. Take 42.5 ml of heteropoly acid to prepare an impregnation solution, add 50 g of support, impregnate the prepared support with an equal volume for 2 h, dry at 120 °C for 4 h, calcine at 500 °C in air atmosphere for 4 h, and add hydrocracking catalyst.

[0088] Comparative Example 1

[0089] 1. Preparation method of composite molecular sieves

[0090] (1) Add 8g of sodium hydroxide to 20.9g of water and stir until the sodium hydroxide is completely dissolved. Then add 1.7g of sodium aluminate and stir until the sodium aluminate is completely dissolved to obtain a sodium aluminate mixed solution. Take 61.8g of the sodium aluminate mixed solution and 31.4g of water glass and pour them into 26.2g of deionized water. After stirring evenly, let it stand at 60℃ for 16h to obtain a molecular sieve nanocrystal precursor slurry containing 5Na2O, 1Al2O3, and 5SiO2 in molar fractions.

[0091] (2) Add 20.6g of ZSM-35 molecular sieve, 2.29g of NU-87 molecular sieve, and 3.44g of carbon aerogel to a stirring container containing 7.4g of Y-type molecular sieve nanocrystal precursor slurry, with a mass ratio of 9:1:1.5:3.2, and add 18.5g of isopropanol. Mix and stir evenly to obtain A mixed slurry.

[0092] (3) Mix 46.75g of water glass with 10.5g of aluminum sulfate octadecylhydrate and 23.75g of water and stir until homogeneous. Then add 10.64g of sodium hydroxide and stir until homogeneous. Finally, add mixture A to form a gel solution with the following composition and molar ratio: 2.85Na2O:Al2O3:8.4SiO2. Stir at 35℃ for 3h. Transfer the gel to a polytetrafluoroethylene liner and crystallize at 96℃ for 24h. After filtration, washing, and drying, calcine at 550℃ for 10h to obtain the supported carbon aerogel Y / ZSM-35 / NU-87 composite molecular sieve.

[0093] 2. Mix 12g of macroporous alumina material, 15g of amorphous silica-alumina, 23g of supported carbon aerogel Y / ZSM-35 / NU-87 composite molecular sieve, and 5.0g of guar gum powder evenly, then dropwise add the mixture to an aqueous solution containing 4.5g of concentrated nitric acid (96wt%), extrude it into strips, dry the above-mentioned material, and calcine it at 400-600℃ for 6-10h to prepare a carrier.

[0094] 3. Prepare an impregnation solution by dissolving 26g of nickel nitrate and 37g of ammonium metatungstate in 100mL of water.

[0095] 4. Take 42.5 ml of metal impregnation solution and 50 g of carrier, impregnate the prepared carrier in equal volume for 2 h, dry at 120 °C for 4 h, and calcine in air atmosphere at 500 °C for 4 h to obtain the catalyst.

[0096] Comparative Example 2

[0097] 1. Preparation method of composite molecular sieves

[0098] (1) Add 8g of sodium hydroxide to 20.9g of water and stir until the sodium hydroxide is completely dissolved. Then add 1.7g of sodium aluminate and stir until the sodium aluminate is completely dissolved to obtain a sodium aluminate mixed solution. Take 61.8g of the sodium aluminate mixed solution and 31.4g of water glass and pour them into 26.2g of deionized water. After stirring evenly, let it stand at 60℃ for 16h to obtain a Y-type molecular sieve nanocrystal precursor slurry containing 5Na2O, 1Al2O3, and 5SiO2 in molar fractions.

[0099] (2) Add 20.6g of ZSM-35 molecular sieve and 2.29g of NU-87 molecular sieve to a stirring container containing 7.4g of Y-type molecular sieve nanocrystal precursor slurry, with a mass ratio of 9:1:3.2, and add 18.5g of deionized water. Mix and stir evenly to obtain A mixed slurry.

[0100] (3) Mix 46.75g of water glass with 10.5g of aluminum sulfate octadecylhydrate and 23.75g of water and stir until homogeneous. Then add 10.64g of sodium hydroxide and stir until homogeneous. Next, add 3.4g of mesoporous template agent TPHAC and finally add the A mixture slurry to form a gel solution with the following composition and molar ratio: 2.85Na2O:Al2O3:8.4SiO2. Stir at 35℃ for 3h. Transfer the gel to a polytetrafluoroethylene liner and crystallize at 96℃ for 24h. After filtration, washing, drying, and calcination at 550℃ for 10h, obtain Y / ZSM-35 / NU-87 composite molecular sieve.

[0101] 2. Mix 12g of macroporous alumina material, 15g of amorphous silica-alumina, 23g of supported carbon aerogel Y / ZSM-35 / NU-87 composite molecular sieve, and 5.0g of guar gum powder evenly, then dropwise add the mixture to an aqueous solution containing 4.5g of concentrated nitric acid (96wt%), extrude it into strips, dry the above-mentioned material, and calcine it at 400-600℃ for 6-10h to prepare a carrier.

[0102] 3. Prepare an impregnation solution by dissolving 26g of nickel nitrate and 37g of ammonium metatungstate in 100mL of water.

[0103] 4. Take 42.5 ml of metal impregnation solution and 50 g of carrier, impregnate the prepared carrier in equal volume for 2 h, dry at 120 °C for 4 h, and calcine in air atmosphere at 500 °C for 4 h to obtain the catalyst.

[0104] The pore structure parameters of the examples and comparative samples are shown in Table 1.

[0105] The catalyst prepared in the examples was used in the hydrocracking process of a mixture of reduced-pressure secondary and reduced-pressure ketone-benzene dewaxed oils to produce high-quality lubricating oil base oil feedstock. The reaction was carried out at a temperature of 360–410°C, a pressure of 12.0–17.0 MPa, and a space velocity of 1.5–2.0 h⁻¹. -1 Hydrocracking was evaluated under a hydrogen-to-oil ratio of 700–1500:1, and the results are shown in Table 2.

[0106] Table 1 Comparison of pore structure parameters between the examples and comparative samples

[0107]

[0108]

[0109] Table 2 Properties of Hydrocracking Products from Examples

[0110]

Claims

1. A hydrocracking catalyst, characterized in that, The catalyst comprises a support and rare earth metals and heteropolyacid metal active components supported on the support, and the specific surface area of ​​the catalyst reaches 337-355 m². 2 ·g -1 The pore size is 0.40-0.46cm. 3 ·g -1 ; The carrier is made by calcining 15-25 wt% macroporous alumina material, 20-30 wt% amorphous silica-alumina and 20-50 wt% supported carbon aerogel Y / ZSM-35 / NU-87 composite molecular sieve with binder and extrusion aid. The supported carbon aerogel Y / ZSM-35 / NU-87 composite molecular sieve was prepared by the following method: (1) Sodium hydroxide, sodium aluminate and water glass are mixed and then statically aged at 25-80 °C for 12-36 h to obtain Y-type molecular sieve nanocrystal precursor, which contains 5-30 parts Na2O, 1 part Al2O3 and 5-40 parts SiO2; further, it also contains 200-800 parts H2O. (2) According to the mass ratio of 7.2~10:1:1~1.5:2.0~3.5, ZSM-35 molecular sieve, NU-87 molecular sieve, carbon aerogel and Y-type molecular sieve nanocrystal precursor are added to a microwave vibrating container, and organic alcohol is added. Under microwave power of 400-600W, microwave irradiation is carried out for 20-40 minutes to obtain the A mixed slurry. (3) Mix the silicon source, aluminum source, alkaline solution, strong oxidant and carbonate evenly, and then add A mixed slurry to fully react and form a gel solution. The components and their molar amounts are 2-80 parts Na2O, 1 part Al2O3, 5-200 parts SiO2, and further, 10-800 parts H2O. Crystallize at 90-150℃ for 12-24h, and calcine to obtain the supported carbon aerogel Y / ZSM-35 / NU-87 composite molecular sieve. The alkaline solution is prepared as follows: dissolve sodium aluminate in hot sodium hydroxide solution, wherein the molar amounts of Na2O and Al2O3 are 10-15 Na2O: 1 Al2O3.

2. The hydrocracking catalyst according to claim 1, characterized in that, The organic alcohol is selected from one or more of ethanol, isopropanol, ethylene glycol, propylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, and triethylene glycol, and the amount added is such that the mass ratio of the Y-type molecular sieve nanocrystal precursor suspension to the organic alcohol is 1:1.5-2.

5.

3. The hydrocracking catalyst according to claim 1, characterized in that, The silicon source is one or more of water glass, tetraethyl orthosilicate, and silicon powder; the aluminum source is one or more of aluminum sulfate octadecylhydrate, aluminum oxide, aluminum chloride, and aluminum isopropoxide.

4. The hydrocracking catalyst according to claim 1, characterized in that, The carbonate is one or more of sodium carbonate, potassium carbonate, and ammonium carbonate; the amount of carbonate added is 1-15% of the amount of SiO2 added to the gel.

5. The hydrocracking catalyst according to claim 1, characterized in that, The strong oxidant is sodium persulfate, and the amount of strong oxidant added is 1-5% of the amount of SiO2 added to the gel.

6. A method for preparing the hydrocracking catalyst according to any one of claims 1-5, characterized in that, include: Rare earth metal salts, heteropoly acids C4H6O4Ni·4H2O, and H3[PW] 12 O 40 ]·XH2O and H3[PMo 12 O 40 ]·XH2O was added to ethyl propyl ether, and a complexing agent was added while stirring. The pH was adjusted to 2-3 to prepare a complexed heteropolyacid impregnation solution, wherein rare earth metal salts, heteropolyacids C4H6O4Ni·4H2O, and H3[PW 12 O 40 ]·XH2O、H3[PMo 12 O 40 The molar ratio of XH2O to complexing agent is 0.5~2:11~24:1:2~5:0.2~0.5, with ethylpropyl ether as the dispersant.

7. The method according to claim 6, characterized in that, The complexing agent is one or more of citric acid, tartaric acid, malic acid, succinic acid, salicylic acid, 1,2,3,4-butanetetracarboxylic acid and 2-phosphonobutane-1,2,4-tricarboxylic acid; the rare earth metal salt is at least one of lanthanum chloride, cerium chloride, lanthanum nitrate and cerium nitrate.

8. The method according to claim 6, characterized in that, Also includes: The above-mentioned carrier was impregnated in an equal volume of complexed heteropoly acid impregnation solution and then dried.

9. The use of the hydrocracking catalyst according to any one of claims 1-5 in the hydrocracking production of lubricating oil base oil.

Images