CN117696061A

CN117696061A - Residual oil hydro-cracking solid base catalyst and preparation method and application thereof

Info

Publication number: CN117696061A
Application number: CN202311751611.5A
Authority: CN
Inventors: 臧甲忠; 马明超; 赵训志; 陈博阳; 季莹辉; 汪洋; 李佳; 彭晓伟
Original assignee: China National Offshore Oil Corp CNOOC; CNOOC Tianjin Chemical Research and Design Institute Co Ltd
Current assignee: China National Offshore Oil Corp CNOOC; CNOOC Tianjin Chemical Research and Design Institute Co Ltd
Priority date: 2023-12-19
Filing date: 2023-12-19
Publication date: 2024-03-15

Abstract

The invention provides a residual oil hydro-cracking solid base catalyst and a preparation method and application thereof, and belongs to the technical field of residual oil hydro-cracking catalysts, wherein the catalyst contains a high-hydrothermal stability modified mesoporous material, so that the catalyst has rich and stable mesoporous channels and no acid center, and the dehydrogenation condensation reaction rate of polycyclic aromatic hydrocarbon is obviously reduced; the heavy oil macromolecule is easier to induce activation of hydrocarbon molecules on an alkaline center, dissociation adsorption can be carried out at a lower temperature to form an active intermediate, olefins in the product are timely hydrogenated and saturated on a hydrogenation center, and coking of the olefins in a reactor wall, an inner member or a pipeline is reduced or prevented. The catalyst prepared by the method is applied to the hydro-catalytic conversion reaction of heavy oil, when the vacuum residuum is treated, the conversion rate of the heavy oil is improved by more than 10 percent, and the coke yield is reduced by more than 2.5 percent.

Description

Residual oil hydro-cracking solid base catalyst and preparation method and application thereof

Technical Field

The invention belongs to the technical field of residual oil hydrocracking catalysts, and particularly relates to a residual oil hydrocracking solid base catalyst, and a preparation method and application thereof.

Background

With the increasing worldwide heavy and poor quality of petroleum resources, the efficient conversion of heavy and poor quality raw oil becomes one of the main trends of future oil refining development; how to clean and process heavy oil, especially vacuum residuum, and produce high added value chemicals is not only a focus of world oil refining industry attention and a worldwide technical problem, but also a great problem to be solved by domestic oil refining industry.

When the residuum hydrocracking technology is used for treating high carbon residue and high metal content cracking raw materials, the method has remarkable competitiveness and good development prospect, reduces the reaction severity, improves the reaction efficiency, improves the oil yield and reduces the coke yield, thereby reducing the residuum processing cost, and being an important development direction of the residuum hydrocracking technology. The existing slurry hydrocracking technology is often added with ferrous sulfate, ore powder, coal dust and the like, and the solid powder has lower catalytic activity, so that the addition amount is larger, the equipment is seriously worn, and the separation cost is increased.

CN106423142a discloses a hydrocracking catalyst for a low-quality heavy oil suspension bed and a preparation method thereof, wherein the catalyst takes bauxite ore powder after high-temperature hydrothermal activation as a carrier, one or more transition metals in a group VIB or VIII are loaded as active components, and the catalyst has lower coking rate when the low-quality heavy oil is treated. However, the catalyst is limited by the lower specific surface area of the catalyst carrier, and the heavy oil conversion activity of the catalyst is lower.

CN104998693a discloses a carrier and a poor-quality oil hydrogenation catalyst based on the carrier and a preparation method thereof. The carrier is bauxite subjected to acid treatment, the specific surface area and pore volume of the modified bauxite are obviously increased, the acid center on the surface of the carrier is redistributed, the pore structure is optimized, the heavy oil conversion activity of the hydrogenation catalyst is obviously improved, and the catalyst has higher coking rate. In addition, the acid treatment method adopted in the preparation process of the catalyst carrier generates a large amount of waste acid, which does not accord with the concept of green chemistry, and the acid treatment leads to the reduction of the utilization rate of raw materials and increases the production cost.

CN110586099B discloses a poor residuum suspension bed hydrocracking catalyst and a preparation method thereof. The catalyst takes ferric chloride and ferric sulfate as inorganic iron sources, takes sawdust powder as a template agent and adopts a sol-gel method to prepare mesoporous gamma-Fe with high specific surface area ₂ O ₃ The catalyst has good application effect in the heavy oil suspension bed hydrocracking reaction. However, the catalyst has a problem of poor hydrothermal stability, and the catalyst is easy to deactivate.

In summary, the existing supported catalyst has the problems of low dispersibility, easy coking, short service life and the like, and the novel synthesis method for partially preparing the high-dispersibility catalyst has the defects of high cost, long process flow and the like, so that the industrial application of the catalyst is limited.

Disclosure of Invention

In view of the above, the invention aims to provide a residual oil hydro-cracking solid base catalyst with high heavy oil conversion rate and low coke yield and a preparation method thereof, which are applied to the hydro-catalytic conversion reaction of heavy oil and can solve the problem that the catalyst prepared in the prior art is difficult to process and treat heavy inferior oil products such as vacuum residual oil and the like with long period and high efficiency.

In order to achieve the above purpose, the technical scheme of the invention is realized as follows: the residual oil hydrocracking solid base catalyst takes the total weight of the residual oil hydrocracking solid base catalyst as a reference, and contains 1 wt-20 wt% of hydrogenation components, and the balance of solid base catalyst; based on the total weight of the solid base catalyst, the solid base catalyst contains 1 wt-99 wt% of modified mesoporous material, 0.1 wt-20 wt% of alkaline metal oxide and the balance of clay;

the alkaline metal oxide is one or more of alkali metal or alkaline earth metal oxides;

the hydrogenation component is one or more of transition metals of the VIB group or the VIII group.

Further, the modified mesoporous material is prepared by the following preparation method:

firstly, preparing modified mesoporous material active gel: preparing a mesoporous material by adopting a sol-gel method, introducing soluble metal salt doped with metal in a sol stage to obtain metal doped mesoporous material gel, sequentially treating the gel with an inorganic acid solution and deionized water, and removing the soluble metal salt doped with metal and the inorganic acid in the gel to obtain modified mesoporous material active gel; the inorganic acid is one or more of nitric acid, sulfuric acid and hydrochloric acid;

then, the dispersed active gel is activated: fully mixing the active gel obtained in the previous step with an activating auxiliary agent, inorganic acid and deionized water in a strong shearing machine, and then performing activation dispersion on a sand mill to obtain homogeneous sol slurry of the modified mesoporous material; the inorganic acid is one or more of nitric acid, sulfuric acid and hydrochloric acid; the mineral acid is added in an amount such that the pH of the slurry is 0.5-5.

Further, the mesoporous material is one or more of silicon-containing composite oxide, silicon dioxide and white carbon black; and the specific surface area of the mesoporous material is 300-800 m ² Per gram, pore volume of 0.3-1.8. 1.8 cm ³ /g, average pore size 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.

Further, the residual oil hydro-cracking solid base catalyst is a microsphere catalyst with the particle size of 0-200 mu m.

The invention further provides a preparation method of the residual oil hydro-cracking solid base catalyst, which comprises the following steps:

step 1, preparing a solid base catalyst;

then, the dispersed active gel is activated: fully mixing the active gel obtained in the previous step with an activating auxiliary agent, inorganic acid and deionized water in a strong shearing machine, and then performing activation dispersion on a sand mill to obtain 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;

finally, stabilizing auxiliary pulping spray: stirring and mixing the soluble salt of the alkaline metal, the stabilizing additive and deionized water uniformly, then sequentially adding the sol slurry and clay obtained in the previous step, stirring and mixing uniformly, and then carrying out spray drying and roasting to obtain a solid base catalyst;

step 2, preparing a residual oil hydro-cracking solid base catalyst;

the soluble metal salt of the hydrogenation component is introduced into the solid base catalyst through one of an ion exchange method, an impregnation method and a coprecipitation method, and then the solid base catalyst for residual oil hydrocracking is obtained through drying and roasting.

Further, the doped metal is one or more of boron, aluminum, gallium, copper, chromium, vanadium, zirconium and molybdenum; the weight ratio of the mass of the doped metal to the mass of the active gel dry basis is 0.001-10:1 based on the mass of the metal oxide.

Further, the activating auxiliary agent is one or more of sodium gluconate, sodium citrate, citric acid, potassium sodium tartrate, tartaric acid, sorbitol, maltitol and polyvinyl alcohol; the weight ratio of the activating auxiliary agent to the active gel dry basis is 0.001-10:1.

Further, the stabilizing auxiliary agent is one or more of polyacrylamide, melamine, ethylenediamine tetraacetic acid disodium, citric acid and methacrylic acid-methoxy polyethylene glycol methacrylate; the weight ratio of the stabilizing auxiliary agent to the active gel is 0.001-10:1.

Further, the roasting condition of the residual oil hydro-cracking solid base catalyst is that roasting treatment is carried out for 0.5-4 hours under the conditions of 450-750 ℃ and 0-100% water vapor.

In addition, the invention also provides application of the residual oil hydro-cracking solid base catalyst in the heavy oil hydro-catalytic conversion reaction.

Compared with the prior art, the residual oil hydro-cracking solid base catalyst and the preparation method and application thereof have the following advantages: compared with the existing catalyst, the residual oil hydro-cracking solid base catalyst prepared by the invention has the advantages of high heavy oil conversion rate, low coke yield and the like. Specifically, when the vacuum residuum of a certain refinery is taken as a raw material, the evaluation result shows that when the vacuum residuum is treated by the catalyst prepared by the method, the conversion rate of heavy oil is improved by more than 10 percent, and the coke yield is reduced by more than 2.5 percent. The reason is that the residual oil hydro-cracking solid base catalyst provided by the invention has rich and stable mesoporous channels and no acid center, so that the dehydrogenation condensation reaction rate of the polycyclic aromatic hydrocarbon is obviously reduced; the heavy oil macromolecules are easier to induce the activation of hydrocarbon molecules on the alkaline center, dissociation and adsorption can be carried out at a lower temperature to form an active intermediate, olefins in the product are timely hydrogenated and saturated on the hydrogenation center, and coking of the olefins in the reactor wall, an inner member or a pipeline is reduced or prevented.

Detailed Description

It should be noted that, without conflict, the embodiments of the present invention and features of the embodiments may be combined with each other.

The invention aims to provide a residual oil hydro-cracking solid base catalyst with high heavy oil conversion rate and low coke yield and a preparation method thereof, in particular relates to a solid base catalyst for hydro-catalytic conversion of vacuum residual oil, and solves the problem that the catalyst prepared in the prior art is difficult to process and treat heavy inferior oil products such as vacuum residual oil and the like in a long period and high efficiency.

The invention relates to a residual oil hydro-cracking solid base catalyst, which takes the total weight of the residual oil hydro-cracking solid base catalyst as a reference, and comprises 1 wt-20 wt percent of hydrogenation components, and the balance of solid base catalyst; based on the total weight of the solid base catalyst, the solid base catalyst contains 1 wt-99 wt% of modified mesoporous material, 0.1 wt-20 wt% of alkaline metal oxide and the balance of clay;

wherein the alkaline metal oxide is one or more of alkali metal or alkaline earth metal oxide, preferably one or more of potassium oxide, rubidium oxide, magnesium oxide, calcium oxide and barium oxide;

the hydrogenation component is one or more of transition metals of VIB group or VIII group, preferably one or more of ferric oxide, ferric sulfate, nickel oxide, molybdenum oxide and tungsten oxide.

The modified mesoporous material is prepared by the following preparation method:

The mesoporous material is one or more of silicon-containing composite oxide, silicon dioxide and white carbon black; and the specific surface area of the mesoporous material is 300-800 m ² Per gram, pore volume of 0.3-1.8. 1.8 cm ³ /g, average pore size 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.

The residual oil hydro-cracking solid base catalyst is microsphere catalyst with particle size of 0-200 μm.

The residual oil hydro-cracking solid base catalyst provided by the invention contains the modified mesoporous material with high hydrothermal stability, so that the catalyst has rich and stable mesoporous channels and no acid center, and the dehydrogenation condensation reaction rate of polycyclic aromatic hydrocarbon is obviously reduced; the heavy oil macromolecules are easier to induce the activation of hydrocarbon molecules on the alkaline center, dissociation and adsorption can be carried out at a lower temperature to form an active intermediate, olefins in the product are timely hydrogenated and saturated on the hydrogenation center, and coking of the olefins in the reactor wall, an inner member or a pipeline is reduced or prevented.

step 1, preparing a solid base catalyst with high hydrothermal stability;

wherein the doped metal is one or more of boron, aluminum, gallium, copper, chromium, vanadium, zirconium and molybdenum; the weight ratio of the mass of the doped metal to the mass of the active gel dry basis is 0.001-10:1 based on the mass of the metal oxide.

wherein the activating auxiliary agent is one or more of sodium gluconate, sodium citrate, citric acid, potassium sodium tartrate, tartaric acid, sorbitol, maltitol and polyvinyl alcohol; the weight ratio of the activating auxiliary agent to the active gel dry basis is 0.001-10:1.

wherein the stabilizing auxiliary agent is one or more of polyacrylamide, melamine, ethylenediamine tetraacetic acid, disodium ethylenediamine tetraacetate, citric acid and methacrylic acid-methoxy polyethylene glycol methacrylate (PCE); the weight ratio of the stabilizing auxiliary agent to the active gel is 0.001-10:1.

Step 2, preparing a residual oil hydro-cracking solid base catalyst;

The roasting condition of the residual oil hydro-cracking solid base catalyst is that the residual oil hydro-cracking solid base catalyst is roasted for 0.5 to 4 hours under the conditions of 450 to 750 ℃ and 0 to 100 percent of water vapor.

The following description of the invention is made by way of example, and it is to be understood that the embodiments described herein are merely illustrative and explanatory of the invention, and are not restrictive of the invention.

Example 1

The residual oil hydro-cracking solid base catalyst consists of a solid base catalyst and a hydrogenation component, wherein the total weight of the residual oil hydro-cracking solid base catalyst is taken as a reference, 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 silicon dioxide, and based on the total weight of the solid base catalyst, the silicon dioxide is 55 wt%, the alkaline metal oxide is 10 wt%, and the kaolin is 35 wt%;

(1) Preparing modified mesoporous material active gel: 2000g of water glass solution with the modulus of 3.2 and the silicon dioxide content of 29.5 and wt percent is taken, placed in a reactor and heated to 50 ℃, 26.3g of gallium nitrate nonahydrate is slowly added according to the weight ratio of the gallium oxide to the silicon dioxide of 0.02:1 under the continuous stirring state, then dilute nitric acid (15 percent) is slowly added, the pH value is regulated to about 6, and the mixture is stirred for 30 minutes to obtain gallium modified silicon dioxide hydrogel; adding 10 wt% dilute nitric acid solution (1000 g) to treat for 15 hours at 50 ℃, and then washing with deionized water until the filtrate is neutral to obtain gallium-modified silica active gel (the solid content of silica in the gel is 19%);

(2) Activating the dispersed active gel: adding 17.7g of citric acid according to the weight ratio of citric acid to gallium-modified silica gel (dry basis) of 0.03:1, then adding a proper amount of nitric acid and deionized water, controlling the pH of slurry to be 1.5 and the solid content of silica to be 17%, mixing the slurry for 30 minutes by using a powerful shearing machine, and then treating the slurry for 60 minutes by using a sand mill at the rotating speed of 3000 r/min to obtain gallium-modified silica homogeneous sol slurry;

(3) Stabilizing auxiliary pulping spray: dissolving 382.8g of calcium nitrate tetrahydrate into 810g of deionized water, adding 9g of disodium ethylenediamine tetraacetate according to the weight ratio of stabilizing auxiliary agent to alkaline metal and auxiliary agent metal oxide of 0.1:1, stirring for 30 minutes, then adding 2912g of gallium-modified silica homogeneous sol slurry (solid content of 17%) and stirring for 30 minutes, finally adding 366g of kaolin (solid content of 86%), stirring for 120 minutes, drying and forming by using a spray drying device, controlling the outlet temperature to 135 ℃, and collecting catalyst samples with the particle size in the range of 0-100 mu m to obtain a solid base catalyst;

(4) Preparing a residual oil hydro-cracking solid base catalyst: dissolving 307.7g of ferric trichloride hexahydrate in 810g of deionized water to prepare an impregnating solution; 810g of solid base catalyst (the water absorption rate is 100%) is taken, the hydrogenation metal is loaded by adopting an isovolumetric impregnation method, the catalyst is dried for 6 hours at 120 ℃, and is roasted for 4 hours at 650 ℃, so as to obtain the residual oil hydro-cracking solid base catalyst.

Example 2

The residual oil hydro-cracking solid base catalyst consists of a solid base catalyst and a hydrogenation component, wherein the total weight of the residual oil hydro-cracking solid base catalyst is taken as a reference, 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 silicon-aluminum composite oxide, and 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%;

(1) Preparing modified mesoporous material active gel: 2000g of water glass solution with the modulus of 3.2 and the silicon dioxide content of 29.5 and wt percent is taken, placed in a reactor and heated to 50 ℃, 20.18g of chromium nitrate nonahydrate is slowly added according to the dry basis weight ratio of gallium oxide to silicon dioxide of 0.005:1 under the continuous stirring state, 215.8g of aluminum nitrate nonahydrate is slowly added, and finally a proper amount of dilute nitric acid (15%) is added, the pH value is adjusted to about 6, and the mixture is stirred for 30 minutes, so as to obtain chromium modified silicon-aluminum composite oxide gel; adding 10 wt% dilute nitric acid solution (1000 g) to treat for 15 hours at 50 ℃, and then washing with deionized water until the filtrate is neutral to obtain chromium modified silicon-aluminum composite oxide active gel (the solid content of the silicon-aluminum composite oxide in the gel is 19%);

(2) The same method as in example 1 was used to activate the dispersion active gel, except that 32.47g of tartaric acid was added in a weight ratio of tartaric acid to chromium-modified silicon-aluminum composite oxide active gel (dry basis) of 0.05:1;

(3) The auxiliary stabilizing spray was used in the same manner as in example 1 except that 97.6g of potassium nitrate was used instead of calcium nitrate tetrahydrate;

(4) Preparing a residual oil hydro-cracking solid base catalyst: 153.9g of ferric trichloride hexahydrate and 164.8g of nickel nitrate hexahydrate are dissolved in 810g of deionized water to prepare an impregnating solution; 810g of solid base catalyst (the water absorption rate is 100%) is taken, the hydrogenation metal is loaded by adopting an isovolumetric impregnation method, the catalyst is dried at 120 ℃ for 6 hours, and is roasted at 650 ℃ for 4 hours in a 100% steam atmosphere, so as to obtain the residual oil hydro-cracking solid base catalyst.

Example 3

The residual oil hydro-cracking solid base catalyst consists of a solid base catalyst and a hydrogenation component, wherein the total weight of the residual oil hydro-cracking solid base catalyst is taken as a reference, the hydrogenation metal oxide is 15 and wt percent, and the solid base catalyst is 85 and wt percent; the mesoporous material in the solid base catalyst is silicon dioxide, and based on the total weight of the solid base catalyst, the silicon dioxide is 55 wt%, the alkaline metal oxide is 15 wt%, and the kaolin is 30 wt%;

(1) The mesoporous material active gel was prepared as in example 1;

(2) The same procedure as in example 1 was used to activate the dispersion active gel, except that 5.9g of polyvinyl alcohol was added in a weight ratio of polyvinyl alcohol to gallium-modified silica active gel (dry basis) of 0.01:1;

(3) Stabilizing auxiliary pulping spray: dissolving 289.2g of magnesium nitrate hexahydrate and 382.8g of calcium nitrate tetrahydrate in 810g of deionized water, adding 67.5g of melamine according to the weight ratio of a stabilizing additive to alkali metal oxide of 0.5:1, stirring for 30 minutes, then adding 2912g of gallium-modified silicon-aluminum composite oxide active gel (solid content of 17%) and stirring for 30 minutes, finally adding 314g of kaolin (solid content of 86%), stirring for 120 minutes, mixing and pulping for 60 minutes, drying and molding by using a spray drying device, controlling the outlet temperature to 135 ℃, and collecting catalyst samples with the particle size in the range of 0-100 mu m to obtain a solid base catalyst;

(4) A residuum hydrocracked solid base catalyst was prepared in the same manner as in example 1 except that the amounts of ferric trichloride hexahydrate and deionized water were 461.6g and 850g, respectively.

For comparison with the performance of the catalysts of the examples of the present invention, two reference catalysts were prepared with reference to the published patent.

Comparative example 1

(1) Bauxite activation treatment: taking 1000g of natural bauxite ore raw powder, and carrying out hydrothermal activation for 6 hours at 700 ℃ in a 100% steam atmosphere to obtain a catalyst carrier after activation;

(2) Comparative example 1 the catalyst was prepared as in example 1.

Comparative example 2

580g of ferric trichloride hexahydrate and 2g of EDTA are dissolved in 4000g of deionized water, 2000g of active carbon is added and stirred uniformly, 250g of ammonia water is added dropwise into the solution while stirring, stirring is continued for 60 minutes, then suction filtration and washing are carried out, and the obtained filter cake is dried at 120 ℃ for 6 hours and baked at 650 ℃ for 4 hours, thus obtaining the catalyst of comparative example 2.

The catalyst performance evaluation methods of the examples and comparative examples of the present invention are as follows:

example and comparative example catalysts catalyst performance evaluation was performed on a low grade heavy oil suspension bed hydrogenation reaction unit: 400g of vacuum residue and 40g of catalyst were charged into a suspension bed reactor, the air in the reactor was replaced with hydrogen at room temperature and pressurized to 5.0MPa, and reacted at 420℃for 2.0 hours. After the reaction is finished, the temperature is reduced to room temperature, and the product is extracted by toluene to obtain a liquid-phase product and toluene insoluble matters.

The properties of the residue are shown in Table 1, and the reaction results are shown in Table 2. The calculation method of each evaluation index is as follows:

heavy oil conversion =

Coking Rate =

Heavy metal removal rate =

Table 1 basic properties of the raw materials used in examples and comparative examples

Table 2 evaluation results of samples of the example and comparative example catalysts after hydrothermal treatment

As can be seen from a comparison of the above tables, when the catalyst prepared by the method of the present invention (example 1-example 3) is used for treating vacuum residuum, the conversion of heavy oil is improved by more than 10 percentage points and the coke yield is reduced by more than 2.5 percentage points compared with the reference catalyst (comparative example 1 and comparative example 2).

The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the invention.

Claims

1. A solid base catalyst for hydrocracking residual oil is characterized in that: taking the total weight of the residual oil hydro-cracking solid base catalyst as a reference, the residual oil hydro-cracking solid base catalyst contains 1 wt% -20 wt% of hydrogenation components, and the balance is the solid base catalyst; based on the total weight of the solid base catalyst, the solid base catalyst contains 1 wt-99 wt% of modified mesoporous material, 0.1 wt-20 wt% of alkaline metal oxide and the balance of clay;

2. The residual oil hydrocracking solid base catalyst as claimed in claim 1, wherein the modified mesoporous material is prepared by the following preparation method:

3. The residuum hydrocracked solid base catalyst of claim 2 wherein: the mesoporous material is one or more of silicon-containing composite oxide, silicon dioxide and white carbon black; and the specific surface area of the mesoporous material is 300-800 m ² Per gram, pore volume of 0.3-1.8. 1.8 cm ³ /g, average pore size 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.

4. The residuum hydrocracked solid base catalyst of claim 1 wherein: the residual oil hydro-cracking solid base catalyst is microsphere catalyst with particle size of 0-200 μm.

5. A process for preparing a resid hydrocracked solid base catalyst as claimed in any one of claims 1 to 4 comprising the steps of:

step 1, preparing a solid base catalyst;

step 2, preparing a residual oil hydro-cracking solid base catalyst;

6. The method for preparing the residual oil hydro-cracking solid base catalyst according to claim 5, which is characterized in that: the doping metal is one or more of boron, aluminum, gallium, copper, chromium, vanadium, zirconium and molybdenum; the weight ratio of the mass of the doped metal to the mass of the active gel dry basis is 0.001-10:1 based on the mass of the metal oxide.

7. The method for preparing the residual oil hydro-cracking solid base catalyst according to claim 5, which is characterized in that: the activating auxiliary agent is one or more of sodium gluconate, sodium citrate, citric acid, potassium sodium tartrate, tartaric acid, sorbitol, maltitol and polyvinyl alcohol; the weight ratio of the activating auxiliary agent to the active gel dry basis is 0.001-10:1.

8. The method for preparing the residual oil hydro-cracking solid base catalyst according to claim 5, which is characterized in that: the stabilizing auxiliary agent is one or more of polyacrylamide, melamine, ethylenediamine tetraacetic acid, disodium ethylenediamine tetraacetate, citric acid and methacrylic acid-methoxy polyethylene glycol methacrylate; the weight ratio of the stabilizing auxiliary agent to the active gel is 0.001-10:1.

9. The method for preparing the residual oil hydro-cracking solid base catalyst according to claim 5, which is characterized in that: the roasting condition of the residual oil hydro-cracking solid base catalyst is that the residual oil hydro-cracking solid base catalyst is roasted for 0.5 to 4 hours under the conditions of 450 to 750 ℃ and 0 to 100 percent of water vapor.

10. Use of the residuum hydrocracked solid base catalyst of any one of claims 1-4 in heavy oil hydrocatalytic conversion reactions.