Aromatic-rich heavy distillate hydrocracking catalyst, preparation method thereof and method for aromatic-rich heavy distillate hydrocracking

Abstract

The present application relates to the field of catalyst, in particular to a kind of rich aromatic refined heavy distillate hydrocracking catalyst, comprising the following components by weight percentage: a) 10-30% MoO3;B) 0.01-5% lanthanide metal oxide;C) 89.99-65% acidic carrier.The present application catalyst has the characteristics of high selectivity rich aromatic heavy distillate BTX production.The present application provides a kind of preparation method of the present application rich aromatic heavy distillate hydrocracking catalyst.The present application also provides a kind of rich aromatic heavy distillate hydrocracking method.The present application method can convert the refined oil with total content of condensed ring aromatic hydrocarbon <10% by volume, total aromatic hydrocarbon >85% by volume into liquid phase product, xylene content is greater than 20% by volume, ethylbenzene content is less than 1% by volume, and BTX yield is greater than 60% by volume of chemical material.

Description

Technical Field

[0001] This invention relates to the field of catalysts, specifically to a catalyst for hydrocracking of aromatic-rich refined heavy distillate oil, its preparation method, and a method for hydrocracking aromatic-rich refined heavy distillate oil. Background Technology

[0002] Heavy aromatic distillate oils, such as light cycle oil (LCO), account for a relatively high proportion of diesel fuel in my country, about 30%, and are the main components of secondary processed diesel fuel. Their total aromatic content is as high as 80%, with naphthalene-based bicyclic aromatics accounting for about 70%, and monocyclic and tricyclic aromatics each accounting for about 15%.

[0003] Ethylene tar is also a heavy distillate oil (>205℃) rich in aromatics (aromatic content greater than 90%). It is a product of the high-temperature condensation of feedstock and products during the steam cracking process of ethylene. Its main components are monocyclic and polycyclic aromatic hydrocarbons with short side chains, high carbon-to-hydrogen ratio, and low content of heavy metals and ash. Ethylene tar also contains heterocyclic compounds containing elements such as N, S, and O. Due to different cracking feedstocks, the yield of ethylene tar varies, generally accounting for about 1 / 5 of the ethylene production. With the increasing use of heavier feedstocks in ethylene production, its yield shows an increasing trend.

[0004] Ethylene tar has a high yield (nearly 60%) in the distillation sections between 205℃ and 300℃, followed by very heavy asphaltic and gum components. Ethylene tar also has a high sulfur content, high polycyclic aromatic hydrocarbon (PAH) content, and high density. The main components in the initial boiling point to 205℃ fraction are indene and its homologues; the 205–225℃ fraction is naphthalene; the 225–245℃ fraction is mainly methylnaphthalene; the 245–300℃ fraction is mainly dimethylnaphthalene; the 300–360℃ fraction contains large amounts of anthracene, acenaphthene, phenanthrene, etc.; and the substances above 360℃ are mainly gums and asphaltenes with a high carbon-to-hydrogen ratio. Naphthalene-based and higher PAHs account for more than 60% of the total composition.

[0005] Abroad, ethylene tar is mainly used as a raw material for carbon black production. Several companies have also begun using cracked fuel oil to produce aromatic solvent oils, with major producers including ExxonMobil (USA), Shell (Netherlands), and Maruzen Oil Company (Japan). Currently, in my country, most ethylene tar is used as fuel or only undergoes primary processing, resulting in low utilization and poor economic benefits.

[0006] C9 pyrolysis + The fraction mainly comes from the cracked gasoline C9 separated after passing through the BTX tower. + The fraction, with an aromatic content of over 70% (and over 90% after removing dicyclopentadiene), accounts for 11% to 22% of ethylene production. Domestically, the vast majority of cracked C9+ is sold only as inexpensive primary raw material fuel oil or after preliminary processing.

[0007] How to utilize these low-value-added LCO, ethylene tar, and cracked C9 + Benzene (B), toluene (T), and xylene (X) are important basic organic chemical raw materials, widely used in the production of polyester, chemical fibers, and other products, closely related to people's basic needs, and their demand has been strong and rapidly increasing in recent years. Considering the abundant aromatic resources in LCO, ethylene tar, and cracked C9+, how to utilize catalytic conversion technology to transform low-value-added LCO, ethylene tar, and cracked C9+ into aromatic hydrocarbons is a pressing issue facing petrochemical scientists. + Converting to BTX will be a huge opportunity and a huge challenge.

[0008] In the field of heavy distillate hydrotreating, catalytic cracking feedstock hydrotreating technology has been industrially applied since the 1970s, and has been used in many refineries processing sulfur-containing or high-sulfur crude oil. Currently, mature catalytic cracking feedstock pretreatment technologies are available both domestically and internationally, primarily including: UOP's VGO Unionfining and APCU (partial conversion hydrocracking) technologies, and Haldor's... The company's Aroshift technology, Chevron's VGO Hydrotreating technology, Exxon's VGO Hydrodesulfurization technology, IFP's T-star technology, and Mobil, AKZO, and Kellogg's MAKfinging technology, among others, are all being utilized. To further improve product quality and conversion rates, catalytic feedstock hydrotreating pretreatment processes are gradually shifting from traditional hydrodesulfurization (HDS) to moderate hydrocracking (MHC) to enhance denitrification, residual carbon, and polycyclic aromatic hydrocarbon saturation capabilities.

[0009] Rich aromatic heavy distillate oils have a high C-H ratio, resulting in low octane numbers for gasoline and cetane numbers for diesel produced by hydrocracking. This leads to high hydrogen consumption and poor economic efficiency. For example, CN120034542 reports the use of rich aromatic oils mixed with heavy distillate oils for hydrocracking to produce diesel; CN102234539A also describes the process of fully saturating rich aromatic oils with aromatics before hydrocracking to produce gasoline and diesel, which results in high production costs and lack of economic viability.

[0010] Existing catalysts used for rich aromatic heavy distillate oils generally employ hydrogenation saturation and cracking. For rich aromatic heavy distillate oils with an aromatic content greater than 80%, this not only results in high hydrogen consumption but also wastes valuable aromatic resources.

[0011] Selective hydrogenation catalysts can be used to selectively hydrogenate and refine rich aromatic heavy distillate oils, and then selectively hydrogenate and crack the refined products to produce benzene (B), toluene (T) and xylene (X) aromatic feedstocks, thereby increasing their added value. Summary of the Invention

[0012] The purpose of this invention is to overcome the problems of high hydrogen consumption and waste of valuable aromatic resources in the hydrocracking process of aromatic-rich heavy distillate oil with high aromatic content using existing catalysts. This invention provides a hydrocracking catalyst for aromatic-rich refined heavy distillate oil, which has the characteristics of highly selectively increasing BTX production from aromatic-rich heavy distillate oil.

[0013] To achieve the above objectives, the present invention provides a hydrocracking catalyst for aromatic-rich refined heavy distillate oils, comprising the following components by weight percentage:

[0014] a) 10–30% MoO3;

[0015] b) 0.01–5% lanthanide metal oxides;

[0016] c) 89.99–65% acidic carrier.

[0017] The second aspect of the present invention provides a method for preparing the hydrocracking catalyst for rich aromatic refined heavy distillate oil of the present invention, the method comprising: impregnating and contacting an impregnation solution composed of a molybdenum source and a lanthanide metal source with an acidic support, followed by drying and calcination.

[0018] A third aspect of the present invention provides a method for hydrocracking a rich aromatic refined heavy distillate oil, the method comprising: after sulfidation of the catalyst described in the present invention, hydrocracking the rich aromatic refined heavy distillate oil under a hydrogen atmosphere.

[0019] Through the above technical solution, the catalyst of the present invention is used for hydrocracking of rich aromatic heavy distillate oil, and the product has high xylene content, low ethylbenzene content, and high yields of benzene, toluene, and xylene. Attached Figure Description

[0020] Figure 1 The XRD pattern is that of the multifunctional acidic support and catalyst in Example 1.

[0021] Figure 2 This is a graph showing the evaluation results of the catalyst in Example 1;

[0022] Figure 3 This is a graph showing the evaluation results of the catalyst in Comparative Example 1. Detailed Implementation

[0023] The endpoints and any values ​​of the ranges disclosed herein 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 the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0024] In this invention, rich aromatic refined heavy distillate oil refers to the hydrorefined product of rich aromatic heavy distillate oil feedstock.

[0025] This invention provides a hydrocracking catalyst for refining heavy distillate oils rich in aromatics, comprising the following components by weight percentage:

[0026] a) 10–30% MoO3;

[0027] b) 0.01–5% lanthanide metal oxides;

[0028] c) 89.99–65% acidic carrier.

[0029] The aromatic heavy distillate hydrocracking catalyst of the present invention, which has the aforementioned characteristics, is characterized by highly selective production of BTX from aromatic heavy distillate.

[0030] According to a preferred embodiment of the present invention, the range of lanthanide metals can be broadly selected. In a preferred embodiment, the lanthanide metals are selected from one or more of lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, and neodymium, preferably from one or more of lanthanum, cerium, praseodymium, and europium, and more preferably from lanthanum and praseodymium. By employing the aforementioned preferred embodiment, the selectivity of BTX can be significantly improved.

[0031] In this invention, the acidic support can be a commonly used acidic support. For this invention, it is preferred that the acidic support contains a hydrogen-type molecular sieve, and the molecular sieve is at least one of H-ZSM-5, HY, H-β, MCM-22, MOR and ZSM-12. Preferably, the molecular sieve is at least two of H-ZSM-5, HY, H-β, MCM-22, MOR and ZSM-12.

[0032] According to a preferred embodiment of the present invention, the acidic support contains H-ZSM-5, HY, and H-β. Preferably, the weight ratio of H-ZSM-5, HY, and H-β molecular sieves is 5-50:5-60:10-80, and more preferably 5-30:10-50:10-75. This can further improve the yield of the target product and the xylene selectivity of the present invention.

[0033] In this invention, as long as the objective of the invention is achieved, there are no particular requirements for the SiO2 / Al2O3 molar ratio of the H-ZSM-5 molecular sieve. According to a preferred embodiment of the invention, the SiO2 / Al2O3 molar ratio of the H-ZSM-5 molecular sieve is 50 to 300. By adopting the aforementioned preferred scheme, the BTX yield can be further improved.

[0034] In this invention, as long as the objective of the invention is achieved, there are no particular requirements for the SiO2 / Al2O3 molar ratio of the HY-type molecular sieve. According to a preferred embodiment of the invention, the SiO2 / Al2O3 molar ratio of the HY-type molecular sieve is 3 to 30. By adopting the aforementioned preferred scheme, the yield of BTX and the xylene yield can be further improved.

[0035] In this invention, as long as the objective of the invention is achieved, there are no particular requirements for the SiO2 / Al2O3 molar ratio of the H-β type molecular sieve. According to a preferred embodiment of the invention, the SiO2 / Al2O3 molar ratio of the H-β type molecular sieve is 10 to 100. By adopting the aforementioned preferred scheme, the yield of BTX and the xylene yield can be further improved.

[0036] According to a preferred embodiment of the present invention, the acidic support contains the molecular sieve composition and a binder, preferably with the molecular sieve composition comprising 70-95% by weight and the binder comprising 5-30% by weight. By adopting the aforementioned preferred embodiment, the yield of BTX and the xylene yield can be further improved.

[0037] In this invention, any acidic support possessing the aforementioned characteristics can achieve the objective of this invention. There are no particular requirements for the preparation method of the acidic support. According to a preferred embodiment of this invention, the preparation method of the acidic support includes:

[0038] (1) Mix the binder source, H-ZSM-5, HY, H-β powder and optional matrix evenly to obtain mixture I;

[0039] (2) Mix mixture I with acidic aqueous solution, knead and shape, dry and calcin.

[0040] According to a preferred embodiment of the present invention, the kneading time is 20 to 50 minutes.

[0041] According to a preferred embodiment of the present invention, steps (1) and / or steps (2) are carried out in the presence of alkali metal salts and / or alkaline earth metal salts, preferably the alkali metal salts and / or alkaline earth metal salts are selected from at least one of sodium salts, potassium salts, calcium salts, and magnesium salts, and preferably calcium salts.

[0042] According to a preferred embodiment of the present invention, the alkali metal salt and / or alkaline earth metal salt, calculated as metal oxides, have a weight ratio of 1:40 to 1:80 with the acidic aqueous solution.

[0043] According to a preferred embodiment of the present invention, the weight ratio of the mixture I to the acidic aqueous solution is 100:5 to 100:150, preferably 100:50 to 100:100.

[0044] According to a preferred embodiment of the present invention, mixture I is kneaded and shaped with an acidic aqueous solution, and then dried after being left to stand for 5 to 15 hours.

[0045] In this invention, the drying conditions in step (2) can be conventional choices in the art. According to a preferred embodiment of the invention, the drying conditions in step (2) include: a temperature of 80 to 150°C and a time of 5 to 10 hours.

[0046] In this invention, the calcination conditions in step (2) can be conventionally chosen in the art. According to a preferred embodiment of this invention, the calcination conditions in step (2) include: a temperature of 450–700°C and a time of 0.5–24 h, preferably 3–10 h. By adopting the aforementioned preferred scheme, the yield of BTX and the xylene yield can be further improved.

[0047] In this invention, as long as the purpose of this invention can be achieved, the binder source can be a conventional choice in the art. According to a preferred embodiment of this invention, the binder source is selected from at least one of silica-containing pseudoboehmite, water glass, silica, and alumina sol.

[0048] According to a preferred embodiment of the present invention, the silicon content of boehmite, on a dry basis (the weight of boehmite powder after dehydration), is 1-30%, preferably 5-20%.

[0049] In this embodiment of the invention, boehmite containing 8% silicon is used as an example to illustrate the advantages of the invention, but the invention is not limited thereto.

[0050] According to a preferred embodiment of the present invention, the matrix content in mixture I is 0-5% by weight, preferably 2-4% by weight.

[0051] In this invention, the matrix can be any conventional choice in the art as long as it can achieve the purpose of this invention. According to a preferred embodiment of this invention, the matrix is ​​selected from at least one of methylcellulose, tianqing powder, polyethylene glycol, calcium nitrate, potassium nitrate and hydroxymethylcellulose, preferably a mixture of methylcellulose and tianqing powder, and the weight ratio of methylcellulose to tianqing powder is 0.5 to 2:1.

[0052] In this invention, as long as the objective of this invention can be achieved, the acidic substance in the acidic aqueous solution can be a conventional choice in the art. According to a preferred embodiment of this invention, the acidic substance in the acidic aqueous solution is selected from at least one of nitric acid, phosphoric acid, acetic acid, citric acid and tartaric acid.

[0053] According to a preferred embodiment of the present invention, the concentration of the acidic aqueous solution is 1 to 6% by weight.

[0054] By adopting the aforementioned preferred scheme, the yield of BTX and the xylene yield can be further improved.

[0055] In this invention, catalysts with the aforementioned characteristics can achieve the purpose of this invention. There are no special requirements for the preparation method of the catalyst. According to a preferred embodiment of this invention, the preparation method of the catalyst includes: impregnating and contacting an impregnation solution composed of a molybdenum source and a lanthanide metal source with an acidic support, followed by drying and calcination.

[0056] According to a preferred embodiment of the present invention, the impregnation solution contains 0.01 to 10% by weight of organic additives, preferably 0.5 to 5% by weight of organic additives.

[0057] In this invention, as long as the objective of this invention can be achieved, the organic additive can be a conventional choice in the art. According to a preferred embodiment of this invention, the organic additive is selected from one or more of diethyl aminomalonate, urea, citric acid and tartaric acid.

[0058] According to a preferred embodiment of the present invention, the organic auxiliary is selected from at least one of diethyl aminomalonate, urea, and citric acid. By adopting the aforementioned preferred embodiment, the solubility of the active component and the dispersibility of the subsequent catalyst active component can be further improved.

[0059] To further improve the solubility of the active component and the dispersibility of the subsequent catalyst active component, according to a preferred embodiment of the present invention, the organic auxiliary agent is urea and diethyl aminomalonate, and the weight ratio of urea to diethyl aminomalonate is 0.5 to 2:1.

[0060] According to a preferred embodiment of the present invention, the preparation method wherein the impregnation contact method includes: equal-volume impregnation using a spray method.

[0061] In this invention, the conditions for impregnation contact can be any conventional selection in the art, as long as the objective of the invention is achieved. According to a preferred embodiment of the invention, the conditions for impregnation contact include: an impregnation temperature of 10–60°C and a post-impregnation period of 0.5–24 hours. By adopting the aforementioned preferred scheme, the stability of the catalyst can be further improved.

[0062] In this invention, as long as the objective of this invention can be achieved, the drying conditions in the catalyst preparation method can be conventionally chosen in the art. According to a preferred embodiment of this invention, the drying conditions include: a temperature of 30–130°C, and a drying time determined according to the temperature, for example, 1–6 hours. By adopting the aforementioned preferred scheme, the stability of the catalyst can be further improved.

[0063] In this invention, as long as the objective of this invention can be achieved, the calcination conditions in the catalyst preparation method can be conventionally selected in the art. According to a preferred embodiment of this invention, the calcination conditions include: a temperature of 200–600°C and a time of 0.5–24 h; preferably, a temperature of 300–500°C and a time of 1–10 h. By adopting the aforementioned preferred scheme, the stability and activity of the catalyst can be further improved.

[0064] This invention provides a method for hydrocracking rich aromatic refined heavy distillate oil, the method comprising: sulfiding the catalyst described in this invention, and hydrocracking the rich aromatic refined heavy distillate oil in the presence of the sulfiding catalyst and under a hydrogen atmosphere.

[0065] Before use, the oxidizing catalyst needs to be converted into a sulfiding catalyst. This method is well known to those skilled in the art, such as at 350°C, 3 MPa, and a volume hourly space velocity (V) of 0.8 h⁻¹. -1 With H2 / Oil(v / v) = 600, sulfurized oil containing 2000ppm sulfur can be vulcanized online for 24-60 hours.

[0066] The method of this invention is particularly suitable for hydrocracking of aromatic heavy distillate oils.

[0067] The present invention does not have any special requirements on the properties of the rich aromatic heavy distillate oil. According to a preferred embodiment of the present invention, the rich aromatic refined heavy distillate oil has an aromatic content of more than 85% by volume, a final boiling point of less than 380°C, an initial boiling point of more than 160°C, a content of bicyclic and above polycyclic aromatic hydrocarbons of less than 10% by volume, a nitrogen content of less than 10 ppm, and a sulfur content of more than 50 ppm.

[0068] The objective of this invention can be achieved using any method of this invention. There are no special requirements for the hydrocracking conditions. According to a preferred embodiment of this invention, the hydrocracking conditions include: a pressure of 5–8 MPa and a space velocity of 0.8–6 h⁻¹. -1 The inlet temperature is 260-500℃, and the volume ratio of hydrogen to distillate oil is 500-3000:1.

[0069] Existing technologies have low BTX yields, typically only 30-40% by volume, and low xylene content with high ethylbenzene content.

[0070] The present invention will be further described below through specific embodiments. However, the scope of the present invention is not limited to the scope covered by the embodiments.

[0071] The XRD pattern of the catalyst was obtained using a RIGAKU D / MAX 2550VB / PC rotating target X-ray polycrystalline diffractometer (XRD), Cu target K αThe X-ray source had a tube voltage of 40kV, a tube current of 100mA, and a scanning step size of 0.02°.

[0072] Example 1

[0073] 130 g of ZSM-5 molecular sieve powder with a hydrogen form SiO2 / Al2O3 ratio of 130 (referring to the molar ratio, the rest are the same) was selected, along with 145 g of Y molecular sieve powder with a hydrogen form SiO2 / Al2O3 ratio of 7, 625 g of β molecular sieve powder with a hydrogen form SiO2 / Al2O3 ratio of 20, 100 g of boehmite (containing 8% silicon, dry basis) (143 g of boehmite raw powder containing 30% water by weight), 15 g each of methylcellulose and Tianqing powder were mixed evenly and set aside. Then, 8 g of nitric acid and 5 g of citric acid were added to 600 g of water and dissolved evenly. Then, calcium nitrate containing 10 g of calcium oxide was added and dissolved evenly. The solution was poured into the above mixed powder and kneaded for 35 minutes. The mixture was extruded into strips, left to stand for 12 hours, dried at 110°C for 6 hours, and then calcined in a muffle furnace at 600°C for 5 hours to obtain a multifunctional acidic carrier.

[0074] An impregnation solution containing 58 g of MoO3 and 2 g of La2O3 was prepared using a soluble metal nitrate precursor. The solution volume was controlled at 140 mL. 1 g of urea and 1 g of diethyl aminomalonate were added to the impregnation solution and stirred until dissolved. 140 g of a multifunctional acidic support was then loaded with an equal volume of the impregnation solution using a rotary drum spray method at 40 °C. The mixture was aged for 16 hours, dried at 100 °C for 4 hours, and calcined at 450 °C for 3 hours to obtain the oxidation catalyst.

[0075] XRD patterns of the multifunctional acidic support and catalyst are shown in [reference needed]. Figure 1 .Depend on Figure 1 It can be seen that no obvious characteristic diffraction peaks of the active component MoO3 and lanthanide metal oxides were observed, indicating that the active component has small particle size and good dispersibility.

[0076] The aromatic heavy distillate oil feedstock and hydrorefined products (referring to the aromatic refined heavy distillate oil of this invention) are shown in Table 1.

[0077] Evaluation conditions: Inlet temperature T = 450℃; Volumetric space velocity V = 0.8h -1 H2 / Oil(v / v) = 1000; Pressure = 6.5 MPa.

[0078] The evaluation results are shown in Table 2 and Figure 2 In this context, B refers to benzene, T refers to toluene, X refers to xylene, EB refers to ethylbenzene, and BTX** refers to benzene, toluene, and xylene.

[0079] Depend on Figure 2 It can be seen that the yields of xylene and BTX are high.

[0080] As shown in Table 2, the yield of ethylbenzene is low, while the yields of xylene and BTX are high and have low added value. The yields of other products are also low, resulting in significant economic benefits.

[0081] Example 2

[0082] 200g of ZSM-5 molecular sieve powder with a hydrogen form SiO2 / Al2O3 ratio of 130, 350g of Y molecular sieve powder with a hydrogen form SiO2 / Al2O3 ratio of 7, 300g of β molecular sieve powder with a hydrogen form SiO2 / Al2O3 ratio of 20, 150g of boehmite (containing 8% silicon, dry basis weight) (214g of boehmite raw powder containing 30% water by weight), 15g each of methylcellulose and Tianqing powder were mixed evenly and set aside. Then, 8g of nitric acid and 5g of citric acid were added to 600g of water and dissolved evenly. Then, calcium nitrate containing 10g of calcium oxide was added and dissolved evenly. The solution was poured into the above mixed powder and kneaded for 35 minutes. It was then extruded into strips, left to stand for 12 hours, dried at 110℃ for 6 hours, and then calcined in a muffle furnace at 600℃ for 5 hours to obtain a multifunctional acidic carrier.

[0083] An impregnation solution containing 58 g of MoO3 and 2 g of La2O3 was prepared using a soluble metal salt precursor. The solution volume was controlled at 140 mL. 1 g of urea and 1 g of diethyl aminomalonate were added to the impregnation solution and stirred until homogeneous. 140 g of a multifunctional acidic support was then loaded with an equal volume of the impregnation solution using a rotary drum spray method at 40 °C. The mixture was aged for 16 hours, dried at 100 °C for 4 hours, and calcined at 450 °C for 3 hours to obtain the oxidized catalyst. The XRD pattern of this oxidized catalyst did not show obvious characteristic diffraction peaks of the active component, indicating that the active component has a small particle size and good dispersibility.

[0084] The raw materials and conditions for evaluation are the same as in Example 1.

[0085] The evaluation results are shown in Table 2.

[0086] Example 3

[0087] 200g of ZSM-5 molecular sieve powder with a hydrogen form SiO2 / Al2O3 ratio of 250, 350g of Y molecular sieve powder with a hydrogen form SiO2 / Al2O3 ratio of 15, 300g of β molecular sieve powder with a hydrogen form SiO2 / Al2O3 ratio of 85, 150g of boehmite (8% silicon content, dry basis) (214g of boehmite raw powder with 30% water content), 15g each of methylcellulose and Tianqing powder were mixed evenly and set aside. Then, 8g of nitric acid and 5g of citric acid were added to 600g of water and dissolved evenly. Then, calcium nitrate containing 10g of calcium oxide was added and dissolved evenly. The solution was poured into the above mixed powder and kneaded for 35 minutes. It was then extruded into strips, left to stand for 12 hours, dried at 110℃ for 6 hours, and then calcined in a muffle furnace at 700℃ for 4 hours to obtain a multifunctional acidic carrier.

[0088] An impregnation solution containing 58 g of MoO3 and 2 g of La2O3 was prepared using a soluble metal salt precursor. The solution volume was controlled at 140 mL. 1 g of urea and 1 g of diethyl aminomalonate were added to the impregnation solution and stirred until homogeneous. 140 g of a multifunctional acidic support was then loaded with an equal volume of the impregnation solution using a rotary drum spray method at 40 °C. The mixture was aged for 16 hours, dried at 100 °C for 4 hours, and calcined at 450 °C for 3 hours to obtain the oxidized catalyst. The XRD pattern of this oxidized catalyst did not show obvious characteristic diffraction peaks of the active component, indicating that the active component has a small particle size and good dispersibility.

[0089] The raw materials and conditions for evaluation are the same as in Example 1.

[0090] The evaluation results are shown in Table 2.

[0091] Example 4

[0092] 130g of ZSM-5 molecular sieve powder with a hydrogen form SiO2 / Al2O3 ratio of 130, 145g of Y molecular sieve powder with a hydrogen form SiO2 / Al2O3 ratio of 7, 625g of β molecular sieve powder with a hydrogen form SiO2 / Al2O3 ratio of 20, 100g of boehmite (8% silicon content, dry basis) (143g of boehmite raw powder with 30% water content), 15g each of methylcellulose and Tianqing powder were mixed evenly and set aside. Then, 8g of nitric acid and 5g of citric acid were added to 600g of water and dissolved evenly. Then, calcium nitrate (calculated as 10g of calcium oxide) was added and dissolved evenly. The solution was poured into the above mixed powder and kneaded for 35 minutes. The mixture was extruded into strips, left to stand for 12 hours, dried at 110℃ for 6 hours, and then calcined in a muffle furnace at 600℃ for 5 hours to obtain a multifunctional acidic carrier.

[0093] An impregnation solution containing 58 g of MoO3 and 2 g of Eu2O3 was prepared using a soluble metal salt precursor. The solution volume was controlled at 140 mL. 1 g of urea and 1 g of diethyl aminomalonate were added to the impregnation solution and stirred until homogeneous. 140 g of a multifunctional acidic support was then loaded with an equal volume of the impregnation solution using a rotary drum spray method at 40 °C. The mixture was aged for 16 hours, dried at 100 °C for 4 hours, and calcined at 450 °C for 3 hours to obtain the oxidation catalyst.

[0094] The raw materials and conditions for evaluation are the same as in Example 1.

[0095] The evaluation results are shown in Table 2.

[0096] Example 5

[0097] 500g of ZSM-5 molecular sieve powder with a hydrogen form SiO2 / Al2O3 ratio of 130, 320g of Y molecular sieve powder with a hydrogen form SiO2 / Al2O3 ratio of 7, 80g of β molecular sieve powder with a hydrogen form SiO2 / Al2O3 ratio of 20, 100g of boehmite (8% silicon content, dry basis) (143g of boehmite raw powder with 30% water content), 15g each of methylcellulose and Tianqing powder were mixed evenly and set aside. Then, 8g of nitric acid and 5g of citric acid were added to 600g of water and dissolved evenly. Then, calcium nitrate (calculated as 10g of calcium oxide) was added and dissolved evenly. The solution was poured into the above mixed powder and kneaded for 35 minutes. The mixture was extruded into strips, left to stand for 12 hours, dried at 110℃ for 6 hours, and then calcined in a muffle furnace at 600℃ for 5 hours to obtain a multifunctional acidic carrier.

[0098] An impregnation solution containing 58 g of MoO3 and 2 g of La2O3 was prepared using a soluble metal salt precursor. The solution volume was controlled at 140 mL. 1 g of urea and 1 g of diethyl aminomalonate were added to the impregnation solution and stirred until homogeneous. 140 g of a multifunctional acidic support was then loaded with an equal volume of the impregnation solution using a rotary drum spray method at 40 °C. The mixture was aged for 16 hours, dried at 100 °C for 4 hours, and calcined at 450 °C for 3 hours to obtain the oxidized catalyst. The XRD pattern of this oxidized catalyst did not show obvious characteristic diffraction peaks of the active component, indicating that the active component has a small particle size and good dispersibility.

[0099] The raw materials and conditions for evaluation are the same as in Example 1.

[0100] The evaluation results are shown in Table 2.

[0101] Example 6

[0102] 130g of ZSM-5 molecular sieve powder with a hydrogen form SiO2 / Al2O3 ratio of 130, 145g of Y molecular sieve powder with a hydrogen form SiO2 / Al2O3 ratio of 7, 625g of β molecular sieve powder with a hydrogen form SiO2 / Al2O3 ratio of 20, 100g of boehmite (8% silicon content, dry basis) (143g of boehmite raw powder with 30% water content), 15g each of methylcellulose and Tianqing powder were mixed evenly and set aside. Then, 8g of nitric acid and 5g of citric acid were added to 600g of water and dissolved evenly. Then, calcium nitrate (calculated as 10g of calcium oxide) was added and dissolved evenly. The solution was poured into the above mixed powder and kneaded for 35 minutes. The mixture was extruded into strips, left to stand for 12 hours, dried at 110℃ for 6 hours, and then calcined in a muffle furnace at 600℃ for 5 hours to obtain a multifunctional acidic carrier.

[0103] An impregnation solution containing 58 g of MoO3 and 2 g of La2O3 was prepared using a soluble metal salt precursor. The solution volume was controlled at 140 mL. 1 g of urea and 1 g of tartaric acid were added to the impregnation solution and stirred until homogeneous. 140 g of a multifunctional acidic support was then loaded with an equal volume of the impregnation solution using a rotary drum spray method at 40 °C. The mixture was aged for 16 hours, dried at 100 °C for 4 hours, and calcined at 450 °C for 3 hours to obtain the oxidation catalyst. The XRD pattern of this oxidation catalyst did not show obvious characteristic diffraction peaks of the active component, indicating that the active component has a small particle size and good dispersibility.

[0104] The raw materials and conditions for evaluation are the same as in Example 1.

[0105] The evaluation results are shown in Table 2.

[0106] Example 7

[0107] 130g of ZSM-5 molecular sieve powder with a hydrogen form SiO2 / Al2O3 ratio of 130, 145g of Y molecular sieve powder with a hydrogen form SiO2 / Al2O3 ratio of 7, 625g of β molecular sieve powder with a hydrogen form SiO2 / Al2O3 ratio of 20, 100g of boehmite (8% silicon content, dry basis) (143g of boehmite raw powder with 30% water content), 15g each of methylcellulose and Tianqing powder were mixed evenly and set aside. Then, 8g of nitric acid and 5g of citric acid were added to 600g of water and dissolved evenly. Then, calcium nitrate (calculated as 10g of calcium oxide) was added and dissolved evenly. The solution was poured into the above mixed powder and kneaded for 35 minutes. The mixture was extruded into strips, left to stand for 12 hours, dried at 110℃ for 6 hours, and then calcined in a muffle furnace at 600℃ for 5 hours to obtain a multifunctional acidic carrier.

[0108] An impregnation solution containing 58 g of MoO3, 1 g of La2O3, and 1 g of Pr2O3 was prepared using a soluble metal precursor. The solution volume was controlled at 140 mL. 1 g of urea and 1 g of diethyl aminomalonate were added to the impregnation solution and stirred until homogeneous. 140 g of a multifunctional acidic support was then loaded with an equal volume of the impregnation solution using a rotary drum spray method at 40 °C. The mixture was aged for 16 hours, dried at 100 °C for 4 hours, and calcined at 450 °C for 3 hours to obtain the oxidation catalyst.

[0109] The raw materials and conditions for evaluation are the same as in Example 1.

[0110] The evaluation results are shown in Table 2.

[0111] Example 8

[0112] 130g of MCM-22 molecular sieve powder with a hydrogen form SiO2 / Al2O3 ratio of 130, 145g of Y molecular sieve powder with a hydrogen form SiO2 / Al2O3 ratio of 7, 625g of β molecular sieve powder with a hydrogen form SiO2 / Al2O3 ratio of 20, 100g of boehmite (8% silicon content, dry basis) (143g of boehmite raw powder with 30% water content), 15g each of methylcellulose and Tianqing powder were mixed evenly and set aside. Then, 8g of nitric acid and 5g of citric acid were added to 600g of water and dissolved evenly. Then, calcium nitrate (calculated as 10g of calcium oxide) was added and dissolved evenly. The solution was poured into the above mixed powder and kneaded for 35 minutes. The mixture was extruded into strips, left to stand for 12 hours, dried at 110℃ for 6 hours, and then calcined in a muffle furnace at 600℃ for 5 hours to obtain a multifunctional acidic carrier.

[0113] An impregnation solution containing 58 g of MoO3 and 2 g of La2O3 was prepared using a soluble metal salt precursor. The solution volume was controlled at 140 mL. 1 g of urea and 1 g of diethyl aminomalonate were added to the impregnation solution and stirred until homogeneous. 140 g of a multifunctional acidic support was then loaded with an equal volume of the impregnation solution using a rotary drum spray method at 40 °C. The mixture was aged for 16 hours, dried at 100 °C for 4 hours, and calcined at 450 °C for 3 hours to obtain the oxidized catalyst. The XRD pattern of this oxidized catalyst did not show obvious characteristic diffraction peaks of the active component, indicating that the active component has a small particle size and good dispersibility.

[0114] The raw materials and conditions for evaluation are the same as in Example 1.

[0115] The evaluation results are shown in Table 2.

[0116] Example 9

[0117] 130 g of ZSM-5 molecular sieve powder with a hydrogen form SiO2 / Al2O3 ratio of 130 (molar ratio, others the same) was selected; 145 g of MOR molecular sieve powder with a hydrogen form SiO2 / Al2O3 ratio of 7 was selected; 625 g of β molecular sieve powder with a hydrogen form SiO2 / Al2O3 ratio of 20 was selected; 100 g of pseudoboehmite (containing 8% silicon, dry basis) (143 g of pseudoboehmite raw powder containing 30% water by weight) was selected; 15 g each of methylcellulose and Tianqing powder were mixed evenly and set aside. Then, 8 g of nitric acid and 5 g of citric acid were added to 600 g of water and dissolved evenly. Then, calcium nitrate containing 10 g of calcium oxide was added and dissolved evenly. The solution was poured into the above mixed powder and kneaded for 35 minutes. It was extruded into strips and placed for 12 hours. After drying at 110°C for 6 hours, it was calcined in a muffle furnace at 600°C for 5 hours to obtain a multifunctional acidic carrier.

[0118] An impregnation solution containing 58 g of MoO3 and 2 g of La2O3 was prepared using a soluble metal salt precursor. The solution volume was controlled at 140 mL. 1 g of urea and 1 g of diethyl aminomalonate were added to the impregnation solution and stirred until homogeneous. 140 g of a multifunctional acidic support was then loaded with an equal volume of the impregnation solution using a rotary drum spray method at 40 °C. The mixture was aged for 16 hours, dried at 100 °C for 4 hours, and calcined at 450 °C for 3 hours to obtain the oxidized catalyst. The XRD pattern of this oxidized catalyst did not show obvious characteristic diffraction peaks of the active component, indicating that the active component has a small particle size and good dispersibility.

[0119] The raw materials and conditions for evaluation are the same as in Example 1.

[0120] The evaluation results are shown in Table 2.

[0121] Example 10

[0122] 130 g of ZSM-5 molecular sieve powder with a hydrogen form SiO2 / Al2O3 ratio of 130 (molar ratio, others the same) was selected; 145 g of Y molecular sieve powder with a hydrogen form SiO2 / Al2O3 ratio of 7 was selected; 625 g of ZSM-12 molecular sieve powder with a hydrogen form SiO2 / Al2O3 ratio of 20 was selected; 100 g of pseudoboehmite (containing 8% silicon, dry basis) (143 g of pseudoboehmite raw powder containing 30% water by weight) was selected; 15 g each of methylcellulose and Tianqing powder were mixed evenly and set aside. Then, 8 g of nitric acid and 5 g of citric acid were added to 600 g of water and dissolved evenly. Then, calcium nitrate (containing 10 g of calcium oxide) was added and dissolved evenly. The solution was poured into the above mixed powder and kneaded for 35 minutes. It was then extruded into strips, left to stand for 12 hours, dried at 110°C for 6 hours, and then calcined in a muffle furnace at 600°C for 5 hours to obtain a multifunctional acidic carrier.

[0123] An impregnation solution containing 58 g of MoO3 and 2 g of La2O3 was prepared using a soluble metal salt precursor. The solution volume was controlled at 140 mL. 1 g of urea and 1 g of diethyl aminomalonate were added to the impregnation solution and stirred until homogeneous. 140 g of a multifunctional acidic support was then loaded with an equal volume of the impregnation solution using a rotary drum spray method at 40 °C. The mixture was aged for 16 hours, dried at 100 °C for 4 hours, and calcined at 450 °C for 3 hours to obtain the oxidized catalyst. The XRD pattern of this oxidized catalyst did not show obvious characteristic diffraction peaks of the active component, indicating that the active component has a small particle size and good dispersibility.

[0124] The raw materials and conditions for evaluation are the same as in Example 1.

[0125] The evaluation results are shown in Table 2.

[0126] Example 11

[0127] 200g of ZSM-5 molecular sieve powder with a hydrogen form SiO2 / Al2O3 ratio of 130, 350g of Y molecular sieve powder with a hydrogen form SiO2 / Al2O3 ratio of 7, 300g of β molecular sieve powder with a hydrogen form SiO2 / Al2O3 ratio of 20, 150g of pseudoboehmite containing 8% by weight of silicon, and 15g each of methylcellulose and Tianqing powder were mixed evenly and set aside. Then, 8g of nitric acid and 5g of citric acid were added to 600g of water and dissolved evenly. Then, calcium nitrate containing 10g of calcium oxide was added and dissolved evenly. The solution was poured into the above mixed powder and kneaded for 35 minutes. The mixture was extruded into strips and left to stand for 12 hours. After drying at 110℃ for 6 hours, it was calcined in a muffle furnace at 600℃ for 5 hours to obtain a multifunctional acidic carrier.

[0128] An impregnation solution containing 58 g of MoO3 and 2 g of La2O3 was prepared using a soluble metal salt precursor. The solution volume was controlled at 140 mL. 1 g of urea and 1 g of citric acid were added to the impregnation solution and stirred until homogeneous. 140 g of a multifunctional acidic support was then loaded with an equal volume of the impregnation solution using a rotary drum spray method at 40 °C. After aging for 16 hours, drying at 100 °C for 4 hours, and calcining at 450 °C for 3 hours, the oxidized catalyst was obtained. The XRD pattern of this oxidized catalyst did not show obvious characteristic diffraction peaks of the active component, indicating that the active component has a small particle size and good dispersibility.

[0129] The raw materials and conditions for evaluation are the same as in Example 1.

[0130] The evaluation results are shown in Table 2.

[0131] Example 12

[0132] 850g of ZSM-5 molecular sieve powder with a hydrogen form SiO2 / Al2O3 ratio of 130, 150g of pseudoboehmite containing 8% by weight of silicon, 15g each of methylcellulose and Tianqing powder were mixed evenly and set aside. Then, 8g of nitric acid and 5g of citric acid were added to 600g of water and dissolved evenly. Then, calcium nitrate containing 10g of calcium oxide was added and dissolved evenly. The solution was poured into the above mixed powder and kneaded for 35 minutes. It was then extruded into strips, left to stand for 12 hours, dried at 110℃ for 6 hours, and then calcined in a muffle furnace at 600℃ for 5 hours to obtain a multifunctional acidic carrier.

[0133] An impregnation solution containing 58 g of MoO3 and 2 g of La2O3 was prepared using a soluble metal salt precursor. The solution volume was controlled at 140 mL. 1 g of urea and 1 g of diethyl aminomalonate were added to the impregnation solution and stirred until dissolved. 140 g of a multifunctional acidic support was then loaded with an equal volume of the impregnation solution using a rotary drum spray method at 40 °C. The mixture was aged for 16 hours, dried at 100 °C for 4 hours, and calcined at 450 °C for 3 hours to obtain the oxidation catalyst.

[0134] The evaluation materials and evaluation conditions are the same as in Example 1.

[0135] The evaluation results are shown in Table 2.

[0136] Comparative Example 1

[0137] 200g of ZSM-5 molecular sieve powder with a hydrogen form SiO2 / Al2O3 ratio of 130, 350g of Y molecular sieve powder with a hydrogen form SiO2 / Al2O3 ratio of 7, 300g of β molecular sieve powder with a hydrogen form SiO2 / Al2O3 ratio of 20, 150g of boehmite (containing 8% silicon, dry basis weight) (214g of boehmite raw powder containing 30% water by weight), 15g each of methylcellulose and Tianqing powder were mixed evenly and set aside. Then, 8g of nitric acid and 5g of citric acid were added to 600g of water and dissolved evenly. Then, calcium nitrate containing 10g of calcium oxide was added and dissolved evenly. The solution was poured into the above mixed powder and kneaded for 35 minutes. It was then extruded into strips, left to stand for 12 hours, dried at 110℃ for 6 hours, and then calcined in a muffle furnace at 600℃ for 5 hours to obtain a multifunctional acidic carrier.

[0138] An impregnation solution containing 16 g of MoO3 and 4 g of La2O3 was prepared using a soluble metal salt precursor. The solution volume was controlled at 180 mL. 1 g of urea and 1 g of diethyl aminomalonic acid were added to the impregnation solution and stirred until dissolved. 180 g of a multifunctional acidic support was used, and the impregnation solution was loaded onto the multifunctional acidic support at 40 °C using a rotary drum spray method. The solution was aged for 16 hours, dried at 100 °C for 4 hours, and calcined at 450 °C for 3 hours to obtain the oxidation catalyst.

[0139] The raw materials and conditions for evaluation are the same as in Example 1.

[0140] The evaluation results are shown in Table 2 and Figure 3 ,Depend on Figure 3 It can be seen that the yields of xylene and BTX are low, far lower than those in Example 1.

[0141] Comparative Example 2

[0142] 200g of ZSM-5 molecular sieve powder with a hydrogen form SiO2 / Al2O3 ratio of 130, 350g of Y molecular sieve powder with a hydrogen form SiO2 / Al2O3 ratio of 7, 300g of β molecular sieve powder with a hydrogen form SiO2 / Al2O3 ratio of 20, 150g of boehmite containing 8% by weight of silicon (214g of boehmite raw powder containing 30% by weight of water), 15g each of methylcellulose and Tianqing powder were mixed evenly and set aside. Then, 8g of nitric acid and 5g of citric acid were added to 600g of water and dissolved evenly. Then, calcium nitrate containing 10g of calcium oxide was added and dissolved evenly. The solution was poured into the above mixed powder and kneaded for 35 minutes. It was then extruded into strips, left to stand for 12 hours, dried at 110℃ for 6 hours, and then calcined in a muffle furnace at 600℃ for 5 hours to obtain a multifunctional acidic carrier.

[0143] A soluble metal salt precursor was prepared to contain 58 g of MoO3. The solution volume was controlled at 140 mL. 1 g of urea and 1 g of diethyl aminomalonic acid were added to the impregnation solution and stirred until dissolved. 140 g of a multifunctional acidic support was taken and loaded with an equal volume of the impregnation solution using a rotary drum spray method at 40 °C. The mixture was aged for 16 hours, dried at 100 °C for 4 hours, and calcined at 450 °C to obtain the oxidation catalyst.

[0144] The raw materials and conditions for evaluation are the same as in Example 1.

[0145] The evaluation results are shown in Table 2.

[0146] Table 1

[0147] Alkanes 5.3 7.1 Monocyclic alkanes 0.4 0.8 Dicycloalkanes 1.2 2.1 Tricycloalkane 0.8 1.7 Total cycloalkanes 2.4 4.6 Total saturated hydrocarbons 7.7 11.7 Alkylbenzene 7.5 19.5 Indene or tetrahydronaphthalene 7.7 42.4 Indigo 1.3 17.2 Total monocyclic aromatic hydrocarbons 16.5 79.1 Naphthalene 0.7 1.0 Naphthalene 39.9 2.7 Acenaparum 15.6 1.7 Acenaphthene 9.5 3.2 Total bicyclic aromatic hydrocarbons 65.7 8.6 Tricyclic aromatic hydrocarbons 10.1 0.6 Total aromatics 92.3 88.3 gelatin 0 0 Total volume 100 100 Initial boiling point, ℃ 171 165 Final boiling point, ℃ 375 370 S / ppm 3650 100 N / ppm 420 3

[0148] The above composition was determined using multidimensional chromatography. Table 1 shows that the total content of polycyclic aromatic hydrocarbons in the hydrogenated product is <10% by volume, and the total aromatic hydrocarbon content is >85% by volume.

[0149] Table 2

[0150] Example 1 9.3 28.6 26.9 0.7 27.6 64.8 34.5 Example 2 10.5 26.3 25.2 0.6 25.8 62.0 37.4 Example 3 10.2 27.0 25.9 0.6 26.5 63.1 36.3 Example 4 11.5 23.6 21.3 1.0 22.3 56.1 42.9 Example 5 28.0 18.5 9.3 0.9 10.2 55.8 43.3 Example 6 8.5 23.8 22.6 1.0 23.6 54.9 44.1 Example 7 10.7 27.5 27.1 0.8 27.9 65.3 33.9 Example 8 12.1 22.3 17.5 2.3 19.8 51.9 45.8 Example 9 13.5 22.3 16.9 3.5 20.4 52.7 43.8 Example 10 16.2 21.9 14.1 2.8 16.9 52.2 45.0 Example 11 6.3 18.6 17.7 1.4 19.1 42.6 56.0 Example 12 18.1 17.7 7.8 2.4 10.2 43.6 54.0 Comparative Example 1 18.6 14.7 4.9 0.8 5.7 38.2 61.0 Comparative Example 2 14.4 9.6 7.7 1.6 9.3 31.7 66.7

[0151] *C8 is the sum of X and EB;** Online response data for 400 hours.

[0152] Wherein, B refers to benzene. This was determined using chromatographic analysis.

[0153] T refers to toluene. This was determined using chromatographic analysis.

[0154] X refers to xylene. It was determined using chromatographic analysis.

[0155] EB refers to ethylbenzene. It was determined using chromatographic analysis.

[0156] BTX** refers to benzene, toluene, and xylene. It was determined using chromatographic analysis.

[0157] Other refers to components other than BTX and EB that were determined by chromatographic analysis;

[0158] The above components were determined by chromatographic analysis. As shown in Table 2, the purified product, after selective hydrocracking, yielded a high BTX product.

[0159] The endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and should be understood to include values ​​close to those ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, as well as individual point values, can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

Claims

1. A catalyst for hydrocracking of aromatic-rich refined heavy distillate oil, characterized in that, It includes the following components by weight percentage: a) 10~30% MoO3; b) 0.01~5% lanthanide metal oxides; wherein the lanthanide metals are selected from lanthanum and / or praseodymium; c) 89.99~65% acidic carrier; The acidic carrier contains a molecular sieve composition and a binder; the molecular sieve composition is a combination of H-ZSM-5, HY and H-β molecular sieves, and the weight ratio of H-ZSM-5, HY and H-β molecular sieves is 5~50:5~60:10~80. The SiO2 / Al2O3 molar ratio of H-ZSM-5 is 50~300; the SiO2 / Al2O3 molar ratio of HY is 3~30; and the SiO2 / Al2O3 molar ratio of H-β is 10~100.

2. The catalyst according to claim 1, wherein, The lanthanide metals are selected from lanthanum and praseodymium.

3. The catalyst according to claim 1 or 2, wherein, The weight ratio of H-ZSM-5, HY and H-β molecular sieves is 5~30:10~50:10~75.

4. The catalyst according to claim 1, wherein, The molecular sieve composition has a content of 70-95% by weight and a binder content of 5-30% by weight.

5. The catalyst according to claim 1 or 2, wherein, The method for preparing the acidic support includes: (1) Mix the binder source, H-ZSM-5, HY, H-β powder and optionally the matrix evenly to obtain mixture I; (2) Mix mixture I with acidic aqueous solution, knead and shape, dry and calcin.

6. The catalyst according to claim 5, wherein, The weight ratio of mixture I to the acidic aqueous solution is 100:5 to 100:150; and / or The roasting conditions include: a temperature of 450~700℃ and a time of 0.5~24h; and / or The binder source is selected from at least one of silica-containing boehmite, water glass, silica, and alumina sol; In mixture I, the matrix content is 0-5% by weight; and / or The matrix is ​​selected from at least one of methylcellulose, fennel powder, polyethylene glycol, and hydroxymethylcellulose; and / or The acidic substance in the acidic aqueous solution is selected from at least one of nitric acid, phosphoric acid, acetic acid, citric acid, and tartaric acid.

7. The catalyst according to claim 6, wherein, The weight ratio of mixture I to the acidic aqueous solution is 100:50 to 100:100; and / or The roasting conditions include: a time of 3 to 10 hours; and / or The pseudoboehmite contains 1-30% silicon by weight on a dry basis; and / or In mixture I, the matrix content is 2-4% by weight; and / or The matrix is ​​a mixture of methylcellulose and Tianqing powder, and the weight ratio of methylcellulose to Tianqing powder is 0.5~2:1; and / or The concentration of the acidic aqueous solution is 1 to 6 by weight.

8. The catalyst according to claim 7, wherein, The silicon content of pseudoboehmite is 5-20% by weight on a dry basis.

9. A method for preparing a hydrocracking catalyst for aromatic-rich refined heavy distillate oil according to any one of claims 1-8, characterized in that, The method includes: step S1, impregnating an impregnation solution prepared from a molybdenum source and a lanthanide metal source with an acidic support, followed by drying and calcination.

10. The preparation method according to claim 9, wherein, The impregnation solution contains 0.01 to 10% by weight of organic additives.

11. The preparation method according to claim 9 or 10, wherein, The impregnation solution contains 0.5-5% by weight of organic additives; and / or The organic additive is selected from one or more of diethyl aminomalonate, urea, citric acid, and tartaric acid.

12. The preparation method according to claim 11, wherein, The organic additive is selected from at least one of diethyl aminomalonate, urea, and citric acid.

13. The preparation method according to claim 12, wherein, The organic additives are urea and diethyl aminomalonate, and the weight ratio of urea to diethyl aminomalonate is 0.5~2:

1.

14. The preparation method according to claim 9 or 10, wherein, Immersion contact methods include: Implantation by spraying with equal volume; and / or The conditions for immersion contact include: immersion temperature of 10~60℃, and post-immersion resting time of 0.5~24h; and / or In step S1, the drying conditions include: a temperature of 30~130℃ and a time of 1~6h; and / or In step S1, the calcination conditions include: a temperature of 200~600℃ and a time of 0.5~24h.

15. The preparation method according to claim 14, wherein, In step S1, the calcination conditions include: a temperature of 300~500℃ and a time of 1~10h.

16. A method for hydrocracking of aromatic-rich refined heavy distillate oil, characterized in that, The method includes: sulfiding the catalyst according to any one of claims 1-8, and then hydrocracking the aromatic refined heavy distillate oil in the presence of the sulfidation catalyst and under a hydrogen atmosphere.

17. The method according to claim 16, wherein, The rich aromatic refined heavy distillate oil has a total aromatic content of more than 85% by volume, a final boiling point of less than 380°C, an initial boiling point of more than 160°C, a bicyclic and above polycyclic aromatic content of less than 10% by volume, a nitrogen content of less than 10ppm, and a sulfur content of more than 50ppm. The conditions for hydrocracking include: a pressure of 5-8 MPa and a volume hourly space velocity of 0.8-6 h⁻¹. -1 The inlet temperature is 260~500℃, and the volume ratio of hydrogen to distillate oil is 500~3000:1.

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