A hydrocracking catalyst carrier, its preparation and use

Abstract

The application discloses a kind of hydrocracking catalyst carriers, the carrier includes supporting carbon aerogel Y / ZSM-35 / NU-87 composite molecular sieve, the carrier specific surface area 457-485m 2 ·g ‑1 , pore structure 0.73-0.80cm 3 ·g ‑1 The application also discloses a preparation method and application thereof.The carrier prepared by using the supporting carbon aerogel Y / ZSM-35 / NU-87 composite molecular sieve has high specific surface area and pore structure, and is applied to a hydrocracking catalyst, so that aromatic saturation, long-chain alkane isomerization and condensation can be realized, wherein the tail oil yield is more than 35ω%, and the viscosity index reaches more than 130.

Description

Technical Field

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

[0002] Hydrocracking follows a carbocation mechanism, involving both primary and secondary cracking reactions. Therefore, the different reaction pathways of petroleum molecules at different acid and hydrogenation sites on the catalyst will affect the selectivity of the target product. For hydrocracking processes that produce naphtha and high-quality hydrocracking tail oil, a rich secondary pore structure in the catalyst is required to reduce misreading cracking reactions. Simultaneously, the catalyst should have moderate acidity and a limited number of acidic sites to minimize secondary cracking reactions. Larger pore sizes are preferred in terms of pore structure, facilitating the entry of polycyclic aromatic hydrocarbons (PAHs) into the catalyst channels. Therefore, the secondary pore size of the support material must be increased to improve the accessibility of active sites, increase the utilization rate of acidic sites, and enhance the activity of the catalyst support. Furthermore, a well-ventilated micro-mesoporous hierarchical structure also facilitates the diffusion of the target product and reduces coke yield. Summary of the Invention

[0003] To achieve suitable specific surface area and pore size in hydrocracking catalysts, thereby improving catalytic activity while reducing energy consumption and ammonia nitrogen emissions, this invention employs a carbonate-synthesized carbon aerogel / Y / ZSM-35 / NU-87 composite molecular sieve. Furthermore, the use of hydroxyl radicals during the molecular sieve framework formation process facilitates carbonate introduction, enabling the removal of silica and alumina and thus achieving in-situ mesopore formation. This in-situ mesopore formation not only simplifies the preparation process and reduces pollution but also plays a crucial role in enhancing catalyst performance. It overcomes the pollution problems associated with organic template agents and significantly reduces costs.

[0004] As one aspect of the present invention, a hydrocracking catalyst support is provided, the support comprising a carbon aerogel / Y / ZSM-35 / NU-87 composite molecular sieve, the support having a specific surface area of ​​457-485 m². 2 ·g -1 The pore size is 0.73-0.80 cm. 3 ·g -1 .

[0005] As another aspect of the present invention, a method for preparing the above-mentioned hydrocracking catalyst support is provided, comprising:

[0006] (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) Na2O, 1Al2O3, and (5-40) SiO2; further, it also contains (200-800) molar H2O;

[0007] (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.

[0008] (3) Mix 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, 1 Al2O3, (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 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: 1 Al2O3.

[0009] (4) Mix macroporous alumina material, carbon aerogel / Y / ZSM-35 / NU-87 composite molecular sieve, highly dispersed binder and extrusion aid evenly. The mass ratio of macroporous alumina material, carbon aerogel / Y / ZSM-35 / NU-87 composite molecular sieve, highly dispersed binder and extrusion aid is (76~40):(20~50):(3.0~5.0):(1.0~5.0). Extrude the material into strips. The extruded carrier is generally cylindrical, but it can also be made into irregular strips such as clover or four-leaf clover. Dry the above-mentioned molded material and calcine it at 400-600°C for 6-10 h to prepare the carrier.

[0010] In the above preparation method, in step (2), 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, 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. The organic alcohol plays a dispersing role, and those skilled in the art can reasonably adjust the amount according to the process requirements.

[0011] In the above preparation method, 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.

[0012] In the above preparation method, in step (3), 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.

[0013] In the above preparation method, in step (3), 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.

[0014] In the above preparation method, the support synthesized using carbon aerogel / Y / ZSM-35 / NU-87 composite molecular sieve achieves a specific surface area of ​​457-485 m². 2 ·g -1 The pore size is 0.73-0.80 cm. 3 ·g -1 .

[0015] As another aspect of the present invention, the application of the above-mentioned hydrocracking catalyst support in the preparation of catalysts is involved.

[0016] As another aspect of the invention, there is a catalyst that uses the above-described hydrocracking catalyst support.

[0017] This invention utilizes carbonates to prepare carbon aerogel / Y / ZSM-35 / NU-87 composite molecular sieves. Furthermore, the use of hydroxyl radicals during the molecular sieve framework formation process facilitates the introduction of carbonates, enabling the removal of silica and aluminum and thus achieving in-situ mesoporous formation. This overcomes the contamination problems associated with organic template agents and significantly reduces costs.

[0018] The support prepared using carbon aerogel / Y / ZSM-35 / NU-87 composite molecular sieve has a high specific surface area and pore structure. When applied to hydrocracking catalysts, it can achieve aromatic saturation and long-chain alkane isomerization and pour point depletion, with a tail oil yield of over 35% and a viscosity index of over 130. Attached Figure Description

[0019] Appendix Figure 1 XRD pattern of the carbon aerogel / Y / ZSM-35 / NU-87 composite molecular sieve in Example 2. Detailed Implementation

[0020] The inventors prepared related molecular sieves and further prepared catalysts by referring to the records in CN 114471668 A, CN 107286980 A, and CN 102211780 A, but the results did not meet the inventors' expectations. The inventors conducted further research and made this invention.

[0021] The following detailed description of specific embodiments of the present invention, in conjunction with the accompanying drawings, aims 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; the reagents and materials mentioned, unless otherwise specified, can be obtained commercially. Specifically, 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 (item number M196701-50g), carbon aerogel (Nanjing Bingzhou New Material Technology Co., Ltd.), and NU-87 (prepared according to CN 102211780 A) are included.

[0022] Example 1

[0023] (1) Take 8g of sodium hydroxide and add it to 20.9g of water. 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, which can be used as an aluminum source. Take 61.8g of 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 Y-type molecular sieve nanocrystal precursor slurry. The components are in the molar ratio of 5Na2O: 1Al2O3: 5SiO2: 200H2O.

[0024] (2) 14.3g of ZSM-35 molecular sieve matrix, 1.6g of NU-87 molecular sieve matrix and 1.98g of carbon aerogel were added 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. 8.75g of isopropanol was added, and the mixture was microwave irradiated for 30min at a microwave power of 400W to obtain the A mixed slurry.

[0025] (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: 150H2O.

[0026] (4) Using a molar ratio of 30Na2O:1Al2O3:20SiO2:400H2O, 20.83 g of tetraethyl orthosilicate and 1.15 g of ammonium carbonate were mixed and stirred evenly. Then, a solution of 1.33 g of aluminum chloride and 36 g of water, and 12 g of alkali solution 1 were added sequentially and stirred evenly to form a gel. Then, 0.238 g of sodium persulfate was added, and finally, mixed slurry A was added. The mixture was stirred at 37°C for 3 h. The gel was transferred to a polytetrafluoroethylene liner and crystallized at 120°C for 24 h. After filtration, washing, and drying, the gel was calcined at 600°C for 10 h to obtain carbon aerogel / Y / ZSM-35 / NU-87 composite molecular sieve.

[0027] (5) Mix 47g of macroporous alumina material, 45g of carbon aerogel / Y / ZSM-35 / NU-87 composite molecular sieve, 5g of aluminum sol and 3g of guar gum powder evenly, extrude into strips, dry the above-mentioned material and calcine at 540°C for 6h to prepare a carrier.

[0028] Example 2

[0029] (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. Add 42g of the sodium aluminate mixed solution and 94.2g of water glass to 57.5g of deionized water and stir evenly. Then let it stand at 35℃ for 16h to obtain a Y-type molecular sieve nanocrystal precursor slurry. The components are in the molar ratio of 16Na2O:1Al2O3:15SiO2:320H2O.

[0030] (2) 20.6g of ZSM-35 molecular sieve matrix, 2.29g of NU-87 molecular sieve matrix, 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 added, and the mixture was microwave irradiated for 30min at a microwave power of 400W to obtain the A mixed slurry.

[0031] (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: 150H2O.

[0032] (4) Using a molar ratio of 2.85Na2O:Al2O3:8.4SiO2:200H2O, 46.75g of water glass and 4g of sodium carbonate were mixed and stirred evenly. Then, a solution of 10.5g of aluminum sulfate octadecylhydrate and 23.75g of water, and 10.64g of alkali solution 1 were added sequentially and stirred evenly to form a gel. Then, 0.98g of sodium persulfate was added, and finally, mixture A was added. The mixture was stirred at 35℃ for 3h. The gel was transferred to a polytetrafluoroethylene liner and crystallized at 96℃ for 12h. After filtration, washing, and drying, the gel was calcined at 550℃ for 10h to obtain a carbon aerogel / Y / ZSM-35 / NU-87 composite molecular sieve.

[0033] (5) The carrier molding process is the same as in Example 1.

[0034] Example 3

[0035] (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. Add 42g of the sodium aluminate mixed solution and 94.2g of water glass to 57.5g of deionized water and stir evenly. Then let it stand at 35℃ for 16h to obtain a Y-type molecular sieve nanocrystal precursor slurry. The components are in the molar ratio of 16Na2O:1Al2O3:15SiO2:320H2O.

[0036] (2) 2.88g of ZSM-35 molecular sieve matrix, 0.4g of NU-87 molecular sieve matrix, and 0.6g of carbon aerogel were added 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. 2.0g of isopropanol was added, and the mixture was microwave irradiated for 30min at a microwave power of 400W to obtain the A mixed slurry.

[0037] (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: 150H2O.

[0038] (4) Using a molar ratio of 2Na2O: Al2O3: 2SiO2: 50H2O, 4.16 g of tetraethyl orthosilicate and 0.048 g of potassium carbonate were mixed and stirred until homogeneous. Then, a solution of 1.02 g of alumina, 9 g of water, and 1.6 g of alkali solution 1 were added and stirred until homogeneous to form a gel. Then, 0.24 g of sodium persulfate was added, and finally, the A mixture was added. The mixture was stirred at 25°C for 3 h. The gel was transferred to a polytetrafluoroethylene liner and crystallized at 95°C for 15 h. After filtration, washing, and drying, the gel was calcined at 400°C for 6 h to obtain a carbon aerogel / Y / ZSM-35 / NU-87 composite molecular sieve.

[0039] (5) The carrier molding process is the same as in Example 1.

[0040] Example 4

[0041] (1) Take 32.1g of sodium hydroxide and add it to 45.9g of water. 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 sodium aluminate mixed solution and 125.6g of water glass and pour them into 79g of deionized water. Stir evenly and then let it stand at 45℃ for 12h to obtain Y-type molecular sieve nanocrystal precursor slurry. The components are in the molar ratio of 20Na2O: Al2O3: 20SiO2: 440H2O.

[0042] (2) 9.75g of ZSM-35 molecular sieve matrix, 1.08g of NU-87 molecular sieve matrix, and 1.35g of carbon aerogel were added to a microwave vibrating container containing 2.34g of Y-type molecular sieve nanocrystal precursor slurry in a mass ratio of 9:1:1.2:2.0. 5.85g of isopropanol was added, and the mixture was microwave irradiated for 30min at a microwave power of 400W to obtain the A mixed slurry.

[0043] (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: 200H2O.

[0044] (3) Using a molar ratio of 2Na2O:Al2O3:8.4SiO2:200H2O, 5.04 g of silicon powder and 1.34 g of sodium carbonate were mixed and stirred evenly. Then, a solution of 4.08 g of aluminum isopropoxide, 36 g of water, and 1.6 g of alkali solution 2 were added and stirred evenly to form a gel. Then, 0.4 g of sodium persulfate was added, and finally, the A mixture was added. The mixture was stirred at 35°C for 3 h. The gel was transferred to a polytetrafluoroethylene liner and crystallized at 150°C for 20 h. After filtration, washing, and drying, the gel was calcined at 500°C for 8 h to obtain a carbon aerogel / Y / ZSM-35 / NU-87 composite molecular sieve.

[0045] (4) The carrier molding process is the same as in Example 1.

[0046] Example 5

[0047] (1) Take 48.2g of sodium hydroxide and add it to 83.5g of water. Stir until the sodium hydroxide is completely dissolved. Then add 9.8g of sodium aluminate and stir until the sodium aluminate is completely dissolved to obtain a sodium aluminate solution. Take 49.6g of the sodium aluminate mixed solution and 251.2g of water glass and pour them into 143.6g of deionized water. Stir evenly and then let it stand at 60℃ for 24h to obtain a Y-type molecular sieve nanocrystal precursor slurry. The components are in the molar ratio of 30Na2O: Al2O3: 40SiO2: 800H2O.

[0048] (2) 2.75g of ZSM-35 molecular sieve matrix, 0.34g of NU-87 molecular sieve matrix, and 0.38g of carbon aerogel were added to a microwave vibrating container containing 0.66g of Y-type molecular sieve nanocrystal precursor slurry, with a mass ratio of 8:1:1.1:2.1. 5.85g of isopropanol was added, and the mixture was microwave irradiated for 30min at a microwave power of 400W to obtain the A mixed slurry.

[0049] (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: 200H2O.

[0050] (4) Using a molar ratio of 2Na2O: Al2O3: 5SiO2: 10H2O, 3 g of silicon powder and 0.048 g of ammonium carbonate were mixed and stirred evenly. Then, 6.7 g of aluminum sulfate octadecylhydrate, 1.6 g of alkali solution 2 and 1.8 g of water were added and stirred evenly to form a gel. Then, 0.6 g of sodium persulfate was added, and finally, mixture A was added. The mixture was stirred at 35°C for 3 h. The gel was transferred to a polytetrafluoroethylene liner and crystallized at 120°C for 12 h. After filtration, washing and drying, the gel was calcined at 600°C for 10 h to obtain carbon aerogel / Y / ZSM-35 / NU-87 composite molecular sieve.

[0051] (5) The carrier molding process is the same as in Example 1.

[0052] Example 6

[0053] (1) Take 8g of sodium hydroxide and add it to 20.9g of water. 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 sodium aluminate mixed solution and 31.4g of water glass and pour them into 26.2g of deionized water. Stir evenly and then let it stand at 60℃ for 16h to obtain Y-type molecular sieve nanocrystal precursor slurry. The components are in the molar ratio of 5Na2O: 1Al2O3: 5SiO2: 200H2O.

[0054] (2) 19.6g of ZSM-35 molecular sieve matrix, 2.2g of NU-87 molecular sieve matrix, 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. 18.5g of isopropanol was added, and the mixture was microwave irradiated for 30min at a microwave power of 400W to obtain the A mixed slurry.

[0055] (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: 200H2O.

[0056] (4) Using a molar ratio of 2.85Na2O:Al2O3:8.4SiO2:200H2O, 46.75 g of water glass and 4 g of sodium carbonate were stirred evenly. Then, 10.5 g of aluminum sulfate octadecylhydrate, 23.75 g of aqueous solution, and 10.64 g of alkali solution 2 were added and stirred evenly to form a gel. Then, 0.98 g of sodium persulfate was added, and finally, the A mixture slurry was added. The mixture was stirred at 35°C for 3 h. The gel was transferred to a polytetrafluoroethylene liner and crystallized at 150°C for 24 h. After filtration, washing, and drying, the gel was calcined at 550°C for 7 h to obtain a carbon aerogel / Y / ZSM-35 / NU-87 composite molecular sieve.

[0057] (5) The carrier molding process is the same as in Example 1.

[0058] Example 7

[0059] (1) Take 48.2g of sodium hydroxide and add it to 83.5g of water. Stir until the sodium hydroxide is completely dissolved. Then add 9.8g of sodium aluminate and stir until the sodium aluminate is completely dissolved to obtain a sodium aluminate solution. Take 49.6g of the sodium aluminate mixed solution and 251.2g of water glass and pour them into 143.6g of deionized water. Stir evenly and then let it stand at 60℃ for 24h to obtain a Y-type molecular sieve nanocrystal precursor slurry. The components are in the molar ratio of 30Na2O: Al2O3: 40SiO2: 800H2O.

[0060] (2) 20.6g of ZSM-35 molecular sieve matrix, 2.29g of NU-87 molecular sieve matrix, and 3.44g 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 9:1:1.5:3.2. 18.5g of isopropanol was added, and the mixture was microwave irradiated for 30min at a microwave power of 400W to obtain the A mixed slurry.

[0061] (3) Dissolve 16g of sodium hydroxide in 10.4g of water, then add 3.3g of sodium aluminate and stir until completely dissolved. The molar ratio of the alkali solution is: 10Na2O: Al2O3: 100H2O.

[0062] (4) Using a molar ratio of 2.85Na2O:Al2O3:8.4SiO2:200H2O, 46.75 g of water glass and 3.26 g of ammonium carbonate were mixed and stirred evenly. Then, 10.5 g of aluminum sulfate octadecylhydrate, 23.75 g of water, and 10.64 g of alkali solution 3 were added and stirred evenly to form a gel. 1.6 g of sodium persulfate was added, and finally, mixture A was added. The mixture was stirred at 35 °C for 3 h. The gel was transferred to a polytetrafluoroethylene liner and crystallized at 120 °C for 15 h. After filtration, washing, and drying, the gel was calcined at 400 °C for 10 h to obtain a carbon aerogel / Y / ZSM-35 / NU-87 composite molecular sieve.

[0063] (5) The carrier molding process is the same as in Example 1.

[0064] Comparative Example 1

[0065] (1) Take 8g of sodium hydroxide and add it to 20.9g of water. 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 sodium aluminate mixed solution and 31.4g of water glass and pour them into 26.2g of deionized water. Stir evenly and then let it stand at 60℃ for 16h to obtain a molecular sieve nanocrystal precursor slurry. The components are in the molar ratio of 5Na2O: 1Al2O3: 5SiO2: 200H2O.

[0066] (2) Add 20.6g of ZSM-35 molecular sieve matrix, 2.29g of NU-87 molecular sieve matrix, 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.

[0067] (3) Using a molar ratio of 2.85Na2O: Al2O3: 8.4SiO2: 200H2O, 46.75 g of water glass, 10.5 g of aluminum sulfate octadecylhydrate, and 23.75 g of water were mixed and stirred until homogeneous. Then, 10.64 g of sodium hydroxide was added and stirred until homogeneous to form a gel. Finally, the A mixture was added and stirred at 35 °C for 3 h. The gel was transferred to a polytetrafluoroethylene liner and crystallized at 96 °C for 24 h. After filtration, washing, and drying, the gel was calcined at 550 °C for 10 h to obtain a carbon aerogel / Y / ZSM-35 / NU-87 composite molecular sieve.

[0068] (4) The carrier molding process is the same as in Example 1.

[0069] Comparative Example 2

[0070] (1) Take 8g of sodium hydroxide and add it to 20.9g of water. 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 sodium aluminate mixed solution and 31.4g of water glass and pour them into 26.2g of deionized water. Stir evenly and then let it stand at 60℃ for 16h to obtain Y-type molecular sieve nanocrystal precursor slurry. The components are in the molar ratio of 5Na2O: 1Al2O3: 5SiO2: 200H2O.

[0071] (2) Add 20.6g of ZSM-35 molecular sieve matrix 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.

[0072] (3) Using a molar ratio of 2.85Na2O:Al2O3:8.4SiO2:200H2O, 46.75 g of water glass, 10.5 g of aluminum sulfate octadecylhydrate, and 23.75 g of water were mixed and stirred until homogeneous. Then, 10.64 g of sodium hydroxide was added and stirred until homogeneous to form a gel. Next, 3.4 g of mesoporous template agent TPHAC was added, and finally, mixture A was added and stirred at 35 °C for 3 h. The gel was transferred to a polytetrafluoroethylene liner and crystallized at 96 °C for 24 h. After filtration, washing, and drying, it was calcined at 550 °C for 10 h to obtain the Y / ZSM-35 / NU-87 composite molecular sieve.

[0073] (4) The carrier molding process is the same as in Example 1.

[0074] The texture properties of the carrier are shown in Table 1.

[0075] The carrier prepared in the examples was impregnated for 2 hours with an impregnation solution prepared by dissolving 26 g of nickel nitrate and 37 g of ammonium metatungstate in 100 mL of water, dried at 120°C for 4 hours, and calcined at 500°C in air for 4 hours to obtain a catalyst. This catalyst is used in the hydrocracking process of a mixture of reduced-pressure II and III ketone-benzene dewaxing oils to produce high-quality lubricating oil base oil feedstock. The reaction conditions are: reaction temperature 360–410°C, reaction pressure 12.0–17.0 MPa, and space velocity 1.5–2.0 h⁻¹. -1 Hydrocracking was evaluated under a hydrogen-to-oil ratio of 700–1500:1.

[0076] Table 1 Comparison of pore structure parameters between the examples and comparative samples

[0077]

[0078] Table 2 Properties of hydrocracking products from examples and comparative samples

[0079]

[0080] Note: Reaction temperature 380℃, hydrogen partial pressure 9.2 MPa, hydrogen-to-oil volume ratio (V / V) 800:1, cracking space velocity 2.52 h⁻¹ -1

Claims

1. A hydrocracking catalyst support, characterized in that, The support comprises a carbon aerogel / Y / ZSM-35 / NU-87 composite molecular sieve, and the specific surface area of ​​the support is 457-485 m². 2 ·g -1 The pore size is 0.73-0.80 cm. 3 ·g -1 ; The preparation method of the hydrocracking catalyst support includes: (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, 1 Al2O3, and (5-40) SiO2. (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 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 parts are (2-80) Na2O, 1 Al2O3, (5-200) SiO2; crystallize at 90-150℃ for 12-24h, and calcine to obtain carbon aerogel / Y / ZSM-35 / NU-87 composite molecular sieve.

2. The hydrocracking catalyst support according to claim 1, characterized in that, In step (1), the Y-type molecular sieve nanocrystal precursor also contains water in a molar ratio of (200-800).

3. The method according to claim 1, characterized in that, In step (2), 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.

4. The hydrocracking catalyst support according to claim 1, characterized in that, In step (3), the gel solution also contains 10-800 molar amounts of water.

5. The hydrocracking catalyst support according to claim 1, characterized in that, In step (3), the alkaline solution is prepared as follows: sodium aluminate is dissolved in a hot sodium hydroxide solution, wherein the molar ratio of Na2O and Al2O3 is (10-15) Na2O and 1 Al2O3.

6. The hydrocracking catalyst support according to claim 1, characterized in that, In step (3), 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.

7. The hydrocracking catalyst support according to claim 1, characterized in that, In step (3), 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.

8. The hydrocracking catalyst support according to claim 1, characterized in that, In step (3), the strong oxidant is sodium persulfate; the amount of the strong oxidant added is 1-5% of the amount of SiO2 added to the gel.

9. The hydrocracking catalyst support according to claim 1, characterized in that, The preparation method of the hydrocracking catalyst support further includes: (4) mixing macroporous alumina material, carbon aerogel / Y / ZSM-35 / NU-87 composite molecular sieve, high-dispersion binder and extrusion aid evenly, wherein the mass ratio of macroporous alumina material, carbon aerogel / Y / ZSM-35 / NU-87 composite molecular sieve, high-dispersion binder and extrusion aid is (40~76):(20~50):(3.0~5.0):(1.0~5.0).

10. The application of the hydrocracking catalyst support according to claim 1 in the preparation of catalysts.

11. A catalyst, characterized in that, The catalyst uses the hydrocracking catalyst support described in claim 1.

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