CN104368351B - A kind of hydrogenation activity guard catalyst and its preparation and application - Google Patents

Abstract

A kind of hydrogenation activity guard catalyst and its preparation and application; described hydrogenation activity guard catalyst contains the halogen-containing alumina support with structure of double peak holes; characterized with mercury injection method, the pore volume of described carrier is 0.6 1.4 mls/g, and specific surface area is 80 400 meters²/ gram, the pore volume in a diameter of 5 20nm holes accounts for the 30 55% of total pore volume, and the pore volume in a diameter of 100 300nm holes accounts for the 15 45% of total pore volume.Compared with prior art, the hydrogenation activity guard catalyst that the present invention provides has preferable HDM activity simultaneously.

Description

A kind of hydrogenation active protection catalyst and its preparation and application

technical field

The invention relates to a hydrogenation active protection catalyst and its preparation and application.

Background technique

As crude oil becomes heavier and inferior, the difficulty of crude oil processing increases, and the yield of light oil products decreases. However, the market demand for high-quality light oil products continues to increase, and environmental protection regulations are becoming more and more inclusive. strict. At present, the processing and full utilization of heavy oil, especially residual oil, is becoming a major topic of concern in the global oil refining industry, and residual oil hydrogenation technology is a widely used processing technology in heavy oil processing technology, and is recognized as an economical and environmentally friendly deep processing technology . Residual oil contains a large amount of metal impurities such as Ni, V, Fe, Ca and solid impurities. If these impurities cannot be effectively removed, it will have an adverse effect on the downstream hydrogenation catalyst and easily deactivate the downstream catalyst. One of the effective ways to solve this problem is to load a protective agent with hydrogenation activity on the top of the hydrogenation catalyst. Therefore, the development of a protective agent with high demetallization activity and strong metal capacity is one of the key technologies for heavy oil hydroprocessing. In the prior art, the disclosed examples of hydrogenation active protected catalysts and their preparation methods include:

CN101890381A discloses a residual oil hydrogenation protection catalyst and its application. The catalyst has large pore volume, large pore diameter, high porosity, reasonable pore distribution, large pores on the outer surface, good pore penetration, and more than 36% of pore channels above 1000nm.

CN00124903.7 discloses a hydrogenation protection catalyst, which contains an alumina carrier and molybdenum and/or tungsten and nickel and/or cobalt loaded on the alumina carrier, wherein the total ammonia of the alumina carrier The integral heat of adsorption is not greater than 25 J/g, and the percentage of the integral heat of adsorption of ammonia with a differential heat of adsorption greater than 100 kJ/mole in the total integral heat of adsorption of ammonia is not greater than 10%.

Patent CN98111379.6 discloses a hydrogenation protection catalyst and its preparation method. The catalyst carrier is a bimodal hole with a super large pore diameter of 0.1-30μm. The pore volume of the catalyst is 0.1-0.8ml/g, and the specific surface is 0.1-20m ² /g, containing 6.65m%-20.0m% of group VIB metal elements and/or 8.7m1% and -26.13m% of group VIII metal elements. The preparation method is to prepare the alumina carrier by particle stacking method, and then impregnate with molybdenum-containing solution and nickel-containing solution in equal amounts, the impregnated catalyst is dried at 100-120°C for 2-5h, and then calcined at 500-550°C for 2-5h .

Contents of the invention

The technical problem to be solved by the present invention is to provide a new hydrogenation activity protected catalyst, the preparation method and application of the hydrogenation activity protected catalyst.

The present invention relates to the following:

1. A hydrogenation activity protected catalyst, containing a halogen-containing alumina support with a bimodal pore structure, characterized by mercury porosimetry, the pore volume of the support is 0.6-1.4 ml/g, and the specific surface area is 80-400 ^m2 /g, the pore volume of pores with a diameter of 5-20nm accounts for 30-55% of the total pore volume, and the pore volume of pores with a diameter of 100-300nm accounts for 15-45% of the total pore volume.

2. according to the described catalyst of 1, it is characterized in that, the pore volume of described carrier is 0.7-1.3 milliliter/gram, and specific surface area is 100-300 meter / gram, and diameter is that the pore volume of ^5-20nm hole accounts for total hole The volume of pores with a diameter of 100-300nm accounts for 20-40% of the total pore volume.

3. The catalyst according to 1, characterized in that the halogen is selected from one of fluorine and chlorine and a mixture thereof, and the content of the halogen is 0.1-6% by weight in terms of elements and based on the carrier.

4. The catalyst according to 3, characterized in that the halogen is fluorine, and the content of the halogen is 0.3-4% by weight based on the element and the support.

5. The catalyst according to 4, characterized in that, in terms of elements and based on the support, the content of the halogen is 0.5-2.5% by weight.

6. The hydrogenation active protected catalyst according to 1, wherein the hydrogenation active metal component is selected from at least one Group VIII metal component and at least one VIB Group metal component, and the oxide Calculated and based on the catalyst, the content of the Group VIII metal component is greater than 0 to less than or equal to 0.8% by weight, and the content of the Group VIB metal component is greater than 0 to less than or equal to 4% by weight.

7. According to the hydrogenation activity protection catalyst described in 6, it is characterized in that, the Group VIII metal component is selected from cobalt and/or nickel, the VIB Group metal component is selected from molybdenum and/or tungsten, and the oxide Calculated and based on the catalyst, the content of the Group VIII metal component is 0.1-0.6% by weight, and the content of the Group VIB metal component is 1.5-3.5% by weight.

8. According to the preparation method of the hydrogenation activity protection catalyst described in 1, comprising preparing a halogen-containing alumina carrier with a bimodal pore structure, the preparation method of the carrier comprises the hydrated alumina PA containing pseudo-boehmite and PB are mixed with a modified PC containing pseudo-boehmite alumina hydrate and a halogen-containing compound is introduced into the mixture, shaped, dried and calcined, wherein the weight of PA, PB and PC is mixed The ratio is 20-60:20-50:5-50, the κ value of PC is 0 to less than or equal to 0.9, the κ=DI ₂ /DI ₁ , DI ₁ is the acid peptization of hydrated alumina before PC modification Index, DI ₂ is the acid peptization index of the PC.

9. The method according to 8, wherein the weight mixing ratio of the PA, PB and PC is 30-50:35-50:10-30; the k value of the PC is 0 to less than or equal to 0.6; The pore volume of the hydrated alumina PA containing pseudoboehmite is 0.75-1 ml/g, the specific surface area is 200-450 ^m2 /g, and the most possible pore diameter is 3-10 nm; The hydrated alumina PB of bauxite has a pore volume of 0.9-1.4 ml/g, a specific surface area of 100-350 ^m2 /g, and a most probable pore diameter greater than 10 to less than or equal to 30 nm; the halogen is selected from fluorine and chlorine, In terms of elements and based on the carrier, the amount of the halogen-containing compound introduced is such that the content of halogen in the final carrier is 0.1-6% by weight.

10. The method according to 9, characterized in that the pore volume of the hydrated alumina PA containing pseudoboehmite is 0.80-0.95 ml/g, and the specific surface is 200-400 ^m2 /g, the most possible The pore diameter is 5-10nm; the pore volume of the hydrated alumina PB containing pseudoboehmite is 0.95-1.3 ml/g, the specific surface area is 120-300 ^m2 /g, and the most possible pore diameter is greater than 10 to Less than or equal to 25nm; the halogen is fluorine, calculated as an element and based on the carrier, and the introduction amount of the halogen-containing compound is such that the content of the halogen in the final carrier is 0.3-4% by weight.

11. The method according to 10, characterized in that, in terms of oxides and based on the support, the amount of the halogen-containing compound introduced is such that the content of halogen in the final support is 0.5-2.5% by weight.

12. The method according to 8 or 9, wherein the PC is 80-300 mesh particles.

13. The method according to 12, characterized in that the PC is 100-200 mesh particles.

14. The method according to 8, wherein the drying conditions include: the temperature is 40-350°C, and the time is 1-24 hours, and the roasting conditions include: the temperature is greater than 500 to less than or equal to 1200°C , the time is 1-8 hours.

15. The method according to 14, wherein the drying conditions include: the temperature is 100-200°C, and the time is 2-12 hours, and the roasting conditions include: the temperature is greater than 800 to less than or equal to 1000°C , The roasting time is 2-6 hours.

16. The method according to 8, characterized in that one of the methods of modifying the hydrated alumina containing pseudo-boehmite to PC is to form and dry the hydrated alumina containing pseudo-boehmite, Then all or part of it is ground and sieved, and the drying conditions include: the temperature is 40-350 ° C, and the time is 1-24 hours; the second method is to roast the molded product obtained in the first method, and the roasting temperature is greater than 350 to less than or equal to 1400 °C, the roasting time is 1-8 hours, and then all or part of it is ground and sieved; the third method is to flash dry the hydrated alumina containing pseudo-boehmite, and the flash-dry temperature is greater than 150 to less than or equal to 1400°C, and the flash-drying time is 0.05-1 hour; the fourth method is obtained by mixing one or more of the modified products obtained by the first method, the second method and the third method.

17. The method according to 16, wherein the drying conditions in the first method include: the temperature is 100-200°C, and the time is 2-12 hours; the calcination temperature in the second method is 500-1200°C , the calcination time is 0.1-6 hours; the flash-drying temperature in method 3 is 200-1000° C., and the flash-drying time is 0.1-0.5 hours.

18. The method according to 8 or 16, characterized in that the PC is 80-300 mesh particles in the modified product of alumina hydrate containing pseudoboehmite.

19. The method according to 18, characterized in that the PC is 100-200 mesh particles in the modified product of alumina hydrate containing pseudoboehmite.

20. The method according to 8, characterized in that it includes loading the hydrogenation active metal component on the carrier, and the method of loading the hydrogenation active metal component on the carrier is an impregnation method, including preparing a hydrogenation active metal component containing A solution of a compound of an active metal selected from at least one metal component of Group VIB and at least one metal of Group VIII with which the support is impregnated, dried, calcined or not calcined Components, calculated as oxides and based on the catalyst, the concentration of the compound containing the hydrogenation active metal in the solution and the amount of the solution make the content of the metal component of Group VIB in the final catalyst greater than 0 to less than or equal to 4% by weight, the content of the metal component of the Group VIII is greater than 0 to less than or equal to 0.8% by weight; the drying conditions include: the temperature is 100-250 ° C, and the time is 1-10 hours; the roasting The conditions include: the temperature is 360-500° C., and the time is 1-10 hours.

21. The method according to 20, characterized in that, the metal component of Group VIB is selected from molybdenum and/or tungsten, and the metal component of Group VIII is selected from cobalt and/or nickel, calculated as oxides and Based on the catalyst, the concentration of the hydrogenation active metal-containing compound in the solution and the amount of the solution make the content of the metal component of Group VIB in the final catalyst be 1.5-3.5% by weight, and Group VIII The content of the metal component is 0.1-0.6% by weight; the drying conditions include: the temperature is 100-140°C, and the time is 1-6 hours; the roasting conditions include: the temperature is 360-450°C, and the time is 2- 6 hours.

22. The application of the catalyst according to any one of claims 1-7 in hydroprocessing of hydrocarbon oil.

According to the catalyst provided by the present invention, depending on different requirements, the carrier can be made into various easy-to-handle shapes, such as spherical, honeycomb, bird's nest, tablet or strip (clover, butterfly, cylindrical, etc.). Wherein, the method of mixing the PA, PB and PC is a conventional method, for example, the powdered PA, PB and PC are put into a stirring mixer according to the feeding ratio and mixed. The method of introducing a halogen-containing compound into the PA, PB and PC mixture is a conventional method, for example, directly mixing a required amount of a halogen-containing compound in the aforementioned PA, PB and PC mixing process.

In a specific embodiment of preparing the carrier, the method of introducing the halogen-containing compound into the mixture of PA, PB and PC is to prepare the halogen-containing compound into an aqueous solution, and the aqueous solution is added to the PA, PB and PC The aqueous solution is mixed in while mixing or after the PA, PB and PC are mixed, and then molded, dried and calcined. The halogen-containing compound may be one or more of any halogen-containing water-soluble compounds. For example, the fluorine-containing compound may be selected from one of hydrofluoric acid, ammonium fluoride and a mixture thereof.

In the present invention, the molding can be carried out by conventional methods, for example, one method or a combination of several methods among ball rolling, tablet pressing and extrusion molding. When molding, such as extrusion molding, in order to ensure that the molding is carried out smoothly, water, extrusion aids and/or adhesives, with or without pore-expanding agents, can be added to the mixture, and then extrusion molding, followed by Dried and roasted. The type and amount of the extrusion aid and the peptizing agent are well known to those skilled in the art, for example, the common extrusion aid can be selected from one of squash powder, methyl cellulose, starch, polyvinyl alcohol, polyethanol or several, the peptizer can be inorganic acid and/or organic acid, and the pore-enlarging agent can be one or more of starch, synthetic cellulose, polymeric alcohol and surfactant. Wherein the synthetic cellulose is preferably one or more in hydroxymethyl cellulose, methyl cellulose, ethyl cellulose, hydroxycellulose fatty alcohol polyvinyl ether, and the polymeric alcohol is preferably polyethylene glycol, polypropylene alcohol, One or more of polyvinyl alcohol, the surfactant is preferably one of fatty alcohol polyvinyl ether, fatty alcohol amide and its derivatives, acrylic alcohol copolymer and maleic acid copolymer with a molecular weight of 200-10000 or several.

The acid peptization index DI in the preparation of the carrier refers to the hydrated alumina containing pseudoboehmite that is peptized within a certain reaction time after adding nitric acid at a certain acid-aluminum ratio. The percentage of aluminum oxide in Al ₂ O ₃ , DI=(1-W ₂ /W ₁ )×100%, W ₁ and W ₂ are respectively before and after the reaction of pseudo-both aluminum and acid with Al ₂ O ₃ gauge weight.

The determination of DI includes: (1) Determination of the ignited base (also called dry base) content of hydrated alumina containing pseudo-boehmite (the ignited base content refers to roasting quantitative pseudo-boehmite at 600°C for 4 hours , the ratio of the weight after burning to the weight before burning, expressed as a percentage), is counted as a; (2) Use an analytical balance to weigh W ₀ grams of hydrated alumina containing pseudo-boehmite, and the amount of W ₀ meets the requirement of Al ₂ O The W ₁ of ₃ is 6 grams (W ₁ /a=W ₀ ), weigh W gram of deionized water, W=40.0-W ₀ , and mix the weighed hydrated alumina containing pseudo-boehmite and Add deionized water into the beaker and mix; (3) use a 20mL pipette to pipette 20mL of dilute nitric acid solution with a concentration of 0.74N, add the acid solution into the beaker of step (2), and react for 8 minutes under stirring; (3) Centrifuge the reacted slurry in a centrifuge, put the precipitate into a weighed crucible, then dry it at 125°C for 4 hours, bake it in a muffle furnace at 850°C for 3 hours, and weigh The weight of the burnt sample is W ₂ grams; (5) is calculated according to the formula DI=(1-W ₂ /W ₁ )×100%.

Under the premise that the final carrier is sufficient to meet the requirements of the present invention, the present invention has no special requirements for the hydrated alumina PA and PB containing pseudo-boehmite, which can be pseudo-boehmite prepared by any prior art, or It may be a mixture of pseudo-boehmite and other hydrated alumina, and the other hydrated alumina is selected from one or more of monohydrate alumina, trihydrate alumina and amorphous hydrate alumina.

In a specific embodiment, the hydrated alumina PA containing pseudoboehmite preferably has a pore volume of 0.75-1 ml/g, a specific surface of 200-450 ^m2 /g, and a most likely pore diameter of 3-10 nm , further preferably the pore volume is 0.80-0.95 ml/g, the specific surface is 200-400 ^m2 /g, and the most possible pore diameter is 5-10nm; the preferred pore volume of the hydrated alumina PB containing pseudo-boehmite is 0.9-1.4 ml/g, the specific surface is 100-350 ^m2 /g, the most probable pore diameter is greater than 10 to less than or equal to 30 nm, more preferably the pore volume is 0.95-1.3 ml/g, and the specific surface is 120-300 ^m2 /g, the most probable pore diameter is greater than 10 to less than or equal to 25nm.

In the present invention, the pore volume, specific surface area and most probable pore diameter of the hydrated alumina containing pseudo-boehmite are determined by BET Nitrogen adsorption was characterized.

In a further preferred embodiment, as characterized by X-ray diffraction, the pseudo-boehmite content in the pseudo-boehmite-containing alumina hydrates PA and PB is not less than 50%, more preferably not less than 60%.

The inventors of the present invention surprisingly found that the modified product PC is obtained by heat-treating alumina hydrate containing pseudo-boehmite. Compared with the original hydrated alumina containing pseudo-boehmite, the peptization of the modified product PC The index changes, and after molding this modification with PA and PB, drying and calcination, the obtained support has a clear bimodal pore distribution. Especially after the 80-300 mesh particles, preferably 100-200 mesh particles are mixed with PA and PB, dried and calcined, the pore distribution of each unimodal in the obtained bimodal carrier is particularly concentrated. Here, the 80-300 mesh particles, preferably 100-200 mesh particles mean that the modified product has been sieved (including the step of crushing or grinding if necessary), and the sieved material (undersize) meets the 80-300 mesh Particles, preferably 100-200 mesh particles, account for a percentage (by weight) of not less than 60% of the total, more preferably not less than 70%. The hydrated alumina containing pseudo-boehmite here can be pseudo-boehmite prepared by any prior art, or a mixture of pseudo-boehmite and other hydrated aluminas, and the other hydrated aluminas One or more selected from alumina monohydrate, alumina trihydrate and amorphous hydrated alumina. In a preferred embodiment, the PC is a modified product of PA and/or PB.

In the present invention, the weight mixing ratio of PA, PB and PC refers to the ratio of the parts by weight of PA, PB and PC in the mixture of PA, PB and PC per hundred parts. Among them, PA:PB:PC is preferably 20-60:20-50:5-50, more preferably 30-50:35-50:10-30.

Among the present invention, described PC can obtain conveniently by following method:

Hereinafter, a method for obtaining PC will be described using the aforementioned PA and PB as starting materials.

⑴Based on drying to obtain PC, including the tailings produced by drying during the preparation of conventional alumina carriers by forming hydrated alumina PA and/or PB containing pseudoboehmite according to conventional methods, for example: in extrusion molding , the tailings (customarily called dry waste) produced by the drying and shaping process of the strip-shaped moldings, the tailings are ground and sieved to obtain PC.

(2) Obtained on the basis of roasting, including the tailings (customarily called roasting waste) produced by roasting during the preparation of conventional alumina carriers from hydrated alumina PA and/or PB containing pseudoboehmite according to conventional methods, For example, in rolling ball molding, the tailings produced by the spherical particles during the roasting process are ground and sieved to obtain PC; or directly obtained by flashing PA and/or PB. And/or when PB is flash-dried, the flash-dry time is preferably 0.05-1 hour, more preferably 0.1-0.5 hour.

(3) Obtained based on the mixture of two or more of the modified PCs obtained by the aforementioned method. When using the mixing method to obtain C, there is no limit to the mixing ratio of the modified PC obtained by the aforementioned methods.

According to the hydrogenation activity protection catalyst provided by the present invention, wherein, the hydrogenation activity metal component is the type and its content known to those skilled in the art, the preferred group VIII metal component is cobalt and/or nickel, VIB group The metal component is molybdenum and/or tungsten, calculated as an oxide and based on the catalyst, the content of the Group VIII metal component is preferably greater than 0 to less than or equal to 0.8% by weight, more preferably 0.1-0.6% by weight, the The content of the Group VIB metal component is preferably greater than 0 to less than or equal to 4% by weight, more preferably 1.5-3.5% by weight.

On the premise that it is sufficient to load the hydrogenation active metal component on the carrier, the present invention has no special limitation on the loading method, and the preferred method is the impregnation method, including the impregnation of preparing the compound containing the metal solution, which is then used to impregnate the carrier. The impregnation method is a conventional method, for example, it may be impregnation with excess liquid or pore saturation method. The metal component compound selected from group VIB is selected from one or more of the soluble compounds in them, such as one or more of molybdenum oxide, molybdate, paramolybdate, preferably among them Molybdenum oxide, ammonium molybdate, ammonium paramolybdate; one or more of tungstate, metatungstate, ethyl metatungstate, preferably ammonium metatungstate, ethyl ammonium metatungstate . The compound containing metal components selected from Group VIII is selected from one or more of their soluble compounds, such as cobalt nitrate, cobalt acetate, basic cobalt carbonate, cobalt chloride and cobalt soluble complexes One or more, preferably cobalt nitrate, basic cobalt carbonate; one or more of nickel nitrate, nickel acetate, basic nickel carbonate, nickel chloride and nickel soluble complexes, preferably nickel nitrate , Basic nickel carbonate.

The catalyst provided by the present invention may also contain any additional components that do not affect the performance of the catalyst provided by the present invention or can improve the catalytic performance of the catalyst provided by the present invention. If it may contain additional components such as phosphorus, the content of the additional components is not more than 10% by weight, preferably 0.1-4% by weight, based on oxides and catalysts.

When the catalyst also contains additional components such as phosphorus, the introduction method of the additional components can be any method, such as directly mixing the compound containing the phosphorus and other components with the pseudo-boehmite Mixing, molding and roasting; it may be that the compound containing the phosphorus and other components and the compound containing the hydrogenation active metal component are formulated into a mixed solution and then impregnated with the carrier; it may also be that the compound containing the phosphorus and other components is separately After preparing the solution, the carrier is impregnated and fired. When additional components such as phosphorus and hydrogenation active metals are respectively introduced into the carrier, it is preferred to firstly impregnate the carrier with a solution containing the compound of the additional components and roast, and then use a solution containing the compound of the hydrogenation active metal Dipping. Wherein, the calcination temperature is 400-600°C, preferably 420-500°C, and the calcination time is 2-6 hours, preferably 3-6 hours.

According to the method for hydrotreating hydrocarbon oil (including residual oil) provided by the present invention, the reaction conditions for the hydrotreating of the hydrocarbon oil are not particularly limited. In a preferred embodiment, the reaction conditions for the hydrotreating are: The reaction temperature is 300-550°C, more preferably 330-480°C, the hydrogen partial pressure is 4-20 MPa, more preferably 6-18 MPa, the volume space velocity is 0.1-3.0 hours ^-1 , more preferably 0.15-2 hours ^-1 , The volume ratio of hydrogen to oil is 200-2500, more preferably 300-2000.

The device for the hydrogenation reaction can be carried out in any reactor sufficient to make the feedstock oil contact with the catalyst under the hydrotreating reaction conditions, for example, in the fixed bed reactor, moving bed reactor or carried out in an ebullating bed reactor.

According to conventional methods in this field, before use, the hydrotreating catalyst can be presulfurized with sulfur, hydrogen sulfide or sulfur-containing raw materials at a temperature of 140-370° C. in the presence of hydrogen, such presulfurization It can be vulcanized outside or in-situ, and the active metal components supported by it can be converted into metal sulfide components.

The catalyst provided by the invention can be used alone or in combination with other catalysts. The catalyst is especially suitable for hydrotreating heavy oil, especially inferior residue oil, so as to provide qualified raw material oil for subsequent processes (such as catalytic cracking process). Compared with the hydrogenation active protective agent provided by the prior art, the hydrogenation active protective agent provided by the present invention has better hydrodemetallization activity while having the function of a conventional protective agent.

detailed description

The following examples will further illustrate the present invention, but should not be construed as a limitation of the present invention.

The reagents used in the examples are chemically pure reagents unless otherwise specified.

The pseudo-boehmite used in the following examples includes:

PA-1: Dry rubber powder produced by Changling Catalyst Branch (pore volume is 0.9 ml/g, specific surface is 280 ^m2 /g, and the most probable pore diameter is 8.5nm. The dry basis is 73%, of which the pseudo-thin water The content of gibbsite is 68%, the content of gibbsite is 5% by weight, and the balance is amorphous alumina (DI value 34.6).

PA-2: Dry rubber powder produced by Zibo Qimao Catalyst Co., Ltd. (the pore volume is 0.9 ml/g, the specific surface is 290 ^m2 /g, the most probable pore diameter is 8.3nm. The dry basis is 73%, of which the pseudo-thin water The content of gibbsite is 68%, the content of gibbsite is 5% by weight, and the balance is amorphous alumina (DI value 33.2).

PB-1: Dry rubber powder produced by Changling Catalyst Branch (pore volume is 1.2 ml/g, specific surface is 280 ^m2 /g, and the most probable pore diameter is 15.8nm. Dry basis is 73%, of which pseudo-thin water The content of gibbsite is 68%, the content of gibbsite is 5% by weight, and the balance is amorphous alumina (DI value 15.8).

PB-2: Dry rubber powder produced by Yantai Henghui Chemical Co., Ltd. (pore volume is 1.1 ml/g, specific surface is 260 ^m2 /g, and the diameter of most pores is 12nm. Dry basis is 71%, of which pseudo-thin water The content of gibbsite is 67%, the content of gibbsite is 5% by weight, and the balance is amorphous alumina (DI value 17.2).

Examples 1-10 illustrate the PC and its preparation method of the present invention.

Example 1

Weigh 1000 grams of PA-1, then add 1000 milliliters of an aqueous solution containing 10 milliliters of nitric acid (product of Tianjin Chemical Reagent No. Dry the wet strips at 120°C for 4 hours to obtain dry strips, shape the dry strips, sieve, grind and sieve the dry strip materials (generally called industrial dry strip waste) with a length of less than 2mm, and take 100-200 Mesh sieving to obtain the modified PC-A1 of PA-1. See Table 1 for the k value of PC-A1.

Example 2

Weigh 1000 grams of PA-1, then add 1000 milliliters of an aqueous solution containing 10 milliliters of nitric acid (product of Tianjin Chemical Reagent No. The wet strips were dried at 120°C for 4 hours, and roasted at 800°C for 4 hours to obtain the carrier. The carrier strips were shaped and sieved, and the carrier strip materials (generally called industrial carrier waste) with a length of less than 2mm were ground, sieved, and collected. Among them, sieve with 100-200 meshes to obtain the modified product PC-A2 of PA-1. See Table 1 for the k value of PC-A2.

Example 3

Weigh 1000g of PA-2, and flash dry at 400°C for 6 minutes to obtain PC-A3, a modified product of PA-2. See Table 1 for the k value of PC-A3.

Example 4

Each 200 grams of PC-A1 obtained in Example 1 and PC-A3 obtained in Example 3 were mixed to obtain the modified product PC-A4 of PA-1 and PA-2. See Table 1 for the k value of PC-A4.

Example 5

Weigh 1000 grams of PB-1, then add 1440 milliliters of aqueous solution containing 10 milliliters of nitric acid (product of Tianjin Chemical Reagent No. The wet strips were dried at 120°C for 4 hours, and roasted at 1200°C for 4 hours to obtain the carrier. The carrier strips were shaped and sieved, and the carrier strip materials (generally called industrial carrier waste) with a length of less than 2mm were ground, sieved, and collected. Among them, 100-200 mesh sieve to obtain the modified product PC-B1 of PB-1. See Table 1 for the k value of PC-B1.

Example 6

Weigh 1000 g of PB-2 and flash dry at 650°C for 10 minutes to obtain PC-B2, a modified product of PB-2. See Table 1 for the k value of PC-B2.

Example 7

Weigh 1000 grams of PB-2, then add 1440 milliliters of aqueous solution containing 10 milliliters of nitric acid (product of Tianjin Chemical Reagent No. Dry the wet strips at 120°C for 4 hours to obtain dry strips, shape the dry strips, sieve, grind and sieve the dry strip materials (generally called industrial dry strip waste) with a length of less than 2mm, and take 100-200 Mesh sieving to obtain the modified product PC-B3 of PB-2. See Table 1 for the k value of PC-B3.

Example 8

Each 200 g of PC-B1 obtained in Example 5 and PC-B2 obtained in Example 6 were mixed to obtain the modified product PC-B4 of PB-1 and PB-2. See Table 1 for the k value of PC-B4.

Example 9

100 grams of PC-A1 obtained in Example 1 and 150 grams of PC-B3 obtained in Example 7 were mixed to obtain PC-B5, a modified product of PA-1 and PB-2. See Table 1 for the k value of PC-B5.

Example 10

Each 150 grams of PC-A3 obtained in Example 3 and PC-B1 obtained in Example 5 were mixed to obtain the modified product PC-B6 of PA-2 and PB-1. See Table 1 for the k value of PC-B6.

Table 1

Example raw material DI k 1 PC-A1 10.0 0.29 2 PC-A2 0.9 0.02 3 PC-A3 3.6 0.11 4 PC-A4 6.7 0.20 5 PC-B1 0 0 6 PC-B2 2.1 0.12 7 PC-B3 5.3 0.31 8 PC-B4 1.0 0.06 9 PC-B5 7.0 0.29 10 PC-B6 1.6 0.07

Examples 11-18 illustrate the preparation method of the halogen-containing bimodal pore carrier provided by the present invention. Comparative Examples 1-5 illustrate the preparation of conventional catalyst supports. .

Example 11

Weigh each 400 grams of PA-1 and PB-1, mix with 200 grams of raw material PC-A2 prepared in Example 2, add 10 milliliters of nitric acid (product of Tianjin Chemical Reagent No. 3 Factory) and 9.8 grams of ammonium fluoride 1300 milliliters of aqueous solution are extruded into outer diameter 2.5mm on the plunger extruder, and the Raschig ring bar of inner diameter 1.0mm. The wet strip was dried at 120° C. for 4 hours to obtain a shaped product, which was calcined at 900° C. for 3 hours to obtain a carrier Z1. The properties of carrier Z1 are listed in Table 2.

Example 12

Take by weighing 300 grams of PA-2, 200 grams of PB-2, after mixing with 500 grams of raw material PC-B2 that embodiment 6 makes, add 10 milliliters of products containing nitric acid Tianjin Chemical Reagent No. 3 Factory) and 7.57 g of ammonium chloride 1300 milliliters of aqueous solution are extruded into outer diameter 2.5mm on the plunger extruder, and the Raschig ring bar of inner diameter 1.0mm. The wet strip was dried at 120° C. for 4 hours to obtain a molded product, which was calcined at 900° C. for 3 hours to obtain a carrier Z2. The properties of carrier Z2 are listed in Table 2.

Example 13

Weigh 500 grams of PA-2, 300 grams of PB-2, mix with 200 grams of raw material PC-B4 prepared in Example 8, add 10 milliliters of nitric acid-containing Tianjin Chemical Reagent No. 3 Factory) and 9.8 g of ammonium fluoride 1300 milliliters of aqueous solution are extruded into outer diameter 2.5mm on the plunger extruder, and the Raschig ring bar of inner diameter 1.0mm. The wet strip was dried at 120° C. for 4 hours to obtain a molded product, which was calcined at 950° C. for 3 hours to obtain a carrier Z3. The properties of carrier Z3 are listed in Table 2.

Comparative example 1

Weigh 500 grams of PA-2, 500 grams of PB-2, add 10 milliliters of nitric acid (product of Tianjin Chemical Reagent No. 2.5mm diameter, 1.0mm inner diameter Raschig ring bar. . The wet strip was dried at 120°C for 4 hours to obtain a molded product, which was calcined at 900°C for 3 hours to obtain a carrier DZ1. The properties of vector DZ1 are listed in Table 2.

Comparative example 2

Weigh 400 grams of PA-1, 600 grams of PB-1, add 10 milliliters of nitric acid (product of Tianjin Chemical Reagent No. 2.5mm diameter, 1.0mm inner diameter Raschig ring bar. The wet strip was dried at 120°C for 4 hours to obtain a molded product, which was calcined at 950°C for 3 hours to obtain the carrier DZ2. The properties of vector DZ2 are listed in Table 2.

Example 14

Weigh 250 grams of PA-1, 500 grams of PB-1, mix with 250 grams of raw material PC-B5 prepared in Example 9, add 10 milliliters of nitric acid (product of Tianjin Chemical Reagent No. 3 Factory), ammonium fluoride ammonia 19.6 1300 milliliters of the aqueous solution of 1 g is extruded into an outer diameter of 2.5 mm on a plunger extruder, and a Raschig ring bar of an inner diameter of 1.0 mm. The wet strip was dried at 120° C. for 4 hours to obtain a shaped product, which was calcined at 1000° C. for 3 hours to obtain a carrier Z4. The properties of carrier Z4 are listed in Table 2.

Example 15

Weigh 350 grams of PA-2, 350 grams of PB-2, mix with 300 grams of raw material PC-B6 prepared in Example 10, add 10 milliliters of nitric acid-containing Tianjin Chemical Reagent No. 3 Factory) and 19.6 g of ammonium fluoride 1440 milliliters of aqueous solution are extruded into outer diameter 2.5mm on the plunger extruder, and the Raschig ring bar of inner diameter 1.0mm. The wet strip was dried at 120° C. for 4 hours to obtain a shaped product, which was calcined at 1000° C. for 3 hours to obtain a carrier Z5. The properties of carrier Z5 are listed in Table 2.

Example 16

Take by weighing 200 grams of PA-1, 600 grams of PB-1, after mixing with 200 grams of raw material PC-B1 that embodiment 5 makes, add 10 milliliters containing nitric acid (product of Tianjin Chemical Reagent No. 3 Factory) and 15.15 g of ammonium chloride 1440 milliliters of aqueous solution are extruded into outer diameter 2.5mm on the plunger extruder, and the Raschig ring bar of inner diameter 1.0mm. The wet strip was dried at 120°C for 4 hours to obtain a molded product, which was calcined at 850°C for 3 hours to obtain a carrier Z6. The properties of carrier Z6 are listed in Table 2.

Example 17

Weigh 200 grams of PA-1, 600 grams of PB-1, mix with 200 grams of raw material PC-A4 prepared in Example 4, add 10 milliliters of nitric acid-containing product of Tianjin Chemical Reagent No. 3 Factory) and 39.2 g of ammonium fluoride 1440 milliliters of aqueous solution are extruded into outer diameter 2.5mm on the plunger extruder, and the Raschig ring bar of inner diameter 1.0mm. The wet strip was dried at 120° C. for 4 hours to obtain a molded product, which was calcined at 850° C. for 3 hours to obtain a carrier Z7. The properties of vector Z76 are listed in Table 2.

Example 18

Weigh 200 grams of PA-1, 600 grams of PB-1, mix with 200 grams of raw material PC-A2 prepared in Example 2, add 10 milliliters of nitric acid-containing Tianjin Chemical Reagent No. 3 Factory) and 39.2 g of ammonium fluoride 1440 milliliters of aqueous solution are extruded into outer diameter 2.5mm on the plunger extruder, and the Raschig ring bar of inner diameter 1.0mm. The wet strip was dried at 120° C. for 4 hours to obtain a molded product, which was calcined at 850° C. for 3 hours to obtain a carrier Z8. The properties of carrier Z8 are listed in Table 2.

Comparative example 3

According to the method provided in Example 7 of the patent CN1782031A, the Raschig annular strip with an outer diameter of 2.5 mm and an inner diameter of 1.0 mm is extruded on a plunger extruder. The wet strip was dried at 120°C for 4 hours to obtain a molded product, which was calcined at 900°C for 3 hours to obtain the carrier DZ3. The properties of vector DZ3 are listed in Table 2.

Comparative example 4

According to the method provided in Example 1 of patent CN1120971A, the Raschig annular strip with an outer diameter of 2.5 mm and an inner diameter of 1.0 mm is extruded on a plunger extruder. The wet strip was dried at 120°C for 4 hours to obtain a molded product, which was calcined at 1000°C for 3 hours to obtain the carrier DZ4. The properties of vector DZ4 are listed in Table 2.

Comparative example 5

Weigh 200 grams of PA-1, 800 grams of PB-2, add 10 milliliters of nitric acid (product of Tianjin Chemical Reagent No. mm, a Raschig ring bar with an inner diameter of 1.0mm. The wet strip was dried at 120°C for 4 hours to obtain a molded product, which was calcined at 1000°C for 3 hours to obtain the carrier DZ5. The properties of vector DZ5 are listed in Table 2.

Table 2

From the results in Table 2, it can be seen that compared with the conventional method, the alumina support prepared by the method provided by the present invention has an obvious bimodal pore structure.

Examples 19-24 illustrate the catalysts provided by the present invention and methods for their preparation.

Example 19

Take 200 grams of carrier Z1, impregnate it with 220 milliliters of a mixed solution of ammonium molybdate and nickel nitrate containing MoO ₃ 28.6 g/L, NiO 5 g/L for 1 hour, dry at 120°C for 4 hours, and roast at 400°C for 3 hours to obtain hydrogenation Active protected catalyst C1. The composition of C1 is listed in Table 3.

Example 20

Take 200 grams of carrier Z2, impregnate 220 milliliters of ammonium metatungstate and nickel nitrate mixed solution containing WO ₃ 28.6 g/L, NiO5 g/L for 1 hour, dry at 120°C for 4 hours, and roast at 400°C for 3 hours to obtain the added Hydrogen activity protects catalyst C2. The composition of C2 is listed in Table 3.

Example 21

Take 200 g carrier Z3, impregnate it with 220 ml mixed solution of ammonium molybdate and nickel nitrate containing MoO ₃ 25 g/L, NiO3 g/L for 1 hour, dry at 120°C for 4 hours, and bake at 400°C for 3 hours to obtain hydrogenation activity Catalyst C3 is protected. The composition of C3 is listed in Table 3.

Example 22

Take 200 grams of carrier Z4, impregnate it with 220 milliliters of a mixed solution of ammonium molybdate and cobalt nitrate containing MoO ₃ 25 g/L, CoO3 g/L for 1 hour, dry at 120°C for 4 hours, and roast at 400°C for 3 hours to obtain hydrogenation Active protection catalyst C4. The composition of C4 is listed in Table 3.

Example 23

Take 200 grams of carrier Z5, impregnate with 220 ml of mixed solution of ammonium molybdate and nickel nitrate containing MoO ₃ 19.0 g/L, NiO2 g/L for 1 hour, dry at 120°C for 4 hours, and roast at 400°C for 3 hours to obtain hydrogenation Active protected catalyst C5. The composition of C5 is listed in Table 3.

Example 24

Take 200 grams of carrier Z8, impregnate 220 milliliters of ammonium metatungstate and nickel nitrate mixed solution containing WO ₃ 19.0 g/L, NiO2 g/L for 1 hour, dry at 120°C for 4 hours, and roast at 400°C for 3 hours to obtain the added Hydrogen activity protection catalyst C6. The composition of C6 is listed in Table 3.

Compare column 6

Take 200 grams of carrier DZ1, impregnate with 220 ml of mixed solution of ammonium molybdate and nickel nitrate containing MoO ₃ 28.6 g/L, NiO 5 g/L for 1 hour, dry at 120°C for 4 hours, and roast at 400°C for 3 hours to obtain hydrogenation Active protection catalyst DC1. The composition of DC1 is listed in Table 3.

Compare column 7

Take 200 grams of carrier DZ2, impregnate 220 milliliters of ammonium metatungstate and nickel nitrate mixed solution containing WO ₃ 28.6 g/L, NiO5 g/L for 1 hour, dry at 120°C for 4 hours, and roast at 400°C for 3 hours to obtain Hydrogen activity protection catalyst DC2. The composition of DC2 is listed in Table 3.

Comparative example 8

Take 200 grams of carrier DZ3, impregnate with 220 ml of mixed solution of ammonium molybdate and nickel nitrate containing MoO ₃ 25 g/L, NiO 3 g/L for 1 hour, dry at 120°C for 4 hours, and roast at 400°C for 3 hours to obtain hydrogenation Active protection catalyst DC3. The composition of DC3 is listed in Table 3.

Comparative example 9

Take 200 grams of carrier DZ4, impregnate with 220 ml of mixed solution of ammonium molybdate and cobalt nitrate containing MoO ₃ 25 g/L, CoO3 g/L for 1 hour, dry at 120°C for 4 hours, and roast at 400°C for 3 hours to obtain hydrogenation Active protection catalyst DC4. The composition of DC4 is listed in Table 3.

Comparative example 10

Take 200 grams of carrier DZ5, impregnate with 220 ml of mixed solution of ammonium molybdate and cobalt nitrate containing MoO ₃ 19 g/L, CoO2 g/L for 1 hour, dry at 120°C for 4 hours, and roast at 400°C for 3 hours to obtain hydrogenation Active Protection Catalyst DC5. The composition of DC5 is listed in Table 3.

table 3

The content of each metal component in the catalyst is a calculated value.

Examples 25-30

Examples 25-30 illustrate the demetallization rate and desulfurization rate of the hydrogenation protection catalyst provided by the present invention.

The protective agent was evaluated in a 100ml small fixed-bed reactor with Yizhong slag as the raw material (see Table 4 for the properties of the raw material oil).

Catalysts C1, C2, C3, C4, C5 and C6 are broken into particles with a diameter of 2-3 mm, and the catalyst loading is 100 milliliters. The reaction conditions are as follows: reaction temperature 380°C, hydrogen partial pressure 14 MPa, liquid hourly space velocity 0.7 hr ^-1 , hydrogen-oil volume ratio 1000, and sample analysis after 200 hours of reaction. The inductively coupled plasma optical emission spectrometer (ICP-AES) was used to measure the metal content in the oil before and after hydrotreatment (the instrument used was PE-5300 plasma light meter of PE Company in the United States, and the specific method was found in the petrochemical analysis method RIPP124-90). Calculate the metal removal rate according to the following formula:

The properties of raw oil are listed in Table 4, and the evaluation results are listed in Table 5.

Comparative example 11-15

The demetallization rate of catalyst DC1, DC2, DC3, DC4 and DC5 is evaluated according to the method of embodiment 25-30, and the results are shown in Table 5.

Table 4

Raw oil name Yi Chong Chang Zha Density (20℃), kg/ ^m3 0.966 average molecular weight 452 Ni, μg/g 47.7 V, μg/g 133 Fe, μg/g 8.4 Ca, μg/g 29.5

Table 5 Protective agent evaluation results

It can be seen from the data in Table 5 that compared with the existing catalysts, the hydrogenation protection agent provided by the present invention has a higher demetallization rate.

Claims (21)

1. A hydrogenation activity protected catalyst, containing a halogen-containing alumina support with a bimodal pore structure, characterized by mercury porosimetry, the pore volume of the support is 0.6-1.4 ml/g, and the specific surface area is 80-400 ^m2 /g, the pore volume of pores with a diameter of 5-20nm accounts for 30-55% of the total pore volume, and the pore volume of pores with a diameter of 100-300nm accounts for 15-45% of the total pore volume; the hydrogenation activity protects the catalyst The hydrogenation active metal component is selected from at least one Group VIII metal component and at least one VIB Group metal component, calculated as an oxide and based on the catalyst, and the content of the Group VIII metal component is greater than 0 to less than or equal to 0.8% by weight, and the content of the Group VIB metal component is more than 0 to less than or equal to 4% by weight. 2. The hydrogenation activity protection catalyst according to claim 1, characterized in that, the pore volume of the carrier is 0.7-1.3 ml/g, the specific surface area is 100-300 ^m2 /g, and the diameter is 5-20nm pores The pore volume of the pores accounts for 35-50% of the total pore volume, and the pore volume of pores with a diameter of 100-300nm accounts for 20-40% of the total pore volume. 3. hydrogenation activity protection catalyst according to claim 1, is characterized in that, described halogen is selected from a kind of in fluorine and chlorine and mixture thereof, in element and with carrier as benchmark, the content of described halogen is 0.1-6% by weight. 4 . The hydrogenation activity-protected catalyst according to claim 3 , wherein the halogen is fluorine, and the content of the halogen is 0.3-4% by weight based on the element and the support. 5 . The hydrogenation activity-protected catalyst according to claim 4 , characterized in that, in terms of elements and based on the carrier, the content of the halogen is 0.5-2.5% by weight. 6. The hydrogenation activity protection catalyst according to claim 1, characterized in that, the metal component of the Group VIII is selected from cobalt and/or nickel, and the metal component of Group VIB is selected from molybdenum and/or tungsten, with In terms of oxides and based on the catalyst, the content of the Group VIII metal component is 0.1-0.6% by weight, and the content of the Group VIB metal component is 1.5-3.5% by weight. 7. The preparation method of the hydrogenation active protection catalyst according to claim 1, comprising preparing a halogen-containing alumina support with a bimodal pore structure, the preparation method of the support comprises hydrating and oxidizing the hydration containing pseudo-boehmite Aluminum PA and PB are mixed with a modified product PC of hydrated alumina containing pseudo-boehmite and a halogen-containing compound is introduced into the mixture, shaped, dried and calcined, wherein the pseudo-boehmite-containing The hydrated alumina PA has a pore volume of 0.75-1 ml/g, a specific surface area of 200-450 ^m2 /g, and a most probable pore diameter of 3-10 nm; the hydrated alumina PB containing pseudoboehmite The pore volume is 0.9-1.4 ml/g, the specific surface area is 100-350 ^m2 /g, and the most probable pore diameter is greater than 10 to less than or equal to 30 nm; the weight mixing ratio of PA, PB and PC is 20-60:20 -50: 5-50, the κ value of PC is 0 to less than or equal to 0.9, said κ=DI ₂ /DI ₁ , DI ₁ is the acid peptization index of hydrated alumina before PC modification, and DI ₂ is the Acid peptization index of PC. 8. The method according to claim 7, wherein the weight mixing ratio of the PA, PB and PC is 30-50:35-50:10-30; the κ value of the PC is 0 to less than or equal to 0.6; the halogen is selected from one of fluorine and chlorine, calculated as elements and based on the carrier, the introduction amount of the halogen-containing compound is such that the content of halogen in the final carrier is 0.1-6% by weight. 9. The method according to claim 8, characterized in that, the pore volume of the alumina hydrate PA containing pseudoboehmite is 0.80-0.95 milliliters/gram, and the specific surface area is ^200-400 m / gram, The most probable pore diameter is 5-10nm; the pore volume of the hydrated alumina PB containing pseudoboehmite is 0.95-1.3 ml/g, the specific surface area is 120-300 ^m2 /g, and the most probable pore diameter is greater than 10 to less than or equal to 25 nm; the halogen is fluorine, calculated as an element and based on a carrier, and the introduction amount of the halogen-containing compound is such that the content of the halogen in the final carrier is 0.3-4% by weight. 10. The method according to claim 9, characterized in that, in terms of elements and based on the carrier, the amount of the halogen-containing compound introduced is such that the content of halogen in the final carrier is 0.5-2.5% by weight. 11. The method according to claim 7 or 8, characterized in that the PC is 80-300 mesh particles. 12. The method according to claim 11, characterized in that, the PC is 100-200 mesh particles. 13. The method according to claim 7, characterized in that, the drying conditions include: the temperature is 40-350°C, and the time is 1-24 hours, and the roasting conditions include: the temperature is greater than 500 to less than or equal to 1200°C, the time is 1-8 hours. 14. The method according to claim 13, characterized in that, the drying conditions include: the temperature is 100-200°C, and the time is 2-12 hours, and the roasting conditions include: the temperature is greater than 800 to less than or equal to 1000°C, the firing time is 2-6 hours. 15. The method according to claim 7, wherein one of the methods for modifying the alumina hydrate containing pseudo-boehmite to PC is to form the alumina hydrate containing pseudo-boehmite, Drying, and then grind and sieve all or part of it, the drying conditions include: the temperature is 40-350°C, and the time is 1-24 hours; the second method is to roast the molded product obtained in one of the methods, The temperature is greater than 350 to less than or equal to 1400°C, the roasting time is 1-8 hours, and then all or part of it is ground and sieved; the third method is to flash dry the hydrated alumina containing pseudoboehmite, flash dry The temperature is greater than 150 to less than or equal to 1400°C, and the flash-drying time is 0.05-1 hour; the fourth method is obtained by mixing several modified products obtained by the first method, the second method and the third method. 16. The method according to claim 15, wherein the drying conditions in one of the methods include: the temperature is 100-200° C., and the time is 2-12 hours; the flash-drying temperature in the third method is 200-1000℃, flash-drying time is 0.1-0.5 hours. 17. The method according to claim 7 or 15, characterized in that the PC is 80-300 mesh particles in the modified product of alumina hydrate containing pseudoboehmite. 18 . The method according to claim 17 , wherein the PC is a 100-200 mesh particle in a modified product of alumina hydrate containing pseudoboehmite. 19 . 19. The method according to claim 7, characterized in that, comprising loading the hydrogenation active metal component on the carrier, the method of loading the hydrogenation active metal component on the carrier is an impregnation method, comprising preparing A solution of a compound of a hydrogenation-active metal selected from at least one metal component of Group VIB and at least one metal component of Group VIII and impregnating the carrier with this solution, followed by drying, calcining or not calcining The metal component of the metal component is calculated as an oxide and based on the catalyst, the concentration of the compound containing the hydrogenation active metal in the solution and the amount of the solution make the content of the metal component of Group VIB in the final catalyst It is greater than 0 to less than or equal to 4% by weight, and the content of the metal component of Group VIII is greater than 0 to less than or equal to 0.8% by weight; the drying conditions include: the temperature is 100-250°C, and the time is 1-10 hours; The calcination conditions mentioned above include: the temperature is 360-500° C., and the time is 1-10 hours. 20. The method according to claim 19, characterized in that, the metal component of the VIB group is selected from molybdenum and/or tungsten, the metal component of the VIII group is selected from cobalt and/or nickel, and the oxide Calculated and based on the catalyst, the concentration of the hydrogenation active metal-containing compound in the solution and the amount of the solution make the content of the metal component of Group VIB in the final catalyst be 1.5-3.5% by weight, and The content of the metal component of Group VIII is 0.1-0.6% by weight; the drying conditions include: the temperature is 100-140°C, and the time is 1-6 hours; the roasting conditions include: the temperature is 360-450°C, and the time is 2-6 hours. 21. The application of the catalyst according to any one of claims 1-6 in hydrotreating of hydrocarbon oil.