A hydrogenation catalyst and its preparation method and application

Abstract

The present invention belongs to the technical field of catalysts, and specifically relates to a hydrogenation catalyst and a preparation method and application thereof; the preparation method comprises the following steps: S1: spraying an auxiliary agent solution on a carrier under stirring, aging, drying, and obtaining a catalyst intermediate; the auxiliary agent comprises molybdate and polyhydroxy alcohol; the carrier comprises an alumina carrier; S2: spraying a potassium ruthenate solution on the catalyst intermediate under stirring, standing, drying, and obtaining the hydrogenation catalyst; the mass ratio of the potassium ruthenate solution to the catalyst intermediate is 0.4 to 1:1; the potassium ruthenate solution contains 1wt% to 2wt% ruthenium; the spraying rate is 100 to 600mL / min. The prepared hydrogenation catalyst is an eggshell-type catalyst, the auxiliary agent is first loaded on the surface of the carrier, and highly dispersed ruthenium is loaded as an active metal later, the active metal utilization rate is high, the catalytic efficiency of the catalyst hydrogenation reaction is high, and the reaction controllability is high.

Description

Technical Field

[0001] The invention belongs to the technical field of catalysts, and specifically relates to a hydrogenation catalyst and a preparation method and application thereof. Background Art

[0002] One of the major ways to obtain cyclohexane and cyclohexene is to use the benzene hydrogenation process. The active metals used in the benzene hydrogenation process are usually platinum, ruthenium, cobalt, nickel, etc.; cobalt and nickel as active metals are generally less active; and although the precious metals platinum and ruthenium have good activity, they are expensive, and the corresponding catalysts produced have a low cost-effectiveness. The reaction carried out in the benzene hydrogenation process is a solid-liquid-gas three-phase reaction. When the pore size of the carrier is too small, or the active component is not on the surface of the carrier but in the inner pore, it will lead to low utilization of active metals and reduced catalyst cost-effectiveness. Moreover, when the product of the hydrogenation reaction stays in the inner pores of the carrier for too long and cannot be quickly desorbed, the situation where cyclohexene is produced but cyclohexane is finally produced may occur, and the reaction is difficult to control and the selectivity is poor. Summary of the invention

[0003] Therefore, in order to overcome the defects of low utilization rate of active metals on the catalyst used in the benzene hydrogenation process in the prior art, excessive presence of active metals in the pores of the carrier, making it difficult to desorb the reaction products and difficult to control the overall reaction, a hydrogenation catalyst, a preparation method and application thereof are provided.

[0004] To this end, the present invention provides the following technical solutions.

[0005] The present invention provides a method for preparing a hydrogenation catalyst, comprising the following steps: S1: spraying an auxiliary agent solution onto a carrier under stirring, aging, and drying to obtain a catalyst intermediate; the auxiliary agent comprises molybdate and a polyhydroxy alcohol; and the carrier comprises an alumina carrier; S2: spraying a potassium ruthenate solution onto the catalyst intermediate under stirring, standing, and drying to obtain the hydrogenation catalyst; the mass ratio of the potassium ruthenate solution to the catalyst intermediate is 0.4 to 1:1; the potassium ruthenate solution contains 1 wt% to 2 wt% of ruthenium; and the spraying rate is 100 to 600 mL / min.

[0006] Optionally, in the additive solution, the concentration of molybdate is 1 wt% to 10 wt%, and the concentration of polyhydroxy alcohol is 1 wt% to 4 wt%.

[0007] Optionally, the mass ratio of the carrier to the auxiliary agent solution is 1:1-2.

[0008] Optionally, the potassium ruthenate solution is alkaline; optionally, the pH of the potassium ruthenate solution is ≥14; further optionally, the pH of the potassium ruthenate solution is adjusted using potassium hydroxide.

[0009] Optionally, in S2, the method for preparing the potassium ruthenate solution includes: mixing ruthenium element and potassium hydroxide, and calcining them in an oxygen-containing atmosphere to obtain a ruthenium precursor; and adding water to the ruthenium precursor to obtain the potassium ruthenate solution.

[0010] Optionally, the mass ratio of the ruthenium element to the base is 1:2-10.

[0011] Optionally, the calcination temperature is 400-800° C. and the calcination time is 2-10 hours.

[0012] Optionally, air is introduced so that the roasting is carried out in an oxygen-containing atmosphere; optionally, the flow rate of the introduced air is 80 to 150 mL / min.

[0013] Optionally, in S1, the aging time is 2 to 24 hours and the aging is carried out at room temperature.

[0014] Optionally, in S1, the drying temperature is 90-130° C. and the drying time is 2-8 hours.

[0015] Optionally, in S1, the spraying rate is 100 to 600 mL / min.

[0016] Optionally, in S1, the stirring rate is 30 to 50 rpm.

[0017] Optionally, in S2, the stirring rate is 30 to 50 rpm.

[0018] Optionally, in S2, the standing time is 2 to 24 hours; the standing time can be carried out at room temperature.

[0019] Optionally, in S2, the drying temperature is 90-130° C. and the drying time is 2-8 hours.

[0020] Optionally, the alumina support comprises a macroporous alumina support; Optionally, the pore volume of the macroporous alumina is ≥ 0.5 cm 3 / g, pore size ≥8nm; further optionally, the pore volume of the macroporous alumina is 0.5-1.0cm 3 / g, pore size is 8.0~30.0nm.

[0021] Optionally, the molybdate includes at least one of zinc molybdate, iron molybdate and nickel molybdate.

[0022] Optionally, the polyhydric alcohol includes at least one of ethylene glycol, glycerol, and pentaerythritol.

[0023] The present invention also provides a hydrogenation catalyst prepared by the above preparation method.

[0024] Optionally, the content of ruthenium in the hydrogenation catalyst is 0.1 wt% to 10 wt%.

[0025] Optionally, the outer side of the hydrogenation catalyst includes a ruthenium shell, and the thickness of the ruthenium shell is 0.1 to 2.5 mm.

[0026] The present invention also provides the use of the above hydrogenation catalyst in a benzene hydrogenation process; optionally, the equipment used in the benzene hydrogenation process includes a fixed bed.

[0027] The beneficial effects of the present invention are:

[0028] The present invention provides a method for preparing a hydrogenation catalyst, comprising the following steps: S1: spraying an auxiliary agent solution onto a carrier, aging, and drying to obtain a catalyst intermediate; the auxiliary agent comprises molybdate and polyhydroxy alcohol; the carrier comprises an alumina carrier; S2: spraying a potassium ruthenate solution onto the catalyst intermediate under stirring, standing, and drying to obtain the hydrogenation catalyst; the mass ratio of the potassium ruthenate solution to the catalyst intermediate is 0.4-0.8:1; the potassium ruthenate solution contains 1wt%-2wt% ruthenium; the spraying rate is 100-600mL / min. The obtained hydrogenation catalyst is an eggshell-type catalyst, the auxiliary agent is first loaded on the carrier surface, and highly dispersed ruthenium is loaded as an active metal later, the active metal utilization rate is high, the catalytic efficiency of the catalyst hydrogenation reaction is high, and the reaction controllability is high.

[0029] In alumina carrier, the surface Al3+, O 2-The coordination number of the two ions is lower than that in the bulk phase, so there are vacancies on the surface, which is the main source of hydroxyl groups on the surface of alumina. The polyhydroxy alcohol in the additive also contains a large number of hydroxyl groups. These two hydroxyl groups with similar properties will form a strong bond through interaction. The polyhydroxy alcohol loaded on the surface of the carrier can be used as a weak reducing agent. When the potassium ruthenate solution is sprayed on the catalyst intermediate, the polyhydroxy alcohol and potassium ruthenate react in situ to generate ruthenium particles and are fixed in situ, so that the ruthenium as an active metal on the hydrogenation catalyst is tightly combined with the carrier, and after drying, a dense ruthenium shell is formed, which has good stability. In addition, during the preparation, when the polyhydroxy alcohol and potassium ruthenate react in situ, the molybdate loaded on the alumina carrier together with the polyhydroxy alcohol will be wrapped on the generated ruthenium to inhibit the strong adsorption of hydrogen, thereby enhancing the activity of the catalyst and improving the hydrogenation activity of the catalyst during use; at the same time, the molybdate can also block some holes in the carrier and prevent the active metal ruthenium from entering the holes. Loading the auxiliary agent solution onto the carrier by spraying can make the molybdate and polyhydroxy alcohol in the auxiliary agent uniformly loaded on the carrier surface, providing uniform reaction sites for the subsequent loading of ruthenium. Adding potassium ruthenate by spraying, and controlling the spraying rate, the mass ratio of potassium ruthenate solution to the carrier, and the concentration of ruthenium in the potassium ruthenate solution can improve the dispersion of ruthenium on the carrier surface and improve the utilization rate of active metals.

[0030] In the preparation method of the hydrogenation catalyst provided by the present invention, in S2, the preparation method of the potassium ruthenate solution includes: mixing ruthenium element and alkali, and roasting in an oxygen-containing atmosphere to obtain a ruthenium precursor; adding water to the ruthenium precursor to obtain the potassium ruthenate solution. Since potassium ruthenate is unstable in nature, and the price of commercially available potassium ruthenate or potassium perruthenate is too expensive, it is not suitable for large-scale industrial use; it is preferred to use ruthenium element and alkali to prepare potassium ruthenate solution, which is relatively low in price and is prepared on the spot, thereby avoiding the deterioration of potassium ruthenate. DETAILED DESCRIPTION

[0031] The following examples are provided for a better understanding of the present invention, but are not intended to limit the best mode of implementation, nor to limit the content and protection scope of the present invention. Any product identical or similar to the present invention obtained by anyone under the inspiration of the present invention or by combining the features of the present invention with other prior arts shall fall within the protection scope of the present invention.

[0032] If no specific experimental steps or conditions are specified in the examples, the conventional experimental steps or conditions described in the literature in the field can be used. If no manufacturer is specified for the reagents or instruments used, they are all conventional reagent products that can be obtained commercially.

[0033] Experimental drugs:

[0034] Macroporous alumina: Baiyang Chemical Technology Co., Ltd., batch 202402, pore volume ≥ 0.5 cm 3 / g, pore size>8nm

[0035] Example 1

[0036] This embodiment provides a hydrogenation catalyst and a preparation method thereof, comprising the following steps:

[0037] (1) An aqueous solution of additives with a zinc molybdate concentration of 1 wt% and a pentaerythritol concentration of 1 wt% was prepared, and macroporous alumina was used as a carrier with a carrier and an additive solution mass ratio of 1:1. The carrier was stirred at a stirring speed of 30 rpm, and the additive solution was sprayed thereon at a spray rate of 300 mL / min. The catalyst was then aged at room temperature for 2 h and dried at 120° C. for 4 h to obtain a catalyst intermediate.

[0038] (2) Ruthenium powder and potassium hydroxide are mixed in a mass ratio of 1:4, air is introduced at a flow rate of 100 mL / min, and calcined at 400° C. for 2 h to obtain a ruthenium precursor, and water is added to the obtained ruthenium precursor until the obtained potassium ruthenate solution contains 1.5 wt % ruthenium and the pH is ≥14.

[0039] (3) The catalyst intermediate prepared in (1) was sprayed with a potassium ruthenate solution at a stirring speed of 30 rpm, the mass ratio of the potassium ruthenate solution to the catalyst intermediate being 1:1, and the spraying rate being 300 mL / min; after the spraying was completed, the mixture was allowed to stand at room temperature for 4 h, and then dried at 120° C. for 4 h to obtain the hydrogenation catalyst.

[0040] The ruthenium content in the catalyst was tested by ICP and found to be 0.94 wt %. The thickness of the ruthenium shell was tested by microscope and found to be 1.2 mm.

[0041] Example 2

[0042] This embodiment provides a hydrogenation catalyst and a preparation method thereof, which differs from Embodiment 1 only in that the mass ratio of ruthenium powder to potassium hydroxide in step (2) is 1:6. The ruthenium content in the catalyst is 0.92wt% as measured by ICP, and the thickness of the ruthenium shell is 1.4mm as measured by microscope.

[0043] Example 3

[0044] This embodiment provides a hydrogenation catalyst and a preparation method thereof, which differs from Embodiment 1 only in that the mass ratio of ruthenium powder to potassium hydroxide in step (2) is 1:10. The ruthenium content in the catalyst is 0.91wt% as measured by ICP, and the thickness of the ruthenium shell is 1.6mm as measured by microscope.

[0045] Example 4

[0046] This embodiment provides a hydrogenation catalyst and a preparation method thereof, which differs from the embodiment 1 only in that the calcination is performed at 600° C. The ruthenium content in the catalyst is 0.94 wt % as measured by ICP, and the thickness of the ruthenium shell is 1.4 mm as measured by microscope.

[0047] Example 5

[0048] This embodiment provides a hydrogenation catalyst and a preparation method thereof, which differs from the embodiment 1 only in that, in step (1), the aging time is 20 hours. The ruthenium content in the catalyst is 0.94 wt % as measured by ICP, and the thickness of the ruthenium shell is 2.0 mm as measured by microscope.

[0049] Example 6

[0050] This embodiment provides a hydrogenation catalyst and a preparation method thereof, comprising the following steps:

[0051] (1) Prepare an auxiliary agent solution with a concentration of 1 wt% of iron molybdate and a concentration of 4 wt% of propylene glycol, use macroporous alumina as a carrier, and use it in a mass ratio of carrier to auxiliary agent solution of 1:2. Stir the carrier at a stirring speed of 50 rpm, spray the auxiliary agent solution thereon at a spray rate of 600 mL / min, then age it at room temperature for 2 h, and dry it at 90° C. for 8 h to obtain a catalyst intermediate.

[0052] (2) Ruthenium powder and potassium hydroxide are mixed in a mass ratio of 1:2, air is introduced at a flow rate of 80 mL / min, and calcined at 800° C. for 2 h to obtain a ruthenium precursor, and water is added to the obtained ruthenium precursor until the obtained potassium ruthenate solution contains 1 wt% of ruthenium and has a pH ≥ 14.

[0053] (3) The catalyst intermediate prepared in (1) was sprayed with a potassium ruthenate solution at a stirring speed of 50 rpm, the mass ratio of the potassium ruthenate solution to the catalyst intermediate being 1:1, and the spraying rate being 600 mL / min; after the spraying was completed, the mixture was allowed to stand at room temperature for 24 h, and then dried at 90° C. for 8 h to obtain the hydrogenation catalyst.

[0054] The ruthenium content in the catalyst was tested by ICP and found to be 0.94 wt %. The thickness of the ruthenium shell was tested by microscope and found to be 2.2 mm.

[0055] Example 7

[0056] This embodiment provides a hydrogenation catalyst and a preparation method thereof, comprising the following steps:

[0057] (1) Prepare an auxiliary agent solution with a nickel molybdate concentration of 10 wt% and an ethylene glycol concentration of 1 wt%, use macroporous alumina as a carrier, and use it in a mass ratio of carrier to auxiliary agent solution of 1:1, stir the carrier at a stirring speed of 30 rpm, spray the auxiliary agent solution thereon at a spray rate of 100 mL / min, then age at room temperature for 24 h, and dry at 130° C. for 2 h to obtain a catalyst intermediate.

[0058] (2) Ruthenium powder and potassium hydroxide are mixed in a mass ratio of 1:10, air is introduced at a flow rate of 150 mL / min, and calcined at 400° C. for 10 h to obtain a ruthenium precursor. Water is added to the obtained ruthenium precursor until the obtained potassium ruthenate solution contains 2 wt% of ruthenium and has a pH ≥14.

[0059] (3) The catalyst intermediate prepared in (1) was sprayed with a potassium ruthenate solution at a stirring speed of 30 rpm, the mass ratio of the potassium ruthenate solution to the catalyst intermediate being 0.4:1, and the spraying rate being 100 mL / min; after the spraying was completed, the mixture was allowed to stand at room temperature for 2 h, and then dried at 130° C. for 2 h to obtain the hydrogenation catalyst.

[0060] The ruthenium content in the catalyst was tested by ICP and was found to be 0.90 wt %. The thickness of the ruthenium shell was tested by microscope and was found to be 1.8 mm.

[0061] Comparative Example 1

[0062] This comparative example provides a hydrogenation catalyst and a preparation method thereof, which is different from Example 1 only in that, in step (3), the mass ratio of the potassium ruthenate solution to the catalyst intermediate is 0.3:1.

[0063] Comparative Example 2

[0064] This comparative example provides a hydrogenation catalyst and a preparation method thereof, which is different from Example 1 only in that, in step (3), the mass ratio of the potassium ruthenate solution to the catalyst intermediate is 1.1:1.

[0065] Comparative Example 3

[0066] This comparative example provides a hydrogenation catalyst and a preparation method thereof, which is different from Example 1 only in that in step (3), the spraying rate is 700 mL / min.

[0067] Comparative Example 4

[0068] This comparative example provides a hydrogenation catalyst and a preparation method thereof, which is different from Example 1 only in that in step (3), the spraying rate is 50 mL / min.

[0069] Comparative Example 5

[0070] This comparative example provides a hydrogenation catalyst and a preparation method thereof, which is different from Example 1 only in that, in step (2), water is added to the obtained ruthenium precursor until the obtained potassium ruthenate solution contains 2.5 wt % of ruthenium.

[0071] Comparative Example 6

[0072] This comparative example provides a hydrogenation catalyst and a preparation method thereof, which is different from Example 1 only in that, in step (2), water is added to the obtained ruthenium precursor until the obtained potassium ruthenate solution contains 0.9 wt % of ruthenium.

[0073] Comparative Example 7

[0074] This comparative example provides a hydrogenation catalyst and a preparation method thereof, which is different from Example 1 only in that, in step (1), when preparing the auxiliary agent solution, an equal amount of zinc cobaltate is used instead of zinc molybdate.

[0075] Comparative Example 8

[0076] This comparative example provides a hydrogenation catalyst and a preparation method thereof, which is different from Example 1 only in that, in step (1), when preparing the auxiliary agent solution, an equal amount of ethanol is used instead of polyhydroxy alcohol.

[0077] Comparative Example 9

[0078] This comparative example provides a hydrogenation catalyst and a preparation method thereof, which differs from Example 1 only in that step (3) is to immerse the catalyst intermediate in a potassium ruthenate solution, wherein the mass ratio of the potassium ruthenate solution to the catalyst intermediate is 1:1, immerse for 5 hours, and dry at 120° C. for 4 hours to obtain a hydrogenation catalyst.

[0079] Comparative Example 10

[0080] This comparative example provides a hydrogenation catalyst and a preparation method thereof, which is different from Example 1 only in that, in step (2), an equal amount of sodium hydroxide is used instead of potassium hydroxide.

[0081] Test Example 1

[0082] Take 1g of each hydrogenation catalyst prepared in the embodiment and the comparative example, and put them into a single tube reactor respectively. The single tube reactor can simulate a fixed bed environment. Hydrogen is introduced into the single tube reactor so that the catalyst contacts hydrogen for reduction reaction. The temperature of the reduction reaction is 450°C, the time is 20h, and the hydrogen pressure is 0.5MPa. After the catalyst is reduced, 300mL of thiophene-free benzene is added thereto through a high-pressure tank. At 140°C and 5.0MPa hydrogen pressure, the timing sampling is started, the oil phase components are analyzed by gas chromatography, and the efficiency of benzene conversion to cyclohexene is calculated. The results are shown in Table 1. It can be seen that the hydrogenation catalyst prepared by the preparation method of the present invention in the embodiment has a benzene conversion efficiency much higher than that of the hydrogenation catalyst prepared in the comparative example without using the preparation parameters specified in the present invention.

[0083] Table 1

[0084] catalyst <![CDATA[Benzene conversion efficiency (g / h·g cat )]]> Example 1 260 Example 2 252 Example 3 243 Example 4 236 Example 5 255 Example 6 233 Example 7 256 Comparative Example 1 159 Comparative Example 2 202 Comparative Example 3 220 Comparative Example 4 151 Comparative Example 5 122 Comparative Example 6 211 Comparative Example 7 185 Comparative Example 8 193 Comparative Example 9 185 Comparative Example 10 122

[0085] Test Example 2

[0086] Take 1g of the hydrogenation catalyst prepared in Example 1, put them into a single tube reactor respectively, and introduce hydrogen into the reactor so that the catalyst contacts with hydrogen for reduction reaction. The temperature of the reduction reaction is 450°C, the time is 20h, and the hydrogen pressure is 0.5MPa. After the catalyst is reduced, 300mL of thiophene-free benzene is added thereto through a high-pressure tank. At 140°C and 5.0MPa hydrogen pressure, start timing sampling, analyze the oil phase components by gas chromatography, calculate the efficiency of benzene conversion to cyclohexene, and test once every 24 hours. The results are shown in Table 2. It can be seen that in the long-term test, the conversion efficiency of the hydrogenation catalyst prepared in Example 1 of the present invention does not decrease significantly, and the service life is long.

[0087] Table 2

[0088] Test time / hour <![CDATA[Benzene conversion efficiency (g / h·g cat )]]> 24 260 48 262 72 259 96 258 120 260 144 258 168 258

[0089] Test Example 3

[0090] Take 1g of the hydrogenation catalyst prepared in the embodiment and the comparative example, respectively, and put them into a single tube reactor, and introduce hydrogen into the reactor to contact the catalyst with hydrogen for reduction reaction. The temperature of the reduction reaction is 450°C, the time is 20h, and the hydrogen pressure is 0.5MPa. After the catalyst is reduced, 300mL of thiophene-free benzene is added thereto through a high-pressure tank, and the timing sampling is started at 140°C and 5.0MPa hydrogen pressure. The oil phase components are analyzed by gas chromatography to calculate the selectivity of benzene to cyclohexene. The results are shown in Table 3. It can be seen that the hydrogenation catalyst prepared in the embodiment has a significantly better selectivity for cyclohexene in the benzene hydrogenation reaction than the comparative example.

[0091] Table 3

[0092]

[0093]

[0094] Obviously, the above embodiments are merely examples for clear explanation, and are not intended to limit the implementation methods. For those skilled in the art, other different forms of changes or modifications can be made based on the above description. It is not necessary and impossible to list all the implementation methods here. The obvious changes or modifications derived therefrom are still within the protection scope of the invention.

Claims

1. A method for preparing a hydrogenation catalyst, characterized in that: The steps include: S1: spraying the additive solution onto the carrier under stirring, aging, and drying to obtain a catalyst intermediate; The auxiliary agent includes molybdate and polyhydroxy alcohol; The carrier comprises an alumina carrier; S2: spraying a potassium ruthenate solution onto the catalyst intermediate under stirring, allowing the catalyst intermediate to stand, and drying the catalyst to obtain the hydrogenation catalyst; The mass ratio of the potassium ruthenate solution to the catalyst intermediate is 0.4 to 1:1; The potassium ruthenate solution contains 1wt% to 2wt% ruthenium; The spraying rate is 100-600 mL / min.

2. The preparation method according to claim 1, characterized in that: In the additive solution, the concentration of molybdate is 1wt% to 10wt%, and the concentration of polyhydroxy alcohol is 1wt% to 4wt%; And / or, the mass ratio of the carrier to the auxiliary agent solution is 1:1-2; And / or, the potassium ruthenate solution is alkaline; optionally, the pH of the potassium ruthenate solution is ≥14; further optionally, the pH of the potassium ruthenate solution is adjusted using potassium hydroxide.

3. The preparation method according to claim 1 or 2, characterized in that: In S2, the preparation method of the potassium ruthenate solution includes: mixing ruthenium element and potassium hydroxide, and calcining them in an oxygen-containing atmosphere to obtain a ruthenium precursor; and adding water to the ruthenium precursor to obtain the potassium ruthenate solution.

4. The preparation method according to claim 3, characterized in that: The mass ratio of the ruthenium element to the base is 1:2-10; and / or, the calcination temperature is 400-800° C. and the calcination time is 2-10 hours; And / or, air is introduced so that the roasting is carried out in an oxygen-containing atmosphere; optionally, the flow rate of the introduced air is 80 to 150 mL / min.

5. The preparation method according to any one of claims 1 to 4, characterized in that: In S1, the aging time is 2 to 24 hours; And / or, in S1, the drying temperature is 90-130° C. and the drying time is 2-8 hours; And / or, in S1, the spraying rate is 100 to 600 mL / min; And / or, in S1, the stirring rate is 30 to 50 rpm.

6. The preparation method according to any one of claims 1 to 5, characterized in that: In S2, the stirring rate is 30 to 50 rpm; And / or, in S2, the standing time is 2 to 24 hours; And / or, in S2, the drying temperature is 90-130° C. and the drying time is 2-8 hours.

7. The preparation method according to any one of claims 1 to 6, characterized in that: The alumina support comprises a macroporous alumina support; optionally, the pore volume of the macroporous alumina is ≥ 0.5 cm 3 / g, pore size ≥8nm; further optionally, the pore volume of the macroporous alumina is 0.5-1.0cm 3 / g, pore size is 8.0~30.0nm; And / or, the molybdate includes at least one of zinc molybdate, iron molybdate and nickel molybdate; And / or, the polyhydric alcohol includes at least one of ethylene glycol, glycerol, and pentaerythritol.

8. A hydrogenation catalyst obtained by the preparation method according to any one of claims 1 to 7.

9. The hydrogenation catalyst according to claim 8, characterized in that The content of ruthenium in the hydrogenation catalyst is 0.1wt% to 10wt%; And / or, the outer side of the hydrogenation catalyst comprises a ruthenium shell, and the thickness of the ruthenium shell is 0.1 to 2.5 mm.

10. Use of the hydrogenation catalyst according to claim 8 or 9 in a benzene hydrogenation process; Optionally, the equipment used in the benzene hydrogenation process includes a fixed bed.

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