Hydrocracking catalyst containing hierarchical pore beta molecular sieve as well as preparation method and application of hydrocracking catalyst

Abstract

The invention relates to the technical field of hydrocracking catalysts, in particular to a hydrocracking catalyst containing a hierarchical pore beta molecular sieve, a preparation method and application of the hydrocracking catalyst, and a method for processing hydrocarbon oil. The hydrocracking catalyst comprises a carrier and an active metal component loaded on the carrier, wherein the carrier contains a hierarchical pore beta molecular sieve, a modified Y molecular sieve, aluminum oxide and amorphous silica-alumina; the porous structure of the hierarchical pore beta molecular sieve is composed of mutually communicated pores in different scales, and the pore size distribution meets the following conditions: the pore volume of micropores is 2-40%, the pore volume ratio of mesopores is 2-50%, and the pore volume ratio of macropores is 2-60%. The hydrocracking catalyst provided by the invention has high catalytic activity and high selectivity; meanwhile, the hydrocracking catalyst is used for processing hydrocarbon oil and has higher activity.

Description

Technical Field

[0001] The present invention relates to the technical field of hydrocracking catalysts, and in particular to a hydrocracking catalyst containing a graded pore beta molecular sieve, a preparation method of the hydrocracking catalyst containing the graded pore beta molecular sieve, an application of the hydrocracking catalyst containing the graded pore beta molecular sieve, and a method for processing hydrocarbon oil. Background Art

[0002] At present, the hydrocracking process that can achieve lightening of heavy oil and cleaning of oil products is highly favored. The key core technology of this process is the preparation of catalyst. Hydrocracking catalyst is a dual-functional catalyst with hydrogenation and cracking functions. The key to the design and development of hydrocracking catalysts is to adjust the relationship between the catalyst hydrogenation active center and the acid activity.

[0003] US5536687 discloses a hydrocracking catalyst containing Y and β molecular sieves. The Y molecular sieve used in the catalyst has a unit cell parameter of less than 2.445 nm and a silicon-aluminum ratio of 4.5-5.2; the silicon-aluminum ratio of the β molecular sieve used is between 20-30, and the constraint index is 0.6-1; the reaction raw material has a liquid hourly space velocity of 1.0 h -1 , the reaction temperature is higher than 392°C. Although there is high selectivity, the catalyst activity is slightly low.

[0004] CN1315883A discloses a hydrocracking catalyst containing modified β zeolite, which comprises, based on the weight percentage of the catalyst: (a) 5-40wt% of β zeolite; (b) 10-70wt% of large-pore refractory oxide; (c) 0-30wt% of small-pore alumina; (d) 10-40wt% of VIB group metal oxide; (e) 1-10wt% of VIII metal oxide; in the β zeolite, SiO 2 / Al 2 O 3 The molar ratio is 20-150, the secondary pore volume >2nm accounts for more than 40% of the total pore volume, and the specific surface area is 500-750m 2 / g, infrared acid is 0.05-0.5mmol / g, Na 2 O content <0.2wt%, at 25℃, P / P 0 When the adsorption capacity is 0.1, the water adsorption capacity is less than 5wt%, the residual value of n-butanol adsorption experiment is less than 0.4, and the ion exchange capacity is less than 0.07. Compared with the catalyst of small pore alumina, the catalyst activity is improved.

[0005] The above-mentioned prior art uses a mixture of Y molecular sieve and β molecular sieve as a carrier, which has good selectivity for heavy oil, but the catalyst activity is not high. This is mainly because the molecular sieve used is a microporous molecular sieve with a single micropore size, which limits the mass transfer and conversion of macromolecular reactants required for oil processing. Summary of the invention

[0006] The purpose of the present invention is to overcome the above technical problems and provide a hydrocracking catalyst containing a hierarchical pore β molecular sieve, a preparation method and application thereof, and a method for processing hydrocarbon oil. The hydrocracking catalyst has a specific hierarchical pore distribution, which is beneficial to the mass transfer and conversion of large molecules and has high catalytic activity and high selectivity; at the same time, the hydrocracking catalyst is used for processing hydrocarbon oil and has higher activity.

[0007] In order to achieve the above-mentioned purpose, the first aspect of the present invention provides a hydrocracking catalyst containing a hierarchical pore β molecular sieve, the hydrocracking catalyst comprising a carrier and an active metal component loaded on the carrier, the carrier containing a hierarchical pore β molecular sieve, a modified Y molecular sieve, alumina and amorphous silica-alumina; the porous structure of the hierarchical pore β molecular sieve is composed of pores interconnected at different scales, and the pore size distribution satisfies: the pore volume of micropores is 2-40%, the pore volume of mesopores is 2-50%, and the pore volume of macropores is 2-60%.

[0008] The second aspect of the present invention provides a method for preparing a hydrocracking catalyst containing a graded pore β molecular sieve, the preparation method comprising the following steps:

[0009] (1) mixing a graded pore β molecular sieve, a modified Y molecular sieve, alumina, amorphous silica-alumina and a lubricant, and mixing the obtained dry powder with a peptizing agent to obtain a total powder; (2) kneading, molding, first drying and first calcining the total powder in sequence to obtain a carrier; (3) mixing a soluble metal salt, an auxiliary agent, a complexing agent and water to obtain an impregnation solution; (4) impregnating the carrier in the impregnation solution, and sequentially performing a second drying and a second calcination on the obtained impregnation product to obtain a hydrocracking catalyst;

[0010] The porous structure of the graded pore β molecular sieve is composed of interconnected pores of different scales, and the pore size distribution satisfies: the pore volume of micropores is 2-40%, the pore volume of mesopores is 2-50%, and the pore volume of macropores is 2-60%.

[0011] The third aspect of the present invention provides a use of the hydrocracking catalyst provided in the first aspect, or the hydrocracking catalyst prepared by the preparation method provided in the second aspect, in hydrocarbon oil processing.

[0012] The fourth aspect of the present invention provides a method for processing hydrocarbon oil, the method comprising: contacting the hydrocracking catalyst provided in the first aspect, or the hydrocracking catalyst prepared by the preparation method provided in the second aspect, with hydrocarbon oil in a hydrogen atmosphere and performing a cracking reaction;

[0013] Wherein, before the cracking reaction, the hydrocracking catalyst is subjected to a sulfurization treatment.

[0014] Compared with the prior art, the present invention has the following advantages:

[0015] The hydrocracking catalyst provided by the present invention has a hierarchical, interpenetrating and regular pore structure by limiting the carrier to contain hierarchical pore beta molecular sieve, modified Y molecular sieve, alumina and amorphous silicon aluminum, and combining the hierarchical pore beta molecular sieve with a specific pore structure, so that the hydrocracking catalyst has a hierarchical, interpenetrating and regular pore structure, which is beneficial to the mass transfer and conversion of macromolecules, thereby improving the activity and selectivity of the hydrocracking catalyst, alleviating the carbon deposition of the catalyst, and extending the life of the catalyst; in particular, combining with specific active metal components and their respective content ranges, the catalytic activity of the catalyst is further improved; at the same time, when the hydrocracking catalyst provided by the present invention is used for hydrocarbon oil processing, it has a higher relative conversion rate. DETAILED DESCRIPTION

[0016] The endpoints and any values ​​of the ranges disclosed in this article are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of each range, the endpoint values ​​of each range and the individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed in this article.

[0017] In the present invention, unless otherwise specified, "first" and "second" do not indicate a sequence or limit the materials or steps, but are only used to distinguish or indicate that they are not the same materials or steps. For example, "first" and "second" in "first drying" and "second drying" are only used to indicate that they are not the same drying.

[0018] The first aspect of the present invention provides a hydrocracking catalyst containing a hierarchical pore β molecular sieve, the hydrocracking catalyst comprising a carrier and an active metal component loaded on the carrier, the carrier containing a hierarchical pore β molecular sieve, a modified Y molecular sieve, alumina and amorphous silica-alumina; the porous structure of the hierarchical pore β molecular sieve is composed of pores interconnected at different scales, and the pore size distribution satisfies: the pore volume of micropores is 2-40%, the pore volume of mesopores is 2-50%, and the pore volume of macropores is 2-60%.

[0019] The inventors of the present invention have found that: compared with the existing hydrocracking catalyst, by optimizing the carrier of the hydrocracking catalyst, the carrier is limited to contain hierarchical pore β molecular sieve, modified Y molecular sieve, alumina and amorphous silicon aluminum, specifically, hierarchical pore β molecular sieve (the entire pore system presents a three-dimensional orderly arrangement that is interconnected), wherein the micropores provide a shape-selective effect for the guest molecules, the mesopores increase the accessibility of the micropores, and the macropores provide an unobstructed transmission path for the guest molecules, and combined with a specific pore size distribution, the catalytic activity and selectivity can be maximized, and the carbon deposition of the catalyst can be alleviated and the life of the catalyst can be extended. In particular, when the hydrocracking catalyst is used to process hydrocarbon oil, it has a higher relative conversion rate.

[0020] In the present invention, unless otherwise specified, the porous structure of the hierarchical pore β molecular sieve is composed of interconnected pores of different scales, and the pores are divided into micropores, mesopores and macropores.

[0021] In the present invention, pore size distribution refers to the sum of the pore volumes of micropores, mesopores and macropores being 100%, the pore volume of micropores being 2-40%, the pore volume of mesopores being 2-50%, and the pore volume of macropores being 2-60%.

[0022] In the present invention, the hierarchical pore distribution of the hierarchical pore β molecular sieve is measured by the following method: nitrogen adsorption and desorption are used to measure the pore volume of pores with a particle size less than 2nm and the pore volume of pores with a particle size of 2-50nm in the molecular sieve by the BET method, and the pore volume of pores with a particle size greater than 50nm in the hydrocracking catalyst is measured by the mercury injection method. The sum of the three is taken as the total pore volume, and the pore volume proportion of various pores is calculated.

[0023] In some embodiments of the present invention, the pore size distribution of the hierarchical pore β molecular sieve satisfies: the pore volume proportion of micropores is 2-40%, for example, 2%, 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, and any value in the range composed of any two numerical values, preferably 10-40%; the pore volume proportion of mesopores is 2-50%, for example, 2%, 10%, 20%, 25%, 30%, 35%, 38%, 40%, 45%, 50%, and any value in the range composed of any two numerical values, preferably 10-50%; the pore volume proportion of macropores is 2-60%, for example, 2%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 60%, and any value in the range composed of any two numerical values, preferably 20-50%.

[0024] In some embodiments of the present invention, further preferably, the pore size distribution of the hierarchical pore β molecular sieve satisfies: the pore volume of micropores accounts for 15-35%, the pore volume of mesopores accounts for 30-45%, and the pore volume of macropores accounts for 30-45%.

[0025] In the present invention, the selectivity and activity of the hydrocracking catalyst are effectively improved by regulating the pore size distribution of the graded pore β molecular sieve and alleviating the carbon deposition of the catalyst.

[0026] In some embodiments of the present invention, preferably, in the hierarchical pore β molecular sieve, the particle size of the micropores is less than 2 nm, the particle size of the mesopores is 2-50 nm, and the particle size of the macropores is greater than 50 nm.

[0027] In some embodiments of the present invention, preferably, based on the total weight of the carrier, the content of the graded pore β molecular sieve is 5-25wt%, for example, 5wt%, 10wt%, 15wt%, 20wt%, 25wt%, and any value in the range of any two values, preferably 10-15wt%; the content of the modified Y molecular sieve is 5-30wt%, for example, 5wt%, 10wt%, 15wt%, 20wt%, 25wt%, 30wt%, and any value in the range of any two values. value, preferably 10-25wt%; the content of aluminum oxide is 15-50wt%, for example, 15wt%, 20wt%, 30wt%, 40wt%, 50wt%, and any value in the range composed of any two values, preferably 20-40wt%; the content of amorphous silicon aluminum is 0-50wt%, for example, 0wt%, 5wt%, 10wt%, 20wt%, 30wt%, 40wt%, 50wt%, and any value in the range composed of any two values, preferably 0-40wt%.

[0028] In the present invention, based on the total weight of the carrier, the sum of the contents of the graded pore β molecular sieve, the modified Y molecular sieve, alumina and amorphous silica-alumina is ≤100wt%, preferably 100wt%.

[0029] In a preferred embodiment of the present invention, the matrix is ​​composed of hierarchical pore β molecular sieve, modified Y molecular sieve, alumina and amorphous silicon aluminum.

[0030] In the present invention, the type of the graded pore size beta molecular sieve has a wide selection range, as long as the graded pore size beta molecular sieve satisfies the above pore size distribution. Preferably, the graded pore size beta molecular sieve includes but is not limited to H-type molecular sieve.

[0031] In some embodiments of the present invention, preferably, the modified Y-type molecular sieve is selected from USY-type molecular sieve and / or PUSY-type molecular sieve. In the present invention, USY-type molecular sieve refers to an ultra-stable Y-type molecular sieve, which can be purchased commercially or prepared; PUSY-type molecular sieve refers to a P-modified ultra-stable Y-type molecular sieve, which can be purchased commercially or prepared.

[0032] In some embodiments of the present invention, preferably, the alumina includes but is not limited to γ-alumina.

[0033] In some embodiments of the present invention, preferably, in the amorphous silicon-aluminum, the aluminum oxide content is 5-95wt%, and the silicon oxide content is 5-95wt%.

[0034] In the present invention, the type of the active metal component has a wide selection range, and can be selected from the active components of conventional hydrocracking catalysts. Preferably, the active metal component is selected from the metal elements of Group VIB and the metal elements of Group VIII; further preferably, in the active metal component, the metal elements of Group VIB are selected from molybdenum and / or tungsten, and the metal elements of Group VIII are selected from nickel and / or cobalt.

[0035] In some embodiments of the present invention, preferably, based on the total weight of the hydrocracking catalyst, the content of the carrier is 55-95%, preferably 60-90 wt%; the content of the active metal component in terms of oxide is 5-45 wt%, preferably 10-40 wt%.

[0036] In some embodiments of the present invention, it is further preferred that, in the hydrocracking catalyst, the content ratio of the metal element of Group VIB to the metal element of Group VIII, calculated as oxide, is 1-5:1, for example, 1:1, 2:1, 3:1, 4:1, 5:1, and any value in the range of any two values. In the present invention, by regulating the above content ratio, it is more conducive to improving the activity and selectivity of the hydrocracking catalyst, thereby obtaining a high yield of the target product.

[0037] In some embodiments of the present invention, more preferably, based on the total weight of the hydrocracking catalyst, the content of the metal element of Group VIB calculated as oxide is 10-35 wt%; the content of the metal element of Group VIII calculated as oxide is 2-10 wt%.

[0038] In a specific embodiment of the present invention, based on the total weight of the hydrocracking catalyst, the content of the carrier is 55-95%, preferably 60-90wt%; the content of the VIB group metal element and the VIII group metal element calculated as oxide is 5-45wt%, preferably 10-40wt%; wherein, calculated as oxide, the content ratio of the VIB group metal element to the VIII group metal element is 1-5:1.

[0039] The second aspect of the present invention provides a method for preparing a hydrocracking catalyst containing a graded pore β molecular sieve, the preparation method comprising the following steps:

[0040] (1) mixing graded pore β molecular sieve, modified Y molecular sieve, alumina, amorphous silica-alumina and lubricant, and mixing the obtained dry powder with a peptizing agent and water to obtain a total powder; (2) kneading, molding, first drying and first calcining the total powder in sequence to obtain a carrier; (3) mixing a soluble metal salt, an auxiliary agent, a complexing agent and water to obtain an impregnation solution; (4) impregnating the carrier in the impregnation solution, and performing a second drying and a second calcination on the obtained impregnation product in sequence to obtain a hydrocracking catalyst;

[0041] The porous structure of the graded pore β molecular sieve is composed of interconnected pores of different scales, and the pore size distribution satisfies: the pore volume of micropores is 2-40%, the pore volume of mesopores is 2-50%, and the pore volume of macropores is 2-60%.

[0042] In the present invention, the types and limitations of the graded pore β molecular sieve, modified Y molecular sieve, alumina and amorphous silica-alumina are in accordance with the above-mentioned definitions, and the present invention will not elaborate on this.

[0043] In the present invention, unless otherwise specified, dry powder refers to graded pore β molecular sieve, modified Y molecular sieve, alumina, amorphous silica-alumina and lubricant; total powder refers to graded pore β molecular sieve, modified Y molecular sieve, alumina, amorphous silica-alumina, lubricant and peptizing agent.

[0044] In some embodiments of the present invention, preferably, in step (1), based on the total weight of the total powder, the content of the lubricant is 1-10wt%, for example, 1wt%, 2wt%, 3wt%, 5wt%, 8wt%, 10wt%, and any value in the range consisting of any two values.

[0045] In some embodiments of the present invention, preferably, the lubricant is selected from at least one of starch, methyl cellulose, tianqing powder and graphite.

[0046] In some embodiments of the present invention, preferably, the weight ratio of the graded pore β molecular sieve, the modified Y molecular sieve, and the amorphous silicon aluminum of the alumina is (5-25): (5-30): (15-50): (0-50), preferably (10-15): (10-25): (20-40): (0-40). In the present invention, unless otherwise specified, the total amount ratio of the above components is equivalent to the content ratio of the components in the carrier.

[0047] In some embodiments of the present invention, preferably, the ratio of the peptizing agent in mol to the dry powder in g is (0.2-5)×10 -4 In the present invention, the amount of the peptizer used is (0.2-5)×10 -4 mol.

[0048] In some embodiments of the present invention, preferably, the peptizing agent is selected from inorganic acids and / or organic acids, preferably at least one selected from nitric acid, hydrochloric acid, sulfuric acid and citric acid.

[0049] In some embodiments of the present invention, it is further preferred that the peptizing agent is present in the form of an aqueous solution, and the ratio of water in grams to the peptizing agent in moles in the aqueous solution of the peptizing agent is (1-40)×10 3 That is, 1 mol of peptizing agent is mixed with (1-40)×10 3 g of water to obtain the above-mentioned peptizing agent aqueous solution.

[0050] In the present invention, in step (2), the kneading is intended to mix the mixture uniformly. Preferably, the kneading time is 10-60 min, preferably 10-30 min.

[0051] In the present invention, in step (2), the molding includes but is not limited to extrusion molding.

[0052] In some embodiments of the present invention, preferably, in step (2), the conditions of the first drying include: a temperature of 80-120° C., preferably 100-120° C.; and a time of 1-20 h, preferably 10-15 h. In the present invention, the first drying is performed in an oven.

[0053] In some embodiments of the present invention, preferably, in step (2), the conditions of the first calcination include: a temperature of 400-600°C, preferably 500-600°C; a time of 1-10h, preferably 1-5h. In the present invention, the first calcination is performed in a muffle furnace.

[0054] In some embodiments of the present invention, preferably, in step (3), the soluble metal salt is selected from at least one of nitrates, chlorates and sulfates containing Group VIB metal elements and Group VIII metal elements, and is preferably selected from at least one of nitrates, chlorates and sulfates containing molybdenum and / or tungsten, and nickel and / or cobalt.

[0055] In some embodiments of the present invention, preferably, the mass ratio of the metal element of Group VIB to the metal element of Group VIII is 1-5:1, calculated as oxide.

[0056] In the present invention, the amount of the soluble metal salt satisfies: based on the total weight of the hydrocracking catalyst, the content of the metal element of Group VIB is 10-35wt% and the content of the metal element of Group VIII is 2-10wt% in terms of oxide.

[0057] In some embodiments of the present invention, preferably, based on the total weight of the total powder, the dosage of the auxiliary agent is 0-5 wt%. In the present invention, preferably, the auxiliary agent is selected from phosphorus sources, including but not limited to phosphoric acid.

[0058] In some embodiments of the present invention, preferably, based on the total weight of the total powder, the dosage of the complexing agent is 0-5 wt%; further preferably, the complexing agent is selected from at least one of ethylene glycol, glycerol, polyethylene glycol, diethylene glycol, butanediol, acetic acid, maleic acid, oxalic acid, citric acid, tartaric acid, ethanolamine, diethanolamine, triethanolamine, glycine, ethylenediamine, and ethylenediaminetetraacetic acid.

[0059] In the present invention, in step (4), by means of an impregnation technique, the soluble metal salt in the impregnation solution is impregnated onto the surface and pore diameter of the carrier to obtain the impregnated product.

[0060] In some embodiments of the present invention, preferably, in step (4), the conditions for the second drying include: the temperature is 80-140 °C, preferably 110-130 °C; the time is 1-15 h, preferably 1-10 h.

[0061] In some embodiments of the present invention, preferably, in step (4), the conditions for the second calcination include: the temperature is 400-600 °C, preferably 500-600 °C; the time is 1-10 h, preferably 1-5 h.

[0062] In the present invention, without special instructions, the hydrocracking catalyst prepared by the above method includes a carrier and an active metal component supported on the carrier, and the active metal component exists in the form of an oxide.

[0063] The third aspect of the present invention provides an application of the hydrocracking catalyst provided in the first aspect, or the hydrocracking catalyst prepared by the preparation method provided in the second aspect, in hydrocarbon oil processing.

[0064] In the present invention, without special instructions, the hydrocarbon oil includes but not limited to residue oil, diesel oil, heavy oil, etc., and preferably residue oil.

[0065] The fourth aspect of the present invention provides a method for processing hydrocarbon oil, the method comprising: contacting the hydrocracking catalyst provided in the first aspect, or the hydrocracking catalyst prepared by the preparation method provided in the second aspect, with hydrocarbon oil in a hydrogen atmosphere and carrying out a cracking reaction;

[0066] Wherein, before the cracking reaction, the hydrocracking catalyst is subjected to a sulfidation treatment.

[0067] In some embodiments of the present invention, preferably, the conditions of the cracking reaction include: temperature of 300-450°C, preferably 350-400°C; pressure of 1-10MPa, preferably 5-10MPa; liquid hourly space velocity of 0.1-5h -1 , preferably 0.5-2h -1 ; time is 10-30h, preferably 15-25h; hydrogen oil volume is 500-1000, preferably 700-900.

[0068] In some embodiments of the present invention, preferably, the sulfurization treatment process includes: in a hydrogen atmosphere, first heating the hydrocracking catalyst to 140-160°C, introducing sulfurized oil, keeping the temperature constant for 0.5-2h, heating to 200-250°C at a heating rate of 55-65°C / h, and keeping the temperature constant for 1-5h; then heating to 350-370°C at a heating rate of 55-65°C / h, and keeping the temperature constant for 5-10h.

[0069] In some embodiments of the present invention, preferably, the content of carbon disulfide in the sulfurized oil is 1-5wt%. In the present invention, the sulfurized oil is kerosene with a carbon disulfide content of 1-5wt%.

[0070] In a specific embodiment of the present invention, the above hydrocracking catalyst is crushed to obtain hydrocracking catalyst particles with a particle size of 2-3mm, and 20mL of the catalyst is loaded into a 30mL fixed bed reactor. Before the cracking reaction, it is first subjected to a sulfurization treatment with kerosene containing 2wt% carbon disulfide under a hydrogen atmosphere, and then the reaction raw materials are switched to react, wherein the sulfurization treatment process: heating to 150°C, introducing sulfurized oil, and keeping the temperature constant for 1h; heating to 230°C at a heating rate of 60°C / h, and keeping the temperature constant for 2h; heating to 360°C at a heating rate of 60°C / h, and keeping the temperature constant for 6h; the cracking reaction process: the reaction temperature is 355°C, the reaction pressure is 6.4MPa, and the liquid hourly space velocity is 1h -1 The volume ratio of hydrogen to oil was 800. After 20 hours of reaction, samples were taken for analysis. The raw materials and the reaction samples were separated by vacuum distillation.

[0071] According to a particularly preferred embodiment of the present invention, a hydrocracking catalyst containing a hierarchical pore β molecular sieve, the hydrocracking catalyst comprises a carrier and an active metal component loaded on the carrier, the carrier is composed of a hierarchical pore β molecular sieve, a modified Y molecular sieve, alumina and amorphous silicon aluminum; the porous structure of the hierarchical pore β molecular sieve is composed of pores interconnected at different scales, and the pore size distribution satisfies: the pore volume of micropores accounts for 15-35%, the pore volume of mesopores accounts for 30-45%, and the pore volume of macropores accounts for 30-45%; in the hierarchical pore β molecular sieve, the particle size of the micropores is less than 2nm, the particle size of the mesopores is 2-50nm, and the particle size of the macropores is greater than 50nm;

[0072] Wherein, based on the total weight of the carrier, the content of the graded pore β molecular sieve is 10-15wt%; the content of the modified Y molecular sieve is 10-25wt%; the content of the alumina is 20-40wt%; the content of the amorphous silicon aluminum is 0-40wt%;

[0073] Wherein, the active metal component is selected from molybdenum and / or tungsten, and nickel and / or cobalt; based on the total weight of the hydrocracking catalyst, the content of the carrier is 60-90wt%; the content of molybdenum and / or tungsten calculated as oxide is 10-35wt%; the content of nickel and / or cobalt calculated as oxide is 2-10wt%.

[0074] The present invention will be described in detail below through examples.

[0075] In the amorphous silicon aluminum, the aluminum oxide content is 30wt% and the silicon oxide content is 70wt%.

[0076] The physical properties of the carriers and hydrocracking catalysts prepared in the examples and comparative examples are listed in Table 2.

[0077] Example 1

[0078] (1) 24.08 g of β molecular sieve B-1 (see Table 1 for relevant pore size distribution), 38.1 g of USY molecular sieve, 54.14 g of alumina, 61.68 g of amorphous silica-alumina and 6.5 g of methyl cellulose were mixed and put into a kneader and mixed for 20 minutes to obtain a dry powder; 125.3 g of an acidic solution prepared by water and nitric acid was added to the dry powder at one time, and the mixture was mixed and kneaded for 20 minutes to obtain a total powder;

[0079] The weight ratio of the above-mentioned β molecular sieve B-1 (related pore size distribution is shown in Table 1), modified Y molecular sieve, alumina and amorphous silicon aluminum is 13.53:21.41:30.42:34.65;

[0080] (2) Extruding the total powder through an extruder equipped with a cylindrical perforated plate, drying the obtained wet strip in an oven at 110° C. for 12 h, and then calcining it in a muffle furnace at 550° C. for 4 h to obtain carrier S1;

[0081] (3) At 25° C., 2 g of citric acid, 19.5 g of nickel nitrate hexahydrate, 5 g of 85 wt% phosphoric acid solution, and 33 g of ammonium metatungstate were sequentially added to 30 mL of deionized water to adjust the volume of the impregnation solution to 65 mL;

[0082] The above 100g carrier S1 was placed in an impregnation tank, and the above impregnation liquid was poured in. After soaking for 4 hours, the impregnated sample was cured in an oven at 30°C for 12 hours, dried in an oven at 120°C for 8 hours, and finally calcined in a muffle furnace at 550°C for 4 hours to obtain catalyst C1.

[0083] Example 2

[0084] According to the method of Example 1, the difference is that

[0085] In step (1), the β molecular sieve B-1 is replaced by the β molecular sieve B-2 (see Table 1 for the relevant pore size distribution);

[0086] The other conditions are the same to obtain carrier S2 and catalyst C2.

[0087] Example 3

[0088] According to the method of Example 1, the difference is that

[0089] In step (1), the β molecular sieve B-1 is replaced by the β molecular sieve B-3 (see Table 1 for the relevant pore size distribution); the USY molecular sieve is replaced by the PUSY molecular sieve;

[0090] The other conditions were the same, and carrier S3 and catalyst C3 were obtained.

[0091] Example 4

[0092] According to the method of Example 1, the difference is that

[0093] In step (1), β molecular sieve B-1 is replaced by β molecular sieve B-4 (see Table 1 for the relevant pore size distribution); USY molecular sieve is replaced by PUSY molecular sieve;.

[0094] The other conditions are the same, and carrier S4 and catalyst C4 are obtained.

[0095] Example 5

[0096] According to the method of Example 1, the difference is that

[0097] In step (1), the weight ratio of β molecular sieve B-1, USY molecular sieve, alumina and amorphous silicon aluminum is adjusted to 19.47:13.86:41.55:25.12;

[0098] The other conditions were the same to obtain carrier S5 and catalyst C5.

[0099] Example 6

[0100] According to the method of Example 1, the difference is that

[0101] In step (1), the weight ratio of β molecular sieve B-1, USY molecular sieve, alumina and amorphous silicon aluminum is adjusted to 25.31:20.86:53.83:0

[0102] The other conditions were the same to obtain carrier S6 and catalyst C6.

[0103] Example 7

[0104] According to the method of Example 1, the difference is that

[0105] In step (3), 33 g of ammonium metatungstate is not added;

[0106] The other conditions were the same to obtain catalyst C7.

[0107] Comparative Example 1

[0108] According to the method of Example 1, the difference is that

[0109] In step (1), the β molecular sieve B-1 is replaced with the β molecular sieve BR-1 (see Table 1 for the relevant pore size distribution);

[0110] The other conditions were the same to obtain carrier DS1 and catalyst DC1.

[0111] Comparative Example 2

[0112] According to the method of Example 1, the difference is that

[0113] In step (1), the β molecular sieve B-1 is replaced by the β molecular sieve BR-2 (see Table 1 for the relevant pore size distribution);

[0114] The other conditions were the same, and carrier DS2 and catalyst DC2 were obtained.

[0115] Comparative Example 3

[0116] According to the method of Example 1, the difference is that

[0117] In step (1), 24.08 β molecular sieve B-1 is not added;

[0118] The other conditions were the same, and carrier DS3 and catalyst DC3 were obtained.

[0119] Table 1

[0120]

[0121] Table 2

[0122]

[0123]

[0124] Table 2

[0125]

[0126] Note: *- In the hydrocracking catalyst, the contents of active metal components, Group VIB metal elements and Group VIII metal elements are all calculated as oxides.

[0127] Test Case

[0128] The catalysts prepared in the above examples and comparative examples were respectively subjected to activity tests.

[0129] The test method includes: crushing the above catalyst into particles with a diameter of 2 mm, loading 20 mL of the catalyst into a 30 mL fixed bed reactor. Before the reaction, the catalyst is first subjected to sulfurization treatment with kerosene containing 2 wt% carbon disulfide in a hydrogen atmosphere according to the following procedure, and then the reaction raw material (residue oil) is switched for cracking reaction;

[0130] The process of the vulcanization treatment includes: heating to 150°C, introducing the above kerosene, keeping the temperature constant for 1 hour, heating to 230°C at a heating rate of 60°C / h, keeping the temperature constant for 2 hours, heating to 360°C at a heating rate of 60°C / h, and keeping the temperature constant for 6 hours;

[0131] The cracking reaction process includes: reaction temperature of 355℃, reaction pressure of 6.4MPa, liquid hourly space velocity of 1h -1 , the volume ratio of hydrogen to oil is 800, and sampling and analysis are carried out after stabilization for 20 hours; the raw materials and reaction samples are separated by vacuum distillation, and the percentage of the fraction greater than 350°C is calculated.

[0132] The activity of the catalyst is evaluated by the conversion rate per unit weight of the catalyst. The calculation method is as follows:

[0133]

[0134] Wherein, m1 is the fraction greater than 350°C in the raw material, m2 is the fraction greater than 350°C in the produced oil, and mc is the catalyst loading. The evaluation results are shown in Table 3. The conversion of the reference catalyst DC-1 is taken as 100%, and the relative activities of other catalysts are calculated.

[0135] Table 3

[0136] catalyst Relative conversion rate, % Example 1 C1 132 Example 2 C2 139 Example 3 C3 145 Example 4 C4 127 Example 5 C5 126 Example 6 C6 121 Example 7 C7 20 Comparative Example 1 DC1 100 Comparative Example 2 DC2 93 Comparative Example 3 DC3 52

[0137] Based on the data in Tables 1-3, it can be seen that compared with Comparative Examples 1-3, Examples 1-6 have a higher relative conversion rate when using the hydrocracking catalyst provided by the present invention to process hydrocarbon oil.

[0138] Compared with Examples 1-4, it can be seen that the technical solution of adjusting the pore size distribution of the graded pore β molecular sieve to meet the preferred protection range has a higher relative conversion rate.

[0139] Compared with Examples 5-6, Example 1 has a higher relative conversion rate by regulating the mass ratio of graded pore β molecular sieve, modified Y molecular sieve, alumina and amorphous silicon aluminum in the carrier to meet the preferred protection range.

[0140] Compared with Example 7, Example 1 uses active metal components of Group VIB metal elements and Group VIII metal elements to increase the active sites, thereby improving the catalytic activity of the hydrocracking catalyst and thus having an excellent relative conversion rate.

[0141] The preferred embodiments of the present invention are described in detail above, but the present invention is not limited thereto. Within the technical concept of the present invention, the technical solution of the present invention can be subjected to a variety of simple modifications, including the combination of various technical features in any other suitable manner, and these simple modifications and combinations should also be regarded as the contents disclosed by the present invention and belong to the protection scope of the present invention.

Claims

1. A hydrocracking catalyst containing a graded pore β molecular sieve, It is characterized in that The hydrocracking catalyst comprises a carrier and an active metal component loaded on the carrier, wherein the carrier contains a hierarchical pore β molecular sieve, a modified Y molecular sieve, alumina and amorphous silicon aluminum; the porous structure of the hierarchical pore β molecular sieve is composed of pores interconnected at different scales, and the pore size distribution satisfies: the pore volume of micropores is 2-40%, the pore volume of mesopores is 2-50%, and the pore volume of macropores is 2-60%.

2. The hydrocracking catalyst according to claim 1, in, The pore size distribution of the hierarchical pore beta molecular sieve satisfies: the pore volume of micropores accounts for 10-40%, the pore volume of mesopores accounts for 10-50%, and the pore volume of macropores accounts for 20-50%; Preferably, the pore size distribution of the hierarchical pore β molecular sieve satisfies: the pore volume of micropores accounts for 15-35%, the pore volume of mesopores accounts for 30-45%, and the pore volume of macropores accounts for 30-45%; And / or, in the hierarchical pore β molecular sieve, the particle size of the micropores is less than 2 nm, the particle size of the mesopores is 2-50 nm, and the particle size of the macropores is greater than 50 nm.

3. The hydrocracking catalyst according to claim 1 or 2, in, Based on the total weight of the carrier, the content of the graded pore β molecular sieve is 5-25wt%, preferably 10-15wt%; the content of the modified Y molecular sieve is 5-30wt%, preferably 10-25wt%; the content of alumina is 15-50wt%, preferably 20-40wt%; the content of amorphous silicon aluminum is 0-50wt%, preferably 0-40wt%; and / or, the hierarchical pore β molecular sieve is selected from H-type molecular sieve; And / or, the modified Y-type molecular sieve is selected from USY-type molecular sieve and / or PUSY-type molecular sieve; And / or, the alumina is selected from γ-alumina; And / or, in the amorphous silicon-aluminum, the aluminum oxide content is 5-95wt%, and the silicon oxide content is 5-95wt%.

4. The hydrocracking catalyst according to any one of claims 1 to 3, in, The active metal component is selected from the group consisting of metal elements of Group VIB and metal elements of Group VIII; Preferably, in the active metal component, the metal element of Group VIB is selected from molybdenum and / or tungsten, and the metal element of Group VIII is selected from nickel and / or cobalt.

5. The hydrocracking catalyst according to claim 4, in, Based on the total weight of the hydrocracking catalyst, the content of the carrier is 55-95wt%, preferably 60-90wt%; the content of the active metal component calculated as oxide is 5-45wt%, preferably 10-40wt%; and / or, in the hydrocracking catalyst, the content ratio of the metal element of Group VIB to the metal element of Group VIII, calculated as oxide, is 1-5:1; And / or, based on the total weight of the hydrocracking catalyst, the content of the metal element of Group VIB calculated as oxide is 10-35 wt%; the content of the metal element of Group VIII calculated as oxide is 2-10 wt%.

6. A method for preparing a hydrocracking catalyst containing a graded pore β molecular sieve, It is characterized in that The preparation method comprises the following steps: (1) mixing a graded pore β molecular sieve, a modified Y molecular sieve, alumina, amorphous silica-alumina and a lubricant, and mixing the obtained dry powder with a peptizing agent to obtain a total powder; (2) kneading, molding, first drying and first calcining the total powder in sequence to obtain a carrier; (3) mixing a soluble metal salt, an auxiliary agent, a complexing agent and water to obtain an impregnation solution; (4) impregnating the carrier in the impregnation solution, and sequentially performing a second drying and a second calcination on the obtained impregnation product to obtain a hydrocracking catalyst; The porous structure of the graded pore β molecular sieve is composed of interconnected pores of different scales, and the pore size distribution satisfies: the pore volume of micropores is 2-40%, the pore volume of mesopores is 2-50%, and the pore volume of macropores is 2-60%.

7. The preparation method according to claim 6, in, In step (1), The pore size distribution of the hierarchical pore beta molecular sieve satisfies: the pore volume of micropores accounts for 10-40%, the pore volume of mesopores accounts for 10-50%, and the pore volume of macropores accounts for 20-50%; Preferably, the pore size distribution of the hierarchical pore β molecular sieve satisfies: the pore volume of micropores accounts for 15-35%, the pore volume of mesopores accounts for 30-45%, and the pore volume of macropores accounts for 30-45%; And / or, in the hierarchical pore β molecular sieve, the particle size of the micropores is less than 2 nm, the particle size of the mesopores is 2-50 nm, and the particle size of the macropores is greater than 50 nm; and / or, based on the total weight of the total powder, the content of the lubricant is 1-10wt%; And / or, the lubricant is selected from at least one of starch, methyl cellulose, tianqing powder and graphite; And / or, the weight ratio of the graded pore β molecular sieve, the modified Y molecular sieve, and the amorphous silicon-aluminum of alumina is (5-25):(5-30):(15-50):(0-50), preferably (10-15):(10-25):(20-40):(0-40); and / or, the ratio of the peptizing agent in mol to the dry powder in g is (0.2-5)×10 -4 ; and / or, the peptizing agent is present in the form of an aqueous solution, wherein the ratio of water in grams to the peptizing agent in moles in the aqueous solution is (1-40)×10 3 .

8. The preparation method according to claim 6 or 7, in, In step (2), The first drying conditions include: temperature of 80-120°C, preferably 100-120°C; time of 1-20h, preferably 10-15h; And / or, the first calcination conditions include: temperature of 400-600°C, preferably 500-600°C; time of 1-10h, preferably 1-5h; In step (3), and / or, the soluble metal salt is selected from at least one of nitrates, chlorates and sulfates containing Group VIB metal elements and Group VIII metal elements, preferably selected from at least one of nitrates, chlorates and sulfates containing molybdenum and / or tungsten, and nickel and / or cobalt; Preferably, the mass ratio of the metal element of Group VIB to the metal element of Group VIII, calculated as oxide, is 1-5:1; Further preferably, the amount of the soluble metal salt satisfies: based on the total weight of the hydrocracking catalyst, the content of the metal element of Group VIB calculated as oxide is 10-35wt%; the content of the metal element of Group VIII calculated as oxide is 2-10wt%; and / or, based on the total weight of the total powder, the amount of the auxiliary agent is 0-5wt%; and / or, based on the total weight of the total powder, the amount of the complexing agent is 0-5wt%; In step (4), The second drying conditions include: temperature of 80-140°C, preferably 110-130°C; time of 1-15h, preferably 1-10h; And / or, the conditions of the second calcination include: temperature of 400-600° C., preferably 500-600° C.; time of 1-10 h, preferably 1-5 h.

9. Use of the hydrocracking catalyst according to any one of claims 1 to 5, or the hydrocracking catalyst prepared by the preparation method according to any one of claims 6 to 8, in hydrocarbon oil processing.

10. A method for processing hydrocarbon oil, It is characterized in that The method comprises: contacting the hydrocracking catalyst according to any one of claims 1 to 5, or the hydrocracking catalyst prepared by the preparation method according to any one of claims 6 to 8, with hydrocarbon oil in a hydrogen atmosphere and performing a cracking reaction; Wherein, before the cracking reaction, the hydrocracking catalyst is subjected to a sulfurization treatment.

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