Vanadium tetrasulfide catalyst for heavy oil hydrogenation as well as preparation and application of vanadium tetrasulfide catalyst

Abstract

The invention discloses a preparation method of a vanadium tetrasulfide catalyst for heavy oil hydrogenation. The preparation method of the VS4 catalyst comprises the following steps: dissolving an organic vanadium source precursor in an organic solvent to form a vanadium source precursor solution; dissolving the organic sulfur source precursor in an organic solvent to form a sulfur source precursor solution; mixing the obtained vanadium source precursor solution with the obtained sulfur source precursor solution, and adding organic acid to obtain VS4 precursor slurry; and crystallizing the VS4 precursor slurry, separating, and drying to obtain the black VS4 hydrogenation catalyst. The obtained VS4 catalyst has excellent heavy oil catalytic hydrogenation performance. The preparation method provided by the invention can solve the problem of catalyst deactivation caused by loss of sulfur in the heavy oil hydrogenation catalyst and surface metal deposition, and realizes rapid and efficient hydrogenation lightening of the heavy oil.

Description

Technical Field:

[0001] The present invention relates to a preparation method of a vanadium tetrasulfide catalyst for heavy oil hydrogenation, belonging to the catalyst preparation technology in the technical field of industrial catalysis, and can realize heavy oil catalytic hydrogenation. Background Art

[0002] With the continuous growth of global energy demand and the gradual reduction of light crude oil supply, the development and utilization of heavy crude oil have become the focus of extensive attention in the academic and industrial circles. The slurry bed hydrogenation technology has attracted much attention due to its high heavy oil conversion rate and adaptability to difficult-to-treat raw materials such as heavy crude oil with high impurity content, and has become a powerful technical means to efficiently convert heavy crude oil into light fuels (J. Catal., 2013, 308, 189 - 200; J. Ind. Eng. Chem., 2015, 27, 12 - 24). Asphaltene is the most polar and structurally complex component in heavy oil, and its molecular structure contains a large number of polycyclic aromatic hydrocarbons and metal heteroatoms (such as nitrogen, sulfur, oxygen, nickel, vanadium, etc.). During the petroleum processing, vanadium compounds in asphaltene are very harmful to the catalysts for heavy oil catalytic cracking and hydrotreating. During the catalytic hydrogenation process, metal heteroatoms are prone to decompose and release a large amount of metal ions, which deposit on the catalyst. At least, it reduces the activity of the catalyst, and at worst, it poisons the catalyst and makes it deactivate (Petrochemical Corrosion and Protection, 2012, 29, 1 - 4).

[0003] Most of the hydrogenation catalysts used in heavy oil hydrogenation technology are Fe-based or Mo-based catalysts (Fuel, 2021, 288, 119686; Energy Fuels, 2019, 33, 7917 - 7949), and the deposition of metal heteroatom V on their surfaces will cause their deactivation. Vanadium has rich valence states from +2 to +5, and vanadium sulfide can achieve multi-electron transfer. Vanadium tetrasulfide (VS 4 ) has a one-dimensional chain structure, and the distance between chains is 0.583 nm. Adjacent two molecular chains are combined together by van der Waals forces (ACS Applied Materials & Interfaces, 2016, 8(29): 18797 - 18805). VS4 has high electrical conductivity and ion exchange rate, and has been widely used in the fields of solar cells, ion batteries, supercapacitors, catalysts, etc. in recent years (CN202310279297.9, CN202110303802.X, CN201811513542.3, CN202310215757.1, CN202210978364.1, CN201910460372.5, ACS Sustainable Chemistry & Engineering, 2015, 54, 2682 - 2689). VS 4With a high S content, in the heavy oil hydrotreating reaction, it can avoid the deactivation of the catalyst caused by the loss of S in the catalyst during the reaction process and solve the problem of catalyst deactivation caused by the deposition of metal heteroatoms in heavy oil on the catalyst surface. In addition, VS 4 The special one-dimensional chain structure of the catalyst can more effectively contact with macromolecular reaction substrates such as asphaltene in heavy oil, so as to achieve the efficient catalytic hydrotreating reaction of heavy oil. Summary of the Invention

[0004] In order to solve the problems of sulfur loss of the catalyst and deactivation caused by the coverage of active sites in the heavy oil hydrotreating reaction, the present invention provides a preparation method of a vanadium tetrasulfide catalyst for heavy oil hydrotreating.

[0005] The preparation method of the vanadium tetrasulfide catalyst for heavy oil hydrotreating of the present invention is obtained by the following steps:

[0006] (1) Dissolve at least one organic vanadium source precursor such as vanadyl triisopropoxide, bis(cyclopentadienyl) vanadium dichloride, cyclopentadienyl vanadium tricarbonyl, vanadyl acetylacetonate in at least one organic solvent such as ethanol, acetone, isopropanol, cyclohexane to form a vanadium source precursor solution;

[0007] (2) Dissolve at least one organic sulfur source precursor such as thioether, disulfide, thiol and thiophene in at least one organic solvent such as ethanol, acetone, benzene, phenol, tetralin, decalin to form a sulfur source precursor solution;

[0008] (3) After mixing the obtained vanadium source and sulfur source precursor solutions, add at least one reducing organic acid such as formic acid, acetic acid, oxalic acid, citric acid, ethylenediaminetetraacetic acid to obtain VS 4 precursor slurry. In the VS 4 precursor slurry, the molar ratio of S / V is 4.0 - 10.0, preferably 5.0 - 7.0; the molar ratio of organic acid / V is 0.1 - 4.0, preferably 1.0 - 2.0.

[0009] (4) Transfer the VS 4 precursor slurry into a high-pressure closed reaction device, the crystallization temperature is 100 - 200 °C, the crystallization time is 2 - 72 hours, preferably the temperature is 140 - 180 °C, and the time is 12 - 24 hours. After crystallization, centrifuge at high speed or separate with a microporous organic filter membrane, wash 3 times with ethanol, and then dry in a vacuum oven or freeze-dry to obtain a black VS 4 hydrotreating catalyst.

[0010] The VS 4The catalyst is used for the catalytic hydro-upgrading reaction of heavy oil with an API gravity less than 22.3 as the raw material, and has excellent catalytic hydro-upgrading performance. The reaction conditions are as follows: the mass percentage of the catalyst / heavy oil is 0.05% - 0.5%, the reaction temperature is 350 - 450 °C, and the hydrogen reaction pressure is 10.0 - 20.0 MPa, and the reaction is carried out for 2 - 12 h.

[0011] The present invention has the following advantages and effects compared with the prior art:

[0012] (1) The XRD results in Figure 1 show that the catalyst prepared in the present invention is a pure-phase one-dimensional chain structure VS 4 . The VS 4 catalyst for heavy oil hydrogenation prepared by the preparation method of the present invention has a high S content, which can avoid the deactivation of the catalyst caused by the loss of S during the hydrogenation process. Moreover, the high S content can react with the metal heteroatoms precipitated during the heavy oil hydrogenation process to form a sulfide catalyst with catalytic hydrogenation activity. This VS 4 catalyst with a special composition effectively avoids the deactivation of the catalyst due to lack of S and the deposition of metals covering the hydrogenation active sites.

[0013] (2) Figure 2 and Figure 3 both show that the catalyst prepared in the present invention is a VS 4 catalyst with a one-dimensional nanorod structure. The VS 4 catalyst for heavy oil hydrogenation prepared by the preparation method of the present invention has a special one-dimensional chain structure. This one-dimensional chain structure can achieve the full contact of the catalyst active sites with the difficult-to-hydrogenate asphaltene components in the heavy oil at the molecular level, thereby realizing an efficient catalytic hydrogenation reaction. This special structure solves the problem of the dispersion of heavy oil hydrogenation catalysts in asphaltene.

[0014] (3) The VS 4 catalyst for heavy oil hydrogenation prepared by the preparation method of the present invention can perform efficient hydrogenation of heavy oil with a high metal heteroatom content and a low sulfur content. The deposition of metal heteroatoms on the edge of its one-dimensional chain structure can create new catalytic hydrogenation active sites, improve the catalytic hydrogenation reaction activity, and improve the stability of the catalyst. BRIEF DESCRIPTION OF THE DRAWINGS

[0015] Figure 1 XRD spectrum of the VS 4 hydrogenation catalyst obtained in Example 1.

[0016] Figure 2 SEM photograph of the VS 4 hydrogenation catalyst obtained in Example 1.

[0017] Figure 3VS obtained in Example 1 4 TEM photograph of the hydrogenation catalyst.

[0018] Figure 4 VS obtained in the comparative example 4 XRD spectrum of the hydrogenation catalyst. Detailed implementation manners

[0019] To further illustrate the present invention, the following examples are listed, but the scope of the present invention is not limited.

[0020] Example 1:

[0021] Weigh 0.1221 g of vanadium triisopropoxide and dissolve it in 30 ml of isopropanol to obtain a vanadium source precursor solution. Weigh 0.2104 g of thiophene and dissolve it in 30 ml of decalin to obtain a sulfur source precursor solution. Mix the vanadium source and sulfur source solutions, and add 0.0230 g of formic acid to the obtained mixed solution to obtain VS 4 precursor slurry, in which the elemental molar ratio of S / V is 5.0 and the molar ratio of organic acid / V is 1.0. Transfer the obtained VS 4 precursor solution into a high-pressure reactor. Heat up to 140 °C and crystallize for 24 h. Cool down to room temperature, relieve the pressure, take out the product, centrifuge and wash it three times with ethanol to obtain a black product, and dry it under vacuum at 60 °C overnight. After cooling, collect to obtain VS 4 hydrogenation catalyst.

[0022] Appendix Figure 1 The XRD pattern of the VS 4 catalyst prepared in this example is given, which shows two strong diffraction peaks at 15.8° and 17.1°. According to the PDF card (PDF: 21-1434), they can be attributed to the (011) and (020) crystal planes of the VS 4 material with lattice spacings of 0.52 nm and 0.56 nm respectively. The remaining diffraction peaks can also be well matched with the standard peaks of the PDF card. This result indicates that the VS 4 catalyst prepared in this example has good crystallinity. Appendix Figure 2 The SEM photograph shows that the prepared VS4 catalyst is a nanosphere formed by the aggregation and assembly of one-dimensional nanorods. Appendix Figure 3 The HETEM photograph in 4 further proves the one-dimensional nanostructure of the VS

[0023] The VS 4 catalyst for heavy oil hydrogenation prepared in this example is used for the catalytic hydrogenation reaction of heavy oil model compounds and heavy oil.

[0024] When the heavy oil model compound phenanthrene was catalytically hydrogenated, 30 ml of tridecane was used as the solvent, the addition amount of the catalyst was 2.5 wt.%, the reaction temperature was 350 °C, and the reaction was carried out for 4 h under a hydrogen reaction pressure of 8.0 MPa. The reaction activity results are shown in Table 1.

[0025] When the heavy oil was catalytically hydrogenated, 30 g of heavy oil was used, the addition amount of the catalyst was 0.3 wt.% of the heavy oil, the reaction temperature was 420 °C, and the reaction was carried out for 6 h under a hydrogen reaction pressure of 12 MPa. 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, and the hydrogenation stability was studied. The heavy oil hydrogenation stability results of the catalyst are shown in Table 3.

[0026] Example 2:

[0027] 0.1260 g of vanadocene dichloride was weighed and dissolved in 30 ml of cyclohexane to obtain a vanadium source precursor solution. 0.2140 g of dimethyl sulfide was weighed and dissolved in 30 ml of benzene to obtain a sulfur source precursor solution. The vanadium source and sulfur source solutions were mixed, and 0.0601 g of acetic acid was added to the resulting mixed solution to obtain a VS 4 precursor slurry, and the element molar ratio of S / V in this solution was 7.0, and the organic acid / V molar ratio was 2.0. The obtained VS 4 precursor solution was transferred into a high-pressure reactor. The temperature was raised to 180 °C and crystallized for 12 h. After cooling to room temperature, the pressure was released, the product was taken out, centrifuged, washed three times with ethanol to obtain a black product, and vacuum dried at 60 °C overnight. After cooling, the VS 4 hydrogenation catalyst was collected.

[0028] The catalyst prepared in this example was used for the catalytic hydrogenation reaction of heavy oil model compounds and heavy oil. The reaction conditions were the same as in Example 1, and the reaction results are shown in Tables 1 and 2.

[0029] Example 3:

[0030] 0.114 g of cyclopentadienylvanadium tetracarbonyl was weighed and dissolved in 30 ml of ethanol to obtain a vanadium source precursor solution. 0.0.1243 g of ethanethiol was weighed and dissolved in 30 ml of ethanol to obtain a sulfur source precursor solution. The vanadium source and sulfur source solutions were mixed, and 0.0.1801 g of oxalic acid was added to the resulting mixed solution to obtain a VS 4 precursor slurry, and the element molar ratio of S / V in this solution was 4.0, and the organic acid / V molar ratio was 4.0. The obtained VS 4 precursor solution was transferred into a high-pressure reactor. The temperature was raised to 100 °C and crystallized for 72 h. After cooling to room temperature, the pressure was released, the product was taken out, centrifuged, washed three times with ethanol to obtain a black product, and vacuum dried at 60 °C overnight. After cooling, the VS 4 hydrogenation catalyst was collected.

[0031] The catalyst prepared in this example was used for the catalytic hydroprocessing of heavy oil model compounds and heavy oil. The reaction conditions were the same as those in Example 1, and the reaction results are shown in Tables 1 and 2.

[0032] Example 4:

[0033] 0.1326 g of vanadyl acetylacetonate was weighed and dissolved in 30 ml of acetone to obtain a vanadium source precursor solution. 0.2355 g of dimethyl disulfide was weighed and dissolved in 30 ml of acetone to obtain a sulfur source precursor solution. The vanadium source and sulfur source solutions were mixed, and 0.0096 g of citric acid was added to the resulting mixed solution to obtain a VS 4 precursor slurry, in which the elemental molar ratio of S / V was 10.0 and the molar ratio of organic acid / V was 0.1. The obtained VS 4 precursor solution was transferred to a high-pressure reactor. The temperature was raised to 200 °C and crystallized for 2 h. After cooling to room temperature, the pressure was released, and the product was taken out, centrifuged, washed three times with ethanol to obtain a black product, and vacuum dried at 60 °C overnight. After cooling, a VS 4 hydrotreating catalyst was collected.

[0034] The catalyst prepared in this example was used for the catalytic hydroprocessing of heavy oil model compounds and heavy oil. The reaction conditions were the same as those in Example 1, and the reaction results are shown in Tables 1 and 2.

[0035] Example 5:

[0036] 0.1326 g of vanadyl acetylacetonate was weighed and dissolved in 30 ml of ethanol to obtain a vanadium source precursor solution. 0.5528 g of dibenzothiophene was weighed and dissolved in 30 ml of phenol to obtain a sulfur source precursor solution. The vanadium source and sulfur source solutions were mixed, and 0.0451 g of acetic acid was added to the resulting mixed solution to obtain a VS 4 precursor slurry, in which the elemental molar ratio of S / V was 6.0 and the molar ratio of organic acid / V was 1.5. The obtained VS 4 precursor solution was transferred to a high-pressure reactor. The temperature was raised to 160 °C and crystallized for 18 h. After cooling to room temperature, the pressure was released, and the product was taken out, centrifuged, washed three times with ethanol to obtain a black product, and vacuum dried at 60 °C overnight. After cooling, a VS 4 hydrotreating catalyst was collected.

[0037] The catalyst prepared in this example was used for the catalytic hydroprocessing of heavy oil model compounds and heavy oil. The reaction conditions were the same as those in Example 1, and the reaction results are shown in Tables 1 and 2.

[0038] Example 6:

[0039] Weigh 0.0829 g of vanadyl acetylacetonate and dissolve it in 30 ml of ethanol to obtain a vanadium source precursor solution. Weigh 0.3455 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 0.0282 g of acetic acid to the resulting mixed solution to obtain a VS 4 precursor slurry, in which the elemental molar ratio of S / V is 6.0 and the molar ratio of organic acid / V is 1.5. Transfer the obtained VS 4 precursor solution into a high-pressure reactor. Heat up to 160 °C and crystallize for 18 h. Cool down to room temperature, relieve the pressure, take out the product, centrifuge and wash it three times with ethanol to obtain a black product, and dry it under vacuum at 60 °C overnight. After cooling down, collect the obtained VS 4 hydrotreating catalyst.

[0040] During the heavy oil hydrotreating reaction, 30 g of heavy oil is used, the addition amount of the catalyst is 0.05 wt.% of the heavy oil, the reaction temperature is 450 °C, and the reaction is carried out for 2 h under a hydrogen reaction pressure of 10 MPa. The reaction activity results are shown in Table 2.

[0041] Example 7:

[0042] Weigh 0.4144 g of vanadyl acetylacetonate and dissolve it in 30 ml of ethanol to obtain a vanadium source precursor solution. Weigh 1.7275 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 0.1409 g of acetic acid to the resulting mixed solution to obtain a VS 4 precursor slurry, in which the elemental molar ratio of S / V is 6.0 and the molar ratio of organic acid / V is 1.5. Transfer the obtained VS 4 precursor solution into a high-pressure reactor. Heat up to 160 °C and crystallize for 18 h. Cool down to room temperature, relieve the pressure, take out the product, centrifuge and wash it three times with ethanol to obtain a black product, and dry it under vacuum at 60 °C overnight. After cooling down, collect the obtained VS 4 hydrotreating catalyst.

[0043] During the heavy oil hydrotreating reaction, 30 g of heavy oil is used, the addition amount of the catalyst is 0.1 wt.% of the heavy oil, the reaction temperature is 425 °C, and the reaction is carried out for 6 h under a hydrogen reaction pressure of 12 MPa. The reaction activity results are shown in Table 2.

[0044] Example 8:

[0045] Weigh 0.5801 g of vanadyl acetylacetonate and dissolve it in 30 ml of ethanol to obtain a vanadium source precursor solution. Weigh 2.4185 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 0.1973 g of acetic acid to the resulting mixed solution to obtain a VS 4Precursor slurry, in which the elemental molar ratio of S / V is 6.0 and the molar ratio of organic acid / V is 1.5. The obtained VS 4 The precursor solution was transferred to a high-pressure reactor. The temperature was raised to 160 °C and crystallized for 18 h. After cooling to room temperature, the pressure was released, and the product was taken out, centrifuged, washed three times with ethanol to obtain a black product, and vacuum dried at 60 °C overnight. After cooling, VS was collected 4 Hydrogenation catalyst.

[0046] In the heavy oil catalytic hydrogenation reaction, 30 g of heavy oil was used, the addition amount of the catalyst was 0.4 wt.% of the heavy oil, the reaction temperature was 375 °C, and the reaction was carried out for 8 h under a hydrogen reaction pressure of 16 MPa. The reaction activity results are shown in Table 2.

[0047] Example 9:

[0048] 0.8288 g of vanadyl acetylacetonate was weighed and dissolved in 30 ml of ethanol to obtain a vanadium source precursor solution. 3.4552 g of dibenzothiophene was weighed and dissolved in 30 ml of phenol to obtain a sulfur source precursor solution. The vanadium source and sulfur source solutions were mixed, and 0.2818 g of acetic acid was added to the obtained mixed solution to obtain VS 4 Precursor slurry, in which the elemental molar ratio of S / V is 6.0 and the molar ratio of organic acid / V is 1.5. The obtained VS 4 The precursor solution was transferred to a high-pressure reactor. The temperature was raised to 160 °C and crystallized for 18 h. After cooling to room temperature, the pressure was released, and the product was taken out, centrifuged, washed three times with ethanol to obtain a black product, and vacuum dried at 60 °C overnight. After cooling, VS was collected 4 Hydrogenation catalyst.

[0049] In the heavy oil catalytic hydrogenation reaction, 30 g of heavy oil was used, the addition amount of the catalyst was 0.5 wt.% of the heavy oil, the reaction temperature was 350 °C, and the reaction was carried out for 12 h under a hydrogen reaction pressure of 20 MPa. The reaction activity results are shown in Table 2.

[0050] Comparative example:

[0051] 0.3082 g of vanadyl protochlorophyllin was weighed and dissolved in 30 ml of dodecane to obtain a vanadium source precursor solution. 0.2523 g of thiophene was weighed and dissolved in 30 ml of decalin to obtain a sulfur source precursor solution. The vanadium source and sulfur source solutions were mixed, and 0.1451 g of acetic acid was added to the obtained mixed solution to obtain VS 4 Precursor solution, in which the elemental molar ratio of S / V is 6.0 and the molar ratio of acetic acid / V is 1.5. The obtained VS 4The precursor solution was transferred into a high-pressure reactor, heated to 160 °C for crystallization for 18 h. After cooling to room temperature, the pressure was released and the product was taken out, centrifuged, washed three times with ethanol to obtain a black product, and vacuum-dried at 60 °C overnight. After cooling, the hydrogenation catalyst was collected.

[0052] From Figure 4 the XRD pattern of the hydrogenation catalyst prepared in the comparative example, it can be seen that the catalyst obtained in the comparative example does not have the VS 4 structure, but is mainly V 5 S 4 . It was used in the catalytic hydrogenation reaction of heavy oil model compounds and heavy oil. The reaction conditions were the same as those in Example 1, and the reaction results are shown in Tables 1 and 2. The hydrogenation activity of the VS 4 catalyst prepared in the comparative example was much lower than that of the catalyst of the present invention.

[0053] Table 1 Hydrogenation activity of the heavy oil model compound of the vanadium tetrasulfide hydrogenation catalyst prepared in the present invention.

[0054]

[0055] Table 2 Heavy oil hydrogenation activity of the vanadium tetrasulfide hydrogenation catalyst prepared in the present invention.

[0056]

[0057] Table 3 High-vanadium heavy oil hydrogenation stability of the vanadium tetrasulfide hydrogenation catalyst prepared in Example 5.

[0058]

[0059]

[0060] The VS 4 catalyst obtained in the present invention has excellent catalytic hydrogenation performance for heavy oil. The preparation method of the present invention can solve the problems of sulfur loss in heavy oil hydrogenation catalysts and catalyst deactivation caused by surface metal deposition, and realize the rapid and efficient hydro-upgrading of heavy oil.

Claims

1. A preparation method of a vanadium tetrasulfide catalyst for heavy oil hydrogenation, characterized in that, it comprises the following steps: (1) Dissolve a vanadium source in an organic solvent to form a vanadium source precursor solution; The vanadium source used is one or a mixture of two or more of vanadium triisopropoxide, dicyclopentadienyl vanadium dichloride, cyclopentadienyl vanadium tetracarbonyl, and vanadyl acetylacetonate; (2) Dissolve an organic sulfur source in an organic solvent to form a sulfur source precursor solution; (3) After mixing the obtained vanadium source and sulfur source precursor solutions, an organic acid is added to obtain a VS 4 precursor slurry; (4) VS 4 After the precursor pulp is liquefied into liquid crystal, it is separated and dried to obtain VS 4 Hydrogenation catalyst 2. The preparation method according to claim 1, characterized in that: The organic solvent used for the vanadium source is one or a mixture of two or more of ethanol, acetone, isopropanol, and cyclohexane; the concentration of the vanadium source in the saturated alkane solvent is 0.01 mol / L to 0.10 mol / L.

3. The preparation method according to claim 1, characterized in that: The organic sulfur source precursor used is one or a mixture of two or more of thioethers, disulfides, thiols, and thiophene-based organic sulfides.

4. The preparation method according to claim 1 or 3, characterized in that: The organic solvent used for the organic sulfur source is one or a mixture of two or more of ethanol, acetone, benzene, phenol, tetralin, and decalin; the concentration of the organic sulfur source in the organic solvent is 0.04 mol / L to 1.00 mol / L.

5. The preparation method according to claim 3, characterized in that: The thioether is one or a mixture of two or more of C1-C5 alkyl thioether compounds; The disulfide is one or a mixture of two or more of C1-C3 alkyl disulfides; The thiol is one or a mixture of two or more of C1-C8 alkyl thiols; The thiophene-based organic sulfide is one or a mixture of two or more of thiophene, benzothiophene, and dibenzothiophene.

6. The preparation method according to claim 1, characterized in that: VS of step (3) 4 The molar ratio of S / V in the precursor slurry is 4.0 to 10.0, preferably 5.0 to 7.0, and more preferably 6.

0.

7. The preparation method according to claim 1, characterized in that: The organic acid used is one or a mixture of two or more of formic acid, acetic acid, oxalic acid, citric acid, and ethylenediaminetetraacetic acid having reducibility; VS in step (3) 4 The molar ratio of the organic acid to V in the precursor slurry is 0.1 to 4.0, preferably 1.0 to 2.0, and more preferably 1.

5.

8. The preparation method according to claim 1, characterized in that: VS in step (4) 4 The liquid crystal temperature of the precursor slurry is 100 to 200 °C, and the crystallization time is 2 to 72 hours; preferably, the temperature is 140 to 180 °C and the time is 12 to 24 hours.

9. A vanadium tetrasulfide catalyst for heavy oil hydrogenation prepared by the preparation method according to any one of claims 1-8.

10. A vanadium tetrasulfide catalyst according to claim 9 can be used to catalyze the hydro-upgrading reaction of heavy oil with high vanadium (V content greater than 100 ppm), and has excellent catalytic hydrogenation stability.

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