A catalyst with an aluminiferous zsm-5 type zeolite as a carrier, its preparation method and use

Abstract

This invention provides a catalyst supported on aluminum-rich ZSM-5 zeolite, its preparation method, and its application. The catalyst comprises an aluminum-rich ZSM-5 zeolite support and a metal component supported on the support. The metal component includes Group VIB metal oxides and optionally Group VIII metal components. The silicon-to-aluminum ratio of the aluminum-rich ZSM-5 zeolite support is between 5 and 18. This catalyst, used in the hydrocracking reaction of diesel fuel, exhibits advantages such as high selectivity and purity for light aromatics, enabling efficient chemical utilization of catalytic diesel fuel.

Description

Technical Field

[0001] This invention belongs to the field of catalyst technology, specifically relating to a catalyst supported on aluminum-rich ZSM-5 zeolite, its preparation method, and its application. Background Technology

[0002] In recent years, refining and chemical enterprises have experienced a massive surplus of low-quality, rich aromatic oil products, primarily catalytic diesel. Catalytic diesel is one of the main products of the catalytic cracking process, with an annual national output of approximately 50 million tons. Although its boiling point is in the diesel fraction, its high content of polycyclic aromatic hydrocarbons makes it uneconomical to process into diesel, forcing some enterprises to use it only as fuel oil. Hydrocracking technology is one of the important means of secondary crude oil processing and the conversion of heavy oil into lighter products. Due to its strong adaptability to feedstocks, flexible operation and product formulation, and high product quality, it has become an important way to produce high-quality light oil products and solve the problem of chemical feedstock sources.

[0003] In existing processes, light oil-based hydrocracking catalysts target gasoline or naphtha as the product, but suffer from problems such as low aromatics yield and purity, and excessively high diesel yield. Related research institutions have developed technologies that can convert catalytic diesel into high-octane gasoline blending components. For example, the technologies disclosed in Chinese patents CN101724454A and CN102839018A yield heavy naphtha fractions with aromatics content between 50-65%, which can be used as high-octane gasoline blending components. The catalysts used contain 20-75 wt% Y-type zeolite. However, due to the open pores of Y-type zeolite, it lacks the shape-selective effect for cracking non-aromatics, resulting in C8, C9, and C6 hydrocarbons. 10 The fraction has a low aromatic content and a high non-aromatic content, which makes it difficult to meet the requirements for reformed oil. As a raw material for the production of benzene and paraxylene in the aromatics complex, it is difficult to use it.

[0004] ZSM-5 exhibits significant shape-selective properties. In hydrodewaxing, under specific operating conditions, the feedstock is mixed with hydrogen and passed through a catalyst bed. The n-alkanes and short-chain isoalkanes in the feedstock undergo hydrocracking to produce low-molecular-weight hydrocarbons, while other components remain largely unchanged, ultimately lowering the pour point (or freezing point). ZSM-5 molecular sieves allow n-alkanes and short-chain isoalkanes to enter their channels, while excluding highly branched isoalkanes, cycloalkanes, and aromatics. Patent CN1219571A discloses a small-crystal ZSM-5 catalytic dewaxing catalyst with a crystal size of 0.1-0.5 μm and a silicon-to-aluminum ratio of 50-120. It exhibits low yields of C1-C4 hydrocarbons and a liquid yield greater than 80%.

[0005] Maximizing the conversion of catalytic diesel into light aromatics that meet the quality standards of aromatics complexes and producing high-quality light hydrocarbons that can be used as feedstock for olefins, directly providing feedstock for aromatics, olefins, and other chemical plants, makes the development of high-performance hydrocracking catalysts a key issue. Therefore, it is necessary to develop hydrocracking catalysts that possess both shape-selective effects and stronger non-aromatic cracking capabilities to efficiently produce high-quality light aromatics and light hydrocarbons from catalytic diesel. The light aromatics can be used to produce benzene and xylene, while the light hydrocarbons can serve as feedstock for ethylene. Furthermore, non-sulfurized hydrocracking catalysts have strong sulfur resistance, eliminating the need for a complex start-up sulfidation process. Summary of the Invention

[0006] To address the aforementioned technical problems, this invention proposes a catalyst supported on aluminum-rich ZSM-5 zeolite. The aluminum-rich ZSM-5 zeolite provides abundant Brønsted acid centers, enabling it to react with polycyclic aromatic hydrocarbons (PAHs) in a cracking reaction. This invention provides a catalyst supported on aluminum-rich ZSM-5 zeolite for use in the hydrocracking reaction of feedstocks rich in PAHs, effectively solving the problem of low selectivity and purity of light aromatics obtained from catalytic diesel hydrocracking, thus achieving efficient chemical utilization of catalytic diesel.

[0007] One objective of this invention is to provide a catalyst supported on an aluminum-rich ZSM-5 zeolite, comprising: an aluminum-rich ZSM-5 zeolite support and a metal component supported on the support, wherein the metal component comprises group VIB metal oxides and optionally group VIII metal components, and the silicon-to-aluminum ratio of the aluminum-rich ZSM-5 zeolite support is between 5 and 18.

[0008] According to the present invention, the catalyst further comprises a binder, which may be a catalyst binder commonly used in the art to provide good mechanical and textural properties. Preferably, the binder is selected from at least one of alumina and silica. The alumina may be obtained from boehmite, and the silica may be obtained from porous silica powder or ammoniacal silica sol. The binder may be incorporated into the catalyst in any suitable manner, for example, by mixing, extruding, curing, drying, and calcining with an alumina-rich ZSM-5 zeolite support to obtain the catalyst support.

[0009] According to the present invention, based on a total of 100 parts by weight of the aluminum-rich ZSM-5 zeolite carrier and binder, the aluminum-rich ZSM-5 zeolite carrier is 5 to 80 parts, preferably 10 to 70 parts, more preferably 15 to 60 parts; the group VIB metal oxide is 1 to 20 parts, preferably 2 to 18 parts, more preferably 3 to 15 parts; and the group VIII metal component, calculated as group VIII metal, is 0 to 10 parts, preferably 0.2 to 8 parts, more preferably 0.5 to 6 parts.

[0010] According to the present invention, in the catalyst supported by the aluminum-rich ZSM-5 zeolite:

[0011] The aluminum-rich ZSM-5 zeolite carrier contains more than 92% aluminum in its framework, preferably more than 95%; the average length of the particles in the aluminum-rich ZSM-5 zeolite carrier is less than 20 nm in at least one dimension.

[0012] The group VIB metal oxide is selected from at least one of molybdenum oxide and tungsten oxide; the group VIB metal oxide can continuously exert a hydrogenation effect in a sulfur-containing atmosphere;

[0013] The group VIII metal component is selected from at least one of nickel-containing components and cobalt-containing components; the group VIII metal component exists in the catalyst in the form of metal oxides or metal elements, which can improve the hydrogenation capacity of group VIB metal oxides; the nickel-containing component and the cobalt-containing component can be chemically combined with one or more other components in the final catalyst composition as elements or as oxides, or exist in the catalyst as metal elements.

[0014] The catalyst described in this invention may also include conventional components of catalysts in the art, such as diatomaceous earth, activated clay, etc., and the amount used may be the usual amount.

[0015] The second objective of this invention is to provide a method for preparing the catalyst supported on the above-mentioned aluminum-rich ZSM-5 zeolite, comprising: loading a component including a group VIB metal oxide and an optional group VIII metal component onto a support containing aluminum-rich ZSM-5 zeolite, and obtaining the catalyst by calcination and reduction.

[0016] The preparation method of the catalyst provided by this invention is not limited to the above-described preparation method, and can be carried out using any method commonly used in the field of catalysts. For example, the preparation of the catalyst of this invention may include the steps of shaping a catalyst support containing the aluminum-rich ZSM-5 zeolite, loading a metal component, and then calcining and reducing it to obtain the catalyst. The support shaping can be carried out by using methods commonly used in the art, such as extrusion, ball rolling, or oil column forming, together with a common binder; the metal component can be added using methods commonly used in the art, such as co-precipitation, co-gelling, kneading, ion exchange, or impregnation, with the catalyst support.

[0017] According to the present invention, the preparation method of the catalyst supported on aluminum-rich ZSM-5 zeolite includes the following steps:

[0018] Step 1) After the components including aluminum-rich ZSM-5 zeolite are shaped, dried and calcined to obtain the catalyst support;

[0019] Step 2) Prepare aqueous solutions of soluble Group VIB and Group VIII metal compounds;

[0020] Step 3) The catalyst support obtained in Step 1) is immersed in the aqueous solution of the metal compound obtained in Step 2), then removed, dried, calcined, and reduced to obtain the catalyst.

[0021] According to the present invention, in the preparation method of the catalyst supported by the aluminum-rich ZSM-5 zeolite, in step 1): the aluminum-rich ZSM-5 zeolite is first mixed with a binder and then molded. The mixing and molding process can use molding equipment and molding process conditions commonly used in the art. The drying treatment after molding is not particularly limited, and can use drying equipment and drying conditions commonly used in the art. For example, the drying temperature is 50-180℃, preferably 60-150℃. The calcination treatment after drying is not particularly limited, and can use calcination equipment and calcination conditions commonly used in the art. For example, the calcination temperature is 520-600℃, preferably 530-580℃. The calcination time is 1-8h, preferably 2-6h.

[0022] According to the present invention, in the preparation method of the catalyst supported by the aluminum-rich ZSM-5 zeolite, in step 2): the soluble Group VIB metal compound is selected from at least one of soluble molybdenum compounds and soluble tungsten compounds, preferably from at least one of ammonium tungstate and ammonium molybdate; the soluble Group VIII metal compound is selected from at least one of soluble nickel compounds and soluble cobalt compounds, preferably from at least one of nickel nitrate, nickel sulfate, nickel halide, nickel oxalate, nickel acetate, cobalt nitrate, cobalt chloride, and cobalt oxalate; the concentration of the metal compound solution is not particularly limited, as long as it can completely dissolve the added metal compound. Specifically, the total concentration of the metal compound in the aqueous solution is 3-45 wt%, preferably 5-40 wt%. An appropriate amount of ammonia can be added to the aqueous solution to obtain a homogeneous solution.

[0023] According to the present invention, in the preparation method of the catalyst supported on the aluminum-rich ZSM-5 zeolite, in step 3): the impregnation can be carried out using impregnation processes commonly used in the art, such as equal-volume impregnation; the drying treatment of the support after impregnation is not particularly limited, and commonly used drying equipment and drying conditions can be used, for example, the drying temperature is 50-150℃, preferably 60-120℃; the calcination treatment after drying is not particularly limited, and commonly used calcination equipment and calcination conditions can be used, for example, the calcination temperature is 450-600℃. The preferred temperature is 480–580℃; the calcination time is 0.5–8 h, preferably 1–6 h; the calcined catalyst precursor is reduced to obtain the catalyst, and the reduction process can adopt reduction conditions commonly used in the art, for example, the reduction of the catalyst precursor is completed in a hydrogen atmosphere. Specifically, the reduction conditions are: the reduction heating rate is 1–20℃ / h, preferably 5–10℃ / h; the reduction endpoint temperature is 300–450℃, preferably 320–420℃; the endpoint temperature is maintained for 1–24 h, preferably 2–16 h.

[0024] According to the present invention, the aluminum-rich ZSM-5 type zeolite is obtained by the following preparation method:

[0025] a) Dissolve sodium hydroxide and alumina source in water, then add silica source and template agent in sequence, and stir to obtain adhesive solution;

[0026] b) The adhesive obtained in step a) is pre-crystallized, hydrothermally crystallized and then cooled to obtain a highly crystalline ZSM-5 slurry;

[0027] c) Add alumina source and water to the highly crystalline ZSM-5 slurry obtained in step b);

[0028] d) Repeat step b) pre-crystallization and hydrothermal crystallization for secondary crystallization;

[0029] e) After filtering, washing, drying and calcining the product obtained after secondary crystallization, the aluminum-rich ZSM-5 type zeolite is obtained.

[0030] According to the present invention, in the preparation method of the aluminum-rich ZSM-5 type zeolite:

[0031] The alumina source is selected from at least one of sodium aluminate, aluminum hydroxide, and aluminum sulfate;

[0032] The silica source is selected from at least one of silica gel, silica sol, and fumed silica;

[0033] The template agent is selected from organic amines, preferably from at least one of tetrapropylammonium hydroxide, tetrapropylammonium bromide, and n-propylamine.

[0034] According to the present invention, in the preparation method of the aluminum-rich ZSM-5 type zeolite:

[0035] In step a), the molar ratio of silica source, template agent, alumina source, sodium hydroxide, and water is (20-50):(2-10):1:(0.01-0.20):(120-500), wherein the silica source is SiO2 and the alumina source is Al2O3.

[0036] The precrystallization conditions in steps b) and d) are independently: precrystallization at 50–100°C for 3–60 h, preferably precrystallization at 60–95°C for 5–30 h;

[0037] The hydrothermal crystallization conditions in steps b) and d) are independently: crystallization at 110–180°C for 12–240 h, preferably pre-crystallization at 120–170°C for 24–200 h;

[0038] In the system obtained in step c), the molar ratio of silica source, template agent, alumina source, sodium hydroxide, and water is (8-18):(0.5-2):1:(0.005-0.015):(40-150), wherein the silica source is calculated as SiO2 and the alumina source is calculated as Al2O3.

[0039] The aluminum-rich ZSM-5 zeolite obtained in step e) further requires ammonium ion exchange and calcination treatment. According to the present invention, sodium-type aluminum-rich ZSM-5 zeolite obtained by the above preparation method requires the exchange of sodium-type aluminum-rich ZSM-5 zeolite into ammonium-type aluminum-rich ZSM-5 zeolite before preparing the catalyst support, followed by calcination to obtain hydrogen-type aluminum-rich ZSM-5 zeolite. Both the exchange treatment and calcination treatment can employ commonly used exchange and calcination processes in the art. For example, ammonium nitrate solution can be used to exchange sodium-type aluminum-rich ZSM-5 zeolite into ammonium-type aluminum-rich ZSM-5 zeolite, and after three exchange treatments, calcination is performed at a temperature of 510–580°C.

[0040] The third objective of this invention is to provide a catalytic diesel hydrocracking catalyst, comprising either the above-mentioned alumina-rich ZSM-5 zeolite as a support or the alumina-rich ZSM-5 zeolite as a support prepared by the above-mentioned preparation method.

[0041] The fourth objective of this invention is to provide an application of the above-mentioned catalytic diesel hydrocracking catalyst in the hydrocracking reaction of rich aromatic diesel, comprising the following steps: loading the hydrorefining catalyst and the catalytic diesel hydrocracking catalyst into separate first and second reactors respectively; adding rich aromatic diesel into the first reactor and reacting it with the hydrorefining catalyst; performing gas-liquid separation; and introducing the resulting liquid oil into the second reactor to react with the catalytic diesel hydrocracking catalyst.

[0042] According to the present invention, in the hydrocracking reaction of the aromatic diesel oil:

[0043] The aromatic diesel fuel contains no less than 50% aromatic hydrocarbons.

[0044] The aromatic diesel oil is selected from at least one of catalytic diesel oil, coking diesel oil, and ethylene tar; and / or,

[0045] The aromatic diesel oil, after hydrorefining, has a nitrogen content of ≤50ppm and a sulfur content of ≤800ppm; preferably, the nitrogen content is ≤20ppm and the sulfur content is ≤500ppm.

[0046] The hydrorefining process can employ catalytic diesel hydrorefining technology known in the art, and the hydrorefining reaction conditions can be those known in the art for catalytic diesel hydrorefining. The hydrorefining catalyst can be any type of hydrorefining catalyst already available in the art, as long as it can achieve the purpose of catalytic diesel hydrorefining. Preferably, the hydrorefining reaction conditions include: a reaction temperature of 280–400°C, a hydrogen partial pressure of 2.0–15.0 MPa, and a liquid hourly space velocity of 0.2–4.0 h⁻¹. -1 The hydrogen-to-hydrogen volume ratio is 500–4000; preferably, the reaction temperature is 300–380℃, the hydrogen partial pressure is 5.0–12.0 MPa, and the liquid hourly space velocity is 0.5–2.0 h⁻¹. -1 The hydrogen-to-hydrogen volume ratio is 1000–3000;

[0047] The hydrocracking reaction conditions include: a reaction temperature of 300–450 °C, a hydrogen partial pressure of 2.0–15.0 MPa, and a liquid hourly space velocity of 0.2–4.0 h⁻¹. -1 The hydrogen-to-hydrogen volume ratio is 500–4000; preferably, the reaction temperature is 320–420°C, the hydrogen partial pressure is 5.0–12.0 MPa, and the liquid hourly space velocity is 0.5–2.0 h⁻¹. -1 The hydrogen-to-hydrogen volume ratio is 1000–3000;

[0048] The single-pass conversion rate of the hydrocracking reaction is greater than 85%;

[0049] In the hydrocracking reaction products, the benzene content in C6 hydrocarbons is greater than 35 wt%, the toluene content in C7 hydrocarbons is greater than 85 wt%, the C6 hydrocarbons are a mixture of benzene and C6 non-aromatic hydrocarbons, and the C7 hydrocarbons are a mixture of toluene and C7 non-aromatic hydrocarbons.

[0050] This invention utilizes an aluminum-rich ZSM-5 zeolite-supported catalyst as a catalytic diesel hydrocracking catalyst. It can be used to produce light aromatics and light hydrocarbons with chemical applications, realizing the conversion of low-value aromatic oils such as diesel into aromatics, olefins, and other chemical products. In this catalyst, ZSM-5 zeolite with a silica-alumina ratio between 5 and 18 and an average particle length of less than 20 nm in at least one dimension is used as the acidic functional component. The high-aluminum-content aluminum-rich ZSM-5 provides abundant Brønsted acid centers, and because the average length in at least one dimension is less than 20 nm, tetrahydronaphthalene hydrocarbons can contact the open outer surface and pores of the Brønsted acid centers to undergo cracking reactions. Compared to ordinary ZSM-5 catalysts, its conversion activity is significantly improved, and its single-pass conversion rate is high. Traditional hydrodewaxing catalysts using ZSM-5 support suffer from low single-pass conversion rates because reactant molecules cannot effectively contact the acidic sites on the zeolite particles. In this invention, a catalyst with group VIB metal oxides supported on aluminum-rich ZSM-5 zeolite is used as a catalyst for diesel hydrocracking. It is suitable for two-stage processes with low sulfur content, has moderate hydrogenation activity, and has higher selectivity and purity in converting catalytic diesel into light aromatics. Attached Figure Description

[0051] Figure 1 TEM image of the aluminum-rich ZSM-5 zeolite prepared in Example 1. Detailed Implementation

[0052] The present invention will now be described in detail with reference to specific embodiments. It should be noted that the following embodiments are only used to further illustrate the present invention and should not be construed as limiting the scope of protection of the present invention. Some non-essential improvements and adjustments made by those skilled in the art based on the content of the present invention are still within the scope of protection of the present invention.

[0053] The testing instruments and conditions used in this embodiment are as follows:

[0054] 1. The content of elements such as Si and Al in the sample was determined by ICP (inductively coupled plasma atomic emission spectrometry), and the SiO2 / Al2O3 (silicon-aluminum ratio, SAR) was calculated. The instrument used was Thermo IR IS Intrepid II XSP. The sample volume was 20-40 mg. The sample was fully dissolved in 40-80 mL of 40% hydrofluoric acid solution before detection.

[0055] 2. The composition of the catalyst was determined by XRF (X-ray fluorescence spectroscopy) using an S4Explorer X-ray fluorescence spectrometer manufactured by Bruker GmbH, Germany.

[0056] 3. Determine the composition and valence state of group VIB metal oxides using XPS (X-ray photoelectron spectroscopy). XPS test conditions: Perkin Elmer PHI 5000C ESCA X-ray photoelectron spectrometer, using Mg K excitation source, operating voltage 10 kV, current 40 mA, vacuum degree 4.0 × 10⁻⁸ Pa.

[0057] 4. 27 Al MAS NMR measurements were performed on a VARIAN VNMRS-400WB NMR spectrometer at a frequency of 104.18 MHz, a rotation speed of 10000 r / s, and a relaxation time of 4 s. KAl(SO4)2.12H2O was used as the standard. The chemical shift signal peaks of ~60 ppm corresponded to skeletal aluminum, and the chemical shift signal peaks of ~0 ppm corresponded to non-skeletal aluminum.

[0058] 5. TEM test: The morphology of aluminum-rich ZSM-5 zeolite crystals was observed using a FEI Tecnai G2 F20 S-Twin field emission transmission electron microscope.

[0059] 6. The composition of the crude oil and light chemical products was determined by gas chromatography. The chromatograph was an Agilent 7890A, equipped with an FID detector. Separation was performed using an FFAP capillary column. The column was programmed with an initial temperature of 90°C, held for 15 minutes, and then increased to 220°C at a rate of 15°C / min, held for 45 minutes.

[0060] The basis for calculating the test data in the specific embodiments of this invention is as follows:

[0061] 1. The formula for calculating the total conversion rate is:

[0062]

[0063] 2. The formula for calculating the selectivity of light aromatics is:

[0064]

[0065] In the formula, BTX refers to light aromatic hydrocarbons (benzene, toluene, ethylbenzene, and xylene).

[0066] 3. In hydrocracking products, the benzene content in C6 hydrocarbons and the toluene content in C7 hydrocarbons are used as indicators of aromatic hydrocarbon purity.

[0067] The following are examples of catalytic cracking feedstocks and hydrorefining catalysts involved in the embodiments:

[0068] 1. To illustrate the effects of the present invention, the raw material composition is shown in Table 1.

[0069] Table 1. Raw material composition

[0070]

[0071] 2. The hydrorefining catalyst involved in the embodiments and comparative examples of this invention is commercially available catalyst HT-1, with a composition of 5.73wt% NiO, 35.15wt% MoO3, 4.66% P2O5, and 54.46% Al2O3. Hydrorefining catalysts with compositions and performance indicators similar to those described above can be used in the technical solutions adopted in this invention. A cyclohexane solution containing 0.5% carbon disulfide is injected into a fixed-bed reactor containing the hydrorefining catalyst. The temperature is increased from room temperature to the sulfidation endpoint temperature of 340°C at a programmed rate of 10°C / h, and maintained at this temperature for 12 hours to complete the pre-sulfidation of the hydrorefining catalyst. The sulfidated HT-1 hydrorefining catalyst is used to refine the catalytic converter feedstock. The hydrorefining reaction conditions are: 6.5 MPa, hydrogen-to-oil ratio 2400, and catalyst space velocity (LHSV) 0.8 h⁻¹. -1 The inlet reaction temperature was 315℃. After gas-liquid separation, the refined product yielded refined catalytic converter, the composition and properties of which are shown in Table 1.

[0072] 3. All other raw materials involved in the embodiments and comparative examples of this invention are commercially available products.

[0073] Comparative Example 1

[0074] Preparation of hydrocracking catalysts:

[0075] Hydrogen-form USY zeolite (SAR=12) was obtained from the Catalyst Division of Sinopec, with an average particle size of 1.7 micrometers. 43g of USY, 72.3g of pseudoboehmite, and 2g of guar gum powder were uniformly mixed, and 12ml of nitric acid and 90ml of water were added. The mixture was kneaded into a dough, extruded, cured at room temperature for 24 hours, dried at 110℃ for 12 hours, and calcined in air at 550℃ for 3 hours to obtain a hydrocracking catalyst support. 4.34g of nickel nitrate, 5.75g of ammonium molybdate, and 20ml of ammonia were dissolved in water to obtain a 50ml aqueous solution of a metal compound. 50g of the hydrocracking catalyst support was impregnated with the above 50ml aqueous solution of the metal compound by equal volume impregnation, allowed to stand for 3 hours, dried at 110℃ for 12 hours, and calcined in air at 500℃ for 4 hours to obtain a hydrocracking catalyst precursor.

[0076] Catalyst reduction: The above-mentioned hydrocracking catalyst precursor was loaded into a fixed-bed reactor, and the temperature was increased from room temperature to the reduction endpoint temperature of 400℃ at a rate of 10℃ / h, and maintained at this temperature for 12h to complete the reduction of the hydrocracking catalyst. After reduction, the CO composition of the hydrocracking catalyst was 1.6wt% Ni-8.1wt% MoO. 2.6 / 40.2wt% USY (SAR=12)-50.1wt% Al2O3, see Table 2.

[0077] Catalyst evaluation:

[0078] The reaction uses refined catalytic converter feedstock, with a reaction pressure of 6.5 MPa, a hydrogen-to-oil ratio of 2400, and a space velocity (LHSV) of 1.0 h⁻¹. -1 The reaction temperature was 370℃. A high-pressure separator was installed at the outlet of the hydrocracking reactor. After 48 hours of stable operation, the gaseous and liquid products were metered and analyzed for composition. The reaction products were classified as CH4, C2-C5 light hydrocarbons, and C6-C4 light hydrocarbons. 10 The total conversion rate and the selectivity of light aromatics were calculated using the aforementioned formula, and the data are summarized in Table 3.

[0079] The single-pass conversion rate was 68.5 wt%, the selectivity for light aromatics was 40.2%, and the benzene content in C6 hydrocarbons and the toluene content in C7 hydrocarbons were 23.8% and 67.3%, respectively.

[0080] Comparative Example 2

[0081] Preparation of hydrocracking catalysts:

[0082] Hydrogen-form ZSM-5 zeolite (SAR=38) was obtained from the Catalyst Division of Sinopec, with an average particle size of 1.5 micrometers. 43g of hydrogen-form ZSM-5 zeolite (SAR=38), 72.3g of pseudoboehmite, and 2g of guar gum powder were uniformly mixed, and 12ml of nitric acid and 90ml of water were added. The mixture was kneaded into a dough, extruded, cured at room temperature for 24 hours, dried at 110℃ for 12 hours, and calcined in air at 550℃ for 3 hours to obtain a hydrocracking catalyst support. 4.34g of nickel nitrate, 5.75g of ammonium molybdate, and 20ml of ammonia were dissolved in water to obtain a 50ml aqueous solution of a metal compound. 50g of the hydrocracking catalyst support was added to the above 50ml metal compound solution by an equal-volume impregnation method, allowed to stand for 3 hours, dried at 110℃ for 12 hours, and calcined in air at 500℃ for 4 hours to obtain a hydrocracking catalyst precursor.

[0083] Catalyst reduction: The above-mentioned hydrocracking catalyst precursor was loaded into a fixed-bed reactor, and the temperature was increased from room temperature to the reduction endpoint temperature of 400℃ at a rate of 10℃ / h, and maintained at this temperature for 12h to complete the reduction of the hydrocracking catalyst. After reduction, the composition of the hydrocracking catalyst C1 was 1.6wt% Ni-8.1wt% MoO. 2.6 / 40.2wt% ZSM-5 (SAR=38)-50.1wt% Al2O3, see Table 2.

[0084] Catalyst evaluation:

[0085] The reaction uses refined catalytic converter feedstock, with a reaction pressure of 6.5 MPa, a hydrogen-to-oil ratio of 2400, and a space velocity (LHSV) of 1.0 h⁻¹. -1The reaction temperature was 370℃. A high-pressure separator was installed at the outlet of the hydrocracking reactor. After 48 hours of stable operation, the gaseous and liquid products were metered and analyzed for composition. The reaction products were classified as CH4, C2-C5 light hydrocarbons, and C6-C4 light hydrocarbons. 10 The total conversion rate and the selectivity of light aromatics were calculated using the aforementioned formula, and the data are summarized in Table 3.

[0086] The single-pass conversion rate was 39.2 wt%, the selectivity for light aromatics was 60.1%, and the benzene content in C6 hydrocarbons and the toluene content in C7 hydrocarbons were 82.4% and 97.6%, respectively.

[0087]

Example 1

[0088] Preparation of aluminum-rich ZSM-5 zeolite:

[0089] First, silica sol, NaOH, sodium bromide, and sodium aluminate were dissolved in deionized water. Then, 25% tetrapropylammonium hydroxide (OSDA) was added and stirred until homogeneous to obtain a milky white gelling solution. The molar ratio of SiO2, OSDA, Al2O3, NaOH, and deionized water in the gelling solution was 40:5:1:3.5:200, and the molar ratio of NaOH to NaBr was 2:1. The gelling solution was then placed in a polytetrafluoroethylene-lined pressure vessel and pre-crystallized at 90℃ for 6 hours. Afterward, it was placed in a rotary oven at 150℃ and a rotation speed of 20 r / min for further hydrothermal crystallization for 160 hours. Finally, it was cooled to room temperature with tap water to obtain a highly crystalline ZSM-5 slurry.

[0090] An appropriate amount of sodium aluminate and deionized water were directly added to the ZSM-5 slurry to obtain a molar ratio of SiO2, OSDA, Al2O3, (NaOH and sodium bromide), and deionized water of 40:5:3.2:0.03:240. The aforementioned crystallization procedure was repeated for secondary crystallization. The resulting product was filtered, washed, and dried, and then calcined in air at 550°C for 3 hours to obtain aluminum-rich ZSM-5 molecular sieve.

[0091] XRD characterization showed that the obtained aluminum-rich ZSM-5 molecular sieve was a pure-phase MFI configuration. 27 Al MAS NMR results showed that 98% of the aluminum species in the aluminate-rich ZSM-5 molecular sieve were in a four-coordinate state. ICP analysis revealed a silica-to-alumina ratio of 13 for the ZSM-5 molecular sieve. Its TEM image is shown below. Figure 1 It appears as irregularly shaped particles with a diameter between 100-300 nm, and these particles are loosely aggregated from basic particles with a diameter of less than 20 nm.

[0092] The obtained aluminum-rich ZSM-5 molecular sieve was added to a 1 mol / L ammonium nitrate solution at 90 °C and exchanged three times to exchange the sodium-type aluminum-rich ZSM-5 (SAR=13) into the ammonium-type aluminum-rich ZSM-5 (SAR=13). Then, it was calcined at 550 °C to obtain the hydrogen-type aluminum-rich ZSM-5 (SAR=13).

[0093] Preparation of hydrocracking catalysts:

[0094] 43g of hydrogen-type aluminum-rich ZSM-5 (SAR=13), 72.3g of pseudoboehmite, and 2g of guar gum powder were uniformly mixed, and 12ml of nitric acid and 90ml of water were added. The mixture was kneaded into a dough, extruded, and cured at room temperature for 24 hours. It was then dried at 110℃ for 12 hours and calcined in air at 550℃ for 3 hours to obtain a hydrocracking catalyst support. 4.34g of nickel nitrate, 5.75g of ammonium molybdate, and 20ml of ammonia were dissolved in water to obtain a 50ml aqueous solution of a metal compound. 50g of the hydrocracking catalyst support was impregnated with the above 50ml aqueous solution of the metal compound by equal volume impregnation. The mixture was allowed to stand for 3 hours, dried at 110℃ for 12 hours, and calcined in air at 500℃ for 4 hours to obtain a hydrocracking catalyst precursor.

[0095] Catalyst reduction: The hydrocracking catalyst precursor was loaded into a fixed-bed reactor, and the temperature was increased from room temperature to the reduction endpoint temperature of 400℃ at a rate of 10℃ / h, and maintained at this temperature for 12h to complete the reduction of the hydrocracking catalyst. After reduction, the C2 composition of the hydrocracking catalyst was 1.6wt% Ni-8.1wt% MoO. 2.6 / 40.2wt% ZSM-5 (SAR=13)-50.1wt% Al2O3, see Table 2.

[0096] Evaluation of hydrocracking catalysts:

[0097] The reaction uses refined catalytic converter feedstock, with a reaction pressure of 6.5 MPa, a hydrogen-to-oil ratio of 2400, and a space velocity (LHSV) of 1.0 h⁻¹. -1 The reaction temperature was 370℃. A high-pressure separator was installed at the outlet of the hydrocracking reactor. After 48 hours of stable operation, the gaseous and liquid products were metered and analyzed for composition. The reaction products were classified as CH4, C2-C5 light hydrocarbons, and C6-C4 light hydrocarbons. 10 The total conversion rate and the selectivity of light aromatics were calculated using the aforementioned formula, and the data are summarized in Table 3.

[0098] The single-pass conversion rate was 89.5 wt%, the selectivity for light aromatics was 56.9%, and the benzene content in C6 hydrocarbons and the toluene content in C7 hydrocarbons were 56.2% and 93.7%, respectively.

[0099]

Example 2

[0100] Preparation of hydrocracking catalysts:

[0101] The hydrocracking catalyst support was prepared according to the method in [Example 1]. 4.34 g of nickel nitrate, 8.78 g of ammonium tungstate, and 20 ml of ammonia were dissolved in water to obtain 50 ml of an aqueous solution of the metal compound. 50 g of the hydrocracking catalyst support was added to the above 50 ml metal compound solution by an equal-volume impregnation method, allowed to stand for 6 hours, dried at 90°C for 24 hours, and calcined at 510°C in air for 3 hours to obtain the hydrocracking catalyst precursor.

[0102] Catalyst reduction: The hydrocracking catalyst precursor was loaded into a fixed-bed reactor, and the temperature was increased from room temperature to the reduction endpoint temperature of 380℃ at a rate of 10℃ / h, and maintained at this temperature for 6 hours to complete the reduction of the hydrocracking catalyst. After reduction, the C3 composition of the hydrocracking catalyst was 1.6wt% NiO. 0.3 -12.5wt% WO 2.8 / 38.2wt% ZSM-5 (SAR=13)-47.7wt% Al2O3, see Table 2.

[0103] The reaction uses refined catalytic converter feedstock, with a reaction pressure of 7.0 MPa, a hydrogen-to-oil ratio of 2000, and a space velocity (LHSV) of 1.0 h⁻¹. -1 The reaction temperature was 375℃. A high-pressure separator was installed at the outlet of the hydrocracking reactor. After 48 hours of stable operation, the gaseous and liquid products were metered and analyzed for composition. The reaction products were classified as CH4, C2-C5 light hydrocarbons, and C6-C4 light hydrocarbons. 10 The total conversion rate and the selectivity of light aromatics were calculated using the aforementioned formula, and the data are summarized in Table 3.

[0104] The single-pass conversion rate was 97.5 wt%, the selectivity for light aromatics was 53.6%, and the benzene content in C6 hydrocarbons and the toluene content in C7 hydrocarbons were 51.8% and 93.7%, respectively.

[0105]

Example 3

[0106] Preparation of aluminum-rich ZSM-5 zeolite:

[0107] First, NaOH, sodium bromide, and sodium aluminate were dissolved in deionized water. Then, 25% tetrapropylammonium hydroxide (OSDA) was added, and the mixture was stirred until homogeneous to obtain a milky white gelling solution. In the obtained gelling solution, the molar ratio of SiO2, OSDA, Al2O3, (NaOH and sodium bromide), and solvent deionized water was 25:3:1:0.02:135, and the molar ratio of NaOH to NaBr was 2:1. The gelling solution was then placed in a polytetrafluoroethylene-lined pressure vessel and pre-crystallized at 70°C for 12 hours. After that, it was placed in a rotary oven at 165°C and a rotation speed of 20 r / min for 36 hours of hydrothermal crystallization. Finally, it was cooled to room temperature with tap water to obtain a highly crystalline ZSM-5 slurry.

[0108] An appropriate amount of aluminum hydroxide and deionized water were directly added to the ZSM-5 slurry to obtain a molar ratio of SiO2, OSDA, Al2O3, (NaOH and sodium bromide), and deionized water of 25:3:2.8:0.02:135. The aforementioned crystallization procedure was repeated for secondary crystallization. The resulting product was filtered, washed, and dried, and then calcined in air at 550°C for 3 hours to obtain aluminum-rich ZSM-5 molecular sieve.

[0109] XRD characterization showed that the aluminum-rich ZSM-5 molecular sieve was a pure-phase MFI configuration. 27 Al MAS NMR results showed that 96% of the aluminum species in the aluminum-rich ZSM-5 molecular sieve were in a four-coordinate state. ICP analysis revealed that the silica-alumina ratio of the ZSM-5 molecular sieve was 8.6.

[0110] The obtained aluminum-rich ZSM-5 molecular sieve was added to a 1 mol / L ammonium nitrate solution at 90 °C, and the mixture was exchanged three times to convert the sodium-form aluminum-rich ZSM-5 (SAR = 8.6) into the ammonium-form aluminum-rich ZSM-5 (SAR = 8.6). Then, it was calcined at 550 °C to obtain the hydrogen-form aluminum-rich ZSM-5 (SAR = 8.6).

[0111] Preparation of hydrocracking catalysts:

[0112] 60g of hydrogen-type aluminum-rich ZSM-5 (SAR=8.6), 57g of pseudoboehmite, and 2g of guar gum powder were uniformly mixed, and 6ml of nitric acid and 85ml of water were added. The mixture was kneaded into a dough, extruded, and cured at room temperature for 24h. It was then dried at 110℃ for 24h and calcined in air at 550℃ for 3h to obtain a hydrocracking catalyst support. 6.06g of cobalt nitrate, 5.75g of ammonium molybdate, 2.64g of ammonium tungstate, and 20ml of ammonia were dissolved in water to obtain a 50ml aqueous solution of a metal compound. 50g of the hydrocracking catalyst support was impregnated with the above 50ml aqueous solution of the metal compound by equal volume impregnation. The mixture was allowed to stand for 3 hours, dried at 90℃ for 24h, and calcined in air at 480℃ for 6h to obtain a hydrocracking catalyst precursor.

[0113] Catalyst reduction: The above-mentioned hydrocracking catalyst precursor was loaded into a fixed-bed reactor, and the temperature was increased from room temperature to the reduction endpoint temperature of 430°C at a rate of 10°C / h, and maintained at this temperature for 4 hours to complete the reduction of the hydrocracking catalyst. After reduction, the C3 composition of the hydrocracking catalyst was 2.1 wt% Co - 7.7 wt% MoO. 2.5 -3.8wt% WO 2.4 / 51.9wt% ZSM-5 (SAR=8.6)-34.5wt% Al2O3, see Table 2.

[0114] The reaction uses refined catalytic converter feedstock, with a reaction pressure of 6.5 MPa, a hydrogen-to-oil ratio of 2000, and a space velocity (LHSV) of 1.2 h⁻¹. -1 The reaction temperature was 385℃. A high-pressure separator was installed at the outlet of the hydrocracking reactor. After 48 hours of stable operation, the gaseous and liquid products were metered and analyzed for composition. The reaction products were classified as CH4, C2-C5 light hydrocarbons, and C6-C4 light hydrocarbons. 10 The total conversion rate and the selectivity of light aromatics were calculated using the aforementioned formula, and the data are summarized in Table 3.

[0115] The single-pass conversion rate was 98.9 wt%, the selectivity for light aromatics was 58.3%, and the benzene content in C6 hydrocarbons and the toluene content in C7 hydrocarbons were 69.0% and 96.7%, respectively.

[0116] Table 2. Catalyst composition obtained in Comparative Examples 1-2 and Examples 1-3

[0117]

[0118] Table 3. Product yields from Comparative Examples 1-2 and Examples 1-3

[0119]

[0120] As can be seen from the results in Table 3, the hydrocracking catalyst using the aluminum-rich ZSM-5 zeolite of the present invention as the support component has a single-pass conversion rate of more than 85% in the hydrocracking reaction, and the benzene content in C6 hydrocarbons of the hydrocracking reaction products is more than 50%, and the toluene content in C7 hydrocarbons is more than 93%. Compared with Comparative Examples 1-2, Examples 1-3 show better feed conversion rate and light aromatic selectivity.

Claims

1. A catalyst supported on aluminum-rich ZSM-5 zeolite, comprising: The aluminum-rich ZSM-5 zeolite support and the metal component supported on the support, wherein the metal component comprises group VIB metal oxides and optional group VIII metal components, the silicon-aluminum molecular ratio of the aluminum-rich ZSM-5 zeolite support is between 5 and 18, the content of skeletal aluminum in the aluminum-rich ZSM-5 zeolite support accounts for more than 92% of the total aluminum, and the average length of the particles of the aluminum-rich ZSM-5 zeolite support is less than 20 nm in at least one dimension. The aluminum-rich ZSM-5 zeolite is obtained by the following preparation method: a) dissolving sodium hydroxide and alumina source in water, then adding silica source and template agent in sequence, and stirring to obtain a colloid; b) pre-crystallizing and hydrothermally crystallizing the colloid obtained in step a), and then cooling to obtain a highly crystalline ZSM-5 slurry. c) Add alumina source and water to the high crystallinity ZSM-5 slurry obtained in step b); d) Repeat the pre-crystallization and hydrothermal crystallization in step b) for secondary crystallization; e) Filter, wash, dry and calcine the product obtained after secondary crystallization to obtain the aluminum-rich ZSM-5 zeolite; the pre-crystallization conditions in steps b) and d) are independently: 50~100℃ for 3~60h; the hydrothermal crystallization conditions in steps b) and d) are independently: 110~180℃ for 12~240h.

2. The catalyst according to claim 1, characterized in that, The catalyst further comprises a binder; and / or, Based on a total weight of 100 parts by weight of the aluminum-rich ZSM-5 zeolite carrier and binder, the aluminum-rich ZSM-5 zeolite carrier comprises 5 to 80 parts, the group VIB metal oxide comprises 1 to 20 parts, and the group VIII metal component comprises 0 to 10 parts (group VIII metals).

3. The catalyst according to claim 2, characterized in that, The adhesive is selected from at least one of alumina and silica; and / or, Based on a total weight of 100 parts by weight of the aluminum-rich ZSM-5 zeolite carrier and binder, the aluminum-rich ZSM-5 zeolite carrier is 10-70 parts, the group VIB metal oxide is 2-18 parts, and the group VIII metal component is 0.2-8 parts (group VIII metals).

4. The catalyst according to claim 3, characterized in that, Based on a total weight of 100 parts by weight of the aluminum-rich ZSM-5 zeolite carrier and binder, the aluminum-rich ZSM-5 zeolite carrier comprises 15 to 60 parts, the group VIB metal oxide comprises 3 to 15 parts, and the group VIII metal component comprises 0.5 to 6 parts (group VIII metals).

5. The catalyst according to claim 1, characterized in that, The aluminum-rich ZSM-5 zeolite carrier contains more than 95% skeletal aluminum; and / or, The group VIB metal oxides are selected from at least one of molybdenum oxides and tungsten oxides; and / or, The group VIII metal component is selected from at least one of nickel-containing components and cobalt-containing components.

6. A method for preparing a catalyst supported on aluminum-rich ZSM-5 type zeolite as described in any one of claims 1 to 5, comprising: The catalyst is obtained by loading a component containing group VIB metal oxides and optional group VIII metal components onto a support containing aluminum-rich ZSM-5 zeolite, followed by calcination and reduction. The aluminum-rich ZSM-5 zeolite is obtained by the following preparation method: a) dissolving sodium hydroxide and alumina source in water, then adding silica source and template agent in sequence, and stirring to obtain a colloid; b) pre-crystallizing and hydrothermally crystallizing the colloid obtained in step a), and then cooling to obtain a highly crystalline ZSM-5 slurry. c) Add alumina source and water to the high crystallinity ZSM-5 slurry obtained in step b); d) Repeat the pre-crystallization and hydrothermal crystallization in step b) for secondary crystallization; e) Filter, wash, dry and calcine the product obtained after secondary crystallization to obtain the aluminum-rich ZSM-5 zeolite; the pre-crystallization conditions in steps b) and d) are independently: 50~100℃ for 3~60h; the hydrothermal crystallization conditions in steps b) and d) are independently: 110~180℃ for 12~240h.

7. The preparation method according to claim 6, characterized in that, The preparation method includes the following steps: Step 1) After the components including aluminum-rich ZSM-5 zeolite are shaped, dried and calcined to obtain the catalyst support; Step 2) Prepare aqueous solutions of soluble Group VIB and Group VIII metal compounds; Step 3) The catalyst support obtained in Step 1) is immersed in the aqueous solution of the metal compound obtained in Step 2), then removed, dried, calcined and reduced to obtain the catalyst.

8. The preparation method according to claim 7, characterized in that, In step 1): The aluminum-rich ZSM-5 zeolite is first mixed with a binder before molding; and / or, The drying temperature is 50~180℃; and / or, The calcination temperature is 520~600℃; and / or, The roasting time is 1 to 8 hours.

9. The preparation method according to claim 8, characterized in that, In step 1): The drying temperature is 60~150℃; and / or, The calcination temperature is 530~580℃; and / or, The roasting time is 2 to 6 hours.

10. The preparation method according to claim 7, characterized in that, In step 2): The soluble Group VIB metal compound is selected from at least one of soluble molybdenum compounds and soluble tungsten compounds; and / or, The soluble Group VIII metal compound is selected from at least one of soluble nickel compounds and soluble cobalt compounds; and / or, The total concentration of the metal compound in the aqueous solution is 3-45 wt%.

11. The preparation method according to claim 10, characterized in that, In step 2): The soluble Group VIB metal compound is selected from at least one of ammonium tungstate and ammonium molybdate; and / or, The soluble Group VIII metal compound is selected from at least one of nickel nitrate, nickel sulfate, nickel halide, nickel acetate, cobalt nitrate, and cobalt chloride; and / or, The total concentration of the metal compound in the aqueous solution is 5-40 wt%.

12. The preparation method according to claim 7, characterized in that, In step 3): The drying temperature is 50~150℃; and / or, The calcination temperature is 450~600℃; and / or, The roasting time is 0.5~8 hours; and / or, The reduction conditions are as follows: the reduction heating rate is 1~20℃ / h, the reduction endpoint temperature is 300~450℃, and the endpoint temperature is maintained for 1~24h.

13. The preparation method according to claim 12, characterized in that, In step 3): The drying temperature is 60~120℃; and / or, The calcination temperature is 480~580℃; and / or, The roasting time is 1-6 hours; and / or, The reduction conditions are as follows: the reduction heating rate is 5~10℃ / h, the reduction endpoint temperature is 320~420℃, and the endpoint temperature is maintained for 2~16h.

14. The preparation method according to claim 6, characterized in that, The alumina source is selected from at least one of sodium aluminate, aluminum hydroxide, and aluminum sulfate; and / or, The silica source is selected from at least one of silica gel, silica sol, and precipitated silica; and / or, The template agent is selected from organic amines.

15. The preparation method according to claim 14, characterized in that, The template agent is selected from at least one of tetrapropylammonium hydroxide, tetrapropylammonium bromide, and n-propylamine.

16. The preparation method according to claim 6, characterized in that, In step a), the molar ratio of silica source, template agent, alumina source, sodium hydroxide, and water is (20~50):(2~10):1:(0.01~0.20):(120~500), wherein the silica source is calculated as SiO2 and the alumina source is calculated as Al2O3; and / or, In the system obtained in step c), the molar ratio of silica source, template agent, alumina source, sodium hydroxide, and water is (8~18):(0.5~2):1:(0.005~0.015):(40~150), wherein the silica source is calculated as SiO2, and the alumina source is calculated as Al2O3; and / or, The aluminum-rich ZSM-5 zeolite obtained in step e) still needs to undergo ammonium ion exchange and calcination treatment.

17. The preparation method according to claim 6, characterized in that, The pre-crystallization conditions in steps b) and d) are independently: pre-crystallization at 60–95°C for 5–30 h; and / or, The hydrothermal crystallization conditions in steps b) and d) are independently: crystallization at 120~170℃ for 24~200h.

18. A catalytic diesel hydrocracking catalyst comprising a catalyst supported on aluminum-rich ZSM-5 type zeolite as described in any one of claims 1 to 5, or a catalyst supported on aluminum-rich ZSM-5 type zeolite prepared by the preparation method described in any one of claims 6 to 17.

19. The application of the catalytic diesel hydrocracking catalyst of claim 18 in the hydrocracking reaction of aromatic diesel fuel, comprising the following steps: The hydrorefining catalyst and the aforementioned catalytic diesel hydrocracking catalyst are respectively loaded into a first reactor and a second reactor. The aromatic diesel is added to the first reactor and reacted with the hydrorefining catalyst. After gas-liquid separation, the resulting liquid oil is fed into the second reactor and reacted with the aforementioned catalytic diesel hydrocracking catalyst. The aromatic diesel contains not less than 50% aromatics.

20. The application according to claim 19, characterized in that, The aromatic diesel oil is selected from at least one of catalytic diesel oil, coking diesel oil, and ethylene tar; and / or, The aromatic diesel oil, after hydrorefining, has a nitrogen content of ≤50ppm and a sulfur content of ≤800ppm. And / or, The reaction conditions for the hydrorefining include: a reaction temperature of 280–400 °C, a hydrogen partial pressure of 2.0–15.0 MPa, and a liquid hourly space velocity of 0.2–4.0 h⁻¹. -1 The hydrogen-to-hydrogen volume ratio is 500~4000; and / or, The hydrocracking reaction conditions include: a reaction temperature of 300–450 °C, a hydrogen partial pressure of 2.0–15.0 MPa, and a liquid hourly space velocity of 0.2–4.0 h⁻¹. -1 The hydrogen-to-hydrogen volume ratio is 500~4000; and / or, Based on a fraction above 200°C, the single-pass conversion rate of the hydrocracking reaction is greater than 85%; and / or, In the hydrocracking reaction products, the benzene content in C6 hydrocarbons is greater than 35 wt%, and the toluene content in C7 hydrocarbons is greater than 85 wt%.

21. The application according to claim 20, characterized in that, The aromatic diesel fuel, after hydrorefining, has a nitrogen content ≤20ppm and a sulfur content ≤500ppm; and / or, The reaction conditions for the hydrorefining include: a reaction temperature of 300~380℃, a hydrogen partial pressure of 5.0~12.0MPa, and a liquid hourly space velocity of 0.5~2.0h. -1 The hydrogen-to-hydrogen volume ratio is 1000~3000; and / or, The hydrocracking reaction conditions include: a reaction temperature of 320–420 °C, a hydrogen partial pressure of 5.0–12.0 MPa, and a liquid hourly space velocity of 0.5–2.0 h⁻¹. -1 The hydrogen-to-hydrogen volume ratio is 1000~3000.

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