CN104338527B - A heavy oil hydrodeasphaltene catalyst and its preparation and application - Google Patents

Abstract

A kind of heavy-oil hydrogenation depitching matter catalyst and preparation and application thereof, this catalyst contains carrier and hydrogenation active metals component, described hydrogenation active metals component is selected from the metal component of at least one group vib and the metal component of at least one VB race, wherein, described carrier is a kind of Bimodal-pore alumina support containing group ivb metal component, characterizing 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 60% 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 catalyst that the present invention provides has preferably hydrogenation depitching matter and demetalization performance when for residual hydrocracking.

Description

A heavy oil hydrodeasphaltene catalyst and its preparation and application

technical field

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

Background technique

The deep processing of heavy oil including residual oil is not only conducive to improving the utilization rate of crude oil and alleviating the tense trend of energy supply, but also reducing environmental pollution and achieving clean utilization of energy. Compared with distillate oil, heavy oil contains a large number of macromolecular reactants such as asphaltenes and colloids, while heteroatom compounds such as sulfur, nitrogen, and oxygen in heavy oil have a large Some of them are concentrated in asphaltenes, and these impurities and heavy metals will pollute the corresponding catalysts in the subsequent processing. Therefore, the hydroconversion of asphaltenes is a key step in the hydrogenation process of residual oil. In the process of converting and removing asphaltene, it is necessary to select a catalyst with high activity and good stability and excellent performance according to the characteristics of asphaltenes.

For deasphaltene hydrogenation catalyst, its pore size distribution is of great significance to the performance of the catalyst. The molecular size of asphaltene is about tens to hundreds of nanometers. If the distance between the active centers of the catalyst is smaller than that of the asphaltene molecules, it is difficult for the asphaltene molecules to contact the active centers of the catalyst through diffusion, and they are mainly adsorbed on the outer surface of the catalyst or The orifice, as the reaction proceeds, can only form coke due to thermal condensation, resulting in catalyst deactivation. Macroporous catalysts are beneficial to the removal of asphaltenes, but the pore size of the catalyst is negatively correlated with the specific surface area, that is, the catalyst with a large average pore size has a small specific surface area. Therefore, in order to take into account this property, the catalyst needs to have a reasonable pore distribution.

The disadvantage of existing heavy oil hydrogenation catalysts is that their S, N removal rates, heavy metal removal rates and asphaltenes removal rates cannot be well matched. For example, catalysts with high metal removal activity often S, N removal rate and asphaltenes removal rate are not high. The reasons for such problems are complex. The first is the raw material. The components in the residual oil are characterized by large molecular weight, complex structure, low saturation (high aromaticity), and high S and N contents. Except for sulfur, the vast majority of impurities exist in asphaltene, so to remove such S and N, it is necessary to carry out moderate transformation of asphaltene molecules (including saturation, ring opening and hydrogenolysis, etc.). The second is the catalyst. In the prior art, catalysts having apertures suitable for such reactions are protection catalysts and demetallization catalysts, such as:

CN1267537C discloses a hydrodemetallization catalyst with lower carbon deposition and higher activity and its preparation method.

CN1796500A discloses a residual oil hydrogenation demetallization catalyst, which is composed of a carrier with double pores and molybdenum and/or tungsten and cobalt and/or nickel metal components loaded on the carrier. The preparation method of the carrier used in the catalyst includes mixing a precursor of alumina and a nitrogen-containing compound other than acid, shaping and calcining.

CN1233795C discloses a heavy oil fixed-bed hydrotreating catalyst and a preparation method thereof.

However, the asphaltenes removal rates of these catalysts are generally low.

Contents of the invention

The technical problem to be solved by the present invention is to provide a new catalyst with better hydrogenation deasphaltene performance, the preparation method and application of the catalyst.

The present invention relates to the following:

1. A heavy oil hydrodeasphaltene catalyst, containing a carrier and a hydrogenation active metal component, the hydrogenation active metal component is selected from at least one metal component of the VIB group and at least one metal group of the VB group points, wherein the carrier is a bimodal pore alumina carrier containing Group IVB metal components, characterized by mercury porosimetry, the pore volume of the carrier 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 30-60% 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 Group IVB metal component is selected from one or more of titanium, zirconium, and hafnium, and based on the support and in terms of oxides, the The content of Group IV metals in the support is 0.1-6% by weight.

4. The catalyst according to 3, characterized in that the Group IVB metal component is titanium, and the content of the Group IVB metal in the carrier is 0.3-4 weight%.

5. The catalyst according to 4, characterized in that, based on the support and calculated as an oxide, the content of the Group IVB metal in the support is 0.5-2.5% by weight.

6. The catalyst according to 1, wherein the hydrogenation active metal component is selected from a combination of at least one metal component of Group VIB and at least one metal component of Group VB, in terms of oxides and Based on the catalyst, the content of the VIB group metal component is 0.2-15% by weight, and the content of the VB group metal component is 0.2-12% by weight.

7. The catalyst according to 3, characterized in that, the metal components of the VIB group are selected from molybdenum and/or tungsten, and the VB group metal components are selected from vanadium and/or niobium, in terms of oxides and in terms of catalysts Standard, the content of the VIB group metal component is 0.5-12% by weight, and the content of the VB group metal component is 0.5-9% by weight.

8. The preparation method of the catalyst according to 1, comprising preparing an alumina support with a bimodal pore structure containing the metal component of Group IVB, the preparation method of the support comprises mixing alumina hydrate PA containing pseudo-boehmite and PB are mixed with a modified product PC of hydrated alumina containing pseudo-boehmite, and a compound containing Group IVB metal components is introduced into the mixture, shaped, dried and calcined, wherein the PA, PB The weight mixing ratio with PC 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 hydration and oxidation of PC before modification The acid peptization index of aluminum, DI ₂ is the acid peptization index of the PC.

9. The method according to 8, characterized in that the weight mixing ratio of PA, PB and PC is 30-50:35-50:10-30.

10. The method according to 8, characterized in that, the Group IVB metal is selected from one of titanium, zirconium, hafnium and a mixture thereof, calculated as an oxide and based on a support, and the metal containing Group IVB The metal compound is introduced in such an amount that the Group IVB metal content in the final support is 0.1-6% by weight.

11. The method according to 10, characterized in that, the metal of Group IVB is titanium, calculated as an oxide and based on the carrier, and the introduction amount of the metal compound containing Group IVB is such that Group IVB in the final carrier is The content of metal is 0.3-4% by weight.

12. The method according to 8, wherein the k value of the PC is 0 to less than or equal to 0.6.

13. The method according to 8 or 9, characterized in that the pore volume of the hydrated alumina PA containing pseudoboehmite is 0.75-1 ml/g, and the specific surface is 200-450 ^m2 /g, The most accessible pore diameter is 3-10nm; the pore volume of the hydrated alumina PB containing pseudoboehmite is 0.9-1.4 ml/g, the specific surface is 100-350 ^m2 /g, and the most accessible pore diameter is greater than 10 to less than or equal to 30nm.

14. The method according to 13, 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 and a pore diameter of 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 accessible pore diameter is greater than 10 to Less than or equal to 25nm.

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

16. The method according to 15, characterized in that the PC is 100-200 mesh particles.

17. 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.

18. The method according to 17, 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.

19. 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.

20. The method according to 19, characterized in that 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.

21. The method according to 19, characterized in that the PC is 80-300 mesh particles in the modified product of alumina hydrate containing pseudoboehmite.

22. The method according to 21, characterized in that the PC is 100-200 mesh particles in the modified product of alumina hydrate containing pseudoboehmite.

23. The method according to 8, characterized in that the method 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 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 VB and impregnating the support with this solution, followed by drying, calcination or no calcination Metal components, in terms of oxides and catalysts, the concentration and dosage of the impregnation solution make the content of the VIB group metal components in the final catalyst be 0.2-15% by weight, and the content of the VB group metal components is 0.2-12% by weight, the drying conditions are: temperature 80-200°C, time 1-8 hours, the roasting conditions are: temperature 400-600°C, time 2-8 hours.

24. The method according to 23, characterized in that, the metal components of the VIB group are selected from molybdenum and/or tungsten, and the VB group metal components are selected from vanadium and/or niobium, in terms of oxides and catalysts Standard, the concentration and amount of the impregnating solution make the content of the VIB group metal component in the final catalyst be 0.5-12% by weight, the content of the VB group metal component is 0.5-9% by weight, and the drying conditions are: The temperature is 100-150° C., and the time is 2-6 hours. The roasting conditions are: temperature 420-500° C., and the time is 3-6 hours.

25. The method according to 24, characterized in that, based on the oxide and the catalyst, the concentration and amount of the impregnation solution make the content of the VIB group metal component in the final catalyst be 5-12% by weight , the content of the VB group metal component is 1-9% by weight.

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

According to the catalyst provided by the present invention, the Group IVB metal component is selected from one or more of titanium, zirconium, and hafnium, preferably titanium, calculated as an oxide and based on the support, and the Group IVB The content of the group metal is 0.1-0.6% by weight, preferably 0.3-4% by weight, more preferably 0.5-2.5% by weight.

If necessary, the carrier can be made into any shape that is easy to handle, such as spherical, honeycomb, bird's nest, tablet or strip (clover, butterfly, cylinder, 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 the compound containing the Group IVB metal into the PA, PB and PC mixture is a conventional method, for example, directly mixing the required amount of the compound containing the Group IVB metal in the aforementioned PA, PB and PC mixed in the process.

In a specific embodiment of preparing the carrier, the method of introducing the compound containing the Group IVB metal into the mixture of PA, PB and PC is to prepare the compound containing the Group IVB metal into an aqueous solution, and the aqueous solution is added to the The PA, PB and PC are mixed together or the aqueous solution is mixed after the PA, PB and PC are mixed, and then shaped, dried and fired. The compound containing Group IVB metal may be one or more of any water-soluble compounds of Group IVB metal. For example, one or more of the water-soluble inorganic salts of Group IVB metals.

In the present invention, the molding is carried out by a conventional method, 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.

In the present invention, the acid peptization index DI refers to the hydrated alumina containing pseudoboehmite and the modified alumina hydrate containing pseudoboehmite after adding nitric acid at a certain acid-aluminum ratio, in a certain reaction Percentage of hydrated alumina containing pseudoboehmite peptized within the time, calculated as Al ₂ O ₃ , DI=(1-W ₂ /W ₁ )×100%, W ₁ and W ₂ are respectively Hydrated alumina of diaspore before and after reaction with _acid by weight in terms of _Al2O3 .

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 accessible pore diameter of 3-10 nm , the further preferred pore volume is 0.80-0.95 ml/g, the specific surface is 200-400 ^m2 /g, and the most accessible pore diameter is 5-10 nm; 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 accessible pore diameter is greater than 10 to less than or equal to 30nm, more preferably the pore volume is 0.95-1.3 ml/g, and the specific surface is 120-300 ^m2 /g, the most accessible 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 accessible 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 means 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 catalyst provided by the present invention, the VIB group metal component is preferably molybdenum and/or tungsten, more preferably molybdenum or tungsten, and the VB group metal component is preferably vanadium and/or niobium, more preferably vanadium. Based on the oxide and based on the catalyst, the content of the Group VIB metal component is preferably 0.2-15% by weight, more preferably 0.5-12% by weight, and even more preferably 5-12% by weight; the Group VB metal The content of the component is preferably 0.2-12% by weight, more preferably 0.5-9% by weight, still more preferably 1-9% 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 the VB group is selected from one or more of their soluble compounds. Taking the vanadium of the VB group as an example, it can be selected from vanadium pentoxide, ammonium vanadate, metavanadate, etc. One or more of ammonium, vanadium sulfate, and vanadium heteropolyacids, preferably ammonium metavanadate and ammonium vanadate.

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 the oxide and the catalyst.

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 prior art, the catalyst provided by the invention has better hydrodeasphaltene and demetallization properties when used in residual oil hydrotreating.

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, most accessible pore diameter is 8.5nm. 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 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 accessible 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, most accessible 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, most accessible pore diameter 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 evenly mixed to obtain the modified 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 grams of PC-B1 obtained in Example 5 and PC-B2 obtained in Example 6 were evenly 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 evenly 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 uniformly 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 bimodal pore supports provided by the present invention and methods for their preparation. Comparative Examples 1-4 illustrate conventional catalyst supports and methods for their preparation.

Example 11

Take by weighing 400 grams each of PA-1 and PB-1, mix evenly 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), 16.6 grams of titanium tetrachloride 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 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, and after mixing evenly with 500 grams of raw material PC-B2 prepared in Example 6, add 10 milliliters of nitric acid-containing Tianjin Chemical Reagent No. 3 Factory) and titanium tetrachloride 16.6 1300 milliliters of the aqueous solution of g is extruded into the butterfly bar of outer diameter φ 1.4mm on twin-screw 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 a carrier Z2. The properties of carrier Z2 are listed in Table 2.

Example 13

Take by weighing 500 grams of PA-2, 300 grams of PB-2, and after mixing evenly with 200 grams of raw material PC-B4 obtained in Example 8, add 10 milliliters of nitric acid-containing Tianjin Chemical Reagent No. 3 Factory) and titanium tetrachloride 16.6 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 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

Take by weighing 500 grams of PA-2, 500 grams of PB-2, after uniform mixing, add 10 milliliters containing nitric acid (product of Tianjin Chemical Reagent No. Form a Raschig ring strip with an outer diameter of 2.5mm and 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 900°C for 3 hours to obtain a carrier DZ1. The properties of vector DZ1 are listed in Table 2.

Example 14

Take by weighing 250 grams of PA-1, 500 grams of PB-1, and after mixing evenly 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) and titanium tetrachloride 1300 milliliters of the aqueous solution of 29.9g is extruded into the butterfly bar of external diameter φ 1.4mm on twin-screw 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 a carrier Z4. The properties of carrier Z4 are listed in Table 2.

Comparative example 2

Take by weighing 400 grams of PA-1, 600 grams of PB-1, after uniform mixing, add 10 milliliters containing nitric acid (the product of Tianjin Chemical Reagent No. Butterfly bar with outer diameter φ1.4mm. 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 15

Take by weighing 350 grams of PA-2, 350 grams of PB-2, and after mixing evenly with 300 grams of raw material PC-B6 obtained in Example 10, add 10 milliliters of nitric acid-containing Tianjin Chemical Reagent No. 3 Factory) and titanium tetrachloride 29.9 The aqueous solution 1440 milliliters of g is extruded into the butterfly bar of external diameter φ 1.4mm on twin-screw extruder. 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 vector Z5 are listed in Table 2.

Example 16

Take by weighing 200 grams of PA-1, 600 grams of PB-1, and after mixing evenly with 200 grams of raw material PC-B1 prepared in Example 5, add 10 milliliters of nitric acid-containing Tianjin Chemical Reagent No. 3 Factory) and titanium tetrachloride containing 29.9 The aqueous solution 1440 milliliters of g is extruded into the outer diameter 2.5mm on the plunger extruder, the Raschig ring bar of internal 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

Take by weighing 200 grams of PA-1, 600 grams of PB-1, and after mixing evenly with 200 grams of raw material PC-A4 obtained in Example 4, add 10 milliliters of nitric acid-containing Tianjin Chemical Reagent No. 3 Factory) and titanium tetrachloride 41.6 The aqueous solution 1440 milliliters of g is extruded into the outer diameter 2.5mm on the plunger extruder, the Raschig ring bar of internal 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

Take by weighing 200 grams of PA-1, 600 grams of PB-1, and after mixing evenly with 200 grams of raw material PC-A2 obtained in Example 2, add 10 milliliters of nitric acid-containing Tianjin Chemical Reagent No. 3 Factory) and titanium tetrachloride 41.6 The aqueous solution 1440 milliliters of g is extruded into the outer diameter 2.5mm on the plunger extruder, the Raschig ring bar of internal 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. 2.5mm, 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 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 19-23 illustrate the catalysts provided by the present invention and methods for their preparation.

Among them, the content of active metal components in the catalyst was measured by X-ray fluorescence spectrometer (all instruments are X-ray fluorescence spectrometer 3271 of Japan Rigaku Electric Industry Co., Ltd., for specific methods, see petrochemical analysis method RIPP133-90).

Example 19

Take 200 grams of carrier Z1, impregnate with 220 milliliters of ammonium heptamolybdate and ammonium metavanadate mixed solution containing MoO ₃ 80 g/L, V ₂ O ₅ 16 g/L for 1 hour, dry at 120°C for 4 hours, and then dry at 400°C Calcined for 3 hours to obtain hydrodemetallization catalyst C1, the composition of which is listed in Table 3.

Comparative example 6

Take 200 grams of DZ1, immerse in 220 ml of mixed solution of ammonium heptamolybdate and nickel nitrate containing MoO ₃ 80 g/L, NiO 16 g/L for 1 hour, dry at 120°C for 4 hours, and roast at 400°C for 2 hours to obtain hydrogenation Demetallization catalyst DC1, the composition of DC1 is listed in Table 3.

Example 20

Take 200 grams of carrier Z2, impregnate with 220 ml of mixed solution of ammonium heptamolybdate and ammonium metavanadate containing 80 g/L MoO ₃ and 16 g/L V ₂ O ₅ for 1 hour, dry at 120°C for 4 hours, and dry at 400°C Calcined for 3 hours to obtain hydrodemetallization catalyst C2, the composition of C2 is listed in Table 3.

Comparative example 7

Take 200 grams of carrier DZ3, impregnate it with 220 ml mixed solution of ammonium heptamolybdate and ammonium metavanadate containing WO ₃ 80 g/L, V ₂ O ₅ 16 g/L for 1 hour, dry at 120°C for 4 hours, and dry at 400°C Calcined for 3 hours to obtain the hydrodemetallization catalyst DC2, the composition of DC2 is listed in Table 3.

Example 21

Take 200 grams of carrier Z3, impregnate with 220 ml of mixed solution of ammonium heptamolybdate and ammonium metavanadate containing MoO ₃ 80 g/L, V ₂ O ₅ 16 g/L for 1 hour, dry at 120°C for 4 hours, and dry at 400°C Calcined for 3 hours to obtain hydrodemetallization catalyst C3, the composition of C3 is listed in Table 3.

Comparative example 8

Take 200 grams of carrier DZ4, impregnate with 220 ml of ammonium heptamolybdate and ammonium metavanadate mixed solution containing WO ₃ 60 g/L, V ₂ O ₅ 60 g/L for 1 hour, dry at 120°C for 4 hours, and dry at 400°C Calcined for 3 hours to obtain the hydrodemetallization catalyst DC3, the composition of DC3 is listed in Table 3.

Example 22

Take 200 grams of Z6, immerse in 220 ml of mixed solution of ammonium heptamolybdate and ammonium metavanadate containing MoO ₃ 90 g/L, V ₂ O ₅ 20 g/L for 1 hour, dry at 120°C for 4 hours, and bake at 400°C After 3 hours, hydrodemetallization catalyst C6 was obtained. The composition of hydrodemetallization catalyst C6 is listed in Table 2.

Example 23

Take 200 grams of Z8, soak in 220 ml of ammonium tungstate and ammonium metavanadate mixed solution containing WO ₃ 60 g/L, V ₂ O ₅ 60 g/L for 1 hour, dry at 120°C for 4 hours, and bake at 400°C for 3 hours. hours, the hydrodemetallization catalyst C8 was obtained. The composition of hydrodemetallization catalyst C8 is listed in Table 2.

Comparative example 9

Take 200 grams of carrier DZ5, impregnate with 500 ml of mixed solution of ammonium heptamolybdate and ammonium metavanadate containing MoO ₃ 90 g/L, V ₂ O ₅ 20 g/L for 1 hour, dry at 120°C for 4 hours, and dry at 400°C Calcined for 3 hours to obtain the hydrodemetallization catalyst DC4, the composition of DC4 is listed in Table 3.

table 3

Examples 24-28

Examples 24-28 illustrate the resid hydrodemetallization performance of the catalysts provided by the present invention.

Catalysts C1, C2, C3, C4 and C5 were broken into particles with a diameter of 2-3 mm and loaded into the reactor. The reaction conditions are: reaction temperature 380°C, hydrogen partial pressure 14 MPa, using inductively coupled plasma emission spectrometer (ICP-AES) to measure the content of nickel and vanadium in the oil before and after hydrotreatment (the instrument used is PE-5300 from American PE Company Plasma light meter, see petrochemical analysis method RIPP124-90 for specific methods). The asphaltene mass fraction in oil before and after hydrotreatment was analyzed by petroleum asphalt component determination method (see SH/T0509-92 for specific methods). The asphaltenes and metals removal rates were calculated according to the following formulas:

The raw material oil is Kuwaiti normal slag with a nickel content of 29.3ppm, a vanadium content of 83ppm, a sulfur content of 4.7%, a nitrogen content of 0.3%, and a residual carbon content of 15.1%.

The activity data of each catalyst are shown in Table 4.

Comparative example 10-13

According to the method evaluation of embodiment 24-28, the demetallization rate and deasphaltene rate of catalyst DC1, DC2, DC3 and DC4, the results are shown in Table 4.

Table 4

Example Catalyst number Deasphaltene rate/% Demetallization rate/% twenty four C1 89 75 Comparative example 10 DC1 65 69 25 C2 91 67 Comparative example 11 DC2 62 65 26 C3 88 76 Comparative example 12 DC3 68 73 27 C4 89 75 28 C5 89 80 Comparative example 13 DC4 76 71

As can be seen from the results in Table 4, the deasphaltene and demetallization activity of the catalyst provided by the present invention is significantly better than that of existing catalysts in the process of hydrotreating inferior residues, indicating that the catalyst of the present invention is more suitable for the processing of inferior residues deal with.

Claims (24)

1. a heavy-oil hydrogenation depitching matter catalyst, containing carrier and hydrogenation active metals component, described hydrogenation active metals Component is selected from the metal component of at least one group vib and the metal component of at least one VB race, in terms of oxide and with catalyst On the basis of, the content of described group vib metal component is 0.2-15 weight %, and the content of VB race metal component is 0.2-12 weight Amount %, wherein, described carrier is a kind of Bimodal-pore alumina support containing group ivb metal component, characterizes with mercury injection method, institute The pore volume stating carrier is 0.6-1.4 ml/g, and specific surface area is 80-400 rice²/ gram, the pore volume in a diameter of 5-20nm hole accounts for The 30-60% of total pore volume, the pore volume in a diameter of 100-300nm hole accounts for the 15-45% of total pore volume.

Catalyst the most according to claim 1, it is characterised in that the pore volume of described carrier is 0.7-1.3 ml/g, than Surface area is 100-300 rice²/ gram, the pore volume in a diameter of 5-20nm hole accounts for the 35-50% of total pore volume, a diameter of 100-300nm The pore volume in hole accounts for the 20-40% of total pore volume.

Catalyst the most according to claim 1, it is characterised in that described group ivb metal component is in titanium, zirconium, hafnium One or more, on the basis of described carrier and in terms of oxide, in described carrier, the content of the IVth B race metal is 0.1-6 Weight %.

Catalyst the most according to claim 3, it is characterised in that described group ivb metal component is titanium, with described carrier On the basis of and in terms of oxide, in described carrier, the content of group ivb metal is 0.3-4 weight %.

Catalyst the most according to claim 4, it is characterised in that on the basis of described carrier and in terms of oxide, described In carrier, the content of group ivb metal is 0.5-2.5 weight %.

Catalyst the most according to claim 1, it is characterised in that the metal component of described vib selected from molybdenum and/or Tungsten, Group VB metal component is selected from vanadium and/or niobium, counts and on the basis of catalyst by oxide, described vib metals component Content be 0.5-12 weight %, the content of Group VB metal component is 0.5-9 weight %.

The preparation method of catalyst the most according to claim 1, including prepare have structure of double peak holes containing the IVth B race metal The alumina support of component, the preparation method of described carrier includes hydrated alumina PA and PB and containing boehmite Plant the modifier PC mixing of the hydrated alumina containing boehmite and introduce in the mixture containing the IVth B race metal component Compound, molding, be dried and roasting, wherein, the Mixing ratio by weight of described PA, PB and PC is 20-60:20-50:5-50, PC κ value be 0 to less than or equal to 0.9, described κ=DI₂/DI₁, DI₁For the sour peptization index of PC hydrated alumina before modified, DI₂ For the sour peptization index of described PC, described dry condition includes: temperature is 40-350 DEG C, and the time is 1-24 hour, described roasting The condition burnt includes: temperature is that the time is 1-8 hour to less than or equal to 1200 DEG C more than 500.

Method the most according to claim 7, it is characterised in that the Mixing ratio by weight of described PA, PB and PC is 30-50:35- 50:10-30.

Method the most according to claim 7, it is characterised in that described IVth B race metal one in titanium, zirconium, hafnium And mixture, to count and on the basis of carrier by oxide, the described introduction volume containing the IVth B race metallic compound makes final carrier In the content of the IVth B race metal be 0.1-6 weight %.

Method the most according to claim 9, it is characterised in that described IVth B race metal is titanium, in terms of oxide and with On the basis of carrier, the described introduction volume containing the IVth B race metallic compound makes the content of the IVth B race metal in final carrier be 0.3- 4 weight %.

11. methods according to claim 7, it is characterised in that the κ value of described PC is 0 to less than or equal to 0.6.

12. according to the method described in claim 7 or 8, it is characterised in that the described hydrated alumina PA containing boehmite Pore volume be 0.75-1 ml/g, specific surface area is 200-450 rice²/ gram, most probable bore dia 3-10nm；Described thin containing intending The pore volume of the hydrated alumina PB of diaspore is 0.9-1.4 ml/g, and specific surface area is 100-350 rice²/ gram, most probable hole is straight Footpath is more than 10 to less than or equal to 30nm.

13. methods according to claim 12, it is characterised in that the described hydrated alumina PA's containing boehmite Pore volume is 0.80-0.95 ml/g, and specific surface area is 200-400 rice²/ gram, most probable bore dia 5-10nm；Described containing plan The pore volume of the hydrated alumina PB of boehmite is 0.95-1.3 ml/g, and specific surface area is 120-300 rice²/ gram, most probable Bore dia is more than 10 to less than or equal to 25nm.

14. according to the method described in claim 7 or 8, it is characterised in that described PC is the particulate matter of 80-300 mesh.

15. methods according to claim 14, it is characterised in that described PC is the particulate matter of 100-200 mesh.

16. methods according to claim 7, it is characterised in that described dry condition includes: temperature is 100-200 DEG C, Time is 2-12 hour, and the condition of described roasting includes: temperature is that roasting time is 2-6 to less than or equal to 1000 DEG C more than 800 Hour.

17. methods according to claim 7, it is characterised in that the hydrated alumina containing boehmite is modified as One of method of PC is by described hydrated alumina molding containing boehmite, is dried, and it is completely or partially entered afterwards Row grinds, screening, and described dry condition includes: temperature is 40-350 DEG C, and the time is 1-24 hour；The two of method are by method The article shaped roasting that one obtains, sintering temperature is that roasting time is 1-8 hour more than 350 to less than or equal to 1400 DEG C, afterwards will It is completely or partially ground, sieves；The three of method are to dodge the hydrated alumina containing boehmite to do, and dodge dry temperature For more than 150 to less than or equal to 1400 DEG C, flash-off time is 0.05-1 hour；The four of method be by one of method, the two of method With one or more in the modifier obtained with the three of method are mixed to get.

18. methods according to claim 17, it is characterised in that the condition being dried in one of described method includes: temperature Degree is for 100-200 DEG C, and the time is 2-12 hour；Sintering temperature in the two of method is 500-1200 DEG C, and roasting time is 0.1-6 Hour；Sudden strain of a muscle in the three of method is done temperature and is 200-1000 DEG C, and flash-off time is 0.1-0.5 hour.

19. methods according to claim 17, it is characterised in that described PC is the hydrated alumina containing boehmite Modifier in the particulate matter of 80-300 mesh.

20. methods according to claim 19, it is characterised in that described PC is the hydrated alumina containing boehmite Modifier in the particulate matter of 100-200 mesh.

21. methods according to claim 7, it is characterised in that described method is included in described supported on carriers hydrogenation and lives Property metal component, the method for load hydrogenation active metals component is infusion process on the carrier, including preparation containing hydrogenation activity The solution of the compound of metal also uses this solution impregnating carrier, is dried afterwards, roasting or not roasting, described hydrogenation activity gold Belong to component and be selected from metal component and at least one Group VB metal component of at least one vib, in terms of oxide and to urge On the basis of agent, the concentration of described impregnation liquid and consumption make the content of group vib metal component described in final catalyst to be 0.2-15 weight %, the content of VB race metal component is 0.2-12 weight %, and described drying condition is: temperature 80-200 DEG C, time Between 1-8 hour, roasting condition is: temperature 400-600 DEG C, 2-8 hour time.

22. methods according to claim 21, it is characterised in that the metal component of described group vib is selected from molybdenum and/or tungsten, VB race metal component is selected from vanadium and/or niobium, counts and on the basis of catalyst by oxide, and concentration and the consumption of described impregnation liquid make Obtaining the content of group vib metal component described in final catalyst is 0.5-12 weight %, and the content of VB race metal component is 0.5-9 Weight %, described drying condition is: temperature 100-150 DEG C, 2-6 hour time, and roasting condition is: temperature 420-500 DEG C, time 3-6 hour.

23. methods according to claim 22, it is characterised in that count and on the basis of catalyst by oxide, described leaching The concentration of stain liquid and consumption make the content of group vib metal component described in final catalyst be 5-12 weight %, VB race metal The content of component is 1-9 weight %.

Catalyst described in any one application in hydrocarbon oil hydrogenation processes in 24. claim 1-6.