Silicon support and method for preparing the same, and acetylene hydrogenation catalyst and method for preparing the same

Abstract

The application relates to the field of hydrogenation catalysts, and discloses a silicon carrier, a preparation method of the silicon carrier, an acetylene hydrogenation catalyst and a preparation method of the acetylene hydrogenation catalyst. The preparation method of the silicon carrier comprises the following steps: 1) mixing and stirring a first silicon ester, a second silicon ester and hydrochloric acid in the presence of water until a gelatinous product is obtained; and 2) aging the gelatinous product obtained in the step 1), wherein the first silicon ester is selected from one or more of the following: aminoethylaminopropyltriethoxysilane, aminomethylaminopropyltriethoxysilane, aminoethylaminomethyltriethoxysilane and aminoethylaminopropyltrimethoxysilane. The carrier does not need to be calcined in the preparation process, the preparation method is simple and easy to implement, the acetylene hydrogenation catalyst prepared from the carrier can realize complete conversion of acetylene at a lower temperature, and the acetylene hydrogenation catalyst has excellent acetylene selectivity.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of hydrogenation catalysts, in particular to a silicon carrier, a preparation method thereof, an acetylene hydrogenation catalyst and a preparation method thereof. BACKGROUND

[0002] Acetylene selective hydrogenation is an important research topic in petroleum chemical industry. The research results in the past decades show that the Pd-loaded acetylene hydrogenation catalyst has good activity and selectivity.

[0003] At present, the content of Pd in the Pd-loaded acetylene hydrogenation catalyst is generally 0.01-0.5 wt%. At the same time, in order to improve the dispersity of Pd and improve the electronic properties of Pd, researchers try to introduce various other metal components into the Pd acetylene hydrogenation catalyst system, such as Ag and Sn, etc.

[0004] In addition, in the Pd-loaded acetylene hydrogenation catalyst, the carrier also has an important influence on the catalytic performance. At present, the carriers used in industry mainly include Al2O3, SiO2, molecular sieve and CaCO3, etc., among which Al2O3 is the most widely used carrier, and researchers also try to modify the carrier to improve the catalytic performance of the acetylene hydrogenation catalyst.

[0005] Although the above-mentioned catalyst modification methods improve the activity of the catalyst to some extent, the acetylene hydrogenation catalyst still has the problems of high temperature required for complete conversion of acetylene and insufficient acetylene conversion rate and acetylene selectivity. SUMMARY

[0006] The purpose of the present application is to overcome the problems of high temperature required for complete conversion of acetylene and insufficient acetylene conversion rate and acetylene selectivity in the prior art, and to provide a silicon carrier and an acetylene hydrogenation catalyst prepared therefrom. The carrier does not need to be calcined in the preparation process, the preparation method is simple and easy to implement, and the acetylene hydrogenation catalyst prepared thereby can realize complete conversion of acetylene at a lower temperature, while having excellent acetylene selectivity.

[0007] In order to achieve the above-mentioned purpose, the present application provides a preparation method of a silicon carrier, which comprises: 1) mixing and stirring a first silicate, a second silicate and hydrochloric acid in the presence of water to a gel-like product;

[0008] 2) aging the gel-like product obtained in step 1),

[0009] wherein the first silicate is selected from one or more of aminoethylaminopropyltriethoxysilane, aminomethylaminopropyltriethoxysilane, aminoethylaminomethyltriethoxysilane and aminoethylaminopropyltrimethoxysilane.

[0010] Preferably, the first silicate, water, the second silicate and the aqueous hydrochloric acid solution are mixed and stirred to be gel-like.

[0011] Preferably, the first silicate is aminoethylaminopropyltriethoxysilane.

[0012] Preferably, the second silicate is selected from one or more of methyl orthosilicate, ethyl orthosilicate, propyl orthosilicate and butyl orthosilicate.

[0013] More preferably, the second silicate is ethyl orthosilicate.

[0014] Preferably, the concentration of the aqueous hydrochloric acid solution is 2-8 mol / L, more preferably 3-5 mol / L.

[0015] Preferably, the volume ratio of the first silicate to the second silicate is 1:1-10, preferably 1:2-8.

[0016] Preferably, the volume ratio of the aqueous hydrochloric acid solution to the second silicate is 1:1-10, preferably 1:8-10.

[0017] Preferably, the volume ratio of the water to the second silicate is 1:1-5, preferably 1:2-3.

[0018] Preferably, the aging condition comprises that the aging temperature is 5-55 ℃ and the aging time is 12-96 h, preferably 36-60 h.

[0019] More preferably, the aging condition comprises that the aging temperature is 20-40 ℃ and the aging time is 36-60 h.

[0020] Preferably, the method further comprises: 3) drying the aging product obtained in step 2);

[0021] Preferably, in step 3), the drying condition comprises that the drying temperature is 50-100 ℃ and the drying time is 4-12 h.

[0022] Preferably, the drying condition comprises that the drying temperature is 50-80 ℃ and the drying time is 6-10 h.

[0023] The second aspect of the present application provides a silicon carrier prepared by the preparation method of the first aspect of the present application.

[0024] The third aspect of the present application provides an ethyne hydrogenation catalyst, which comprises a carrier and an active metal component supported on the carrier, wherein the carrier is the silicon carrier of the second aspect of the present application.

[0025] Preferably, the active metal component is one or more of Pd, Pt, Mo, Co, Ni and Au, preferably Pd.

[0026] Preferably, the content of the active metal component is 0.1-1 wt%, preferably 0.2-0.7 wt% based on the total amount of the acetylene hydrogenation catalyst.

[0027] The fourth aspect of the present application provides a method for preparing an acetylene hydrogenation catalyst, wherein the method comprises:

[0028] 1) impregnating the carrier in an impregnation solution containing an active metal component;

[0029] 2) separating the carrier from the impregnation solution of step 1) and drying;

[0030] Preferably, the active metal component in step 1) is one or more of Pd, Pt, Mo, Co, Ni and Au, preferably Pd.

[0031] Preferably, the content of the active metal component in the impregnation solution in step 1) is such that the content of the active metal in the acetylene hydrogenation catalyst prepared is 0.1-1 wt%, preferably 0.2-0.7 wt%.

[0032] Preferably, the content of the active metal component in the impregnation solution is 0.02-0.2 g / L.

[0033] Preferably, the content of the active metal component in the impregnation solution is 0.03-0.12 g / L.

[0034] Preferably, the content of the active metal component in the impregnation solution is 0.03-0.12 g / L.

[0035] Preferably, the amount of the impregnation solution used is 40-80 mL, preferably 50-70 mL, per 1 g of the carrier.

[0036] Preferably, the impregnation conditions in step 1) include a temperature of 5-55°C, preferably 30-50°C, and a time of 1-5 h, preferably 2-4 h.

[0037] By the above technical solution, the silicon carrier obtained can make the dispersion of the active metal component on the carrier more uniform, especially can achieve high dispersion of Pd, and at the same time, the Pd is modified, thereby significantly improving the catalytic performance of the acetylene hydrogenation catalyst prepared.

[0038] The acetylene hydrogenation catalyst prepared using the silicon carrier in the present application can achieve 100% conversion of acetylene at a relatively low reaction temperature, and at the same time, can ensure that the ethylene selectivity is as high as 80% or more, and the catalytic performance of the catalyst is stable. DETAILED DESCRIPTION

[0039] The endpoints of the ranges and any values disclosed herein are not limited to the precise values recited as the exact dimensions are not considered critical for the purposes of the application. The ranges should be interpreted as being inclusive of the recited endpoints and any point or points within the ranges. For ranges having an upper and lower limit, the range includes any point or points between the upper and lower limits. For ranges having an upper limit, the range includes any point or points less than the upper limit. For ranges having a lower limit, the range includes any point or points greater than the lower limit.

[0040] The first aspect of the present application provides a method for preparing a silicon support, wherein the method comprises:

[0041] 1) mixing and stirring a first silicate, a second silicate and hydrochloric acid in the presence of water to form a gel;

[0042] 2) aging the gel obtained in step 1),

[0043] wherein the first silicate is selected from one or more of aminoethylaminopropyltriethoxysilane, aminomethylaminopropyltriethoxysilane, aminoethylaminomethyltriethoxysilane and aminoethylaminopropyltrimethoxysilane.

[0044] The inventors of the present application found that, by using the above method to prepare the silicon support, the dispersion of the active metal component on the support can be more uniform when the acetylene hydrogenation catalyst is prepared, especially the high dispersion of Pd can be achieved, thereby significantly improving the catalytic performance of the prepared acetylene hydrogenation catalyst, thus completing the present application.

[0045] According to the first aspect of the present application, preferably, mixing and stirring the first silicate, the second silicate and the aqueous hydrochloric acid in the presence of water can cause the first silicate and the second silicate to polymerize under stirring to form a gel, thereby obtaining the silicon support.

[0046] In the present application, preferably, the first silicate is aminoethylaminopropyltriethoxysilane. Thereby the performance of the prepared silicon support can be further ensured, and the catalytic performance of the acetylene hydrogenation catalyst is improved.

[0047] In the present application, the second silicate is not particularly limited and can be various silicates commonly used in the art, preferably, the second silicate is orthosilicate.

[0048] Preferably, the second silicate can be selected from one or more of methyl orthosilicate, ethyl orthosilicate, propyl orthosilicate and butyl orthosilicate; more preferably, the second silicate is ethyl orthosilicate. Thereby the performance of the prepared silicon support can be further ensured, and the catalytic performance of the acetylene hydrogenation catalyst is improved.

[0049] In the present application, the concentration of the aqueous hydrochloric acid solution is not particularly limited, and preferably, the concentration of the aqueous hydrochloric acid solution is 2-8 mol / L, more preferably 2-6 mol / L, and further preferably 3-5 mol / L, in order to further promote the full progress of the reaction.

[0050] In the present application, the first silicate and the second silicate need to be stirred to be gelatinous in the presence of water, which can provide a hydrolysis environment to ensure the smooth progress of the reaction of the first silicate and the second silicate.

[0051] According to the present application, preferably, in step 1), the volume ratio of the first silicate and the second silicate can be 1:1-10, and preferably 1:2-8. By controlling the amount of the two within the above range, it can be ensured that the silicon carrier of the present application is prepared smoothly, and the silicon carrier thus prepared can make the supported active metal component disperse more well when prepared into an acetylene hydrogenation catalyst, thereby improving the catalytic performance of the acetylene hydrogenation catalyst.

[0052] In the present application, the volume ratio of the aqueous hydrochloric acid solution and the second silicate can be 1:1-10, and preferably 1:8-10. Thus, the smooth progress of the hydrolysis of the first silicate and the second silicate can be better promoted.

[0053] In addition, in the present application, the volume ratio of the water and the second silicate can be 1:1-5, and preferably 1:2-3. By controlling the amount of the water within the above range, the smooth progress of the hydrolysis reaction can be ensured, which is beneficial to the preparation of the silicon carrier of the present application.

[0054] In addition, in the present application, the temperature of the stirring is not particularly limited, for example, the stirring can be carried out at 5-45℃, and preferably at 20-40℃.

[0055] Then, the obtained gelatinous product is aged. The conditions of the aging are not particularly limited, and preferably, the conditions of the aging include that the aging temperature is 5-55℃, and the aging time is 12-96h, and more preferably, the conditions of the aging include that the aging temperature is 20-40℃, and the aging time is 36-60h. By aging within the above conditions, a better skeleton structure can be formed, which ensures the performance of the prepared silicon carrier, thereby further ensuring the performance of the acetylene hydrogenation catalyst thus prepared.

[0056] In the present application, the preparation method of the silicon carrier further comprises: 3) a step of drying the aged product obtained in step 2).

[0057] In the present application, the washing is a routine operation in the art, which is not described here.

[0058] The drying can be carried out in a conventional manner in the art without particular limitation. In order to make the drying more thorough and obtain a better performance of the silicon support, the drying conditions can include a drying temperature of 50-100°C and a drying time of 4-12h; preferably, the drying conditions include a drying temperature of 50-80°C and a drying time of 6-10h.

[0059] The second aspect of the present application provides a silicon support prepared by the method of the first aspect of the present application, which can not only realize the high dispersion of the supported active metal component, especially Pd, but also modify the Pd to improve the hydrogenation performance of the prepared acetylene hydrogenation catalyst.

[0060] The third aspect of the present application provides an acetylene hydrogenation catalyst containing a support and an active metal component supported on the support, wherein the support is the silicon support of the second aspect of the present application.

[0061] According to the third aspect of the present application, the active metal component is one or more of Pd, Pt, Mo, Co, Ni and Au, preferably Pd.

[0062] According to a preferred embodiment of the present application, the active metal component is Pd. When the silicon support of the present application is used and Pd is supported on the support as the active metal component, the conversion rate of acetylene can reach 100% when the prepared catalyst is used for the catalytic hydrogenation reaction of acetylene, and the complete conversion of acetylene can be realized at a lower temperature while maintaining a high ethylene selectivity.

[0063] According to the present application, preferably, the content of the active metal can be 0.1-1wt%, preferably 0.2-0.7wt% based on the total amount of the catalyst. By controlling the content of the active metal in the above range, the catalytic performance of the obtained acetylene hydrogenation catalyst can be ensured on the basis of saving the preparation cost of the catalyst.

[0064] The fourth aspect of the present application provides a preparation method of an acetylene hydrogenation catalyst, which comprises:

[0065] 1) dipping the support into an impregnation solution containing an active metal component;

[0066] 2) separating the support from the impregnation solution of step 1) and drying;

[0067] wherein the support is the silicon support of the second aspect of the present application.

[0068] According to the fourth aspect of the present application, the active metal component is one or more of Pd, Pt, Mo, Co, Ni and Au, preferably Pd.

[0069] The active metal component in the impregnation solution can be added to the impregnation solution in a manner conventional in the art, for example, in the form of a chloride, nitrate, acetate, sulfate or the like of the active metal component, without any particular limitation.

[0070] In the present application, in order to further ensure the catalytic performance of the prepared catalyst, preferably, in step 1), the content of the active metal component in the impregnation solution is such that the content of the active metal in the prepared acetylene hydrogenation catalyst is 0.1-1% by weight, preferably 0.2-0.7% by weight.

[0071] In the present application, in order to ensure that the content of the active metal in the prepared acetylene hydrogenation catalyst is within the above range, the content of the active metal component in the impregnation solution during impregnation can be 0.02-0.2 g / L (calculated based on active metal ions), preferably the content of the active metal component in the impregnation solution is 0.03-0.12 g / L.

[0072] According to the present application, the amount of the impregnation solution used is 40-80 mL, preferably 50-70 mL, relative to 1 g of the carrier. In this way, the amount of the active metal component can be saved, the production cost can be reduced, at the same time, the prepared acetylene hydrogenation catalyst can achieve complete conversion of acetylene at a lower temperature, and the acetylene conversion rate can be ensured while improving the ethylene selectivity.

[0073] In the present application, the conditions for impregnation are not particularly limited and can be carried out using the impregnation methods commonly used in the art. For example, the conditions for impregnation can include a temperature of 5-55°C and a time of 1-5 h. In order to further improve the impregnation effect and obtain a catalyst with better performance, preferably, the conditions for impregnation include a temperature of 30-50°C and a time of 2-4 h.

[0074] In addition, in order to facilitate the impregnation and make the active component more uniformly loaded after impregnation, the impregnation can be carried out under stirring.

[0075] According to the fourth aspect of the present application, after impregnation is completed, in order to remove impurities in the obtained catalyst, the obtained impregnated acetylene hydrogenation catalyst is further filtered and washed. The method for filtering and washing is a conventional method in the art, which will not be described here.

[0076] Preferably, the impregnated catalyst is dried, and more preferably, the drying is vacuum drying, and the drying conditions include a drying temperature of 50-80℃ and a drying time of 8-20h.

[0077] According to a particularly preferred embodiment of the present application, when preparing the silicon carrier, the aminoethylaminopropyltriethoxysilane, the tetraethyl orthosilicate and the aqueous hydrochloric acid solution are mixed and stirred to be gelatinous in the presence of water to obtain a gelatinous product, wherein the volume ratio of the aminoethylaminopropyltriethoxysilane to the tetraethyl orthosilicate is 1:8-10, the concentration of the aqueous hydrochloric acid solution is 3-5mol / L, the volume ratio of the aqueous hydrochloric acid solution to the tetraethyl orthosilicate is 1:8-10, and the volume ratio of the water to the tetraethyl orthosilicate is 1:2-3.

[0078] Then, the obtained gelatinous product is aged at 20-40℃ for 36-60h, and then the aged product is filtered, washed and dried at 50-80℃ for 6-10h to obtain the silicon carrier of the present application.

[0079] Then, the silicon carrier prepared above is impregnated in the impregnation solution containing Pd to obtain an impregnated catalyst, and the impregnated catalyst is filtered, washed and dried to obtain the acetylene hydrogenation catalyst.

[0080] The present application will be described in detail by way of examples below. In the following examples, the raw materials used are all commercially available unless otherwise specified.

[0081] Example 1

[0082] 1) The tetraethyl orthosilicate, the water, the aqueous hydrochloric acid solution and the aminoethylaminopropyltriethoxysilane are mixed in a volume ratio of 10:4:1:2, wherein the concentration of the aqueous hydrochloric acid solution is 5mol / L, and the mixture is stirred to be gelatinous at 25℃;

[0083] 2) The gelatinous product obtained in step 1) is aged at 25℃ for 48h;

[0084] 3) The aged product obtained in step 2) is washed and dried at 60℃ for 6h to obtain the silicon carrier S1;

[0085] 4) 1.5g of the silicon carrier S1 is added into 90mL of a palladium chloride solution with a concentration of 0.033g / L (in terms of the weight of palladium ions, the same below), and the mixture is stirred and impregnated at 40℃ for 3h;

[0086] 5) The impregnated catalyst is filtered, washed and vacuum dried at 60℃ for 12h to obtain the acetylene hydrogenation catalyst C1.

[0087] Example 2

[0088] 1) Tetraethoxysilane, water, aqueous hydrochloric acid solution and aminoethylaminopropyltriethoxysilane were mixed in a volume ratio of 40:16:4:5, wherein the concentration of the aqueous hydrochloric acid solution was 4 mol / L, and stirred at 25°C until gelled;

[0089] 2) The gelled product obtained in step 1) was aged at 20°C for 60 h;

[0090] 3) The aged product obtained in step 2) was washed and dried at 50°C for 10 h to obtain a silicon carrier S2;

[0091] 4) 1.5 g of the silicon carrier S2 was added to 90 mL of a palladium chloride solution having a concentration of 0.05 g / L, and impregnated by stirring at 40°C for 3 h;

[0092] 5) The impregnated catalyst was filtered, washed and vacuum dried at 60°C for 12 h to obtain an acetylene hydrogenation catalyst C2.

[0093] Example 3

[0094] 1) Tetraethoxysilane, water, aqueous hydrochloric acid solution and aminoethylaminopropyltriethoxysilane were mixed in a volume ratio of 8:3:1:3, wherein the concentration of the aqueous hydrochloric acid solution was 3 mol / L, and stirred at 25°C until gelled;

[0095] 2) The gelled product obtained in step 1) was aged at 40°C for 36 h;

[0096] 3) The aged product obtained in step 2) was washed and dried at 80°C for 6 h to obtain a silicon carrier S3;

[0097] 4) 1.5 g of the silicon carrier S3 was added to 90 mL of a palladium chloride solution having a concentration of 0.066 g / L, and impregnated by stirring at 40°C for 3 h;

[0098] 5) The impregnated catalyst was filtered, washed and vacuum dried at 60°C for 12 h to obtain an acetylene hydrogenation catalyst C3.

[0099] Example 4

[0100] The procedure of Example 1 was followed, except that,

[0101] In step 4), the concentration of the palladium chloride solution was 0.083 g / L to obtain an acetylene hydrogenation catalyst C4.

[0102] Example 5

[0103] The procedure of Example 1 was followed, except that,

[0104] In step 4), the concentration of the palladium chloride solution was 0.1 g / L to obtain an acetylene hydrogenation catalyst C5.

[0105] Example 6

[0106] The method of Example 1 was followed, except that,

[0107] In Step 4), the concentration of the palladium chloride solution was 0.113 g / L, and ethyne hydrogenation catalyst C6 was obtained.

[0108] Test Example

[0109] 1) 0.5 g of the ethyne hydrogenation catalyst S1-S6 prepared in Examples 1-6 was charged into a glass reaction tube having an inner diameter of 4 mm after being pulverized into a catalyst particle having a mesh size of 40-60;

[0110] 2) H2 was introduced into the glass tube at a flow rate of 30 ml / min, and reduction was performed at 60°C for 90 min;

[0111] 3) Then, a mixed gas of H2 at a flow rate of 30 mL / min and C2H2 at a flow rate of 40 mL / min was introduced into the glass tube, and the temperature at which the ethyne conversion rate was 100% was measured.

[0112] The obtained product was analyzed by gas chromatography, and the results of the performance of the obtained catalyst are shown in Table 1.

[0113] Table 1

[0114] Catalyst Temperature at complete conversion of acetylene (°C) Conversion of acetylene (%) Selectivity to ethylene (%) C1 90 86.7 82.3 C2 100 100 82.4 C3 120 100 86.1 C4 120 100 84.3 C5 110 100 82.2 C6 130 100 86.3

[0115] As can be seen from the results of Table 1, when the ethyne hydrogenation catalyst is prepared using the silicon support prepared by the method of the present application, the ethyne conversion rate of 100% can be achieved, the temperature at which the ethyne is completely converted can be lowered, and the ethylene selectivity of 80% or more can be maintained.

[0116] The preferred embodiments of the present application have been described in detail above, but the present application is not limited thereto. Various simple modifications can be made to the technical solutions of the present application within the technical concept of the present application, including the combination of various technical features in any other suitable manner, and these simple modifications and combinations should also be considered as disclosed by the present application and fall within the protection scope of the present application.

Claims

1. An acetylene hydrogenation catalyst comprising a support and an active metal component supported on the support, characterized in that, The preparation method of the carrier comprises: 1) mixing and stirring the first silicate, the second silicate and hydrochloric acid in the presence of water to a gel state; 2) aging the gel product obtained in step 1), wherein the first silicate is aminoethylaminopropyltriethoxysilane, the second silicate is selected from one or more of methyl orthosilicate, ethyl orthosilicate, propyl orthosilicate and butyl orthosilicate, the volume ratio of the first silicate to the second silicate is 1:2-8, the active metal component is one or more of Pd, Pt, Mo, Co, Ni and Au, the content of the active metal component is 0.1-1% by weight based on the total amount of the acetylene hydrogenation catalyst.

2. The ethyne hydrogenation catalyst according to claim 1, wherein, mixing and stirring the first silicate, water, the second silicate and an aqueous hydrochloric acid solution to a gel state; the concentration of the aqueous hydrochloric acid solution is 2-8 mol / L.

3. The ethyne hydrogenation catalyst according to claim 2, wherein, the second silicate is ethyl orthosilicate; the concentration of the aqueous hydrochloric acid solution is 3-5 mol / L.

4. The ethylene hydrogenation catalyst of claim 2, wherein, the volume ratio of the aqueous hydrochloric acid solution to the second silicate is 1:1-10; the volume ratio of the water to the second silicate is 1:1-5.

5. The ethyne hydrogenation catalyst according to any one of claims 1 to 4, wherein the aging conditions comprise: an aging temperature of 5-55℃ and an aging time of 12-96h.

6. The ethyne hydrogenation catalyst according to claim 5, wherein, the aging conditions comprise: an aging temperature of 20-40℃ and an aging time of 36-60h.

7. The ethylene hydrogenation catalyst of any of claims 1-4, wherein, The method further comprises: 3) a step of drying the aged product obtained in step 2); the drying conditions comprise: a drying temperature of 50-100℃ and a drying time of 4-12h.

8. The ethyne hydrogenation catalyst according to claim 1, wherein, the active metal component is Pd; the content of the active metal component is 0.2-0.7% by weight based on the total amount of the acetylene hydrogenation catalyst.

9. Process for the preparation of an ethyne hydrogenation catalyst according to any one of claims 1 to 8, characterized in that The method comprises: 1) immersing the carrier in an impregnation solution containing an active metal component; 2) separating the carrier from the impregnation solution of step 1) and drying.

10. The production method according to claim 9, wherein In step 1), the content of the active metal component in the impregnation solution is such that the content of the active metal in the acetylene hydrogenation catalyst prepared is 0.1-1% by weight; the content of the active metal component in the impregnation solution is 0.02-0.2g / L; the amount of the impregnation solution used is 40-80mL per 1g of the carrier; the impregnation conditions comprise: a temperature of 5-55℃ and a time of 1-5h.

11. The production method according to claim 10, wherein In step 1), the active metal component is Pd; In step 1), the content of the active metal component in the impregnation solution is such that the content of the active metal in the acetylene hydrogenation catalyst prepared is 0.2-0.7% by weight; the content of the active metal component in the impregnation solution is 0.03-0.12g / L; the amount of the impregnation solution used is 50-70mL per 1g of the carrier; the impregnation conditions comprise: a temperature of 30-50℃ and a time of 2-4h.