Vanadium disulfide hydrogenation catalyst as well as preparation and application thereof

Abstract

The invention discloses a preparation method of a vanadium disulfide (VS2) hydrogenation catalyst. The preparation method of the VS2 catalyst comprises the following steps: dissolving a porphyrin vanadium source precursor in a saturated alkane solvent to form a vanadium source precursor solution; dissolving an organic sulfur source precursor in an organic solvent to form a sulfur source precursor solution; mixing the molybdenum source solution and the sulfur source solution, and adding organic amine to obtain a VS2 precursor solution; and crystallizing the VS2 precursor solution, separating to form a black product, and fully drying to obtain the VS2 hydrogenation catalyst. The obtained VS2 catalyst has excellent high-vanadium heavy oil catalytic hydrogenation stability. The preparation method provided by the invention can solve the inactivation problem caused by metal deposition on the surface of the heavy oil hydrogenation catalyst, and realizes high-efficiency and high-economy hydrogenation lightening of the high-vanadium heavy oil.

Description

Technical field:

[0001] The invention relates to a method for preparing a vanadium disulfide hydrogenation catalyst, belonging to a catalyst preparation technology in the technical field of industrial catalysis. Background Art

[0002] With the continuous growth of global 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 extensive attention in academia and industry. 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. It has become a powerful technical means to achieve efficient conversion of 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 complex component in heavy oil, and its molecular structure contains a large number of polycyclic aromatic hydrocarbons and heteroatoms (such as nitrogen, sulfur, oxygen, nickel, vanadium, etc.). Asphaltene is the most unstable component in heavy oil, which is easy to coke during processing and seriously poison the catalyst.

[0003] For heavy oil raw materials, the vanadium element can reach up to 1200μg / g, mainly concentrated in asphaltene. In the process of oil processing, vanadium compounds in asphaltene are very harmful to the catalysts of heavy oil catalytic cracking and hydrotreating. Vanadium compounds in oil usually exist in the form of porphyrin organometallic complexes. In the process of catalytic cracking, organometallic complexes are prone to decomposition and release a large amount of metal vanadium ions, which are deposited on the catalyst, which can reduce the activity of the catalyst at the least and poison and deactivate the catalyst at the worst (Petrochemical Corrosion and Protection, 2012, 29, 1-4).

[0004] The hydrogenation catalysts used in heavy oil hydrogenation technology are mostly Fe-based or Mo-based catalysts (Fuel, 2021, 288, 119686; Energy Fuels, 2019, 33, 7917-7949). The deposition of V on their surfaces will lead to their deactivation. Therefore, it is very necessary to develop new high-stability hydrogenation catalysts. Summary of the invention

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

[0006] The present invention provides a method for preparing a vanadium disulfide hydrogenation catalyst, which is obtained by the following steps:

[0007] (1) dissolving at least one of vanadium source precursors such as vanadium oxide, octaethylporphine vanadium oxide, tetraphenylporphine vanadium oxide in at least one solvent of saturated straight-chain alkane, saturated cycloalkane, and aromatic hydrocarbon to form a vanadium source precursor solution;

[0008] (2) Dissolve at least one of thioethers, disulfides, mercaptans, and thiophene-based organic sulfur source precursors in the oil product in at least one organic solvent such as ethanol, acetone, benzene, ether, phenol, tetralin, and decalin to form a sulfur source precursor solution;

[0009] (3) After mixing the obtained vanadium source and sulfur source precursor solution, add at least one organic amine such as fatty amine, alkanolamine, and amide to obtain a VS 2 precursor solution. The molar ratio of S / V in the VS 2 precursor solution is 1.0 to 4.0, preferably 2.0 to 3.0. 2 The molar ratio of organic amine / V in the VS precursor solution is 0.5 to 3.0, preferably 1.0 to 2.0.

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

[0011] The VS 2 hydrotreating catalyst prepared by the present invention has excellent catalytic hydrogenation stability in the hydro-upgrading reaction of high-vanadium heavy oil. When performing the catalytic hydrogenation reaction of a heavy oil model compound, the solvent used is 30 ml of tridecane, the addition amount of the catalyst is 2.5 wt.%, the reaction temperature is 350 °C, and the reaction is carried out for 4 h under a hydrogen reaction pressure of 8.0 MPa. When using heavy oil with an API gravity less than 22.3 as the raw material for the catalytic hydrogenation reaction, the heavy oil used is 30 g, the addition amount of the catalyst is 0.05% to 0.35% of the heavy oil, the reaction temperature is 350 to 450 °C, and the reaction is carried out for 2 to 12 h under a hydrogen reaction pressure of 10.0 to 20.0 MPa. The reaction activity results are shown in Table 2. The heavy oil hydrotreating stability results of the catalyst are shown in Table 3.

[0012] The present invention has the following advantages and effects compared with the prior art:

[0013] (1) According to the appendix Figure 1 and 3 it can be seen that the VS 2 catalyst prepared by the present invention is a catalyst with a two-dimensional layered structure, and the VS 2The interlayer spacing of the nanosheets is 0.576 nm. The synthesis system adopted in the present invention precisely simulates the vanadium precipitation and deposition reaction system in the hydro-upgrading reaction of high-vanadium heavy oil. A vanadium complex with a porphyrin structure similar to the vanadium structure in two-dimensional layered asphaltene is used as the vanadium source precursor, the organic sulfur-containing compounds contained in the oil are used as the sulfur source precursor, and organic amines are introduced to simulate the organic matter generated from the remaining porphyrin structure after vanadium removal in heavy oil after vanadium removal from asphaltene. This design can provide consistent crystallization conditions for the vanadium precipitated in heavy oil, so that the precipitated vanadium generates highly active VS 2 Hydrogenation catalyst.

[0014] (2) The VS prepared in the present invention 2 has a microflower morphology with a diameter of 3 - 4 μm. This VS 2 microflower is assembled by the aggregation of VS 2 nanosheets. When the prepared VS 2 catalyst is used in the hydro-upgrading reaction of high-vanadium heavy oil, the vanadyl porphyrin in the heavy oil reacts with the organic sulfur heteroatom compound and then deposits on the surface of the microflower of the VS 2 catalyst to form a new VS 2 island-shaped high-hydrogenation activity catalyst. The development of this preparation method effectively solves the problem that vanadium precipitation and deposition on the catalyst surface in heavy oil cover the active sites of the catalyst and cause deactivation.

[0015] (3) The VS 2 catalyst obtained in the present invention has excellent lipophilic properties and a two-dimensional layered structure similar to the unit sheet of asphaltene. As shown in the attached Figure 1 figure, the contact angle of the oily solvent of the VS 2 catalyst prepared in the present invention is 9°, indicating that the catalyst has extremely excellent lipophilic characteristics. This characteristic ensures that the VS 2 hydrogenation catalyst can fully contact with asphaltene and carry out an efficient hydrogenation reaction, thereby realizing the island-shaped precipitation of asphaltene vanadium on its surface. BRIEF DESCRIPTION OF THE DRAWINGS

[0016] Figure 1 XRD spectrum of the VS 2 hydrogenation catalyst obtained in Example 1.

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

[0018] Figure 3 TEM photograph of the VS 2 hydrogenation catalyst obtained in Example 1.

[0019] Figure 4 Contact angle photograph of the VS 2 hydrogenation catalyst obtained in Example 1.

[0020] Figure 5 VS obtained from the comparative example 2 XRD pattern of the hydrofining catalyst Detailed implementation manners

[0021] To further illustrate the present invention, the following implementation examples are listed, but the scope of the present invention is not limited thereby.

[0022] Example 1

[0023] Weigh 0.3082 g of vanadium protoporphyrin oxide and dissolve it in 30 ml of dodecane to obtain a vanadium source precursor solution. Weigh 0.0841 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 0.0927 g of dodecylamine to the resulting mixed solution to obtain a VS 2 precursor solution, in which the elemental molar ratio of S / V is 2.0 and the organic amine / V molar ratio is 1.0. Transfer the obtained VS 2 precursor solution into a high-pressure reactor. After purging with nitrogen three times, introduce hydrogen to 2.0 MPa. Heat up to 320 °C and crystallize for 4 h. Cool down to room temperature, relieve the pressure, take out the product, perform centrifugal separation, wash the obtained solid with ethanol three times to obtain a black product, and dry it in vacuum at 60 °C overnight. After cooling down, collect to obtain a VS 2 hydrofining catalyst

[0024] Appendix Figure 1 It can be seen that the diffraction peaks in the XRD pattern of VS 2 at the angles of 15.4, 32.1, 35.7, 45.2, 57.1 and 69.3 degrees respectively correspond to the (001), (100), (011), (012), (103) and (201) crystal planes of VS 2 . The diffraction peaks of the VS 2 sample match well with the standard peaks of the PDF card (PDF: 89-1640) of the two-dimensional layered VS 2 with a hexagonal structure. From the appendix Figure 2 it can be known that the VS 2 prepared by the present invention has a micro-flower morphology with a diameter of 3-4 μm, and this VS 2 micro-flower is assembled by agglomeration of VS 2 nano-sheets. From the appendix Figure 3 it can be known that the VS 2 prepared by the present invention is a two-dimensional layered structure catalyst with an interlayer spacing of 0.576 nm. As shown in appendix Figure 4 , the contact angle of the VS 2 catalyst prepared by the present invention with an oily solvent is 9°, which is far less than 90°, indicating that the catalyst has extremely excellent lipophilic properties.

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

[0026] When the catalytic hydrogenation reaction of the heavy oil model compound phenanthrene was carried out, the solvent used was 30 ml of tridecane, 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.

[0027] When the catalytic hydrogenation reaction of heavy oil was carried out, 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 catalytic hydrogenation reaction of heavy oil was recovered by extraction with heptane 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.

[0028] Example 2:

[0029] 0.3082 g of vanadyl protochlorophyll was weighed and dissolved in 30 ml of ethylcyclohexane to obtain a vanadium source precursor solution. 0.0236 g of dimethyl disulfide was weighed and dissolved in 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 VS 2 precursor solution, in which the elemental molar ratio of S / V was 1.0 and the organic amine / V molar ratio was 0.5. The obtained VS 2 precursor solution was transferred into a high-pressure reaction kettle. After purging with nitrogen three times, hydrogen was introduced to 1.0 MPa. The temperature was raised to 200 °C and crystallized for 12 h. After cooling to room temperature, the pressure was released, and the product was taken out, centrifuged, and the obtained solid was washed three times with ethanol to obtain a black product, which was vacuum dried at 60 °C overnight. After cooling, a VS 2 hydrogenation catalyst was collected.

[0030] The catalyst prepared in this example 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.

[0031] Example 3:

[0032] 0.3398 g of vanadyl tetraphenylporphyrin was weighed and dissolved in 30 ml of toluene to obtain a vanadium source precursor solution. 0.0932 g of dimethyl sulfide 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 0.0451 g of dimethylamine was added to the obtained mixed solution to obtain a VS 2 precursor solution, in which the elemental molar ratio of S / V was 3.0 and the organic amine / V molar ratio was 2.0. The obtained VS 2The precursor solution was transferred into a high-pressure reactor. After purging with nitrogen three times, hydrogen was introduced to 5.0 MPa. The temperature was raised to 400 °C for crystallization for 0.5 h. After cooling to room temperature, the pressure was released and the product was taken out, followed by centrifugal separation. The obtained solid was washed three times with ethanol to obtain a black product, which was dried in vacuo at 60 °C overnight. After cooling, VS was collected. 2 Hydrogenation catalyst.

[0033] The catalyst prepared in this example 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.

[0034] Example 4:

[0035] 0.3398 g of vanadium(IV) oxide tetraphenylporphyrin was dissolved in 30 ml of butane to obtain a vanadium source precursor solution. 0.2684 g of benzothiophene was dissolved in 30 ml of phenol to obtain a sulfur source precursor solution. The vanadium source and sulfur source solutions were mixed, and 0.0676 g of dimethylamine was added to the resulting mixed solution to obtain a VS 2 precursor solution, in which the elemental molar ratio of S / V was 4.0 and the organic amine / V molar ratio was 3.0. The obtained VS 2 precursor solution was transferred into a high-pressure reactor. After purging with nitrogen three times, hydrogen was introduced to 3.0 MPa. The temperature was raised to 280 °C for crystallization for 6 h. After cooling to room temperature, the pressure was released and the product was taken out, followed by centrifugal separation. The obtained solid was washed three times with ethanol to obtain a black product, which was dried in vacuo at 60 °C overnight. After cooling, VS was collected. 2 Hydrogenation catalyst.

[0036] The catalyst prepared in this example 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.

[0037] Example 5:

[0038] 0.2664 g of vanadyl octaethylporphyrin was dissolved in 30 ml of cyclohexane to obtain a vanadium source precursor solution. 0.0777 g of ethanethiol was dissolved in 30 ml of acetone to obtain a sulfur source precursor solution. The vanadium source and sulfur source solutions were mixed, and 0.1119 g of triethanolamine was added to the resulting mixed solution to obtain a VS 2 precursor solution, in which the elemental molar ratio of S / V was 2.5 and the organic amine / V molar ratio was 1.5. The obtained VS 2 precursor solution was transferred into a high-pressure reactor. After purging with nitrogen three times, hydrogen was introduced to 2.5 MPa. The temperature was raised to 300 °C for crystallization for 2 h. After cooling to room temperature, the pressure was released and the product was taken out, followed by centrifugal separation. The obtained solid was washed three times with ethanol to obtain a black product, which was dried in vacuo at 60 °C overnight. After cooling, VS was collected. 2 Hydrogenation catalyst.

[0039] The catalyst prepared in this example 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.

[0040] Example 6:

[0041] 0.2664 g of octaethylporphyrinoxovanadium was weighed and dissolved in 30 ml of heptane to obtain a vanadium source precursor solution. 0.1842 g of dibenzothiophene 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 0.1348 g of octadecylamine was added to the resulting mixed solution to obtain a VS 2 precursor solution, in which the elemental molar ratio of S / V was 2.0 and the organic amine / V molar ratio was 1.0. The resulting VS 2 precursor solution was transferred into a high-pressure reactor. After purging with nitrogen three times, hydrogen was introduced to 2.0 MPa. The temperature was raised to 320 °C and crystallized for 4 h. After cooling to room temperature, the pressure was released, and the product was taken out, centrifuged, and the obtained solid was washed three times with ethanol to obtain a black product, which was vacuum dried at 60 °C overnight. After cooling, the hydrogenation catalyst was collected.

[0042] The catalyst prepared in this example 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.

[0043] Example 7:

[0044] 0.1926 g of vanadyl protochlorophyllin was weighed and dissolved in 30 ml of dodecane to obtain a vanadium source precursor solution. 0.0526 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 0.0579 g of dodecylamine was added to the resulting mixed solution to obtain a VS 2 precursor solution, in which the elemental molar ratio of S / V was 2.0 and the organic amine / V molar ratio was 1.0. The resulting VS 2 precursor solution was transferred into a high-pressure reactor. After purging with nitrogen three times, hydrogen was introduced to 2.0 MPa. The temperature was raised to 320 °C and crystallized for 4 h. After cooling to room temperature, the pressure was released, and the product was taken out, centrifuged, and the obtained solid was washed three times with ethanol to obtain a black product, which was vacuum dried at 60 °C overnight. After cooling, the VS 2 hydrogenation catalyst was collected.

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

[0046] Example 8:

[0047] Weigh 0.9631 g of vanadium proto-porphyrin oxide and dissolve it in 30 ml of dodecane to obtain a vanadium source precursor solution. Weigh 0.2628 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 0.2897 g of dodecylamine to the resulting mixed solution to obtain a VS 2 precursor solution, in which the elemental molar ratio of S / V is 2.0 and the molar ratio of organic amine / V is 1.0. Transfer the obtained VS 2 precursor solution into a high-pressure reactor. After purging with nitrogen three times, introduce hydrogen to 2.0 MPa. Heat up to 320 °C and crystallize for 4 h. Cool down to room temperature, relieve the pressure, take out the product, centrifuge, wash the obtained solid with ethanol three times to obtain a black product, and dry it under vacuum at 60 °C overnight. After cooling down, collect to obtain a VS 2 hydrogenation catalyst.

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

[0049] Example 9:

[0050] Weigh 1.3484 g of vanadium proto-porphyrin oxide and dissolve it in 30 ml of dodecane to obtain a vanadium source precursor solution. Weigh 0.3679 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 0.4056 g of dodecylamine to the resulting mixed solution to obtain a VS 2 precursor solution, in which the elemental molar ratio of S / V is 2.0 and the molar ratio of organic amine / V is 1.0. Transfer the obtained VS 2 precursor solution into a high-pressure reactor. After purging with nitrogen three times, introduce hydrogen to 2.0 MPa. Heat up to 320 °C and crystallize for 4 h. Cool down to room temperature, relieve the pressure, take out the product, centrifuge, wash the obtained solid with ethanol three times to obtain a black product, and dry it under vacuum at 60 °C overnight. After cooling down, collect to obtain a VS 2 hydrogenation catalyst.

[0051] During the heavy oil catalytic hydrogenation reaction, 30 g of heavy oil is used, the addition amount of the catalyst is 0.4 wt.% of the heavy oil, and the reaction is carried out at 375 °C under a hydrogen reaction pressure of 16 MPa for 8 h. The reaction activity results are shown in Table 2.

[0052] Example 10:

[0053] 1.9263 g of vanadium proto-porphyrin oxide was weighed and dissolved in 30 ml of dodecane to obtain a vanadium source precursor solution. 0.5256 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 0.5792 g of dodecylamine was added to the resulting mixed solution to obtain a VS 2 precursor solution, in which the elemental molar ratio of S / V was 2.0 and the molar ratio of organic amine / V was 1.0. The obtained VS 2 precursor solution was transferred into a high-pressure reactor. After purging with nitrogen three times, hydrogen was introduced to 2.0 MPa. The temperature was raised to 320 °C for crystallization for 4 h. After cooling to room temperature, the pressure was released and the product was taken out, centrifuged, and the obtained solid was washed three times with ethanol to obtain a black product, which was vacuum dried at 60 °C overnight. After cooling, the VS 2 hydrogenation catalyst was collected.

[0054] During the catalytic hydroprocessing of heavy oil, 30 g of heavy oil was used, the addition amount of the catalyst was 0.5 wt.% of the heavy oil, and the reaction was carried out at a reaction temperature of 350 °C and a hydrogen reaction pressure of 20 MPa for 12 h. The reaction activity results are shown in Table 2.

[0055] Comparative example:

[0056] 0.1326 g of vanadyl acetylacetonate was weighed and dissolved in 30 ml of ethanol to obtain a vanadium source precursor solution. 0.2764 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 0.0927 g of dodecylamine was added to the resulting mixed solution to obtain a VS 2 precursor slurry, in which the elemental molar ratio of S / V was 3.0 and the molar ratio of organic amine / V was 1.0. The obtained VS 2 precursor solution was transferred into a high-pressure reactor. After purging with nitrogen three times, hydrogen was introduced to 2.0 MPa. The temperature was raised to 320 °C for crystallization for 4 h. After cooling to room temperature, the pressure was released and the product was taken out, centrifuged, and washed three times with ethanol to obtain a black product, which was vacuum dried at 60 °C overnight. After cooling, the hydrogenation catalyst was collected.

[0057] It can be seen from the attached Figure 5 XRD that the comparative example could not prepare a pure-phase two-dimensional layered VS 2 catalyst, and the obtained product was a mixture of VS 2 , VS 4 , V 3 S 4 . The catalyst prepared in the comparative example was used for the catalytic hydroprocessing of heavy oil model compounds and heavy oil, and the reaction conditions were the same as those in Example 1. The reaction results are shown in Tables 1 and 2. Its catalytic hydroprocessing activity was far lower than that of the pure-phase VS 2 catalyst prepared in the example of the present invention.

[0058] Table 1 Hydrocracking activity of phenanthrene, a heavy oil model compound, over the vanadium disulfide hydrocracking catalyst prepared in the present invention.

[0059]

[0060] Table 2 Hydrocracking activity of heavy oil over the vanadium disulfide hydrocracking catalyst prepared in the present invention.

[0061]

[0062] Table 3 Hydrocracking stability of high-vanadium heavy oil over the vanadium disulfide hydrocracking catalyst prepared in Example 1.

[0063]

[0064] The VS 2 catalyst obtained in the present invention has excellent hydrocracking stability for high-vanadium heavy oil. The preparation method of the present invention can solve the deactivation problem caused by metal deposition on the surface of heavy oil hydrocracking catalysts, and achieve efficient and highly economical hydro-upgrading of high-vanadium heavy oil.

Claims

1. A preparation method of a vanadium disulfide hydrogenation catalyst, characterized in that, it comprises the following steps: (1) Dissolve a porphyrin vanadium source precursor in a saturated alkane solvent to form a vanadium source precursor solution; The porphyrin vanadium source precursor used is one or a mixture of two or more of vanadium protochlorophyllide, octaethylporphine oxovanadium, and tetraphenylporphine oxovanadium; (2) Dissolve an organic sulfur source precursor 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 amine is added to obtain a VS 2 precursor solution; (4) VS 2 After the precursor solution is crystallized in a hydrogen atmosphere, VS is separated and dried 2 Hydrogenation catalyst 2. The preparation method according to claim 1, characterized in that: The saturated alkane solvent used is one or a mixture of two or more of C4 - C12 saturated straight-chain alkanes, C6 - C14 saturated cycloalkanes, and C6 - C10 aromatic hydrocarbons; the concentration of the porphyrin vanadium source in the saturated alkane solvent is 0.01 mol / L - 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 in oils.

4. The preparation method according to claim 3, characterized in that: The thioether is one or two or more of C1 - C3 alkyl thioether compounds; The disulfide is one or two or more of C1 - C3 alkyl disulfides; The thiol is one or two or more of C1 - C4 alkyl thiols; The thiophene-based organic sulfides are one or two or more of thiophene, benzothiophene, and dibenzothiophene.

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

6. The preparation method according to claim 1, characterized in that: VS of step (3) 2 The molar ratio of S / V in the precursor solution is 1.0 to 4.0, preferably 2.0 to 3.0, more preferably 2.

5.

7. The preparation method according to claim 1, characterized in that: The organic amine used is one or a mixture of two or more of C1 - C20 aliphatic amines, alkanolamines, and amides.

8. The preparation method according to claim 1, characterized in that: VS in step (3) 2 The molar ratio of organic amine to V in the precursor solution is 0.5 to 3.0, preferably 1.0 to 2.0; VS in step (4) 2 The precursor solution is transferred into an autoclave and crystallized under a hydrogen atmosphere. The crystallization pressure is 1.0 to 5.0 MPa, the crystallization temperature is 200 to 400 °C, and the crystallization time is 0.5 to 12 hours; preferably, the pressure is 2.0 to 3.0 MPa, the temperature is 280 to 320 °C, and the time is 2 to 6 hours.

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

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

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