CN113559884A

CN113559884A - Hydrogenation catalyst for sulfurized heavy oil and its preparing process and application

Info

Publication number: CN113559884A
Application number: CN202010348265.6A
Authority: CN
Inventors: 王振; 胡大为; 杨清河; 孙淑玲; 韩伟; 户安鹏; 邓中活
Original assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Current assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Priority date: 2020-04-28
Filing date: 2020-04-28
Publication date: 2021-10-29

Abstract

The invention provides a sulfurized heavy oil hydrogenation catalyst, and a preparation method and application thereof, wherein the sulfurized heavy oil hydrogenation catalyst comprises inorganic heat-resistant oxide and sulfurized active components, wherein the active components comprise at least one VIB group metal and at least one VIII group metal, and when the sulfurized heavy oil hydrogenation catalyst is measured by diffuse reflection ultraviolet visible spectrum, the absorbances at 630nm and 500nm are respectively F₆₃₀And F₅₀₀And the ratio Q ═ F of the two₆₃₀/F₅₀₀Is 1.3 to 3.0. The composition of the sulfurized heavy oil hydrogenation catalyst contains a spinel structure, so that the initial activity of the catalyst is ensured, the stability of the catalyst is greatly improved, and the service life is prolongedGreatly improves the production efficiency, reduces the production cost and has good application prospect.

Description

Hydrogenation catalyst for sulfurized heavy oil and its preparing process and application

Technical Field

The invention relates to the field of catalysts, and particularly relates to a sulfurized heavy oil hydrogenation catalyst, and a preparation method and application thereof.

Background

The heavy oil processing, especially the deep processing of the residual oil, is not only beneficial to improving the utilization rate of the crude oil and relieving the tension trend of energy supply, but also can reduce the environmental pollution and realize the high-efficiency clean utilization of energy.

For heavy raw oil, after being pretreated by a hydrogenation process, secondary processing is carried out, so that the yield of light oil can be improved, and the content of pollutants such as sulfur, nitrogen and the like in the oil can be reduced, therefore, the demand of the market on the light oil is continuously increased, and the environmental protection regulations tend to be strict today, and the heavy raw oil is generally favored by oil refining manufacturers. Compared with light oil products, heavy oil contains a large amount of impurities such as sulfur, nitrogen, metal and the like, and contains easily coking species such as asphaltene and the like, so that the heavy oil has higher requirements on the activity and the stability of the catalyst. The deactivation of the heavy oil hydrogenation catalyst is caused by two factors, namely, the deposition of metal to destroy the original active phase structure of the catalyst, and carbon deposits on the surface of the active phase to cover the active center, so that the reaction performance of the catalyst is reduced. Therefore, how to improve the stability of the active phase structure of the catalyst and reduce the damage, aggregation and poisoning of the active phase structure of the catalyst in the reaction process is a key technology for improving the activity stability of the catalyst.

CN107583659A discloses a gasoline selective hydrodesulfurization catalyst, wherein a composite alumina carrier containing zinc aluminate spinel is prepared by a non-constant pH alternative titration method, and the catalyst prepared by loading cobalt and molybdenum has good selectivity and reaction stability in the gasoline hydrodesulfurization process.

Compared with distillate oil, the heavy oil hydrogenation catalyst needs higher reaction activity and has higher requirement on activity stability, and the prior art which is not disclosed can well meet the requirements of both the activity and the stability of the catalyst, thereby seriously influencing the actual industrial application effect of the catalyst.

Furthermore, generally speaking, the active metal component of a hydrogenation catalyst will only have a high catalytic activity when converted to the sulfided state. The sulfurized state hydrogenation catalyst is prepared by reacting an oxidized state hydrogenation catalyst with a sulfurization medium and further converting metal components in the hydrogenation catalyst from an oxidized state to a sulfurized state, wherein the sulfurized state metal is an active center of the corresponding hydrogenation catalyst. At present, most of catalysts used for oil product hydrotreating are sulfided metal catalysts, and the usage amount of the catalysts is increasing year by year.

Therefore, how to obtain a sulfurized heavy oil hydrogenation catalyst with high reactivity and good stability is a problem to be solved in the field.

It is noted that the information disclosed in the foregoing background section is only for enhancement of background understanding of the invention and therefore it may contain information that does not constitute prior art that is already known to a person of ordinary skill in the art.

Disclosure of Invention

The main purpose of the present invention is to overcome at least one of the above drawbacks of the prior art, and to provide a sulfurized heavy oil hydrogenation catalyst, and a preparation method and an application thereof, so as to solve the problem that the activity and stability of the existing heavy oil hydrogenation catalyst are difficult to be considered.

In order to achieve the purpose, the invention adopts the following technical scheme:

the invention provides a hydrogenation catalyst for sulfurized heavy oil, which comprises inorganic heat-resistant oxide and sulfurized active component, wherein the active component comprisesComprises at least one VIB group metal and at least one VIII group metal, and the absorbances at 630nm and 500nm of the vulcanized heavy oil hydrogenation catalyst are respectively F when the vulcanized heavy oil hydrogenation catalyst is measured by diffuse reflection ultraviolet visible spectrum₆₃₀And F₅₀₀And the ratio Q ═ F of the two₆₃₀/F₅₀₀Is 1.3 to 3.0.

According to one embodiment of the invention, the active ingredient has a degree of vulcanization of not less than 50%.

According to one embodiment of the invention, the inorganic refractory oxide is alumina.

According to one embodiment of the present invention, the group VIB metal content is 5% to 20% and the group VIII metal content is 0.7% to 6% on an elemental basis and based on the total weight of the heavy oil hydrogenation catalyst.

According to one embodiment of the present invention, the sulfurized heavy oil hydrogenating catalyst further comprises a metal promoter and/or a non-metal promoter.

According to one embodiment of the invention, the at least one group VIB metal is molybdenum and/or tungsten and the at least one group VIII metal is nickel and/or cobalt.

The invention also provides a preparation method of the hydrogenation catalyst for the sulfurized heavy oil, which comprises the following steps: mixing an inorganic heat-resistant oxide precursor and a forming auxiliary agent to obtain a mixture, and forming; dipping the formed product in a solution containing at least one VIB group metal and at least one VIII group metal; drying the impregnated product, and roasting at 600-800 ℃ for 1-10 h to obtain an oxidation state heavy oil hydrogenation catalyst; and under the condition of a vulcanization reaction, the oxidation-state heavy oil hydrogenation catalyst is in contact reaction with a vulcanization medium to obtain the vulcanization-state heavy oil hydrogenation catalyst.

The invention also provides another preparation method of the hydrogenation catalyst for the sulfurized heavy oil, which comprises the following steps: mixing an inorganic heat-resistant oxide precursor and a forming auxiliary agent to obtain a mixture, and forming; soaking the formed product in solution containing at least one VIII group metal for the first time, drying the product after the first soaking, and roasting at the temperature of 600-800 ℃ for 1-10 h to obtain a carrier; the carrier is dipped for the second time in a solution containing at least one VIB group metal, and the product after the second dipping is dried and activated at the temperature of 300-550 ℃ to obtain the oxidation state heavy oil hydrogenation catalyst; and under the condition of a vulcanization reaction, the oxidation-state heavy oil hydrogenation catalyst is in contact reaction with a vulcanization medium to obtain the vulcanization-state heavy oil hydrogenation catalyst.

The invention also provides another preparation method of the hydrogenation catalyst for the sulfurized heavy oil, which comprises the following steps: mixing an inorganic heat-resistant oxide precursor, at least one VIII group metal precursor and a forming auxiliary agent to obtain a mixture, and forming; roasting the formed product at 600-800 deg.c for 1-10 hr to obtain carrier; dipping a carrier in a solution containing at least one VIB group metal, drying the dipped product, and activating at the temperature of 300-550 ℃ to obtain an oxidation state heavy oil hydrogenation catalyst; and under the condition of a vulcanization reaction, the oxidation-state heavy oil hydrogenation catalyst is in contact reaction with a vulcanization medium to obtain the vulcanization-state heavy oil hydrogenation catalyst.

According to one embodiment of the invention, the inorganic refractory oxide precursor is pseudo-boehmite and the aqueous solution containing at least one group VIB metal is selected from one or more of molybdenum oxide, ammonium molybdate, ammonium paramolybdate, tungsten oxide, ammonium tungstate and ammonium paratungstate; the aqueous solution containing at least one group VIII metal is selected from one or more of cobalt nitrate, cobalt sulfate, cobalt hydroxycarbonate, nickel nitrate, nickel sulfate and nickel hydroxycarbonate.

According to one embodiment of the invention, the inorganic refractory oxide precursor is pseudo-boehmite, the at least one group VIII metal precursor is selected from one or more of nickel nitrate, nickel sulfate, nickel carbonate hydroxide, cobalt nitrate, cobalt sulfate, and cobalt carbonate hydroxide, and the solution containing the at least one group VIB metal is selected from an aqueous solution containing one or more of molybdenum oxide, ammonium molybdate, ammonium paramolybdate, tungsten oxide, ammonium tungstate, and ammonium paratungstate.

According to an embodiment of the present invention, the forming process further comprises adding an auxiliary precursor to the mixture, so that the catalyst carrier contains an auxiliary selected from a metal auxiliary and/or a non-metal auxiliary.

According to one embodiment of the present invention, the forming aid comprises a peptizing agent selected from one or more of aqueous nitric acid, aqueous hydrochloric acid and aqueous citric acid, and a lubricant selected from one or more of sesbania powder, citric acid, starch and carboxymethyl cellulose.

According to one embodiment of the invention, the at least one group VIB metal is molybdenum; the at least one VIII group metal is cobalt and nickel, and the atomic ratio of cobalt to nickel is 2-4.

According to one embodiment of the invention, the sulfiding medium is selected from one or more of sulfur, carbon disulfide, dimethyl sulfide, t-butyl polysulfide and ethanethiol.

According to one embodiment of the invention, the sulfidation reaction conditions include: the temperature is 140-400 ℃, the pressure is normal pressure-20 MPa, and the liquid hourly space velocity of the vulcanized medium and the oxidation state heavy oil hydrogenation catalyst is 0.5h^-1～5h^-1。

The invention also provides the application of the sulfurized heavy oil hydrogenation catalyst in heavy oil hydrogenation reaction.

According to the technical scheme, the invention has the beneficial effects that:

compared with an oxidation-state catalyst, the sulfurized heavy oil hydrogenation catalyst provided by the invention has better catalytic activity, and the spinel structure contained in the composition can greatly improve the stability of the catalyst while ensuring the initial activity of the catalyst, greatly prolong the service life, facilitate the improvement of the production efficiency and the reduction of the production cost, and has good application prospect.

Detailed Description

The following presents various embodiments or examples in order to enable those skilled in the art to practice the invention with reference to the description herein. These are, of course, merely examples and are not intended to limit the invention. The endpoints of the ranges and any values disclosed in the present application are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to yield one or more new ranges of values, which ranges of values should be considered as specifically disclosed herein.

The invention provides a hydrogenation catalyst for sulfurized heavy oil, which comprises inorganic heat-resistant oxide and a sulfurized active component, wherein the active component comprises at least one VIB group metal and at least one VIII group metal, and the absorbances at 630nm and 500nm of the sulfurized heavy oil hydrogenation catalyst are respectively F when the sulfurized heavy oil hydrogenation catalyst is measured by diffuse reflection ultraviolet and visible spectrum₆₃₀And F₅₀₀And the ratio Q ═ F of the two₆₃₀/F₅₀₀Is 1.3 to 3.0.

In the field of catalysis, it is generally accepted that the formation of spinel structures generally affects the initial activity of the catalyst. However, the inventor of the present invention found that although the formation of the spinel structure affects the initial activity of the catalyst, the formation of a proper amount of the spinel structure does not greatly affect the total activity of the catalyst, and the spinel structure gradually releases the reaction activity with the extension of the catalyst participating in the reaction process, so that the activity stability of the catalyst is better, and the service life of the catalyst is greatly prolonged and the production efficiency is improved on the premise of meeting the basic activity requirement. Furthermore, compared with an oxidation state catalyst, the sulfidation state catalyst has higher catalytic activity, so that the sulfidation state heavy oil hydrogenation catalyst has good application prospect in practical production.

In some embodiments, the degree of sulfidation of the aforementioned active component is not less than 50%, preferably not less than 70%, and the increase in the degree of sulfidation is advantageous for further increasing the catalytic activity.

In some embodiments, the inorganic refractory oxide is preferably alumina, which is typically used as a catalyst support. The aforementioned group VIB metal is preferably molybdenum (Mo) and/or tungsten (W), more preferably molybdenum. The aforementioned group VIII metal is preferably nickel and/or cobalt, and more preferably nickel. For example, when the inorganic refractory oxide is alumina and the group VIII metal is nickel, a nickel aluminate spinel structure is formed inside the catalyst.

Experiments show that when the ratio Q is 1.3-3.0, the catalyst can obtain better initial activity and better activity stability, namely, the catalyst provided by the invention with the parameter characteristics has the characteristics of high initial activity and good stability. Preferably, the ratio Q is 1.4 to 2.8. When the Q value is less than 1.3, the improvement of the activity stability is not obvious; when the Q value is more than 3.0, the initial activity is too low, which affects the normal use of the catalyst.

In some embodiments, the group VIII metal content is 0.7% to 6%, such as 1%, 2%, 3%, 4%, 5%, 6%, etc., on an elemental basis and based on the total weight of the heavy oil hydrogenation catalyst. By controlling the content of the VIII group metal, the amount of the formed spinel can be controlled, so that the stability of the catalytic activity is improved, and the initial catalytic activity is not too low. The group VIB metal content is from 5% to 20%, such as 5%, 7%, 10%, 13%, 16%, 18%, 20%, etc.

The carrier can further comprise an auxiliary agent, wherein the auxiliary agent can be a metal auxiliary agent and/or a nonmetal auxiliary agent, the metal auxiliary agent is selected from one or more of alkali metals, alkaline earth metals and rare earth metals, such as potassium, sodium, magnesium, lanthanum and the like, and the nonmetal auxiliary agent is selected from one or more of boron and silicon.

When the metal additive is added, the content of the metal additive is 0.1-3% by element and based on the total weight of the vulcanized heavy oil hydrogenation catalyst. For example, when the carrier contains magnesium, the content of magnesium is 0.4% to 3%, and the content of magnesium can be adjusted to adjust the acidity or basicity of the carrier, thereby reducing the amount of carbon deposition. When the carrier contains lanthanum, the lanthanum content is 0.1-1.5%. By adding a proper amount of lanthanum on the carrier, the growth of carrier grains can be inhibited during high-temperature roasting, the dispersion degree of active components is improved, and further the catalytic activity is improved.

When the non-metal additive is added, the content of the non-metal additive is 0.5 to 15 percent by element and based on the total weight of the vulcanized heavy oil hydrogenation catalyst. For example, when the carrier contains boron, the content of the boron is 0.5% -5%, and the pore structure of the carrier can be improved by adding the boron, so that the diffusion performance of the carrier is improved. When the carrier contains silicon, the content of the silicon is 3% -15%, the carrier property can be adjusted by controlling the content of the silicon in the carrier, and the stability of the catalytic activity is improved.

The invention also provides a preparation method of the hydrogenation catalyst for the sulfurized heavy oil, which comprises the following steps:

mixing an inorganic heat-resistant oxide precursor and a forming auxiliary agent to obtain a mixture, and forming; dipping the formed product in a solution containing at least one VIB group metal and at least one VIII group metal; drying the impregnated product, and roasting at 600-800 ℃ for 1-10 h to obtain an oxidation state heavy oil hydrogenation catalyst; and under the condition of a vulcanization reaction, the oxidation-state heavy oil hydrogenation catalyst is in contact reaction with a vulcanization medium to obtain the vulcanization-state heavy oil hydrogenation catalyst.

First, an inorganic heat-resistant oxide precursor and a forming aid are mixed to obtain a mixture, and the mixture is subjected to forming treatment. Wherein the precursor of the inorganic heat-resistant oxide is pseudo-boehmite. The forming aids generally include peptizers and lubricants, and may include other materials, as the present invention is not limited thereto. Peptizing agents include, but are not limited to, one or more of aqueous nitric acid, aqueous hydrochloric acid, and aqueous citric acid, and lubricants include, but are not limited to, one or more of sesbania powder, citric acid, starch, and carboxymethyl cellulose.

The molding treatment comprises the following steps: kneading the mixture to obtain a plastic body; the plastic body is dried and roasted after being molded to obtain a molded product; wherein the shaping method is selected from one or more of extruding, rolling, tabletting and granulating. Specifically, the method of forming is selected from one or more of extruding, rolling, tabletting and granulating. The catalyst carrier may be formed into various shapes which are easy to handle, such as spheres, honeycombs, bird nests, tablets or strips (such as clover, butterfly, cylinder, etc.), according to different requirements. The addition amount of each raw material meets the content range of each element of the catalyst carrier by taking the total weight of the catalyst as a reference; the dosage of the water and the dosage of each forming auxiliary agent are that the materials formed by mixing the pseudo-boehmite, each auxiliary agent and the like are enough to meet the requirement of subsequent forming. Sufficient for subsequent forming is to mean that the water/powder ratio in the mixed material is suitable, as is well known to those skilled in the art. In some embodiments, the plastic body is dried at 100-250 deg.C, such as 100 deg.C, 120 deg.C, 135 deg.C, 170 deg.C, 210 deg.C, 230 deg.C, etc. for 1-6 h, such as 1h, 2h, 4h, 5h, 6h, etc. Then, the mixture is roasted for 1h to 10h, for example, 1h, 3h, 4h, 5h, 7h, 8h, 9h and the like at the temperature of 600 ℃ to 1000 ℃, for example, at the temperature of 600 ℃, 700 ℃, 720 ℃, 750 ℃, 800 ℃, 830 ℃, 900 ℃, 970 ℃, 1000 ℃ and the like, so as to obtain the formed product, namely the carrier.

It is noted that the present invention may also include the addition of a promoter precursor prior to the shaping process to incorporate the desired promoter into the carrier. For example, when magnesium is introduced, the magnesium source may be one or more of magnesium oxide, magnesium salt; when boron is introduced, the boron source is one or more of boron trioxide, boric acid and borate; when lanthanum is introduced, the lanthanum source is one or more of lanthanum nitrate and lanthanum salt; when silicon is introduced, the silicon source is one or more of silicon dioxide, silicic acid, and silicate. Of course, one skilled in the art can select other water-soluble salts of these metals or non-metals according to specific circumstances, and the present invention is not particularly limited thereto.

Further, dipping the formed product in a solution containing at least one VIB group metal and at least one VIII group metal, drying the dipped product, and roasting at the temperature of 600-800 ℃ for 1-10 h to obtain the oxidation state heavy oil hydrogenation catalyst.

Experiments show that in the preparation method, the carrier with the spinel structure can be formed only by roasting at the temperature of 600-800 ℃ for 1-10 hours. The roasting temperature is too low or the roasting time is too short, the content of spinel in the obtained carrier is too low, and the activity stability improvement effect is not obvious; if the roasting temperature is too high or the roasting time is too long, the spinel content in the obtained carrier is too high, and the initial activity of the catalyst is influenced.

According to the present invention, the temperature of the calcination is preferably 610 to 780 ℃, more preferably 630 to 750 ℃, and most preferably 650 to 730 ℃, for example 650 ℃, 660 ℃, 680 ℃, 700 ℃, 710 ℃, 720 ℃ or the like. One skilled in the art should be able to select the appropriate firing time according to the firing temperature. In the present invention, the above-mentioned calcination refers to activation that is conventional in the art, and can be raised from ambient temperature to calcination temperature, and the temperature rise rate during calcination can be 50 ℃/hr to 600 ℃/hr, preferably 100 ℃/hr to 550 ℃/hr, for example, 110 ℃/hr, 130 ℃/hr, 150 ℃/hr, 200 ℃/hr, 230 ℃/hr, 350 ℃/hr, 400 ℃/hr, 500 ℃/hr, 520 ℃/hr, and the like.

In the process according to the invention, the active components comprise at least one group VIB metal and at least one group VIII metal. In a specific embodiment, the at least one group VIB metal is molybdenum, the at least one group VIII metal is cobalt and nickel, and the atomic ratio of cobalt to nickel is 2 to 4. When the active component is molybdenum, the oxide or salt thereof is one or more selected from molybdenum oxide, ammonium molybdate and ammonium paramolybdate; when the active component is tungsten, the oxide or salt thereof is one or more selected from tungsten oxide, ammonium tungstate and ammonium paratungstate; when the active component is cobalt, the oxide or salt thereof is one or more selected from cobalt nitrate, cobalt sulfate and basic cobalt carbonate; when the active component is nickel, the oxide or salt thereof is one or more selected from nickel nitrate, nickel sulfate and basic nickel carbonate. Of course, the person skilled in the art can select other water-soluble salts or complex salts of these metals in combination with the specific circumstances, and there is no particular limitation thereto.

In the method according to the present invention, in order to ensure effective activation of the catalyst, it is necessary to dry the support after introduction of the active component at a temperature of 100 to 250 ℃ for 1 to 10 hours. It is to be noted that although the introduction of the metal element by the impregnation method is exemplified above, the introduction of the active metal element may be performed by other methods known in the art. In addition, it is easily understood by those skilled in the art that depending on the concentration of the aqueous solution of the active component and the impregnation time, the final catalyst may be made to contain 8% to 30% of at least one group VIB metal and 1% to 8% of at least one group VIII metal, calculated as oxides and based on the total weight of the catalyst.

In the method according to the present invention, when the catalyst of the present invention contains an auxiliary, the method for introducing the auxiliary may be any conventional method, such as a method of impregnating the support after separately preparing a solution containing the auxiliary, or a method of impregnating the support with a mixed solution containing the metal component and the auxiliary; can be introduced for a single time or can be introduced for multiple times; each introduction may be followed by a drying, firing or unfired step.

When the phosphorus-containing auxiliary agent is contained, the adopted phosphorus-containing compound is selected from one or more of phosphoric acid, phosphorous acid, phosphate and phosphite, and phosphoric acid is preferred; when the organic additive is contained, the organic additive is preferably selected from one or more of oxygen-containing organic compounds or nitrogen-containing organic compounds, wherein the oxygen-containing organic compounds can be one or more of organic alcohols and organic acids, and the nitrogen-containing organic compounds can be one or more of organic amines. More specifically, the oxygen-containing organic compound is one or more of ethylene glycol, glycerol, polyethylene glycol (molecular weight is 200-1500), diethylene glycol, butanediol, acetic acid, maleic acid, oxalic acid, nitrilotriacetic acid, 1, 2-cyclohexanediamine tetraacetic acid, citric acid, tartaric acid and malic acid, and the nitrogen-containing organic compound is ethylenediamine, EDTA and ammonium salt thereof.

And finally, the obtained oxidation-state heavy oil hydrogenation catalyst is in contact reaction with a vulcanization medium under the condition of vulcanization reaction, so that the vulcanization-state heavy oil hydrogenation catalyst is obtained.

In some embodiments, the sulfidation reaction conditions include: the temperature is 140 ℃ to 400 ℃, for example, 140 ℃, 150 ℃, 170 ℃, 180 ℃, 200 ℃, 230 ℃, 280 ℃, 300 ℃, 340 ℃, 390 ℃, etc. The pressure is from normal pressure to 20MPa, for example, 1MPa, 4MPa, 7MPa, 10MPa, 13MPa, 16MPa, 20MPa, etc. The liquid hourly space velocity of the sulfuration medium and the oxidation state heavy oil hydrogenation catalyst is 0.5h^-1～5h^-1E.g. 0.5h^-1、1h^-1、2h^-1、3h^-1、5h^-1And the like. The vulcanization medium is selected from sulfur, carbon disulfide, dimethylOne or more of dithioether, dimethyl sulfide, t-butyl polysulfide and ethanethiol, although other suitable sulfiding media may be selected, and the invention is not limited thereto.

Furthermore, the invention also comprises the step of passivating the vulcanized heavy oil hydrogenation catalyst so as to improve the storage stability of the vulcanized heavy oil hydrogenation catalyst. In the actual industrial application of the catalyst, compared with an oxidation-state catalyst, the passivated sulfuration-state catalyst is used, so that the conventional in-situ sulfuration step in the start-up process can be omitted, the start-up time of the device is saved, and the harm of hydrogen sulfide to field operators and the pollution risk to the environment in the start-up process can be greatly reduced.

The passivation treatment method can be a conventional technical means in the field, for example, distillate oil is firstly adopted at the temperature of 100-300 ℃ for 1h^-1～10h^-1The space velocity and the pressure of 0 MPa-20 MPa, wherein the distillation range of the distillate oil is 40-500 ℃, preferably 40-360 ℃, and further preferably 100-300 ℃; then, oxygen-containing substances are adopted to carry out the reaction at the temperature of not more than 100 ℃ and the mass ratio of the oxygen agent is 0.1h^-1～10h^-1And passivating for 1-24 h under the pressure of 0-20 MPa, wherein the oxygen-containing substance is an oxidizing substance or a substance containing oxygen atoms, and is preferably one or more of water, hydrogen peroxide, oxygen, carbon dioxide, carbon monoxide and sulfur dioxide, but the invention is not limited to the passivating method.

The hydrogenation catalyst for the sulfurized heavy oil can also be prepared by the following method: mixing an inorganic heat-resistant oxide precursor and a forming auxiliary agent to obtain a mixture, and forming; soaking the formed product in solution containing at least one VIII group metal for the first time, drying the product after the first soaking, and roasting at the temperature of 600-800 ℃ for 1-10 h to obtain a carrier; the carrier is dipped for the second time in a solution containing at least one VIB group metal, and the product after the second dipping is dried and activated at the temperature of 300-550 ℃ to obtain the oxidation state heavy oil hydrogenation catalyst; and under the condition of a vulcanization reaction, the oxidation-state heavy oil hydrogenation catalyst is in contact reaction with a vulcanization medium to obtain the vulcanization-state heavy oil hydrogenation catalyst.

The inventor of the present invention also finds that the active component, such as group VIB metal of molybdenum (Mo), tungsten (W), etc., can cause too strong acting force with the carrier at an excessively high activation temperature, so that the activity cannot be released, and the activity stability of the catalyst is reduced. Therefore, the spinel structure is firstly formed on the carrier, namely the active component is impregnated step by adopting the second preparation method, and the active component is loaded and activated at a lower temperature after the carrier with the spinel structure is formed, so that the characteristic of gradually releasing the reaction activity provided by the spinel structure can be utilized, the activity stability of the catalyst is improved, the service life of the catalyst is prolonged, and meanwhile, the loaded active component can also contribute to improving the activity stability, so that the catalyst has excellent performance.

Specifically, the method of molding and the method of adding other additives are the same as the first preparation method, and are not described herein again.

And for primary impregnation, performing primary impregnation on the formed product in a solution containing at least one VIII group metal, drying the primary impregnated product, and roasting at the temperature of 600-800 ℃ for 1-10 h to obtain the carrier. Wherein, the drying temperature of the product after primary impregnation is 100-150 ℃, such as 100 ℃, 120 ℃, 135 ℃, 140 ℃, 150 ℃ and the like, and the drying time is 1-6 h, such as 1h, 2h, 4h, 5h, 6h and the like. Preferably, the solution containing at least one group VIII metal is selected from one or more of nickel nitrate, nickel sulfate, and basic nickel carbonate.

Then, the carrier obtained by primary impregnation and high-temperature roasting at 600-800 ℃ is subjected to secondary impregnation in a solution containing at least one VIB group metal, and the product obtained after secondary impregnation is dried and then activated at 300-550 ℃, such as 300 ℃, 320 ℃, 350 ℃, 370 ℃, 400 ℃, 500 ℃ and the like, so as to obtain the oxidation state heavy oil hydrogenation catalyst.

Wherein, the drying temperature of the product after the secondary impregnation is 100-150 ℃, such as 100 ℃, 120 ℃, 135 ℃, 140 ℃, 150 ℃ and the like, and the drying time is 1-6 h, such as 1h, 2h, 4h, 5h, 6h and the like. The activation time is 1h to 10h, for example, 1h, 2h, 4h, 5h, 6h, 7h, 8h, 9h, 10h, etc.

The aforementioned solution containing at least one group VIB metal is an aqueous solution comprising at least one group VIB metal oxide or salt selected from one or more of molybdenum oxide, ammonium molybdate, ammonium paramolybdate, tungsten oxide, ammonium tungstate and ammonium paratungstate. Of course, the skilled person can also select other water-soluble salts or complex salts of the active ingredient in combination with the specific circumstances, which are not particularly limited.

Alternatively, the aqueous solution containing at least one group VIB metal oxide or salt may also contain other components such as ammonia, phosphoric acid or citric acid, etc. to facilitate the introduction of the group VIB metal. Wherein, when the other components are phosphorus additives, the adopted phosphorus-containing compound is selected from one or more of phosphoric acid, phosphorous acid, phosphate and phosphite, and phosphoric acid is preferred; when the other component is an organic additive, the organic additive is preferably selected from one or more of oxygen-containing or nitrogen-containing organic compounds, wherein the oxygen-containing organic compound can be one or more of organic alcohol and organic acid, and the nitrogen-containing organic compound can be one or more of organic amine. More specifically, the oxygen-containing organic compound is one or more of ethylene glycol, glycerol, polyethylene glycol (molecular weight is 200-1500), diethylene glycol, butanediol, acetic acid, maleic acid, oxalic acid, nitrilotriacetic acid, 1, 2-cyclohexanediamine tetraacetic acid, citric acid, tartaric acid and malic acid, and the nitrogen-containing organic compound is ethylenediamine, EDTA and ammonium salt thereof.

And finally, after obtaining the oxidation-state heavy oil hydrogenation catalyst, carrying out contact reaction on the oxidation-state heavy oil hydrogenation catalyst and a vulcanization medium under the vulcanization reaction condition to obtain the vulcanization-state heavy oil hydrogenation catalyst. The vulcanization reaction conditions and the vulcanization medium are the same as those in the first preparation method, and are not described herein again. Of course, the hydrogenation catalyst of the sulfurized heavy oil obtained by the preparation method can also be treated by the passivation method, and the invention is not limited to the method.

The hydrogenation catalyst for the sulfurized heavy oil can also be prepared by the following method: mixing an inorganic heat-resistant oxide precursor, at least one VIII group metal precursor and a forming auxiliary agent to obtain a mixture, and forming; roasting the formed product at 600-800 deg.c for 1-10 hr to obtain carrier; dipping a carrier in a solution containing at least one VIB group metal, drying the dipped product, and activating at the temperature of 300-550 ℃ to obtain an oxidation state heavy oil hydrogenation catalyst; and under the condition of a vulcanization reaction, the oxidation-state heavy oil hydrogenation catalyst is in contact reaction with a vulcanization medium to obtain the vulcanization-state heavy oil hydrogenation catalyst.

In the method, the carrier obtained by molding treatment and roasting at 600-800 ℃ for 1-10 h forms a spinel structure. And loading an active component, namely a VIB group metal, on the carrier forming the spinel structure. Specifically, the carrier is dipped in a solution containing at least one VIB group metal, and the dipped product is dried and then activated at the temperature of 300-550 ℃, such as 300 ℃, 320 ℃, 350 ℃, 370 ℃, 400 ℃, 500 ℃ and the like, so as to obtain the oxidation state heavy oil hydrogenation catalyst. Wherein the drying temperature of the impregnated product is 100-150 ℃, such as 100 ℃, 120 ℃, 135 ℃, 140 ℃, 150 ℃ and the like, and the drying time is 1-6 h, such as 1h, 2h, 4h, 5h, 6h and the like. The activation time is 1h to 10h, for example, 1h, 2h, 4h, 5h, 6h, 7h, 8h, 9h, 10h, etc.

In some embodiments, the inorganic refractory oxide precursor is pseudo-boehmite, the at least one group VIII metal precursor is selected from one or more of nickel nitrate, nickel sulfate, nickel hydroxycarbonate, cobalt nitrate, cobalt sulfate, and cobalt hydroxycarbonate, and the solution containing the at least one group VIB metal is selected from an aqueous solution containing one or more of molybdenum oxide, ammonium molybdate, ammonium paramolybdate, tungsten oxide, ammonium tungstate, and ammonium paratungstate. Of course, the skilled person can also select other water-soluble salts or complex salts of the active ingredient in combination with the specific circumstances, which are not particularly limited.

In conclusion, the sulfurized heavy oil hydrogenation catalyst containing the spinel structure has good stability and high activity, the service life is greatly prolonged, the production efficiency is improved, the production cost is greatly reduced, and the catalyst has good application prospect.

The following examples further illustrate the invention but should not be construed as limiting it. The reagents used in these examples, except where specifically indicated, were chemically pure reagents and were commercially available.

In the following examples and comparative examples, the composition of the catalyst was determined by X-ray fluorescence spectroscopy (XRF), as specified in petrochemical analysis method RIPP 133-90.

In the following examples and comparative examples, the formation of nickel aluminate spinel structure in the catalyst was determined by ultraviolet visible light spectroscopy (DRUVS). The instrument adopts a Cary300 ultraviolet visible light analyzer of Agilent company, and the wavelength ranges are as follows: 190 nm-1100 nm, wavelength precision: ± 0.1nm, wavelength reproducibility: ± 0.1nm, baseline stability: 0.0003/h, stray light: 0.02% or less, photometric accuracy: + -0.003.

In the following examples and comparative examples, the degree of sulfidation of the active metals in the catalysts was characterized by X-ray photoelectron spectroscopy. The instrument adopts an ESCALAB 250 type X-ray photoelectron spectrometer of Thermo Fischer-VG company, and an excitation source is AlK alpha X-rays with the monochromatization power of 150W. The activity of the catalyst is characterized by desulfurization rate, denitrification rate, carbon residue removal rate and demetalization rate, and the activity stability of the catalyst is characterized by the change of the desulfurization rate, the denitrification rate, the carbon residue removal rate and the demetalization rate after the catalyst works for 100 hours and 1000 hours.

Example 1

1) The preparation method comprises the steps of uniformly mixing 1 kg of pseudoboehmite dry rubber powder RPB100 produced by a Changling catalyst factory with 30 g of sesbania powder, uniformly mixing the mixture with 1.2L of aqueous solution containing 21 g/L of sulfuric acid at room temperature, kneading the mixture on a double-screw extruder into a plastic body, extruding the plastic body into butterfly-shaped strips with phi of 1.1 mm, drying wet strips at 120 ℃ for 3 hours, and keeping the temperature at 800 ℃ for 3 hours to obtain the carrier.

2) Weighing 100 g of the carrier, and using 120 ml of MoO-containing carrier₃Dipping the mixed solution of molybdenum oxide, basic nickel carbonate and phosphoric acid with the concentration of 135 g/L and NiO with the concentration of 30 g/L for 1 hour, drying the mixed solution at the temperature of 120 ℃ for 2 hours, heating the dried catalyst to 650 ℃ at the temperature of 300 ℃/hour, and keeping the temperature of 650 ℃ for 3 hours to obtain the catalyst.

3) The oxidation state heavy oil hydrogenation catalyst is contacted and reacted with carbon disulfide at the temperature of 320 ℃ and the pressure of 14MPa, and the hourly space velocity of reaction liquid is 1h^-1Obtaining the hydrogenation catalyst for the sulfurized heavy oil.

Measuring nickel aluminate spinel NiAl on catalyst by using ultraviolet visible light spectrometry based on total weight of sulfurized heavy oil hydrogenation catalyst₂O₄The formation condition of the catalyst is characterized by the sulfidation degree of active metal in the catalyst by adopting an X-ray photoelectron spectroscopy, the content of the catalyst components is measured by adopting an X-ray fluorescence spectrometer, and the measurement result is shown in Table 1.

Example 2

1) The preparation method comprises the steps of uniformly mixing 1 kg of pseudoboehmite dry rubber powder RPB100 produced by a Changling catalyst factory with 30 g of sesbania powder, uniformly mixing the mixture with 1.2L of aqueous solution containing 21 g/L of sulfuric acid at room temperature, kneading the mixture on a double-screw extruder into a plastic body, extruding the plastic body into butterfly-shaped strips with phi of 1.1 mm, drying wet strips at 120 ℃ for 3 hours, and keeping the temperature at 800 ℃ for 4 hours to obtain the carrier.

2) 100 g of the carrier is weighed, the carrier is soaked for 1 hour by 120 ml of mixed solution of 30 g/L NiO-containing basic nickel carbonate and phosphoric acid, and the carrier is roasted for 3 hours at the temperature of 630 ℃ after being dried for 4 hours at the temperature of 110 ℃ to obtain the nickel-containing carrier.

3) Using 120 ml of MoO₃135 g/l of a mixed solution of molybdenum oxide and phosphoric acid was impregnated in the nickel-containing support for 1 hourAfter being dried for 3 hours at 120 ℃, the oxidized heavy oil hydrogenation catalyst is prepared after being activated for 3 hours at 400 ℃.

4) The oxidation state heavy oil hydrogenation catalyst is contacted with hydrogen sulfide for reaction at the temperature of 320 ℃ and under the pressure of 14MPa, and the hourly space velocity of reaction liquid is 1h^-1Obtaining the hydrogenation catalyst for the sulfurized heavy oil.

Example 3

1) The preparation method comprises the steps of uniformly mixing 1 kg of pseudoboehmite dry rubber powder RPB100 produced by a Changling catalyst factory and 30 g of sesbania powder, uniformly mixing the mixture with 1.2L of a mixed aqueous solution of sulfuric acid and lanthanum nitrate containing 21.1 g/L of sulfuric acid and 2.8 g/L of lanthanum at room temperature, kneading the mixture on a double-screw extruder into a plastic body, extruding the plastic body into butterfly-shaped strips with phi of 1.1 mm, drying the wet strips at 120 ℃ for 3 hours, and keeping the temperature at 800 ℃ for 4 hours to obtain the carrier.

2) 100 g of the carrier is weighed, and is soaked for 1 hour by 120 ml of mixed solution of 30 g/L NiO-containing basic nickel carbonate and phosphoric acid, dried for 4 hours at 110 ℃, and roasted for 3 hours at 630 ℃ to obtain an intermediate product.

3) Using 120 ml of MoO₃The intermediate product is soaked in 135 g/L mixed solution of molybdenum oxide and phosphoric acid for 1 hour, dried at 120 ℃ for 3 hours and activated at 400 ℃ for 3 hours to prepare the oxidation state heavy oil hydrogenation catalyst.

Measuring nickel aluminate spinel NiAl on catalyst by using ultraviolet visible light spectrometry based on total weight of sulfurized heavy oil hydrogenation catalyst₂O₄By characterization of the catalyst by X-ray photoelectron spectroscopyThe vulcanization degree of the medium active metal is measured by an X-ray fluorescence spectrometer, and the measurement result is shown in Table 1.

Example 4

1) Mixing uniformly the dry powder RPB100 of pseudo-boehmite produced by 1 kg of Changling catalyst factory and 30 g of sesbania powder, mixing the mixture with 1.2 l of mixed aqueous solution of basic nickel carbonate and sulfuric acid containing 20.6 g/l of NiO and 37.9 g/l of sulfuric acid at room temperature, kneading the mixture on a double-screw extruder into plastic bodies, extruding the plastic bodies into butterfly-shaped strips with phi of 1.1 mm, drying the wet strips at 120 ℃ for 3 hours, heating to 780 ℃ at 200 ℃/hour, and keeping the temperature at 780 ℃ for 4 hours to obtain the nickel-containing catalyst carrier.

2) Weighing 100 g of the nickel-containing carrier, and using 120 ml of MoO-containing carrier₃The catalyst is prepared by immersing 130 g/L of mixed solution of ammonium molybdate and ammonia water for 1 hour, drying at 110 ℃ for 3 hours, and activating at 400 ℃ for 3 hours.

3) The oxidation state heavy oil hydrogenation catalyst is contacted with hydrogen sulfide for reaction at the temperature of 320 ℃ and under the pressure of 14MPa, and the hourly space velocity of reaction liquid is 1h^-1Obtaining the hydrogenation catalyst for the sulfurized heavy oil.

Based on the total weight of the catalyst carrier, a carbon-sulfur analyzer is adopted to determine the sulfur content in the catalyst carrier, and an ultraviolet visible light spectrum method is adopted to determine the nickel aluminate spinel NiAl on the catalyst₂O₄The content of the catalyst component was measured by an X-ray fluorescence spectrometer, and the measurement results are shown in Table 1.

Comparative example 1

A sulfurized heavy oil hydrogenation catalyst was prepared by the method of example 2, except that the calcination temperature in step 2) was 400 ℃.

Comparative example 2

A sulfided heavy oil hydrogenation catalyst was prepared by the method of example 2, except that the calcination temperature in step 2) was 900 ℃.

Comparative example 3

1) The preparation method comprises the steps of uniformly mixing 1 kg of pseudoboehmite dry rubber powder RPB100 produced by a Changling catalyst factory with 30 g of sesbania powder by a conventional method, uniformly mixing the mixture with 1.2L of aqueous solution containing 21 g/L of sulfuric acid at room temperature, kneading the mixture on a double-screw extruder into a plastic body, extruding the plastic body into butterfly-shaped strips with phi of 1.1 mm, drying wet strips at 120 ℃ for 3 hours, and keeping the temperature at 800 ℃ for 4 hours to obtain the carrier.

2) Weighing 100 g of the carrier, and using 120 ml of MoO-containing carrier₃The mixed solution of molybdenum oxide, basic nickel carbonate and phosphoric acid with 135 g/L and NiO with 30 g/L is soaked for 1 hour, dried for 3 hours at 120 ℃ and activated for 3 hours at 400 ℃ to prepare the catalyst.

Based on the total weight of the catalyst, a carbon-sulfur analyzer is adopted to determine the sulfur content in the catalyst, and an ultraviolet visible light spectrum method is adopted to determine the nickel aluminate spinel NiAl on the catalyst₂O₄The content of the catalyst component was measured by an X-ray fluorescence spectrometer, and the measurement results are shown in Table 1. TABLE 1

Test example

The catalysts of examples 1 to 4 and comparative examples 1 to 3 were used in hydrogenation reactions to evaluate their respective catalytic performances.

The catalyst was evaluated on a 100 ml small fixed bed reactor using an atmospheric residue having a nickel content of 19ppm, a vanadium content of 27ppm, a sulfur content of 3.1%, a carbon residue of 11%, and a nitrogen content of 0.3% as a raw material (these are in weight percent concentrations).

And respectively crushing the obtained catalysts into particles with the diameter of 0.8-1.2 mm, wherein the loading of the catalyst is 100 ml. The reaction conditions are as follows: the reaction temperature is 380 ℃, the hydrogen partial pressure is 14MPa, and the liquid hourly space velocity is 0.6 h^-1The volume ratio of hydrogen to oil is 1000, samples are taken after the reaction is carried out for 100 hours and 1000 hours respectively, and the content of nickel and vanadium in the treated oil is measured by adopting an inductively coupled plasma emission spectrometer (ICP-AES). (the apparatus is PE-5300 plasma photometer of PE company, USA, see petrochemical analysis method RIPP124-90)

The sulfur content was measured by an electric method (see petrochemical analysis method RIPP 62-90).

The nitrogen content was determined by an electrometric method (see petrochemical analysis method RIPP 63-90).

The carbon residue content is determined by a micro-method (the specific method is shown in petrochemical analysis method RIPP 148-90).

The removal rates of sulfur, carbon residue, nitrogen and metals were calculated according to the following formulas:

the results of removing impurities of the catalysts of examples 1 to 4 and comparative examples 1 to 3 are shown in Table 2.

TABLE 2

From the results in table 2, it can be seen that the overall impurity removal activity stability of the sulfided catalyst of the present invention is significantly improved compared with the prior art, the initial reaction activity of the catalyst (i.e. the removal performance of each impurity when the catalyst is operated for 100 hours) is close to the prior art, but the reaction stability of the catalyst (i.e. the reduction of the removal performance of each impurity after the catalyst is operated for 1000 hours) is greatly improved, so that the overall performance of the catalyst is significantly improved. Therefore, the vulcanized catalyst has good activity and stability, the service life of the catalyst is greatly prolonged, the production efficiency is further improved, and the catalyst has good application prospect.

It should be noted by those skilled in the art that the described embodiments of the present invention are merely exemplary and that various other substitutions, alterations, and modifications may be made within the scope of the present invention. Accordingly, the present invention is not limited to the above-described embodiments, but is only limited by the claims.

Claims

1. The hydrogenation catalyst for the sulfurized heavy oil is characterized by comprising an inorganic heat-resistant oxide and a sulfurized active component, wherein the active component comprises at least one VIB group metal and at least one VIII group metal, and the absorbances at 630nm and 500nm of the hydrogenation catalyst for the sulfurized heavy oil are respectively F when the hydrogenation catalyst is measured by diffuse reflection ultraviolet and visible spectrum₆₃₀And F₅₀₀And the ratio Q ═ F of the two₆₃₀/F₅₀₀Is 1.3 to 3.0.

2. The hydrogenation catalyst for heavy oil in a sulfurized state as defined in claim 1, wherein the active component has a degree of sulfurization of not less than 50%.

3. The hydrogenation catalyst for heavy oil in a sulfurized state as defined in claim 1, wherein the inorganic refractory oxide is alumina.

4. The sulfurized heavy oil hydrogenation catalyst as defined in claim 1, wherein the group VIB metal content is 5-20% and the group VIII metal content is 0.7-6% calculated as element and based on the total weight of the sulfurized heavy oil hydrogenation catalyst.

5. The sulfurized heavy oil hydrogenation catalyst of claim 1, further comprising a metal promoter and/or a non-metal promoter.

6. The hydrogenation catalyst for heavy oil in a sulfurized state as defined in claim 1, wherein the at least one group VIB metal is molybdenum and/or tungsten and the at least one group VIII metal is nickel and/or cobalt.

7. A preparation method of a hydrogenation catalyst for sulfurized heavy oil is characterized by comprising the following steps:

mixing an inorganic heat-resistant oxide precursor and a forming auxiliary agent to obtain a mixture, and forming;

dipping the formed product in a solution containing at least one VIB group metal and at least one VIII group metal;

drying the impregnated product, and roasting at 600-800 ℃ for 1-10 h to obtain an oxidation state heavy oil hydrogenation catalyst; and

under the condition of a sulfurization reaction, the oxidation state heavy oil hydrogenation catalyst is in contact reaction with a sulfurization medium to obtain the sulfurization state heavy oil hydrogenation catalyst.

8. A preparation method of a hydrogenation catalyst for sulfurized heavy oil is characterized by comprising the following steps:

soaking the formed product in a solution containing at least one VIII group metal for the first time, drying the product after the first soaking, and roasting at the temperature of 600-800 ℃ for 1-10 h to obtain a carrier;

the carrier is subjected to secondary impregnation in a solution containing at least one VIB group metal, and a product obtained after the secondary impregnation is dried and then activated at the temperature of 300-550 ℃ to obtain an oxidation state heavy oil hydrogenation catalyst; and

9. A preparation method of a hydrogenation catalyst for sulfurized heavy oil is characterized by comprising the following steps:

mixing an inorganic heat-resistant oxide precursor, at least one VIII group metal precursor and a forming auxiliary agent to obtain a mixture, and forming;

roasting the formed product at 600-800 ℃ for 1-10 h to obtain a carrier;

dipping the carrier in a solution containing at least one VIB group metal, drying the dipped product, and activating at the temperature of 300-550 ℃ to obtain an oxidation state heavy oil hydrogenation catalyst; and

10. The method according to claim 7 or 8, wherein the inorganic refractory oxide precursor is pseudo-boehmite, and the solution containing the at least one group VIB metal is selected from an aqueous solution containing one or more of molybdenum oxide, ammonium molybdate, ammonium paramolybdate, tungsten oxide, ammonium tungstate and ammonium paratungstate; the aqueous solution containing the at least one group VIII metal is selected from aqueous solutions containing one or more of cobalt nitrate, cobalt sulfate, cobalt carbonate hydroxide, nickel nitrate, nickel sulfate, and nickel carbonate hydroxide.

11. The method according to claim 9, wherein the inorganic refractory oxide precursor is pseudo-boehmite, the at least one group VIII metal precursor is selected from one or more of nickel nitrate, nickel sulfate, nickel hydroxycarbonate, cobalt nitrate, cobalt sulfate, and cobalt hydroxycarbonate, and the solution containing the at least one group VIB metal is selected from an aqueous solution containing one or more of molybdenum oxide, ammonium molybdate, ammonium paramolybdate, tungsten oxide, ammonium tungstate, and ammonium paratungstate.

12. The preparation method according to any one of claims 7 to 9, further comprising adding an auxiliary agent precursor to the mixture before the forming treatment, so that the catalyst carrier contains an auxiliary agent selected from a metal auxiliary agent and/or a non-metal auxiliary agent.

13. The preparation method according to any one of claims 7 to 9, wherein the forming aid comprises a peptizing agent selected from one or more of aqueous nitric acid, aqueous hydrochloric acid and aqueous citric acid, and a lubricant selected from one or more of sesbania powder, citric acid, starch and carboxymethyl cellulose.

14. The method according to any one of claims 7 to 9, wherein the at least one group VIB metal is molybdenum; the at least one VIII group metal is cobalt and nickel, and the atomic ratio of the cobalt to the nickel is 2-4.

15. The method according to any one of claims 7 to 9, wherein the vulcanizing medium is one or more selected from the group consisting of sulfur, carbon disulfide, dimethyl sulfide, t-butyl polysulfide and ethanethiol.

16. The production method according to any one of claims 7 to 9, wherein the vulcanization reaction conditions include: the temperature is 140-400 ℃, the pressure is normal pressure-20 MPa, and the liquid hourly space velocity of the vulcanized medium and the oxidized heavy oil hydrogenation catalyst is 0.5h^-1～5h^-1。

17. The invention discloses an application of the vulcanized heavy oil hydrogenation catalyst as claimed in any one of claims 1-6 in heavy oil hydrogenation reaction.