Residue hydrocracking solid base catalyst, and preparation method and application thereof

Abstract

The application provides a solid base catalyst for residue hydrotreating and a preparation method and application thereof, and belongs to the technical field of residue hydrotreating catalysts. The catalyst contains a modified mesoporous material with high hydrothermal stability, so that the catalyst has rich and stable mesoporous channels and no acidic center, and the dehydrogenation condensation reaction rate of polycyclic aromatic hydrocarbons is significantly reduced. The activation of hydrocarbon molecules is more easily induced on the basic center, and dissociative adsorption of the active intermediate is formed at a lower temperature, so that the olefins in the product are timely hydrogenated and saturated on the hydrogenation center, and coking in the reactor wall, internal components or pipelines is reduced or prevented. The preparation method comprises the following steps: firstly, a solid base catalyst is prepared; and then, a solid base catalyst for residue hydrotreating is prepared. When the catalyst prepared by the method is applied to heavy oil hydrotreating catalytic conversion reaction and is used for treating vacuum residue, the conversion rate of the heavy oil is increased by more than 10 percentage points, and the coke yield is reduced by more than 2.5 percentage points.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of residue hydroupgrading catalysts, and particularly relates to a residue hydroupgrading solid alkali catalyst and a preparation method and application thereof. BACKGROUND

[0002] With the increasing heaviness and inferiority of oil resources worldwide, efficient conversion of heavy and inferior feed oil has become one of the main trends in future development of oil refining; how to clean and efficiently process heavy oil, especially vacuum residue, and produce high-value-added chemicals is not only a focus of the world's oil refining industry and a worldwide technical problem, but also a major problem that needs to be solved by domestic oil refining industry.

[0003] Residue hydrocracking technology has a significant competitive advantage and good development prospects when processing cracking feedstocks with high carbon residue and high metal content, and reduces the reaction severity, improves the reaction efficiency, increases the oil yield, and reduces the coke yield, thereby reducing the cost of residue processing, which is an important development direction of residue hydrocracking technology. The existing slurry bed hydrocracking technology often adds ferrous sulfate, ore powder and coal powder, etc. Due to the low catalytic activity of these solid powders, a large amount of them needs to be added, which causes serious equipment wear and increases the separation cost.

[0004] CN106423142A discloses a poor-quality heavy oil suspension bed hydrocracking catalyst and a preparation method thereof. The catalyst uses high-temperature hydrothermally activated bauxite ore powder as a carrier, and loads one or more transition metals in Group VIB or Group VIII as an active component, and has a low coke formation rate when processing poor-quality heavy oil. However, due to the low specific surface area of the catalyst carrier, the heavy oil conversion activity of the catalyst is low.

[0005] CN104998693A discloses a carrier and a poor-quality oil hydrogenation catalyst based on the carrier and a preparation method thereof. The carrier is an acid-treated bauxite, and after modification, the specific surface area and pore volume of the bauxite are significantly increased, the acid centers on the surface of the carrier are redistributed, the pore structure is optimized, and the heavy oil conversion activity of the hydrogenation catalyst is significantly improved. However, the catalyst has a high coke formation rate. In addition, the acid treatment method used in the preparation process of the catalyst carrier produces a large amount of waste acid, which does not meet the concept of green chemistry, and the acid treatment reduces the utilization rate of raw materials and increases the production cost.

[0006] CN110586099B discloses a poor-quality residue suspension bed hydrocracking catalyst and a preparation method thereof. The catalyst uses iron chloride and iron sulfate as inorganic iron sources, and uses sawdust powder as a template to prepare a mesoporous γ-Fe2O3 catalyst with a high specific surface area by a sol-gel method. The catalyst has good application effect in heavy oil suspension bed hydrocracking reaction. However, the catalyst has poor hydrothermal stability and is prone to deactivation.

[0007] In summary, the existing supported catalysts have problems of low dispersity, easy coking and short service life, and some new synthesis methods for preparing high-dispersity catalysts have defects of high cost and long process flow, which limit their industrial application. SUMMARY

[0008] Therefore, the present application aims to provide a solid base catalyst for residue hydrotreating, which has high heavy oil conversion rate and low coke yield, and a preparation method thereof.

[0009] To achieve the above-mentioned purposes, the technical scheme of the present application is as follows: a solid base catalyst for residue hydrotreating, based on the total weight of the solid base catalyst for residue hydrotreating, contains 1 wt%-20 wt% of a hydrogenation component, and the balance is a solid base catalyst; based on the total weight of the solid base catalyst, the solid base catalyst contains 1 wt%-99 wt% of a modified mesoporous material and 0.1 wt%-20 wt% of an alkaline metal oxide, and the balance is clay.

[0010] The alkaline metal oxide is one or more of alkali metal or alkaline earth metal oxides.

[0011] The hydrogenation component is one or more of Group VIB or Group VIII transition metals.

[0012] Further, the modified mesoporous material is prepared by the following method:

[0013] First, an active gel of the modified mesoporous material is prepared: a mesoporous material is prepared by a sol-gel method, a soluble metal salt of a doping metal is introduced in the sol stage to obtain a mesoporous material gel doped with metal, and the gel is then treated with an inorganic acid solution and deionized water in sequence to remove the soluble metal salt of the doping metal and the inorganic acid in the gel, thereby obtaining an active gel of the modified mesoporous material; the inorganic acid is one or more of nitric acid, sulfuric acid and hydrochloric acid.

[0014] Then, the active gel is activated and dispersed: the active gel obtained in the previous step is mixed with an activation aid, an inorganic acid and deionized water in a strong shearing machine, and then activated and dispersed on a sand mill to obtain a homogeneous sol slurry of the modified mesoporous material; the inorganic acid is one or more of nitric acid, sulfuric acid and hydrochloric acid; the inorganic acid is added in an amount such that the pH of the slurry is 0.5-5.

[0015] Further, the mesoporous material is one or more of silicon-containing composite oxides, silicon dioxide and white carbon black; and the specific surface area of the mesoporous material is 300-800 m 2 / g, pore volume 0.3-1.8 cm³ 3 / g, with an average pore size of 5-50 nm; the silicon-containing composite oxide is one or more of silicon-aluminum composite oxide, silicon-calcium composite oxide, silicon-magnesium composite oxide, and silicon-potassium composite oxide.

[0016] Furthermore, the solid alkaline catalyst for hydrocracking of residual oil is a microsphere catalyst with a particle size of 0-200 μm.

[0017] The present invention further provides a method for preparing the above-mentioned solid alkaline catalyst for hydrocracking of residual oil, comprising the following steps:

[0018] Step 1: Prepare a solid base catalyst;

[0019] First, a modified mesoporous material active gel is prepared: the mesoporous material is prepared by sol-gel method, and a soluble metal salt of doped metal is introduced in the sol stage to obtain a metal-doped mesoporous material gel. The gel is then treated sequentially with an inorganic acid solution and deionized water to remove the soluble metal salt of doped metal and the inorganic acid in the gel, thus obtaining the modified mesoporous material active gel; the inorganic acid is one or more of nitric acid, sulfuric acid, and hydrochloric acid.

[0020] Then, the active gel is activated and dispersed: the active gel obtained in the previous step is thoroughly mixed with the activating agent, inorganic acid and deionized water in a high-strength shear mill, and then activated and dispersed in a sand mill to obtain a homogeneous sol slurry of modified mesoporous material; the inorganic acid is one or more of nitric acid, sulfuric acid and hydrochloric acid; the amount of inorganic acid added makes the pH of the slurry 0.5-5;

[0021] Finally, the stabilizer is spray-dried: the soluble salt of the alkali metal is mixed with the stabilizer and deionized water, and then the sol slurry and clay obtained in the previous step are added in sequence. After mixing evenly, the mixture is spray-dried and calcined to obtain a solid alkali catalyst.

[0022] Step 2: Prepare solid alkaline catalyst for hydrocracking of residue oil;

[0023] The soluble metal salt of the hydrogenation component is introduced into the solid base catalyst by one of the following methods: ion exchange, impregnation, or co-precipitation. The catalyst is then dried and calcined to obtain a solid base catalyst for hydrocracking of residue oil.

[0024] Furthermore, the doped metal is one or more of boron, aluminum, gallium, copper, chromium, vanadium, zirconium, and molybdenum; the mass of the doped metal, expressed as the mass of the metal oxide, is in a weight ratio of 0.001-10:1 to the mass of the dry substrate of the active gel.

[0025] Further, the activation aid is one or more of sodium gluconate, sodium citrate, citric acid, potassium sodium tartrate, tartaric acid, sorbitol, maltitol, polyvinyl alcohol; the weight ratio of the activation aid to the dry base of the active gel is 0.001-10:1.

[0026] Further, the stabilizing aid is one or more of polyacrylamide, melamine, ethylenediaminetetraacetic acid, disodium ethylenediaminetetraacetate, citric acid, methacrylic acid-methoxy polyethylene glycol methacrylate; the weight ratio of the stabilizing aid to the active gel is 0.001-10:1.

[0027] Further, the calcination condition of the solid base catalyst for residue hydroupgrading is calcination treatment at 450-750 DEG C under 0-100% water vapor for 0.5-4h.

[0028] In addition, the application further provides the application of the solid base catalyst for residue hydroupgrading in heavy oil hydroupgrading catalytic conversion reaction.

[0029] Compared with the prior art, the solid base catalyst for residue hydroupgrading and the preparation method and application thereof have the following advantages: compared with the existing catalyst, the solid base catalyst for residue hydroupgrading prepared by the application has the advantages of high heavy oil conversion rate and low coke yield. Specifically, taking the vacuum residue of a certain refinery as the raw material, the evaluation results show that when the catalyst prepared by the method of the application is used to treat the vacuum residue, the heavy oil conversion rate is increased by more than 10 percentage points, and the coke yield is reduced by more than 2.5 percentage points. The reason is that the solid base catalyst for residue hydroupgrading provided by the application has rich and stable mesoporous channels and no acidic center, which significantly reduces the dehydrogenation condensation reaction rate of polycyclic aromatic hydrocarbons; the activation of hydrocarbon molecules is more easily induced on the basic center, and the dissociative adsorption of active intermediates can occur at a lower temperature, and the olefins in the product are timely hydrogenated and saturated on the hydrogenation center, thereby reducing or preventing coking in the reactor wall, internal components or pipelines. DETAILED DESCRIPTION

[0030] It should be noted that the embodiments in the application and the features in the embodiments can be combined with each other without conflict.

[0031] The application aims to provide a solid base catalyst for residue hydroupgrading with high heavy oil conversion rate and low coke yield, and a preparation method thereof, and specifically relates to a solid base catalyst for vacuum residue hydroupgrading catalytic conversion, which solves the problem that the catalyst prepared by the prior art is difficult to process heavy and poor quality oil products such as vacuum residue for a long period of time and with high efficiency.

[0032] The application discloses a solid base catalyst for residue hydrotreating, wherein the solid base catalyst contains 1 wt%-20 wt% of a hydrogenation component and the rest is a solid base catalyst; the solid base catalyst contains 1 wt%-99 wt% of a modified mesoporous material and 0.1 wt%-20 wt% of an alkaline metal oxide, and the rest is clay.

[0033] The alkaline metal oxide is one or more of alkali metal or alkaline earth metal oxides, preferably one or more of potassium oxide, rubidium oxide, magnesium oxide, calcium oxide and barium oxide.

[0034] The hydrogenation component is one or more of VIB group or VIII group transition metals, preferably one or more of iron oxide, iron sulfate, nickel oxide, molybdenum oxide and tungsten oxide.

[0035] The modified mesoporous material is prepared by the following method:

[0036] Firstly, an active gel of the modified mesoporous material is prepared: a mesoporous material is prepared by a sol-gel method, a soluble metal salt of a doping metal is introduced in a sol stage to obtain a mesoporous material gel doped with the metal, and the gel is treated with an inorganic acid solution and deionized water in sequence to remove the soluble metal salt of the doping metal and the inorganic acid in the gel, so as to obtain the active gel of the modified mesoporous material; the inorganic acid is one or more of nitric acid, sulfuric acid and hydrochloric acid.

[0037] Then, the active gel is activated and dispersed: the active gel obtained in the last step is mixed with an activation aid, an inorganic acid and deionized water in a strong shearing machine, and then activated and dispersed on a sand mill to obtain a homogeneous sol slurry of the modified mesoporous material; the inorganic acid is one or more of nitric acid, sulfuric acid and hydrochloric acid; the inorganic acid is added in an amount such that the PH of the slurry is 0.5-5.

[0038] The mesoporous material is one or more of a silicon-containing composite oxide, silicon dioxide and white carbon black; and the mesoporous material has a specific surface area of 300-800 m 2 / g, a pore volume of 0.3-1.8 cm 3 / g and an average pore size of 5-50 nm; the silicon-containing composite oxide is one or more of a silicon-aluminum composite oxide, a silicon-calcium composite oxide, a silicon-magnesium composite oxide and a silicon-potassium composite oxide.

[0039] The solid base catalyst for residue hydrotreating is a microspherical catalyst with a particle size of 0-200 μm.

[0040] The solid base catalyst for residue hydroupgrading provided by the present application contains a modified mesoporous material with high hydrothermal stability, so that the catalyst has abundant and stable mesoporous channels and no acidic center, and the dehydrogenation condensation reaction rate of polycyclic aromatic hydrocarbons is significantly reduced; the macromolecules of heavy oil are more likely to induce the activation of hydrocarbon molecules on the basic center, and dissociative adsorption is formed to form active intermediates at a lower temperature, and the olefins in the product are hydrogenated and saturated in time on the hydrogenation center, so that coking in the reactor wall, internal components or pipelines is reduced or prevented.

[0041] The present application further provides a preparation method of the solid base catalyst for residue hydroupgrading.

[0042] Step 1, preparation of a solid base catalyst with high hydrothermal stability;

[0043] Firstly, the modified mesoporous material active gel is prepared: the mesoporous material is prepared by a sol-gel method, a soluble metal salt of a doped metal is introduced in the sol stage to obtain a mesoporous material gel doped with the metal, and the gel is then treated with an inorganic acid solution and deionized water in sequence to remove the soluble metal salt of the doped metal and the inorganic acid in the gel, thereby obtaining the modified mesoporous material active gel; the inorganic acid is one or more of nitric acid, sulfuric acid and hydrochloric acid;

[0044] The doped metal is one or more of boron, aluminum, gallium, copper, chromium, vanadium, zirconium and molybdenum; and the weight ratio of the doped metal (calculated as the mass of the metal oxide) to the dry base mass of the active gel is 0.001-10:1.

[0045] Then, the active gel is activated and dispersed: the active gel obtained in the last step is mixed with an activation aid, an inorganic acid and deionized water in a strong shearing machine, and then activated and dispersed on a sand mill to obtain a homogeneous sol slurry of the modified mesoporous material; the inorganic acid is one or more of nitric acid, sulfuric acid and hydrochloric acid; and the inorganic acid is added in an amount such that the PH of the slurry is 0.5-5;

[0046] The activation aid is one or more of sodium gluconate, sodium citrate, citric acid, potassium sodium tartrate, tartaric acid, sorbitol, maltitol and polyvinyl alcohol; and the weight ratio of the activation aid to the dry base mass of the active gel is 0.001-10:1.

[0047] Finally, the stable aid is slurried and sprayed: a soluble salt of an alkaline metal is mixed with a stable aid and deionized water, and then the sol slurry obtained in the last step and clay are added in sequence, and then mixed uniformly, followed by spray drying and calcination to obtain the solid base catalyst.

[0048] The stabilizing agent is one or more of polyacrylamide, melamine, ethylenediaminetetraacetic acid, disodium ethylenediaminetetraacetic acid, citric acid, and methoxy polyethylene glycol methacrylate (PCE); the weight ratio of the stabilizing agent to the active gel is 0.001-10:1.

[0049] Step 2: Prepare solid alkaline catalyst for hydrocracking of residue oil;

[0050] The soluble metal salt of the hydrogenation component is introduced into the solid base catalyst by one of the following methods: ion exchange, impregnation, or co-precipitation. The catalyst is then dried and calcined to obtain a solid base catalyst for hydrocracking of residue oil.

[0051] The roasting conditions for the solid alkaline catalyst for hydrocracking of residual oil are 450-750℃ and 0-100% steam for 0.5-4 hours.

[0052] Furthermore, this invention also provides the application of the above-mentioned solid alkaline catalyst for hydrocracking of residual oil in the hydrocatalytic conversion reaction of heavy oil.

[0053] The invention process is illustrated below with examples. It should be understood that the specific embodiments described herein are for illustration and explanation only, and are not intended to limit the invention.

[0054] Example 1

[0055] The solid base catalyst for hydrocracking of residual oil consists of a solid base catalyst and a hydrotreating component. Based on the total weight of the solid base catalyst, the hydrotreating metal oxide is 10 wt% and the solid base catalyst is 90 wt%. The modified mesoporous material in the solid base catalyst is silica, which, based on the total weight of the solid base catalyst, consists of 55 wt% silica, 10 wt% alkaline metal oxide, and 35 wt% kaolin.

[0056] (1) Preparation of modified mesoporous material active gel: Take 2000g of water glass solution with modulus of 3.2 and silica content of 29.5 wt%, place it in a reactor and heat it to 50℃. Under continuous stirring, slowly add 26.3g of gallium nitrate nonahydrate at a dry weight ratio of gallium oxide to silica of 0.02:1, followed by slow addition of dilute nitric acid (15%) to adjust the pH value to about 6. Stir for 30 minutes to obtain gallium-modified silica hydrogel; add 10 wt% dilute nitric acid solution (1000g) and treat at 50℃ for 15 hours, then wash with deionized water until the filtrate is neutral to obtain gallium-modified silica active gel (silica solid content in gel is 19%).

[0057] (2) Activated dispersion of active gel: according to the weight ratio of citric acid to gallium modified silica gel (dry basis) of 0.03:1, 17.7 g of citric acid was added, followed by adding appropriate amount of nitric acid and deionized water, controlling the slurry PH to be 1.5, the silica solid content to be 17%, the above slurry was mixed for 30 minutes by using a strong shear machine, and then treated by a sand mill for 60 minutes at a speed of 3000 rpm, to obtain a gallium modified silica homogeneous sol slurry;

[0058] (3) Stabilizing additive slurry spray: 382.8 g of calcium nitrate tetrahydrate was dissolved in 810 g of deionized water, according to the weight ratio of stabilizing additive to alkaline metal and additive metal oxide of 0.1:1, 9 g of disodium ethylenediaminetetraacetate was added and stirred for 30 minutes, followed by adding 2912 g of gallium modified silica homogeneous sol slurry (solid content 17%) and stirring for 30 minutes, finally adding 366 g of kaolin (solid content 86%) and stirring for 120 minutes, using a spray drying device for drying and forming, controlling the outlet temperature to be 135℃, collecting the catalyst sample with particle size in the range of 0-100 μm, to obtain a solid base catalyst;

[0059] (4) Preparation of residue hydrocracking solid base catalyst: 307.7 g of ferric chloride hexahydrate was dissolved in 810 g of deionized water to prepare an impregnation solution; 810 g of solid base catalyst (water absorption rate 100%) was used to load hydrogenation metal by using an equal volume impregnation method, the catalyst was dried at 120℃ for 6 hours and calcined at 650℃ for 4 hours, to obtain a residue hydrocracking solid base catalyst.

[0060] Example 2

[0061] The residue hydrocracking solid base catalyst is composed of a solid base catalyst and a hydrogenation component, based on the total weight of the residue hydrocracking solid base catalyst, the hydrogenation metal oxide is 10 wt%, and the solid base catalyst is 90 wt%; the modified mesoporous material in the solid base catalyst is a silicon-aluminum composite oxide, based on the total weight of the solid base catalyst, the silicon-aluminum composite oxide is 55 wt%, the alkaline metal oxide is 10 wt%, and the kaolin is 35 wt%;

[0062] (1) Preparation of modified mesoporous material active gel: 2000 g of water glass solution with modulus of 3.2 and silica content of 29.5 wt% is taken in a reactor and heated to 50°C, 20.18 g of chromium nitrate nonahydrate is slowly added under constant stirring at a weight ratio of gallium oxide to silica of 0.005:1, followed by the slow addition of 215.8 g of aluminum nitrate nonahydrate, and finally the addition of an appropriate amount of dilute nitric acid (15%) to adjust the pH to about 6, and stirring for 30 minutes to obtain a chromium-modified silica-alumina composite oxide gel; 10 wt% of dilute nitric acid solution (1000 g) is added at 50°C for 15 hours, followed by washing with deionized water until the filtrate is neutral to obtain a chromium-modified silica-alumina composite oxide active gel (the silica-alumina composite oxide solid content in the gel is 19%);

[0063] (2) The active gel is activated and dispersed by the same method as in Example 1, except that 32.47 g of tartaric acid is added at a weight ratio of tartaric acid to chromium-modified silica-alumina composite oxide active gel (dry basis) of 0.05:1;

[0064] (3) The auxiliary agent is stabilized by the same method as in Example 1 to make a pulp spray, except that 97.6 g of potassium nitrate is used instead of calcium nitrate tetrahydrate;

[0065] (4) Preparation of a solid base catalyst for residual oil hydrocracking: 153.9 g of iron trichloride hexahydrate and 164.8 g of nickel nitrate hexahydrate are dissolved in 810 g of deionized water to prepare an impregnation solution; 810 g of a solid base catalyst (water absorption rate of 100%) is loaded with hydrogenation metals by an equal volume impregnation method, the catalyst is dried at 120°C for 6 hours, and calcined at 650°C for 4 hours in a 100% water vapor atmosphere to obtain a solid base catalyst for residual oil hydrocracking.

[0066] Example 3

[0067] The solid base catalyst for residual oil hydrocracking is composed of a solid base catalyst and a hydrogenation component, with the hydrogenation metal oxide being 15 wt% and the solid base catalyst being 85 wt% based on the total weight of the solid base catalyst for residual oil hydrocracking; the mesoporous material in the solid base catalyst is silica, with the silica being 55 wt%, the basic metal oxide being 15 wt%, and the kaolin being 30 wt% based on the total weight of the solid base catalyst;

[0068] (1) Preparation of mesoporous material active gel is the same as in Example 1;

[0069] (2) The active gel is activated and dispersed by the same method as in Example 1, except that 5.9 g of polyvinyl alcohol is added at a weight ratio of polyvinyl alcohol to gallium-modified silica active gel (dry basis) of 0.01:1;

[0070] (3) Stabilizing additive pulping spray: 289.2 g of magnesium nitrate hexahydrate and 382.8 g of calcium nitrate tetrahydrate were dissolved in 810 g of deionized water, 67.5 g of melamine was added according to the weight ratio of stabilizing additive to alkali metal oxide of 0.5:1, stirred for 30 minutes, then 2912 g of gallium modified silicon-aluminum composite oxide active gel (solid content 17%) was added and stirred for 30 minutes, finally 314 g of kaolin (solid content 86%) was added and stirred for 120 minutes, mixed and pulped for 60 minutes, dried and formed using a spray drying device, the outlet temperature was controlled at 135℃, and the catalyst sample with a particle size in the range of 0-100 μm was collected to obtain a solid base catalyst;

[0071] (4) The same method as in Example 1 was used to prepare a residue hydrocracking solid base catalyst, except that the amounts of iron trichloride hexahydrate and deionized water were 461.6 g and 850 g, respectively.

[0072] In order to compare the performance of the catalysts of the examples of the present application, two reference catalysts were prepared according to the published patent.

[0073] Comparative Example 1

[0074] (1) Bauxite activation treatment: 1000 g of natural bauxite ore powder was hydrothermally activated in a 100% steam atmosphere at 700℃ for 6 hours to obtain a catalyst carrier;

[0075] (2) The catalyst of Comparative Example 1 was prepared in the same way as in Example 1.

[0076] Comparative Example 2

[0077] 580 g of iron trichloride hexahydrate and 2 g of EDTA were dissolved in 4000 g of deionized water, 2000 g of activated carbon was added and stirred uniformly, 250 g of ammonia water was added dropwise while stirring, and the stirring was continued for 60 minutes, then the filter cake was obtained by suction filtration and washing, and the filter cake was dried at 120℃ for 6 hours and calcined at 650℃ for 4 hours to obtain the catalyst of Comparative Example 2.

[0078] The performance evaluation method of the catalysts of the examples and comparative examples of the present application is as follows:

[0079] The catalysts of the examples and comparative examples were evaluated for their performance in a poor-quality heavy oil suspension bed hydrogenation reaction device: 400 g of vacuum residue and 40 g of catalyst were added to a suspension bed reactor, the air in the reactor was replaced with hydrogen at room temperature and the pressure was increased to 5.0 Mpa, and the reaction was carried out at 420℃ for 2.0 hours. After the reaction was completed, the temperature was lowered to room temperature, and the product was extracted with toluene to obtain a liquid phase product and a toluene insoluble product.

[0080] The properties of the residue are shown in Table 1, and the reaction results are shown in Table 2. The calculation methods of the evaluation indexes are as follows:

[0081] Heavy oil conversion rate

[0082] Coke yield

[0083] Heavy metal removal rate

[0084] Table 1 Basic properties of raw materials used in examples and comparative examples

[0085]

[0086] Table 2 Evaluation results of catalysts after hydrothermal treatment in examples and comparative examples

[0087]

[0088] From the comparison of the above tables, it can be seen that the catalysts prepared by the method of the present application (Examples 1-3) have a heavy oil conversion rate increased by more than 10 percentage points and a coke yield decreased by more than 2.5 percentage points when treating vacuum residue, as compared with the reference catalysts (Comparative Examples 1 and 2).

[0089] The above only describes the preferred embodiments of the present application and is not intended to limit the present application. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application shall be included in the protection scope of the present application.

Claims

1. A solid base catalyst for hydrocracking of residual oil, characterized by: The solid base catalyst component contains 1 wt%-20 wt% of the modified mesoporous material and 0.1 wt%-20 wt% of the basic metal oxide, with the balance being clay, based on the total weight of the solid base catalyst component; the sum of the mass fractions of the components in the solid base catalyst component is 100%; The basic metal oxide is one or more of alkali metal or alkaline earth metal oxides; The hydrogenation component is one or more of Group VIB or Group VIII transition metals; Preparation of the solid base catalyst component: First, a mesoporous material is prepared by a sol-gel method, and a soluble metal salt of a doping metal is introduced in the sol stage to obtain a metal-doped mesoporous material gel, which is then treated with an inorganic acid solution and deionized water in sequence to remove the soluble metal salt of the doping metal and the inorganic acid in the gel, thereby obtaining a modified mesoporous material active gel; the inorganic acid is one or more of nitric acid, sulfuric acid, and hydrochloric acid; The mesoporous material is one or more of silicon-containing composite oxide, silicon dioxide, white carbon black; and the specific surface area of the mesoporous material is 300-800 m 2 / g, the pore volume is 0.3-1.8 cm 3 / g, and the average pore size is 5-50 nm; the silicon-containing composite oxide is one or more of silicon-aluminum composite oxide, silicon-calcium composite oxide, silicon-magnesium composite oxide, silicon-potassium composite oxide. The doping metal is one or more of aluminum, gallium, copper, chromium, vanadium, zirconium, and molybdenum; the weight ratio of the mass of the doping metal in the form of metal oxide to the dry mass of the active gel is (0.001-10):1; Then, the active gel obtained in the previous step is mixed with an activation aid, an inorganic acid, and deionized water in a strong shear machine, and then activated and dispersed on a sand mill to obtain a homogeneous sol slurry of the modified mesoporous material; the inorganic acid is one or more of nitric acid, sulfuric acid, and hydrochloric acid; the inorganic acid is added in an amount such that the pH of the slurry is 0.5-5; The activation aid is one or more of sodium gluconate, sodium citrate, citric acid, potassium sodium tartrate, tartaric acid, sorbitol, maltitol, and polyvinyl alcohol; Finally, a soluble salt of a basic metal and a stabilizing aid are stirred and mixed with deionized water, and then the sol slurry obtained in the previous step and clay are added in sequence, stirred and mixed uniformly, and then spray dried and calcined to obtain the solid base catalyst component; The stabilizing aid is one or more of polyacrylamide, melamine, ethylenediaminetetraacetic acid, disodium ethylenediaminetetraacetate, citric acid, and methacrylic acid-methoxy polyethylene glycol methacrylate; The calcination conditions are calcination treatment at 450-750°C under 0-100% water vapor for 0.5-4h.

2. The solid base catalyst for hydrocracking of residual oil according to claim 1, characterized by: The solid base catalyst for residue hydrocracking is a microspherical catalyst with a particle size of 0-200μm.

3. A process for the preparation of the solid base catalyst for hydrocracking of residual oil according to claim 1 or 2, characterized in that, The method comprises the following steps: Step 1, preparation of the solid base catalyst component; First, the modified mesoporous material active gel is prepared: A mesoporous material is prepared by a sol-gel method, and a soluble metal salt of a doping metal is introduced in the sol stage to obtain a metal-doped mesoporous material gel, which is then treated with an inorganic acid solution and deionized water in sequence to remove the soluble metal salt of the doping metal and the inorganic acid in the gel, thereby obtaining a modified mesoporous material active gel; the inorganic acid is one or more of nitric acid, sulfuric acid, and hydrochloric acid; The mesoporous material is one or more of silicon-containing composite oxide, silicon dioxide, white carbon black; and the specific surface area of the mesoporous material is 300-800 m 2 / g, the pore volume is 0.3-1.8 cm 3 / g, and the average pore size is 5-50 nm; the silicon-containing composite oxide is one or more of silicon-aluminum composite oxide, silicon-calcium composite oxide, silicon-magnesium composite oxide, silicon-potassium composite oxide. The doping metal is one or more of aluminum, gallium, copper, chromium, vanadium, zirconium, and molybdenum; the weight ratio of the mass of the doping metal to the mass of the active gel dry base is (0.001-10):

1. Then, the active gel is activated and dispersed: The active gel obtained in the previous step is mixed with an activation aid, an inorganic acid, and deionized water in a strong shearing machine, and then activated and dispersed on a sand mill to obtain a homogeneous sol slurry of the modified mesoporous material; the inorganic acid is one or more of nitric acid, sulfuric acid, and hydrochloric acid; the inorganic acid is added in an amount such that the pH of the slurry is 0.5-5; The activation aid is one or more of sodium gluconate, sodium citrate, citric acid, potassium sodium tartrate, tartaric acid, sorbitol, maltitol, and polyvinyl alcohol; Finally, the stable aid is slurried and sprayed: The soluble salt of an alkali metal and the stable aid are stirred and mixed with deionized water, and then the sol slurry obtained in the previous step and clay are sequentially added, stirred and mixed uniformly, and then spray dried, calcined to obtain a solid alkali catalytic component; The stable aid is one or more of polyacrylamide, melamine, ethylenediaminetetraacetic acid, disodium ethylenediaminetetraacetate, citric acid, and methacrylic acid-methoxy polyethylene glycol methacrylate; The calcination conditions are calcination treatment at 450-750°C under 0-100% water vapor for 0.5-4h; Step 2, preparation of a residue hydrotreating solid alkali catalyst; The soluble metal salt of the hydrogenation component is introduced into the solid alkali catalytic component by any one of ion exchange method, impregnation method, and coprecipitation method, and then dried and calcined to obtain a residue hydrotreating solid alkali catalyst.

4. The method for preparing the solid base catalyst for residue hydrocracking according to claim 3, characterized in that: The weight ratio of the activation aid to the mass of the active gel dry base is (0.001-10):

1.

5. The method for preparing the solid alkaline catalyst for hydrocracking of residual oil according to claim 3, characterized in that: The weight ratio of the stable aid to the active gel is (0.001-10):

1.

6. Application of the residue hydrotreating solid alkali catalyst of claim 1 or 2 in a residue hydrotreating reaction.

Images