Catalyst for the hydrogenation of phenyl derivatives and its preparation

Abstract

The present application relates to the field of catalyst, specifically disclose a kind of catalyst for phenyl derivative hydrogenation and preparation thereof, the catalyst uses SiO2As carrier, using ortho-chlorobenzene glycine carries out template positioning of ruthenium ion and palladium ion, after positioning, ruthenium, palladium metal ion is reduced, calcination is carried out under inert and reducing mixed gas atmosphere, after reduction, ruthenium, palladium atom is positioned and loaded on SiO2, the catalyst can be expressed by formula 2.0Och-0.43Ru-0.53Pd / SiO2, the present application develops a kind of universal SiO2Carrier loaded ruthenium palladium catalyst, under the action of the catalyst, benzene ring can be selectively hydrogenated, functional groups remain unchanged during hydrogenation, such as 1,4-benzenedicarboxylic acid, can be targeted to benzene ring hydrogenation, without affecting the carboxyl group on ring, by adjusting different process parameters, in batch reactor, a variety of raw material conversion rate >98%, target product selectivity >96%, and catalyst still maintains higher activity under multiple application.

Description

Technical Field

[0001] This invention belongs to the field of catalytic hydrogenation, and in particular relates to a catalyst for the hydrogenation of phenyl derivatives and its preparation. Background Technology

[0002] Benzene and its derivatives are fundamental raw materials in the petrochemical industry. Due to their relative reactivity, a wide variety of phenyl derivatives can be synthesized by adding substituent groups. The hydrogenation reaction of the benzene ring with substituent groups is an extremely important reaction, not only addressing health issues but also playing a crucial role in the production of various aliphatic compounds. These substances are also important fine chemicals, widely used as key intermediates in pharmaceuticals and pesticides, or as critical starting materials for the synthesis of dyes, resins, and polymers. Because benzene is carcinogenic, phenyl derivatives containing a benzene ring also pose potential health hazards to humans.

[0003] The main catalysts used in the benzene ring hydrogenation industry are nickel-based and ruthenium-based catalysts, such as the following:

[0004] CN110105223A discloses a continuous method for preparing 1,3-cyclohexanedimethylamine, wherein the catalyst has a ruthenium metal content of 0.5-3%, the auxiliary metals Mn, Co, and Mg content is 0.2-2%, the support is alumina, and the continuous hydrogenation of m-phenylenediamine is carried out under the condition of adding a small amount of auxiliary agents to achieve a conversion rate of >90% and a selectivity of 91%.

[0005] CN112058259A discloses a highly efficient catalyst for the conversion of syngas into industrial fuels. The catalyst is supported by TiO2 and the active component is Ru metal with a content of 0.1-5 wt%. The preparation steps are Ru metal loading, drying, muffle furnace sintering, dilute ammonia water treatment, drying and reduction. The preparation process is relatively complex and the application is catalytic syngas.

[0006] Some existing catalysts can have a certain impact on the substituents on the benzene ring during the hydrogenation process, for example:

[0007] CN 117776868 A discloses a ruthenium-carbon catalyst:

[0008]

[0009] While this catalyst enables hydrogenation of the benzene ring, it also affects the functional groups on the ring, reducing the methyl formate group to a methanol group. In some production processes, it is often necessary to retain these functional groups. For example, 1,4-cyclohexanecarboxylic acid is used in peptic ulcer medications and polyester resin modification, possessing broad application scenarios and value. Using this catalyst would require a secondary oxidation of the methanol group on the ring, increasing production steps and costs. Summary of the Invention

[0010] To address the problems existing in the prior art, the first aspect of this invention proposes a catalyst for the hydrogenation of phenyl derivatives, comprising:

[0011] S1: The carrier is pretreated by acid soaking. After washing, the carrier is dispersed in water and o-chlorophenylglycine and ruthenium solution are added.

[0012] S2: Slowly add palladium solution dropwise, maintaining the solution pH to 7-8;

[0013] S3: After the dripping is complete, add a reducing agent to the solution from step S2 to reduce it, adjust the pH of the solution, remove water, and obtain the catalyst;

[0014] S4: The solid after dehydration of S3 is calcined and pulverized in an inert and reducing mixed gas atmosphere.

[0015] In some specific embodiments of the preparation method of the first aspect, the carrier of step S1 is selected from silicon dioxide, aluminum oxide, and activated carbon.

[0016] In some specific embodiments of the preparation method of the first aspect, the acid in step S1 is selected from hydrochloric acid, nitric acid, and sulfuric acid.

[0017] In some specific embodiments of the preparation method of the first aspect, the mass fraction of acid in step S1 is 0.5-1.5%, in some embodiments it is 0.5%, in some embodiments it is 0.6%, in some embodiments it is 0.7%, in some embodiments it is 0.8%, in some embodiments it is 0.9%, in some embodiments it is 1.0%, in some embodiments it is 1.1%, in some embodiments it is 1.2%, in some embodiments it is 1.3%, in some embodiments it is 1.4%, and in some embodiments it is 1.5%.

[0018] In some specific embodiments of the preparation method of the first aspect, the o-chlorophenylglycine feed in step S1 is calculated as 1 to 3 mmol per 1g of carrier, in some embodiments as 1 mmol per 1g of carrier, in some embodiments as 2 mmol per 1g of carrier, and in some embodiments as 3 mmol per 1g of carrier.

[0019] In some specific embodiments of the preparation method of the first aspect, the specific surface area of ​​the carrier is 800–1400 m². 2 / g, in some embodiments the carrier specific surface area is 800m². 2 / g, in some embodiments the carrier specific surface area is 900m² 2 / g, in some embodiments the carrier specific surface area is 1000m²2 / g, in some embodiments the carrier specific surface area is 1100m² 2 / g, in some embodiments the carrier specific surface area is 1200m². 2 / g, in some embodiments the carrier specific surface area is 1300m². 2 / g, in some embodiments the carrier specific surface area is 1400m². 2 / g.

[0020] In some specific embodiments of the preparation method of the first aspect, the ruthenium solution in step S1 is selected from ruthenium chloride salt and ruthenium nitrate salt solution.

[0021] In some specific embodiments of the preparation method of the first aspect, the concentration of the ruthenium solution in step S1 is 0.15–0.19 mmol / mL. In some embodiments, the concentration of the ruthenium solution is 0.15 mmol / mL. In some embodiments, the concentration of the ruthenium solution is 0.16 mmol / mL. In some embodiments, the concentration of the ruthenium solution is 0.17 mmol / mL. In some embodiments, the concentration of the ruthenium solution is 0.18 mmol / mL. In some embodiments, the concentration of the ruthenium solution is 0.19 mmol / mL.

[0022] In some specific embodiments of the preparation method of the first aspect, the palladium solution in step S2 is selected from palladium chloride and palladium nitrate.

[0023] In some specific embodiments of the preparation method of the first aspect, the palladium solution concentration in step S2 is 0.30–0.35 mmol / mL, in some embodiments it is 0.30 mmol / mL, in some embodiments it is 0.31 mmol / mL, in some embodiments it is 0.32 mmol / mL, in some embodiments it is 0.33 mmol / mL, in some embodiments it is 0.34 mmol / mL, and in some embodiments it is 0.35 mmol / mL.

[0024] In some specific embodiments of the preparation method of the first aspect, the reducing agent in step S3 is selected from potassium borohydride, sodium borohydride, and lithium aluminum hydride.

[0025] In some specific embodiments of the preparation method of the first aspect, the concentration of the reducing agent in step S3 is 2.0–3.0 mmol / mL, in some embodiments the concentration of the reducing agent is 2.0 mmol / mL, in some embodiments the concentration of the reducing agent is 2.2 mmol / mL, in some embodiments the concentration of the reducing agent is 2.4 mmol / mL, in some embodiments the concentration of the reducing agent is 2.6 mmol / mL, in some embodiments the concentration of the reducing agent is 2.8 mmol / mL, and in some embodiments the concentration of the reducing agent is 3.0 mmol / mL.

[0026] In some specific embodiments of the preparation method of the first aspect, the pH value adjusted in step S3 is 9 to 10.

[0027] In some specific embodiments of the preparation method of the first aspect, the inert gas in step S4 is selected from either nitrogen or argon, or a mixture thereof.

[0028] In some specific embodiments of the preparation method of the first aspect, the reducing gas in step S4 is selected from hydrogen.

[0029] In some specific embodiments of the preparation method of the first aspect, the volume ratio of inert gas to reducing gas in step S4 is (8-10):1, in some embodiments it is 8:1, in some embodiments it is 9:1, and in some embodiments it is 10:1.

[0030] In some specific embodiments of the preparation method of the first aspect, the calcination method in step S4 is as follows:

[0031] 1. Increase the temperature to 180-220°C at any rate of 30°C-60°C per minute, or 40°C-50°C per minute, or 45°C per minute, and hold for 1-3 minutes;

[0032] 2. Increase the temperature to 750-850℃ at a rate of 20-35℃ / min, or 25-35℃ / min, or 30℃ / min, and hold for 5-15 minutes;

[0033] 3. Slowly cool to room temperature at a rate not exceeding 10℃ / min.

[0034] In some specific embodiments of the preparation method of the first aspect, the particle diameter after pulverization in step S4 is [missing information].

[0035] The diameter is 0.08–0.12 mm, with some embodiments having a diameter of 0.08 mm, some embodiments having a diameter of 0.09 mm, some embodiments having a diameter of 0.10 mm, some embodiments having a diameter of 0.11 mm, and some embodiments having a diameter of 0.12 mm.

[0036] The second aspect of this invention provides a catalyst prepared by the method of the first aspect.

[0037] In some specific embodiments of the preparation method of the second aspect, the catalyst can be represented by the general formula aOch-bRu-cPd / SiO2, wherein Och represents o-chlorophenylglycine, a is the micromolar amount of o-chlorophenylglycine per gram of SiO2 support, a is selected from 1 to 3, preferably 2, b is the micromolar amount of ruthenium metal supported per gram of SiO2 support, b is selected from 0.3 to 0.6, preferably 0.43, and c is the micromolar amount of palladium metal supported per gram of SiO2 support, c is selected from 0.4 to 0.6, preferably 0.53.

[0038] The third aspect of this invention proposes the application of a catalyst prepared in the second aspect in the catalytic hydrogenation of phenyl derivatives.

[0039] In some applications of the catalyst proposed in the third aspect, the phenyl derivative used as the substrate is selected from m-phenylenediamine, bisphenol A, 2,4-toluenediamine, 4,4'-diaminodiphenylmethane, 1,4-phthalic acid, and p-phenylenediamine.

[0040] Yield in this invention

[0041] Where, n b n represents the maximum theoretical molar yield of the target product. a The actual molar yield of the target product;

[0042] Yield in this invention

[0043] Where, n c n is the molar amount of the reaction substrate consumed. d This represents the initial molar amount of the reaction substrate;

[0044] Glycine ethyl ester (CAS: 120746-42-1); Glycine (CAS: 56-40-6);

[0045] o-chlorophenylglycine (CAS: 141196-64-7);

[0046] This invention provides a substituent-retaining selective catalyst that can be expressed using the general formula aTemp-bRu-cPd / SiO2:

[0047] After calcination, the complexing and positioning template is destroyed. The formula aTemp-bRu-cPd / SiO2 does not mean that the catalyst retains the complexing and positioning template after calcination. The formula Temp only indicates the type of complexing and positioning template used in the preparation process.

[0048] a represents the molar amount of complexing template agent Temp added per 1g of carrier SiO2, and the value of a ranges from 1mmol to 3mmol.

[0049] In the following examples or comparative examples, Temp refers to Ges, Gly, and Och, respectively. Ges indicates that glycine ethyl ester (CAS: 120746-42-1) was used as a complexing template agent, Gly indicates that glycine (CAS: 56-40-6) was used as a complexing template agent, and Och indicates that o-chlorophenylglycine (CAS: 141196-64-7) was used as a complexing template agent.

[0050] Where b is the molar amount of ruthenium atoms loaded per 1g of SiO2 support, and the value of b ranges from 0.3mmol to 0.6mmol.

[0051] Where c is the molar amount of palladium atoms loaded per 1g of SiO2 support, and the value of c ranges from 0.4mmol to 0.6mmol.

[0052] In this invention, the room temperature is 5–40°C in some embodiments, 10–35°C in some embodiments, 15–30°C in some embodiments, 20–25°C in some embodiments, and 25°C in some embodiments.

[0053] All reagents used in this invention are purchased from the open and legal market, such as those from companies like Sinopharm Shanghai Laboratory, Sigma, McLean, and Xilong, and have not undergone further purification.

[0054] Advantages of this invention:

[0055] This invention uses SiO2 as a support and o-chlorophenylglycine as a template for the positioning of ruthenium and palladium ions. The positioned ruthenium and palladium metal ions are reduced and calcined under an inert and reducing mixed gas atmosphere. The reduced ruthenium and palladium atoms are then loaded onto SiO2. This invention develops a universal ruthenium / palladium-based SiO2 supported catalyst. This catalyst is applied to the hydrogenation of benzene rings with retained substituents. In particular, this catalyst can selectively hydrogenate phenyl derivatives, while retaining no change in functional groups during hydrogenation. By adjusting different process parameters, multiple feed conversion rates >98% and target product selectivity >96% can be achieved in a batch reactor. Furthermore, the catalyst can be reused multiple times. Detailed Implementation

[0056] The technical solution of the present invention will be further described below, but it is not limited thereto. Any modifications or equivalent substitutions to the technical solution of the present invention that do not depart from the spirit and scope of the technical solution of the present invention should be covered within the protection scope of the present invention.

[0057] Example 1

[0058] Step 1: For surfaces with a specific surface area of ​​1000–1200 m² 2 20g of silica carrier was soaked in a 1% (w / w) dilute hydrochloric acid solution and stirred for 20 min. After soaking, the carrier was filtered and washed three times with ultrapure water. After filtration, the washed carrier was dispersed in 100ml of ultrapure water, and 40mmol of o-chlorophenylglycine and 50ml of ruthenium chloride with a concentration of 0.173mmol / mL were added. The mixture was stirred at 200rpm for 10 min.

[0059] Step 2: While stirring, slowly add 32 ml of palladium nitrate and sodium bicarbonate solution with a concentration of 0.33 mmol / mL to the solution simultaneously, and maintain the pH of the solution at 7-8.

[0060] Step 3: After the addition is complete, add 38 ml of potassium borohydride with a concentration of 2.5 mmol / mL to the above solution for reduction. Finally, adjust the pH of the solution to between 9 and 10, and evaporate and dehydrate under reduced pressure at 40°C.

[0061] Step 4: Under a mixed gas of N2 and H2 with a volume ratio of 9:1, the solid dehydrated in Step 3 is calcined. The calcination temperature is increased to 200℃ in 5 minutes, held for 1 minute, then increased to 800℃ at a rate of 20℃ / min, held for 10 minutes, and then slowly cooled to room temperature at a rate not exceeding 10℃ / min. After grinding to particles of about 0.1 mm, a catalyst for selective hydrogenation with retained substituents is obtained, represented by the formula 2.0Och-0.43Ru-0.53Pd / SiO2, where Och represents o-chlorophenylglycine (CAS: 141196-64-7) in the preparation process.

[0062] Comparative Example 1:

[0063] The difference between Comparative Example 1 and Example 1 is that the o-chlorophenylglycine in step 1 was replaced with an equimolar amount of glycine, resulting in a catalyst of 2.0Gly-0.43Ru-0.53Pd / SiO2, where Gly represents the glycine used as the complexing template agent in the preparation process. Comparative Example 2:

[0064] The difference between Comparative Example 2 and Example 1 is that o-chlorophenylglycine in step 1 is replaced with an equimolar amount of glycine ethyl ester, resulting in catalyst 2.0Ges-0.43Ru-0.53Pd / SiO2, where Ges indicates that glycine ethyl ester is used as the complexing template agent in the preparation process.

[0065] Comparative Example 3:

[0066] The difference between Comparative Example 3 and Example 1 is that in step S2, instead of adding palladium nitrate, an equimolar amount of nickel nitrate is added to obtain catalyst 2.0Och-0.43Ru-0.53Ni / SiO2, where Och indicates that the complexing template agent used in the preparation process is o-chlorophenylglycine.

[0067] Comparative Example 4:

[0068] The difference between Comparative Example 4 and Example 1 is that potassium borohydride reduction is not used.

[0069] Comparative Example 5:

[0070] The difference between Comparative Example 5 and Example 1 is that ruthenium chloride was not added dropwise, resulting in a catalyst of 2.0 Och-0.53 Pd / SiO2, where Och indicates that the complexing template agent used in the preparation process is o-chlorophenylglycine.

[0071] Comparative Example 6:

[0072] The difference between Comparative Example 6 and Example 1 is that after adding palladium nitrate in step S2, 30% of the molar amount of palladium nitrate, platinum nitrate, is added dropwise to obtain catalyst 2.0Och-0.43Ru-0.53Pd-0.16Pt / SiO2, where Och indicates that the complexing template agent used in the preparation process is o-chlorophenylglycine.

[0073] Example 2:

[0074] 735 mmol of m-phenylenediamine and 1000 ml of chloroform were added to a high-pressure reactor, followed by 2 wt% of the catalyst prepared in Example 1 (based on the mass of m-phenylenediamine). The catalytic temperature was maintained between 150 and 160 °C, and hydrogen gas was introduced at a pressure range of 4.0 to 4.5 MPa. The catalytic reaction was carried out for 5.0 h to obtain a hydrogenated mixed solution. The conversion rate of the raw material m-phenylenediamine was 99.1% (conv.%), and the selectivity of the target product 1,3-cyclohexanedimethylamine was 96.21% (yield%).

[0075] Example 3:

[0076] 439 mmol of bisphenol A was reacted with 600 ml of chloroform in a high-pressure reactor, and 3 wt% of the catalyst prepared in Example 1 (based on the mass of bisphenol A) was added. The catalytic temperature was maintained between 150 and 160 °C, and hydrogen gas was introduced at a pressure range of 3.0 to 3.5 MPa. The catalytic reaction was carried out for 5.0 h to obtain a hydrogenated mixed solution. The conversion rate of the raw material bisphenol A was 99.95% (conv.%), and the selectivity of the target product hydrogenated bisphenol A (yield%) was 97.1%.

[0077] Example 4:

[0078] 819.6 mmol of 2,4-toluenediamine and 1200 ml of tetrahydrofuran were added to a high-pressure reactor, along with 1 wt% of the catalyst prepared in Example 1 (based on the mass of 2,4-toluenediamine). The catalytic temperature was maintained between 130 and 140 °C, and hydrogen gas at a pressure of 4.0 MPa was introduced. The catalytic reaction was carried out for 3 h to obtain a hydrogenated mixed solution. The conversion of the starting material 2,4-toluenediamine was 99.91% (conv.%), and the selectivity of the target product 1-methyl-2,4-cyclohexanediamine (yield%) was 98.40%.

[0079] Example 5:

[0080] 505 mmol of MDA (4,4'-diaminodiphenylmethane) and 800 ml of tetrahydrofuran were added to an autoclave, along with 3 wt% of the catalyst prepared in Example 1 (based on the mass of 4,4'-diaminodiphenylmethane). The catalytic temperature was maintained between 140 and 150 °C, and hydrogen gas at a pressure of 4.5 MPa was introduced. The catalytic reaction was carried out for 3 h to obtain a hydrogenated mixed solution. The conversion of the feedstock 4,4'-diaminodiphenylmethane was 99.93% (conv.%), and the selectivity of the target product 4,4'-diaminodicyclohexylmethane (yield%) was 98.64%.

[0081] Example 6:

[0082] The catalysts prepared in Examples 1 and 1-6 were mixed with 603 mmol of 1,4-phthalic acid and 900 ml of chloroform, respectively, and added to an autoclave. 5 wt% of the catalyst (based on the mass of 1,4-phthalic acid) was added. The catalytic temperature was 180 °C, and hydrogen gas at a pressure of 5.0 MPa was introduced. The catalytic reaction was carried out for 12 h to obtain a hydrogenated mixed solution. The yield (yield%) of the target product 1,4-cyclohexanedicarboxylic acid and the conversion (conv.%) of the starting material 1,4-phthalic acid were determined by GC. The results are shown in Table 1.

[0083] Table 1: Effect of the catalysts in Example 1 and Comparative Examples 1-6 on the selective hydrogenation of 1,4-phthalic acid

[0084] conv.(%) 99.1 62.9％ 41.3％ 5.1％ 52.1％ 3.2％ 15.3％ yield(%) 95.2 1.5％ 2.6％ 0.2％ 7.8％ 4.3％ 3.6％

[0085] In Table 1, the conversion rates (conv.%) of 1,4-phthalic acid using catalysts from Comparative Examples 1 and 2 were 62.9% and 41.3%, respectively, and the yields (yield%) of the product 1,4-cyclohexanedicarboxylic acid were 1.5% and 2.6%, respectively. The yields of 1,4-cyclohexanediethanol in Comparative Examples 1 to 6 were much higher than those of 1,4-cyclohexanedicarboxylic acid, where the carboxyl group on the benzene ring was reduced to a methanol group by hydrogen. However, when the catalyst prepared in Example 1 was used, the conversion rate (conv.%) of 1,4-phthalic acid was 99.1%, and the yield (yield%) of 1,4-cyclohexanedicarboxylic acid was as high as 95.2%.

[0086] Example 7:

[0087] 926 mmol of p-phenylenediamine and 1000 ml of chloroform were added to a high-pressure reactor, along with the catalyst prepared in Example 1. The catalyst dosage was 4 wt% of the initial feed, with an additional 0.4 wt% added during reprocessing. The catalytic temperature was 150 °C, and hydrogen gas was introduced at a pressure of 4.5 MPa. The catalytic reaction was carried out for 3.0–4.0 h to obtain a hydrogenated solution. The catalyst was recycled 10 times. GC analysis was performed to determine the selectivity (yield%) of the target product 1,4-cyclohexanediamine and the conversion (conv.%) of the reactant p-phenylenediamine. The results are shown in Table 2.

[0088] Table 2: Activity Test of Catalyst After Multiple Cycles

[0089] conv.(%) 99.9％ 97.9％ 99.9％ 98.9％ 99.9％ 99.9％ 99.9％ 99.9％ 99.9％ 99.9％ yield(%) 97.8％ 97.8％ 97.8％ 97.8％ 97.8％ 97.8％ 97.8％ 97.8％ 97.8％ 97.8％

[0090] It can be seen that for the catalyst 2.0Och-0.43Ru-0.53Pd / SiO2 prepared in Example 1 of this invention, only 0.4wt% of catalyst needs to be added in each production cycle to maintain a high conversion rate (conv.%) and selectivity (yield).

[0091] Example 8:

[0092] The feed amounts of each component in Example 1 were adjusted to prepare catalysts with different a, b, and c values. Each catalyst was then mixed with 1,4-phenylenediamine and chloroform according to the method and feed amounts used in Example 6. The mixture was added to a high-pressure reactor, heated, and pressurized with hydrogen gas to catalyze the reaction, resulting in a hydrogenated mixed solution. GC analysis was performed, and the selectivity (yield%) of the target product 1,4-cyclohexanedicarboxylic acid and the conversion rate (conv.%) of the raw material 1,4-phenylenediamine are shown in Table 3.

[0093] Table 3: Performance of catalysts with different ratios

[0094]

[0095] The preferred embodiments of the present invention have been described in detail above. However, the present invention is not limited to the specific details in the above embodiments. Within the scope of the technical concept of the present invention, various simple modifications can be made to the technical solution of the present invention, and these simple modifications all fall within the protection scope of the present invention.

Claims

1. A method for preparing a catalyst for the hydrogenation of phenyl derivatives, comprising: S1: The carrier is pretreated by acid soaking. After washing, the carrier is dispersed in water and o-chlorophenylglycine and ruthenium solution are added. S2: Slowly add palladium solution dropwise, maintaining the solution pH at 7-8; S3: After the dripping is complete, add a reducing agent to the solution from step S2 to reduce it, adjust the pH of the solution, and remove the water. S4: The solid after dehydration of S3 is calcined and pulverized in an inert and reducing gas atmosphere; The catalyst has the general formula aOch-bRu-cPd / SiO2, where Och represents the complexing and positioning template agent o-chlorophenylglycine, which is destroyed during calcination. Och only indicates the type of complexing and positioning template used in the preparation process. a is the micromolar amount of o-chlorophenylglycine per gram of SiO2 support, and a is selected from 1 to 3. b is the micromolar amount of ruthenium metal loaded per gram of SiO2 support, and b is selected from 0.3 to 0.

6. c is the micromolar amount of palladium metal loaded per gram of SiO2 support, and c is selected from 0.4 to 0.

6.

2. The method for preparing the catalyst according to claim 1, characterized in that, The acid in step S1 is selected from hydrochloric acid, nitric acid, sulfuric acid, and / or the mass fraction of the acid in step S1 is 0.5% to 1.5%, and / or the specific surface area of ​​the carrier is 800 to 1400 m². 2 / g.

3. The method for preparing the catalyst according to claim 2, characterized in that, The mass fraction of acid in step S1 is 1%. And / or, in step S1, the o-chlorophenylglycine feed is calculated at 2 mmol per 1g of carrier. And / or, the specific surface area of ​​the carrier is 1000~1200 m² 2 / g.

4. The method for preparing the catalyst according to any one of claims 1 to 3, characterized in that, The ruthenium solution in step S1 is selected from ruthenium chloride salt, ruthenium nitrate salt solution, and / or the concentration of the ruthenium solution in step S1 is 0.15~0.19 mmol / mL.

5. The method for preparing the catalyst according to claim 4, characterized in that, The concentration of the ruthenium solution in step S1 is 0.173 mmol / mL.

6. The method for preparing the catalyst according to any one of claims 1 to 5, characterized in that, The palladium solution in step S2 is selected from palladium chloride, palladium nitrate, and / or the concentration of the palladium solution in step S2 is 0.30~0.35 mmol / mL.

7. The method for preparing the catalyst according to claim 6, characterized in that, The concentration of the palladium solution in step S2 is 0.33 mmol / mL.

8. The method for preparing the catalyst according to any one of claims 1 to 7, characterized in that, The reducing agent in step S3 is selected from potassium borohydride, sodium borohydride, lithium aluminum hydride, and / or the concentration of the reducing agent in step S3 is 2.0~3.0 mmol / mL, and / or the pH value adjusted in step S3 is 9~10.

9. The method for preparing the catalyst according to any one of claims 8, characterized in that, The concentration of the reducing agent in step S3 is 2.5 mmol / mL.

10. The method for preparing the catalyst according to any one of claims 1 to 9, characterized in that, In step S4, the inert gas is selected from nitrogen, argon, or a mixture thereof, and / or; the reducing gas in step S4 is selected from hydrogen, and / or; the volume ratio of inert gas to reducing gas in step S4 is (8~10):1, and / or; the calcination method in step S4 is to heat to 180~220℃ at a rate of 30℃~60℃ per minute, hold for 1~3 minutes, then heat to 750~850℃ at a rate of 20~35℃ / min, hold for 5~15 minutes, and then slowly cool to room temperature at a rate not exceeding 10℃ / min, and / or; the diameter of the pulverized particles is 0.08~0.12mm.

11. The method for preparing the catalyst according to any one of claims 10, characterized in that, In step S4, the volume ratio of inert gas to reducing gas is 9:1, and / or the diameter of the pulverized particles is 0.1 mm.

12. A catalyst prepared by any one of claims 1 to 11.

13. The catalyst according to claim 12, characterized in that, The value of a is the molar amount of o-chlorophenylglycine per gram of SiO2 carrier, and a is selected from 2. The value of b is the molar amount of ruthenium metal loaded per gram of SiO2 carrier, and b is selected from 0.

43. The value of c is the molar amount of palladium metal loaded per gram of SiO2 carrier, and c is selected from 0.

53.

14. The use of any one of the catalysts of claims 12 to 13 in the hydrogenation of phenyl derivatives.

15. The application according to claim 14, wherein the phenyl derivative is selected from m-phenylenediamine, 2,4-toluenediamine, 1,4-phenylenediic acid, p-phenylenediamine, bisphenol A, and 4,4'-diaminodiphenylmethane.

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