A modified y-type molecular sieve, a preparation method and application thereof

Abstract

The application discloses a modified Y-type molecular sieve, a preparation method and application thereof. The pyridine infrared acid content of the modified Y-type molecular sieve is 0.65-1.03 mmol / g, preferably 0.75-0.88 mmol / g; and the ratio of the pyridine infrared acid content to the ammonia gas infrared acid content is 0.8-0.95, preferably 0.85-0.92. Compared with the existing molecular sieve, the modified Y-type molecular sieve has high pyridine acid content and high mesopore volume, macromolecular materials can effectively contact the pyridine acid sites, and the hydrogenation cracking reaction of polycyclic aromatic hydrocarbons in catalytic diesel oil is facilitated, and secondary cracking is reduced.

Description

TECHNICAL FIELD

[0001] The present application belongs to the field of molecular sieve, and relates to a modified Y-type molecular sieve, a preparation method and application thereof, in particular to a modified Y-type molecular sieve, a preparation method and application thereof in hydrocracking. BACKGROUND

[0002] Y-type molecular sieve, as a kind of large-pore molecular sieve, is widely used in catalytic cracking, hydrocracking, isomerization and other oil refining fields due to its special acid properties and pore structure, and has been applied for more than 50 years. The Y-type molecular sieve has a pore opening composed of a twelve-membered ring, an effective pore opening diameter of 0.74 nm, and an internal cavity volume of up to 50%, which is very suitable for being used as an active component for cracking reactions. In recent years, the trend of crude oil becoming heavier and poorer has gradually become obvious, and the pore size of the traditional Y-type molecular sieve is limited, so that large molecule reactants cannot enter the inside of the molecular sieve and can only react on the limited outer surface, greatly reducing the catalytic efficiency. At the same time, due to the large grain size and long pore of the traditional Y-type molecular sieve, carbon deposition is easily formed during the reaction, which also shortens the service life of the catalyst to a certain extent. Nanocrystallization of the Y-type molecular sieve can expose more acid sites, which is an effective means to solve the diffusion efficiency of large molecules. Although the nanometer Y-type molecular sieve solves the diffusion problem, it has the problem of separation difficulty in actual industrial production. Self-assembly of nanometer molecular sieve to form aggregates with a cluster-like morphology not only retains the advantages of nanometer zeolite, but also overcomes the problem of separation difficulty after synthesis, and has become a research direction in this field. At present, there are some literatures reported.

[0003] Yu Jiao et al. reported a synthesis method of nanometer self-assembled Y-type molecular sieve in Chemical Physics Letters, Vol. 749, "Nanocrystal zeolite Y assembly synthesized with CTAB under low gelling and aging temperature". The literature uses CTAB as a template to synthesize molecular sieve, and the specific surface area is 824 m 2 / g, the external specific surface area is 163 m 2 / g, the grain size is 40 nm, and the framework silica-alumina ratio is 4.4.

[0004] Ting Tang et al. in RSC Advances, Vol. 7, No. 13, P 7711-7717, "Organic template-free synthesis of zeolite Y nanoparticle assemblies and their application in the catalysis of the Ritter reaction" reported a method for synthesizing nano self-assembled Y zeolite under template-free conditions, which is synthesized at high alkalinity, and the molecular sieve crystal can be controlled at nanoscale, with a specific surface area of 647 m 2 / g, and an external specific surface area of 111 m 2 / g.

[0005] CN107055567 A discloses a method for preparing nano Y zeolite aggregates, which uses water glass as a silicon source, dissolves it in a sodium hydroxide solution, then adds an aluminum source solution to the silicon source, stirs it uniformly, and then crystallizes at 60-100°C for 12-36h to obtain nano Y zeolite aggregates. The specific surface area is 650-780 m 2 / g, micropore volume 0.23-0.27 ml / g, and mesopore volume 0.16-0.25 ml / g.

[0006] CN108046287 A discloses a method for synthesizing nano self-assembled zeolites using long-chain alkyl trimethyl ammonium bromide surfactant as a template agent, which forms a gel under a relatively concentrated ingredient system, and is crystallized by controlling the gelation, aging, and crystallization temperature at low temperature.

[0007] Although many nano Y zeolite self-assemblies and their preparation methods are disclosed in the prior art, nano Y zeolite needs to be modified before it can be used as an acidic cracking material, but during the modification process, the nano Y zeolite is prone to pore damage, which reduces the pyridine acid content and prevents its normal application. SUMMARY

[0008] In view of the deficiencies of the prior art, the present application discloses a modified Y-type molecular sieve, a preparation method thereof, and an application. The modified Y-type molecular sieve has a high pyridine acid content and a high mesopore volume compared to existing molecular sieves, and macromolecular materials can effectively contact with pyridine acid sites, which is beneficial to the hydrogenation cracking reaction of polycyclic aromatic hydrocarbons in catalytic diesel oil and reduces secondary cracking.

[0009] A modified Y-type molecular sieve has a pyridine infrared acid content of 0.65-1.03 mmol / g, preferably 0.75-0.88 mmol / g, and a ratio of pyridine infrared acid content to ammonia gas infrared acid content of 0.8-0.95, preferably 0.85-0.92.

[0010] The total pore volume of the modified Y-type molecular sieve is 0.63-0.78 mL / g, preferably 0.67-0.76 mL / g; the mesopore volume is 0.35-0.49 mL / g, preferably 0.38-0.46 mL / g.

[0011] The specific surface area of the modified Y-type molecular sieve is 750-870 m 2 / g, preferably 780-840 m 2 / g.

[0012] The relative crystallinity of the modified Y-type molecular sieve is 75-94%, preferably 80-90%.

[0013] The framework silica-alumina ratio SiO2 / Al2O3 of the modified Y-type molecular sieve is 10-30, preferably 12-20.

[0014] A modified Y-type molecular sieve, the method comprising the following steps:

[0015] (1) synthesis of the nano self-assembled Y-type molecular sieve, the synthesis method comprising:

[0016] ① a mixture containing an alkali source, a sodium source, an aluminum source, a tetramethylammonium template, a cationic surfactant, and a silicon source is aged and crystallized to obtain a crystallized material;

[0017] ② the crystallized material is mixed with tetramethylammonium fluoride (TMA) F, a silicon source, and water, and then crystallized, washed, filtered, and dried to obtain the final nano self-assembled Y-type molecular sieve;

[0018] (2) the nano self-assembled Y-type molecular sieve in step (1) is subjected to acid treatment;

[0019] (3) the nano self-assembled Y-type molecular sieve after acid treatment in step (2) is calcined under an inert atmosphere;

[0020] (4) the nano self-assembled Y-type molecular sieve after calcination under an inert atmosphere in step (3) is subjected to ammonium exchange;

[0021] (5) the nano self-assembled Y-type molecular sieve after ammonium exchange in step (4) is subjected to high-temperature hydrothermal treatment;

[0022] (6) the nano self-assembled Y-type molecular sieve after high-temperature hydrothermal treatment in step (5) is calcined in an oxygen-containing atmosphere;

[0023] (7) the nano self-assembled Y-type molecular sieve obtained by calcination in step (6) is subjected to alkali treatment;

[0024] (8) The nano self-assembled Y-type molecular sieve in step (7) is treated with alkali, and then subjected to ammonium exchange, washing, filtration, drying, and air calcination to obtain the final modified Y molecular sieve.

[0025] In step (1) ① of the method, the concentration of the cationic surfactant in the mixed material is 0.040-0.072 mol / L, preferably 0.045-0.067 mol / L, and more preferably 0.050-0.061 mol / L; and the molar ratio of the tetramethylammonium template agent to the cationic surfactant is 50-110, preferably 60-90, and more preferably 65-85. By controlling the molar ratio of the cationic surfactant to the tetramethylammonium template agent in the solution, a nano Y-type molecular sieve with a high silicon-to-aluminum ratio can be prepared. The molar ratio of the materials in the mixed material is: Al2O3: (6.5-12.5)SiO2: (0.1-1.0)Na2O: (6.0-10.0)(TMA)2O: (160-310)H2O: (0.1-0.4) CTAB; preferably Al2O3: (7.2-10.0)SiO2: (0.3-0.7)Na2O: (7.7-9.0)(TMA)2O: (180-270)H2O: (0.15-0.30) CTAB. The alkali source is one or more of sodium hydroxide, tetramethylammonium hydroxide solution TMAOH, and tetramethylammonium hydroxide pentahydrate. The aluminum source is one or more of aluminum isopropoxide, aluminum powder, sodium metaaluminate, and aluminum sulfate octadecahydrate. The silicon source is one or more of silica sol, sodium silicate, tetraethyl orthosilicate, nano silicon dioxide, and water glass. The sodium source is one or more of sodium hydroxide, sodium chloride, and sodium bromide. The tetramethylammonium template agent is one or more of tetramethylammonium hydroxide solution, tetramethylammonium hydroxide pentahydrate, tetramethylammonium bromide, and tetramethylammonium chloride. The cationic surfactant is one or more of dodecyltrimethylammonium bromide DTAB, hexadecyltrimethylammonium bromide CTAB, and octadecyltrimethylammonium bromide STAB. The aging temperature is 25-35℃, preferably 28-31℃; the aging time is 20-40 h, preferably 25-35 h; the crystallization temperature is 80-100℃, preferably 85-95℃; and the crystallization time is 60-100 h, preferably 70-90 h.

[0026] In step (1) 2 of the method, after the crystallized material is added with tetramethylammonium fluoride, a silicon source and water, the molar ratio of the material in the solution is Al2O3:(14-20)SiO2:(0.1-1.0)Na2O:(6-10)(TMA)2O:(4-8)(TMA)F:(320-540)H2O:(0.1-0.4)CTAB; preferably Al2O3:(15-18)SiO2:(0.30-0.7)Na2O:(7.7-9.0)(TMA)2O:(5.2-6.6)(TMA)F:(380-430)H2O:(0.15-0.30)CTAB. The crystallization temperature is 85-105℃, preferably 90-101℃; the crystallization time is 30-70h, preferably 40-60h. The drying temperature of the molecular sieve is 80-120℃, the time is 7-13h, the calcination temperature is 450-550℃, and the time is 3-5h.

[0027] In step (1) 2 of the method, the nano self-assembled molecular sieve is an aggregate formed by clusters of nano crystalline grains, the size of the nano crystalline grains is 40-100 nm, preferably 60-85 nm; the size of the aggregate is 1.3 μm-3.5 μm, preferably 1.8 μm-2.8 μm; the framework silica-alumina ratio SiO2 / Al2O3 is 8.0-13.0, preferably 10.0-12.0. The specific surface area of the molecular sieve is 800-930m 2 / g, preferably 840-900m 2 / g, the external specific surface area is 100-170m 2 / g, preferably 140-160m 2 / g.

[0028] In step (2) of the method, the acid used for acid treatment is an inorganic acid or an organic acid, or a combination of the two. When inorganic acid and organic acid are used in combination, the inorganic acid can be used first, followed by the organic acid, or the organic acid can be used first, followed by the inorganic acid. The inorganic acid used can be one or more of nitric acid, hydrochloric acid, and sulfuric acid, and the organic acid can be one or more of citric acid, oxalic acid, EDTA, and tartaric acid. In the solution used for acid treatment, the acid concentration is 0.1-1.0 mol / L, preferably 0.3-0.5 mol / L; the acid treatment temperature is 20-90℃, preferably 40-70℃. The acid treatment time is 0.5-6h, preferably 2-3h. The solid-liquid volume ratio during acid treatment is 1:5-1:20, preferably 1:10-1:15.

[0029] In step (3) of the method, the inert gas used for calcination is one or a mixture of several of N2, He, and Ar, the calcination temperature is 500-600℃, preferably 530-570℃, and the calcination time is 2-7h, preferably 4-6h.

[0030] In step (4) of the method, the ammonium salt used in the ammonium exchange is one or more of ammonium nitrate, ammonium chloride, ammonium sulfate, ammonium acetate, and ammonium oxalate, the ammonium exchange temperature is 40-96°C, preferably 60-80°C, the exchange times is 1-3 times, and the ammonium salt concentration is 0.5-3.0 mol / L. The solid-liquid ratio in the ammonium exchange is 1:5-1:20, preferably 1:8-1:15.

[0031] In step (5) of the method, the high-temperature hydrothermal treatment temperature is 500-700°C, preferably 550-650°C; the hydrothermal pressure is 0.05-0.20 MPa, preferably 0.08-0.15 MPa; and the hydrothermal treatment time is 1-8 h, preferably 3-5 h.

[0032] In step (6) of the method, the calcination atmosphere is air or a mixed atmosphere of O2 and one or more of N2, He, and Ar. The calcination temperature is 450-600°C, preferably 500-550°C, and the calcination time is 3-6 h, preferably 4-5 h.

[0033] In step (7) of the method, the alkali used in the alkali treatment is sodium hydroxide, the alkali concentration is 0.3-1.0 mol / L, preferably 0.5-0.7 mol / L; the alkali treatment temperature is 20-90°C, preferably 40-70°C; and the alkali treatment time is 0.5-5 h, preferably 2-3 h. The solid-liquid volume ratio in the alkali treatment is 1:5-1:20, preferably 1:10-1:15.

[0034] In step (8) of the method, the ammonium salt used in the ammonium exchange is one or more of ammonium nitrate, ammonium chloride, ammonium sulfate, ammonium acetate, and ammonium oxalate, the ammonium exchange temperature is 40-96°C, preferably 70-80°C, the exchange times is 1-2 times, and the ammonium salt concentration is 2.0-3.0 mol / L. The solid-liquid ratio in the ammonium exchange is 1:5-1:20, preferably 1:8-1:15.

[0035] A hydrocracking catalyst, which contains 30-70% of the modified nanocluster Y molecular sieve, preferably 40-60% of the modified nanocluster Y molecular sieve, and 3-35 wt%, preferably 5-25 wt% of active metal oxides, the active metal being a Group VIB metal and / or a Group VIII metal, the Group VIB metal being preferably Mo or W, and the Group VIII metal being preferably Co or Ni, based on the weight of the hydrocracking catalyst.

[0036] A preparation method of a hydrocracking catalyst, which adopts a kneading method or an impregnation method. The kneading method is to mix the modified Y molecular sieve, alumina and / or amorphous silica-alumina, active metal oxide and / or active metal salt uniformly, then add dilute nitric acid solution and distilled water, and obtain the shaped catalyst after kneading and extruding. The shaped catalyst is dried and calcined to obtain the final hydrocracking catalyst. The impregnation method is to load active metal on the modified Y molecular sieve, alumina and / or amorphous silica-alumina after shaping, and obtain the final hydrocracking catalyst after drying and calcining.

[0037] In the preparation method of the hydrocracking catalyst, the drying temperature of the shaped catalyst is 100-150 DEG C, and the calcination temperature of the catalyst is 450-550 DEG C.

[0038] The hydrocracking catalyst is used for the hydrocracking reaction of catalytic diesel oil, and the reaction conditions are as follows: the reaction temperature is 350-430 DEG C, the reaction pressure is 5-10 MPa, the cracking reaction volume space velocity is 0.5-2.0 h -1 , and the hydrogen / oil ratio is 800:1-1400:1.

[0039] Compared with the prior art, the modified Y molecular sieve has the following advantages:

[0040] 1. The Y molecular sieve nanocluster precursor is synthesized under the double template system of cationic surfactant and tetramethylammonium ion (TMA + ), and the electrostatic repulsion force exists between the cationic hydrophilic end and TMA + . By controlling the molar ratio of the tetramethylammonium template and the cationic surfactant in the solution, the TMA + is more easily entered into the sodalite cage of the molecular sieve, and the nanocluster Y type molecular sieve precursor with high silica-alumina ratio is prepared. The sodalite cage structure wrapped with TMA + is stable, and the sodalite cage structure without TMA + is poor in stability. Under the action of fluoride ions, the Si-O-Al bond is opened, and silicon atoms and aluminum atoms form a fluoride complex. Under the joint action of Y molecular sieve crystal grains, Na + and TMA + , the silicon and aluminum are recombined, and a part of TMA + is wrapped in the sodalite cage, and the silica-alumina ratio of the molecular sieve framework is further improved.

[0041] 2. In the acid treatment process of the nanocluster Y molecular sieve, the aluminum atoms on the sodalite cage wrapped with TMA + are stable and not easy to be dealuminated. The acid treatment preferentially removes part of the aluminum atoms on the supercage of the Y molecular sieve, and hydroxyl vacancies appear at the dealuminated positions. The molecular sieve after acid dealuminization is calcined in an inert gas to remove the TMA+ Carbonization. Since the TMA + atoms in the sodalite cages have been carbonized and lost their protection to the aluminum atoms, during the subsequent high temperature hydrothermal treatment, the aluminum atoms in the sodalite cages are oriented to migrate to the hydroxyl holes in the Y supercage. Then the molecular sieve is calcined in air atmosphere to remove the carbon in the sodalite cages, and subsequently the silicon atoms in the sodalite cages are removed by alkali treatment to open the Y molecular sieve wall, so that the acid sites of the Y molecular sieve are more accessible to the macromolecular reactants. The metal ions in the alkali treatment process are exchanged by ammonium, and after drying and calcination, the final modified Y molecular sieve is obtained. The nano-cluster Y molecular sieve modified by the method realizes the concentration of aluminum atoms in the supercage which is easy to approach the reactant molecules, and further improves the accessibility of the acid sites of the nano-cluster Y molecular sieve, the diffusion and the catalytic efficiency. BRIEF DESCRIPTION OF DRAWINGS

[0042] Figure 1 XRD diffraction pattern of the Y-type molecular sieve prepared for Example 1.

[0043] Figure 2 SEM image of the Y-type molecular sieve prepared for Example 1 at 30k magnification.

[0044] Figure 3 SEM image of the Y-type molecular sieve prepared for Example 1 at 10k magnification. DETAILED DESCRIPTION

[0045] The characterization method of the nano Y-type molecular sieve self-assembly body in the present application is as follows:

[0046] The relative crystallinity of the Y molecular sieve sample after modification treatment is determined by X-ray diffraction method, and the method is determined according to the China Petroleum Chemical Industry Standard SH / T 0340-92.

[0047] The specific surface area and pore volume of the molecular sieve are measured by N2-adsorption desorption method. Before measurement, the sample is first calcined in air at 500℃ for 3h, then pretreated at 300℃ for 3h, and then tested by adsorbing nitrogen at 77K. The specific surface area of the molecular sieve is calculated by BET method, the total pore volume is measured at p / p 0 =0.98, and the external specific surface area is obtained by t-Plot method.

[0048] The acid content of the molecular sieve is measured by pyridine / ammonia-infrared spectroscopy method. The sample is prepared into a self-supporting sheet, heated to 500℃ for 2h, then vacuumized, and then naturally cooled. After cooling to room temperature, pyridine / ammonia is adsorbed at room temperature for 30min, and then heated to 150℃ for vacuumization to remove the physically adsorbed pyridine / ammonia molecules. The pyridine / ammonia infrared spectrum at this temperature is recorded, and the infrared acid content is obtained after integrating the peak area of the spectrum.

[0049] The silica-alumina ratio of the molecular sieve framework was measured by X-ray diffraction. The cell parameter a0 was measured by using the Chinese Petroleum Chemical Industry Standard SH / T0339-92, and then substituted into the Breck formula Si / Al = ((192 x 0.00868) / (a0-24.191))-1 for calculation. The obtained silica-alumina ratio was expressed as the molar ratio SiO2 / Al2O3.

[0050] The nanometer Y-type molecular sieve crystal grain size was measured by a scanning electron microscope (SEM).

[0051] The role and effect of the method of the present application are further illustrated by the following examples and comparative examples, but the following examples do not constitute a limitation to the method of the present application.

[0052] Example 1

[0053] (1) Under stirring, sodium hydroxide and tetramethylammonium hydroxide were added to water, and after stirring to uniformity, aluminum isopropoxide was added, followed by the addition of cetyltrimethylammonium bromide, and stirring for a period of time until complete dissolution. Silica sol was added to the above solution, and gelling was carried out at room temperature. The solution composition was Al2O3: 6.8SiO2: 0.2Na2O: 6.0(TMA)2O: 160H2O: 0.13CTAB, and the concentration of cationic surfactant in the mixture was 0.045 mol / L; the molar ratio of the tetramethylammonium template agent and the cationic surfactant was 92. The solution was statically aged at 25°C for 36 h, and the aged solution was crystallized at 80°C for 100 h.

[0054] (2) The crystallized solution was taken out, and under stirring, tetramethylammonium fluoride, nanometer silicon dioxide and water were added to the solution, and after stirring to uniformity, the solution composition was Al2O3: 14.0SiO2: 0.2Na2O: 6.0(TMA)2O: 4.0(TMA)F: 320H2O: 0.13CTAB. The solution was crystallized at 86°C for 70 h, and the product was obtained by washing, filtering and drying.

[0055] Modification of nanocluster Y zeolite: The product is added to distilled water, hydrochloric acid is added, the concentration of hydrochloric acid is 1.0 mol / L, the acid treatment temperature is 90℃, the treatment time is 1h, the solid-liquid volume ratio is 1:5, after treatment, the molecular sieve is washed to PH 7, and then dried at 100℃. The dried sample is carbonized by calcination at 600℃ under N2 atmosphere, and the calcination time is 7h. The carbonized molecular sieve is added to distilled water, and 2.5 mol / L of ammonium nitrate is added, and exchanged 2 times at 95℃, and the solid-liquid ratio is 1:20. Subsequently, the ammonium-exchanged molecular sieve is hydrothermally treated at 700℃, 0.05MPa for 1h. The hydrothermally treated molecular sieve is calcined in a mixture of O2 and He (O2 volume fraction is 25% at normal temperature and pressure) for 3h, and the calcination temperature is 600℃. The calcined molecular sieve is treated in 0.9 mol / L sodium hydroxide aqueous solution for 0.5h, the alkali treatment temperature is 90℃, and the solid-liquid volume ratio is 1:20. The alkali-treated molecular sieve is ammonium-exchanged once in 3 mol / L ammonium sulfate aqueous solution, the exchange solid-liquid ratio is 1:20, then washed, dried at 100℃, and calcined in air at 500℃ for 4h to obtain the modified nanocluster Y zeolite.

[0056] The modified nanocluster Y zeolite with a dry content of 55wt%, 27wt% alumina powder, 4.5wt% nickel nitrate containing 4.5wt% nickel oxide, and 13.5wt% molybdenum oxide material are added to a kneader, mixed uniformly, then a certain concentration of nitric acid solution and distilled water are added, mixed uniformly, extruded into strips, dried at 100℃ for 6h, then placed in a 500℃ muffle furnace for calcination for 4h to obtain the final hydrocracking catalyst.

[0057] Example 2

[0058] (1) Under stirring, sodium hydroxide and tetramethylammonium hydroxide are added to water, after stirring uniformly, aluminum isopropoxide is added, then cetyltrimethylammonium bromide is added, and stirred for a period of time until completely dissolved. Silica sol is added to the above solution, and gelled at room temperature. The solution composition is Al2O3: 12.2SiO2: 0.95Na2O: 10.0(TMA)2O: 310H2O: 0.4CTAB, and the concentration of cationic surfactant in the mixture is 0.072 mol / L; the molar ratio of the tetramethylammonium template and the cationic surfactant is 50. The aged solution is statically aged at 35℃ for 20h, and then crystallized at 100℃ for 65h.

[0059] (2) The solution after crystallization was taken out, and under stirring condition, tetramethylammonium fluoride, nano-silicon dioxide and water were added into the solution. After stirring, the solution composition was Al203: 20.0 Si02: 0.95 Na20: 10.0 (TMA)20: 7.8 (TMA)F: 537 H20: 0.4 CTAB. The solution was crystallized at 105°C for 30h, and then the product was taken out, washed, filtered and dried to obtain the product.

[0060] Modification of nanocluster Y zeolite: The product was added into distilled water, and hydrochloric acid was added. The concentration of the hydrochloric acid was 0.2 mol / L, the acid treatment temperature was 26°C, the treatment time was 6h, and the solid-liquid volume ratio was 1:20. After the treatment, the zeolite was washed until the pH was 7, and then dried at 100°C. The dried sample was carbonized by calcination at 500°C under N2 atmosphere, and the calcination time was 3h. The carbonized zeolite was added into distilled water, and 1.5 mol / L of ammonium nitrate was added. The exchange was performed 3 times at 45°C, and the solid-liquid ratio was 1:5. Subsequently, the ammonium-exchanged zeolite was subjected to high-temperature hydrothermal treatment at 500°C and 0.20 MPa for 8h. The hydrothermally treated zeolite was calcined in a mixed gas of O2 and He (the volume fraction of O2 was 25% at normal temperature and pressure) for 6h, and the calcination temperature was 480°C. The calcined zeolite was treated in 0.3 mol / L of sodium hydroxide aqueous solution for 5h, the alkaline treatment temperature was 26°C, and the solid-liquid volume ratio was 1:5. The alkaline-treated zeolite was subjected to ammonium exchange 2 times in 2 mol / L of ammonium sulfate aqueous solution, the solid-liquid ratio was 1:5, and then washed, dried at 100°C, and calcined in air at 500°C for 4h to obtain the modified nanocluster Y zeolite.

[0061] The modified nanocluster Y zeolite with a dry content of 55wt%, 27wt% of alumina powder, 4.5wt% of nickel nitrate with a nickel oxide content, and 13.5wt% of molybdenum oxide material with a molybdenum oxide content were added into a kneader, mixed uniformly, and then a certain concentration of nitric acid solution and distilled water were added and mixed uniformly. The mixture was extruded into a strip, dried at 100°C for 6h, and then placed in a 500°C muffle furnace for calcination for 4h to obtain the final hydrocracking catalyst.

[0062] Example 3

[0063] (1) Under stirring, sodium hydroxide, tetramethylammonium hydroxide were added into water, and then aluminum isopropoxide was added after stirring uniformly, and then cetyltrimethylammonium bromide was added, and stirring was continued until complete dissolution. Then, silica sol was added into the above solution, and gelation was carried out at room temperature. The solution composition was Al2O3: 10.9SiO2: 0.8Na2O: 9.3(TMA)2O: 280H2O: 0.35CTAB, and the concentration of cationic surfactant in the mixture was 0.069 mol / L; the molar ratio of the tetramethylammonium template agent and the cationic surfactant was 53, and static aging was carried out at 27℃ for 22h, and then the solution was crystallized at 96℃ for 93h.

[0064] (2) The crystallized solution was taken out, and under stirring, tetramethylammonium fluoride, nano-silicon dioxide and water were added into the solution, and then the solution was stirred uniformly. The solution composition was Al2O3: 14.8SiO2: 0.8Na2O: 9.3(TMA)2O: 7.1(TMA)F: 450H2O: 0.33CTAB. The solution was crystallized at 96℃ for 46h, and then the product was obtained by washing, filtering and drying.

[0065] Modification of nanocluster Y zeolite: The product was added into distilled water, and hydrochloric acid was added. The concentration of the hydrochloric acid was 0.2 mol / L, the acid treatment temperature was 36℃, the treatment time was 5h, and the solid-liquid volume ratio was 1:20. After the treatment, the zeolite was washed until the pH was 7, and then was dried at 100℃. The dried sample was calcined and carbonized at 500℃ in a N2 atmosphere, and the calcination time was 3h. The carbonized zeolite was added into distilled water, and ammonium nitrate with a concentration of 1.5 mol / L was added, and the exchange was carried out 3 times at 45℃ with a solid-liquid ratio of 1:5. Subsequently, the ammonium-exchanged zeolite was subjected to high-temperature hydrothermal treatment at 530℃ and 0.07 MPa for 8h. The hydrothermally treated zeolite was calcined in a mixed gas of O2 and He (O2 volume fraction was 25% at normal temperature and pressure) for 3h at a calcination temperature of 480℃. The calcined zeolite was treated in a 0.4 mol / L sodium hydroxide aqueous solution for 5h at a solid-liquid volume ratio of 1:5. The alkali-treated zeolite was subjected to ammonium exchange 2 times in a 2 mol / L ammonium sulfate aqueous solution with a solid-liquid ratio of 1:5, and then was washed, dried at 100℃, and calcined in air at 500℃ for 4h to obtain the modified nanocluster Y zeolite.

[0066] The modified nanocluster Y zeolite with a dry content of 55wt%, 27wt% alumina powder, 4.5wt% nickel nitrate containing 4.5wt% nickel oxide, and 13.5wt% molybdenum oxide containing 13.5wt% molybdenum oxide were added into a kneader, and then a certain concentration of nitric acid solution and distilled water were added and mixed uniformly. Extrusion molding was carried out, and then drying was carried out at 100℃ for 6h. Subsequently, the product was placed in a 500℃ muffle furnace for calcination for 4h to obtain the final hydrocracking catalyst.

[0067] Example 4

[0068] (1) Sodium hydroxide, tetramethylammonium hydroxide were added to water under stirring, after stirring evenly, aluminum isopropoxide was added, then cetyltrimethylammonium bromide was added, and stirred for a period of time until completely dissolved. Silica sol was added to the above solution, and gelled at room temperature. The solution composition was Al2O3: 7.2SiO2: 0.3Na2O: 7.8(TMA)2O: 185H2O: 0.20STAB, the concentration of cationic surfactant in the mixture was 0.060 mol / L; the molar ratio of the tetramethylammonium template and the cationic surfactant was 78, and the solution was aged at 28°C for 25h, and then crystallized at 85°C for 88h.

[0069] (2) The crystallized solution was taken out, and tetramethylammonium fluoride, nanosilica and water were added to the solution under stirring, and the solution composition was Al2O3: 15.2SiO2: 0.3Na2O: 7.8(TMA)2O: 5.3(TMA)F: 383H2O: 0.15STAB after stirring evenly. The solution was crystallized at 90°C for 60h, and then washed, filtered, and dried to obtain the product.

[0070] Modification of nanocluster Y zeolite: The product was added to distilled water, and hydrochloric acid was added, the concentration of hydrochloric acid was 0.4 mol / L, the acid treatment temperature was 50°C, the treatment time was 3h, and the solid-liquid ratio was 1:13. After treatment, the zeolite was washed to a pH of 7, and then dried at 100°C. The dried sample was calcined and carbonized at 560°C under N2 atmosphere, and the calcination time was 5h. The carbonized zeolite was added to distilled water, and ammonium nitrate with a concentration of 1.5 mol / L was added, and exchanged at 70°C for 2 times, with a solid-liquid ratio of 1:10. Subsequently, the ammonium-exchanged zeolite was subjected to high-temperature hydrothermal treatment at 600°C and 0.10 MPa for 4h. The hydrothermally treated zeolite was calcined in a mixture of O2 and He (O2 volume fraction was 25% at normal temperature and pressure) for 4h, and the calcination temperature was 530°C. The calcined zeolite was treated with 0.6 mol / L sodium hydroxide solution for 3h, the alkaline treatment temperature was 60°C, and the solid-liquid ratio was 1:11. The alkali-treated zeolite was ammonium-exchanged twice in 2.3 mol / L ammonium sulfate solution, with a solid-liquid ratio of 1:10, and then washed, dried at 100°C, and calcined in air at 500°C for 4h to obtain the modified nanocluster Y zeolite.

[0071] Modified nanocluster Y molecular sieve with a dry basis content of 55wt%, 27wt% alumina powder, 4.5wt% nickel nitrate with a nickel oxide content of 13.5wt% molybdenum oxide material were added into a kneader, mixed uniformly, then a certain concentration of nitric acid solution and distilled water were added, mixed until uniform, extruded into strips, dried at 100°C for 6h, then placed in a 500°C muffle furnace for calcination for 4h, to obtain the final hydrocracking catalyst.

[0072] Example 5

[0073] (1) Under stirring, sodium hydroxide and tetramethylammonium hydroxide were added to water, after stirring uniformly, aluminum isopropoxide was added, then cetyltrimethylammonium bromide was added, and stirred for a period of time until completely dissolved. Silica sol was added to the above solution, and gelled at room temperature. The solution composition was Al2O3: 9.8SiO2: 0.7Na2O: 9.0(TMA)2O: 270H2O: 0.25DTAB, and the concentration of cationic surfactant in the mixture was 0.051mol / L; the molar ratio of the tetramethylammonium template and the cationic surfactant was 72. The solution was aged at 31°C for 35h, and then crystallized at 95°C for 70h.

[0074] (2) The crystallized solution was taken out, and under stirring, tetramethylammonium fluoride, nanosilica and water were added to the solution, which was stirred uniformly, and the solution composition was Al2O3: 18.0SiO2: 0.7Na2O: 8.8(TMA)2O: 6.6(TMA)F: 430H2O: 0.29DTAB. The solution was crystallized at 101°C for 40h, and then taken out, washed, filtered and dried to obtain the product.

[0075] Modification of nanocluster Y zeolite: the product is added to distilled water, hydrochloric acid is added, the concentration of hydrochloric acid is 0.5 mol / L, the acid treatment temperature is 70℃, the treatment time is 3h, the solid-liquid volume ratio is 1:15, after treatment, the molecular sieve is washed to PH 7, and then dried at 100℃. The dried sample is carbonized by calcination at 530℃ under N2 atmosphere, and the calcination time is 5h. The carbonized molecular sieve is added to distilled water, and 1.5 mol / L of ammonium nitrate is added, and exchanged at 70℃ for 2 times, and the solid-liquid ratio is 1:10. Subsequently, the ammonium-exchanged molecular sieve is hydrothermally treated at 650℃, 0.10 MPa for 3h. The hydrothermally treated molecular sieve is calcined in a mixed gas of O2 and He (O2 volume fraction is 25% at normal temperature and pressure) for 4h, and the calcination temperature is 530℃. The calcined molecular sieve is treated in 0.7 mol / L of sodium hydroxide aqueous solution for 3h, the alkali treatment temperature is 60℃, and the solid-liquid volume ratio is 1:11. The alkali-treated molecular sieve is ammonium-exchanged in 2.3 mol / L of ammonium sulfate aqueous solution for 2 times, the exchange solid-liquid ratio is 1:10, then washed, dried at 100℃, and calcined in air at 500℃ for 4h, to obtain the modified nanocluster Y zeolite.

[0076] The modified nanocluster Y zeolite with a dry content of 55wt%, 27wt% of alumina powder, 4.5wt% of nickel nitrate containing 4.5wt% of nickel oxide, and 13.5wt% of molybdenum oxide material containing 13.5wt% of molybdenum oxide are added to a kneader, mixed uniformly, then a certain concentration of nitric acid solution and distilled water are added, mixed uniformly, extruded into strips, dried at 100℃ for 6h, then placed in a 500℃ muffle furnace for calcination for 4h, to obtain the final hydrocracking catalyst.

[0077] Comparative Example 1 (TMA + Pre-calcination

[0078] The synthesis part of the nanocluster Y zeolite is consistent with Example 1.

[0079] Modification of nanocluster Y zeolite: the product is calcined in air for 4h, the calcination temperature is 500℃, and TMA +Template agent. After demoulding, the molecular sieve was added to distilled water, hydrochloric acid was added, the concentration of hydrochloric acid was 0.5 mol / L, the acid treatment temperature was 70℃, the treatment time was 2h, the solid-liquid volume ratio was 1:10, after treatment, the molecular sieve was washed to PH 7, and then dried at 100℃. The dried molecular sieve was added to distilled water, 1.5 mol / L of ammonium nitrate was added, and the exchange was carried out twice at 80℃, and the solid-liquid ratio was 1:11. Subsequently, the ammonium-exchanged molecular sieve was subjected to high-temperature hydrothermal treatment at 600℃ and 0.10 MPa for 3h. The molecular sieve after high-temperature hydrothermal treatment was treated in 0.6 mol / L sodium hydroxide aqueous solution for 2h, the alkali treatment temperature was 60℃, and the solid-liquid volume ratio was 1:10. The molecular sieve after alkali treatment was subjected to ammonium exchange once in 2 mol / L ammonium sulfate aqueous solution, the exchange solid-liquid ratio was 1:10, then washed, dried at 100℃, and calcined in air at 500℃ for 4h to obtain the modified nanocluster Y molecular sieve.

[0080] The modified nanocluster Y molecular sieve with a dry basis content of 55wt%, 27wt% of alumina powder, 4.5wt% of nickel nitrate with a nickel oxide content of 13.5wt% of molybdenum oxide material were added to a kneader, mixed uniformly, then a certain concentration of nitric acid solution and distilled water were added, mixed uniformly, extruded into strips, dried at 100℃ for 6h, then placed in a 500℃ muffle furnace for calcination for 4h to obtain the final hydrocracking catalyst.

[0081] The performance evaluation of the catalyst was carried out on a small micro-reactor device, and a one-pass process was adopted. The raw oil passed through the refining reactor and the cracking reactor in sequence. The evaluation conditions and results are shown in Tables 3 and 4, respectively. In the hydrocracking reaction, the cracking catalyst, the raw oil was catalytic diesel, and the properties of the raw oil were as follows: the density at 20℃ was 0.9310~0.9410kg / m 3 , the distillation range was 197~360℃, the S content was 4020~7900ppm, the N content was 760~1100ppm, the total aromatic hydrocarbon content was 75.8~79.9wt%, the monocyclic aromatic hydrocarbon content was 15.6~20.6wt%, and the polycyclic aromatic hydrocarbon content was 59.3~60.2wt%.

[0082] The target product was heavy naphtha. The catalyst evaluation experiment was carried out on a micro-reactor device, and a one-pass process was adopted. The raw oil passed through two reactors in sequence, and no fractionation device was provided between the two reactors. The raw oil first passed through the refining reactor, which was filled with conventional refining agent to remove impurities such as S and N, and then passed through the cracking reactor filled with the catalyst for cracking reaction. The collected reaction product was analyzed.

[0083] From the catalyst evaluation conditions and results, it can be seen that the catalyst in the present application has better ring-opening activity for bicyclic and above aromatic hydrocarbons, high heavy naphtha yield, and good product quality.

[0084] Table 1 Structural properties of products in examples and comparative examples

[0085]

[0086] Table 2 Structural properties of modified molecular sieves

[0087]

[0088] Table 3 Catalyst evaluation conditions

[0089]

[0090] Table 4 Catalyst evaluation results

[0091]

Claims

1. A process for preparing a modified Y-type molecular sieve, characterized by: The method comprises the following steps: (1) synthesis of the nano self-assembled Y-type molecular sieve, the synthesis method comprising: ①obtaining a crystallized material by aging and crystallizing a mixture material containing an alkali source, a sodium source, an aluminum source, a tetramethylammonium template agent, a cationic surfactant, and a silicon source; the molar ratio of the tetramethylammonium template agent to the cationic surfactant is 50-110; the cationic surfactant is one or more of dodecyltrimethylammonium bromide DTAB, hexadecyltrimethylammonium bromide CTAB, and octadecyltrimethylammonium bromide STAB; ②obtaining the final nano self-assembled Y-type molecular sieve by crystallizing, washing, filtering, and drying the crystallized material mixed with tetramethylammonium fluoride (TMA) F, a silicon source, and water; (2) subjecting the nano self-assembled Y-type molecular sieve in step (1) to acid treatment; (3) calcining the nano self-assembled Y-type molecular sieve after acid treatment in step (2) under an inert atmosphere; (4) subjecting the nano self-assembled Y-type molecular sieve after calcination under an inert atmosphere in step (3) to ammonium exchange; (5) subjecting the nano self-assembled Y-type molecular sieve after ammonium exchange in step (4) to high-temperature hydrothermal treatment; (6) calcining the nano self-assembled Y-type molecular sieve after high-temperature hydrothermal treatment in step (5) in an oxygen-containing atmosphere; (7) subjecting the nano self-assembled Y-type molecular sieve after calcination in step (6) to alkali treatment; (8) obtaining the final modified Y-type molecular sieve by subjecting the nano self-assembled Y-type molecular sieve after alkali treatment in step (7) to ammonium exchange, washing, filtering, drying, and air calcination; The modified Y-type molecular sieve has a pyridine infrared acid content of 0.65-1.03 mmol / g, and the ratio of the pyridine infrared acid content to the ammonia gas infrared acid content is 0.8-0.95; The modified Y-type molecular sieve has a total pore volume of 0.63-0.78 mL / g and a mesopore volume of 0.35-0.49 mL / g; The modified Y-type molecular sieve has a specific surface area of 750-870 m 2 / g. The modified Y-type molecular sieve has a relative crystallinity of 75-94%.

2. The method of claim 1, wherein: In step (1) ①, the concentration of the cationic surfactant in the mixture material is 0.040-0.072 mol / L; the molar ratio of the tetramethylammonium template agent to the cationic surfactant is 60-90; and the molar ratio of the materials in the mixture material is Al2O3: (6.5-12.5)SiO2: (0.1-1.0)Na2O: (6.0-10.0)(TMA)2O: (160-310)H2O: (0.1-0.4) CTAB.

3. The method of claim 2, wherein: In step (1) ①, the concentration of the cationic surfactant in the mixture material is 0.045-0.067 mol / L; the molar ratio of the tetramethylammonium template agent to the cationic surfactant is 65-85; and the molar ratio of the materials in the mixture material is Al2O3: (7.2-10.0)SiO2: (0.3-0.7)Na2O: (7.7-9.0)(TMA)2O: (180-270)H2O: (0.15-0.30) CTAB.

4. The method of claim 2, wherein: In step (1) ①, the concentration of the cationic surfactant in the mixture is 0.050-0.061 mol / L.

5. The method of claim 1, wherein: In step (1) ②, after the crystallized material is added with tetramethylammonium fluoride, a silicon source and water, the molar ratio of the materials in the solution is Al2O3:(14-20)SiO2:(0.1-1.0)Na2O:(6-10)(TMA)2O:(4-8)(TMA)F:(320-540)H2O:(0.1-0.4)CTAB; the crystallization temperature is 85-105℃; the crystallization time is 30-70h; the drying temperature of the nano self-assembled Y-type molecular sieve is 80-120℃, the time is 7-13h, and the calcination temperature is 450-550℃, the time is 3-5h.

6. The method of claim 5, wherein: In step (1) ②, after the crystallized material is added with tetramethylammonium fluoride, a silicon source and water, the molar ratio of the materials in the solution is Al2O3:(15-18)SiO2:(0.30-0.7)Na2O:(7.7-9.0)(TMA)2O:(5.2-6.6)(TMA)F:(380-430)H2O:(0.15-0.30)CTAB; the crystallization temperature is 90-101℃; the crystallization time is 40-60h.

7. The method of claim 1, wherein: In step (1) ②, the nano self-assembled Y-type molecular sieve is an aggregate formed by clusters of nanocrystals, the size of the nanocrystals is 40-100 nm, the size of the aggregate is 1.3 μm-3.5 μm, the framework silica-alumina ratio SiO2 / Al2O3 of the nano self-assembled Y-type molecular sieve is 8.0-13.0, and the specific surface area of the nano self-assembled Y-type molecular sieve is 800-930 m 2 / g, and the external specific surface area is 100-170 m 2 / g.

8. The method of claim 7, wherein: In step (1) ②, the nano self-assembled Y-type molecular sieve is an aggregate formed by clusters of nanocrystals, the size of the nanocrystals is 60-85 nm, the size of the aggregate is 1.8 μm-2.8 μm, the framework silica-alumina ratio SiO2 / Al2O3 of the nano self-assembled Y-type molecular sieve is 10.0-12.0, and the specific surface area of the nano self-assembled Y-type molecular sieve is 840-900 m 2 / g, and the external specific surface area is 140-160 m 2 / g.

9. The method of claim 1, wherein: In step (2), the acid used for the acid treatment is an inorganic acid or an organic acid, and the acid concentration in the solution used for the acid treatment is 0.1-1.0 mol / L; the acid treatment temperature is 20-90℃; the acid treatment time is 0.5-6h; and the solid-liquid ratio during the acid treatment is 1:5-1:

20.

10. The method of claim 9, wherein: In the solution used for the acid treatment, the acid concentration is 0.3-0.5 mol / L; the acid treatment temperature is 40-70℃; the acid treatment time is 2-3h; and the solid-liquid ratio during the acid treatment is 1:10-1:

15.

11. The method of claim 1, wherein: In step (3), the inert atmosphere used for the calcination is one or more of N2, He and Ar; the calcination temperature is 500-600℃; and the calcination time is 2-7h.

12. The method of claim 11, wherein: In step (3), the calcination temperature is 530-570℃, and the calcination time is 4-6h.

13. The method of claim 1, wherein: In step (4), the ammonium salt used for the ammonium exchange is one or more of ammonium nitrate, ammonium chloride, ammonium sulfate, ammonium acetate and ammonium oxalate; the ammonium exchange temperature is 40-96℃; the exchange times is 1-3 times; the ammonium salt concentration is 0.5 mol / L-3.0 mol / L; and the solid-liquid ratio during the ammonium exchange is 1:5-1:

20.

14. The method of claim 13, wherein: In step (4), the ammonium exchange temperature is 60-80℃, and the solid-liquid ratio during the ammonium exchange is 1:8-1:

15.

15. The method of claim 1, wherein: In step (5), the high-temperature hydrothermal treatment temperature is 500-700℃; the hydrothermal pressure is 0.05-0.20 MPa; and the hydrothermal treatment time is 1-8h.

16. The method of claim 15, wherein: In step (5), the high-temperature hydrothermal treatment temperature is 550-650℃; the hydrothermal pressure is 0.08-0.15 MPa; and the hydrothermal treatment time is 3-5h.

17. The method of claim 1, wherein: In step (6), the oxygen-containing atmosphere is air or a mixed gas of O2 and one or more of N2, He and Ar; the calcination temperature is 450-600℃; and the calcination time is 3-6h.

18. The method of claim 17, wherein: The calcination temperature is 500-550℃, and the calcination time is 4-5h.

19. The method of claim 1, wherein: In step (7), the alkali used in the alkali treatment is sodium hydroxide, and the concentration of the alkali is 0.3-1.0 mol / L; the temperature of the alkali treatment is 20-90℃, the time of the alkali treatment is 0.5-5h, and the solid-liquid volume ratio during the alkali treatment is 1:5-1:

20.

20. The method of claim 19, wherein: In step (7), the concentration of the alkali is 0.5-0.7 mol / L; the temperature of the alkali treatment is 40-70℃, the time of the alkali treatment is 2-3h, and the solid-liquid volume ratio during the alkali treatment is 1:5-1:

20.

21. The method of claim 1, wherein: In step (8), the ammonium salt used in the ammonium exchange is one or more of ammonium nitrate, ammonium chloride, ammonium sulfate, ammonium acetate, and ammonium oxalate; the temperature of the ammonium exchange is 40-96℃, the number of exchanges is 1-2, the concentration of the ammonium salt is 2.0 mol / L-3.0 mol / L, and the solid-liquid ratio of the ammonium exchange is 1:5-1:

20.

22. The method of claim 21, wherein: In step (8), the temperature of the ammonium exchange is 70-80℃, and the solid-liquid ratio of the ammonium exchange is 1:8-1:

15.

23. The modified Y-type molecular sieve prepared by the method of any one of claims 1 to 22, characterized by: The pyridine infrared acid content of the modified Y-type molecular sieve is 0.75-0.88 mmol / g; and the ratio of the pyridine infrared acid content to the ammonia infrared acid content of the modified Y-type molecular sieve is 0.85-0.

92.

24. The molecular sieve of claim 23, wherein: The total pore volume of the modified Y-type molecular sieve is 0.67-0.76 mL / g; and the mesopore volume is 0.38-0.46 mL / g.

25. The molecular sieve of claim 23, wherein: The modified Y-type molecular sieve has a specific surface area of 780-840 m 2 / g.

26. The molecular sieve of claim 23, wherein: The relative crystallinity of the modified Y-type molecular sieve is 80-90%.

27. The molecular sieve of claim 23, wherein: The framework silicon-aluminum ratio SiO2 / Al2O3 of the modified Y-type molecular sieve is 10-30.

28. The molecular sieve of claim 27, wherein: The framework silicon-aluminum ratio SiO2 / Al2O3 of the modified Y-type molecular sieve is 12-20.

29. A hydrocracking catalyst characterized by: The hydrocracking catalyst contains 30-70% of the modified Y-type molecular sieve obtained by the preparation method of any one of claims 1-22, and contains 3-35 wt% of active metal oxides, wherein the active metal is a Group VIB metal and / or a Group VIII metal.

30. The catalyst of claim 29, wherein: The hydrocracking catalyst contains 40-60% of the modified Y-type molecular sieve obtained by the preparation method of any one of claims 1-22, and contains 5-25 wt% of active metal oxides; wherein the Group VIB metal is Mo and / or W, and the Group VIII metal is Co and / or Ni.

31. A method of preparing a hydrocracking catalyst characterized by: The hydrocracking catalyst is obtained by a kneading method or an impregnation method; in the kneading method, the modified Y-type molecular sieve obtained by the preparation method of any one of claims 1-22, alumina and / or amorphous silicon-aluminum, active metal oxides and / or active metal salts are mixed uniformly, and then diluted nitric acid solution and distilled water are added, followed by kneading and extrusion to obtain a shaped catalyst, which is dried and calcined to obtain the final hydrocracking catalyst; in the impregnation method, the modified Y-type molecular sieve of any one of claims 1-22, alumina and / or amorphous silicon-aluminum are shaped, and then loaded with active metals, followed by drying and calcination to obtain the final hydrocracking catalyst.

32. The method of claim 31, wherein: The drying temperature of the shaped catalyst is 100-150℃, and the calcination temperature is 450-550℃.

33. Use of the hydrocracking catalyst of claim 29 for catalyzing hydrocracking reaction of diesel oil under the following conditions: reaction temperature of 350 to 430°C, reaction pressure of 5 to 10 MPa, hydrocracking reaction volume space velocity of 0.5 to 2.0 h"1, and hydrogen / oil ratio of 800: 1 to 1400:

1. -1 , hydrogen / oil ratio of 800: 1 to 1400: 1.

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