Vanadium disulfide hydrogenation catalyst, preparation and application thereof

Abstract

The application discloses a preparation method of a vanadium disulfide (VS2) hydrogenation catalyst. The VS2 catalyst is prepared according to the following method: a vanadium porphyrin source precursor is dissolved in a saturated alkane solvent to form a vanadium source precursor solution; an organic sulfur source precursor is dissolved in an organic solvent to form a sulfur source precursor solution; the obtained molybdenum source sulfur source solution is mixed, and then an organic amine is added to obtain a VS2 precursor solution. The VS2 precursor solution is subjected to crystallization treatment, and then a black product formed is separated and fully dried to obtain the VS2 hydrogenation catalyst. The obtained VS2 catalyst has excellent high-vanadium heavy oil catalytic hydrogenation stability. The preparation method can solve the deactivation problem caused by the metal deposition on the surface of a heavy oil hydrogenation catalyst, and realizes efficient and high-economic hydrogenation lightening of high-vanadium heavy oil.

Description

TECHNICAL FIELD

[0001] The application relates to a preparation method of a vanadium disulfide hydrogenation catalyst and belongs to the technical field of catalyst preparation in the technical field of industrial catalysis. BACKGROUND

[0002] With the increasing demand for energy and the gradual reduction of light crude oil supply, the development and utilization of heavy crude oil has become the focus of attention in the academic and industrial circles. The slurry bed hydrogenation technology is concerned due to its high heavy oil conversion rate and adaptability to difficult-to-handle materials such as heavy oil with high impurity content, and has become a powerful technical means for realizing the efficient conversion of heavy oil into light fuel (J. Catal., 2013, 308, 189-200; J. Ind. Eng. Chem., 2015, 27, 12-24). Asphaltene is the most polar and complex component in heavy oil, and its molecular structure contains a large amount of polycyclic aromatic hydrocarbons and heteroatoms (such as nitrogen, sulfur, oxygen, nickel, vanadium, etc.). Asphaltene is the most unstable component in heavy oil and is prone to coking during processing, which seriously poisons the catalyst.

[0003] For heavy oil feedstocks, the vanadium element can be as high as 1200 mu g / g, mainly concentrated in asphaltene. In the petroleum processing process, vanadium compounds in asphaltene have a great harm to the catalysts for heavy oil catalytic cracking and hydrotreating. Vanadium compounds in petroleum usually exist in the form of porphyrin organometallic complexes. In the catalytic cracking process, the organometallic complex is easy to decompose and release a large amount of vanadium ions, which are deposited on the catalyst, which may reduce the activity of the catalyst or even poison and deactivate the catalyst (Corrosion and Protection of Petroleum Chemical Industry, 2012, 29, 1-4).

[0004] The hydrogenation catalysts used in heavy oil hydrogenation technology are mainly Fe-based or Mo-based catalysts (Fuel, 2021, 288, 119686; Energy Fuels, 2019, 33, 7917-7949), and the deposition of V on the surface of the catalysts will cause the deactivation of the catalysts. Therefore, it is necessary to develop a new type of hydrogenation catalyst with high stability. SUMMARY

[0005] In order to solve the problem of catalyst deactivation in the hydrogenation reaction of high-vanadium heavy oil, the application provides a preparation method of a vanadium disulfide hydrogenation catalyst.

[0006] The preparation method of the vanadium disulfide hydrogenation catalyst according to the application is obtained by the following steps:

[0007] (1) Dissolve at least one of vanadium source precursors such as vanadyl octaethylporphyrin, vanadyl octaethylporphyrin and tetraphenylporphyrin vanadyl in at least one of saturated linear alkanes, saturated cycloalkanes and aromatic hydrocarbons to form a vanadium source precursor solution;

[0008] (2) Dissolve at least one of the organic sulfur source precursors of sulfide, disulfide, mercaptan and thiophene in at least one of the organic solvents of ethanol, acetone, benzene, diethyl ether, phenol, tetralin and decalin to form a sulfur source precursor solution;

[0009] (3) Mix the obtained vanadium source and sulfur source precursor solutions, and then add at least one of the organic amines of aliphatic amine, alcohol amine and amide to obtain a VS2 precursor solution. The molar ratio of S / V in the VS2 precursor solution is 1.0-4.0, preferably 2.0-3.0. The molar ratio of organic amine / V in the VS2 precursor solution is 0.5-3.0, preferably 1.0-2.0.

[0010] (4) After crystallization of the VS2 precursor solution in a hydrogen atmosphere, separate and dry to obtain a black VS2 hydrogenation catalyst. The crystallization pressure is 1.0-5.0 MPa, the crystallization temperature is 200-400°C, and the crystallization time is 0.5-12 hours, preferably the pressure is 2.0-3.0 MPa, the temperature is 280-320°C, and the time is 2-6 hours. After pressure relief, high-speed centrifugation or organic filter membrane filtration can be used, and then the catalyst is washed with ethanol three times and vacuum or freeze-dried.

[0011] The VS2 hydrogenation catalyst prepared by the present application has excellent catalytic hydrogenation stability for high-vanadium heavy oil hydrogenation lightening reaction. In the catalytic hydrogenation reaction of heavy oil model compounds, the solvent used is tridecane 30 ml, the catalyst is added in an amount of 2.5 wt.%, the reaction temperature is 350°C, and the hydrogen reaction pressure is 8.0 MPa under the condition of reaction for 4h. In the catalytic hydrogenation reaction of heavy oil with an American Petroleum Institute (API) gravity less than 22.3, the heavy oil used is 30g, the catalyst is added in an amount of 0.05%-0.35% of the heavy oil, the reaction temperature is 350-450°C, and the hydrogen reaction pressure is 10.0-20.0 MPa under the condition of reaction for 2-12h. The reaction activity results are shown in Table 2. The heavy oil hydrogenation stability results of the catalyst are shown in Table 3.

[0012] Compared with the prior art, the present application has the following advantages and effects:

[0013] (1) According to the attached Figure 1 and 3It can be seen that the VS2 catalyst prepared in the application is a two-dimensional layered structure catalyst, and the interlayer spacing of the VS2 nanosheet is 0.576 nm. The synthesis system used in the application accurately simulates the vanadium precipitation and deposition reaction in the high-vanadium heavy oil hydrogenation lightening reaction system. The vanadium complex with a porphyrin structure similar to the vanadium structure in the two-dimensional layered asphaltene is used as a vanadium source precursor, the organic sulfur compound contained in the oil product is used as a sulfur source precursor, and the organic amine is introduced to simulate the organic matter generated by the porphyrin structure after the vanadium is removed from the asphaltene in the heavy oil. This design can provide consistent crystallization conditions for the vanadium precipitated in the heavy oil, so that the precipitated vanadium generates a highly active VS2 hydrogenation catalyst.

[0014] (2) The VS2 prepared in the application has a micron flower morphology with a diameter of 3-4 μm, and the VS2 micron flower is assembled by agglomeration of VS2 nanosheets. When the prepared VS2 catalyst is used for high-vanadium heavy oil hydrogenation reaction, the porphyrin vanadium and the organic sulfur heteroatomic compound in the heavy oil react to form a new VS2 island-shaped high hydrogenation activity catalyst on the surface of the VS2 catalyst. The development of this preparation method effectively solves the problem that the catalyst active site is covered and deactivated due to the deposition of vanadium precipitated in the heavy oil on the surface of the catalyst.

[0015] (3) The VS2 catalyst obtained in the application has excellent lipophilicity and a two-dimensional layered structure similar to that of the asphaltene unit sheet. As shown in the accompanying drawings, the oil solvent contact angle of the VS2 catalyst prepared in the application is 9°, indicating that the catalyst has extremely excellent lipophilic properties. This property ensures that the VS2 hydrogenation catalyst can fully contact the asphaltene and undergo efficient hydrogenation reaction, thereby realizing the island-shaped precipitation of asphaltene vanadium on the surface thereof. Figure 1 BRIEF DESCRIPTION OF DRAWINGS

[0016] Figure 1 XRD spectrum of the VS2 hydrogenation catalyst obtained in Example 1.

[0017] Figure 2 SEM photograph of the VS2 hydrogenation catalyst obtained in Example 1.

[0018] Figure 3 TEM photograph of the VS2 hydrogenation catalyst obtained in Example 1.

[0019] Figure 4 Contact angle photograph of the VS2 hydrogenation catalyst obtained in Example 1.

[0020] Figure 5 XRD spectrum of the VS2 hydrogenation catalyst obtained in the comparative example. DETAILED DESCRIPTION

[0021] In order to further illustrate the application, the following examples are given, but the scope of the application is not limited thereto.​

[0022] Example 1

[0023] 0.3082 g of vanadium proto-porphyrin oxide was weighed into 30 ml of dodecane to obtain a vanadium source precursor solution. 0.0841 g of thiophene was weighed into 30 ml of decaline to obtain a sulfur source precursor solution. The vanadium source and sulfur source solutions were mixed, and 0.0927 g of dodecylamine was added to the obtained mixed solution to obtain a VS2 precursor solution, the element molar ratio of S / V in the solution being 2.0, and the molar ratio of organic amine / V being 1.0. The obtained VS2 precursor solution was transferred into a high-pressure reaction kettle, and after being replaced with nitrogen for 3 times, hydrogen was introduced to 2.0 MPa. The temperature was raised to 320℃ for crystallization for 4 h. After cooling to room temperature, the product was taken out after pressure relief, centrifuged, and the obtained solid was washed with ethanol for 3 times to obtain a black product, which was vacuum dried at 60℃ overnight. After cooling, the VS2 hydrogenation catalyst was collected.

[0024] Figure 1 Figure 1 It can be seen from the XRD spectrum of the VS2 that the diffraction peaks at 15.4, 32.1, 35.7, 45.2, 57.1 and 69.3 degrees correspond to the (001), (100), (011), (012), (103) and (201) crystal planes of VS2, respectively. The diffraction peaks of the VS2 sample are well matched with the standard peaks of the PDF card (PDF: 89-1640) of the two-dimensional layered VS2 of hexagonal structure. Figure 2 It can be seen from Figure 1 that the VS2 prepared in the present application has a micron flower morphology with a diameter of 3-4 μm, and the VS2 micron flower is assembled by agglomeration of VS2 nanosheet. Figure 3 It can be seen from Figure 1 that the VS2 prepared in the present application has a two-dimensional layered structure catalyst with an interlayer spacing of 0.576 nm. As shown in Figure 1, the VS2 catalyst prepared in the present application has an oil solvent contact angle of 9°, which is much smaller than 90°, indicating that the catalyst has extremely excellent lipophilic properties. Figure 4

[0025] The catalyst prepared in the present example was used for catalytic hydrogenation reaction of heavy oil model compound and heavy oil.

[0026] In the catalytic hydrogenation reaction of the heavy oil model compound phenanthrene, the solvent used was tridecane 30 ml, the addition amount of the catalyst was 2.5 wt.%, the reaction temperature was 350℃, the hydrogen reaction pressure was 8.0 MPa, and the reaction time was 4 h. The reaction activity results are shown in Table 1.

[0027] ​The heavy oil catalytic hydrogenation reaction was carried out under the conditions of 30 g of heavy oil, 0.3 wt.% of catalyst, 420 ℃ of reaction temperature, 12 MPa of hydrogen reaction pressure and 6 h of reaction time. The reaction activity results are shown in Table 2. The catalyst after the heavy oil catalytic hydrogenation reaction was recovered by heptane extraction and reused. The reaction process and conditions were the same as above to study the hydrogenation stability. The heavy oil hydrogenation stability of the catalyst is shown in Table 3.

[0028] Example 2:

[0029] 0.3082 g of vanadyl meso-tetraphenylporphyrin was weighed into 30 ml of ethylcyclohexane to obtain a vanadium source precursor solution. 0.0236 g of dimethyl disulfide was weighed into 30 ml of tetralin to obtain a sulfur source precursor solution. The vanadium source and sulfur source solutions were mixed, and 0.0263 g of diethanolamine was added to the obtained mixed solution to obtain a VS2 precursor solution, in which the element molar ratio of S / V was 1.0 and the molar ratio of organic amine / V was 0.5. The obtained VS2 precursor solution was transferred into a high-pressure reaction kettle, replaced with nitrogen for 3 times, and then hydrogen was introduced to 1.0 MPa. The temperature was increased to 200 ℃ for crystallization for 12 h. After cooling to room temperature, the product was taken out after pressure relief, centrifuged and separated, and the obtained solid was washed with ethanol for 3 times to obtain a black product, which was vacuum dried at 60 ℃ overnight. After cooling, the VS2 hydrogenation catalyst was collected.

[0030] The catalyst prepared in this example was used for heavy oil model compound and heavy oil catalytic hydrogenation reaction, and the reaction conditions were the same as in Example 1. The reaction results are shown in Tables 1 and 2.

[0031] Example 3:

[0032] 0.3398 g of vanadyl tetraphenylporphyrin was weighed into 30 ml of toluene to obtain a vanadium source precursor solution. 0.0932 g of dimethyl sulfide was weighed into 30 ml of ethanol to obtain a sulfur source precursor solution. The vanadium source and sulfur source solutions were mixed, and 0.0451 g of dimethylamine was added to the obtained mixed solution to obtain a VS2 precursor solution, in which the element molar ratio of S / V was 3.0 and the molar ratio of organic amine / V was 2.0. The obtained VS2 precursor solution was transferred into a high-pressure reaction kettle, replaced with nitrogen for 3 times, and then hydrogen was introduced to 5.0 MPa. The temperature was increased to 400 ℃ for crystallization for 0.5 h. After cooling to room temperature, the product was taken out after pressure relief, centrifuged and separated, and the obtained solid was washed with ethanol for 3 times to obtain a black product, which was vacuum dried at 60 ℃ overnight. After cooling, the VS2 hydrogenation catalyst was collected.

[0033] The catalyst prepared in this example was used for heavy oil model compound and heavy oil catalytic hydrogenation reaction, and the reaction conditions were the same as in Example 1. The reaction results are shown in Tables 1 and 2.

[0034] Example 4:

[0035] A solution of vanadium source precursor was prepared by dissolving 0.3398 g of vanadyl tetraphenylporphyrin in 30 ml of butane. A solution of sulfur source precursor was prepared by dissolving 0.2684 g of benzothiophene in 30 ml of phenol. The vanadium source and sulfur source solutions were mixed, and 0.0676 g of dimethylamine was added to the resulting mixture to obtain a VS2 precursor solution, which had an elemental molar ratio of S / V of 4.0 and a molar ratio of organic amine / V of 3.0. The resulting VS2 precursor solution was transferred into a high-pressure reactor, which was purged with nitrogen three times and then filled with hydrogen to a pressure of 3.0 MPa. The temperature was raised to 280°C and the reactor was held at this temperature for 6 h. After cooling to room temperature, the product was removed from the reactor, centrifuged, and washed with ethanol three times to obtain a black product, which was dried at 60°C under vacuum overnight. After cooling, the VS2 hydrogenation catalyst was collected.

[0036] The catalyst prepared in this example was used in the catalytic hydrogenation of a heavy oil model compound and a heavy oil, under the same conditions as in Example 1. The results are shown in Tables 1 and 2.

[0037] Example 5:

[0038] A solution of vanadium source precursor was prepared by dissolving 0.2664 g of vanadyl octaethylporphyrin in 30 ml of cyclohexane. A solution of sulfur source precursor was prepared by dissolving 0.0777 g of ethanethiol in 30 ml of acetone. The vanadium source and sulfur source solutions were mixed, and 0.1119 g of triethanolamine was added to the resulting mixture to obtain a VS2 precursor solution, which had an elemental molar ratio of S / V of 2.5 and a molar ratio of organic amine / V of 1.5. The resulting VS2 precursor solution was transferred into a high-pressure reactor, which was purged with nitrogen three times and then filled with hydrogen to a pressure of 2.5 MPa. The temperature was raised to 300°C and the reactor was held at this temperature for 2 h. After cooling to room temperature, the product was removed from the reactor, centrifuged, and washed with ethanol three times to obtain a black product, which was dried at 60°C under vacuum overnight. After cooling, the VS2 hydrogenation catalyst was collected.

[0039] The catalyst prepared in this example was used in the catalytic hydrogenation of a heavy oil model compound and a heavy oil, under the same conditions as in Example 1. The results are shown in Tables 1 and 2.

[0040] Example 6:

[0041] A solution of vanadium source precursor was prepared by dissolving 0.2664 g of vanadyl octaethyl-porphyrin in 30 ml of heptane. A solution of sulfur source precursor was prepared by dissolving 0.1842 g of dibenzothiophene in 30 ml of benzene. The vanadium source and sulfur source solutions were mixed, and 0.1348 g of octadecylamine was added to the resulting mixture to obtain a VS2 precursor solution, which had an elemental molar ratio of S / V of 2.0 and a molar ratio of organic amine / V of 1.0. The resulting VS2 precursor solution was transferred into a high-pressure reactor, which was purged with nitrogen three times and then filled with hydrogen to a pressure of 2.0 MPa. The reactor was heated to 320°C and held at this temperature for 4 h. After cooling to room temperature, the product was removed, centrifuged, and washed with ethanol three times to obtain a black product, which was dried at 60°C under vacuum overnight. After cooling, the hydrogenation catalyst was collected.

[0042] The catalyst prepared in this example was used in the catalytic hydrogenation of a heavy oil model compound and a heavy oil, under the same conditions as in Example 1. The results are shown in Tables 1 and 2.

[0043] Example 7:

[0044] A solution of vanadium source precursor was prepared by dissolving 0.2664 g of vanadyl octaethyl-porphyrin in 30 ml of heptane. A solution of sulfur source precursor was prepared by dissolving 0.1842 g of dibenzothiophene in 30 ml of benzene. The vanadium source and sulfur source solutions were mixed, and 0.1348 g of octadecylamine was added to the resulting mixture to obtain a VS2 precursor solution, which had an elemental molar ratio of S / V of 2.0 and a molar ratio of organic amine / V of 1.0. The resulting VS2 precursor solution was transferred into a high-pressure reactor, which was purged with nitrogen three times and then filled with hydrogen to a pressure of 2.0 MPa. The reactor was heated to 320°C and held at this temperature for 4 h. After cooling to room temperature, the product was removed, centrifuged, and washed with ethanol three times to obtain a black product, which was dried at 60°C under vacuum overnight. After cooling, the hydrogenation catalyst was collected.

[0045] In the catalytic hydrogenation of a heavy oil, 30 g of heavy oil was used, and the catalyst was added in an amount of 0.05 wt.% of the heavy oil. The reaction was carried out at a temperature of 450°C and a hydrogen pressure of 10 MPa for 2 h. The results are shown in Table 2. The

[0046] Example 8:

[0047] A solution of vanadium source precursor was prepared by dissolving 0.9631 g of vanadyl proto-porphyrin in 30 ml of dodecane. A solution of sulfur source precursor was prepared by dissolving 0.2628 g of thiophene in 30 ml of decaline. The vanadium source and sulfur source solutions were mixed, and 0.2897 g of dodecylamine was added to the resulting mixture to obtain a VS2 precursor solution, which had an elemental molar ratio of S / V of 2.0 and a molar ratio of organic amine / V of 1.0. The resulting VS2 precursor solution was transferred into a high-pressure reactor, which was purged with nitrogen three times and then filled with hydrogen to a pressure of 2.0 MPa. The reactor was heated to 320 °C and held at this temperature for 4 h. After cooling to room temperature, the product was removed, centrifuged, and washed with ethanol three times to obtain a black product, which was dried at 60 °C under vacuum overnight. After cooling, the VS2 hydrogenation catalyst was collected.

[0048] For the catalytic hydrogenation of heavy oil, 30 g of heavy oil was used, and the amount of catalyst added was 0.1 wt.% of the heavy oil. The reaction was carried out at a temperature of 425 °C and a hydrogen reaction pressure of 12 MPa for 6 h. The results of the reaction activity are shown in Table 2. The

[0049] Example 9:

[0050] A solution of vanadium source precursor was prepared by dissolving 0.9631 g of vanadyl proto-porphyrin in 30 ml of dodecane. A solution of sulfur source precursor was prepared by dissolving 0.2628 g of thiophene in 30 ml of decaline. The vanadium source and sulfur source solutions were mixed, and 0.2897 g of dodecylamine was added to the resulting mixture to obtain a VS2 precursor solution, which had an elemental molar ratio of S / V of 2.0 and a molar ratio of organic amine / V of 1.0. The resulting VS2 precursor solution was transferred into a high-pressure reactor, which was purged with nitrogen three times and then filled with hydrogen to a pressure of 2.0 MPa. The reactor was heated to 320 °C and held at this temperature for 4 h. After cooling to room temperature, the product was removed, centrifuged, and washed with ethanol three times to obtain a black product, which was dried at 60 °C under vacuum overnight. After cooling, the VS2 hydrogenation catalyst was collected.

[0051] For the catalytic hydrogenation of heavy oil, 30 g of heavy oil was used, and the amount of catalyst added was 0.1 wt.% of the heavy oil. The reaction was carried out at a temperature of 425 °C and a hydrogen reaction pressure of 12 MPa for 6 h. The results of the reaction activity are shown in Table 2. The

[0052] Example 10:

[0053] Take 1.9263 g of vanadium proto-porphyrin oxide and dissolve it in 30 ml of dodecane to obtain a vanadium source precursor solution. Take 0.5256 g of thiophene and dissolve it in 30 ml of decaline to obtain a sulfur source precursor solution. Mix the vanadium source and sulfur source solutions, and add 0.5792 g of dodecylamine to the obtained mixed solution to obtain a VS2 precursor solution, in which the element molar ratio of S / V is 2.0, and the molar ratio of organic amine / V is 1.0. Transfer the obtained VS2 precursor solution into a high-pressure reaction kettle, replace it with nitrogen for 3 times, and then introduce hydrogen to 2.0 MPa. Increase the temperature to 320°C and crystallize for 4 h. After cooling to room temperature, the product is taken out after pressure relief, centrifuged, and washed with ethanol for 3 times to obtain a black product, which is dried at 60°C overnight. After cooling, the VS2 hydrogenation catalyst is collected.

[0054] In the catalytic hydrogenation reaction of heavy oil, the heavy oil used is 30 g, the catalyst is added in an amount of 0.5 wt.% of the heavy oil, the reaction temperature is 3500°C, the hydrogen reaction pressure is 20 MPa, and the reaction time is 12 h. The reaction activity results are shown in Table 2. The

[0055] Comparative Example:

[0056] Take 0.1326 g of vanadyl acetylacetonate and dissolve it in 30 ml of ethanol to obtain a vanadium source precursor solution. Take 0.2764 g of dibenzothiophene and dissolve it in 30 ml of phenol to obtain a sulfur source precursor solution. Mix the vanadium source and sulfur source solutions, and add 0.0927 g of dodecylamine to the obtained mixed solution to obtain a VS2 precursor slurry, in which the element molar ratio of S / V is 3.0, and the molar ratio of organic amine / V is 1.0. Transfer the obtained VS2 precursor solution into a high-pressure reaction kettle, replace it with nitrogen for 3 times, and then introduce hydrogen to 2.0 MPa. Increase the temperature to 320°C and crystallize for 4 h. After cooling to room temperature, the product is taken out after pressure relief, centrifuged, and washed with ethanol for 3 times to obtain a black product, which is dried at 60°C overnight. After cooling, the hydrogenation catalyst is collected.

[0057] From the XRD attached Figure 5 It can be known from the XRD that the comparative example cannot prepare a pure-phase two-dimensional layered VS2 catalyst, and the obtained product is a mixture of VS2, VS4, and V3S4. The catalyst prepared in the comparative example is used for catalytic hydrogenation reaction of a heavy oil model compound and heavy oil, and the reaction conditions are the same as those in Example 1. The reaction results are shown in Tables 1 and 2. It has a catalytic hydrogenation activity far lower than that of the pure-phase VS2 catalyst prepared in the present application.

[0058] Table 1 Hydrogenation activity of the vanadium disulfide hydrogenation catalyst prepared in the present application for a heavy oil model compound phenanthrene.

[0059]

[0060] Table 2 Hydrogenation activity of the vanadium disulfide hydrogenation catalyst prepared in the application for heavy oil.

[0061]

[0062] Table 3 High-vanadium heavy oil hydrogenation stability of the vanadium disulfide hydrogenation catalyst prepared in Example 1.

[0063]

[0064] The VS2 catalyst obtained in the application has excellent high-vanadium heavy oil catalytic hydrogenation stability. The preparation method of the application can solve the problem of deactivation caused by metal deposition on the surface of the heavy oil hydrogenation catalyst, and realize efficient and economical hydrogenation lightening of high-vanadium heavy oil.

Claims

1. A process for the preparation of a vanadium disulfide hydrogenation catalyst characterized by, The method comprises the following steps: (1) dissolving vanadium porphyrin source precursor in saturated alkane solvent to form vanadium source precursor solution; The vanadium porphyrin source precursor used is one of vanadium proto-porphyrin oxide, octaethyl vanadyl porphyrin and tetraphenyl vanadyl porphyrin or a mixture of two or more thereof; (2) dissolving organic sulfur source precursor in organic solvent to form sulfur source precursor solution; (3) mixing the obtained vanadium source and sulfur source precursor solutions, and then adding organic amine to obtain VS2 precursor solution; (4) crystallizing the VS2 precursor solution in hydrogen atmosphere, and then separating and drying to obtain VS2 hydrogenation catalyst.

2. The production method according to claim 1, characterized by: The saturated alkane solvent used is one of C4-C12 saturated linear alkane, C6-C14 saturated cycloalkane and C6-C10 aromatic hydrocarbon or a mixture of two or more thereof; the concentration of vanadium porphyrin source in saturated alkane solvent is 0.01-0.10 mol / L.

3. The method of claim 1, wherein: The organic sulfur source precursor used is one of sulfide, disulfide, mercaptan and thiophene organic sulfur compound or a mixture of two or more thereof.

4. The preparation method according to claim 3, characterized in that: the sulfide is one of C1-C3 alkyl sulfide compound or two or more thereof; the disulfide is one of C1-C3 alkyl disulfide or two or more thereof; the mercaptan is one of C1-C4 alkyl mercaptan or two or more thereof; the thiophene organic sulfur compound is one of thiophene, benzothiophene and dibenzothiophene or two or more thereof.

5. The method of claim 1, wherein: The organic solvent used is one of ethanol, acetone, benzene, diethyl ether, phenol, tetralin and decalin or a mixture of two or more thereof; the concentration of organic sulfur source in organic solvent is 0.01-0.40 mol / L.

6. The method of claim 1, wherein: The molar ratio of S / V in the VS2 precursor solution of step (3) is 1.0-4.

0.

7. The method of claim 1, wherein: The organic amine used is one of C1-C20 aliphatic amine, alcohol amine and amide or a mixture of two or more thereof.

8. The method of claim 1, wherein: The molar ratio of organic amine / V in the VS2 precursor solution of step (3) is 0.5-3.0; in step (4), the VS2 precursor solution is transferred into autoclave for crystallization in hydrogen atmosphere, the crystallization pressure is 1.0-5.0 MPa, the crystallization temperature is 200-400℃, and the crystallization time is 0.5-12 hours.

9. The method of claim 8, wherein: The molar ratio of organic amine / V in the VS2 precursor solution of step (3) is 1.0-2.0; in step (4), the VS2 precursor solution is transferred into autoclave for crystallization in hydrogen atmosphere, the crystallization pressure is 2.0-3.0 MPa, the crystallization temperature is 280-320℃, and the crystallization time is 2-6 hours.

10. A vanadium disulfide hydrogenation catalyst prepared by the preparation method of any one of claims 1-9.

11. The vanadium disulfide hydrogenation catalyst of claim 10 is used for catalyzing high-vanadium heavy oil hydrogenation lightening reaction, and has excellent catalytic hydrogenation stability, and the vanadium content of high-vanadium is higher than 100 ppm.

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