N-doped activated carbon loaded Ru-based catalyst as well as preparation method and application thereof

Abstract

The invention provides an N-doped activated carbon loaded Ru-based catalyst as well as a preparation method and application thereof. The method comprises the following steps: carrier pretreatment and N functionalization modification, loading of an active component Ru, preparation of the catalyst and reduction of the catalyst. The invention also provides an N-doped activated carbon loaded Ru-based catalyst which is prepared by the method. The invention also provides an application of the catalyst as a catalyst in a phthalate hydrogenation reaction. The N-doped activated carbon loaded Ru-based catalyst has the advantages of high catalytic activity, simple preparation process, facilitation of industrial large-scale production and the like, and is suitable for a DOP catalytic hydrogenation synthesis process of a green plasticizer DEHCH.

Description

Technical Field

[0001] The present invention relates to an N-doped activated carbon supported Ru-based catalyst, a preparation method thereof and an application thereof, and belongs to the technical field of phthalate hydrogenation catalysts. Background Art

[0002] Phthalate compounds, as the most widely used plasticizers in many plastic products, account for the largest proportion in plasticizers, accounting for 70% of the consumer market, including more than 30 esters formed by esterification of phthalic acid substances. Among them, diisooctyl phthalate (DOP) is the most widely used.

[0003] However, with the widespread use of DOP, researchers have found that this type of plasticizer is harmful to the human reproductive system and liver. The hydrogenation product of DOP, diisooctyl cyclohexane-1,2-dicarboxylate (DEHCH), can be biodegradable and metabolized by the human body naturally, and its plasticizing performance is similar to that of phthalate plasticizers. Therefore, DEHCH is a new type of environmentally friendly plasticizer with great application prospects in terms of safety, industrialization and plasticizing ability. Developing a suitable production process for DEHCH has important industrial significance for its industrialization.

[0004] The existing mature DEHCH synthesis processes mainly include the olefin method and the catalytic hydrogenation method. Among them, the catalytic hydrogenation method has a simple production process and a high product yield. More importantly, since there is already a mature phthalate production industrial system in the existing technology, only a hydrogenation reaction device needs to be added for large-scale production. Therefore, this method has good application prospects.

[0005] In this catalytic hydrogenation reaction, the regulation and use of the catalyst are the entry points for many researchers to improve the reaction conversion rate. For the hydrogenation reaction of aromatic hydrocarbons, carbon-supported Ru-based catalysts have irreplaceable advantages. Due to their suitable cost and good catalytic effect, they are currently widely used catalysts. However, in this reaction system, the conversion rate of the intermediate product to further hydrogenate to DEHCH is the rate-determining step of the reaction, and its reaction rate and conversion rate have always been unsatisfactory. Therefore, how to modify the catalyst to further improve the reaction yield has been a hot research topic.

[0006] CN114602497B discloses a preparation method and application of a Co-Rh bimetallic catalyst supported on an N-doped porous carbon material. The preparation method includes the following steps: (1) Using urea as a modification reagent, the support is functionalized by a hydrothermal method, and then high-temperature calcination and grinding are carried out to achieve non-metallic modification of the support; (2) The support is washed and ultrasonicated with deionized water to obtain a support suspension; (3) A Rh / CN monometallic catalyst is prepared by an impregnation method; (4) On the basis of the prepared Rh / CN, a Co-Rh / CN bimetallic catalyst is synthesized again by an impregnation method. The bimetallic Co-Rh / CN catalyst synthesized by the above means in the present invention. This method can significantly improve the stability of the catalyst, improve the dispersion of the metal, so that the catalyst shows excellent catalytic activity in the hydroformylation reaction of isooctene.

[0007] However, first of all, in this invention, the good performance of the synthesized Co-Rh / CN bimetallic catalyst in the reaction may be due to the introduction of the second metal Co. There is no evidence in this invention that the excellent performance of the catalyst is only caused by the modification of a single non-metallic element N. In addition, in this invention, a comparative experiment of the Rh / CN catalyst catalyzing the same reaction after removing the promoter Co is provided, and the result shows a decrease in catalytic performance. This result is contradictory evidence for proving whether the improvement of the reaction activity is caused by N modification or the introduction of Co. Secondly, in this invention, the preparation cycle of the bimetallic catalyst is long, the preparation process is complex, and the operation is inconvenient. It is not conducive to the realization of actual production.

[0008] CN110813359B discloses a ruthenium-based ammonia synthesis catalyst supported on a nitrogen-doped porous carbon material and a preparation method thereof. The synthesized catalyst is mainly used for ammonia synthesis reaction. In the preparation process of this catalyst, zinc nitrate hexahydrate is first dissolved in an alkaline aqueous solution, 2-methylimidazole is dissolved in N,N-dimethylformamide and then added to the alkaline aqueous solution. After the above solutions are mixed evenly, a hydrothermal reaction and carbonization are carried out to obtain a nitrogen-doped porous carbon material. Then, a ruthenium compound without chlorine and polyvinylpyrrolidone are dissolved in an ethylene glycol solution and heated, washed with an ethanol-acetone mixed solution, and then an ethanol solution is added; the above nitrogen-doped porous carbon material is added and stirred, and then left standing, separated, dried and reduced to obtain a ruthenium-based ammonia synthesis catalyst supported on a nitrogen-doped porous carbon material. The catalyst synthesized by this method has a higher specific surface area and a higher nitrogen doping amount, so it has higher ammonia synthesis activity and has a good application prospect.

[0009] However, the invention examines a relatively narrow range of N content, and the trend presented is that as the N content increases, the activity of the ammonia synthesis reaction increases accordingly. However, the influence of low or higher N content on the catalyst activity is not considered, that is, no further exploration is carried out on the optimal addition of the best N content. Existing research shows that when modifying the activated carbon carrier by specific physicochemical experimental methods, due to the too high concentration of the modifying solution, the internal pore channels of the carrier may collapse, resulting in a decrease in the specific surface area of the carrier, further leading to a decrease in the active sites and a decrease in the catalytic activity. In addition, the synthesis process of this catalyst is complex and does not have the operability for large-scale industrial production.

[0010] Therefore, developing a new type of Ru-based catalyst supported on N-doped activated carbon and its preparation method is still one of the urgent problems to be solved in this field. Summary of the Invention

[0011] To solve the above technical problems, the purpose of the present invention is to provide an Ru-based catalyst supported on N-doped activated carbon, its preparation method and application. The Ru-based catalyst supported on N-doped activated carbon of the present invention has the advantages of high catalytic activity, simple preparation process, and being conducive to large-scale industrial production.

[0012] To achieve the above purpose, the first aspect of the present invention provides a preparation method of an Ru-based catalyst supported on N-doped activated carbon, which includes the following steps:

[0013] (1) Carrier pretreatment and N-functionalization modification

[0014] Place activated carbon (AC) in a nitric acid solution for treatment for a period of time, and then after washing, separation and drying, obtain the pretreated carrier; place the pretreated carrier in ammonia water for reaction for a period of time, and then after washing, separation and drying, obtain the modified carrier N-AC;

[0015] (2) Loading of active component Ru

[0016] Dropwise add the Ru precursor solution into the modified carrier N-AC and stir evenly, and after drying, obtain the Ru-loaded N-AC;

[0017] (3) Preparation of the catalyst

[0018] Calcine the Ru-loaded N-AC in a nitrogen atmosphere, and then after ultrasonic washing, separation and drying, obtain the catalyst semi-finished product;

[0019] (4) Reduction of the catalyst

[0020] Reduce the catalyst semi-finished product in a hydrogen atmosphere, and after reduction, cool it to room temperature to obtain the Ru-based catalyst supported on N-doped activated carbon.

[0021] In the above preparation method, preferably, in step (1), the specific surface area of the activated carbon is 472.41 - 481.52 m 2 / g, the pore diameter is 2.54 - 3.00 nm, the mesopore volume is 0.1868 - 0.1945 cm 3 / g, and the micropore volume is 0.1788 - 0.1892 cm 3 / g.

[0022] In the above preparation method, preferably, in step (1), based on the total mass of the activated carbon being 100%, the content of N therein is 0.66%.

[0023] In the above preparation method, preferably, in step (1), the concentration of the nitric acid solution is 4 - 6 mol / L, more preferably 4 mol / L. The present invention uses a nitric acid solution with a specific concentration to treat AC, which can effectively remove the impurity functional groups on the surface of AC.

[0024] In the above preparation method, preferably, in step (1), placing the activated carbon in the nitric acid solution for treatment is carried out under stirring conditions, the temperature of the treatment is 50 - 100 °C, and the time is 3 - 6 h. More preferably, the temperature of the treatment is 60 °C and the time is 3 h.

[0025] In the above preparation method, preferably, in step (1), the concentration of the ammonia water is 5 - 14 mol / L, more preferably 12 mol / L. The present invention uses ammonia water with a specific concentration to carry out N-functionalization modification on the pretreated activated carbon carrier, and pyridine groups are successfully modified on the surface of AC.

[0026] In the above preparation method, preferably, in step (1), placing the pretreated carrier in the ammonia water for reaction is carried out under stirring conditions, the temperature of the reaction is 50 - 100 °C, and the time is 3 - 6 h. More preferably, the temperature of the reaction is 60 °C and the time is 6 h.

[0027] In the above preparation method, preferably, in step (1), the washing is carried out with deionized water until neutral, and the separation is carried out by suction filtration.

[0028] In the above preparation method, preferably, in step (1), the drying is vacuum drying, the temperature of the vacuum drying is 60 - 100 °C, and the time is 3 - 5 h. More preferably, the temperature of the vacuum drying is 70 °C and the time is 3 h.

[0029] In the above preparation method, preferably, in step (2), the Ru precursor solution includes ruthenium chloride (RhCl3 ) Solution. Those skilled in the art can routinely adjust the concentration of the Ru precursor solution according to the actual situation based on the Ru loading in the catalyst, and the present invention does not specifically limit it.

[0030] In the above preparation method, preferably, in step (2), the drying includes: first performing natural drying for 24 to 48 hours, and then performing vacuum drying at 60 to 100 °C for 3 to 5 hours. More preferably, the time for natural drying is 24 hours; the temperature for vacuum drying is 70 °C, and the time is 3 hours.

[0031] In the above preparation method, preferably, in step (3), the calcination temperature is 300 to 400 °C, and the time is 3 to 5 hours. More preferably, the calcination temperature is 300 °C, and the time is 4 hours.

[0032] In the above preparation method, preferably, in step (3), the ultrasonic washing is carried out with deionized water and the separation is filtration separation to remove Cl - , and washing is completed until Cl cannot be detected in the filtrate. -

[0033] In the above preparation method, preferably, in step (3), the drying is vacuum drying, the temperature of the vacuum drying is 60 to 100 °C, and the time is 3 to 5 hours. More preferably, the temperature of the vacuum drying is 70 °C, and the time is 3 hours.

[0034] In the above preparation method, preferably, in step (4), the reduction temperature is 150 to 250 °C, and the time is 3 to 5 hours. More preferably, the reduction temperature is 200 °C, and the time is 3 hours.

[0035] In the above preparation method, preferably, based on the total mass of the Ru-based catalyst supported on the N-doped activated carbon being 100%, the content of N therein is 0.96% to 1.45%, more preferably 1.44%.

[0036] In the above preparation method, preferably, based on the total mass of the Ru-based catalyst supported on the N-doped activated carbon being 100%, the Ru loading is 0.5% to 1%, more preferably 0.5%.

[0037] The second aspect of the present invention provides a Ru-based catalyst supported on N-doped activated carbon, which is prepared by the above preparation method.

[0038] According to a specific embodiment of the present invention, preferably, based on the total mass of the Ru-based catalyst supported on N-doped activated carbon being 100%, the content of N therein is 0.96% to 1.45%, more preferably 1.44%.

[0039] According to a specific embodiment of the present invention, preferably, based on the total mass of the Ru-based catalyst supported on N-doped activated carbon being 100%, the loading amount of Ru therein is 0.5% to 1%, more preferably 0.5%.

[0040] The third aspect of the present invention provides an application of the above-mentioned Ru-based catalyst supported on N-doped activated carbon as a catalyst in the hydrogenation reaction of phthalate.

[0041] In the above application, preferably, the phthalate is diisooctyl phthalate (DOP), and the product of the hydrogenation reaction is diisooctyl cyclohexane-1,2-dicarboxylate (DEHCH).

[0042] The present invention provides a Ru-based catalyst supported on N-doped activated carbon, its preparation method and application. The present invention mainly uses specific physical and chemical means to modify the activated carbon (AC) carrier with ammonia water, and successfully modifies the N-containing functional group - pyridine group on the surface of the activated carbon (AC), and finally prepares a Ru-based catalyst supported on N-doped activated carbon - Ru / AC catalyst. Since the pyridine group containing N is successfully introduced on the surface of the Ru / N-AC catalyst prepared by the present invention, the presence of this group enhances the anchoring ability of AC to Ru, improves the adsorption ability of the catalyst to reactants, reduces the activation energy barrier of the DOP hydrogenation reaction, improves the reaction rate from the kinetic mechanism, overcomes the deficiencies of traditional catalysts, fundamentally improves the reaction conversion rate, and significantly improves the catalytic activity. At the same time, the present invention successfully explores the optimal concentration of the modification reagent (i.e., ammonia water) and the N doping amount. Based on the existence of the modification reagent, there is an optimal concentration and an optimal N doping amount for the N-modified activated carbon carrier. The inventors of this case have found through research that the activity of the DOP hydrogenation reaction will first increase and then decrease with the increase of the N content in the catalyst, because as the concentration of the modification reagent increases, the pores inside the carrier are corroded and collapsed, resulting in a decrease in the specific surface area of the catalyst. Therefore, the present invention proves that blindly pursuing a high N content and using a high concentration of the modification reagent will cause the pore structure of AC to collapse, reduce the specific surface area, and lead to a decrease in catalytic activity. The Ru / N-AC catalyst of the present invention has the advantages of high catalytic activity, simple preparation process, and being conducive to large-scale industrial production. This catalyst is suitable for the DOP catalytic hydrogenation synthesis process of the green plasticizer DEHCH.

[0043] The technical solution of the present invention has at least the following beneficial effects:

[0044] (1) The present invention uses ammonia water as a modification reagent and successfully modifies pyridine groups on the surface of AC. The pyridine groups enhance the anchoring ability of AC to Ru, improve the adsorption ability of the catalyst to reactants, and lower the activation energy barrier of the DOP hydrogenation reaction. Compared with the unmodified Ru / AC catalyst, the catalytic activity is significantly improved;

[0045] (2) The present invention proves that the modification of the AC support with too high a concentration of the modification reagent (i.e., ammonia water) is instead disadvantageous. The present invention proves that there is an optimal modification concentration for the N modification of the AC support, that is, the ammonia water concentration is 12 mol / L;

[0046] (3) The preparation process of the catalyst of the present invention is simple and is conducive to large-scale industrial production. Description of the Drawings

[0047] Figure 1 XPS diagrams of the catalysts prepared in Comparative Example 1 and Examples 1 to 4. Detailed Description of the Invention

[0048] For a clearer understanding of the technical features, objectives, and beneficial effects of the present invention, the technical solutions of the present invention are described in detail below, but it should not be construed as a limitation on the scope of implementation of the present invention.

[0049] Example 1

[0050] This example provides an Ru-based catalyst supported on N-doped activated carbon. The preparation method of the catalyst includes the following steps:

[0051] (1) Carrier pretreatment and N-functionalization modification

[0052] Weigh 5.0 g of activated carbon (specific surface area is 472.41 - 481.52 m 2 / g, pore diameter is 2.54 - 3.00 nm, mesopore volume is 0.1868 - 0.1945 cm 3 / g, micropore volume is 0.1788 - 0.1892 cm 3 / g. Calculated based on the total mass of this activated carbon being 100%, the N content is 0.66%). Place it in 50 mL of a nitric acid solution with a concentration of 4.0 mol / L, treat it at 60 °C under stirring conditions for 3 h, then perform suction filtration and separation, wash it with deionized water until neutral, and then dry it in vacuum at 70 °C for 3 h to obtain the pretreated carrier; place the pretreated carrier in 50 mL of ammonia water with a concentration of 5 mol / L, react at 60 °C under stirring conditions for 6 h, then perform suction filtration and separation, wash it with deionized water until neutral, and then dry it in vacuum at 70 °C for 3 h to obtain the modified carrier N-AC;

[0053] (2) Loading of the active component Ru

[0054] Weigh the corresponding anhydrous RuCl according to the loading amount 3 , prepare a Ru precursor solution with deionized water, dropwise add the Ru precursor solution into the modified support N-AC and stir evenly, then conduct natural ventilation drying for about 24 h. After observing that there is no redundant water on the surface, conduct vacuum drying at 70 °C for 3 h to further remove the moisture in the pores, and obtain N-AC loaded with Ru;

[0055] (3) Preparation of the catalyst

[0056] Place the N-AC loaded with Ru in a tubular furnace, calcine it at 300 °C for 4 h in a nitrogen atmosphere, then use deionized water for ultrasonic washing to remove Cl− until Cl− cannot be detected in the filtrate, and separate by suction filtration, and then conduct vacuum drying at 70 °C for 3 h to obtain a catalyst semi-finished product;

[0057] (4) Reduction of the catalyst

[0058] Place the catalyst semi-finished product in a tubular furnace, reduce it at 200 °C for 3 h in a hydrogen atmosphere, and after reduction, cool it to room temperature to obtain the Ru-based catalyst supported on N-doped activated carbon, denoted as Ru / N 5 -AC.

[0059] After testing, based on the total mass of the Ru-based catalyst supported on N-doped activated carbon being 100%, the content of N is 0.96%, and the loading amount of Ru is 0.5%.

[0060] Example 2

[0061] This example provides a Ru-based catalyst supported on N-doped activated carbon. The preparation method of this catalyst is basically the same as that of Example 1, except that: in step (1), ammonia water with a concentration of 10 mol / L is used, and the obtained catalyst is denoted as Ru / N 10 -AC.

[0062] After testing, based on the total mass of the Ru-based catalyst supported on N-doped activated carbon being 100%, the content of N is 1.05%, and the loading amount of Ru is 0.5%.

[0063] Example 3

[0064] This example provides a Ru-based catalyst supported on N-doped activated carbon. The preparation method of this catalyst is basically the same as that of Example 1, except that: in step (1), ammonia water with a concentration of 12 mol / L is used, and the obtained catalyst is denoted as Ru / N 12 -AC.

[0065] After testing, based on the total mass of the Ru-based catalyst supported on the N-doped activated carbon being 100%, the content of N is 1.44% and the loading amount of Ru is 0.5%.

[0066] Example 4

[0067] This example provides an Ru-based catalyst supported on N-doped activated carbon. The preparation method of this catalyst is basically the same as that of Example 1, except that: in step (1), ammonia water with a concentration of 14 mol / L is used, and the obtained catalyst is denoted as Ru / N 14 -AC.

[0068] After testing, based on the total mass of the Ru-based catalyst supported on the N-doped activated carbon being 100%, the content of N is 1.45% and the loading amount of Ru is 0.5%.

[0069] Comparative Example 1

[0070] This comparative example provides an Ru-based catalyst supported on activated carbon. The preparation method of this catalyst is basically the same as that of Example 1, except that: in step (1), N-functionalization modification is not carried out, and the pretreated carrier is directly subjected to the subsequent step (2), and the obtained catalyst is denoted as Ru / AC.

[0071] After testing, based on the total mass of the Ru-based catalyst supported on the activated carbon being 100%, the content of N is 0.66% and the loading amount of Ru is 0.5%.

[0072] The elemental analysis and characterization results of the catalysts prepared in the above Comparative Example 1 and Examples 1 to 4 are shown in Table 1 below.

[0073] Table 1 Elemental analysis and characterization results of Ru / N X -AC series catalysts

[0074]

[0075] Test Example 1

[0076] The catalysts prepared in the above Comparative Example 1 and Examples 1 to 4 were respectively applied to the catalytic hydrogenation reaction of DOP to synthesize DEHCH.

[0077] Table 2 is the catalytic reaction activity result table of the catalyst prepared in the above Comparative Example 1 and the Ru / N 5 -AC to Ru / N 14 -AC catalysts.

[0078] Table 2 Results of catalytic DOP hydrogenation reaction

[0079]

[0080] Reaction conditions: P = 4.0 MPa, T = 363 K, CDOP = 0.10 mol·L -1 , Vsol = 50 mL, mcat = 0.10 g, t = 3 h.

[0081] As can be seen from Table 2, compared with the unmodified Ru / AC catalyst prepared in Comparative Example 1, the catalytic activities of the catalysts prepared in Examples 1-4 of the present invention are significantly improved; meanwhile, the catalyst obtained by using ammonia water with a concentration of 12 mol / L as the modification reagent has the highest catalytic activity compared with other catalysts.

[0082] Test Example 2

[0083] XPS analysis was performed on the catalysts prepared in the above Comparative Example 1 and Examples 1-4. Figure 1 For the unmodified Ru / AC catalyst prepared in Comparative Example 1 and the Ru / N 5 -AC~Ru / N 14 -AC catalysts' XPS patterns. It can be seen from the XPS analysis results that N modification successfully modified the N-containing pyridine groups on the AC surface. The presence of this group can significantly improve the catalytic activity of the catalyst. The evidence is that as the concentration of the modification reagent (i.e., ammonia water) increases, the conversion rate of the reaction increases, and the reason for the improvement of the catalytic activity is the increase of pyridine nitrogen, which makes the binding sites between the surface of the catalyst and Ru increase, can more effectively anchor the Ru active metal, and improves the adsorption ability of the catalyst to the reactants, reducing the activation energy barrier of the DOP hydrogenation reaction, and showing better catalytic activity during the catalytic process; however, a modification reagent with too high a concentration reduces the activity of the catalyst, which is due to the collapse of the pore channels inside the carrier caused by too high a concentration of the modification reagent, reducing the specific surface area and the active sites that can anchor Ru decrease.

[0084] Obviously, the above embodiments of the present invention are merely examples for clearly illustrating the present invention, rather than limiting the implementation manners of the present invention. For those of ordinary skill in the art, other different forms of changes or modifications can be made on the basis of the above description. It is impossible to list all the implementation manners here. Any obvious changes or modifications derived from the technical solutions of the present invention still fall within the protection scope of the present invention.

Claims

1. A preparation method of an N-doped activated carbon supported Ru-based catalyst, which comprises the following steps: (1) Carrier pretreatment and N-functionalization modification Place activated carbon in a nitric acid solution for a period of time, then after washing, separation and drying, obtain the pretreated carrier; place the pretreated carrier in ammonia water for a period of time, then after washing, separation and drying, obtain the modified carrier N-AC; (2) Loading of the active component Ru Dropwise add the Ru precursor solution into the modified carrier N-AC and stir evenly, after drying, obtain the Ru-loaded N-AC; (3) Preparation of the catalyst Calcine the Ru-loaded N-AC in a nitrogen atmosphere, then after ultrasonic washing, separation and drying, obtain the catalyst semi-finished product; (4) Reduction of the catalyst Reduce the catalyst semi-finished product in a hydrogen atmosphere, and after reduction, cool it to room temperature to obtain the N-doped activated carbon supported Ru-based catalyst.

2. The preparation method according to claim 1, wherein, In step (1), the specific surface area of the activated carbon is 472.41 - 481.52 m 2 / g, the pore diameter is 2.54 - 3.00 nm, the mesopore volume is 0.1868 - 0.1945 cm 3 / g, and the micropore volume is 0.1788 - 0.1892 cm 3 / g.

3. The preparation method according to claim 1, wherein, In step (1), the concentration of the nitric acid solution is 4-6 mol / L; Preferably, in step (1), placing the activated carbon in the nitric acid solution for treatment is carried out under stirring conditions, the temperature of the treatment is 50-100 °C, and the time is 3-6 h.

4. The preparation method according to claim 1, wherein, In step (1), the concentration of the ammonia water is 5-14 mol / L; Preferably, in step (1), placing the pretreated carrier in the ammonia water for reaction is carried out under stirring conditions, the temperature of the reaction is 50-100 °C, and the time is 3-6 h.

5. The preparation method according to claim 1, wherein, In step (2), the Ru precursor solution includes ruthenium chloride solution.

6. The preparation method according to claim 1, wherein, In step (2), the drying includes: first performing natural drying for 24-48 h, and then performing vacuum drying at 60-100 °C for 3-5 h.

7. The preparation method according to claim 1, wherein, In step (3), the calcination temperature is 300-400 °C, and the time is 3-5 h.

8. The preparation method according to claim 1, wherein, In step (4), the reduction temperature is 150-250 °C, and the time is 3-5 h.

9. An N-doped activated carbon supported Ru-based catalyst, which is prepared by the preparation method according to any one of claims 1-8; Preferably, based on the total mass of the N-doped activated carbon supported Ru-based catalyst being 100%, the content of N therein is 0.96%-1.45%; Preferably, based on the total mass of the N-doped activated carbon supported Ru-based catalyst being 100%, the loading amount of Ru therein is 0.5%-1.0%.

10. Application of the N-doped activated carbon supported Ru-based catalyst according to claim 9 as a catalyst in the hydrogenation reaction of phthalate; Preferably, the phthalate is diisooctyl phthalate, and the product of the hydrogenation reaction is diisooctyl cyclohexane-1,2-dicarboxylate.

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