A catalytic diesel ebullated bed hydroconversion method

Abstract

The present invention discloses a catalytic diesel ebullated bed hydroconversion method. In the presence of hydrogen, catalytic diesel enters a first ebullated bed reaction zone and contacts a first catalytic diesel hydroconversion catalyst for reaction. The reaction effluent obtained in the first ebullated bed reaction zone enters a second ebullated bed reaction zone and reacts in the presence of hydrogen and a second catalytic diesel hydroconversion catalyst. The reaction effluent is separated to obtain different fractions of the desired product. The first catalytic diesel hydroconversion catalyst is a core-shell catalyst with a low molecular sieve content, and the second catalytic diesel hydroconversion catalyst is a core-shell catalyst with a high molecular sieve content. The method can hydroconvert low-quality catalytic diesel to obtain a high-octane gasoline blending component or a BTX product.

Description

Technical Field

[0001] The invention belongs to the technical field of petroleum refining, and relates to a method for hydrogenating and converting inferior diesel, in particular to a method for converting catalytic diesel by hydrogenating and converting the diesel using an ebullient bed. Background Art

[0002] Catalytic cracking (FCC) technology is one of the most important technologies for converting heavy oil to lighter fuels, and it plays a crucial role in oil refining companies worldwide. my country's total annual processing capacity for FCC units has exceeded 170 million tons, with annual FCC diesel production reaching 35 million tons, accounting for approximately 30% of diesel production. In recent years, as crude oil quality has steadily deteriorated, the feedstock processed by FCC units has also shown a trend toward heavier and lower-quality fuels. Furthermore, refineries have increased the operating severity of FCC units to produce more high-value products such as gasoline and propylene, further deteriorating the quality of FCC diesel. In summary, with the accelerated progress in China towards cleaner oil products and the need to transition from refining to chemical production, FCC diesel production has become a constraint on the development of refining companies.

[0003] Catalytic diesel has high density (density is 0.87~0.97g / cm 3 Due to its high aromatic content (60wt%-90wt%), low cetane number (20-35 cetane number), and low hydrogen content (9.0wt%-11.0wt%), conventional hydrogenation technologies cannot produce high-quality diesel products. Conversion of low-value-added catalytic diesel into high-value-added high-octane gasoline blending components, or BTX, can effectively reduce refinery diesel-to-gasoline ratios, address market fluctuations, and improve enterprise profitability, and is currently a hot research topic.

[0004] At present, the catalytic diesel hydroconversion process mainly adopts fixed-bed reactors. There are two problems in the actual industrial application process. On the one hand, during the fixed-bed hydrogenation reaction, the reaction temperature presents a gradient distribution, gradually increasing from the reactor inlet to the outlet, which will lead to multiple reactions occurring simultaneously and resulting in the diversification of reaction products, which is not conducive to the directional conversion of polycyclic aromatic hydrocarbons into high-value-added products; on the other hand, the hydrocracking reaction of polycyclic aromatic hydrocarbons is a highly exothermic process, and the catalyst bed will be accompanied by hot spots, pressure drop and other problems, which are not conducive to the activity of the catalyst and affect the long-term stable operation of the device.

[0005] When using an ebullated bed reactor to treat catalytic diesel, on the one hand, the temperature and material concentration in the ebullated bed reactor are uniformly distributed, which can be controlled at a reaction temperature suitable for the efficient conversion of polycyclic aromatic hydrocarbons, greatly improving the selectivity of the target product; on the other hand, the ebullated bed fully back-mixed reaction system is particularly suitable for highly exothermic reaction processes. The reaction heat energy of the reaction process is quickly diluted and dispersed to reach equilibrium, avoiding problems such as hot spots and pressure drops; at the same time, the ebullated bed catalyst can be replaced online to ensure the stability of product properties throughout the entire operating cycle, and achieve long-term stable operation, thereby realizing efficient conversion of catalytic diesel.

[0006] Catalytic diesel hydrogenation conversion catalyst is an important component of this technology. Existing hydrocracking catalysts and hydrorefining catalysts cannot simultaneously meet the performance requirements of catalytic diesel hydrogenation, cracking and directional conversion of aromatics. Generally, more than two catalyst grades are required to achieve hydrogenation and conversion. How to achieve hydrogenation and cracking reactions on one catalyst and improve the yield of target products has always been the goal pursued by researchers.

[0007] US Pat. No. 6,174,429 discloses a hydrocracking catalyst comprising 1% to 99% by weight of at least one acidified aluminum-containing amorphous matrix, 0.1% to 80% by weight of a Y-type molecular sieve having a unit cell parameter of 2.438 nm, a SiO2 / Al2O3 chemical molar ratio of approximately 8, and a SiO2 / Al2O3 framework molar ratio of approximately 20, 0.1% to 30% by weight of at least one Group VIII metal component, 1% to 40% by weight of at least one Group VIB metal component, 0.1% to 20% by weight of a promoter, and 0% to 20% by weight of at least one Group VIIA element. This catalyst is prepared by first preparing the support and then loading the hydrogenation metal. While the catalyst exhibits good activity and stability, its hydroconversion performance and heavy naphtha and jet fuel yields need to be further improved.

[0008] CN201510764606.7 discloses a catalyst grading method for catalytic diesel hydroconversion, comprising the following: (1) under hydrorefining process conditions, a mixture of catalytically cracked diesel and hydrogen first enters a hydrorefining reactor for contact reaction with a hydrorefining catalyst; (2) the hydrorefining reaction effluent enters a cracking reactor for contact reaction with a graded hydrocracking catalyst bed in the cracking reactor; (3) the hydrocracking reaction effluent is separated and fractionated to obtain a naphtha component and a diesel component; by grading catalyst systems with different reaction properties in the cracking reactor, the goal of improving the hydrogenation selectivity of the diesel / gasoline components in the conversion process and increasing the production of high-octane gasoline products is achieved. In this patent, catalytic diesel conversion is achieved through catalyst grading, and the process is relatively complicated. Summary of the Invention

[0009] In response to the deficiencies in the prior art, the main purpose of the present invention is to provide a catalytic diesel ebullated bed hydroconversion method, which can achieve the hydroconversion of low-quality catalytic diesel to obtain high-octane gasoline blending components or BTX products. The method fully utilizes the advantages of the ebullated bed process, such as low temperature rise, no hot spot temperature fluctuations, low cold hydrogen consumption, low energy consumption, stable product properties, and long operating cycle. At the same time, a core-shell structured catalytic diesel hydroconversion catalyst with a molecular sieve as a core and an alumina shell is used to achieve gradual hydrogenation, cracking and directional conversion of aromatics of low-quality diesel, thereby producing high-octane gasoline blending components or BTX.

[0010] The first aspect of the present invention provides a catalytic diesel ebullated bed hydroconversion method, comprising the following steps:

[0011] S1: In the presence of hydrogen, the catalytic diesel enters the first ebullated bed reaction zone and contacts with the first catalytic diesel hydroconversion catalyst to react;

[0012] S2: The reaction effluent obtained in the first ebullated bed reaction zone enters the second ebullated bed reaction zone, and reacts in the presence of hydrogen and a second catalytic diesel hydroconversion catalyst. The reaction effluent is separated to obtain target products in different fractions.

[0013] The first catalytic diesel hydroconversion catalyst used in the first ebullated bed reaction zone is a core-shell structured catalytic diesel hydroconversion catalyst with a low molecular sieve content. The catalyst comprises a support and an active metal component. The support comprises a molecular sieve as a core layer and an alumina shell layer. The support particles have a diameter of 0.5 to 3 mm, preferably 0.8 to 2 mm. The thickness of the support shell layer is 50 to 95%, preferably 60 to 95%, of the support diameter. The active metal components are a Group VIII metal and a Group VIB metal. Based on the weight of the catalyst, the molecular sieve content is 5 wt% to 25 wt%, preferably 10 wt% to 25 wt%. The Group VIII metal content, calculated as oxide, is 2 wt% to 6 wt%, and the Group VIB metal content, calculated as oxide, is 15 wt% to 30 wt%. Molecular sieves can generally be selected from one or more of Y-type molecular sieves, β-molecular sieves, ZSM-5 molecular sieves, SAPO molecular sieves, and MCM-41 molecular sieves. Furthermore, the molecular sieves can be modified appropriately according to the performance requirements. The molecular sieve is preferably Y-type molecular sieve. Furthermore, the properties of Y-type molecular sieves are as follows: pore volume of 0.35mL / g to 0.50mL / g, specific surface area of 700m 2 / g~950m 2 / g, the total infrared acid content is 0.6-1.0 mmol / g, the relative crystallinity is 90%-120%, the SiO2 / Al2O3 molar ratio is 10-30, and the unit cell parameter is 2.436-2.450 nm. The Group VIII metal is preferably Ni and / or Co, and the Group VIB metal is preferably W and / or Mo. Furthermore, the specific surface area of the first catalytic diesel hydroconversion catalyst is 120-250 m 2 / g, the pore volume is 0.35~0.50mL / g, the total acid value is 0.30~0.50mmol / g, and the B / L acid ratio is 0.1~0.8.

[0014] The second catalytic diesel hydroconversion catalyst used in the second ebullating bed reaction zone is a core-shell structured catalytic diesel hydroconversion catalyst with a high molecular sieve content. The catalyst comprises a support and an active metal component. The support comprises a molecular sieve as a core layer and an alumina shell layer. The support particles have a diameter of 0.5 to 3 mm, preferably 0.8 to 2 mm. The thickness of the support shell layer is 30 to 60%, preferably 30 to 55%, of the support diameter. The active metal components are Group VIII and Group VIB metals. Based on the weight of the catalyst, the molecular sieve content is 25 wt% to 50 wt%, preferably 30 wt% to 50 wt%. The Group VIII metal content, calculated as oxide, is 1 wt% to 3 wt%, and the Group VIB metal content, calculated as oxide, is 8 wt% to 15 wt%. Molecular sieves can generally be selected from one or more of Y-type molecular sieves, β-molecular sieves, ZSM-5 molecular sieves, SAPO molecular sieves, and MCM-41 molecular sieves. Furthermore, the molecular sieves can be modified appropriately according to the performance requirements. The molecular sieve is preferably Y-type molecular sieve. Furthermore, the properties of Y-type molecular sieves are as follows: pore volume of 0.35mL / g to 0.50mL / g, specific surface area of 700m 2 / g~950m 2 / g, infrared total acid content of 0.6-1.0 mmol / g, relative crystallinity of 90%-120%, SiO2 / Al2O3 molar ratio of 10-30, unit cell parameter of 2.436-2.450 nm. The Group VIII metal is preferably Ni and / or Co, and the Group VIB metal is preferably W and / or Mo. Furthermore, the specific surface area of the second catalytic diesel hydroconversion catalyst is 250-450 m 2 / g, the pore volume is 0.30~0.50mL / g, the total acid value is 0.35~0.65mmol / g, and the B / L acid ratio is 0.6~1.1.

[0015] Furthermore, in the above-mentioned catalytic diesel ebullated bed hydroconversion method, the molecular sieve content of the second catalytic diesel hydroconversion catalyst is 20% to 45% higher than that of the first catalytic diesel hydroconversion catalyst, preferably 20% to 40% higher.

[0016] Furthermore, in the above-mentioned catalytic diesel ebullating bed hydroconversion method, the content of Group VIII metal in the first catalytic diesel hydroconversion catalyst, calculated as oxide, is 0.5% to 5% higher than the content of Group VIII metal in the second catalytic diesel hydroconversion catalyst, calculated as oxide, preferably 1% to 3% higher.

[0017] Furthermore, in the above-mentioned catalytic diesel ebullating bed hydroconversion method, the content of the Group VIB metal in the first catalytic diesel hydroconversion catalyst, calculated as oxide, is 7% to 22% higher than the content of the Group VIB metal in the second catalytic diesel hydroconversion catalyst, calculated as oxide, preferably 7% to 15% higher.

[0018] Further according to the present invention, preferably, the distribution coefficient φ of the active metal component in the core layer and shell layer of the carrier is 0.6-0.95:1, for example, 0.6, 0.7, 0.8, 0.9, 0.95, or any value therebetween.

[0019] Furthermore, in the above-mentioned catalytic diesel ebullated bed hydrogenation conversion method, the properties of the catalytic diesel are generally as follows: density (20°C) is 0.88-0.99 g / cm 3 The dry point is generally 360-400°C, the aromatic content is generally 50wt%-90wt%, the sulfur content is generally 0.2wt%-3.0wt%, and the nitrogen content is 500-4000 μg / g.

[0020] Furthermore, in the above-mentioned catalytic diesel ebullated bed hydroconversion method, the operating conditions of the first ebullated bed reaction zone are generally as follows: reaction pressure of 6-10 MPa, reaction temperature of 350-400°C, liquid hourly volume space velocity of 0.3-3.0 h -1 , the volume ratio of hydrogen to oil is 100~1000.

[0021] Furthermore, in the above-mentioned catalytic diesel ebullated bed hydroconversion method, the operating conditions of the second ebullated bed reaction zone are generally as follows: reaction pressure of 6-10 MPa, reaction temperature of 380-430°C, liquid hourly volume space velocity of 0.3-3.0 h -1 , the volume ratio of hydrogen to oil is 100~1000.

[0022] Furthermore, in the above-mentioned catalytic diesel ebullated bed hydroconversion method, the reaction temperature of the second ebullated bed reaction zone is 20°C to 80°C higher than the reaction temperature of the first ebullated bed reaction zone, preferably 20°C to 50°C higher.

[0023] Furthermore, in the above-mentioned catalytic diesel ebullated bed hydrogenation conversion method, at least one ebullated bed reactor is provided in the first ebullated bed reaction zone. The ebullated bed reactor can adopt any one of the existing ebullated bed reactors in the art, and preferably adopts the STRONG ebullated bed reactor with a built-in three-phase separator developed by Dalian Research Institute of Petrochemicals, Sinopec.

[0024] Furthermore, in the above-mentioned catalytic diesel ebullated bed hydrogenation conversion method, at least one ebullated bed reactor is provided in the second ebullated bed reaction zone. The ebullated bed reactor can adopt any one of the existing ebullated bed reactors in the art, preferably adopting the STRONG ebullated bed reactor with a built-in three-phase separator developed by Dalian Research Institute of Petrochemicals, Sinopec.

[0025] Furthermore, in the above-mentioned catalytic diesel ebullated-bed hydroconversion method, the target products in step S2 may include high-octane gasoline blending components, BTX (B refers to benzene, T refers to toluene, and X refers to xylene), and diesel products as needed. When the high-octane gasoline blending component is the main target product, the fraction with a fractionation temperature of <210°C is directly used as the gasoline blending component; when BTX is the main target product, the fraction with a fractionation temperature of <180°C is subjected to aromatics extraction to obtain the BTX product.

[0026] Furthermore, in the above-mentioned catalytic diesel ebullated bed hydroconversion method, the first catalytic diesel hydroconversion catalyst and the second catalytic diesel hydroconversion catalyst are prepared using the same preparation method. During the preparation process, the first catalytic diesel hydroconversion catalyst and the second catalytic diesel hydroconversion catalyst are obtained by adjusting the amount of molecular sieve and active metal component. The preparation method of the catalyst comprises the following steps:

[0027] (1) mixing an aluminum source, a curing agent, a dispersant, and a molecular sieve to obtain a stream B;

[0028] (2) Mixing stream B with the oil phase to obtain stream C;

[0029] (3) The material stream C obtained in step (2), the emulsifier, and the auxiliary agent are mixed to obtain a material stream D, and the material stream D is molded, aged, washed, dried, and calcined to obtain a carrier.

[0030] (4) Introducing active metal components onto the support obtained in step (3) to obtain a catalyst.

[0031] The present invention does not particularly limit the specific manner of mixing in step (1), as long as a uniform material flow B can be formed. Preferably, step (1) includes:

[0032] (1-1) Mixing an aluminum source, a curing agent, and a dispersant to obtain a stream A;

[0033] (1-2) Molecular sieves are added to the material stream A for dispersion to obtain the material stream B.

[0034] The present invention has no particular limitation on the specific conditions of the mixing in step (1-1), as long as a uniform material flow A can be formed.

[0035] Preferably, the dispersion in step (1-2) is carried out under ultrasonic conditions, and the frequency of the ultrasonic waves is preferably 25KHz to 130KHz.

[0036] In the above-mentioned preferred embodiment of the present invention, by introducing a dispersant and combining the effect of ultrasound, the problem of high surface energy of the fine molecular sieve is overcome, making the surface of the molecular sieve easier to wet and disperse more evenly, while ensuring the stability of the dispersion system, laying the foundation for the subsequent preparation of core-shell structure catalysts.

[0037] Preferably, the solid content of the material stream B is 35 wt% to 55 wt%, preferably 35 wt% to 50 wt%.

[0038] According to the method provided by the present invention, preferably, the aluminum source is selected from aluminum sol and / or acidified pseudo-boehmite, preferably aluminum sol.

[0039] The present invention has a wide range of choices for the aluminum sol. Preferably, the aluminum sol has an Al2O3 mass content of 20% to 45%, more preferably 25% to 40%. The aluminum sol can be purchased commercially.

[0040] Preferably, the curing agent is selected from organic amines, preferably hexamethylenetetramine and / or urea, more preferably hexamethylenetetramine. The curing agent of the present invention can be purchased commercially.

[0041] Preferably, the mass concentration of the curing agent is 30% to 70%.

[0042] According to a preferred embodiment of the present invention, the amount of the curing agent added is 1% to 15% of the mass of the aluminum source calculated as alumina, preferably 2.5% to 12%. In the present invention, the amount of the curing agent added refers to the amount of the substance in the curing agent that actually plays a role, and is calculated as a pure substance, excluding the solvent in the curing agent.

[0043] The present invention allows for a wide range of dispersants, as long as they can facilitate wetting and dispersion on the molecular sieve surface. Preferably, the dispersant is selected from at least one of sodium lauryl sulfate, methylpentanol, trioctyl phosphate, a cellulose derivative, guar gum, and polyethylene glycol fatty acid esters. The dispersant can be purchased commercially.

[0044] Preferably, the cellulose derivative is selected from at least one of cellulose ether, cellulose ester, and cellulose ether ester; more preferably, the cellulose derivative is selected from at least one of methyl cellulose, ethyl cellulose, carboxymethyl cellulose, carboxyethyl cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose, cellulose nitrate, cellulose acetate, cellulose acetate butyrate, and cellulose xanthate.

[0045] Preferably, the mass concentration of the dispersant is 20% to 40%.

[0046] According to a preferred embodiment of the present invention, the amount of dispersant added is 5% to 15% of the mass of the aluminum source calculated as alumina. In the present invention, the amount of dispersant added refers to the amount of the substance that actually plays a role in the dispersant, calculated as a pure substance, and does not include the solvent in the dispersant.

[0047] In the method provided by the present invention, the selection range of the type of the molecular sieve can be the same as the selection range of the type of the molecular sieve in the carrier described in the first aspect, and will not be repeated here.

[0048] Preferably, the molecular sieve has a particle size of 1 to 10 microns, preferably 1.5 to 8 microns. Specifically, the molecular sieve can be placed in a grinding device with a crushing function such as a ball mill for processing to obtain a molecular sieve sample with a desired particle size.

[0049] Preferably, the amount of molecular sieve added is 0.1 to 2 times the mass of the aluminum source calculated as alumina.

[0050] In the present invention, the mixing in step (2) and the type and amount of the oil phase can be selected in a wide range, so as to enable the stream C to form a water-in-oil primary emulsion.

[0051] According to a preferred embodiment of the present invention, the kinematic viscosity of the oil phase at 40°C in step (2) is 20 to 40 mm 2 / s, preferably 25 to 35 mm 2 This preferred embodiment is more conducive to forming a water-in-oil microemulsion.

[0052] Preferably, the oil phase is selected from at least one of white oil, diesel, kerosene, lubricating oil and C10-C15 alkane compounds, preferably white oil and / or diesel.

[0053] Preferably, the amount of the oil phase added is 1 to 2.5 times the mass of stream B, preferably 1.2 to 2.5 times.

[0054] The present invention has a wide range of selection for the stirring rate of the mixing in step (2). Preferably, the stirring rate is 8000-15000 rpm.

[0055] According to the method provided by the present invention, preferably, the emulsifier in step (3) is a non-ionic emulsifier; further preferably, the hydrophilic-lipophilic balance value of the emulsifier is 3 to 10, preferably 4 to 9. This preferred embodiment is more conducive to emulsification to form a microemulsion.

[0056] Preferably, the emulsifier is selected from at least one of octylphenol polyoxyethylene ether, Span 20 and Span 40. The emulsifier can be purchased commercially.

[0057] Preferably, the amount of the emulsifier added is 3 wt% to 8 wt%, preferably 4 wt% to 7 wt%, of the mass of the aluminum source calculated as alumina.

[0058] According to the method provided by the present invention, the auxiliary agent is used to agglomerate and aggregate the molecular sieve, and the type of the auxiliary agent can be selected from a wide range, for example, it can be a nucleating agent and / or a coagulant.

[0059] Preferably, the auxiliary agent is selected from a polymer organic auxiliary agent, more preferably at least one of starch, protein, animal glue, sodium alginate, sodium carboxymethyl cellulose, polyacrylamide, sodium polyacrylate, polyvinyl pyridinium salt and polyethyleneimine, further preferably polyacrylamide. The auxiliary agent can be purchased commercially.

[0060] The present invention does not particularly limit the molecular weight of the auxiliary agent, and those skilled in the art can make an appropriate selection according to the specific type of auxiliary agent.

[0061] According to the present invention, preferably, the amount of the auxiliary agent added is 2 wt% to 10 wt% of the amount of the molecular sieve added, preferably 3 wt% to 10 wt%.

[0062] The present invention has a wide range of selection for the stirring rate of the mixing in step (3). Preferably, the stirring rate is 300-1000 rpm.

[0063] According to the present invention, there is no particular limitation on the order of mixing the substances in step (3). Preferably, the emulsifier is added first and then the auxiliary agent.

[0064] According to the method provided by the present invention, preferably, the solid content of the material stream D is 10 wt% to 20 wt%, and more preferably, the material stream D is a water-in-oil (W / O) emulsion.

[0065] According to the present invention, preferably, the forming in step (3) comprises: adding the material stream D dropwise into water for forming, preferably at a dropping speed of 60-100 drops / min.

[0066] According to a preferred embodiment of the present invention, the molding temperature is 85°C to 98°C, preferably 93°C to 97°C.

[0067] According to the method provided by the present invention, aging after the forming is more conducive to obtaining a spherical carrier with suitable pore volume and pore channel concentration.

[0068] The present invention has a wide range of selection for the aging conditions. Preferably, the aging conditions include: an aging temperature of 30 to 100° C., preferably 80 to 100° C., and an aging time of 1 to 48 hours, preferably 2 to 10 hours.

[0069] According to a preferred embodiment of the present invention, the method further includes performing an extraction before the washing. In this preferred embodiment, the extraction and washing after aging can recover organic matter from the material, preventing environmental pollution and also avoiding the problem of organic matter decomposition during the roasting process, which can cause strength loss.

[0070] The present invention has a wide range of selection for the extraction solvent and specific conditions, as long as the organic matter in the material can be recovered. Preferably, the extraction solvent is selected from at least one of petroleum ether, cyclohexane, toluene and anhydrous ethanol, more preferably a mixed solvent of at least one of petroleum ether, cyclohexane and toluene and anhydrous ethanol, and further preferably, the volume content of anhydrous ethanol in the mixed solvent is 25% to 50%.

[0071] According to the present invention, preferably, the extraction conditions include: extraction temperature of 90° C. to 110° C., and extraction time of 2 to 4 hours.

[0072] The present invention has no particular limitation on the equipment for performing the extraction, and for example, it can be a Soxhlet fat extractor.

[0073] The present invention has a wide range of conditions for washing. Preferably, the washing in step (3) is performed with deionized water until the filtrate is neutral. The preferred washing temperature is 65°C to 75°C.

[0074] The present invention does not particularly limit the drying and calcining conditions of step (3). Those skilled in the art can select them according to conventional technical means. Preferably, the drying temperature in step (3) is 100°C to 150°C, and the drying time is 6 to 10 hours. Preferably, the calcining temperature in step (3) is 450°C to 750°C, and the calcining time is 1 to 4 hours.

[0075] Furthermore, in the above-mentioned method for preparing the carrier, the carrier obtained in step (3) is a spherical carrier.

[0076] Furthermore, in the above-mentioned method for preparing the catalyst, the introduction of the active metal component onto the support obtained in step (3) in step (4) can be carried out by any one or more methods available in the art, specifically, at least one of kneading, impregnation, or a combination of kneading and impregnation, preferably an impregnation method. When the impregnation method is adopted, the metal salt containing the active metal component is first prepared into an impregnation solution, which is then loaded onto the support, and finally dried and calcined to obtain the catalyst, wherein the drying temperature is 100°C to 150°C, the drying time is 2 to 24 hours, and the calcination temperature is 400°C to 600°C, and the calcination time is 2 to 8 hours.

[0077] In combination with the above content, compared with the prior art, the catalytic diesel ebullated bed hydroconversion method provided by the present invention has the following advantages:

[0078] 1. The present invention adopts a two-stage ebullated bed series process and uses a core-shell structured catalytic diesel hydroconversion catalyst to process catalytic diesel. This can effectively solve the hot spot temperature fluctuation problem existing in the existing fixed bed reactor and the material backmixing problem existing in the single ebullated bed reactor. At the same time, by using different catalytic diesel hydroconversion catalysts in different reaction zones, the adaptability of the raw materials is enhanced, the functional division of the catalyst is clearer, the activity stability of the entire reaction system and the yield of the target product are improved, and the operation cycle of the device is extended.

[0079] 2. In the catalytic diesel boiling bed hydroconversion method provided by the present invention, the first catalytic diesel hydroconversion catalyst and the second catalytic diesel hydroconversion catalyst used are core-shell structure catalysts, which can realize the gradual reaction of catalytic diesel first hydrogenation and then cracking, improve the activity and stability of the catalyst, and can realize catalytic diesel hydroconversion to produce gasoline high-octane blending components or BTX, supporting the transformation of refining to chemical industry.

[0080] 3. In the catalytic diesel boiling bed hydroconversion method provided by the present invention, the surface energy of the fine molecular sieve used in the first catalytic diesel hydroconversion catalyst and the second catalytic diesel hydroconversion catalyst preparation method is very high. By using a dispersant and combining the effect of ultrasound, the surface of the molecular sieve is easier to wet and disperse more evenly, while ensuring the stability of the dispersed system, laying the foundation for the subsequent preparation of core-shell structure catalysts.

[0081] 4. In the catalytic diesel ebullating bed hydroconversion method provided by the present invention, the aluminum sol is made into a water-in-oil (W / O) emulsion in the preparation method of the first catalytic diesel hydroconversion catalyst and the second catalytic diesel hydroconversion catalyst. During the drop ball formation, the emulsion droplets enter the medium water and automatically shrink into a sphere with an oil film on the outer surface and the emulsion inside due to the action of surface tension. The stability of the emulsion is destroyed due to changes in temperature and pH value. The molecular sieve is in a free state in the aluminum sol solution. By adding a high molecular organic additive, physical and chemical changes occur. Through adsorption, bridging, cross-linking, and neutralization of the surface charge of the suspended matter, the particles are changed from the original repulsion to attraction, thereby forming a molecular sieve mixture and aggregation to form a core structure. At the same time, the curing agent in the emulsion is decomposed by heat, and the released alkaline gas causes the aluminum sol that wraps the core structure to form gel balls, thereby forming a catalyst carrier with a core-shell structure.

[0082] 5. In the catalytic diesel ebullating bed hydroconversion method provided by the present invention, the first and second catalytic diesel hydroconversion catalysts are prepared using extraction after aging to recover organic matter from the materials, preventing environmental pollution and avoiding the decomposition of organic matter during the calcination process, which can cause strength loss. Aluminum sol and molecular sieves are prepared as a water-in-oil (W / O) emulsion and then drop-shaped into spheres in water, overcoming the pollution issues associated with the formation of oil and oil-ammonia columns. The overall preparation process is environmentally friendly and pollution-free. BRIEF DESCRIPTION OF THE DRAWINGS

[0083] Figure 1 This is a schematic SEM line scan diagram of the carrier A1 sample prepared in Example 1 of the present invention.

[0084] Figure 2 The SiO2 distribution diagram along the radial direction of the carrier in the carrier samples prepared in the first reactor of Example 1, Comparative Example 1 and Comparative Example 2.

[0085] Figure 3 Schematic diagram of SEM dot plot of catalyst C-A1 prepared in Example.

[0086] Figure 4 This is a schematic SEM line scan diagram of the carrier B1 sample prepared in Example 1 of the present invention.

[0087] Figure 5 The SiO2 distribution diagram along the radial direction of the carrier in the carrier samples prepared in the second reactor of Example 1, Comparative Example 1 and Comparative Example 2.

[0088] Figure 6 Schematic diagram of SEM dot plot of catalyst C-B1 prepared in Example. DETAILED DESCRIPTION

[0089] The endpoints of the ranges and any values 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 endpoints of each range, the endpoints of each range and individual point values, and the individual point values can be combined with each other to obtain one or more new numerical ranges, which should be considered to be specifically disclosed herein.

[0090] The effects of the present invention are further illustrated by the following examples. The examples are based on the technical solution of the catalytic diesel ebullated bed hydroconversion method of the present invention and provide detailed implementation methods and specific operating procedures, but the scope of protection of the present invention is not limited to the following examples.

[0091] The experimental methods in the following examples, unless otherwise specified, are all conventional methods in the art. The experimental materials used in the following examples, unless otherwise specified, were purchased from conventional biochemical reagent stores.

[0092] In the present invention, the carrier is spherical and presents a macroscopic core-shell structure, with molecular sieve as the core layer and alumina as the shell layer. The core-shell structure of the carrier of the present invention and the ratio of the carrier shell thickness to the carrier diameter can be obtained by SEM characterization. SEM line scan is to determine the distribution of substances on the particles by measuring the strength of the measurement signal caused by a specific substance. Specifically for the present invention, Figure 2 As shown, the present invention determines the distribution of molecular sieve and alumina by the signal strength of SiO2 along the radial direction of the carrier sample. Figure 2 The SiO2 signal is normally distributed, and the signal appears in the middle of the carrier particle size, indicating that the carrier has a core-shell structure. The present invention defines the length corresponding to the peak width of the carrier SiO2 signal as the diameter of the core in the carrier, and the difference between the carrier diameter and the core diameter is defined as the shell thickness.

[0093] In the present invention, unless otherwise specified, SEM characterization was performed using a JSM-7500 scanning electron microscope manufactured by JEOL Ltd. at an accelerating voltage of 5 kV, an accelerating current of 20 A, and a working distance of 8 mm.

[0094] In the present invention, the contents of molecular sieve and alumina in the carrier are calculated based on the feed amount according to the requirements of the catalyst.

[0095] In the present invention, the spherical shape refers to a spherical shape in a broad sense, and quasi-spherical shapes are also within the protection scope of the present invention.

[0096] The distribution coefficient φ of the active metal component is used to represent the distribution pattern of the active metal component in the core layer and shell layer of the carrier. φ is used to represent the ratio of the active metal component content in the core layer to the active metal component content in the shell layer. SEM-EDS analysis can be performed using a JSM-7500F scanning electron microscope-energy dispersive spectrometer to analyze the structure and content of the sample, with an accelerating voltage of 5KV, an accelerating current of 20mA, and a working distance of 8mm. Specifically, Figure 6 As shown, starting from the center of the catalyst particle, seven points are marked at equal distances toward the edge of the catalyst particle. The center is designated as point 001, and points 002, 003, 004, 005, 006, and 007 are marked from the inside out. The present invention defines the distribution coefficient φ as the ratio of the total active metal content at points 001 to 005.

[0097] In the present invention, the carrier particle diameter is obtained by testing using the Q / SH 361 933-2020 method. Analytical method of the present invention: specific surface area, pore volume, external specific surface area, and pore distribution are measured using low-temperature liquid nitrogen physical adsorption. The instruments used are ASAP2405 and 2420 physical adsorption instruments produced by American companies. Relative crystallinity and unit cell parameters are measured using X-ray diffraction, using a D / max2500 X-ray diffraction analyzer produced by RIGAKU of Japan. The infrared acid content is measured using pyridine adsorption infrared spectroscopy using a NICOLET 6700 Fourier transform infrared spectrometer. The wear index is measured using a rotary drum method using a KM-ZV abrasion tester. The metal composition is measured using inorganic spectrophotometry. The lateral compression strength is measured using a ZQJ-II intelligent particle strength testing machine.

[0098] The technical features of the present invention are further described below through examples, but are not limited to the examples.

[0099] Example 1

[0100] (1) Preparation of the first catalytic diesel hydroconversion catalyst

[0101] The pore volume was 0.43 mL / g and the specific surface area was 814 m 2 / g, relative crystallinity 98%, SiO2 / Al2O3 molar ratio of 12, unit cell parameter 2.446nm, infrared total acidity of 0.8mmol / g Y-type molecular sieve is ground to a particle size of £1.5 micron powder.

[0102] To 150 g of aluminum sol with an Al2O3 mass content of 40% prepared by reacting aluminum with a hydrochloric acid solution, 15 g of a 40% hexamethylenetetramine solution and 19 g of a 25% sodium lauryl sulfate solution were added, and the mixture was stirred to obtain a uniform mixed solution.

[0103] Weigh 10 g of ground molecular sieve powder and add it to the above mixed solution. Under the action of ultrasound at a frequency of 100 kHz, a dispersed system solution containing molecular sieve with a solid content of 36.08 wt% is formed.

[0104] The above dispersion solution containing molecular sieve was added with 291g of a 40℃ kinematic viscosity of 28mm 2 / s white oil, and obtain a water-in-oil primary emulsion at a stirring speed of 800 rpm;

[0105] To the primary emulsion were added 75.5 g of a condensate of alkylphenol and ethylene oxide (OP-4, Jiangsu Plus Biotechnology Co., Ltd.) with a hydrophilic-lipophilic balance (HLB) of 8.0 at a concentration of 4.5 wt % and 0.43 g of polyacrylamide (weight-average molecular weight, 3,000,000, Sinopharm Group). The stirring speed was adjusted to 3500 rpm to obtain a water-in-oil (W / O) emulsion with a solid content of 12.5 wt %.

[0106] The obtained emulsion was added dropwise to water at a temperature of 95°C using a syringe to form the emulsion. After forming, the gel pellets were aged at 95°C for 1.5 hours. After the aging was completed, they were extracted with a mixed solution of petroleum ether and anhydrous ethanol in a volume ratio of 1:1 in a Soxhlet fat extractor at a temperature of 100°C for 2.5 hours, and then washed with 70°C deionized water until neutral, dried at 120°C for 6 hours, and calcined at 550°C for 3 hours to obtain a 1.01 mm spherical carrier A1.

[0107] Weigh 46.86 g of phosphoric acid and add 450 mL of distilled water. Then, add 169.71 g of molybdenum oxide and 63.78 g of basic nickel carbonate. Heat and stir until completely dissolved. Then, dilute the solution to 500 mL with distilled water to obtain Solution L-1. Carrier A1 was saturated with Solution L-1, dried at 110°C for 2 hours, and calcined at 450°C for 5 hours to obtain Catalyst C-A1. Its properties are shown in Table 1.

[0108] (2) Preparation of the second catalytic diesel hydroconversion catalyst

[0109] The pore volume was 0.43 mL / g and the specific surface area was 814 m 2 / g, relative crystallinity 98%, SiO2 / Al2O3 molar ratio of 12, unit cell parameter 2.446nm, infrared total acidity of 0.8mmol / g Y-type molecular sieve is ground to a particle size of £1.5 micron powder;

[0110] To 185 g of aluminum sol with an Al2O3 mass content of 27% were added 9.5 g of a 40 wt% hexamethylenetetramine solution and 20 g of a 25 wt% sodium lauryl sulfate solution, and the mixture was stirred to obtain a uniform mixed solution.

[0111] Weigh 50g of ground Y-type molecular sieve powder and add it to the above mixed solution. Under the action of ultrasound at a frequency of 100KHz, a dispersion system solution containing molecular sieve with a solid content of 37.78wt% is formed;

[0112] The above dispersion solution containing molecular sieve was added with 476.1 g of a 40°C kinematic viscosity of 28 mm 2 / s white oil, and obtain a water-in-oil primary emulsion at a stirring speed of 800 rpm;

[0113] To the primary emulsion, 55.8 g of 4.5 wt% octylphenol polyoxyethylene ether (OP-4, Jiangsu Plus Biotechnology Co., Ltd.) with a hydrophilic-lipophilic balance (HLB) of 8.0 and 2.0 g of polyacrylamide (weight-average molecular weight, 3,000,000, Sinopharm Group) were added. The stirring speed was adjusted to 3,500 rpm to obtain a water-in-oil (W / O) emulsion with a solid content of 12.5 wt%.

[0114] The obtained emulsion was added dropwise (80 drops / min) to water at 95°C using a syringe to form the emulsion. After forming, the gel pellets were aged at 95°C for 1.5 h. After aging, they were extracted with a mixed solution of petroleum ether and anhydrous ethanol in a volume ratio of 1:1 in a Soxhlet fat extractor at 100°C for 2.5 h, then washed with 70°C deionized water until neutral, dried at 120°C for 8 h, and calcined at 500°C for 3 h to obtain a 1.03 mm spherical carrier B1. Its properties are shown in Table 1.

[0115] Weigh 26.81 g of phosphoric acid and add 450 mL of distilled water. Then, add 72.81 g of molybdenum oxide and 30.70 g of basic nickel carbonate. Heat and stir until completely dissolved. Then, dilute the solution to 500 mL with distilled water to obtain Solution L-2. Carrier B1 was saturated with Solution L-2, dried at 110°C for 2 hours, and calcined at 450°C for 5 hours to obtain Catalyst C-B1. Its properties are shown in Table 2.

[0116] (3) Catalytic diesel fluidized bed hydrogenation conversion process

[0117] A series CSTR device was used, with inferior catalytic diesel as the raw material. The properties are shown in Table 3. The first reactor was filled with the first catalytic diesel hydroconversion catalyst prepared above, and the second reactor was filled with the second catalytic diesel hydroconversion catalyst prepared above. The temperature of the first reactor was 380°C, the temperature of the second reactor was 410°C, the reaction pressure was 8 MPa, and the space velocity was 0.5 h -1 The catalytic diesel was hydroconverted under the condition of hydrogen-to-oil volume ratio of 600:1. The generated oil after conversion was fractionated and cut. The fraction <210℃ was analyzed. The results are shown in Table 4.

[0118] Example 2

[0119] (1) Preparation of the first catalytic diesel hydroconversion catalyst

[0120] Other conditions were the same as those in Example 1, except that in the preparation of the first catalytic diesel hydroconversion catalyst, polyacrylamide was replaced with polyethyleneimine, the 40 wt% hexamethylenetetramine solution was replaced with a 50 wt% urea solution, and the dispersant sodium lauryl sulfate was replaced with trioctyl phosphate. After molding, the gel pellets were aged at 95°C for 1.5 h, then at 100°C for 4 h, and then calcined at 550°C, then at 500°C, to obtain a 1.03 mm spherical catalyst C-A2.

[0121] (2) Preparation of the second catalytic diesel hydroconversion catalyst

[0122] Other conditions were the same as in Example 1 to prepare Carrier B2. Weigh 28.00 g of phosphoric acid and add 450 mL of distilled water. Then, add 98.88 g of molybdenum oxide and 41.83 g of basic nickel carbonate. Heat and stir until completely dissolved. Then, dilute the solution to 500 mL with distilled water to obtain Solution L-3. Carrier B2 was saturated with Solution L-3, dried at 110°C for 2 h, and calcined at 450°C for 5 h to obtain Catalyst C-B2. Its properties are shown in Table 2.

[0123] (3) Catalytic diesel fluidized bed hydrogenation conversion process

[0124] The process conditions are the same as in Example 1.

[0125] Example 3

[0126] (1) Preparation of the first catalytic diesel hydroconversion catalyst

[0127] Other conditions were the same as those in Example 1. The amount of ground molecular sieve powder (10 g) was adjusted to 18 g, and the carrier calcination temperature was adjusted from 550°C to 500°C to obtain a 1.03 mm spherical catalyst C-A3.

[0128] (2) Preparation of the second catalytic diesel hydroconversion catalyst

[0129] Other conditions were the same as in Example 1, except that 50 g of ground molecular sieve powder was adjusted to 40 g to obtain 1.0 mm spherical carrier B3. Carrier B3 was saturated with solution L-3, dried at 110°C for 2 h, and calcined at 480°C for 3 h to obtain catalyst C-B3. Its properties are shown in Table 2.

[0130] (3) Catalytic diesel fluidized bed hydrogenation conversion process

[0131] The process conditions were the same as those in Example 1. The temperature of the second reactor was adjusted from 410° C. to 420° C., and the reaction pressure was adjusted from 8 MPa to 10 MPa.

[0132] Example 4

[0133] (1) Preparation of the first catalytic diesel hydroconversion catalyst

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

[0135] (2) Preparation of the second catalytic diesel hydroconversion catalyst

[0136] The conditions are the same as in Example 1.

[0137] (3) Catalytic diesel fluidized bed hydrogenation conversion process

[0138] A series CSTR device was used, with inferior catalytic diesel as the raw material. The properties are shown in Table 3. The first reactor was filled with the first catalytic diesel hydroconversion catalyst prepared above, and the second reactor was filled with the second catalytic diesel hydroconversion catalyst prepared above. The temperature of the first reactor was 385°C, the temperature of the second reactor was 420°C, the reaction pressure was 10 MPa, and the space velocity was 0.75 h -1 The catalytic diesel was hydroconverted under the condition of hydrogen-to-oil volume ratio of 600:1. The generated oil after conversion was fractionated and cut. The fraction <180℃ was analyzed. The results are shown in Table 4.

[0139] Example 5

[0140] (1) Preparation of the first catalytic diesel hydroconversion catalyst

[0141] The conditions are the same as in Example 1.

[0142] (2) Preparation of the second catalytic diesel hydroconversion catalyst

[0143] The conditions are the same as in Example 1.

[0144] (3) Catalytic diesel fluidized bed hydrogenation conversion process

[0145] A series CSTR device was used, with inferior catalytic diesel as the raw material. The properties are shown in Table 3. The first reactor was filled with the first catalytic diesel hydroconversion catalyst prepared above, and the second reactor was filled with the second catalytic diesel hydroconversion catalyst prepared above. The temperature of the first reactor was 390°C, the temperature of the second reactor was 425°C, the reaction pressure was 10 MPa, and the space velocity was 0.6 h -1 The catalytic diesel was hydroconverted under the condition of hydrogen-to-oil volume ratio of 600:1. The generated oil after conversion was fractionated and cut. The fraction <210℃ was analyzed. The results are shown in Table 4.

[0146] Example 6

[0147] (1) Preparation of the first catalytic diesel hydroconversion catalyst

[0148] The pore volume was 0.36 mL / g and the specific surface area was 743 m2 / g, relative crystallinity 97%, SiO2 / Al2O3 molar ratio of 15, unit cell parameter 2.442nm, infrared total acidity of 0.9mmol / g Y-type molecular sieve is ground to a particle size of £2.0 micron powder;

[0149] To 150 g of aluminum sol with an Al2O3 mass content of 35% prepared by reacting aluminum with a hydrochloric acid solution, 12.6 g of a 50% urea solution and 10.5 g of a 30 wt% trioctyl phosphate were added, and the mixture was stirred to obtain a uniform mixed solution.

[0150] 5 g of ground molecular sieve powder was weighed and added to the above mixture, and a dispersion solution containing molecular sieve with a solid content of 32.28 wt% was formed under the action of ultrasound at a frequency of 100 kHz;

[0151] The above dispersion solution containing molecular sieve was added with 270g of a 40℃ kinematic viscosity of 30mm 2 / s white oil, and obtain a water-in-oil primary emulsion at a stirring speed of 1000 rpm;

[0152] To the primary emulsion were added 52.5 g of Span 40 with a hydrophilic-lipophilic balance (HLB) of 6.7 at a concentration of 5 wt % and 0.25 g of polyacrylamide, and the stirring speed was adjusted to 5000 rpm to obtain a water-in-oil (W / O) emulsion with a solid content of 11.48 wt %.

[0153] The obtained emulsion was added dropwise to water at a temperature of 95°C using a syringe to form the emulsion. After forming, the gel pellets were aged at 95°C for 2.0 h. After the aging, they were extracted with a mixed solution of petroleum ether and anhydrous ethanol in a volume ratio of 1:1 in a Soxhlet fat extractor at 100°C for 3 h, then washed with 70°C deionized water until neutral, dried at 120°C for 8 h, and calcined at 500°C for 3 h to obtain a 1.01 mm spherical carrier A4.

[0154] The carrier A4 was saturated with the solution L-1, dried at 110°C for 2 h, and calcined at 450°C for 5 h to obtain the catalyst C-A4. The properties of the catalyst are shown in Table 1.

[0155] (2) Preparation of the second catalytic diesel hydroconversion catalyst

[0156] The pore volume was 0.36 mL / g and the specific surface area was 743 m 2 / g, relative crystallinity 97%, SiO2 / Al2O3 molar ratio of 15, unit cell parameter 2.442nm, infrared total acidity of 0.9mmol / g Y-type molecular sieve is ground to a particle size of £2.0 micron powder;

[0157] To 150 g of aluminum sol with an Al2O3 mass content of 30% prepared by reacting aluminum with a hydrochloric acid solution, 9.5 g of a 40% mass concentration of hexamethylenetetramine solution and 20 g of a 25wt% concentration of sodium lauryl sulfate solution were added, and the mixture was stirred to obtain a uniform mixed solution.

[0158] Weigh 30 g of ground molecular sieve powder and add it to the above mixture. Under the action of ultrasound at a frequency of 100 kHz, a dispersion solution containing molecular sieve with a solid content of 35.80 wt% is formed.

[0159] The above dispersion solution containing molecular sieve was added with 419g of a 40℃ kinematic viscosity of 28mm 2 / s white oil, and obtain a water-in-oil primary emulsion at a stirring speed of 800 rpm;

[0160] To the primary emulsion were added 60 g of Span 40 (commercially available from Guangdong Huana Chemical Co., Ltd.) with a hydrophilic-lipophilic balance (HLB) of 6.7 at a concentration of 5 wt % and 2.8 g of polyacrylamide (same as in Example 1). The stirring speed was adjusted to 5000 rpm to obtain a water-in-oil (W / O) emulsion with a solid content of 11.9 wt %.

[0161] The obtained emulsion was added dropwise to water at a temperature of 95°C using a syringe to form the emulsion. After forming, the gel balls were aged at 95°C for 1.5 hours. After the aging, they were extracted with a mixed solution of petroleum ether and anhydrous ethanol in a volume ratio of 1:1 in a Soxhlet fat extractor at a temperature of 100°C for 2.5 hours, and then washed with 70°C deionized water until neutral, dried at 120°C for 8 hours, and calcined at 500°C for 3 hours to obtain a 1.03 mm spherical carrier B4.

[0162] The carrier B4 was saturated with the solution L-3, dried at 110°C for 2 h, and calcined at 450°C for 5 h to obtain the catalyst C-B4. The properties of the catalyst are shown in Table 2.

[0163] (3) Catalytic diesel fluidized bed hydrogenation conversion process

[0164] A series CSTR device was used, with inferior catalytic diesel as the raw material. The properties are shown in Table 3. The first reactor was filled with the first catalytic diesel hydroconversion catalyst prepared above, and the second reactor was filled with the second catalytic diesel hydroconversion catalyst prepared above. The temperature of the first reactor was 380°C, the temperature of the second reactor was 410°C, the reaction pressure was 8 MPa, and the space velocity was 0.75 h -1 The catalytic diesel was hydroconverted under the condition of hydrogen-to-oil volume ratio of 600:1. The generated oil after conversion was fractionated and cut. The fraction <210℃ was analyzed. The results are shown in Table 4.

[0165] Comparative Example 1

[0166] (1) Preparation of the first catalytic diesel hydroconversion catalyst

[0167] The pore volume was 0.43 mL / g and the specific surface area was 814 m 2 / g, relative crystallinity 98%, SiO2 / Al2O3 molar ratio of 12, unit cell parameter 2.446nm, infrared total acidity of 0.8mmol / g Y-type molecular sieve is ground to a particle size of £1.5 micron powder;

[0168] To 150 g of aluminum sol having an Al2O3 content of 40% by mass, prepared by reacting aluminum with a hydrochloric acid solution, was added 15 g of a 40% by mass hexamethylenetetramine solution, and the mixture was stirred to obtain a uniform mixed solution.

[0169] Weigh 10 g of ground molecular sieve powder and add it to the above mixed solution. Under the action of ultrasound at a frequency of 100 kHz, a dispersion solution containing molecular sieve with a solid content of 40 wt% is formed.

[0170] The above dispersion solution containing molecular sieve was added with 291g of a 40℃ kinematic viscosity of 28mm 2 / s white oil, and obtain a water-in-oil primary emulsion at a stirring speed of 800 rpm;

[0171] To the primary emulsion were added 75.5 g of a 4.5 wt% condensate of alkylphenol and ethylene oxide (OP-4, Jiangsu Plus Biotechnology Co., Ltd.) with a hydrophilic-lipophilic balance (HLB) of 8.0 and 0.43 g of polyacrylamide (weight-average molecular weight, 3,000,000, Sinopharm Group). The stirring speed was adjusted to 3500 rpm to obtain a water-in-oil (W / O) emulsion with a solids content of 13.9%.

[0172] The obtained emulsion was added dropwise to water at a temperature of 95°C using a syringe to form the gel pellets. After forming, the gel pellets were aged at 95°C for 1.5 hours. After aging, they were extracted with a mixed solution of petroleum ether and anhydrous ethanol in a volume ratio of 1:1 in a Soxhlet fat extractor at 100°C for 2.5 hours. The pellets were then washed with deionized water at 70°C until neutral, dried at 120°C for 6 hours, and calcined at 550°C for 3 hours to obtain 1.01 mm spherical carrier F1. The SiO2 distribution of the spherical carrier F1 is shown in the figure below. Figure 2 As shown. Figure 2 It can be seen from the figure that the SiO2 distribution diagram is scattered, which proves that the spherical carrier F1 obtained in Comparative Example 1 does not have a core-shell structure.

[0173] The carrier F1 was saturated with the solution L-1, dried at 110°C for 2 h, and calcined at 450°C for 5 h to obtain the catalyst C-F1. The properties of the catalyst are shown in Table 1.

[0174] (2) Preparation of the second catalytic diesel hydroconversion catalyst

[0175] The pore volume was 0.43 mL / g and the specific surface area was 814 m 2 / g, relative crystallinity 98%, SiO2 / Al2O3 molar ratio of 12, unit cell parameter 2.446nm, infrared total acidity of 0.8mmol / g Y-type molecular sieve is ground into a powder with a particle size of 1.5 microns;

[0176] To 185 g of aluminum sol having an Al2O3 content of 27% by mass, prepared by reacting aluminum with a hydrochloric acid solution, was added 9.5 g of a 40% by mass hexamethylenetetramine solution, and the mixture was stirred to obtain a uniform mixed solution.

[0177] Weigh 50 g of ground molecular sieve powder and add it to the above mixed solution. Under the action of ultrasound at a frequency of 100 kHz, a dispersed system solution containing molecular sieve with a solid content of 40.88 wt% is formed.

[0178] The above dispersion solution containing molecular sieve was added with 476.1 g of a 40°C kinematic viscosity of 28 mm 2 / s white oil, and obtain a water-in-oil primary emulsion at a stirring speed of 800 rpm;

[0179] To the primary emulsion were added 55.8 g of a 4.5 wt% condensate of alkylphenol and ethylene oxide (OP-4, Jiangsu Plus Biotechnology Co., Ltd.) with a hydrophilic-lipophilic balance (HLB) of 8.0 and 2.0 g of polyacrylamide (weight-average molecular weight, 3,000,000, Sinopharm Group). The stirring speed was adjusted to 3500 rpm to obtain a water-in-oil (W / O) emulsion with a solids content of 13.1%.

[0180] The obtained emulsion was added dropwise to water at a temperature of 95°C using a syringe to form the gel pellets. After forming, the gel pellets were aged at 95°C for 1.5 hours. After aging, they were extracted with a mixed solution of petroleum ether and anhydrous ethanol in a volume ratio of 1:1 in a Soxhlet fat extractor at a temperature of 100°C for 2.5 hours. The pellets were then washed with deionized water at 70°C until neutral, dried at 120°C for 8 hours, and calcined at 500°C for 3 hours to obtain 1.03 mm spherical carrier F2. The SiO2 distribution diagram of the spherical carrier F2 is shown in FIG. Figure 2 As shown. Figure 2 It can be seen from the figure that the SiO2 distribution diagram is scattered, which proves that the spherical carrier F2 obtained in Comparative Example 1 does not have a core-shell structure.

[0181] The carrier F2 was saturated with the solution L-2, dried at 110°C for 2 h, and calcined at 450°C for 5 h to obtain the catalyst C-F2. The properties of the catalyst are shown in Table 2.

[0182] (3) Catalytic diesel fluidized bed hydrogenation conversion process

[0183] A series CSTR device was used, with inferior catalytic diesel as raw material. The properties are shown in Table 3. The first reactor was filled with the first catalytic diesel hydroconversion catalyst prepared above, and the second reactor was filled with the second catalytic diesel hydroconversion catalyst prepared above. The first reactor temperature was 380°C, the second reactor temperature was 410°C, the reaction pressure was 8 MPa, and the space velocity was 0.5 h -1 The volume ratio of hydrogen to oil was 600:1, and the catalytic diesel was hydroconverted. The oil generated after conversion was fractionated and cut, and the fraction <210℃ was analyzed. The results are shown in Table 4.

[0184] Comparative Example 2

[0185] (1) Preparation of the first catalytic diesel hydroconversion catalyst

[0186] The pore volume was 0.43 mL / g and the specific surface area was 814 m 2 / g, relative crystallinity 98%, SiO2 / Al2O3 molar ratio of 12, unit cell parameter 2.446nm, infrared total acidity of 0.8mmol / g Y-type molecular sieve is ground to a particle size of £1.5 micron powder.

[0187] To 150 g of aluminum sol with an Al2O3 mass content of 40% prepared by reacting aluminum with a hydrochloric acid solution, 15 g of a 40% hexamethylenetetramine solution and 19 g of a 25 wt% sodium lauryl sulfate solution were added, and the mixture was stirred to obtain a uniform mixed solution.

[0188] Weigh 10 g of ground molecular sieve powder and add it to the above mixed solution. Under the action of ultrasound at a frequency of 100 kHz, a dispersed system solution containing molecular sieve with a solid content of 36.08 wt% is formed.

[0189] The above dispersion solution containing molecular sieve was added with 291g of a 40℃ kinematic viscosity of 28mm 2 / s white oil, and obtain a water-in-oil primary emulsion at a stirring speed of 800 rpm;

[0190] To the primary emulsion, 75.5 g of a condensate of alkylphenol and ethylene oxide (OP-4, Jiangsu Plus Biotechnology Co., Ltd.) with a hydrophilic-lipophilic balance (HLB) of 8.0 was added at a concentration of 4.5 wt %. The stirring speed was adjusted to 3500 rpm to obtain a water-in-oil (W / O) emulsion with a solid content of 12.5 wt %.

[0191] The obtained emulsion was added dropwise to water at a temperature of 95°C using a syringe to form the gel pellets. After forming, the gel pellets were aged at 95°C for 1.5 hours. After aging, they were extracted with a mixed solution of petroleum ether and anhydrous ethanol in a volume ratio of 1:1 in a Soxhlet fat extractor at 100°C for 2.5 hours. The pellets were then washed with deionized water at 70°C until neutral, dried at 120°C for 6 hours, and calcined at 550°C for 3 hours to obtain 1.01 mm spherical carrier F3. The SiO2 distribution diagram of the spherical carrier F3 is shown in FIG. Figure 2 As shown. Figure 2 It can be seen from the figure that the SiO2 distribution diagram is scattered, which proves that the spherical carrier F3 obtained in Comparative Example 2 does not have a core-shell structure.

[0192] The carrier F3 was saturated with the solution L-1, dried at 110°C for 2 h, and calcined at 450°C for 5 h to obtain the catalyst C-F3. The properties of the catalyst are shown in Table 1.

[0193] (2) Preparation of the second catalytic diesel hydroconversion catalyst

[0194] The pore volume was 0.43 mL / g and the specific surface area was 814 m 2 / g, relative crystallinity 98%, SiO2 / Al2O3 molar ratio of 12, unit cell parameter 2.446nm, infrared total acidity of 0.8mmol / g Y-type molecular sieve is ground into a powder with a particle size of 1.5 microns;

[0195] To 185 g of aluminum sol with an Al2O3 mass content of 27% prepared by reacting aluminum with a hydrochloric acid solution, 9.5 g of a 40% hexamethylenetetramine solution and 20 g of a 25 wt% sodium lauryl sulfate solution were added, and the mixture was stirred to obtain a uniform mixed solution.

[0196] Weigh 50 g of ground molecular sieve powder and add it to the above mixture. Under the action of ultrasound at a frequency of 100 kHz, a dispersion solution containing molecular sieve with a solid content of 37.78 wt% is formed.

[0197] The above dispersion solution containing molecular sieve was added with 476.1 g of a 40°C kinematic viscosity of 28 mm 2 / s white oil, and obtain a water-in-oil primary emulsion at a stirring speed of 800 rpm;

[0198] To the primary emulsion, 55.8 g of a condensate of alkylphenol and ethylene oxide (OP-4) with a hydrophilic-lipophilic balance (HLB) of 8.0 was added at a concentration of 4.5 wt %, and the stirring speed was adjusted to 3500 rpm to obtain a water-in-oil (W / O) emulsion with a solid content of 12.5%.

[0199] The obtained emulsion was added dropwise to water at a temperature of 95°C using a syringe to form the gel pellets. After forming, the gel pellets were aged at 95°C for 1.5 hours. After aging, they were extracted with a mixed solution of petroleum ether and anhydrous ethanol in a volume ratio of 1:1 in a Soxhlet fat extractor at a temperature of 100°C for 2.5 hours. The pellets were then washed with deionized water at 70°C until neutral, dried at 120°C for 8 hours, and calcined at 500°C for 3 hours to obtain a 1.03 mm spherical carrier F4. The SiO2 distribution diagram of the spherical carrier F4 is shown in FIG. Figure 2 As shown. Figure 2 It can be seen from the figure that the SiO2 distribution diagram is scattered, which proves that the spherical carrier F4 obtained in Comparative Example 2 does not have a core-shell structure.

[0200] The carrier F4 was saturated with the solution L-2, dried at 110°C for 2 h, and calcined at 450°C for 5 h to obtain the catalyst C-F4. The properties of the catalyst are shown in Table 2.

[0201] (3) Catalytic diesel fluidized bed hydrogenation conversion process

[0202] A series CSTR device was used, with inferior catalytic diesel as the raw material. The properties are shown in Table 3. The first reactor was filled with the first catalytic diesel hydroconversion catalyst prepared above, and the second reactor was filled with the second catalytic diesel hydroconversion catalyst prepared above. The temperature of the first reactor (first reactor temperature) was 380°C, the temperature of the second reactor (second reactor temperature) was 410°C, the reaction pressure was 8 MPa, and the space velocity was 0.5 h -1 The catalytic diesel was hydroconverted under the condition of hydrogen-to-oil volume ratio of 600:1. The generated oil after conversion was fractionated and cut. The fraction <210℃ was analyzed. The results are shown in Table 4.

[0203] The physicochemical properties of the catalyst obtained above are listed in Table 1 and Table 2. The SiO2 distribution results are shown in Table 2. Figure 1 .

[0204] Table 1 Properties of the first catalytic diesel hydroconversion catalyst

[0205]

[0206] Note: In Table 1, the contents of alumina and molecular sieve refer to the mass percentage.

[0207] Table 2 Properties of the Second Catalytic Diesel Hydroconversion Catalyst

[0208]

[0209] The catalysts prepared in Tables 1 and 2 were loaded onto two CSTR devices connected in series, respectively. Catalytic diesel was used for process evaluation. The properties of the feedstock oil used are shown in Table 3, and the evaluation conditions are shown in Table 4. The generated oil after 1000 hours of operation was cut, and the results are shown in Table 4.

[0210] Table 3 Properties of crude oil

[0211]

[0212] Table 4 Evaluation process conditions and evaluation results

[0213]

[0214] Note: The products in Table 4 refer to the fractions with a temperature of <210°C (for Examples 1-3, 5, and 6) or the fractions with a temperature of <180°C (for Example 4).

[0215] The generated oils of Example 1, Comparative Example 1 and Comparative Example 2, which were operated for 2000 h, were cut. The results are shown in Table 5.

[0216] Table 5 Evaluation results after 2000 hours of operation

[0217]

[0218] It can be seen from the data in the table that compared with the comparative example, the catalytic diesel hydroconversion catalyst of the present invention has a higher impurity removal rate, higher product yield and light aromatic hydrocarbon content after grading, and can be used as a gasoline blending component or to produce BTX after cutting.

Claims

1. A catalytic diesel ebullated bed hydroconversion method comprising the following steps: S1: In the presence of hydrogen, the catalytic diesel enters the first ebullated bed reaction zone and contacts with the first catalytic diesel hydroconversion catalyst to react; S2: The reaction effluent obtained in the first ebullated bed reaction zone enters the second ebullated bed reaction zone and reacts in the presence of hydrogen and a second catalytic diesel hydroconversion catalyst. The reaction effluent is separated to obtain target products of different fractions; wherein, The first catalytic diesel hydroconversion catalyst used in the first ebullated bed reaction zone is a catalytic diesel hydroconversion catalyst with a core-shell structure having a low molecular sieve content. The first catalytic diesel hydroconversion catalyst comprises a carrier and an active metal component. The carrier comprises a molecular sieve as a core layer and an alumina shell layer. The carrier particle diameter is 0.5 to 3 mm, and the thickness of the carrier shell layer is 50 to 95% of the carrier diameter. The active metal components are Group VIII metal and Group VIB metal. Based on the weight of the catalyst, the molecular sieve content is 5 wt% to 25 wt%, the content of the Group VIII metal as oxide is 2 wt% to 6 wt%, and the content of the Group VIB metal as oxide is 15 wt% to 30 wt%. The second catalytic diesel hydroconversion catalyst used in the second ebullating bed reaction zone is a catalytic diesel hydroconversion catalyst with a core-shell structure and a high molecular sieve content. The second catalytic diesel hydroconversion catalyst includes a carrier and an active metal component. The carrier has a molecular sieve as a core layer and an alumina shell layer. The diameter of the carrier particles is 0.5 to 3 mm, and the thickness of the carrier shell is 30 to 60% of the carrier diameter. The active metal components are Group VIII metals and Group VIB metals. Based on the weight of the catalyst, the molecular sieve content is 30 wt% to 50 wt%, the content of the Group VIII metal as oxide is 1 wt% to 3 wt%, and the content of the Group VIB metal as oxide is 8 wt% to 15 wt%.

2. The catalytic diesel ebullated bed hydroconversion method according to claim 1, characterized in that: The first catalytic diesel hydroconversion catalyst includes a carrier and an active metal component. The carrier has a molecular sieve as a core layer and an alumina shell layer. The diameter of the carrier particles is 0.8 to 2 mm, and the thickness of the carrier shell is 60 to 95% of the carrier diameter. Based on the weight of the catalyst, the molecular sieve content is 10 wt% to 25 wt%.

3. The catalytic diesel ebullated bed hydroconversion method according to claim 1, characterized in that: The second catalytic diesel hydroconversion catalyst includes a carrier and an active metal component. The carrier has a molecular sieve as a core layer and an alumina shell layer. The diameter of the carrier particles is 0.8 to 2 mm, and the thickness of the carrier shell layer is 30 to 55% of the carrier diameter.

4. The catalytic diesel ebullated bed hydroconversion method according to claim 1, characterized in that: The molecular sieves in the first catalytic diesel hydroconversion catalyst and the second catalytic diesel hydroconversion catalyst are selected from one or more of Y-type molecular sieve, β molecular sieve, ZSM-5 molecular sieve, SAPO molecular sieve, and MCM-41 molecular sieve.

5. The catalytic diesel ebullated bed hydroconversion method according to claim 1, characterized in that: The Group VIII metal in the first catalytic diesel hydroconversion catalyst and the second catalytic diesel hydroconversion catalyst is Ni and / or Co, and the Group VIB metal in the first catalytic diesel hydroconversion catalyst and the second catalytic diesel hydroconversion catalyst is W and / or Mo.

6. The catalytic diesel ebullated bed hydroconversion method according to claim 1, characterized in that: The molecular sieve content of the second catalytic diesel hydroconversion catalyst is 20% to 45% higher than that of the first catalytic diesel hydroconversion catalyst.

7. The catalytic diesel ebullated bed hydroconversion method according to claim 1 or 6, characterized in that: The molecular sieve content of the second catalytic diesel hydroconversion catalyst is 20% to 40% higher than that of the first catalytic diesel hydroconversion catalyst.

8. The catalytic diesel ebullated bed hydroconversion method according to claim 1, characterized in that: The specific surface area of the first catalytic diesel hydroconversion catalyst is 120 to 250 m 2 / g, the pore volume is 0.35~0.50mL / g, the total acid value is 0.30~0.50mmol / g, and the B / L acid ratio is 0.1~0.

8.

9. The catalytic diesel ebullated bed hydroconversion method according to claim 1, characterized in that: The specific surface area of the second catalytic diesel hydroconversion catalyst is 250 to 450 m 2 / g, the pore volume is 0.30~0.50mL / g, the total acid value is 0.35~0.65mmol / g, and the B / L acid ratio is 0.6~1.

1.

10. The catalytic diesel ebullated bed hydroconversion method according to claim 1, characterized in that: The content of the Group VIII metal in the first catalytic diesel hydroconversion catalyst, calculated as oxide, is 0.5% to 5% higher than the content of the Group VIII metal in the second catalytic diesel hydroconversion catalyst, calculated as oxide.

11. The catalytic diesel ebullated bed hydroconversion method according to claim 1, characterized in that: The content of the Group VIII metal in the first catalytic diesel hydroconversion catalyst, calculated as oxide, is 1% to 3% higher than the content of the Group VIII metal in the second catalytic diesel hydroconversion catalyst, calculated as oxide.

12. The catalytic diesel ebullated bed hydroconversion method according to claim 1, characterized in that: The content of the Group VIB metal in the first catalytic diesel hydroconversion catalyst, calculated as oxide, is 7% to 22% higher than the content of the Group VIB metal in the second catalytic diesel hydroconversion catalyst, calculated as oxide.

13. The catalytic diesel ebullated bed hydroconversion method according to claim 1, characterized in that: The content of the Group VIB metal in the first catalytic diesel hydroconversion catalyst, calculated as oxide, is 7% to 15% higher than the content of the Group VIB metal in the second catalytic diesel hydroconversion catalyst, calculated as oxide.

14. The catalytic diesel ebullated bed hydroconversion method according to claim 1, characterized in that: The distribution coefficient φ of the active metal components in the first catalytic diesel hydroconversion catalyst and the second catalytic diesel hydroconversion catalyst in the carrier core layer and the shell layer is 0.6~0.95:1, and φ represents the ratio of the content of the active metal components in the carrier core layer to the content of the active metal components in the shell layer.

15. The catalytic diesel ebullated bed hydroconversion method according to claim 1, characterized in that: The properties of catalytic diesel are: density 0.88~0.99g / cm 3 , dry point is 360~400℃, aromatic hydrocarbon content is 50wt%~90wt%, sulfur content is 0.2wt%~3.0wt%, and nitrogen content is 500~4000 μg / g.

16. The catalytic diesel ebullated bed hydroconversion method according to claim 1, characterized in that: The operating conditions of the first ebullated bed reaction zone are: reaction pressure of 6-10 MPa, reaction temperature of 350-400°C, liquid hourly volume space velocity of 0.3-3.0 h -1 , the volume ratio of hydrogen to oil is 100~1000.

17. The catalytic diesel ebullated bed hydroconversion method according to claim 1, characterized in that: The operating conditions of the second ebullated bed reaction zone are: reaction pressure of 6-10 MPa, reaction temperature of 380-430°C, liquid hourly volume space velocity of 0.3-3.0 h -1 , the volume ratio of hydrogen to oil is 100~1000.

18. The catalytic diesel ebullated bed hydroconversion method according to claim 1, characterized in that: The reaction temperature of the second ebullated bed reaction zone is 20° C. to 80° C. higher than the reaction temperature of the first ebullated bed reaction zone.

19. The catalytic diesel ebullated bed hydroconversion method according to claim 1, characterized in that: The reaction temperature of the second ebullated bed reaction zone is 20° C. to 50° C. higher than the reaction temperature of the first ebullated bed reaction zone.

20. The catalytic diesel ebullated bed hydroconversion method according to claim 1, characterized in that: The first catalytic diesel hydroconversion catalyst and the second catalytic diesel hydroconversion catalyst are prepared by the same preparation method. During the preparation process, the first catalytic diesel hydroconversion catalyst and the second catalytic diesel hydroconversion catalyst are obtained by adjusting the amount of molecular sieve and active metal component. The preparation method comprises the following steps: (1) mixing an aluminum source, a curing agent, a dispersant, and a molecular sieve to obtain a stream B; (2) Mixing stream B with the oil phase to obtain stream C; (3) Mixing the stream C obtained in step (2), an emulsifier, and an auxiliary agent to obtain a stream D, and molding, aging, washing, drying, and calcining the stream D to obtain a carrier; the auxiliary agent is a polymer organic auxiliary agent; (4) Introducing active metal components onto the support obtained in step (3) to obtain a catalyst.

21. The catalytic diesel ebullated bed hydroconversion method according to claim 20, characterized in that: Step (1) includes: (1-1) An aluminum source, a curing agent, and a dispersant are mixed to obtain a stream A, wherein the curing agent is an organic amine; (1-2) Molecular sieves are added to the material stream A for dispersion to obtain the material stream B.

22. The catalytic diesel ebullated bed hydroconversion method according to claim 20 or 21, characterized in that: The aluminum source is selected from aluminum sol and / or acidified pseudo-boehmite.

23. The catalytic diesel ebullated bed hydroconversion method according to claim 20 or 21, characterized in that: The aluminum source is aluminum sol.

24. The catalytic diesel ebullated bed hydroconversion method according to claim 22, characterized in that: The mass content of Al2O3 in aluminum sol is 20% to 45%.

25. The catalytic diesel ebullated bed hydroconversion method according to claim 22, characterized in that: The mass content of Al2O3 in aluminum sol is 25% to 40%.

26. The catalytic diesel ebullated bed hydroconversion method according to claim 20, characterized in that: The curing agent is hexamethylenetetramine and / or urea.

27. The catalytic diesel ebullated bed hydroconversion method according to claim 20 or 21, characterized in that: The curing agent is hexamethylenetetramine.

28. The catalytic diesel ebullated bed hydroconversion method according to claim 20 or 21, characterized in that: The dispersant is selected from at least one of sodium lauryl sulfate, methylpentanol, trioctyl phosphate, cellulose derivatives, guar gum and fatty acid polyethylene glycol esters, and the amount of the dispersant added is 5% to 15% of the mass of the aluminum source calculated as alumina.

29. The catalytic diesel ebullated bed hydroconversion method according to claim 28, characterized in that: The cellulose derivative is at least one selected from cellulose ether and cellulose ester.

30. The catalytic diesel ebullated bed hydroconversion method according to claim 28, characterized in that: The cellulose derivative is selected from cellulose ethers and esters.

31. The catalytic diesel ebullated bed hydroconversion method according to claim 28, characterized in that: The cellulose derivative is at least one selected from methyl cellulose, ethyl cellulose, carboxymethyl cellulose, carboxyethyl cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose, cellulose nitrate, cellulose acetate, cellulose acetate butyrate, and cellulose xanthate.

32. The catalytic diesel ebullated bed hydroconversion method according to claim 20, characterized in that: In step (1), the molecular sieve particle size is 1 to 10 microns, and the molecular sieve is selected from one or more of Y-type molecular sieve, β molecular sieve, ZSM-5 molecular sieve, SAPO molecular sieve, and MCM-41 molecular sieve. The amount of molecular sieve added is 0.1 to 2 times the mass of the aluminum source calculated as alumina.

33. The catalytic diesel ebullated bed hydroconversion method according to claim 20 or 32, characterized in that: In step (1), the particle size of the molecular sieve is 1.5 to 8 microns.

34. The catalytic diesel ebullated bed hydroconversion method according to claim 20, characterized in that: The kinematic viscosity of the oil phase in step (2) at 40°C is 20-40 mm 2 / s, the oil phase is selected from at least one of white oil, diesel, kerosene, lubricating oil and C10-C15 alkane compounds; the amount of the oil phase added is 1-2.5 times the mass of the material flow B.

35. The catalytic diesel ebullated bed hydroconversion method according to claim 20 or 34, characterized in that: The kinematic viscosity of the oil phase in step (2) at 40°C is 25-35 mm 2 / s; the oil phase is white oil and / or diesel; the amount of oil phase added is 1.2 to 2.5 times the mass of stream B.

36. The catalytic diesel ebullated bed hydroconversion method according to claim 20, characterized in that: The emulsifier in step (3) is a nonionic emulsifier; the hydrophilic-lipophilic balance value of the emulsifier is 3 to 10, and the amount of the emulsifier added is 3 wt% to 8 wt% of the mass of the aluminum source calculated as alumina.

37. The catalytic diesel ebullated bed hydroconversion method according to claim 20 or 36, characterized in that: The emulsifier in step (3) is a non-ionic emulsifier; the hydrophilic-lipophilic balance value of the emulsifier is 4 to 9, and the amount of the emulsifier added is 4 wt% to 7 wt% of the mass of the aluminum source calculated as alumina.

38. The catalytic diesel ebullated bed hydroconversion method according to claim 20, characterized in that: The emulsifier is selected from at least one of octylphenol polyoxyethylene ether, Span 20 and Span 40.

39. The catalytic diesel ebullated bed hydroconversion method according to claim 20, characterized in that: The auxiliary agent is at least one of starch, protein, animal glue, sodium alginate, sodium carboxymethyl cellulose, polyacrylamide, sodium polyacrylate, polyvinyl pyridinium salt and polyethyleneimine, and the added amount of the auxiliary agent is 2wt% to 10wt% of the added amount of the molecular sieve.

40. The catalytic diesel ebullated bed hydroconversion method according to claim 39, characterized in that: The auxiliary agent is polyacrylamide; the amount of the auxiliary agent added is 3wt% to 10wt% of the amount of the molecular sieve added.

41. The catalytic diesel ebullated bed hydroconversion method according to claim 20, characterized in that: The molding temperature is 85℃~98℃.

42. The catalytic diesel ebullated bed hydroconversion method according to claim 20 or 41, characterized in that: The molding temperature is 93℃~97℃.

43. The catalytic diesel ebullated bed hydroconversion method according to claim 20, characterized in that: The aging conditions include: aging temperature of 30 to 100° C., and aging time of 1 to 48 hours.

44. The catalytic diesel ebullated bed hydroconversion method according to claim 20 or 43, characterized in that: The aging conditions include: aging temperature of 80°C to 100°C, and aging time of 2 to 10 hours.

45. The catalytic diesel ebullated bed hydroconversion method according to claim 20, characterized in that: Extraction is performed before washing. The solvent used for extraction is selected from at least one of petroleum ether, cyclohexane, toluene and anhydrous ethanol. The extraction conditions include: extraction temperature of 90° C. to 110° C. and extraction time of 2 to 4 hours.

46. The catalytic diesel ebullated bed hydroconversion method according to claim 20 or 45, characterized in that: Extraction is performed before washing. The solvent used for extraction is a mixed solvent of at least one of petroleum ether, cyclohexane and toluene and anhydrous ethanol. The volume content of anhydrous ethanol in the mixed solvent is 25% to 50%.

47. The catalytic diesel ebullated bed hydroconversion method according to claim 20, characterized in that: The drying temperature in step (3) is 100° C. to 150° C., and the drying time is 6 to 10 hours; the roasting temperature in step (3) is 450° C. to 750° C., and the roasting time is 1 to 4 hours.

48. The catalytic diesel ebullated bed hydroconversion method according to claim 20, characterized in that: In step (4), the active metal component is introduced into the carrier obtained in step (3) by at least one of kneading, impregnation, and a combination of kneading and impregnation.

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