Catalyst carrier for producing high yield of light naphtha and heavy naphtha by hydrocracking and preparation method of catalyst carrier

Abstract

The invention discloses a catalyst carrier for high yield of light naphtha and heavy naphtha by hydrocracking and a preparation method of the catalyst carrier. The catalyst carrier contains Y / La2O3 / PMo heteropolyacid / KIT-6 molecular sieve mesoporous composite oxide. According to the preparation method disclosed by the invention, the pore size distribution of mesopores is improved, the selective cracking performance of distillate oil is improved, and the yield of light naphtha and heavy naphtha is improved. According to the preparation method, the selective cracking performance of the carrier to distillate oil is improved, and the yield of light naphtha and heavy naphtha is improved.

Description

Technical Field

[0001] The invention relates to a catalyst carrier for producing more light naphtha and heavy naphtha by hydrocracking and a preparation method thereof, belonging to the technical field of carrier materials. Background Art

[0002] Molecular sieves are widely used in adsorption, separation, catalysis and other fields due to their unique pore structure, especially in petrochemicals. With the continuous development of molecular sieve catalytic applications, molecular sieves with a single pore can no longer meet the various catalyst preparation requirements. Microporous molecular sieves are mainly known for their strong acid properties and high structural stability in heterogeneous catalytic applications. However, since most microporous molecular sieves have small pore sizes and long and narrow pores, it is difficult for the macromolecules in the reaction raw materials, such as heavy oil, to diffuse into the pores, which will reduce the utilization rate of the acid sites inside the microporous molecular sieve pores. At the same time, the narrow and long pores have a large diffusion resistance, which affects the rapid diffusion and overflow of the reaction product molecules, and easily leads to deep cracking and coking. Although mesoporous molecular sieves can make up for the limitations of microporous molecular sieves in the diffusion of reactants and reaction products, 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 effects and catalytic performance by complementing the strengths of several single materials, making their overall performance better than the original component materials. This molecular sieve with multiple structures and superimposed functions can avoid the defects of a single pore structure, and the multi-level pore system can provide pores of different sizes at the same time, which will be of great help in solving problems such as mass transfer of large molecules.

[0003] Chinese patent CN111484037A discloses a method for synthesizing SSZ-13 molecular sieves with different silicon-aluminum ratios by crystallization of Y molecular sieves, wherein TMADaOH is used as a structure directing agent, an alkali source, a silicon source, a structure directing agent, a mesoporous template agent and water are evenly mixed, different amounts of aluminum sources are added to obtain a sol, and then a Y-type molecular sieve is added to obtain an initial gel, and a hydrothermal crystallization reaction is performed. After the reaction is completed, a crystallization reaction product is obtained, which is cooled and washed to neutrality, and dried to obtain a molecular sieve raw powder, and then the molecular sieve raw powder is calcined to obtain SSZ-13 molecular sieves with different silicon-aluminum ratios. However, the pore size and pore volume of the SSZ-13 molecular sieve obtained by this method are relatively low, and La2O3 / PMo heteropoly acid / KIT-6 molecular sieve is not involved.

[0004] Chinese patent CN110357121A discloses a method for preparing a small-grain nano-multi-level pore SSZ-13 molecular sieve, which uses TMADaOH as a structure directing agent and TPOAC as a mesoporous template agent, mixes an alkali source, a silicon source, a structure directing agent, a mesoporous template agent and water evenly, adds or does not add an aluminum source to obtain a sol, and then adds a Y-type molecular sieve to obtain an initial gel, performs a hydrothermal crystallization reaction, and calcines the reaction product to obtain a small-grain nano-multi-level pore SSZ-13 molecular sieve. However, this technology only synthesizes the SSZ-13 molecular sieve, and does not involve the La2O3 / PMo heteropoly acid / KIT-6 molecular sieve, and the molecular sieve function is limited.

[0005] Chinese patent CN114130427A discloses a Y / SSZ-13 / rare earth / ASA composite material, a hydrocracking catalyst, a catalyst carrier, and a preparation method thereof, comprising the following steps: Step 1, mixing Y molecular sieve, SSZ-13 molecular sieve, aluminum source, alkaline compound and water, heating and stirring; Step 2, adding silicon source and rare earth precursor to the mixture of step 1, heating and stirring to obtain Y / SSZ-13 / rare earth / ASA composite material. However, this technology only synthesizes Y / SSZ-13 / rare earth / ASA composite material, and does not involve La2O3 / PMo heteropoly acid / KIT-6 molecular sieve, and the molecular sieve function is limited.

[0006] Chinese patent CN106311319A discloses a hydrocracking catalyst containing a micro-mesoporous composite molecular sieve and its application. The catalyst includes a catalyst carrier and an active component. Calculated by weight percentage of the catalyst carrier, the catalyst carrier includes 5-50wt% of the micro-mesoporous composite molecular sieve, 5-30wt% of the Y microporous molecular sieve, 10-50wt% of alumina, 20-55wt% of amorphous silicon-alumina, 5-25wt% of a binder and 1-5wt% of an extrusion aid; calculated by weight percentage of the catalyst carrier, the active component includes 10%-40% of a VIB group metal oxide, 1%-20% of a VIII group metal oxide and / or 0.1%-10% of a VA group oxide. However, although the catalyst is added with 5 to 50 wt% of micro-mesoporous composite molecular sieves, the molecular sieve composition is Beta / KIT-6 composite molecular sieves. Since the Beta molecular sieve is a microporous molecular sieve of isomerization, it is not as good as the Y molecular sieve in terms of pore size and acid strength. The KIT-6 mesoporous molecular sieve is an all-silicon molecular sieve. Although it has a large pore size, it has no acidity without modification. Therefore, the Beta / KIT-6 micro-mesoporous composite molecular sieve used in this technology is not as strong as the Y / La2O3 / PMo heteropolyacid / KIT-6 molecular sieve mesoporous composite oxide of the present invention in terms of molecular sieve acid strength, resulting in relatively low cracking activity. Therefore, the yields of the resulting light naphtha and heavy naphtha products are low. Summary of the invention

[0007] The object of the present invention is to provide a catalyst carrier for producing more light naphtha and heavy naphtha by hydrocracking and a preparation method thereof, so as to solve the problems of low selectivity of existing catalysts for distillate oil cracking and low yield of light naphtha and heavy naphtha as hydrocracking products.

[0008] To achieve the above object, the present invention provides a method for preparing a catalyst carrier for hydrocracking to produce more light naphtha and heavy naphtha, wherein the catalyst carrier contains a Y / La2O3 / PMo heteropoly acid / KIT-6 molecular sieve mesoporous composite oxide, and the preparation method comprises the following steps:

[0009] (1) spraying and adsorbing a KIT-6 molecular sieve and a phosphomolybdic heteropoly acid complex aqueous solution containing lanthanum nitrate, and drying and calcining to obtain La2O3 / PMo heteropoly acid / KIT-6 mesoporous molecular sieve oxide;

[0010] (2) adding the La2O3 / PMo heteropoly acid / KIT-6 mesoporous molecular sieve oxide, Y molecular sieve directing agent, aluminum sulfate solution, sodium aluminate solution B and organic matter obtained in step (1) to a water glass solution, stirring evenly, then adding deionized water, mixing evenly, and crystallizing to obtain a slurry of Y / La2O3 / PMo heteropoly acid / KIT-6 molecular sieve mesoporous composite oxide, wherein La2O3 / PMo heteropoly acid / KIT-6 molecular sieve mesoporous composite oxide is The mass ratio of 6 mesoporous molecular sieve oxide: Y molecular sieve directing agent: Al2O3: Na2O: SiO2: organic matter: H2O is = (0.8-1.5): (0.09-0.15): 1: (0.08-0.96): (2.4-3.2): (0.3-0.7): (13-41); after solid-liquid separation, Y / La2O3 / PMo heteropoly acid / KIT-6 molecular sieve mesoporous composite oxide is obtained;

[0011] (3) treating the Y / La2O3 / PMo heteropoly acid / KIT-6 molecular sieve mesoporous composite oxide under water vapor conditions;

[0012] (4) treating the Y / La2O3 / PMo heteropoly acid / KIT-6 molecular sieve mesoporous composite oxide after water vapor treatment in a mixed solution of ammonium sulfate and citric acid to obtain a slurry;

[0013] (5) Amorphous aluminum phosphide, phosphomolybdic acid and macroporous alumina binder are added to the slurry in step (4), and the mixture is kneaded, rolled and extruded to obtain a catalyst carrier containing Y / La2O3 / PMo heteropoly acid / KIT-6 molecular sieve mesoporous composite oxide.

[0014] In the preparation method of the present invention, in step (1), the mass ratio of KIT-6 molecular sieve: lanthanum nitrate: phosphomolybdic heteropoly acid: aqueous solution is 1: (0.01-0.12): (0.1-0.25): (0.5-2).

[0015] In the preparation method of the present invention, preferably, in step (1), the mass ratio of KIT-6 molecular sieve: lanthanum nitrate: Pmo heteropoly acid: aqueous solution is 1: (0.05-0.1): (0.15-0.2): (0.5-2).

[0016] In the preparation method of the present invention, in step (1), the drying temperature is 80-100°C; and the calcining temperature is 300-400°C.

[0017] In the preparation method of the present invention, in step (2), the preparation method of the Y molecular sieve directing agent comprises: adding sodium aluminate solution A and water glass solution into deionized water, aging, and obtaining the Y molecular sieve directing agent.

[0018] In the preparation method of the present invention, the molar ratio of each component of the Y molecular sieve directing agent is (6-8) Na2O:Al2O3:(7-12)SiO2:(206-321)H2O.

[0019] In the preparation method of the present invention, preferably, the molar ratio of the components of the Y molecular sieve directing agent is (6.5-7.5) Na2O:Al2O3:(9-11)SiO2:(220-300)H2O.

[0020] In the preparation method of the present invention, in the sodium aluminate solution A, the content of Al2O3 is 4-8wt%, preferably 5-7wt%, and the content of Na2O is 20-30wt%, preferably 25-30wt%.

[0021] In the preparation method of the present invention, the water glass solution has a SiO2 content of 20 to 40 wt%, preferably 25 to 30 wt%.

[0022] In the preparation method of the present invention, in the preparation of the Y molecular sieve directing agent, the aging temperature is 20 to 60° C., preferably 25 to 40° C., and the time is 10 to 24 hours, preferably 12 to 24 hours.

[0023] In the preparation method of the present invention, in step (2), the content of Al2O3 in the aluminum sulfate solution is 2 to 6 wt%, preferably 3 to 5 wt%.

[0024] In the preparation method of the present invention, in step (2), in the sodium aluminate solution B, the content of Al2O3 is 5 to 15wt%, preferably 8 to 12wt%, and the content of Na2O is 5 to 20wt%, preferably 8 to 15wt%.

[0025] In the preparation method of the present invention, in step (2), the organic matter includes at least one of hydroxypropyl methylcellulose, PEG2000, PEG200, and CTAB.

[0026] In the preparation method of the present invention, in step (2), the water glass solution has a SiO2 content of 20 to 40 wt%, preferably 25 to 30 wt%, calculated as SiO2.

[0027] In the preparation method of the present invention, in step (2), the crystallization temperature is 90 to 100° C., preferably 95 to 100° C., and the crystallization time is 24 to 48 hours.

[0028] In the preparation method of the present invention, in step (3), the treatment temperature is 500-800° C., preferably 600-700° C., and the treatment time is 0.5-2.5 hours, preferably 1-1.5 hours.

[0029] In the preparation method of the present invention, in step (4), the content of ammonium sulfate in the mixed solution is 10 to 20 wt%, preferably 10 to 15 wt%.

[0030] In the preparation method of the present invention, in step (4), the content of citric acid in the mixed solution is 10 to 20 wt%, preferably 10 to 15 wt%.

[0031] In the preparation method of the present invention, in step (4), the treatment time is 0.5 to 2 hours, preferably 0.5 to 1 hour.

[0032] In the preparation method of the present invention, in step (5), the amount of amorphous aluminum phosphorus added is 10 to 20 wt%, preferably 15 to 18 wt%.

[0033] In the preparation method of the present invention, in step (5), the amount of the phosphomolybdic heteropoly acid added is 1 to 5 wt%, preferably 2 to 4 wt%.

[0034] In the preparation method of the present invention, in step (5), the addition amount of the macroporous alumina binder is 15 to 20 wt%, preferably 17 to 18 wt%.

[0035] The present invention also provides a catalyst carrier for hydrocracking to produce more light naphtha and heavy naphtha, wherein the specific surface area of ​​the catalyst carrier is 550 to 680 m 2 / g, the pore volume is 0.4~0.62mL / g, and the pore size distribution is 4~25nm.

[0036] The preparation method of the present invention is to construct a Y / La2O3 / PMo heteropoly acid / KIT-6 microporous-mesoporous composite oxide for preparing a hydrocracking carrier, and the surface area of ​​the obtained carrier is 550-680m2 / g, the pore volume is 0.4~0.62mL / g, and the pore size distribution is 4~25nm, which increases the mesopore size and infrared acid content of the carrier, thereby improving the selective cracking performance of the carrier for distillate oil and increasing the yield of light naphtha and heavy naphtha. DETAILED DESCRIPTION

[0037] The present invention is described in detail below by way of examples. It is necessary to point out that the following examples are only used to further illustrate the present invention and cannot be construed as limiting the scope of protection of the present invention. Those skilled in the art in this field can make some non-essential improvements and adjustments to the present invention based on the above content of the present invention. The raw materials used in the following examples and comparative examples, unless otherwise specified, are all commercially available.

[0038] Example 1

[0039] (1) Synthesis of Y molecular sieve directing agent: 87 g of sodium aluminate solution A (Al2O3 content of 4 wt%, Na2O content of 20 wt%) and 120 g of water glass solution (SiO2 content of 20 wt%) were added to 35 g of deionized water in sequence, and aged at 20°C for 24 h to obtain Y molecular sieve directing agent. The molar ratio of each component in the Y molecular sieve directing agent was 8Na2O:Al2O3:12SiO2:321H2O.

[0040] (2) According to the feed mass ratio of KIT-6 molecular sieve: lanthanum nitrate: phosphomolybdic heteropoly acid: H2O=1:0.01:0.1:0.5, the KIT-6 molecular sieve and the phosphomolybdic heteropoly acid complex aqueous solution containing lanthanum nitrate are sprayed for adsorption, and after drying and calcination, La2O3 / PMo heteropoly acid / KIT-6 mesoporous molecular sieve oxide is obtained.

[0041] (3) 5 g of La2O3 / PMo heteropolyacid / KIT-6 mesoporous molecular sieve oxide obtained in step (2), 5 g of Y molecular sieve directing agent, 80 g of aluminum sulfate solution (Al2O3 content is 2 wt%), 80 g of sodium aluminate solution B (Al2O3 content is 5 wt%, Na2O content is 5 wt%) and 2 g of PEG2000 are added to 90 g of water glass solution (SiO2 content is 20 wt%), stirred evenly, and then 5 g of deionized water is added and mixed evenly to prepare a reaction mixture of Y / La2O3 / PMo heteropolyacid / KIT-6 molecular sieve, which is crystallized at 95°C for 24 h to obtain a slurry of Y / La2O3 / PMo heteropolyacid / KIT-6 molecular sieve mesoporous composite oxide, and after solid-liquid separation, a Y / La2O3 / PMo heteropolyacid / KIT-6 molecular sieve mesoporous composite oxide is obtained.

[0042] (4) The Y / La2O3 / PMo heteropolyacid / KIT-6 molecular sieve mesoporous composite oxide obtained in step (3) is treated under 800°C water vapor conditions for 0.5 hours.

[0043] (5) The Y / La2O3 / PMo heteropoly acid / KIT-6 molecular sieve mesoporous composite oxide treated with water vapor was treated in a mixed solution of 10 wt% ammonium sulfate and 10 wt% citric acid for 2 hours to obtain a slurry.

[0044] (6) Add 20 wt% of amorphous phosphorus aluminum, 1 wt% of phosphorus molybdenum heteropoly acid powder, and 20 wt% of macroporous alumina binder to the slurry in step (5), and obtain a catalyst carrier containing Y / La2O3 / PMo heteropoly acid / KIT-6 molecular sieve mesoporous composite oxide through kneading, rolling, and extrusion.

[0045] Example 2

[0046] (1) Synthesis of Y molecular sieve directing agent: 77 g of sodium aluminate solution A (Al2O3 content of 6 wt%, Na2O content of 25 wt%) and 100 g of water glass solution (SiO2 content of 30 wt%) were added to 65 g of deionized water in sequence, and aged at 30°C for 18 h to obtain Y molecular sieve directing agent. The molar ratio of each component in the Y molecular sieve directing agent was 7Na2O:Al2O3:7SiO2:242H2O.

[0047] (2) According to the feed mass ratio of KIT-6 molecular sieve: lanthanum nitrate: phosphomolybdic heteropoly acid: H2O=1:0.06:0.13:1, the KIT-6 molecular sieve and the phosphomolybdic heteropoly acid complex aqueous solution containing lanthanum nitrate are sprayed for adsorption, and after drying and calcination, La2O3 / PMo heteropoly acid / KIT-6 mesoporous molecular sieve oxide is obtained.

[0048] (3) 10 g of La2O3 / PMo heteropolyacid / KIT-6 mesoporous molecular sieve oxide obtained in step (2), 10 g of Y molecular sieve directing agent, 65 g of aluminum sulfate solution (Al2O3 content is 3 wt%), 65 g of sodium aluminate solution B (Al2O3 content is 10 wt%, Na2O content is 12.5 wt%) and 5 g of PEG200 are added to 75 g of water glass solution (SiO2 content is 27 wt%), stirred evenly, and then 50 g of deionized water is added and mixed evenly to prepare a reaction mixture of Y / La2O3 / PMo heteropolyacid / KIT-6 molecular sieve, which is crystallized at 95°C for 36 h to obtain a slurry of Y / La2O3 / PMo heteropolyacid / KIT-6 molecular sieve mesoporous composite oxide, and after solid-liquid separation, a Y / La2O3 / PMo heteropolyacid / KIT-6 molecular sieve mesoporous composite oxide is obtained.

[0049] (4) The Y / La2O3 / PMo heteropolyacid / KIT-6 molecular sieve mesoporous composite oxide obtained in step (3) is treated under 650°C water vapor conditions for 1.5 hours.

[0050] (5) The Y / La2O3 / PMo heteropoly acid / KIT-6 molecular sieve mesoporous composite oxide treated with water vapor was treated in a mixed solution of 15 wt% ammonium sulfate and 15 wt% citric acid for 1.25 hours to obtain a slurry.

[0051] (6) Add 15wt% amorphous aluminum phosphide, 2.5wt% phosphorus molybdenum heteropoly acid powder, and 18wt% macroporous alumina binder to the slurry in step (5), and obtain a catalyst carrier containing Y / La2O3 / PMo heteropoly acid / KIT-6 molecular sieve mesoporous composite oxide through kneading, rolling, and extrusion.

[0052] Example 3

[0053] (1) Synthesis of Y molecular sieve directing agent: 65 g of sodium aluminate 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 added to 100 g of deionized water in sequence, and aged at 40°C for 24 h to obtain Y molecular sieve directing agent. The molar ratio of each component in the Y molecular sieve directing agent was 6Na2O:Al2O3:11SiO2:206H2O.

[0054] (2) According to the feed mass ratio of KIT-6 molecular sieve: lanthanum nitrate: phosphomolybdic heteropoly acid: H2O=1:0.12:0.25:2, the KIT-6 molecular sieve and the phosphomolybdic heteropoly acid complex aqueous solution containing lanthanum nitrate are sprayed for adsorption, and after drying and calcination, La2O3 / PMo heteropoly acid / KIT-6 mesoporous molecular sieve oxide is obtained.

[0055] (3) 15 g of La2O3 / PMo heteropolyacid / KIT-6 mesoporous molecular sieve oxide obtained in step (2), 15 g of Y molecular sieve directing agent, 70 g of aluminum sulfate solution (Al2O3 content of 6 wt%), 40 g of sodium aluminate solution B (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%), stirred evenly, and then 82 g of deionized water is added and mixed evenly to prepare a reaction mixture of Y / La2O3 / PMo heteropolyacid / KIT-6 molecular sieve, which is crystallized at 100°C for 48 h to obtain a slurry of Y / La2O3 / PMo heteropolyacid / KIT-6 molecular sieve mesoporous composite oxide, and after solid-liquid separation, a Y / La2O3 / PMo heteropolyacid / KIT-6 molecular sieve mesoporous composite oxide is obtained.

[0056] (4) The Y / La2O3 / PMo heteropolyacid / KIT-6 molecular sieve mesoporous composite oxide obtained in step (3) is treated under 800°C water vapor conditions for 0.5 hours.

[0057] (5) The Y / La2O3 / PMo heteropoly acid / KIT-6 molecular sieve mesoporous composite oxide treated with water vapor was treated in a mixed solution of 20 wt% ammonium sulfate and 20 wt% citric acid for 2 hours to obtain a slurry.

[0058] (6) Add 10 wt% of amorphous phosphorus aluminum, 5 wt% of phosphorus molybdenum heteropoly acid powder, and 15 wt% of macroporous alumina binder to the slurry in step (5), and obtain a catalyst carrier containing Y / La2O3 / PMo heteropoly acid / KIT-6 molecular sieve mesoporous composite oxide through kneading, rolling, and extrusion.

[0059] Comparative Example 1

[0060] The difference from Example 3 is that La2O3 / PMo heteropoly acid / KIT-6 molecular sieve oxide is not added.

[0061] (1) Synthesis of Y molecular sieve directing agent: 65 g of sodium aluminate 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 added to 100 g of deionized water in sequence, and aged at 40°C for 24 h to obtain Y molecular sieve directing agent. The molar ratio of each component in the Y molecular sieve directing agent was 6Na2O:Al2O3:11SiO2:206H2O.

[0062] (2) 15 g of Y molecular sieve directing agent, 70 g of aluminum sulfate solution (Al2O3 content of 6 wt%), 40 g of sodium aluminate solution B (Al2O3 content of 15 wt%, Na2O content of 20 wt%) and 7 g of CATB were added to 63 g of water glass solution (SiO2 content of 40 wt%), stirred evenly, and then 82 g of deionized water was added to prepare a reaction mixture for synthesizing Y, which was crystallized at 100°C for 48 h to obtain a slurry of Y molecular sieve. After solid-liquid separation, Y molecular sieve was obtained.

[0063] (3) Treat the Y molecular sieve obtained in step (2) under 800° C. steam conditions for 0.5 hour.

[0064] (4) The Y molecular sieve treated with water vapor is treated in a mixed solution of 20 wt % ammonium sulfate and 20 wt % citric acid for 2 hours to obtain a slurry.

[0065] (5) Add 10 wt% of amorphous aluminum phosphide, 5 wt% of phosphorus molybdenum heteropoly acid powder, and 15 wt% of macroporous alumina binder to the slurry in step (4), and obtain a catalyst carrier containing Y molecular sieve through kneading, rolling, and extrusion.

[0066] Comparative Example 2

[0067] The difference from Example 3 is that Beta zeolite and La2O3 / PMo heteropolyacid / KIT-6 mesoporous molecular sieve are co-assembled to obtain Beta / La2O3 / PMo heteropolyacid / KIT-6 micro-mesoporous composite molecular sieve.

[0068] (1) Synthesis of Y molecular sieve directing agent: 65 g of sodium aluminate 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 added to 100 g of deionized water in sequence, and aged at 40°C for 24 h to obtain Y molecular sieve directing agent. The molar ratio of each component in the Y molecular sieve directing agent was 6Na2O:Al2O3:11SiO2:206H2O.

[0069] (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 NaOH and 7.6 g NaAlO2 were added to 295 g TEAOH solution in sequence, and stirred vigorously to mix them evenly. Then 215 g TEOS was slowly added and stirred at room temperature for 4 h. The mixture was transferred to an autoclave and crystallized at 120°C for 24 h to obtain a Beta zeolite seed solution. 2g P123 was added to 80g 1mol / L HCl solution, and then 30g n-butanol was added. After stirring for 4h, 50g TEOS was added, and stirring was continued at 40°C for 2h. Then 80g of the Beta zeolite seed solution prepared above was added, and then 5g La2O3 / PMo heteropolyacid / KIT-6 molecular sieve was added. The mixture was stirred at 40°C for 24h, and then transferred to a self-pressure reactor for crystallization at 100°C for 24h. After filtering, washing, drying and calcining at 550°C, Beta / La2O3 / PMo heteropolyacid / KIT-6 micro-mesoporous composite molecular sieve was finally obtained.

[0070] (3) 15 g of 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 aluminum sulfate solution (Al2O3 content of 6 wt%), 40 g of sodium aluminate solution B (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%), stirred evenly and then added with 82 g of deionized water to prepare a reaction mixture for synthesizing Y / La2O3 / PMo heteropolyacid / KIT-6 molecular sieve, crystallized at 100°C for 48 h, and obtained a slurry of Y / Beta / La2O3 / PMo heteropolyacid / KIT-6 molecular sieve mesoporous composite oxide, and after solid-liquid separation, obtained a Y / Beta / La2O3 / PMo heteropolyacid / KIT-6 molecular sieve mesoporous composite oxide.

[0071] (4) The Y / Beta / La2O3 / PMo heteropolyacid / KIT-6 molecular sieve mesoporous composite oxide obtained in step (3) is treated under 800°C water vapor conditions for 0.5 hours.

[0072] (5) The Y / Beta / La2O3 / PMo heteropoly acid / KIT-6 molecular sieve mesoporous composite oxide treated with water vapor was treated in a mixed solution of 20 wt% ammonium sulfate and 20 wt% citric acid for 2 hours to obtain a slurry.

[0073] (6) Add 10 wt% amorphous phosphorus aluminum, 5 wt% phosphorus molybdenum heteropoly acid powder, and 15 wt% macroporous alumina binder to the slurry in step (5), and obtain a catalyst carrier containing Y / Beta / La2O3 / PMo heteropoly acid / KIT-6 molecular sieve mesoporous composite oxide through kneading, rolling, and extrusion.

[0074] Table 1 Properties of molecular sieve composite oxides

[0075]

[0076] Table 2 Carrier properties

[0077]

[0078]

[0079] Evaluation Example 1

[0080] The performance of the catalyst carrier was evaluated using the feedstock oil in Table 3. The reaction conditions and evaluation results are shown in Table 4.

[0081] Table 3 Raw oil properties

[0082] project High aromatic distillate <![CDATA[Density, g / cm 3 (at 20 °C)]]> 0.855 Distillation range, ℃ 280～500 Nitrogen, μg / g 901 Sulfur, μg / g 1220 Mass spectrometry composition Paraffin, wt% 36.1 Cycloalkanes, wt% 23.8 Aromatics, wt% 40.1 Monocyclic aromatic hydrocarbons 18.0 Bicyclic aromatic hydrocarbons 19.2 Tricyclic aromatic hydrocarbons 2.9

[0083] Table 4 Hydrocracking catalyst reaction performance

[0084]

[0085]

[0086] It can be seen from the results in Table 4 that the preparation method of the present invention improves the mesopore size distribution, improves the selective cracking performance of the distillate oil, and improves the yield of light naphtha and heavy naphtha by constructing a catalyst carrier for hydrocracking to produce more light naphtha and heavy naphtha containing Y molecular sieve and La2O3 / PMo heteropolyacid / KIT-6 molecular sieve.

[0087] Of course, the present invention may have many other embodiments. Without departing from the spirit and essence of the present invention, technicians familiar with the field may make various corresponding changes and deformations based on the present invention, but these corresponding changes and deformations should all fall within the scope of protection of the claims of the present invention.

Claims

1. A method for preparing a catalyst carrier for hydrocracking to produce more light naphtha and heavy naphtha, characterized in that: The catalyst carrier contains Y / La2O3 / PMo heteropoly acid / KIT-6 molecular sieve mesoporous composite oxide, and the preparation method comprises the following steps: (1) spraying and adsorbing a KIT-6 molecular sieve and a phosphomolybdic heteropoly acid complex aqueous solution containing lanthanum nitrate, and drying and calcining to obtain La2O3 / PMo heteropoly acid / KIT-6 mesoporous molecular sieve oxide; (2) adding the La2O3 / PMo heteropoly acid / KIT-6 mesoporous molecular sieve oxide, Y molecular sieve directing agent, aluminum sulfate solution, sodium aluminate solution B and organic matter obtained in step (1) to a water glass solution, stirring evenly, then adding deionized water, mixing evenly, and crystallizing to obtain a slurry of Y / La2O3 / PMo heteropoly acid / KIT-6 molecular sieve mesoporous composite oxide, wherein La2O3 / PMo heteropoly acid / KIT-6 molecular sieve mesoporous composite oxide is The mass ratio of 6 mesoporous molecular sieve oxide: Y molecular sieve directing agent: Al2O3: Na2O: SiO2: organic matter: H2O is = (0.8-1.5): (0.09-0.15): 1: (0.08-0.96): (2.4-3.2): (0.3-0.7): (13-41); after solid-liquid separation, Y / La2O3 / PMo heteropoly acid / KIT-6 molecular sieve mesoporous composite oxide is obtained; (3) treating the Y / La2O3 / PMo heteropoly acid / KIT-6 molecular sieve mesoporous composite oxide under water vapor conditions; (4) treating the Y / La2O3 / PMo heteropoly acid / KIT-6 molecular sieve mesoporous composite oxide after water vapor treatment in a mixed solution of ammonium sulfate and citric acid to obtain a slurry; (5) Amorphous aluminum phosphide, phosphomolybdic acid and macroporous alumina binder are added to the slurry in step (4), and the mixture is kneaded, rolled and extruded to obtain a catalyst carrier containing Y / La2O3 / PMo heteropoly acid / KIT-6 molecular sieve mesoporous composite oxide.

2. The preparation method according to claim 1, characterized in that: In step (1), the mass ratio of KIT-6 molecular sieve: lanthanum nitrate: phosphomolybdic heteropoly acid: water is 1: (0.01-0.12): (0.1-0.25): (0.5-2).

3. The preparation method according to claim 1, characterized in that: In step (2), the preparation method of the Y molecular sieve directing agent comprises: Sodium aluminate solution A and water glass solution are added into deionized water and aged to obtain a Y molecular sieve directing agent.

4. The preparation method according to claim 1 or 3, characterized in that: The molar ratio of each component of the Y molecular sieve directing agent is (6-8) Na2O: Al2O3: (7-12) SiO2: (206-321) H2O.

5. The preparation method according to claim 3, characterized in that: In the sodium aluminate solution A, the content of Al2O3 is 4-8wt%, and the content of Na2O is 20-30wt%; The water glass solution has a SiO2 content of 20 to 40 wt%.

6. The preparation method according to claim 1, characterized in that: In step (2), the content of Al2O3 in the aluminum sulfate solution is 2 to 6 wt%; In the sodium aluminate solution B, the content of Al2O3 is 5-15wt%, and the content of Na2O is 5-20wt%.

7. The preparation method according to claim 1, characterized in that: In step (2), the organic matter includes at least one of hydroxypropyl methylcellulose, PEG2000, PEG200, and CTAB.

8. The preparation method according to claim 1, characterized in that: In step (2), the water glass solution has a SiO2 content of 20 to 40 wt%.

9. The preparation method according to claim 1, characterized in that: In step (4), in the mixed solution, the content of ammonium sulfate is 10-20wt%, and the content of citric acid is 10-20wt%.

10. The preparation method according to claim 1, characterized in that: Based on the total weight in step (5) being 100 wt%, the amount of amorphous aluminum phosphide added is 10 to 20 wt%; The addition amount of the phosphomolybdic heteropoly acid is 1 to 5 wt %; The addition amount of the macroporous alumina binder is 15-20wt%.

11. A catalyst carrier for hydrocracking to produce more light naphtha and heavy naphtha, characterized in that: The preparation method according to any one of claims 1 to 10 is obtained, wherein the specific surface area of ​​the carrier is 550 to 680 m 2 / g, the pore volume is 0.4~0.62mL / g, and the pore size distribution is 4~25nm.

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