Hydrocracking catalysts, their preparation methods and applications, and methods for hydrocracking aromatic-rich cracked distillate oils.

Abstract

This invention relates to a hydrocracking catalyst, its preparation method and application, and a method for hydrocracking aromatic-rich distillate oils. The hydrocracking catalyst contains: a) 5-20% Ni; b) 0.01-5% CeO2; c) 55.00-89.99% ZSM-5; d) 5.00-20.00% binder; wherein the catalyst's TPR hydrogen atmosphere reduction temperature is below 420℃, and the dispersion of the active component Ni is greater than 8%. Through selective hydrocracking of tetrahydronaphthalene derivatives in the two-stage hydrocracking products, selective ring-opening and dealkylation of polycyclic aromatic hydrocarbons are carried out to generate BTX, while C2-C5 light hydrocarbons are produced as byproducts. For aromatic-rich distillate oils with a final boiling point below 280℃ and a total aromatic content greater than 90%, the liquid yield of the hydrocracking products is greater than 80%, and the liquid phase yield of BTX is greater than 55%.

Description

Technical Field

[0001] This invention relates to a hydrocracking catalyst, its preparation method and application, and a method for hydrocracking aromatic cracked distillate oil. Background Technology

[0002] Aromatic cracked distillate is a product of high-temperature condensation of feedstock and products during the steam cracking process of ethylene cracking. It mainly originates from the bottom of the quench oil tower and the bottom of the heavy fuel oil stripping tower. Aromatic cracked distillate is a heavy distillate oil (>205℃) rich in aromatics (aromatic content greater than 90%). Its main components are monocyclic and polycyclic aromatic compounds with short side chains, high carbon-to-hydrogen ratios, and low heavy metal and ash content. Ethylene tar also contains heterocyclic compounds containing elements such as N, S, and O. The yield of ethylene tar varies depending on the cracking feedstock, 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.

[0003] The yield of rich aromatic cracked distillate oil is relatively high, nearly 60%, in the sections between 170℃ and 300℃, followed by very heavy gum and asphaltenes. Simultaneously, rich aromatic cracked distillate oil has high sulfur content, high polycyclic aromatic hydrocarbon (PAH) content, and high density. The main components of the initial boiling point to 205℃ section are indene and its homologues; the 205–225℃ section contains naphthalene; the 225–245℃ section is mainly methylnaphthalene; the 245–300℃ section is mainly dimethylnaphthalene; the 300–360℃ section contains large amounts of anthracene, acenaphthene, phenanthrene, etc.; and the substances above 360℃ are mainly gums and asphaltenes with a high C-H ratio. Naphthalene-based and higher PAHs account for more than 60% of the total.

[0004] In foreign countries, aromatic cracked distillate oil is mainly used as a raw material for carbon black production. Several companies have also begun using cracked fuel oil to produce aromatic solvent oil. Currently, most of my country's ethylene tar is used as fuel or only undergoes primary processing, resulting in low utilization and poor economic benefits.

[0005] Cracked C9 fraction is also a type of aromatic cracked distillate, mainly derived from the cracked gasoline C9 fraction separated after passing through a BTX tower. Its aromatic content is as high as 70% or more, accounting for 11% to 22% of ethylene production. In China, the vast majority of cracked C9 is sold only as inexpensive primary raw material fuel oil or after preliminary processing.

[0006] How to utilize these low-value-added aromatic-rich cracked distillates is an urgent problem facing petrochemical scientists. Benzene (B), toluene (T), and xylene (X) are important basic organic chemical raw materials, widely used in the production of polyester, synthetic fibers, and other products, closely related to national economic development and people's basic needs. In recent years, demand has been strong and growing rapidly. Considering the abundant aromatic resources in ethylene tar and cracked C9, how to convert these low-value-added aromatic-rich cracked distillates, such as ethylene tar, into BTX through catalytic conversion technology will be both a huge opportunity and a significant challenge.

[0007] In the field of hydrotreating rich aromatic distillate oils, 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 oils. 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.

[0008] A comprehensive analysis of the above technologies reveals that they generally employ hydrogenation saturation and hydrocracking processes. This not only results in high hydrogen consumption for aromatic-rich cracked distillate oils with an aromatic content greater than 90%, but also wastes valuable aromatic resources.

[0009] Based on technologies such as hydrodesulfurization (HDS) and denitrification (HDN) of distillate oil, optimization and innovation are carried out. Through hydrotreating, cracking, alkyl transfer and other means, benzene (B), toluene (T) and xylene (X) can be produced to the maximum extent. Ethylene tar and C9 cracking can be fully utilized to increase their added value. Summary of the Invention

[0010] The purpose of this invention is to solve the problem of low BTX yield in the prior art, and to provide a hydrocracking catalyst, its preparation method and application, and a method for hydrocracking aromatic cracked distillate oil. Using the catalyst described in this invention, the liquid yield of hydrocracking products is greater than 80%, and the liquid BTX yield is greater than 55%.

[0011] The first aspect of the present invention provides a hydrocracking catalyst, which, by weight percentage, contains:

[0012] a)5~20% Ni;

[0013] b) 0.01–5% CeO2;

[0014] c) 55.00~89.99% ZSM-5;

[0015] d) 5-20% adhesive;

[0016] The catalyst has a TPR hydrogen atmosphere reduction temperature of less than 420°C and a dispersion of Ni greater than 8%.

[0017] A second aspect of the present invention provides the application of the catalyst described herein in the hydrocracking of aromatic cracked distillate oil.

[0018] A third aspect of the present invention provides a method for preparing the hydrocracking catalyst, the method comprising: contacting a composite support containing CeO2 and ZSM-5 with an impregnation solution containing a nickel source, a chelating surfactant and an alkanolamine for aging impregnation, a first drying, a first calcination and optionally reduction.

[0019] The fourth aspect of the present invention provides a method for hydrocracking a rich aromatic cracked distillate, the method comprising: using a rich aromatic cracked distillate with an aromatic content greater than 90% by weight and a final boiling point less than 280°C as raw material, and contacting it with a hydrocracking catalyst under a hydrogen atmosphere to carry out hydrocracking, wherein the hydrocracking catalyst is the hydrocracking catalyst described in the present invention.

[0020] The hydrocracking catalyst provided by the present invention incorporates chelating surfactants, such as alkyl ethylenediamine triacetic acid surfactants and alkanolamine organic compounds, during the preparation process to reduce the reduction temperature of the catalyst TPR in a hydrogen atmosphere. At the same time, cerium oxide is added to the support to improve the BTX yield.

[0021] The hydrocracking catalyst described in this invention is a selective hydrocracking catalyst. Through the selective hydrocracking of tetrahydronaphthalene series compounds, it selectively ring-opening and dealkylating of polycyclic aromatic hydrocarbons to generate BTX, while simultaneously producing C2-C5 light hydrocarbons as byproducts. For aromatic-rich distillate oils with a final boiling point of less than 280°C and a total aromatic content of more than 90% by weight, the liquid yield of hydrocracking products is greater than 80%, and the liquid phase yield of BTX is greater than 55%, achieving good technical results. Attached Figure Description

[0022] Figure 1 The XRD pattern of the hydrocracking catalyst in Example 1 of this invention;

[0023] Figure 2 The temperature-programmed reduction (TPR) spectrum of the hydrocracking catalyst in Example 1 of this invention is shown.

[0024] Figure 3 This is a product distribution-online time graph from Example 1 of the present invention;

[0025] Figure 4 The temperature-programmed reduction (TPR) spectrum of the catalyst described in Comparative Example 1;

[0026] Figure 5 The product distribution-online time plot is for Comparative Example 1. Detailed Implementation

[0027] 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.

[0028] The first aspect of the present invention provides a hydrocracking catalyst, which, by weight percentage, contains:

[0029] a)5~20% Ni;

[0030] b) 0.01–5% CeO2;

[0031] c) 55.00~89.99% ZSM-5;

[0032] d) 5-20% adhesive;

[0033] The catalyst has a TPR hydrogen atmosphere reduction temperature of less than 420°C and a dispersion of Ni greater than 8%.

[0034] In this invention, the dispersion of the active component Ni is tested by hydrogen-oxygen titration.

[0035]

[0036] In the formula: R-----the dispersion of Ni;

[0037] [Ni] ----- Number of nickel atoms on the surface;

[0038] [Ni] 总 -----Total number of nickel atoms;

[0039] V0-----Titration volume of hydrogen, mL;

[0040] N A -----Avogadro's constant (6.023) × 10 23 ;

[0041] W-----Sample mass, g;

[0042] P-----Mass fraction of nickel in the sample, %;

[0043] M ----- The atomic weight of nickel is 58.7.

[0044] In this invention, the test method for TPR hydrogen atmosphere reduction is hydrogen-oxygen titration.

[0045] The hydrocracking catalyst described in this invention is particularly suitable as a selective hydrocracking catalyst, capable of selectively hydrocracking tetrahydronaphthalene compounds and selectively ring-opening and dealkylating polycyclic aromatic hydrocarbons to generate BTX, while simultaneously producing C2-C5 light hydrocarbons as byproducts. For hydrocracking of aromatic-rich distillate oils with a final boiling point of less than 280°C and a total aromatic content of more than 90% by weight, the BTX liquid phase yield can be greater than 55%, demonstrating excellent hydrocracking performance.

[0046] According to a preferred embodiment of the present invention, the TPR hydrogen atmosphere reduction peak temperature of the catalyst is less than 400°C, preferably less than 390°C; the dispersion of the active component Ni in the catalyst is greater than 8%, preferably greater than 10%.

[0047] According to a preferred embodiment of the present invention, the catalyst contains, by weight percentage, 10-15% Ni, 0.5-3% CeO2, 8-15% binder, and the balance is ZSM-5.

[0048] In this invention, adding an anti-coking agent to the hydrocracking catalyst is a conventional choice in the art for the hydrogenation of components prone to coking. For this invention, alkaline earth metals such as calcium can be added to the hydrocracking catalyst as an anti-coking agent. According to a preferred embodiment of the invention, the catalyst preferably contains 0.1-3.0 wt% alkaline earth metal oxides, preferably calcium oxide and / or magnesium oxide.

[0049] In this invention, there are no special requirements for the adhesive. Conventional adhesives in the art are applicable to this invention. For this invention, the adhesive is selected from alumina and / or silicon oxide. Preferably, the adhesive source is selected from at least one of silica sol, water glass, boehmite, silica and alumina sol.

[0050] Catalysts possessing the aforementioned properties of this invention can all be used in this invention, and there are no special requirements for their preparation methods. According to a preferred embodiment of this invention, a method for preparing the hydrocracking catalyst is provided. This method includes: contacting a composite support containing CeO2 and ZSM-5 with an impregnation solution containing a nickel source, a chelating surfactant, and an alkanolamine for aging impregnation, followed by a first drying, a first calcination, and reduction. In this method, a chelating surfactant, such as an alkylethylenediamine triacetic acid surfactant or an alkanolamine organic compound, is added during the preparation of the hydrocracking catalyst to lower the reduction temperature of the catalyst under hydrogen atmosphere (TPR). Simultaneously, cerium oxide is added to the support to increase the BTX yield.

[0051] In this invention, adding an anti-coking agent to the hydrocracking catalyst is a conventional choice in the art for the hydrogenation of components prone to coking. For this invention, alkaline earth metals such as calcium can be added to the hydrocracking catalyst as an anti-coking agent. According to a preferred embodiment of the invention, the composite support containing CeO2 and ZSM-5 contains alkaline earth metal oxides, and the specific amount used is selected as needed.

[0052] In this invention, the range of nickel sources that can be selected is relatively wide. According to a preferred embodiment of this invention, the nickel source is selected from at least one of nickel nitrate, nickel acetate, and basic nickel carbonate.

[0053] In this invention, the range of alkanolamines that can be selected is relatively wide. According to a preferred embodiment of this invention, the alkanolamine is one or more of triethanolamine, diethanolamine, and ethanolamine. This can improve the selective hydrogenation effect of hydrocracking.

[0054] In this invention, the range of chelating surfactants is relatively wide. According to a preferred embodiment of the invention, the chelating surfactant is an alkylethylenediamine triacetic acid (EDTA) surfactant; preferably, the EDTA surfactant is selected from one or more of sodium N-dodecylethylenediamine triacetate, sodium N-hexadecylethylenediamine triacetate, and sodium N-octadecylethylenediamine triacetate. This improves the selective hydrogenation effect of hydrocracking.

[0055] According to a preferred embodiment of the present invention, the amount of chelating surfactant and the amount of alcohol amine in the impregnation solution are 0.01-5% based on the total weight of the impregnation solution. This improves the selective hydrogenation effect of hydrocracking.

[0056] In this invention, there are no special requirements for the impregnation method; conventional impregnation methods and conditions can be used. According to a preferred embodiment of this invention, the impregnation conditions include: equal volume impregnation, for example, impregnation by spraying.

[0057] According to a preferred embodiment of the present invention, the impregnation conditions include: an aging temperature of 10-80°C, preferably 15-20°C.

[0058] According to a preferred embodiment of the present invention, the aging time is 0.5 to 24 hours.

[0059] The present invention does not have special requirements for drying conditions, and commonly used drying conditions can be used in the present invention. According to a preferred embodiment of the present invention, the first drying conditions include a temperature of 30 to 200°C.

[0060] The present invention does not have special requirements for the roasting conditions, and commonly used roasting conditions can be used in the present invention. According to a preferred embodiment of the present invention, the conditions for the first roasting include: a temperature of 300 to 600°C and a time of 0.5 to 24 hours.

[0061] According to a preferred embodiment of the present invention, the catalyst is prepared by an equal-volume impregnation method, with an impregnation temperature of 10-80°C. The catalyst is impregnated onto the composite support by a spray method, and after impregnation, it is placed for 0.5-24 hours, dried at 30-200°C, and then calcined at 300-600°C for 0.5-24 hours to obtain the finished catalyst.

[0062] According to a preferred embodiment of the present invention, the preparation method of the composite carrier containing CeO2 and ZSM-5 includes: mixing and contacting ZSM-5 powder, optionally an alkaline earth metal source, a cerium source, a binder source, optionally an auxiliary agent source, and an acid solution for kneading, molding, second drying, and second calcination; thereby improving the selective hydrogenation effect of hydrocracking.

[0063] According to a preferred embodiment of the present invention, the preparation method of the composite carrier containing CeO2 and ZSM-5 preferably includes: mixing a binder source, ZSM-5 powder, and optionally an additive to obtain a first mixture; then mixing and contacting the first mixture with an acid solution containing a cerium source and optionally an alkaline earth metal source, followed by kneading, molding, second drying, and second calcination; preferably, the weight ratio of the first mixture to the acid solution is 100:5 to 100:100. This can improve the selective hydrogenation effect of hydrocracking.

[0064] According to a preferred embodiment of the present invention, the ZSM-5 powder is in the hydrogen form, and the SiO2 / Al2O3 molar ratio is 50-500, preferably 50-300, and more preferably 100-250.

[0065] This invention does not have any special requirements for the type of binder source. Commonly used binder sources can be used in this invention. According to a preferred embodiment of this invention, the binder source is selected from at least one of silica sol, water glass, boehmite, silica, and alumina sol, preferably at least one of boehmite, water glass, and silica sol.

[0066] This invention does not have special requirements for the type of auxiliary agent source; commonly used auxiliary agent sources can be used in this invention. According to a preferred embodiment of this invention, the auxiliary agent source is selected from at least one of methylcellulose, fennel powder, polyethylene glycol, calcium nitrate, magnesium nitrate, and hydroxymethylcellulose.

[0067] This invention does not have any special requirements for the type of acid source; any commonly used acid source can be used in this invention. According to a preferred embodiment of this invention, the acid substance of the acid solution is selected from at least one of nitric acid, phosphoric acid, acetic acid, citric acid, and tartaric acid.

[0068] According to a preferred embodiment of the present invention, the acid solution is an acidic aqueous solution with a concentration of 1 to 6% by weight. This improves the selective hydrogenation effect of hydrocracking.

[0069] In this invention, the alkaline earth metal source has no special requirements. For example, it can be a commonly used alkaline earth metal compound. For example, when the alkaline earth metal is calcium, it can be calcium nitrate. This is only an illustrative example and should not be used to limit the scope of this invention.

[0070] The present invention does not have special requirements for the roasting conditions. According to a preferred embodiment of the present invention, the second roasting conditions include: roasting at 450-750℃ for 0.5-24h, preferably roasting at 480-650℃ for 1-24h.

[0071] This invention provides an application of the catalyst described above in the hydrocracking of aromatic-rich cracked distillate oils. The catalyst of this invention is particularly suitable for the hydrocracking of aromatic-rich cracked distillate oils, exhibiting excellent selective hydrogenation performance.

[0072] This invention provides a method for hydrocracking rich aromatic cracked distillate oil. The method includes: using rich aromatic cracked distillate oil with an aromatic content greater than 90% by weight and a final boiling point less than 280°C as feedstock, and contacting it with a hydrocracking catalyst under a hydrogen atmosphere to carry out hydrocracking. The hydrocracking catalyst is the hydrocracking catalyst described in this invention. The hydrocracking of rich aromatic cracked distillate oil using this invention exhibits good selective hydrogenation effects.

[0073] In this invention, the range of selectable hydrocracking conditions is relatively wide. According to a preferred embodiment of this invention, the hydrocracking conditions include a pressure of 2 to 8 MPa.

[0074] In this invention, the range of selectable hydrocracking conditions is relatively wide. According to a preferred embodiment of this invention, the hydrocracking conditions include: space velocity of 0.8-6 h⁻¹. -1 .

[0075] In this invention, the range of selectable hydrocracking conditions is relatively wide. According to a preferred embodiment of this invention, the hydrocracking conditions include a temperature of 260–500°C.

[0076] According to a preferred embodiment of the present invention, aromatic-rich distillate oil with an aromatic content greater than 90% and a final boiling point less than 280°C is used as feedstock, and hydrocracking is carried out by contacting it with a hydrocracking catalyst under a hydrogen atmosphere; the hydrocracking conditions include: pressure 2-8 MPa; space velocity 0.8-6 h⁻¹. -1 The temperature ranges from 260 to 500°C. The hydrocracking catalyst described in this invention exhibits excellent hydrocracking performance for aromatic-rich distillate oils with a final boiling point below 280°C and a total aromatic content greater than 90% by weight, achieving a BTX liquid-phase yield greater than 55%.

[0077] To facilitate understanding of the present invention, the following embodiments are provided. However, these embodiments are merely for the purpose of helping to understand the present invention and should not be regarded as specific limitations of the present invention.

[0078] In the following examples, the evaluation method for hydrocracking of aromatic cracked distillate oil includes:

[0079] Aromatic cracking feedstock: distillation range 165-258℃, sulfur content = 0.5ppm, nitrogen content = 0.2ppm; feedstock composition: non-aromatic 5.08wt%; alkylbenzene 35.96wt%; indene 22.05wt%; tetrahydronaphthalene 32.37wt%; naphthalene 2.50wt%; benzene 0.204wt%.

[0080] Evaluation conditions: Inlet temperature T = 400℃; Volumetric space velocity V = 1.2; H2 / Oil(v / v) = 600; Pressure = 4.0MPa.

[0081] Liquid phase product yield = W 液体产物 / W 原料

[0082] W 液体产物 -----Weight of the liquid phase reaction products (in grams) after 24 hours of online processing;

[0083] W 原料 ----Feed rate of cracked distillate oil (online 24-hour operation), in grams.

[0084] The dispersion of the active component Ni was tested using the hydrogen-oxygen titration method, as follows:

[0085]

[0086] In the formula: R-----the dispersion of Ni;

[0087] [Ni] ----- Number of nickel atoms on the surface;

[0088] [Ni] 总 -----Total number of nickel atoms;

[0089] V0-----Titration volume of hydrogen, mL;

[0090] N A -----Avogadro's constant (6.023) × 10 23 ;

[0091] W-----Sample mass, g;

[0092] P-----Mass fraction of nickel in the sample, %;

[0093] M ----- The atomic weight of nickel is 58.7.

[0094] Methods for calculating the yield of liquid phase products

[0095] Liquid phase product yield = W 液体产物 / W 原料

[0096] W 液体产物 -----Weight of the liquid phase reaction products (in grams) after 24 hours of online processing;

[0097] W 原料 ----Feed rate of cracked distillate oil (online 24-hour operation), in grams.

[0098] Determination of the reduction peak temperature of the active component Ni

[0099] The TPR (Temperature Propagation) reduction method was adopted, with a hydrogen atmosphere used for reduction, and a heating rate of 10℃ / min, reaching 900℃.

[0100] Example 1

[0101] 850 g of ZSM-5 molecular sieve powder with a hydrogen form SiO2 / Al2O3 molar ratio of 150, 15 g of boehmite, 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 dissolved evenly in 600 g of water. Cerium nitrate (calculated as 8 g of cerium oxide) and calcium nitrate (calculated as 10 g of calcium oxide) were then added and dissolved evenly. The solution was poured into the above-mentioned mixed powder and kneaded for 35 minutes. The mixture was then extruded into strips, placed at 20°C for 12 hours, dried at 110°C for 6 hours, and finally calcined in a muffle furnace at 600°C for 5 hours to obtain the composite carrier, which had a water absorption rate of 102%. The raw material composition, reaction conditions, and water absorption rate of the composite carrier are shown in Tables 1 and 2.

[0102] A soluble metal salt precursor, basic nickel carbonate, was used to prepare an impregnation solution containing 30 g of Ni. The solution volume was controlled at 170 mL. 1 g of sodium N-dodecylethylenediaminetriacetate and 1 g of triethanolamine were added to the impregnation solution and stirred until homogeneous. 170 g of the composite support was then loaded with an equal volume of the impregnation solution using a rotary drum spray method. After aging for 16 hours, drying at 100℃ for 4 hours, and calcining at 400℃ for 4 hours, the oxidized catalyst was obtained. Reduction at 350℃ under a hydrogen atmosphere for 48 hours yielded the hydrocracking catalyst. The composition of the raw materials, reaction conditions, and water absorption rate of the composite support are shown in Tables 1 and 2. The XRD patterns of the hydrogen-form ZSM-5 powder, the composite support, and the catalyst are shown in [Table 1]. Figure 1 ,Depend on Figure 1 It can be seen that the structure of ZSM-5 was not affected during the support molding and catalyst active component loading process; the Ni dispersion of the reduced catalyst is shown in Table 5; the temperature-programmed reduction (TPR) spectrum of the oxidizing catalyst is shown in Table 5. Figure 2 ,Depend on Figure 2 It can be seen that the peak reduction temperature of the active component under hydrogen atmosphere is 376℃, indicating that the active component is well dispersed, easy to reduce, and has high activity.

[0103] The TPR reduction peak temperatures of the oxidizing catalysts are shown in Table 5. The catalyst preparation conditions are shown in Tables 3 and 4.

[0104] The evaluation results are shown in Table 5 and Figure 3 ,Depend on Figure 3 It can be seen that the catalyst activity remains basically unchanged after 500 hours of online operation.

[0105] Example 2

[0106] 850 g of ZSM-5 molecular sieve powder with a hydrogen form SiO2 / Al2O3 ratio of 100, 150 g of boehmite, 15 g each of methylcellulose and tianqing powder were selected and mixed evenly for later use. Then, 8 g of nitric acid and 5 g of citric acid were added to 600 g of water and dissolved evenly. Cerium nitrate (calculated as 40 g of cerium oxide) and calcium nitrate (calculated as 20 g of calcium oxide) were added and dissolved evenly. The solution was poured into the above mixed powder and kneaded for 35 minutes. The mixture was extruded into strips, placed at 15°C for 20 hours, dried at 100°C for 8 hours, and then calcined in a muffle furnace at 600°C for 5 hours to obtain the composite carrier. Its water absorption rate was 101%. The raw material composition, reaction conditions, and water absorption rate of the composite carrier are shown in Tables 1 and 2.

[0107] A soluble metal salt precursor, nickel nitrate, was used to prepare an impregnation solution containing 35 g of Ni. The solution volume was controlled at 165 mL. 1 g of sodium N-hexadecylethylenediaminetriacetate and 1 g of diethanolamine were added to the impregnation solution and stirred until homogeneous. 165 g of a composite support was then loaded with an equal volume of the impregnation solution using a rotary drum spray method. The mixture was aged at 15 °C for 20 hours, dried at 110 °C for 4 hours, and calcined at 380 °C for 4 hours to obtain the oxidizing catalyst. Reduction under a hydrogen atmosphere at 400 °C for 48 hours yielded the reducing catalyst. The Ni dispersion of the reducing catalyst is shown in Table 5. The catalyst preparation conditions are shown in Tables 3 and 4. The TPR (temperature programmed reduction) reduction peak temperatures of the oxidizing catalyst are shown in Table 5.

[0108] The evaluation results are shown in Table 5.

[0109] Example 3

[0110] 850 g of ZSM-5 molecular sieve powder with a hydrogen form SiO2 / Al2O3 ratio of 250, 150 g of boehmite, 15 g each of methylcellulose and Tianqing powder were selected and mixed evenly for later use. Then, 13 g of nitric acid was added to 600 g of water and dissolved evenly. Cerium nitrate (calculated as 20 g of cerium oxide) and calcium nitrate (calculated as 15 g of calcium oxide) were added and dissolved evenly. The solution was poured into the above mixed powder and kneaded for 35 minutes. The mixture was extruded into strips, placed at 20°C for 12 hours, dried at 110°C for 6 hours, and then calcined in a muffle furnace at 550°C for 6 hours to obtain the composite carrier. Its water absorption rate was 105%. The raw material composition, reaction conditions, and water absorption rate of the composite carrier are shown in Tables 1 and 2.

[0111] A soluble metal salt precursor, basic nickel carbonate, was used to prepare an impregnation solution containing 40 g of Ni. The solution volume was controlled at 160 mL. 1 g of sodium N-dodecylethylenediaminetriacetate, 0.8 g of ethanolamine, and 0.8 g of triethanolamine were added to the impregnation solution and stirred until homogeneous. 160 g of a composite support was then loaded with an equal volume of the impregnation solution using a rotary drum spray method. The mixture was aged at 20 °C for 16 hours, dried at 180 °C for 3 hours, and calcined at 600 °C for 2 hours to obtain the oxidizing catalyst. Reduction at 450 °C under a hydrogen atmosphere for 40 hours yielded the reducing catalyst. The Ni dispersion of the reducing catalyst is shown in Table 5. The catalyst preparation conditions are shown in Tables 3 and 4. The TPR (temperature programmed reduction) reduction peak temperatures of the oxidizing catalyst are shown in Table 5.

[0112] The evaluation results are shown in Table 5.

[0113] Example 4

[0114] 850 g of ZSM-5 molecular sieve powder with a hydrogen form SiO2 / Al2O3 ratio of 200, 150 g of boehmite, and 30 g of Tianqing powder were mixed evenly and set aside. 12 g of citric acid was added to 600 g of water and dissolved evenly. Then, cerium nitrate containing 20 g of cerium oxide was added and dissolved evenly. The solution was poured into the above mixed powder and kneaded for 35 minutes. The mixture was then extruded into strips, placed at 20°C for 12 hours, dried at 110°C for 6 hours, and then calcined in a muffle furnace at 480°C for 24 hours to obtain the composite carrier. Its water absorption rate was 102%. The composition of the raw materials, reaction conditions, and water absorption rate of the composite carrier are shown in Tables 1 and 2.

[0115] A soluble metal salt precursor, nickel acetate, was used to prepare an impregnation solution containing 20 g of Ni. The solution volume was controlled at 170 mL. 1 g of sodium N-hexadecylethylenediaminetriacetate and 2 g of diethanolamine were added to the impregnation solution and stirred until homogeneous. 170 g of a composite support was then loaded with an equal volume of the impregnation solution using a rotary drum spray method. The mixture was aged at 25 °C for 16 hours, dried at 180 °C for 2 hours, and calcined at 500 °C for 3 hours to obtain the oxidizing catalyst. Reduction at 400 °C under a hydrogen atmosphere for 40 hours yielded the reducing catalyst. The Ni dispersion of the reducing catalyst is shown in Table 5. The catalyst preparation conditions are shown in Tables 3 and 4. The TPR (temperature programmed reduction) reduction peak temperatures of the oxidizing catalyst are shown in Table 5.

[0116] The evaluation results are shown in Table 5.

[0117] Example 5

[0118] 900g of ZSM-5 molecular sieve powder with a hydrogen form SiO2 / Al2O3 ratio of 200, 100g of boehmite, and 30g of methylcellulose were mixed evenly and set aside. Then, 8g of nitric acid and 5g of citric acid were added to 550g of water and dissolved evenly. Cerium nitrate (calculated as 30g of cerium oxide) and calcium nitrate (calculated as 8g of calcium oxide) were added and dissolved evenly. The solution was poured into the above mixed powder and kneaded for 35 minutes. The mixture was then extruded into strips, placed at 20℃ for 24 hours, dried at 100℃ for 8 hours, and then calcined in a muffle furnace at 650℃ for 1 hour to obtain the composite carrier, which has a water absorption rate of 110%. The raw material composition, reaction conditions, and water absorption rate of the composite carrier are shown in Tables 1 and 2.

[0119] A soluble metal salt precursor, basic nickel carbonate, was used to prepare an impregnation solution containing 25 g of Ni. The solution volume was controlled at 175 mL. 1 g of sodium N-dodecylethylenediaminetriacetate, 0.4 g of ethanolamine, 0.4 g of diethanolamine, and 0.2 g of triethanolamine were added to the impregnation solution and stirred until homogeneous. An equal volume of the impregnation solution was loaded onto a 175 g composite support using a rotary drum spray method. The mixture was aged at 25 °C for 16 hours, dried at 100 °C for 10 hours, and calcined at 450 °C for 3 hours to obtain the oxidizing catalyst. Reduction at 350 °C under a hydrogen atmosphere for 52 hours yielded the reducing catalyst. The Ni dispersion of the reducing catalyst is shown in Table 5. The catalyst preparation conditions are shown in Tables 3 and 4. The TPR (temperature programmed reduction) reduction peak temperatures of the oxidizing catalyst are shown in Table 5.

[0120] The evaluation results are shown in Table 5.

[0121] Example 6

[0122] 900g of ZSM-5 molecular sieve powder with a hydrogen form SiO2 / Al2O3 ratio of 200, 100g of water glass, 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. Cerium nitrate containing 15g of cerium oxide was added and dissolved evenly. The solution was poured into the above mixed powder and kneaded for 35 minutes. The mixture was then extruded into strips, placed at 20℃ for 12 hours, dried at 120℃ for 5 hours, and then calcined in a muffle furnace at 500℃ for 10 hours to obtain the composite carrier, which has a water absorption rate of 108%. The raw material composition, reaction conditions, and water absorption rate of the composite carrier are shown in Tables 1 and 2.

[0123] A soluble metal salt precursor, basic nickel carbonate, was used to prepare an impregnation solution containing 30 g of Ni. The solution volume was controlled at 170 mL. 2 g of sodium N-hexadecylethylenediaminetriacetate and 2 g of ethanolamine were added to the impregnation solution and stirred until homogeneous. 170 g of a composite support was then loaded with an equal volume of the impregnation solution using a rotary drum spray method. The mixture was aged at 25 °C for 16 hours, dried at 100 °C for 4 hours, and calcined at 400 °C for 6 hours to obtain the oxidizing catalyst. Reduction at 400 °C under a hydrogen atmosphere for 42 hours yielded the reducing catalyst. The Ni dispersion of the reducing catalyst is shown in Table 5. The catalyst preparation conditions are shown in Tables 3 and 4. The TPR (temperature programmed reduction) reduction peak temperatures of the oxidizing catalyst are shown in Table 5.

[0124] The evaluation results are shown in Table 5.

[0125] Example 7

[0126] 800g of ZSM-5 molecular sieve powder with a hydrogen form SiO2 / Al2O3 ratio of 150, 200g of boehmite, and 15g each of methylcellulose and tianqing powder were selected and mixed evenly for later use. Then, 8g of nitric acid and 5g of citric acid were added to 550g of water and dissolved evenly. Cerium nitrate containing 15g of cerium 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, placed at 20℃ for 12 hours, dried at 110℃ for 6 hours, and then calcined in a muffle furnace at 600℃ for 4 hours to obtain the composite carrier. Its water absorption rate was 103%. The raw material composition, reaction conditions, and water absorption rate of the composite carrier are shown in Tables 1 and 2.

[0127] A soluble metal salt precursor, basic nickel carbonate, was used to prepare an impregnation solution containing 30 g of Ni. The solution volume was controlled at 170 mL. 4 g of sodium N-octadecylethylenediaminetriacetate and 0.5 g of diethanolamine were added to the impregnation solution and stirred until homogeneous. 170 g of a composite support was then loaded with an equal volume of the impregnation solution using a rotary drum spray method. The mixture was aged at 25 °C for 16 hours, dried at 100 °C for 4 hours, and calcined at 400 °C for 4 hours to obtain the oxidizing catalyst. Reduction at 400 °C under a hydrogen atmosphere for 42 hours yielded the reducing catalyst. The Ni dispersion of the reducing catalyst is shown in Table 5. The catalyst preparation conditions are shown in Tables 3 and 4. The TPR (temperature programmed reduction) reduction peak temperatures of the oxidizing catalyst are shown in Table 5.

[0128] The evaluation results are shown in Table 5.

[0129] Example 8

[0130] 900g of ZSM-5 molecular sieve powder with a hydrogen form SiO2 / Al2O3 ratio of 150, 100g of silica sol, and 15g each of methylcellulose and tianqing powder were selected and mixed evenly for later use. Then, 8g of nitric acid and 5g of citric acid were added to 550g of water and dissolved evenly. Cerium nitrate (calculated as 5g of cerium oxide) and calcium nitrate (calculated as 10g of calcium oxide) were added and dissolved evenly. The solution was poured into the above mixed powder and kneaded for 35 minutes. The mixture was extruded into strips, placed at 20℃ for 12 hours, dried at 110℃ for 6 hours, and then calcined in a muffle furnace at 600℃ for 4 hours to obtain the composite carrier. Its water absorption rate was 103%. The raw material composition, reaction conditions, and water absorption rate of the composite carrier are shown in Tables 1 and 2.

[0131] A soluble metal salt precursor, basic nickel carbonate, was used to prepare an impregnation solution containing 30 g of Ni. The solution volume was controlled at 170 mL. 0.02 g of sodium N-hexadecylethylenediaminetriacetate and 8 g of ethanolamine were added to the impregnation solution and stirred until homogeneous. 170 g of a composite support was then loaded with an equal volume of the impregnation solution using a rotary drum spray method. The mixture was aged at 25 °C for 16 hours, dried at 100 °C for 4 hours, and calcined at 400 °C for 4 hours to obtain the oxidizing catalyst. Reduction at 400 °C under a hydrogen atmosphere for 42 hours yielded the reducing catalyst. The Ni dispersion of the reducing catalyst is shown in Table 5. The catalyst preparation conditions are shown in Tables 3 and 4. The TPR (temperature programmed reduction) reduction peak temperatures of the oxidizing catalyst are shown in Table 5.

[0132] The evaluation results are shown in Table 5.

[0133] Example 9

[0134] 900g of ZSM-5 molecular sieve powder with a hydrogen form SiO2 / Al2O3 ratio of 150, 100g of boehmite, and 20g each of methylcellulose and tianqing powder were selected and mixed evenly for later use. Then, 8g of nitric acid and 5g of citric acid were added to 550g of water and dissolved evenly. Cerium nitrate (calculated as 10g of cerium oxide) and calcium nitrate (calculated as 10g of calcium oxide) were added and dissolved evenly. The solution was poured into the above mixed powder and kneaded for 35 minutes. The mixture was extruded into strips, placed at 20℃ for 12 hours, dried at 110℃ for 6 hours, and then calcined in a muffle furnace at 600℃ for 4 hours to obtain the composite carrier. Its water absorption rate was 101%. The raw material composition, reaction conditions, and water absorption rate of the composite carrier are shown in Tables 1 and 2.

[0135] A soluble metal salt precursor, basic nickel carbonate, was used to prepare an impregnation solution containing 30 g of Ni. The solution volume was controlled at 170 mL. 8 g of sodium N-dodecylethylenediaminetriacetate and 0.02 g of diethanolamine were added to the impregnation solution and stirred until homogeneous. 170 g of a composite support was then loaded with an equal volume of the impregnation solution using a rotary drum spray method. The mixture was aged at 25 °C for 16 hours, dried at 100 °C for 4 hours, and calcined at 400 °C for 4 hours to obtain the oxidizing catalyst. Reduction at 400 °C under a hydrogen atmosphere for 42 hours yielded the reducing catalyst. The Ni dispersion of the reducing catalyst is shown in Table 5. The catalyst preparation conditions are shown in Tables 3 and 4. The TPR (temperature programmed reduction) reduction peak temperatures of the oxidizing catalyst are shown in Table 5.

[0136] The evaluation results are shown in Table 5.

[0137] Example 10

[0138] 850 g of ZSM-5 molecular sieve powder with a hydrogen form SiO2 / Al2O3 molar ratio of 150, 15 g of boehmite, 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 dissolved evenly in 600 g of water. Cerium nitrate (calculated as 8 g of cerium oxide) and calcium nitrate (calculated as 10 g of calcium oxide) were then added and dissolved evenly. The solution was poured into the above-mentioned mixed powder and kneaded for 35 minutes. The mixture was then extruded into strips, placed at 20°C for 12 hours, dried at 110°C for 6 hours, and finally calcined in a muffle furnace at 600°C for 5 hours to obtain the composite carrier, which had a water absorption rate of 102%. The raw material composition, reaction conditions, and water absorption rate of the composite carrier are shown in Tables 1 and 2.

[0139] A soluble metal salt precursor, basic nickel carbonate, was used to prepare an impregnation solution containing 30 g of Ni. The solution volume was controlled at 170 mL. 0.0085 g of sodium N-dodecylethylenediaminetriacetate and 0.0085 g of triethanolamine were added to the impregnation solution and stirred until homogeneous. 170 g of a composite support was then loaded with an equal volume of the impregnation solution using a rotary drum spray method. After aging for 16 hours, drying at 100℃ for 4 hours, and calcining at 400℃ for 4 hours, the oxidizing catalyst was obtained. Reduction at 350℃ under a hydrogen atmosphere for 48 hours yielded the hydrocracking catalyst. The composition of the raw materials, reaction conditions, and water absorption rate of the composite support are shown in Tables 1 and 2. The Ni dispersion of the reduced catalyst is shown in Table 5.

[0140] The TPR reduction peak temperatures of the oxidizing catalysts are shown in Table 5. The catalyst preparation conditions are shown in Tables 3 and 4.

[0141] The evaluation results are shown in Table 5.

[0142] Example 11

[0143] 850 g of ZSM-5 molecular sieve powder with a hydrogen form SiO2 / Al2O3 molar ratio of 500, 15 g of boehmite, 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 dissolved evenly in 600 g of water. Cerium nitrate (calculated as 8 g of cerium oxide) and calcium nitrate (calculated as 10 g of calcium oxide) were then added and dissolved evenly. The solution was poured into the above-mentioned mixed powder and kneaded for 35 minutes. The mixture was then extruded into strips, placed at 20°C for 12 hours, dried at 110°C for 6 hours, and finally calcined in a muffle furnace at 600°C for 5 hours to obtain the composite carrier, which had a water absorption rate of 102%. The raw material composition, reaction conditions, and water absorption rate of the composite carrier are shown in Tables 1 and 2.

[0144] A soluble metal salt precursor, basic nickel carbonate, was used to prepare an impregnation solution containing 30 g of Ni. The solution volume was controlled at 170 mL. 1 g of sodium N-dodecylethylenediaminetriacetate and 1 g of triethanolamine were added to the impregnation solution and stirred until homogeneous. 170 g of a composite support was then loaded with an equal volume of the impregnation solution using a rotary drum spray method. After aging for 16 hours, drying at 100℃ for 4 hours, and calcining at 400℃ for 4 hours, the oxidizing catalyst was obtained. Reduction at 350℃ under a hydrogen atmosphere for 48 hours yielded the hydrocracking catalyst. The composition of the raw materials, reaction conditions, and water absorption rate of the composite support are shown in Tables 1 and 2. The Ni dispersion of the reduced catalyst is shown in Table 5.

[0145] The TPR reduction peak temperatures of the oxidizing catalysts are shown in Table 5. The catalyst preparation conditions are shown in Tables 3 and 4.

[0146] The evaluation results are shown in Table 5.

[0147] Example 12

[0148] 850 g of ZSM-5 molecular sieve powder with a hydrogen form SiO2 / Al2O3 molar ratio of 150, 15 g of boehmite, 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 dissolved evenly in 600 g of water, followed by the addition of calcium nitrate (calculated as 10 g of calcium oxide) and dissolved evenly. This solution was poured into the above-mentioned mixed powder and kneaded for 35 minutes. The mixture was then extruded into strips, placed at 20°C for 12 hours, dried at 110°C for 6 hours, and finally calcined in a muffle furnace at 600°C for 5 hours to obtain the composite carrier, which had a water absorption rate of 102%. The raw material composition, reaction conditions, and water absorption rate of the composite carrier are shown in Tables 1 and 2.

[0149] A solution containing 12 g of Ni and 8 g of cerium nitrate (calculated as cerium oxide) was prepared using the soluble metal salt precursor basic nickel carbonate. The solution volume was controlled at 188 mL. 1 g of N-dodecylethylenediaminetriacetic acid sodium salt and 1 g of triethanolamine were added to the impregnation solution and stirred until homogeneous. An equal volume of the impregnation solution was loaded onto a 188 g composite support using a rotary drum spray method. After aging for 16 hours, drying at 100 °C for 4 hours, and calcination at 400 °C for 4 hours, the oxidizing catalyst was obtained. Reduction at 350 °C under a hydrogen atmosphere for 48 hours yielded the hydrocracking catalyst. The Ni dispersion of the reduced catalyst is shown in Table 5. The TPR (temperature programmed reduction) peak temperatures of the oxidizing catalyst are shown in Table 5. The catalyst preparation conditions are shown in Tables 3 and 4.

[0150] Comparative Example 1

[0151] 850g of ZSM-5 molecular sieve powder with a hydrogen form SiO2 / Al2O3 ratio of 150, 15g of boehmite, 15g each of methylcellulose and tianqing powder were selected and mixed evenly for later use. Then, 8g of nitric acid and 5g of citric acid were added to 600g of water and dissolved evenly. Cerium nitrate containing 8g of cerium oxide and calcium nitrate containing 10g of calcium oxide were 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 for 5 hours to obtain the composite carrier with a water absorption rate of 102%.

[0152] A soluble metal salt precursor, basic nickel carbonate, was used to prepare an impregnation solution containing 30 g of Ni. The solution volume was controlled at 170 mL. 170 g of a composite support was loaded with an equal volume of the impregnation solution using a rotary drum spray method. After aging for 16 hours, drying at 100 °C for 4 hours, and calcination at 400 °C, the oxidizing catalyst was obtained. Reduction at 350 °C under a hydrogen atmosphere for 48 hours yielded the reducing catalyst. The preparation conditions of the composite support and catalyst are shown in Tables 1 and 2. The temperature-programmed reduction (TPR) spectrum of the oxidizing catalyst is shown in [Table 1]. Figure 4 ,Depend on Figure 4 It can be seen that the peak reduction temperature of the active component under hydrogen atmosphere is 442℃, indicating that the active component is poorly dispersed, difficult to reduce, and has low activity.

[0153] The evaluation results are shown in Table 5 and Figure 5 ,Depend on Figure 5 It can be seen that the catalyst exhibits poor reaction stability and rapid deactivation after 500 hours of online operation.

[0154] Comparative Example 2

[0155] 850g of ZSM-5 molecular sieve powder with a hydrogen form SiO2 / Al2O3 ratio of 150, 15g of boehmite, 15g each of methylcellulose and tianqing powder were selected and mixed evenly for later use. 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, placed at 20℃ for 12 hours, dried at 110℃ for 6 hours, and then calcined in a muffle furnace at 600℃ for 5 hours to obtain the composite carrier with a water absorption rate of 102%.

[0156] A soluble metal salt precursor, basic nickel carbonate, was used to prepare an impregnation solution containing 30 g of Ni. The solution volume was controlled at 170 mL. 1 g of sodium N-dodecylethylenediaminetriacetate and 1 g of triethanolamine were added to the impregnation solution and stirred until homogeneous. 170 g of a composite support was then loaded with an equal volume of the impregnation solution using a rotary drum spray method. The mixture was aged at 25 °C for 16 hours, dried at 100 °C for 4 hours, and calcined at 400 °C for 4 hours to obtain the oxidized catalyst. Reduction under a hydrogen atmosphere at 350 °C for 48 hours yielded the reduced catalyst. The Ni dispersion of the reduced catalyst is shown in Table 5. The preparation conditions of the composite support and catalyst are shown in Tables 1 and 2.

[0157] The evaluation results are shown in Table 5.

[0158] If the data in the following tables differs from the examples, the examples shall prevail.

[0159] Since the initial reactivity of catalysts is not significantly different, the differences in reactivity between different catalysts only become apparent after 100 hours of reaction. For example, the yields of target products such as benzene, toluene, and xylene have little impact on the liquid phase yield. Therefore, this invention uses the liquid phase yield at 400 hours as an example to illustrate the catalytic effect. In this invention, liquid yield *wt% (*product data is online data after 400 hours) refers to the liquid phase yield at 400 hours online.

[0160] Table 1

[0161]

[0162] Table 2

[0163]

[0164] Table 3

[0165]

[0166]

[0167] Table 4

[0168]

[0169] Table 5

[0170]

[0171]

[0172] *Product data are liquid phase yield data obtained online over 400 hours; **Heating rate was 10℃ / minute under hydrogen atmosphere.

[0173] As shown in Table 5, the catalyst prepared by the composite support and the new impregnation solution preparation method of the present invention has significantly lower TPR reduction peak temperature of active component nickel, significantly higher dispersion, and significantly improved reaction activity and stability compared with the traditional method.

[0174] The preferred embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combinations of various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.

Claims

1. A hydrocracking catalyst characterized in that, The catalyst contains, in percentage by weight: a) 5-20% Ni; b) 0.01-5% CeO2; c) 55.00-89.99% hydrogen type ZSM-5; d) 5-20% binder; wherein the TPR hydrogen atmosphere reduction temperature of the catalyst is lower than 400℃, and the dispersion of the active component Ni is greater than 8%.

2. The catalyst according to claim 1, wherein, in the catalyst, the content of Ni is 10-15% by weight, the content of CeO2 is 0.5-3% by weight, and the content of binder is 8-15% by weight, and the balance is hydrogen type ZSM-5.

3. The catalyst according to claim 1, wherein, the catalyst contains 0.1-3wt% of alkaline earth metal oxide.

4. The catalyst according to claim 3, wherein, the alkaline earth metal oxide is calcium oxide and / or magnesium oxide.

5. The catalyst according to claim 1, wherein, the TPR hydrogen atmosphere reduction temperature of the catalyst is lower than 390℃.

6. The catalyst according to claim 1, wherein, the dispersion of the active component Ni is greater than 10%.

7. Use of the catalyst according to any one of claims 1-6 in the hydrocracking of aromatic-rich cracking distillate oil.

8. Process for the preparation of the catalyst according to any one of claims 1 to 6, characterized in that, The method comprises: contacting a composite carrier containing CeO2 and hydrogen type ZSM-5 with an impregnation solution containing a nickel source, a chelating surfactant and an alcohol amine, aging, first drying, first calcination and optionally reduction; The preparation method of the composite carrier containing CeO2 and hydrogen type ZSM-5 comprises: mixing and kneading, molding, second drying and second calcination of hydrogen type ZSM-5 powder, optionally an alkaline earth metal source, a cerium source, a binder source, optionally an additive source and an acid solution.

9. The preparation method according to claim 8, wherein, the composite carrier containing CeO2 and hydrogen type ZSM-5 contains alkaline earth metal oxide; and / or the alcohol amine is one or more of triethanolamine, diethanolamine and ethanolamine; and / or the chelating surfactant is an alkyl ethylenediamine triacetate surfactant.

10. The preparation method according to claim 9, wherein, the alkyl ethylenediamine triacetate surfactant is selected from one or more of N-dodecyl ethylenediamine triacetate sodium, N-hexadecyl ethylenediamine triacetate sodium and N-octadecyl ethylenediamine triacetate sodium.

11. The preparation method according to claim 8, wherein, the amount of chelating surfactant in the impregnation solution is 0.01-5% and the amount of alcohol amine is 0.01-5%, based on the total weight of the impregnation solution.

12. The preparation method according to any one of claims 8-11, wherein, the impregnation conditions comprise: equal volume impregnation; and / or the aging temperature is 10-80℃, and / or the aging time is 0.5-24h; and / or the first drying conditions comprise: a temperature of 30-200℃; and / or the first calcination conditions comprise: a temperature of 300-600℃ and a time of 0.5-24h.

13. The method of making according to claim 12, wherein, The aging temperature is 15-20℃.

14. The preparation method according to claim 8, wherein, The preparation method of the composite carrier containing CeO2 and hydrogen type ZSM-5 comprises: mixing a binder source, hydrogen type ZSM-5 powder and optional additives to obtain a first mixture, and then mixing and contacting the first mixture with an acid liquid containing a cerium source and optionally an alkaline earth metal source to perform the kneading, molding, second drying and second calcination.

15. The method of making according to claim 14, wherein, The weight ratio of the first mixture to the acid liquid is 100:5-100:

100.

16. The preparation method according to claim 8, wherein, the SiO2 / Al2O3 molar ratio of the hydrogen type ZSM-5 powder is 50-500; and / or the binder source is selected from at least one of silica sol, water glass, pseudo-boehmite, white carbon black and aluminum sol; and / or the additive source is selected from at least one of methyl cellulose, tianq powder, polyethylene glycol, calcium nitrate, magnesium nitrate and hydroxymethyl cellulose; and / or the acid substance of the acid liquid is selected from at least one of nitric acid, phosphoric acid, acetic acid, citric acid and tartaric acid; and / or the acid liquid is an acidic aqueous solution with a concentration of 1-6% by weight; and / or the second calcination conditions comprise: calcination at 450-750℃ for 0.5-24h.

17. The preparation method according to claim 16, wherein, the SiO2 / Al2O3 molar ratio of the hydrogen type ZSM-5 powder is 50-300; and / or the binder source is selected from at least one of pseudo-boehmite, water glass and silica sol; and / or the second calcination conditions comprise: calcination at 480-650℃ for 1-24h.

18. The preparation method according to claim 17, wherein, the SiO2 / Al2O3 molar ratio of the hydrogen type ZSM-5 powder is 100-250.

19. A process for hydrocracking of a rich-aromatics pyrolysis distillate characterized by, The method comprises: using a rich aromatic pyrolysis distillate oil with an aromatic content of greater than 90% by weight and a final boiling point of less than 280℃ as a raw material, and performing hydrocracking under a hydrogen atmosphere with a hydrocracking catalyst, wherein the hydrocracking catalyst is the hydrocracking catalyst according to any one of claims 1-6.

20. The method of claim 19, wherein, The hydrocracking conditions comprise: Pressure 2-8 Mpa; and / or space velocity 0.8-6 h -1 Temperature 260-500 °C.

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