CN116037141A

CN116037141A - Regeneration method of deactivated catalyst

Info

Publication number: CN116037141A
Application number: CN202111261160.8A
Authority: CN
Inventors: 薛杨; 季洪海; 隋宝宽; 朱慧红; 王少军
Original assignee: China Petroleum and Chemical Corp; Sinopec Dalian Research Institute of Petroleum and Petrochemicals
Current assignee: Sinopec Dalian Petrochemical Research Institute Co ltd; China Petroleum and Chemical Corp
Priority date: 2021-10-28
Filing date: 2021-10-28
Publication date: 2023-05-02

Abstract

The invention discloses a regeneration method of an inactivated catalyst, which comprises the following steps: (1) Deoiling, roasting and crushing the deactivated catalyst to obtain a pretreated material; (2) Placing the pretreated material into propylene oxide solution, performing heat treatment under a closed condition, removing liquid phase from the treated material, and drying to obtain an activated powder material A; (3) Kneading the activated powder material A and pseudo-boehmite for molding, drying and roasting to obtain a material B; (4) Carrying out acid treatment and alkali treatment on the material B, and drying to obtain a material C; (5) Impregnating the material C with hydrogenation active component impregnating solution to obtain regenerated hydrogenation catalyst. The method prepares the hydrogenation catalyst by activating treatment and taking the activated material as part of raw materials, thereby realizing the reutilization of waste agents, and the regenerated catalyst has higher catalytic activity.

Description

Regeneration method of deactivated catalyst

Technical Field

The invention belongs to the field of catalyst regeneration, and particularly relates to a regeneration method of an inactivated catalyst.

Background

With the development of industry, the advancement of technology and the perfection of environmental regulations, the demand of human beings for petroleum and petrochemical products is increasing, and the use of catalysts for producing various products is also increasing. During the hydrogenation reaction, the activity of the catalyst gradually decreases with the increase of the running time and eventually becomes inactive. A large amount of spent hydrogenation catalyst is produced worldwide each year that cannot be regenerated. Refineries typically choose to discard or use these spent catalysts as fillers in the construction industry, etc., and this treatment has the following disadvantages: 1. because the hydrogenation catalyst generally contains a certain amount of molybdenum, tungsten, cobalt, nickel and other valuable metal oxides, such as discarding treatment can cause resource waste; 2. the discarded catalyst will pollute the environment, especially the water resource, due to the loss of the metals. Thus, many countries now prohibit the random disposal or other use of spent catalysts, and how to dispose of such spent catalysts has been a matter of great concern to researchers.

CN1258754a discloses a method for recovering metals from Co-Mo-based spent catalysts. The method comprises the steps of roasting, crushing, ammonolysis and filtering the waste catalyst, replacing cobalt in the complex with zinc, and then adding nitric acid to recycle MoO ₃ The filter residue was dissolved with sulfuric acid and ammonium alum was separated with ammonium sulfate to remove most of the aluminum.

CN101435027a discloses a method for recovering high purity molybdenum from a molybdenum-containing spent catalyst. The method comprises the steps of pretreating the molybdenum-containing waste catalyst, leaching molybdenum into the solution, purifying and recovering molybdenum from the solution, wherein the pretreatment of the molybdenum-containing waste catalyst is to fully mix the crushed waste catalyst with alkaline substances and magnesium oxide in a proper proportion, and then roasting the mixture at a high temperature.

In the above method, when the deactivated hydrogenation catalyst is treated, valuable metals in the catalyst can be recovered, but the alumina carrier material in the catalyst is not effectively utilized.

CN111097440a discloses a method for regenerating an inactivated residuum hydrotreating catalyst, which comprises: and (3) carrying out charcoal burning and sulfur removal pretreatment on the deactivated residual oil hydrotreating catalyst, then carrying out unsaturated impregnation or saturated impregnation by using an acidic solution containing a complexing agent, carrying out heat treatment under an ammonia-containing atmosphere after carrying out impregnation treatment by using an alkaline solution, and obtaining the regenerated hydrotreating catalyst after drying and roasting. The method can utilize deposited metal impurities to make the deposited metal impurities serve as active metals in the regenerated catalyst and improve the pore structure of the catalyst, but the regeneration process is complex, the cost is high, and the method is not beneficial to industrial production.

Disclosure of Invention

Aiming at the defects in the prior art, the invention provides a regeneration method of an inactivated catalyst, which is used for preparing a hydrogenation catalyst by activating treatment and taking activated materials as partial raw materials, thereby realizing the reutilization of waste agents, and the regenerated catalyst has higher catalytic activity.

The regeneration method of the deactivated hydrogenation catalyst comprises the following steps:

(1) Deoiling, roasting and crushing the deactivated catalyst to obtain a pretreated material;

(2) Placing the pretreated material into propylene oxide solution, performing heat treatment under a closed condition, removing liquid phase from the treated material, and drying to obtain an activated powder material A;

(3) Kneading the activated powder material A and pseudo-boehmite for molding, drying and roasting to obtain a material B;

(4) Carrying out acid treatment and alkali treatment on the material B, and drying to obtain a material C;

(5) Impregnating the material C with hydrogenation active component impregnating solution to obtain regenerated hydrogenation catalyst.

In the method of the invention, the deactivated catalyst in the step (1) generally refers to a catalyst which is partially deactivated or does not meet the reaction requirement due to deposition of metallic impurities such as metallic nickel, vanadium and the like in the heavy and residual oil hydrotreating process, and the catalyst generally takes alumina or modified alumina as a carrier; the catalyst can be a catalyst in the residual oil hydrotreating process of a fixed bed, a boiling bed, a suspension bed and the like, and the catalyst can be cylindrical bar-shaped, clover-shaped, pentadentate sphere or sphere; the vanadium content is 5-25% by weight of the catalyst, the molybdenum content is 3-20% by weight of the catalyst, and the nickel content is 2-15% by weight of the catalyst.

In the method, the deoiling in the step (1) is to remove the reaction raw materials on the surface and in the pore canal of the deactivated catalyst, the deoiling pretreatment generally adopts organic solvent extraction treatment or nitrogen extraction treatment, the organic solvent is preferably a mixed solvent of petroleum ether and ethanol, the materials after the extraction treatment are dried, and the materials can be naturally air-dried at normal temperature or can be dried by adopting a blast oven, the drying temperature is 80-120 ℃, and the drying time is 4-10 hours until the organic solvent in the materials is completely volatilized.

In the process of the present invention, the calcination treatment in step (1) is carried out at a calcination temperature of 450 to 650℃and a calcination time of 1 to 10 hours, and the calcination may be carried out in air, preferably in an oxygen atmosphere.

In the method of the present invention, the pulverization treatment in the step (1) is to pulverize the material to a mesh number of 80 mesh or more, preferably 200 mesh or more, more preferably 400 to 800 mesh.

In the method, the mass percentage concentration of the propylene oxide aqueous solution in the step (2) is 2.5-12%, preferably 4-8%, and the mass ratio of the dosage of the propylene oxide aqueous solution to the pretreatment material is 3:1-10:1, preferably 4:1-8:1. more preferably, polyethylene glycol 2000-20000 is added into the epoxypropane water solution at the same time, and the mass ratio of the addition amount of the polyethylene glycol 2000-20000 to the pretreatment material powder is 0.01:1-0.05:1.

in the method of the present invention, the heat treatment in the step (2) is performed in a sealed container, preferably an autoclave, at a treatment temperature of 110 to 180 ℃, preferably 120 to 160 ℃ for 4 to 8 hours, and at a treatment pressure of autogenous pressure in the sealed container.

In the method of the present invention, the liquid phase removal in the step (2) may be performed by conventional filtration, centrifugation or the like.

In the method, the drying temperature in the step (2) is 80-160 ℃ and the drying time is 1-6 hours.

In the method of the present invention, the pseudo-boehmite in the step (3) may be commercially available or prepared according to the existing methods, such as acid precipitation, alkali precipitation, aluminum alkoxide hydrolysis, etc., preferably pseudo-boehmite having a pore diameter of more than 10 nm.

In the method, the mass ratio of the activated powder material A to the pseudo-boehmite in the step (3) is 1:4-2: and 3, kneading and forming are carried out by adopting a conventional method in the field, and an extrusion aid can be added according to requirements in the forming process, wherein the extrusion aid is sesbania powder. The peptizing agent is one or more of hydrochloric acid, nitric acid, sulfuric acid, acetic acid or oxalic acid, and the concentration of the peptizing agent is 0.1-3 wt%.

In the method, the drying temperature in the step (3) is 100-160 ℃ and the drying time is 6-10 hours; the roasting temperature is 550-650 ℃ and the roasting time is 4-6 hours; the calcination is carried out in an oxygen-containing atmosphere, preferably in an air atmosphere.

In the method of the invention, the acid treatment process in the step (4) is as follows: spraying and impregnating alumina carrier material with acid solution to saturate adsorption of the carrier, then placing the carrier in an autoclave, heating at 40-60 ℃ for 4-8 hours, cooling, and drying at 80-160 ℃ for 4-10 hours; the acid solution is one or more of acetic acid, oxalic acid, citric acid, tartaric acid and the like, preferably oxalic acid, and the concentration of the solution is 5-15 wt%, preferably 7.5-12.5 wt%.

In the method of the invention, the alkali treatment process in the step (4) is as follows: spraying alkali solution to impregnate the acid activated alumina carrier material to saturate the adsorption of the carrier, then placing the carrier in an autoclave, heating the carrier at 40-60 ℃ for 4-8 hours, cooling the carrier, and drying the carrier at 80-160 ℃ for 4-10 hours to obtain the alkali activated material; the alkali solution is one or more of ammonia water, ammonium carbonate aqueous solution or ammonium bicarbonate aqueous solution, preferably ammonia water, and the concentration of the alkali solution is 10-30wt%, preferably 15-25wt%.

In the method of the present invention, the acid treatment and the alkali treatment in the step (4) are not particularly limited, and the acid treatment may be performed first and then the alkali treatment may be performed, or the alkali treatment may be performed first and then the acid treatment may be performed.

In the method of the invention, the impregnation liquid of the hydrogenation active component in the step (5) is an impregnation liquid containing Mo, W, ni, co active metals, preferably Mo and Co active metals, and the content of Mo in the impregnation liquid is 0.5g/100mL-10g/100mL, preferably 1g/100mL-8g/100mL, calculated as oxide. Co content is 0.1g/100mL-3g/100mL, preferably 0.3g/100mL-2.0g/100mL in terms of oxide.

The hydrogenation catalyst prepared by the method has the following properties: the specific surface area is 150-240m ² Per g, wherein the pore volume is 0.8-1.0mL/g, and the pore volume with the pore diameter of 10-30nm accounts for 45% -60% of the total pore volume; the content of molybdenum oxide is 5% -10%, the content of nickel oxide is 2.5% -5%, the content of vanadium pentoxide is 5% -10%, the content of cobalt oxide is 0.2% -1.0%, and the content of alumina carrier is 74% -87.3%.

The hydrogenation catalyst prepared by the method is suitable for heavy oil hydrodemetallization and hydrodesulphurization processes.

Compared with the prior art, the invention has the following advantages:

(1) According to the invention, through the sealing heat treatment of the inactivated catalyst powder in the epoxypropane solution, partial alumina in the inactivated catalyst is rehydrated and converted into pseudo-boehmite phase, and directionally grows into flaky structure grains, and the flaky pseudo-boehmite grains are mutually interwoven to form loose pore channels, so that the formed pseudo-boehmite has higher pore volume and specific surface area; after the aluminum oxide carrier is extruded with the conventional pseudo-boehmite powder again, the stacking state of particles in the aluminum oxide carrier is regulated, and the content of macropores in the carrier is improved;

(2) The metals such as Mo, ni, V and the like in the inactivated catalyst powder after the hydrothermal activation treatment of propylene oxide are also migrated and dispersed, and when the carrier is subjected to the acid and alkali activation treatment, the redispersion of the metals such as Mo, ni, V and the like in the activated pseudo-boehmite powder in the alumina carrier can be effectively promoted, so that the metals in the inactivated catalyst are used as active components for secondary use. In addition, during the acid and alkali activation treatment, the penetrability of the pore canal of the carrier can be improved due to the dissolution of the acid and the alkali, the activation treatment condition is mild, the pore canal structure of the carrier can not be damaged, and the carrier can have higher pore volume and specific surface area.

Drawings

FIG. 1 is a scanning electron microscope image of a material A1 in example 1.

FIG. 2 is a scanning electron microscope image of the material A5 of comparative example 1.

Detailed Description

The technical scheme and effect of the present invention will be further described with reference to the following examples, but is not limited thereto.

BET method: application N ₂ Physical adsorption-desorption characterization examples and comparative examples the pore structure of the carriers were as follows: using ASAP-2420 type N ₂ The physical adsorption-desorption instrument characterizes the structure of the sample hole. And (3) taking a small amount of sample, vacuum-treating for 3-4 hours at 300 ℃, and finally placing the product under the condition of low temperature (-200 ℃) of liquid nitrogen for nitrogen adsorption-desorption test. The specific surface area is obtained according to a BET equation, and the distribution ratio of the pore volume and the pore diameter is obtained according to a BJH model.

XRF characterization: analyzing sample components by using a Japan-based ZSX100 e-type X-ray fluorescence spectrometer, and performing light path atmosphere on a target Rh: vacuum conditions.

SEM characterization: the microstructure of the sample is characterized by adopting a Japanese electronic JSM-7500F type scanning electron microscope, and the accelerating voltage is 20kV.

And (3) measuring the sulfur content in the oil product by adopting an SH/T0689-2000 standard method.

And determining the Ni and V contents in the oil product by using a GB/T34099-2017 standard method.

The v+ni removal rate% = (raw oil metal v+ni content-product metal v+ni content)/raw oil metal v+ni content×100%.

Desulfurization percentage = (sulfur content of raw oil-sulfur content of product)/sulfur content of raw oil x 100%.

Calculating the relative demetallization rate and the relative desulfurization rate: the demetallization rate and the desulfurization rate of a certain catalyst are measured, the relative demetallization rate and the relative desulfurization rate are defined as 100 percent, and the impurity removal rate of other catalysts/the impurity removal rate of the defined catalyst is multiplied by 100 percent to be the relative impurity removal rate.

The deactivated catalyst used in the examples is a deactivated catalyst of a certain industrial apparatus, and the oil on the surface of the catalyst is removed by extraction and dried. MoO as the main component of the catalyst ₃ ：8.2%，NiO：7.3%，V ₂ O ₅ ：18.7%， Al ₂ O ₃ ：55.1%，C：8.9%。

Preparation of activated powder material A

Example 1

200 g of the deoiled and deactivated catalyst is weighed and placed in an oxygen atmosphere to be roasted for 8 hours at 600 ℃ so that the surface of the deactivated catalyst is completely oxidized, and the roasted catalyst is crushed and sieved.

100 g of inactive catalyst powder with the granularity smaller than 200 meshes is weighed, 650 g of propylene oxide solution with the mass percent concentration of 5.7% is added, magnetic stirring is carried out for 30 minutes, then the mixed material is transferred into an autoclave, is sealed and then heated at 135 ℃ for 6 hours, the solid material is filtered and washed after cooling, and is dried at 110 ℃ for 6 hours, thus obtaining an active powder material A1, the properties of the material are shown in Table 1, and a scanning electron microscope picture is shown in figure 1.

Example 2

As in example 1 except that the amount of propylene oxide solution was 770 g, the mass percent concentration of the solution was 4.6%, the heat treatment temperature was 145℃and the treatment time was 5 hours, an activated powder material A2 was obtained, the properties of which are shown in Table 1.

Example 3

As in example 1 except that the amount of propylene oxide solution was 530 g, the mass percent concentration of the solution was 7.5%, the heat treatment temperature was 125℃and the treatment time was 7 hours, an activated powder material A3 was obtained, the properties of which are shown in Table 1.

Example 4

As in example 1 except that the amount of the propylene oxide solution was 440 g, the mass percentage concentration of the solution was 6.8%, 1.2 g of ethylene glycol-10000 was added to the mixture, the heat treatment temperature was 155℃and the treatment time was 4 hours, an activated powder material A4 was obtained, and the properties of the material were shown in Table 1.

Comparative example 1

As in example 1, except that the mass percentage concentration of propylene oxide was 1.5%, a comparative activated powder material A5 was prepared, the properties of which are shown in Table 1, and a scanning electron microscope picture is shown in FIG. 2.

Comparative example 2

Comparative activated powder material A6 was prepared as in example 1, except that propylene oxide was replaced with the same amount of ethylene oxide, and the properties of this material are shown in Table 1.

Comparative example 3

Comparative activated powder material A7 was prepared as in example 1 except that propylene oxide was replaced with the same amount of distilled water, and the properties of the material are shown in table 1.

TABLE 1 Properties of the activated Material

Example 5

(1) 100 g of pseudo-boehmite is weighed, 43 g of activated material A1 in example 1 and 0.5g of sesbania powder are uniformly mixed, an appropriate amount of acetic acid solution with the mass percent concentration of 0.5% is added for uniformly mixing and kneading, extrusion molding is carried out, the molded material is dried at 120 ℃ for 8 hours, and then baked at 600 ℃ for 5 hours, thus obtaining the alumina carrier.

(2) Placing the carrier prepared in the step (1) in a spray-dipping rolling pot, spraying and dipping the carrier by using oxalic acid solution with the mass percent concentration of 9.5% to saturate the adsorption of the carrier, then placing the carrier in an autoclave, sealing the carrier at 50 ℃ for 6.5 hours, and drying the treated material at 100 ℃ for 6 hours; and (3) putting the dried material into a spray-dipping roller pot again, spraying and dipping the carrier by using an ammonia water solution with the mass percent concentration of 20% to saturate the adsorption of the carrier, then putting the carrier into an autoclave, sealing the carrier at 60 ℃ for 5 hours, and drying the treated material at 100 ℃ for 6 hours to obtain the activated carrier.

(3) Weighing 50 g of the activating carrier in the step (2), spraying and impregnating the alumina carrier with an active component impregnating solution with the concentration of molybdenum oxide of 2.5g/100mL and the concentration of cobalt oxide of 0.55g/100mL, drying the impregnated material at 120 ℃ for 5 hours, and roasting at 450 ℃ for 5 hours to obtain a hydrogenation catalyst Cat-1, wherein the catalyst properties are shown in Table 2.

Example 6

The same as in example 5, except that the activated material A1 in step (1) was changed to A2, the amount added was 53 g; the mass percentage concentration of oxalic acid is 11% when the step (2) is acid activated, the activation temperature is 45 ℃, the activation time is 7.5 hours, the mass percentage concentration of ammonia water is 22.5% when the step (2) is alkali activated, the activation temperature is 50 ℃, and the activation time is 6 hours; when the active component is immersed in the step (3), the concentration of molybdenum oxide in the immersion liquid is 2.0g/100mL, and the concentration of cobalt oxide is 0.45g/100mL, so that the hydrogenation catalyst Cat-2 is prepared, and the catalyst properties are shown in Table 2.

Example 7

The same as in example 5, except that the activated material A1 in step (1) was changed to A3, the amount added was 35 g; in the step (2), the mass percentage concentration of oxalic acid is 12%, the activation temperature is 55 ℃, the activation time is 5.5 hours, the mass percentage concentration of ammonia water is 15.5% in the alkali activation, the activation temperature is 70 ℃, and the activation time is 4 hours; when the active component is immersed in the step (3), the concentration of molybdenum oxide in the immersion liquid is 3.5g/100mL, and the concentration of cobalt oxide is 0.8g/100mL, so as to prepare the hydrogenation catalyst Cat-3, and the catalyst properties are shown in Table 2.

Example 8

The same as in example 5, except that the activated material A1 in step (1) was changed to A4, the amount added was 60 g; and (2) firstly performing alkali activation, then performing acid activation, wherein the mass percentage concentration of ammonia water is 17.5% during the alkali activation, the activation temperature is 40 ℃, and the activation time is 7 hours. When the acid is activated, the mass percentage concentration of oxalic acid is 8%, the activation temperature is 50 ℃, and the activation time is 4.5 hours; when the active component is immersed in the step (3), the concentration of molybdenum oxide in the immersion liquid is 2.0g/100mL, and the concentration of cobalt oxide is 0.3g/100mL, so as to prepare the hydrogenation catalyst Cat-4, and the catalyst properties are shown in Table 2.

Comparative example 4

Comparative hydrogenation catalyst Cat-5 was prepared as in example 5 except that the activated material A1 of step (1) was changed to A5, and the catalyst properties are shown in Table 2.

Comparative example 5

Comparative hydrogenation catalyst Cat-6 was prepared as in example 5 except that the activated material A1 of step (1) was changed to A6, and the catalyst properties are shown in Table 2.

Comparative example 6

Comparative hydrogenation catalyst Cat-7 was prepared as in example 5 except that the activated material A1 of step (1) was changed to A7, and the catalyst properties are shown in Table 2.

Table 2 hydrogenation catalyst properties

Catalytic performance evaluation:

the catalyst (Cat-1-Cat-7) after activation was subjected to catalytic performance evaluation as follows:

taking a residual oil as a raw material, wherein the content of metal (Ni+V) in the raw material oil is 98 mug/g, the content of sulfur is 2.6wt%, and the catalytic performance of the catalyst Cat-1-Cat-7 is evaluated on a small evaluation device under the following reaction conditions: the reaction temperature is 380 ℃, the hydrogen partial pressure is 14MPa, and the liquid hourly space velocity is 0.5h ^-1 The hydrogen oil volume ratio is 850, the content of each impurity in the generated oil is measured after the reaction is carried out for 500 hours, the impurity removal rate is calculated, and the evaluation result is shown in table 3.

TABLE 3 comparative hydrogenation catalyst Activity

As can be seen from the data in Table 3, the hydrodemetallization and hydrodesulphurisation activation of the hydrogenation catalyst prepared by the process of the present invention is higher than the comparative catalyst.

Claims

1. A method for regenerating an inactivated hydrogenation catalyst, which is characterized by comprising the following steps: (1) Deoiling, roasting and crushing the deactivated catalyst to obtain a pretreated material; (2) Placing the pretreated material into propylene oxide solution, performing heat treatment under a closed condition, removing liquid phase from the treated material, and drying to obtain an activated powder material A; (3) Kneading the activated powder material A and pseudo-boehmite for molding, drying and roasting to obtain a material B; (4) Carrying out acid treatment and alkali treatment on the material B, and drying to obtain a material C; (5) Impregnating the material C with hydrogenation active component impregnating solution to obtain regenerated hydrogenation catalyst.

2. The method according to claim 1, characterized in that: the deactivated catalyst in the step (1) refers to a catalyst which is partially deactivated or does not meet the reaction requirement due to deposition of metallic nickel and vanadium impurities in the heavy and residual oil hydrotreating process, and the catalyst takes alumina or modified alumina as a carrier.

3. The method according to claim 1, characterized in that: the deoiling in the step (1) is to remove the reaction raw materials on the surface of the deactivated catalyst and in the pore channels; the deoiling pretreatment adopts organic solvent extraction treatment or nitrogen extraction treatment, and the materials after the extraction treatment are dried.

4. The method according to claim 1, characterized in that: the roasting temperature of the roasting treatment in the step (1) is 450-650 ℃ and the roasting time is 1-10 hours.

5. The method according to claim 1, characterized in that: the crushing treatment in the step (1) is to crush the material to a mesh number of 80 mesh or more, preferably 200 mesh or more, more preferably 400-800 mesh.

6. The method according to claim 1, characterized in that: the mass percentage concentration of the propylene oxide aqueous solution in the step (2) is 2.5% -12%, and the mass ratio of the dosage of the propylene oxide aqueous solution to the pretreated material is 3:1-10:1.

7. the method according to claim 1, characterized in that: in the step (2), polyethylene glycol 2000-20000 is added into the epoxypropane water solution, and the mass ratio of the addition amount of the polyethylene glycol 2000-20000 to the pretreatment material powder is 0.01:1-0.05:1.

8. the method according to claim 1, characterized in that: the heat treatment in the step (2) is carried out in a sealed container, the treatment temperature is 110-180 ℃, the treatment time is 4-8 hours, and the treatment pressure is the autogenous pressure in the sealed container.

9. The method according to claim 1, characterized in that: the pseudo-boehmite in the step (3) is prepared by adopting commercial products or according to the existing method, and preferably the pseudo-boehmite with the pore diameter of more than 10nm can be selected.

10. The method according to claim 1, characterized in that: the mass ratio of the activated powder material A to the pseudo-boehmite in the step (3) is 1:4-2:3.

11. the method according to claim 1, characterized in that: the drying temperature in the step (3) is 100-160 ℃, and the drying time is 6-10 hours; the roasting temperature is 550-650 ℃ and the roasting time is 4-6 hours; the calcination is carried out in an oxygen-containing atmosphere.

12. The method according to claim 1, characterized in that: the acid treatment process in the step (4) comprises the following steps: spraying and impregnating alumina carrier material with acid solution to saturate adsorption of the carrier, then placing the carrier in an autoclave, heating at 40-60 ℃ for 4-8 hours, cooling, and drying at 80-160 ℃ for 4-10 hours; the acid solution is one or a mixture of more than one of acetic acid, oxalic acid, citric acid and tartaric acid, and the concentration of the solution is 5-15 wt%.

13. The method according to claim 1, characterized in that: the alkali treatment process in the step (4) is as follows: spraying alkali solution to impregnate the acid activated alumina carrier material to saturate the adsorption of the carrier, then placing the carrier in an autoclave, heating the carrier at 40-60 ℃ for 4-8 hours, cooling the carrier, and drying the carrier at 80-160 ℃ for 4-10 hours to obtain the alkali activated material; the alkali solution is one or more of ammonia water, ammonium carbonate aqueous solution or ammonium bicarbonate aqueous solution, and the concentration of the alkali solution is 10-30wt%.

14. The method according to claim 1, characterized in that: the impregnation liquid of the hydrogenation active component in the step (5) is impregnation liquid containing Mo, W, ni, co active metal.

15. The method according to claim 1, characterized in that: the impregnation liquid of the hydrogenation active component in the step (5) is impregnation liquid containing active metals of Mo and Co, wherein the content of Mo in the impregnation liquid is 0.5g/100mL-10g/100mL in terms of oxide, and the content of Co in the impregnation liquid is 0.1g/100mL-3g/100mL in terms of oxide.

16. The hydrogenation catalyst prepared by the method according to any one of claims 1 to 15, which is characterized in that: the specific surface area is 150-240m ² Per g, the pore volume is 0.8-1.0mL/g, and the pore volume with the pore diameter of 10-30nm accounts for 45-60% of the total pore volume.

17. The hydrogenation catalyst prepared by the process of claim 15, wherein: the content of molybdenum oxide is 5% -10%, the content of nickel oxide is 2.5% -5%, the content of vanadium pentoxide is 5% -10%, the content of cobalt oxide is 0.2% -1.0%, and the content of alumina carrier is 74% -87.3%.

18. Use of the hydrogenation catalyst according to any one of claims 1-15 in heavy oil hydrodemetallization and hydrodesulphurisation processes.