Hydrocracking catalyst, method for preparing the same, and use thereof

Abstract

The application provides a hydrocracking catalyst and a preparation method and application thereof. The preparation method comprises the following steps: mixing La2O3 / PMo heteropoly acid / KIT-6 mesoporous molecular sieve oxide, a Y molecular sieve directing agent, an organic matter, an aluminum source, an alkali source, a silicon source and water to obtain a mixture A, performing crystallization on the mixture A, and performing solid-liquid separation to obtain a molecular sieve composite material; mixing the molecular sieve composite material with amorphous phosphorus aluminum, a phosphorus molybdenum heteropoly acid and a macroporous binder to obtain a mixture B, and performing molding on the mixture B to obtain a catalyst carrier; mixing the catalyst carrier with a nano metal oxide and a binder to obtain a mixture C, and performing molding and calcination on the mixture C to obtain the hydrocracking catalyst. The hydrocracking catalyst has high aromatic hydrocarbon poor distillate selective cracking performance and can realize high light naphtha and heavy naphtha yield in hydrocracking.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of catalyst material preparation, and particularly relates to a hydrocracking catalyst suitable for preparing light naphtha and heavy naphtha by hydrocracking, and a preparation method and application thereof. BACKGROUND

[0002] Molecular sieves are widely used in adsorption, separation, catalysis and other fields due to their unique pore structure, especially in petroleum and chemical industry. With the continuous development of molecular sieve catalytic applications, single-pore molecular sieves cannot meet the diverse needs of catalyst preparation. Microporous molecular sieves are mainly characterized by strong acidity and high structural stability in heterogeneous catalysis applications. However, due to the small pore size and long and narrow pore channel of microporous molecular sieves, it is difficult for large molecules in heavy oil to diffuse into the pore channel, which reduces the utilization rate of acid sites inside the microporous molecular sieve channel. At the same time, the narrow and long pore channel has a large diffusion resistance, which affects the rapid diffusion of reaction product molecules, and easily leads to deep cracking and coking. Mesoporous molecular sieves can make up for the limitations of microporous molecular sieves in internal diffusion of reactants and reaction products, but the structural stability of mesoporous molecular sieves is often poor, which also limits their catalytic applications. Microporous-mesoporous composite molecular sieve materials can produce good synergistic effect and catalytic performance by taking the advantages of each other in performance, and their comprehensive performance is better than that of the original component materials. This kind of molecular sieve with multiple structures and superimposed functions can avoid the defects of single pore structure, and the multi-level pore system can provide different size channels, which will be very helpful to solve the problem of mass transfer of large molecules.

[0003] CN111484037A discloses a method for synthesizing SSZ-13 molecular sieves with different silicon-aluminum ratios by Y molecular sieve transformation, which is to mix alkali source, silicon source, structure directing agent, mesoporous template agent and water uniformly, add different contents of aluminum source to prepare a sol, then add Y type molecular sieve to obtain an initial gel, perform hydrothermal crystallization reaction, cool and wash to neutral after the reaction is completed, dry to obtain a molecular sieve raw powder, and then calcine the molecular sieve raw powder to obtain SSZ-13 molecular sieves with different silicon-aluminum ratios. However, the SSZ-13 molecular sieves obtained by this method have relatively low pore size and pore volume, poor selective cracking performance of aromatic hydrocarbon inferior distillate, and low yield of light naphtha and heavy naphtha prepared by hydrocracking, which is not suitable for preparing light naphtha and heavy naphtha by hydrocracking.

[0004] CN110357121A discloses a preparation method of small crystal grain nano multi-level hole SSZ-13 molecular sieve, which is prepared by using TMADaOH as a structure directing agent, TPOAC as a mesoporous template agent, mixing an alkali source, a silicon source, a structure directing agent, a mesoporous template agent and water uniformly, adding or not adding an aluminum source to prepare a sol, adding a Y type molecular sieve to obtain an initial gel, and performing a hydrothermal crystallization reaction, and then calcining a reaction product to obtain the small crystal grain nano multi-level hole SSZ-13 molecular sieve. However, the SSZ-13 molecular sieve synthesized by the method has poor aromatic hydrocarbon inferior fraction oil selective cracking performance, low yield of light naphtha and heavy naphtha prepared by hydrocracking, and is not suitable for preparing light naphtha and heavy naphtha by hydrocracking.

[0005] CN114130427A discloses a Y / SSZ-13 / rare earth / ASA composite material, which is prepared by mixing Y molecular sieve, SSZ-13 molecular sieve, an aluminum source, an alkaline compound, water, a silicon source and a rare earth. However, the Y / SSZ-13 / rare earth / ASA composite material has poor aromatic hydrocarbon inferior fraction oil selective cracking performance, low yield of light naphtha and heavy naphtha prepared by hydrocracking, and is not suitable for preparing light naphtha and heavy naphtha by hydrocracking.

[0006] CN106311319A discloses a hydrocracking catalyst containing micro-mesoporous composite molecular sieve, which is a micro-mesoporous composite Beta / KIT-6 composite molecular sieve. The composite molecular sieve has low acid strength, poor aromatic hydrocarbon inferior fraction oil selective cracking performance, low yield of light naphtha and heavy naphtha prepared by hydrocracking, and is not suitable for preparing light naphtha and heavy naphtha by hydrocracking.

[0007] In short, the existing molecular sieves generally have the problem of poor aromatic hydrocarbon inferior fraction oil selective cracking performance, low yield of light naphtha and heavy naphtha prepared by hydrocracking in the process of hydrocracking. Therefore, there is still a need to study a hydrocracking catalyst with high aromatic hydrocarbon inferior fraction oil selective cracking performance and high yield of light naphtha and heavy naphtha prepared by hydrocracking. SUMMARY

[0008] The present application aims to provide a hydrocracking catalyst with high aromatic hydrocarbon inferior fraction oil selective cracking performance and high yield of light naphtha and heavy naphtha prepared by hydrocracking, and a method for preparing the hydrocracking catalyst and applications of the hydrocracking catalyst.

[0009] In order to achieve the above-mentioned purpose, the present application provides the following three technical solutions.

[0010] In a first aspect, the present application provides a method for preparing a hydrocracking catalyst, wherein the method comprises:

[0011] The KIT-6 molecular sieve is sprayed and adsorbed with a phosphomolybdic heteropoly acid complex aqueous solution containing lanthanum salt, dried and calcined to obtain a La2O3 / PMo heteropoly acid / KIT-6 mesoporous molecular sieve oxide;

[0012] The La2O3 / PMo heteropoly acid / KIT-6 mesoporous molecular sieve oxide, the Y molecular sieve directing agent, the organic matter, the aluminum source, the alkali source, the silicon source and the water are mixed to obtain a mixture A, the mixture A is crystallized to obtain a slurry of the Y / La2O3 / PMo heteropoly acid / KIT-6 molecular sieve composite oxide, and the Y / La2O3 / PMo heteropoly acid / KIT-6 molecular sieve composite oxide slurry is subjected to solid-liquid separation to obtain a solid-phase Y / La2O3 / PMo heteropoly acid / KIT-6 molecular sieve composite oxide material, which is the molecular sieve composite material; wherein the organic matter includes at least one of hydroxypropyl methyl cellulose, polyethylene glycol and cetyltrimethylammonium bromide;

[0013] The molecular sieve composite material is mixed with amorphous phosphorus aluminum, phosphomolybdic heteropoly acid and macroporous binder to obtain a mixture B, and the mixture B is formed to obtain a catalyst carrier;

[0014] The catalyst carrier is mixed with a nano metal oxide and a binder to obtain a mixture C, and the mixture C is formed and calcined to obtain a hydrocracking catalyst.

[0015] The technical scheme provided by the present application is that the La2O3 / PMo heteropoly acid / KIT-6 mesoporous molecular sieve oxide, the Y molecular sieve directing agent, the organic matter (hydroxypropyl methyl cellulose, polyethylene glycol and cetyltrimethylammonium bromide) and the silicon aluminum alkali source are mixed and then crystallized to obtain a special Y / La2O3 / PMo heteropoly acid / KIT-6 molecular sieve mesoporous composite oxide material. The Y / La2O3 / PMo heteropoly acid / KIT-6 molecular sieve mesoporous composite oxide material has a micropore-mesopore composite structure, has a high mesopore pore size distribution and has a high infrared acid amount. The catalyst carrier prepared by using the material and then the hydrocracking catalyst prepared by using the catalyst carrier have high aromatic poor distillate selective cracking performance and can realize high light naphtha and heavy naphtha yield in hydrocracking.

[0016] According to the preferred embodiment of the first aspect, the polyethylene glycol includes at least one of PEG2000 and PEG200.

[0017] According to the preferred embodiments of the first aspect, the lanthanum salt is selected from lanthanum nitrate.

[0018] According to the preferred embodiments of the first aspect, the aluminum source comprises at least one of aluminum sulfate and sodium aluminate.

[0019] According to the preferred embodiments of the first aspect, the alkali source comprises at least one of sodium aluminate and potassium hydroxide.

[0020] According to the preferred embodiments of the first aspect, the silicon source comprises at least one of water glass and silica sol.

[0021] According to the preferred embodiments of the first aspect, the Y zeolite directing agent is prepared by the following method:

[0022] mixing the alkali source, the aluminum source, the silicon source and water in a molar ratio of (6-9)Na2O:1Al2O3:(7-13)SiO2:(200-350)H2O, and aging to obtain the Y zeolite directing agent;

[0023] Further, the aging temperature is 20-60℃; more further, the aging temperature is 25-40℃.

[0024] Further, the aging time is 10-24h; more further, the aging time is 12-24h.

[0025] Further, the aluminum source used for preparing the Y zeolite directing agent comprises at least one of aluminum sulfate and sodium aluminate.

[0026] Further, the alkali source used for preparing the Y zeolite directing agent comprises at least one of sodium aluminate and potassium hydroxide.

[0027] Further, the silicon source used for preparing the Y zeolite directing agent comprises at least one of water glass and silica sol.

[0028] Further, mixing the alkali source, the aluminum source, the silicon source and water in a molar ratio of (6.5-7.5)Na2O:1Al2O3:(9-11)SiO2:(220-300)H2O, and aging to obtain the Y zeolite directing agent.

[0029] Further, the sodium metaaluminate solution A, the water glass solution A and water are mixed to obtain the Y molecular sieve directing agent through aging; wherein, the content of Al2O3 in the sodium metaaluminate solution A is 4-8wt%, and the content of Na2O is 20-30wt%, based on the total mass of the sodium metaaluminate solution A being 100%; the content of SiO2 in the water glass solution A is 20-40wt%, based on the total mass of the water glass solution A being 100%; further, the content of Al2O3 in the sodium metaaluminate solution A is 5-7wt%, and the content of Na2O is 25-30wt%, based on the total mass of the sodium metaaluminate solution A being 100%; the content of SiO2 in the water glass solution A is 25-30wt%, based on the total mass of the water glass solution A being 100%.

[0030] According to the preferred embodiments of the first aspect, in the preparation of the La2O3 / PMo heteropoly acid / KIT-6 mesoporous molecular sieve oxide, the mass ratio of KIT-6 mesoporous molecular sieve: lanthanum nitrate: phosphomolybdic heteropoly acid: water is 1: (0.01-0.12): (0.1-0.25): (0.5-2).

[0031] Further, in the preparation of the La2O3 / PMo heteropoly acid / KIT-6 mesoporous molecular sieve oxide, the mass ratio of KIT-6 mesoporous molecular sieve: lanthanum nitrate: phosphomolybdic heteropoly acid: water is 1: (0.05-0.1): (0.15-0.2): (0.5-2).

[0032] According to the preferred embodiments of the first aspect, in the preparation of the La2O3 / PMo heteropoly acid / KIT-6 mesoporous molecular sieve oxide, the temperature of drying is 80-100℃.

[0033] According to the preferred embodiments of the first aspect, in the preparation of the La2O3 / PMo heteropoly acid / KIT-6 mesoporous molecular sieve oxide, the temperature of calcination is 300-400℃.

[0034] According to the preferred embodiments of the first aspect, in the preparation of the La2O3 / PMo heteropoly acid / KIT-6 mesoporous molecular sieve oxide, the atmosphere of calcination is air atmosphere.

[0035] According to the preferred embodiments of the first aspect, the temperature of crystallization is 90-100℃; further, the temperature of crystallization is 95-100℃.

[0036] According to the preferred embodiments of the first aspect, the time of crystallization is 24-48h.

[0037] According to the preferred embodiment of the first aspect, wherein the mixing of the La2O3 / PMo heteropoly acid / KIT-6 mesoporous molecular sieve oxide, the Y molecular sieve directing agent, the organic matter, the aluminum source, the alkali source, the silicon source and the water Y molecular sieve directing agent, the La2O3 / PMo heteropoly acid / KIT-6 mesoporous molecular sieve oxide, the organic matter, the aluminum source, the alkali source, the silicon source and the water is achieved by the following way:

[0038] The La2O3 / PMo heteropoly acid / KIT-6 mesoporous molecular sieve oxide, the Y molecular sieve directing agent, the organic matter, the aluminum sulfate solution, the sodium metaaluminate solution B, the water glass solution B and the water are mixed to obtain the mixture A;

[0039] wherein the content of Al2O3 in the sodium metaaluminate solution B is 5-15wt%, the content of Na2O is 5-20wt%, based on the total mass of the sodium metaaluminate solution B; the content of SiO2 in the water glass solution A is 20-40wt%, based on the total mass of the water glass solution B; the content of Al2O3 in the aluminum sulfate solution is 2-6wt%, based on the total mass of the aluminum sulfate solution;

[0040] Further, the content of Al2O3 in the sodium metaaluminate solution B is 8-12wt%, the content of Na2O is 8-15wt%, based on the total mass of the sodium metaaluminate solution B; the content of SiO2 in the water glass solution A is 25-30wt%, based on the total mass of the water glass solution B; the content of Al2O3 in the aluminum sulfate solution is 3-5wt%, based on the total mass of the aluminum sulfate solution.

[0041] According to the preferred embodiment of the first aspect, wherein the preparation method further comprises:

[0042] The solid-phase Y / La2O3 / PMo heteropoly acid / KIT-6 molecular sieve composite oxide material is subjected to water vapor treatment before the preparation of the mixture B;

[0043] Further, the temperature of the water vapor treatment is 500-800℃; more further, the temperature of the water vapor treatment is 600-700℃;

[0044] Further, the time of the water vapor treatment is 0.5-2.5h; more further, the time of the water vapor treatment is 1-1.5h;

[0045] Further, the preparation method further comprises: the Y / La2O3 / PMo heteropoly acid / KIT-6 molecular sieve composite oxide material after the water vapor treatment is treated with a mixed solution of ammonium sulfate and citric acid, and then is used for the preparation of the mixture B;

[0046] Further, the mass concentration of ammonium sulfate in the mixed solution of ammonium sulfate and citric acid is 10-20%, and the mass concentration of citric acid is 10-20%, based on the total mass of the mixed solution of ammonium sulfate and citric acid being 100%; further, the mass concentration of ammonium sulfate in the mixed solution of ammonium sulfate and citric acid is 10-15%, and the mass concentration of citric acid is 10-15%, based on the total mass of the mixed solution of ammonium sulfate and citric acid being 100%;

[0047] Further, the treatment time of the treatment with the mixed solution of ammonium sulfate and citric acid is 0.5-2h; further, the treatment time of the treatment with the mixed solution of ammonium sulfate and citric acid is 0.5-1h.

[0048] Further, the treatment temperature of the treatment with the mixed solution of ammonium sulfate and citric acid is room temperature.

[0049] According to the preferred embodiments of the first aspect, the macroporous binder used for preparing the mixture B is selected from macroporous alumina binder.

[0050] According to the preferred embodiments of the first aspect, the forming of the mixture B is achieved by mixing, rolling, and extrusion.

[0051] According to the preferred embodiments of the first aspect, the addition amount of amorphous phosphorus aluminum is 10-20wt%, based on the mass of the mixture B being 100%; further, the addition amount of amorphous phosphorus aluminum is 15-18wt%, based on the mass of the mixture B being 100%.

[0052] According to the preferred embodiments of the first aspect, the addition amount of phosphomolybdic heteropoly acid is 1-5wt%, based on the mass of the mixture B being 100%; further, the addition amount of phosphomolybdic heteropoly acid is 2-4wt%, based on the mass of the mixture B being 100%.

[0053] According to the preferred embodiments of the first aspect, the addition amount of macroporous binder is 15-20wt%, based on the mass of the mixture B being 100%; further, the addition amount of macroporous binder is 17-18wt%, based on the mass of the mixture B being 100%.

[0054] According to the preferred embodiments of the first aspect, the nano metal oxide includes nano tungsten oxide and nano nickel oxide.

[0055] Further, the addition amount of nano tungsten oxide is 18-25wt%, based on the mass of the mixture C being 100%; further, the addition amount of nano tungsten oxide is 20-23wt%, based on the mass of the mixture C being 100%.

[0056] Further, the amount of the nano nickel oxide added is 2-5wt% based on 100wt% of the mixture C; further, the amount of the nano nickel oxide added is 3-4wt% based on 100wt% of the mixture C.

[0057] According to the preferred embodiment of the first aspect, the binder used for preparing the mixture C is selected from alumina binder.

[0058] According to the preferred embodiment of the first aspect, the amount of the binder added is 20-25wt% based on 100wt% of the mixture C.

[0059] According to the preferred embodiment of the first aspect, the temperature of the calcination is 450-650℃ during the process of forming, calcining the mixture C to obtain the hydrocracking catalyst.

[0060] According to the preferred embodiment of the first aspect, the time of the calcination is 1.5-3.5h during the process of forming, calcining the mixture C to obtain the hydrocracking catalyst.

[0061] According to the preferred embodiment of the first aspect, the atmosphere of the calcination is air atmosphere during the process of forming, calcining the mixture C to obtain the hydrocracking catalyst.

[0062] The second aspect of the present application provides a hydrocracking catalyst prepared by the method for preparing the hydrocracking catalyst according to the first aspect.

[0063] According to the preferred embodiment of the second aspect, the specific surface area of the hydrocracking catalyst is 350-400m 2 / g, the total pore volume is 0.3-0.52mL / g, and the pore size distribution is 4-22nm.

[0064] The third aspect of the present application provides the application of the hydrocracking catalyst according to the second aspect in the preparation of light naphtha and heavy naphtha from the hydrocracking of aromatic distillate oil.

[0065] The technical method provided by the present application is to mix La2O3 / PMo heteropoly acid / KIT-6 mesoporous molecular sieve oxide, Y molecular sieve directing agent, organic matter (hydroxypropyl methyl cellulose, polyethylene glycol and cetyl trimethyl ammonium bromide) and silicon aluminum alkali source, and then crystallize to construct a surface area of 600-850m 2 / g, the total pore volume is 0.45-0.8 mL / g, the pore size distribution is 4-25 nm, the infrared acid amount is 0.8-1.5 mmol / g, the microporous-mesoporous La2O3 / PMo heteropolyacid / KIT-6 molecular sieve composite oxide has a high mesopore size distribution and a high infrared acid amount. The support prepared by using the material is used to prepare a hydrocracking catalyst, and the specific surface area of the hydrocracking catalyst is 350-400 m 2 / g, the total pore volume is 0.3-0.52 mL / g, the pore size distribution is 4-22 nm, the microporous-mesoporous La2O3 / PMo heteropolyacid / KIT-6 molecular sieve composite oxide has a high mesopore size distribution and a high infrared acid amount. The support prepared by using the material is used to prepare a hydrocracking catalyst, and the specific surface area of the hydrocracking catalyst is 350-400 m DETAILED DESCRIPTION

[0066] In order to have a clearer understanding of the technical features, objectives and beneficial effects of the present application, the technical solutions of the present application are described in detail below, but it should not be understood as limiting the scope of the present application. Those skilled in the art can make some non-essential improvements and adjustments to the present application according to the above content of the present application. The raw materials used in the following examples and comparative examples are commercially available, unless otherwise specified.

[0067] Example 1

[0068] The present embodiment provides a hydrocracking catalyst, which is prepared by the following preparation method:

[0069] (1) 87 g of sodium metaaluminate solution (Al2O3 content is 4 wt%, Na2O content is 20 wt%) and 120 g of water glass solution (SiO2 content is 20 wt%) are sequentially added to 35 g of deionized water (i.e. 8.2 Na2O:1 Al2O3:11.7 SiO2:321 H2O), and aged at 20℃ for 24 h to prepare a Y molecular sieve directing agent;

[0070] (2) KIT-6 molecular sieve and a phosphomolybdic acid complex aqueous solution containing lanthanum nitrate are spray adsorbed according to the mass ratio of KIT-6 molecular sieve:lanthanum nitrate:phosphomolybdic acid:H2O=1:0.01:0.1:0.5, dried (drying temperature is 80℃, time is 2 h) and calcined (calcination temperature is 300℃, time is 2 h, atmosphere is air) to obtain a La2O3 / PMo heteropolyacid / KIT-6 mesoporous molecular sieve oxide;

[0071] (3) 5 g of La2O3 / PMo heteropolyacid / KIT-6 mesoporous molecular sieve oxide, 5 g of Y molecular sieve directing agent, 80 g of aluminum sulfate solution (Al2O3 content of 2 wt%), 80 g of sodium metaaluminate solution (Al2O3 content of 5 wt%, Na2O content of 5 wt%), and 2 g of PEG2000 are added to 90 g of water glass solution (SiO2 content of 20 wt%), after being stirred uniformly, 5 g of deionized water is added, to form a mixture A, the mixture A is crystallized at 95°C for 24 h to obtain a slurry of Y / La2O3 / PMo heteropolyacid / KIT-6 molecular sieve composite oxide, and the slurry of Y / La2O3 / PMo heteropolyacid / KIT-6 molecular sieve composite oxide is subjected to solid-liquid separation to obtain a solid Y / La2O3 / PMo heteropolyacid / KIT-6 molecular sieve composite oxide;

[0072] (4) The Y / La2O3 / PMo heteropolyacid / KIT-6 molecular sieve composite oxide obtained in step (3) is treated under water vapor at 800°C for 0.5 h.

[0073] (5) The Y / La2O3 / PMo heteropolyacid / KIT-6 molecular sieve composite oxide treated by water vapor obtained in step (4) is treated in a mixed solution of ammonium sulfate and citric acid (ammonium sulfate concentration of 10 wt%, citric acid concentration of 10 wt%) at room temperature for 2 h to obtain a treated molecular sieve composite material.

[0074] (6) The treated molecular sieve composite material is mixed with amorphous phosphorus aluminum, phosphorus molybdenum heteropolyacid powder, and macroporous alumina binder (amorphous phosphorus aluminum addition amount of 20 wt%, phosphorus molybdenum heteropolyacid powder addition amount of 1 wt%, macroporous alumina binder addition amount of 20 wt% based on the total mass after mixing), and after mixing, rolling, and extruding, a hydrocracking catalyst carrier is obtained.

[0075] (7) The hydrocracking catalyst carrier is mixed with nano-nickel oxide powder and nano-tungsten oxide powder, and after adding an alumina binder and rolling, a hydrocracking catalyst is obtained by calcining at 550°C for 3 h; wherein, based on the total mass of the hydrocracking catalyst carrier, nano-nickel oxide powder, nano-tungsten oxide powder, and alumina binder being 100%, the addition amount of nano-tungsten oxide powder is 25 wt%, the addition amount of nano-nickel oxide powder is 2 wt%, and the addition amount of alumina binder is 20 wt%.

[0076] Example 2

[0077] The present embodiment provides a hydrocracking catalyst prepared by the following preparation method:

[0078] (1) 77 g of sodium metaaluminate solution (Al2O3 content of 6 wt%, Na2O content of 25 wt%) and 100 g of water glass solution (SiO2 content of 30 wt%) were sequentially added to 65 g of deionized water (i.e. 6.8 Na2O: 1 Al2O3: 11.0 SiO2: 230.8 H2O), and the mixture was aged at 30°C for 18 h to prepare a Y molecular sieve directing agent;

[0079] (2) KIT-6 molecular sieve and a phosphomolybdic acid complex aqueous solution containing lanthanum nitrate were spray-adsorbed according to a mass ratio of KIT-6 molecular sieve: lanthanum nitrate: phosphomolybdic acid: H2O = 1:0.06:0.13:1, and then dried (drying temperature of 90°C, time of 1.5 h) and calcined (calcination temperature of 350°C, time of 1.5 h, atmosphere of air) to obtain La2O3 / PMo heteropoly acid / KIT-6 mesoporous molecular sieve oxide;

[0080] (3) 10 g of La2O3 / PMo heteropoly acid / KIT-6 mesoporous molecular sieve oxide, 10 g of Y molecular sieve directing agent, 65 g of aluminum sulfate solution (Al2O3 content of 3 wt%), 65 g of sodium metaaluminate solution (Al2O3 content of 10 wt%, Na2O content of 12.5 wt%) and 5 g of PEG200 were added to 75 g of water glass solution (SiO2 content of 27 wt%), and then 50 g of deionized water was added to prepare a mixture A. The mixture A was crystallized at 95°C for 36 h to obtain a slurry of Y / La2O3 / PMo heteropoly acid / KIT-6 molecular sieve composite oxide. The slurry of Y / La2O3 / PMo heteropoly acid / KIT-6 molecular sieve composite oxide was subjected to solid-liquid separation to obtain a solid Y / La2O3 / PMo heteropoly acid / KIT-6 molecular sieve composite oxide.

[0081] (4) The Y / La2O3 / PMo heteropoly acid / KIT-6 molecular sieve composite oxide obtained in step (3) was treated under water vapor at 800°C for 1 h.

[0082] (5) The Y / La2O3 / PMo heteropoly acid / KIT-6 molecular sieve composite oxide treated under water vapor obtained in step (4) was treated in a mixed solution of ammonium sulfate and citric acid (ammonium sulfate concentration of 15 wt%, citric acid concentration of 15 wt%) at room temperature for 2 h to obtain a treated molecular sieve composite material.

[0083] (6) The treated molecular sieve composite material is mixed with amorphous phosphorus aluminum, phosphomolybdic acid powder, and macroporous alumina binder (amorphous phosphorus aluminum is added in an amount of 15 wt%, phosphomolybdic acid powder is added in an amount of 2.5 wt%, and macroporous alumina binder is added in an amount of 18 wt% based on the total mass of the mixture being 100%), kneaded, roll-pressed, and extruded into strips to obtain a hydrocracking catalyst carrier.

[0084] (7) The hydrocracking catalyst carrier is mixed with nano nickel oxide powder and nano tungsten oxide powder, and an alumina binder is added and roll-pressed, and then calcined at 500°C for 4 hours to obtain a hydrocracking catalyst; wherein the total mass of the hydrocracking catalyst carrier, nano nickel oxide powder, nano tungsten oxide powder, and alumina binder is 100%, the nano tungsten oxide powder is added in an amount of 21.5 wt%, the nano nickel oxide powder is added in an amount of 3.5 wt%, and the alumina binder is added in an amount of 22.5 wt%.

[0085] Example 3

[0086] The present embodiment provides a hydrocracking catalyst prepared by the following preparation method:

[0087] (1) 65 g of sodium metaaluminate solution (Al2O3 content of 8 wt%, Na2O content of 30 wt%) and 82 g of water glass solution (SiO2 content of 40 wt%) are sequentially added to 100 g of deionized water (i.e. 6.2 Na2O: 1 Al2O3: 10.7 SiO2: 206 H2O), and aged at 40°C for 24 h to prepare a Y molecular sieve directing agent;

[0088] (2) KIT-6 molecular sieve is spray-adsorbed with a phosphomolybdic acid complex aqueous solution containing lanthanum nitrate according to a mass ratio of KIT-6 molecular sieve: lanthanum nitrate: phosphomolybdic acid: H2O = 1:0.12:0.25:2, dried (drying temperature of 100°C, time of 1 h), and calcined (calcination temperature of 400°C, time of 1 h, atmosphere of air) to obtain a La2O3 / PMo heteropoly acid / KIT-6 mesoporous molecular sieve oxide;

[0089] (3) 15 g of La2O3 / PMo heteropolyacid / KIT-6 mesoporous molecular sieve oxide, 15 g of Y molecular sieve directing agent, 70 g of aluminum sulfate solution (Al2O3 content of 6 wt%), 40 g of sodium metaaluminate solution (Al2O3 content of 15 wt%, Na2O content of 20 wt%), and 7 g of CATB are added to 63 g of water glass solution (SiO2 content of 40 wt%), after being stirred uniformly, 82 g of deionized water is added, to prepare a mixture A, the mixture A is crystallized at 100°C for 48 h to obtain a slurry of Y / La2O3 / PMo heteropolyacid / KIT-6 molecular sieve composite oxide, the slurry of Y / La2O3 / PMo heteropolyacid / KIT-6 molecular sieve composite oxide is subjected to solid-liquid separation to obtain a solid Y / La2O3 / PMo heteropolyacid / KIT-6 molecular sieve composite oxide, which is the molecular sieve composite material.

[0090] (4) The Y / La2O3 / PMo heteropolyacid / KIT-6 molecular sieve composite oxide obtained in step (3) is treated under water vapor at 800°C for 0.5 h.

[0091] (5) The Y / La2O3 / PMo heteropolyacid / KIT-6 molecular sieve composite oxide treated by water vapor obtained in step (4) is treated in a mixed solution of ammonium sulfate and citric acid (ammonium sulfate concentration of 20 wt%, citric acid concentration of 20 wt%) at room temperature for 2 h to obtain a treated molecular sieve composite material.

[0092] (6) The treated molecular sieve composite material is mixed with amorphous phosphorus aluminum, phosphorus molybdenum heteropolyacid powder, and macroporous alumina binder (amorphous phosphorus aluminum addition amount of 10 wt%, phosphorus molybdenum heteropolyacid powder addition amount of 5 wt%, macroporous alumina binder addition amount of 15 wt% based on the total mass after mixing of 100%), and after kneading, rolling, and extrusion forming, a hydrocracking catalyst carrier is obtained.

[0093] (7) The hydrocracking catalyst carrier is mixed with nano nickel oxide powder and nano tungsten oxide powder, and after adding an alumina binder and rolling forming, a hydrocracking catalyst is obtained by calcining at 580°C for 2 h; wherein, based on the total mass of the hydrocracking catalyst carrier, nano nickel oxide powder, nano tungsten oxide powder, and alumina binder of 100%, the addition amount of nano tungsten oxide powder is 25 wt%, the addition amount of nano nickel oxide powder is 2 wt%, and the addition amount of alumina binder is 25 wt%.

[0094] Comparative Example 1

[0095] This comparative example provides a hydrocracking catalyst, which is different from Example 3 in that La2O3 / PMo heteropolyacid / KIT-6 mesoporous molecular sieve oxide is not added, and is prepared by the following preparation method:

[0096] (1) 65 g of sodium metaaluminate solution (Al203 content of 8 wt%, Na20 content of 30 wt%) and 82 g of water glass solution (Si02 content of 40 wt%) were sequentially added to 100 g of deionized water (i.e. 6.2 Na20: 1 Al203: 10.7 Si02: 206 H20), and the mixture was aged at 40 °C for 24 h to prepare a Y molecular sieve directing agent;

[0097] (2) 15 g of the Y molecular sieve directing agent, 70 g of aluminum sulfate solution (Al203 content of 6 wt%), 40 g of sodium metaaluminate solution (Al203 content of 15 wt%, Na20 content of 20 wt%) and 7 g of CATB were added to 63 g of water glass solution (Si02 content of 40 wt%), and then 82 g of deionized water was added after stirring to prepare a mixture A. The mixture A was crystallized at 100 °C for 48 h to obtain a Y molecular sieve slurry. The Y molecular sieve slurry was subjected to solid-liquid separation to obtain a solid Y molecular sieve.

[0098] (3) The Y molecular sieve obtained in step (2) was treated with water vapor at 800 °C for 0.5 h.

[0099] (4) The Y molecular sieve treated with water vapor obtained in step (3) was treated in a mixed solution of ammonium sulfate and citric acid (ammonium sulfate concentration of 20 wt%, citric acid concentration of 20 wt%) at room temperature for 2 h to obtain a treated molecular sieve material.

[0100] (5) The treated molecular sieve material was mixed with amorphous phosphorus aluminum, phosphomolybdic acid powder and large-pore alumina binder (amorphous phosphorus aluminum was added in an amount of 10 wt%, phosphomolybdic acid powder was added in an amount of 5 wt%, and large-pore alumina binder was added in an amount of 15 wt% based on the total mass of the mixture after mixing, which was 100%), and then the mixture was subjected to kneading, rolling, and extrusion to obtain a hydrocracking catalyst carrier.

[0101] (6) The hydrocracking catalyst carrier was mixed with nano-nickel oxide powder and nano-tungsten oxide powder, and then alumina binder was added and the mixture was rolled and formed, and then the mixture was calcined at 580 °C for 2 h to obtain a hydrocracking catalyst; wherein the total mass of the hydrocracking catalyst carrier, nano-nickel oxide powder, nano-tungsten oxide powder and alumina binder was 100%, the addition amount of nano-tungsten oxide powder was 25 wt%, the addition amount of nano-nickel oxide powder was 2 wt%, and the addition amount of alumina binder was 25 wt%.

[0102] Comparative Example 2

[0103] The present comparative example provides a hydrocracking catalyst, which is different from Example 3 in that a Beta zeolite is co-assembled with La2O3 / PMo heteropolyacid / KIT-6 mesoporous molecular sieve to obtain a Beta / La2O3 / PMo heteropolyacid / KIT-6 micro-mesoporous composite molecular sieve, and is prepared by the following preparation method:

[0104] (1) Synthesis of Y zeolite directing agent: 65 g of sodium metasilicate solution A (Al2O3 content of 8 wt%, Na2O content of 30 wt%) and 82 g of water glass solution (SiO2 content of 40 wt%) were sequentially added to 100 g of deionized water, and aged at 40 °C for 24 h to obtain a Y zeolite directing agent. The molar ratio of each component in the Y zeolite directing agent was 6Na2O:Al2O3:11SiO2:206H2O.

[0105] (2) Beta / La2O3 / PMo heteropolyacid / KIT-6 micro-mesoporous composite molecular sieve was prepared by the preparation method of Example 1 of CN106311319A: 1.9 g of NaOH and 7.6 g of NaAlO2 were sequentially added to 295 g of TEAOH solution, and stirred intensively to mix uniformly, then 215 g of TEOS was slowly added and stirred at room temperature for 4 h, and then transferred to a self-pressure reaction kettle and crystallized at 120 °C for 24 h to obtain a Beta zeolite seed solution. 2 g of P123 was added to 80 g of 1 mol / L HCl solution, then 30 g of n-butanol was added, stirred for 4 h, then 50 g of TEOS was added, and the stirring was continued at 40 °C for 2 h, then 80 g of the above prepared Beta zeolite seed solution was added, and then 5 g of La2O3 / PMo heteropolyacid / KIT-6 molecular sieve was added, and stirred at 40 °C for 24 h, then transferred to a self-pressure reaction kettle and crystallized at 100 °C for 24 h, then filtered, washed, dried and calcined at 550 °C to finally obtain a Beta / La2O3 / PMo heteropolyacid / KIT-6 micro-mesoporous composite molecular sieve.

[0106] (3) 15 g of the Y / Beta / La2O3 / PMo heteropolyacid / KIT-6 micro-mesoporous composite molecular sieve obtained in step (2), 15 g of Y molecular sieve directing agent, 70 g of an aluminum sulfate solution (Al2O3 content of 6 wt%), 40 g of a sodium metaaluminate solution B (Al2O3 content of 15 wt% and Na2O content of 20 wt%), and 2 g of CATB are added to 63 g of a water glass solution (SiO2 content of 40 wt%), and after being stirred uniformly, 82 g of deionized water is added to prepare a mixture A. The mixture A is crystallized at 100°C for 48 h to obtain a slurry of Y / Beta / La2O3 / PMo heteropolyacid / KIT-6 composite oxide. The slurry of Y / Beta / La2O3 / PMo heteropolyacid / KIT-6 composite oxide is subjected to solid-liquid separation to obtain a solid Y / Beta / La2O3 / PMo heteropolyacid / KIT-6 composite oxide.

[0107] (4) The Y / Beta / La2O3 / PMo heteropolyacid / KIT-6 composite oxide obtained in step (3) is treated under water vapor at 800°C for 0.5 h.

[0108] (5) The Y / Beta / La2O3 / PMo heteropolyacid / KIT-6 composite oxide after the water vapor treatment is treated in a mixed solution of ammonium sulfate and citric acid (ammonium sulfate concentration of 20 wt% and citric acid concentration of 20 wt%) at room temperature for 2 h to obtain a treated molecular sieve composite material.

[0109] (6) The treated molecular sieve composite material is mixed with amorphous phosphorus aluminum, phosphorus molybdenum heteropolyacid powder, and macroporous alumina binder (amorphous phosphorus aluminum addition amount of 10 wt%, phosphorus molybdenum heteropolyacid powder addition amount of 5 wt%, and macroporous alumina binder addition amount of 15 wt% based on the total mass after mixing of 100%), and after being kneaded, rolled, and extruded into a strip, a hydrocracking catalyst carrier is obtained.

[0110] (7) The hydrocracking catalyst carrier is mixed with nano nickel oxide powder and nano tungsten oxide powder, and after an alumina binder is added and is rolled into a shape, a hydrocracking catalyst is obtained by calcining at 580°C for 2 h; wherein the addition amount of the nano tungsten oxide powder is 25 wt%, the addition amount of the nano nickel oxide powder is 2 wt%, and the addition amount of the alumina binder is 25 wt% based on the total mass of the hydrocracking catalyst carrier, the nano nickel oxide powder, the nano tungsten oxide powder, and the alumina binder of 100%.

[0111] Evaluation Example 1

[0112] The molecular sieve composite materials (before water vapor treatment) provided by Example 1-Example 3, Comparative Example 1-Comparative Example 2 were respectively tested for specific surface area, pore volume, pore size distribution, infrared acid amount, and the results are shown in Table 1.

[0113] Table 1

[0114] Sample Specific surface area (m 2 / g) Pore volume (mL / g) Pore size distribution (nm) Infrared acid amount (mmol / g) Example 1 650 0.50 4～15 0.9 Example 2 700 0.60 4～20 1.1 Example 3 780 0.72 4～25 1.4 Comparative Example 1 600 0.40 4～8 0.8 Comparative Example 2 700 0.65 4～20 0.6

[0115] The hydrocracking catalysts provided by Example 1-Example 3, Comparative Example 1-Comparative Example 2 were respectively tested for specific surface area, pore volume, pore size distribution, and the results are shown in Table 2.

[0116] Table 2

[0117] Sample Specific surface area (m 2 / g) Pore volume (mL / g) Pore size distribution (nm) Example 1 350 0.30 4-13 Example 2 400 0.40 4-18 Example 3 480 0.52 4-22 Comparative Example 1 300 0.25 4-8 Comparative Example 2 405 0.45 4-20

[0118] Evaluation Example 2

[0119] The hydrocracking catalysts provided by Example 1-Example 3, Comparative Example 1-Comparative Example 2 were respectively tested for specific surface area, pore volume, pore size distribution, and the results are shown in Table 2.

[0120] Table 3 Properties of raw oil

[0121]

[0122]

[0123] Table 4 Reaction performance of hydrocracking catalyst

[0124] Item Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Reaction pressure, MPa 12 12 12 12 12 Hydrogen to oil volume ratio 1200 1200 1200 1200 1200 airspeed, h -1 ]]> 1.2 1.2 1.2 1.2 1.2 Reaction temperature, °C 378 376 374 372 372 Light naphtha yield, wt% 18.1 16.5 15.2 10 13 Heavy naphtha yield, wt% 71.5 69.5 67.5 55 64

[0125] From the results of Table 2 and Table 4, it can be seen that the hydrocracking catalyst prepared by the preparation method of the present application improves the mesopore size distribution, and when used for hydrocracking to produce light naphtha and heavy naphtha, it improves the selective cracking performance of distillate oil and increases the yield of light naphtha and heavy naphtha.

[0126] Of course, the present application can have other various embodiments, and those skilled in the art can make various corresponding changes and modifications according to the present application without departing from the spirit and essence of the present application, but these corresponding changes and modifications should all belong to the protection scope of the claims of the present application.

Claims

1. A method for preparing a hydrocracking catalyst, wherein, The preparation method includes: KIT-6 molecular sieve was spray-adsorbed with an aqueous solution of phosphomolybdic heteropolyacid containing lanthanum salt, and then dried and calcined to obtain La2O3 / PMo heteropolyacid / KIT-6 mesoporous molecular sieve oxide. According to the mass ratio: (0.8-1.5) La2O3 / PMo heteropolyacid / KIT-6 mesoporous molecular sieve oxide: (0.08 – 1.5) Y molecular sieve directing agent: 1 Al2O3: (0.08-1.0) Na2O: (2.3-3.3) SiO2: (0.3-0.7) organic matter: (13-41) H2O is used to mix La2O3 / PMo heteropolyacid / KIT-6 mesoporous molecular sieve oxide, Y molecular sieve directing agent, aluminum source, sodium source, silicon source, organic matter, and water to obtain mixture A. Mixture A is crystallized to obtain a slurry of Y / La2O3 / PMo heteropolyacid / KIT-6 molecular sieve composite oxide. The slurry of Y / La2O3 / PMo heteropolyacid / KIT-6 molecular sieve composite oxide is subjected to solid-liquid separation to obtain a solid-phase Y / La2O3 / PMo heteropolyacid / KIT-6 molecular sieve composite oxide material, which is the molecular sieve composite material. The organic matter includes at least one of hydroxypropyl methylcellulose, polyethylene glycol, and hexadecyltrimethylammonium bromide. The molecular sieve composite material is mixed with amorphous aluminum phosphide, phosphomolybdate heteropoly acid and macroporous binder to obtain mixture B. Mixture B is then shaped to obtain a catalyst support. The catalyst support is mixed with nano-metal oxide and binder to obtain mixture C. Mixture C is then shaped and calcined to obtain a hydrocracking catalyst. Among them, sodium source, aluminum source, silicon source and water are mixed according to the molar ratio of (6-9)Na2O:1Al2O3: (7-13)SiO2: (200-350)H2O, and then aged to obtain Y molecular sieve directing agent.

2. The preparation method according to claim 1, wherein, The lanthanum salt is selected from lanthanum nitrate; in the preparation process of La2O3 / PMo heteropoly acid / KIT-6 mesoporous molecular sieve oxide, the mass ratio of KIT-6 molecular sieve to lanthanum nitrate to phosphomolybdenum heteropoly acid to water is 1: (0.01-0.12): (0.1-0.25): (0.5-2).

3. The preparation method according to claim 2, wherein, KIT-6 molecular sieve mass: Lanthanum nitrate mass: Phosphomolybdic acid mass: Water mass = 1: (0.05-0.1): (0.15-0.2): (0.5-2).

4. The preparation method according to claim 1, wherein, The aging temperature is 20-60℃.

5. The preparation method according to claim 4, wherein, The aging temperature is 25-40℃.

6. The preparation method according to claim 1, wherein, Sodium source, aluminum source, silicon source and water were mixed according to the molar ratio of (6.5-7.5)Na2O:1Al2O3: (9-11)SiO2:(220-300)H2O, and then aged to obtain Y molecular sieve directing agent.

7. The preparation method according to claim 1, wherein, The aluminum source used in the preparation of Y molecular sieve directing agents includes at least one of aluminum sulfate and sodium aluminate.

8. The preparation method according to claim 1, wherein, Sodium sources used in the preparation of Y molecular sieve directing agents include sodium aluminate.

9. The preparation method according to claim 1, wherein, The silicon source used to prepare the Y molecular sieve directing agent includes at least one of water glass and silica sol.

10. The preparation method according to claim 1, wherein, The preparation method also includes: The solid-phase Y / La2O3 / PMo heteropolyacid / KIT-6 molecular sieve composite oxide material was subjected to steam treatment before the preparation of mixture B.

11. The preparation method according to claim 10, wherein, The temperature for steam treatment is 500-800℃.

12. The preparation method according to claim 11, wherein, The temperature for the steam treatment is 600-700℃.

13. The preparation method according to claim 10, wherein, The preparation method further includes: treating the Y / La2O3 / PMo heteropoly acid / KIT-6 molecular sieve composite oxide material after steam treatment with a mixed solution of ammonium sulfate and citric acid, and then using it to prepare mixture B.

14. The preparation method according to claim 13, wherein, Taking the total mass of the mixed solution of ammonium sulfate and citric acid as 100%, the mass concentration of ammonium sulfate in the mixed solution of ammonium sulfate and citric acid is 10-20%, and the mass concentration of citric acid is 10-20%.

15. The preparation method according to claim 14, wherein, Taking the total mass of the mixed solution of ammonium sulfate and citric acid as 100%, the mass concentration of ammonium sulfate in the mixed solution of ammonium sulfate and citric acid is 10-15% and the mass concentration of citric acid is 10-15%.

16. The preparation method according to claim 1, wherein, Based on the mass of mixture B as 100%, the amount of amorphous aluminum phosphide added is 10-20 wt%, the amount of phosphomolybdic heteropoly acid added is 1-5 wt%, and the amount of macroporous binder added is 15-20 wt%.

17. The preparation method according to claim 16, wherein, Based on the mass of mixture B as 100%, the amount of amorphous aluminum phosphide added is 15-18 wt%, the amount of phosphomolybdic heteropoly acid added is 2-4 wt%, and the amount of macroporous binder added is 17-18 wt%.

18. The preparation method according to claim 1, wherein, Nanometal oxides include nanotungsten oxide and nanonickel oxide.

19. The preparation method according to claim 18, wherein, Based on the mass of mixture C as 100%, the amount of nano-tungsten oxide added is 18-25 wt%, and the amount of nano-nickel oxide added is 2-5 wt%.

20. The preparation method according to claim 19, wherein, Based on the mass of mixture C as 100%, the amount of nano-tungsten oxide added is 20-23 wt%, and the amount of nano-nickel oxide added is 3-4 wt%.

21. The preparation method according to claim 1, wherein, Based on the mass of mixture C being 100%, the amount of binder added is 20-25 wt%.

22. The preparation method according to claim 1, wherein, The crystallization temperature is 90-100℃.

23. The preparation method according to claim 22, wherein, The crystallization temperature is 95-100℃.

24. The preparation method according to claim 1, wherein, During the preparation of La2O3 / PMo heteropolyacid / KIT-6 mesoporous molecular sieve oxide, the calcination temperature is 300-400℃.

25. The preparation method according to claim 1, wherein, In the process of obtaining hydrocracking catalyst by molding and calcining mixture C, the calcination temperature is 450-650℃.

26. The preparation method according to claim 1, wherein, In the process of obtaining hydrocracking catalyst by molding and calcining mixture C, the calcination atmosphere is air.

27. The preparation method according to claim 1, wherein, The polyethylene glycol includes at least one of PEG2000 and PEG200.

28. The preparation method according to claim 1, wherein, The lanthanum salt is selected from lanthanum nitrate.

29. The preparation method according to claim 1, wherein, The aluminum source used to prepare mixture A includes at least one of aluminum sulfate and sodium aluminate.

30. The preparation method according to claim 1, wherein, The sodium source used to prepare mixture A includes sodium aluminate.

31. The preparation method according to claim 1, wherein, The silicon source used to prepare mixture A includes at least one of water glass and silica sol.

32. The preparation method according to claim 1, wherein, The macroporous binder used to prepare mixture B is a macroporous alumina binder.

33. The preparation method according to claim 1, wherein, Alumina binder was selected as the binder for preparing mixture C.

34. The hydrocracking catalyst prepared by the method according to any one of claims 1-33.

35. The hydrocracking catalyst according to claim 34, wherein, The specific surface area of ​​this hydrocracking catalyst is 350-400 m². 2 / g, with a total pore volume of 0.3-0.52mL / g and a pore size distribution of 4-22nm.

36. The application of the hydrocracking catalyst according to claim 34 or 35 in the hydrocracking of aromatic distillate oils to produce light naphtha and heavy naphtha.

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