Hydrodesulfurization catalyst, method for preparing the same, and use thereof

Abstract

The application discloses a hydrodesulfurization catalyst and a preparation method and application thereof. The catalyst comprises a carrier and an organic hydrogenation active metal compound and an organic sulfur-containing compound, wherein the organic sulfur-containing compound is selected from at least one of substituted and / or functional group-containing benzothiophene sulfur-containing compounds, diphenylthiophene sulfur-containing compounds or naphthothiophene sulfur-containing compounds. The preparation method of the hydrodesulfurization catalyst comprises the following steps: preparing an impregnation solution containing the organic sulfur-containing compound and the organic hydrogenation active metal compound; impregnating the carrier with the impregnation solution, and drying to obtain the catalyst. The catalyst is used in a distillate hydrodesulfurization process, and can obviously improve deep hydrodesulfurization activity.

Description

Technical Field

[0001] This invention belongs to the field of hydrogenation technology, and specifically relates to a hydrodesulfurization catalyst, its preparation method, and its application in the hydrotreating of distillate oil. Background Technology

[0002] Sulfides in distillate oils have a significant negative impact on the performance of oil products and their subsequent processing capabilities, and are also a crucial limiting indicator in oil product environmental standards. For example, in gasoline and diesel products, the sulfur content is strictly limited to no more than 10 ppm, or even lower. This places high demands on the ultra-deep desulfurization performance of catalysts. Improving the deep hydrodesulfurization performance of catalysts is also one of the key research focuses in this field.

[0003] CN201811322030.9 discloses a method for preparing a hydrodesulfurization catalyst. The method involves loading active metals Co and Mo onto a support via impregnation, followed by drying to obtain a first-stage catalyst. This is then treated with a mixed aqueous solution of aluminum salt and organic acid to prepare a second-stage catalyst. The second-stage catalyst is then saturated with liquid olefins, followed by heat treatment to form coke, and finally, the heat-treated catalyst undergoes sulfidation treatment. The catalyst prepared by this method exhibits high selectivity and high stability, but it is not suitable for deep hydrodesulfurization of high-sulfur feedstocks.

[0004] CN106268916A discloses a hydrodesulfurization catalyst supported on a synthetic framework structure doped with heteroatoms, Cu. 2+ The MCM-41 catalyst is an active component consisting of a mixture of molybdenum dinitride (Mo2N), tungsten nitride (W2N), molybdenum carbide (Mo2C), and tungsten carbide (WC). This catalyst effectively retains the octane number of gasoline feedstock during hydrodesulfurization; however, its deep desulfurization effect is poor when processing components with high sulfur content and heavier fractions.

[0005] CN107961795A discloses a hydrodesulfurization catalyst and a sulfide-state hydrodesulfurization catalyst, as well as their preparation method. The method involves impregnating a support with an impregnation solution containing a hydrodesulfurization active component and one or more organic compounds with a molecular weight less than 80, followed by drying to obtain the catalyst. During use, the catalyst bypasses the drying stage and is directly converted from an oxidized state to a sulfide-state catalyst using a programmed temperature sulfidation method. This catalyst can treat inferior distillate oils to improve their quality. However, in deep desulfurization zones, the catalyst exhibits poor hydrodesulfurization performance and is only suitable for shallow hydrodesulfurization. Summary of the Invention

[0006] To achieve deep desulfurization of distillate oil feedstock, this invention provides a hydrodesulfurization catalyst, its preparation method, and its application. The catalyst of this invention, when used in the hydrodesulfurization process of distillate oil, can significantly improve the deep hydrodesulfurization activity of the catalyst.

[0007] While studying the hydrodesulfurization mechanism of distillate oils, the inventors discovered that when the sulfur content in the oil is less than 40 ppm, the remaining sulfides are mainly benzothiophenes, dibenzothiophenes, and naphthothiophenes, and these sulfide molecules contain two or more alkyl substituent groups. These sulfides have significant steric hindrance, making them difficult to effectively adsorb near conventional active sites, thus hindering their removal. Further research revealed that introducing these difficult-to-remove organic sulfur-containing compounds and organic hydrogenation active metal compounds onto the hydrodesulfurization catalyst support achieves efficient adsorption and conversion of these compounds during the hydrodesulfurization process of distillate oils.

[0008] The first aspect of the present invention provides a hydrodesulfurization catalyst, comprising a support and an organic hydrogenation active metal compound and an organic sulfur-containing compound, wherein the organic sulfur-containing compound is selected from at least one of benzothiophene sulfur-containing compounds, dibenzothiophene sulfur-containing compounds, or naphthothiophene sulfur-containing compounds containing substituents and / or functional groups.

[0009] Furthermore, the active metal for hydrogenation is preferably a Group VIB metal or a Group VIII metal.

[0010] Furthermore, the Group VIB metal is preferably one or more of molybdenum and tungsten, preferably molybdenum, and the corresponding organic hydrogenation active metal compound is an organomolybdenum compound, preferably including one or more of molybdenum carbonyl, bis(ethylbenzene)molybdenum, triammonium tricarbonyl molybdenum, dialkyl dithiophosphate molybdenum, dialkyl dithiocarbamate molybdenum, cycloalkanoate molybdenum, and molybdenum acetylacetonate.

[0011] Furthermore, the Group VIII metals are preferably one or more of cobalt and nickel. The corresponding organohydrogenation active metal compounds are organonitrile compounds and organocobalt compounds.

[0012] Furthermore, the organonitrile preferably includes one or more of nickel acetylacetonate, nickel bis(dibutylaminodithiocarboxylic acid), nickel naphthenate, nickel tartrate, nickel dimethylglyoxime, and nickel citrate.

[0013] Furthermore, the organocobalt compound preferably includes one or more of cobalt acetylacetonate, cobalt isooctanoate, cobalt naphthenate, cobalt tartrate, cobalt dimethyl oxime, and cobalt citrate.

[0014] Furthermore, the organic sulfur-containing compound either contains at least two substituents, or at least two functional groups, or at least one substituent and at least one functional group. Preferably, the molecular weight of the organic sulfur-containing compound is below 400. Preferably, the organic sulfur-containing compound includes, but is not limited to, at least one of: 4,6-dimethyldibenzothiophene, 4,6-diethyldibenzothiophene, 3-methylbenzothiophene-2-carboxylic acid, methyl 3-aminobenzo[b]thiophene-2-carboxylic acid, 3-bromobenzothiophene-2-carboxylic acid, ethyl 2-amino-4,5,6,7-tetrahydrobenzothiophene-3-carboxylic acid, 2-acetyl-3-methylbenzothiophene, 2-amino-6-tert-pentyl-N-(2-methoxyphenyl)-4,5,6,7-tetrahydrobenzothiophene-3-carboxamide, 2-amino-6-tert-pentyl-N-cyclopentyl-4,5,6,7-tetrahydrobenzothiophene-3-carboxamide, and 2-hydroxymethylnaphtho[1,2-B]thiophene.

[0015] Furthermore, the support can be a conventional support for distillate oil hydrotreating catalysts, preferably a support for distillate oil hydrodesulfurization catalysts. The support is an inorganic refractory oxide support, selected from at least one of alumina, silicon oxide, amorphous silicon-aluminum, titanium-aluminum composite oxides, and titanium-silicon composite oxides, preferably an alumina-based support, with γ-alumina being the most preferred. The support may also contain conventional additives, such as one or more of silicon, phosphorus, boron, fluorine, and magnesium. The conventional additives in the support account for less than 5% by mass, based on elemental composition.

[0016] Furthermore, the carrier has the following properties: specific surface area of ​​170-380 m². 2 / g, preferably 210-360m 2 / g, pore volume 0.4-1.1m 3 / g, preferably 0.5-0.9m 3 / g.

[0017] Furthermore, based on the mass of the catalyst, the mass content of the organic sulfur-containing compound is 0.5%-8.0%, preferably 1.0%-6.0%.

[0018] Further, the mass of the product obtained by fully calcining the catalyst in air (calcination time 5-7 hours, calcination temperature 450-650℃) is recorded as the dry basis mass of the catalyst. The dry basis mass of the catalyst is 60%-90% of the total mass of the catalyst, preferably 65%-85%.

[0019] Furthermore, based on the dry weight of the catalyst, the mass content of the support is 50%-80%, preferably 45%-75%.

[0020] Furthermore, based on the dry weight of the catalyst, the mass content of Group VIB metals as oxides is 8%-22%, preferably 10%-18%, and the mass content of Group VIII metals as oxides is 1%-4%, preferably 1.5%-3%.

[0021] Furthermore, the catalyst contains an auxiliary metal, preferably copper. The auxiliary copper exists in the catalyst in the form of an organometallic copper compound, and more preferably, the organometallic copper compound includes one or more of copper naphthenate, copper acetylacetonate, copper 8-hydroxyquinoline, copper pinoresinate, copper methionine, and copper citrate.

[0022] Furthermore, based on the dry weight of the catalyst, the mass content of the auxiliary copper, calculated as copper oxide, is 0.5%-4.0%, preferably 0.8%-3.0%.

[0023] A second aspect of the present invention provides a method for preparing the above-mentioned hydrodesulfurization catalyst, comprising:

[0024] (1) Prepare an impregnation solution containing organic sulfur compounds and organic hydrogenated active metal compounds;

[0025] (2) The carrier is impregnated with the impregnation solution of step (1) and then dried to obtain the catalyst.

[0026] Furthermore, in step (1), the solvent used in the impregnation solution includes one or more of xylene, toluene, ethylbenzene, cyclohexane, acetone, tetrahydronaphthalene, decahydronaphthalene, and benzene.

[0027] Furthermore, in step (1), the concentration of organic sulfur compounds in the impregnation solution is 5g-200g / L, preferably 8g-180g / L.

[0028] Further, in step (1), the organic hydrogenation active metal compound in the impregnation solution is preferably an organomolybdenum compound, an organonitrile compound, and / or an organocobalt compound, wherein the concentration of the organomolybdenum compound is 0.1-4.0 mol / L, preferably 0.1-3.0 mol / L, and the concentration of the organonitrile compound and / or organocobalt compound is 0.02-2.0 mol / L, preferably 0.03-1.5 mol / L.

[0029] Furthermore, in step (1), the impregnation solution also contains an organocopper compound, the concentration of which is 0.01-1.0 mol / L, preferably 0.02-1.0 mol / L.

[0030] Furthermore, the impregnation in step (2) can be carried out using conventional impregnation methods, preferably equal-volume impregnation methods.

[0031] Further, in step (2), the drying temperature is 80-150℃, preferably 100-140℃, and the drying time is 2-10 hours, preferably 4.0-8.0 hours.

[0032] The third aspect of the present invention provides the application of the above-mentioned hydrodesulfurization catalyst in the hydrotreating of distillate oil.

[0033] Furthermore, in the aforementioned application, the catalyst is used as a hydrodesulfurization catalyst.

[0034] Furthermore, the distillate feedstock can be at least one of wax oil fraction and heavy diesel oil fraction. The wax oil fraction feedstock can be one or more of straight-run wax oil, coking wax oil, fluidized bed generated wax oil, and catalytic cracking heavy cycle oil. The heavy diesel oil fraction feedstock can be derived from one or more of straight-run diesel, catalytic cracking diesel, and coking diesel.

[0035] Further, the hydrogenation treatment conditions are as follows: reaction temperature 280-450℃, preferably 300-420℃; reaction pressure 2.0-18.0 MPa, preferably 4.0-16.0 MPa; hydrogen-to-oil volume ratio 300-1500, preferably 500-1300; and liquid hourly space velocity (LHSV) 0.3-4.0 h⁻¹. -1 Preferably 0.5-3.5h -1 .

[0036] Compared with the prior art, the present invention has the following advantages:

[0037] The catalyst of this invention introduces difficult-to-remove organic sulfur-containing compounds and organic hydrogenation active metal compounds onto a hydrodesulfurization catalyst support. This utilizes the pre-adsorption and site-occupancy effect of the difficult-to-remove organic sulfur-containing compounds and the effect of the plastic active phase. During the formation of the sulfidated active phase by the active metal, a catalytic space is created that can effectively adsorb and transform the difficult-to-remove organic sulfur-containing compounds. Simultaneously, the use of organometallic compounds allows the active metal to undergo sulfidation at low temperatures, which is more conducive to the rearrangement and plasticity of the active phase, thereby achieving efficient adsorption and removal of difficult-to-remove organic sulfur-containing compounds during the hydrodesulfurization of distillate oils.

[0038] The catalyst of this invention is particularly suitable for the hydrotreating of distillate oils (wax oil fractions and / or heavy diesel oil fractions), exhibiting high hydrodesulfurization activity, especially capable of ultra-deep hydrodesulfurization. Detailed Implementation

[0039] The present invention will be further described below with reference to embodiments, but it should be understood that the scope of protection of the present invention is not limited to the embodiments. In the present invention, unless otherwise expressly stated, percentages and contents are all expressed by mass.

[0040] The alumina support S-0 used in the following embodiments and comparative examples of this invention was prepared by the following method:

[0041] Weigh 3000.0g of alumina dry adhesive powder, add 30.0g of acetic acid, 50.0g of citric acid, 50.0g of sorbitol, 20.0g of guar gum powder, and 30.0g of cellulose, mix well, then add 2500.0g of an aqueous solution containing 2.0% nitric acid. After rolling for 20.0min, extrude the mixture using a cloverleaf perforated plate with a diameter of 1.8mm. Dry at 120℃ for 5.0h, then calcine at 600℃ for 5.0h. The calcined carrier is designated S-0. The pore properties of the S-0 carrier are as follows: specific surface area is 322m². 2 / g, pore volume is 0.81cm 3 / g.

[0042] Example 1

[0043] Weigh 5.0g of 4,6-dimethyldibenzothiophene, 30.0g of molybdenum carbonyl, 10.0g of nickel acetylacetonate, and 5.0g of copper acetylacetonate, and dissolve them in a mixed solution of 50ml toluene and 50ml acetone. The resulting solution is denoted as NQ-1.

[0044] Weigh 100g of S-0, impregnate S-0 with NQ-1, and dry at 120℃ for 5.0 hours. The resulting catalyst is denoted as Cat-1.

[0045] Example 2

[0046] Weigh 2.0g of 4,6-diethyldibenzothiophene, 40.0g of molybdenum acetylacetonate, 8.0g of nickel tartrate, and 8.0g of copper naphthenate, and dissolve them in 100ml of toluene solution. The resulting solution is denoted as NQ-2.

[0047] Weigh 100g of S-0, impregnate S-0 with NQ-2, and dry at 120℃ for 5.0 hours. The resulting catalyst is denoted as Cat-2.

[0048] Example 3

[0049] Weigh 6.0 g of 2-amino-6-tert-pentyl-N-(2-methoxyphenyl)-4,5,6,7-tetrahydrobenzothiophene-3-carboxamide, 35.0 g of bis(ethylphenyl)molybdenum, 10.0 g of cobalt acetylacetonate, and 8.0 g of 8-hydroxyquinoline copper, and dissolve them in 100 ml of tetrahydronaphthalene. The resulting solution is denoted as NQ-3.

[0050] Weigh 100g of S-0, impregnate S-0 with NQ-3, and dry at 120℃ for 5.0 hours. The resulting catalyst is denoted as Cat-3.

[0051] Example 4

[0052] Weigh 5.0g of 2-hydroxymethylnaphtho[1,2-B]thiophene, 30.0g of triamminetricarbonylmolybdenum, 10.0g of cobalt tartrate, and 15.0g of copper rosinate and dissolve them in 100ml of p-xylene. The resulting solution is denoted as NQ-4.

[0053] Weigh 100g of S-0, impregnate S-0 with NQ-4, and dry at 120℃ for 5.0 hours. The resulting catalyst is denoted as Cat-4.

[0054] Example 5

[0055] Weigh 5.0g of 4,6-dimethyldibenzothiophene, 30.0g of molybdenum carbonyl, and 10.0g of nickel acetylacetonate, and dissolve them in a mixed solution of 50ml toluene and 50ml acetone. The resulting solution is denoted as NQ-5.

[0056] Weigh 100g of S-0, impregnate S-0 with NQ-5, and dry at 120℃ for 5.0 hours. The resulting catalyst is denoted as Cat-5.

[0057] Example 6

[0058] Weigh 2.0g of 4,6-dimethyldibenzothiophene, 2.0g of 4,6-diethyldibenzothiophene, 2.0g of 3-methylbenzothiophene-2-carboxylic acid, 40.0g of molybdenum carbonyl, 13.0g of nickel acetylacetonate and 7.0g of copper acetylacetonate, and dissolve them in a mixed solution of 50ml toluene and 50ml acetone. The resulting solution is denoted as NQ-6.

[0059] Weigh 100g of S-0, impregnate S-0 with NQ-6, and dry at 120℃ for 5.0 hours. The resulting catalyst is denoted as Cat-6.

[0060] Comparative Example 1

[0061] Weigh 30.0g of molybdenum carbonyl, 10.0g of nickel acetylacetonate, and 5.0g of copper acetylacetonate, and dissolve them in a mixed solution of 50ml toluene and 50ml acetone. The resulting solution is denoted as DQ-1.

[0062] Weigh 100g of S-0, impregnate S-0 with DQ-1, and dry at 120℃ for 5.0 hours. The resulting catalyst is denoted as DCT-1.

[0063] Comparative Example 2

[0064] Weigh 35.0g of bis(ethylbenzene)molybdenum, 10.0g of cobalt acetylacetonate, and 8.0g of 8-hydroxyquinoline copper and dissolve them in 100ml of tetrahydronaphthalene. The resulting solution is denoted as DQ-2.

[0065] Weigh 100g of S-0, impregnate S-0 with DQ-2, and dry at 120℃ for 5.0 hours. The resulting catalyst intermediate is denoted as DCT-2.

[0066] Comparative Example 3

[0067] Weigh out 20.0g of ammonium heptamolybdate tetrahydrate, 12.0g of nickel nitrate hydrate, and 4.0g of anhydrous copper nitrate to prepare a solution, which is denoted as DQ-3.

[0068] Weigh 100g of S-0, impregnate S-0 with DQ-3, dry at 120℃ for 5.0 hours, and then calcine at 480℃ for 5.0 hours. The resulting catalyst intermediate is denoted as DM-3.

[0069] Weigh 5.0g of 4,6-dimethyldibenzothiophene and dissolve it in 100ml of toluene solution. The resulting impregnation solution is denoted as DNQ-3.

[0070] The catalyst obtained by impregnating DM-3 with DNQ-3 and drying it at 120°C for 5.0 hours is designated as DCT-3.

[0071] Comparative Example 4

[0072] Weigh out 20.0g of ammonium heptamolybdate tetrahydrate, 12.0g of cobalt nitrate hydrate, and 4.0g of anhydrous copper nitrate to prepare a solution, labeled DQ-4.

[0073] Weigh 100g of S-0, impregnate S-0 with DQ-4, dry at 120℃ for 5.0 hours, and then calcine at 480℃ for 5.0 hours. The resulting catalyst intermediate is denoted as DM-4.

[0074] Weigh 5.0g of 3-methylbenzothiophene-2-carboxylic acid and dissolve it in 100ml of toluene solution. The resulting impregnation solution is denoted as DNQ-4.

[0075] The catalyst intermediate obtained by impregnating DM-4 with DNQ-4 and drying at 120°C for 5.0 hours is designated as DCT-4.

[0076] Comparative Example 5

[0077] Weigh 5.0g benzothiophene, 30.0g molybdenum carbonyl, 10.0g nickel acetylacetonate, and 5.0g copper acetylacetonate, and dissolve them in a mixed solution of 50ml toluene and 50ml acetone. The resulting solution is denoted as DQ-5.

[0078] Weigh 100g of S-0, impregnate S-0 with DQ-5, and dry at 120℃ for 5.0 hours. The resulting catalyst is denoted as DCT-5.

[0079] Comparative Example 6

[0080] Weigh out 20.0g of ammonium heptamolybdate tetrahydrate, 12.0g of nickel nitrate hydrate, and 4.0g of anhydrous copper nitrate to prepare a solution labeled DQ-6.

[0081] Weigh 100g of S-0, impregnate S-0 with DQ-6, dry at 120℃ for 5.0 hours, and then calcine at 480℃ for 5.0 hours. The resulting catalyst intermediate is denoted as DCT-6.

[0082] Table 1. Composition of the catalysts obtained in each example.

[0083]

[0084]

[0085] Note in Table 1: The catalyst was calcined in air at a temperature of 550°C for 6 hours. The resulting product is denoted as catalyst dry basis.

[0086] Examples 7-12

[0087] Conventional wet vulcanization was performed on catalysts Cat-1, Cat-2, Cat-3, Cat-4, Cat-5, and Cat-6, respectively:

[0088] The sulfiding solution was a cyclohexane solution of dimethyl disulfide, with a dimethyl disulfide mass concentration of 5.0%. The sulfidation conditions were: a sulfidation solution flow rate of 2.0 ml / h·g catalyst, a sulfidation temperature of 350℃, a sulfidation time of 12 hours, a reaction pressure of 6.0 MPa, and a hydrogen flow rate of 30.0 N ml / min·g catalyst. The samples obtained after sulfidation were designated as Cat-1S, Cat-2S, Cat-3S, Cat-4S, Cat-5S, and Cat-6S, respectively.

[0089] Comparative Examples 7-12

[0090] Conventional wet vulcanization was performed on catalysts DCT-1, DCT-2, DCT-3, DCT-4, DCT-5, and DCT-6, respectively:

[0091] The sulfiding solution was a cyclohexane solution of dimethyl disulfide, with a dimethyl disulfide mass concentration of 5.0%. The sulfidation conditions were: a sulfidation solution flow rate of 2.0 ml / h·g catalyst, a sulfidation temperature of 350℃, a sulfidation time of 12 hours, a reaction pressure of 6.0 MPa, and a hydrogen flow rate of 30.0 N ml / min·g catalyst. The samples obtained after sulfidation were designated as DCT-1S, DCT-2S, DCT-3S, DCT-4S, DCT-5S, and DCT-6S, respectively.

[0092] Examples 13-18

[0093] Straight-run heavy diesel oil was used as feedstock, and hydrogenation evaluation experiments were conducted on Cat-1S, Cat-2S, Cat-3S, Cat-4S, Cat-5S, and Cat-6S, respectively. The properties of the heavy diesel oil are shown in Table 2.

[0094] Table 2 Properties of Heavy Diesel Oil

[0095] <![CDATA[Density / g·cm -3 > 0.833 H / C atomic ratio 1.72 Sulfur content, μg / g 16550 Monocyclic aromatic hydrocarbons wt% 18.9 Nitrogen content, μg / g 612 Bicyclic and above aromatic hydrocarbons wt% 11.4

[0096] The hydrogenation operating conditions were: reaction temperature 350℃, total reaction pressure 8.0 MPa, hydrogen-to-oil volume ratio 600:1, and liquid hourly space velocity (LHSV) 2.0 h⁻¹. -1 After 600 hours of reaction evaluation, the sulfur content in the hydrogenated oil was analyzed, and the results are shown in Table 3.

[0097] Comparative Examples 13-18

[0098] Heavy diesel oil was used as feedstock, and hydrogenation evaluation experiments were conducted on DCT-1S, DCT-2S, DCT-3S, DCT-4S, DCT-5S, and DCT-6S. The properties of the heavy diesel oil are shown in Table 2. The hydrogenation operating conditions were: reaction temperature 350℃, total reaction pressure 8.0 MPa, hydrogen-to-oil volume ratio 600:1, and liquid hourly space velocity 2.0 h⁻¹. -1 After 600 hours of reaction evaluation, the sulfur content in the hydrogenated oil was analyzed, and the results are shown in Table 3.

[0099] Table 3 Sulfur content in hydrotreated oils

[0100] Example 13 Cat-1S 2.4 Example 14 Cat-2S 2.0 Example 15 Cat-3S 2.6 Example 16 Cat-4S 1.8 Example 17 Cat-5S 3.9 Example 18 Cat-6S 1.3 Comparative Example 13 DCT-1S 24.3 Comparative Example 14 DCT-2S 22.8 Comparative Example 15 DCT-3S 20.1 Comparative Example 16 DCT-4S 19.0 Comparative Example 17 DCT-5S 17.9 Comparative Example 18 DCT-7S 26.8

[0101] As can be seen from the evaluation results in Table 3, the catalyst of the present invention has good hydrodesulfurization performance when processing heavy diesel oil components.

Claims

1. A hydrodesulfurization catalyst, comprising a support and an organic hydrogenation active metal compound and an organic sulfur-containing compound, wherein the organic sulfur-containing compound is selected from at least one of 4,6-dimethyldibenzothiophene, 4,6-diethyldibenzothiophene, 3-methylbenzothiophene-2-carboxylic acid, methyl 3-aminobenzo[b]thiophene-2-carboxylic acid, dibenzothiophene-2,8-diboronic acid, 3-bromobenzothiophene-2-carboxylic acid, ethyl 2-amino-4,5,6,7-tetrahydrobenzothiophene-3-carboxylic acid, 2-acetyl-3-methylbenzothiophene, 2-amino-6-tert-pentyl-N-(2-methoxyphenyl)-4,5,6,7-tetrahydrobenzothiophene-3-carboxamide, 2-amino-6-tert-pentyl-N-cyclopentyl-4,5,6,7-tetrahydrobenzothiophene-3-carboxamide, and 2-hydroxymethylnaphtho[1,2-B]thiophene; Based on the mass of the catalyst, the mass content of organic sulfur compounds ranges from 0.5% to 8.0%. The preparation method of the hydrodesulfurization catalyst includes: (1) Prepare an impregnation solution containing organic sulfur compounds and organic hydrogenated active metal compounds; (2) Impregnate the carrier with the impregnation solution of step (1), and then dry it to obtain the catalyst; The hydrogenation active metals are Group VIB and Group VIII metals.

2. The catalyst according to claim 1, characterized in that, The Group VIB metals are one or more of molybdenum and tungsten, and the Group VIII metals are one or more of cobalt and nickel.

3. The catalyst according to claim 2, characterized in that, The Group VIB metal is molybdenum.

4. The catalyst according to claim 1, characterized in that, The organic hydrogenation active metal compound is an organomolybdenum compound, an organonitrile compound, and / or an organocobalt compound.

5. The catalyst according to claim 4, characterized in that, The organomolybdenum compounds include one or more of molybdenum carbonyl, bis(ethylbenzene)molybdenum, triamminetricarbonylmolybdenum, dialkyldithiophosphate molybdenum, dialkyldithiocarbamate molybdenum, naphthenate molybdenum, and acetylacetonate molybdenum; the organonitrile compounds include one or more of nickel acetylacetonate, bis(dibutylaminodithiocarbamate) nickel, naphthenate nickel, nickel tartrate, dimethylglyoxime nickel, and nickel citrate; the organcobalt compounds include one or more of cobalt acetylacetonate, cobalt isooctanoate, cobalt naphthenate, cobalt tartrate, dimethylglyoxime cobalt, and cobalt citrate.

6. The catalyst according to claim 1, characterized in that, The carrier is an inorganic refractory oxide carrier, selected from at least one of alumina, silicon oxide, amorphous silicon-aluminum, titanium-aluminum composite oxide, and titanium-silicon composite oxide.

7. The catalyst according to claim 1, characterized in that, The carrier is an alumina-based carrier.

8. The catalyst according to claim 6, characterized in that, The carrier contains one or more of the conventional additives silicon, phosphorus, boron, fluorine, and magnesium.

9. The catalyst according to claim 6, characterized in that, The carrier has the following properties: specific surface area of ​​170-380 m² 2 / g, pore volume 0.4-1.1 m 3 / g.

10. The catalyst according to claim 9, characterized in that, The carrier has the following properties: specific surface area of ​​210-360 m² 2 / g, pore volume 0.5-0.9 m 3 / g.

11. The catalyst according to claim 1, characterized in that, Based on the mass of the catalyst, the mass content of organic sulfur compounds is 1.0%-6.0%.

12. The catalyst according to claim 1, characterized in that, Based on the dry weight of the catalyst, the mass content of the support is 50%-80%; And / or, based on the dry weight of the catalyst, the mass content of Group VIB metals as oxides is 8%-22%, and the mass content of Group VIII metals as oxides is 1%-4%.

13. The catalyst according to claim 12, characterized in that, Based on the dry weight of the catalyst, the mass content of the support is 45%-75%; And / or, based on the dry weight of the catalyst, the mass content of Group VIB metals as oxides is 10%-18%, and the mass content of Group VIII metals as oxides is 1.5%-3%.

14. The catalyst according to claim 1, characterized in that, The catalyst contains an auxiliary metal, which is copper, and the auxiliary copper exists in the catalyst in the form of an organometallic copper compound; based on the dry weight of the catalyst, the mass content of the auxiliary copper, calculated as copper oxide, is 0.5%-4.0%.

15. The catalyst according to claim 14, characterized in that, Organometallic copper compounds include one or more of copper naphthenate, copper acetylacetonate, copper 8-hydroxyquinoline, copper pinoresinate, copper methionine, and copper citrate.

16. The catalyst according to claim 14, characterized in that, Based on the dry weight of the catalyst, the mass content of the auxiliary copper, calculated as copper oxide, is 0.8%-3.0%.

17. A method for preparing the hydrodesulfurization catalyst according to any one of claims 1-16, comprising: (1) Prepare an impregnation solution containing organic sulfur compounds and organic hydrogenated active metal compounds; (2) The carrier is impregnated with the impregnation solution of step (1) and then dried to obtain the catalyst.

18. The preparation method according to claim 17, characterized in that, In step (1), the solvent used in the impregnation solution includes one or more of xylene, toluene, ethylbenzene, cyclohexane, acetone, tetrahydronaphthalene, decahydronaphthalene, and benzene.

19. The preparation method according to claim 17 or 18, characterized in that, In step (1), the organic hydrogenation active metal compound in the impregnation solution is an organomolybdenum compound, an organonitrile compound, and / or an organocobalt compound; And / or, in step (2), the drying temperature is 80-150°C and the drying time is 2-10 hours.

20. The preparation method according to claim 19, characterized in that, In step (1), the impregnation solution also contains an organic copper compound.

21. The preparation method according to claim 19, characterized in that, In step (2), the drying temperature is 100-140°C and the drying time is 4.0-8.0 hours.

22. The application of the hydrodesulfurization catalyst according to any one of claims 1-16 in the hydrotreating of distillate oil.

23. The application according to claim 22, characterized in that, The distillate feedstock is at least one of wax oil fraction and heavy diesel oil fraction.

24. The application according to claim 22, characterized in that, The hydrotreating conditions are as follows: reaction temperature 280-450℃, reaction pressure 2.0-18.0 MPa, hydrogen-to-oil volume ratio 300-1500, and liquid hourly space velocity (LHSV) 0.3-4.0 h⁻¹. -1 .

25. The application according to claim 24, characterized in that, The hydrotreating conditions are as follows: reaction temperature 300-420℃, reaction pressure 4.0-16.0 MPa, hydrogen-to-oil volume ratio 500-1300, and liquid hourly space velocity (LHSV) 0.5-3.5 h⁻¹. -1 .

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