Nitrogen-doped spherical activated carbon loaded platinum-cerium catalyst as well as preparation and application thereof

Abstract

The invention belongs to the technical field of noble metal catalysts, and particularly relates to a preparation method and application of a long-life catalyst for continuous hydrogenation of a fixed bed. The catalyst (Pt-Ce / N-SAC) takes nitrogen-doped spherical activated carbon as a carrier, and platinum nanoparticles and cerium oxide nanoparticles are loaded; wherein the loading capacity of the platinum nanoparticles is 1-5% of the mass of the carrier, and the loading capacity of the cerium oxide nanoparticles is 0.1-0.5% of the mass of the carrier. The catalyst is applied to a reaction for preparing 1-amino-anthraquinone through hydrogenation of 1-nitroanthraquinone. The nitrogen-doped spherical activated carbon loaded platinum-cerium catalyst Pt-Ce / N-SAC provided by the invention is higher in 1-nitroanthraquinone hydrogenation reaction rate and higher in selectivity, and has longer service life when being applied to microchannel continuous flow hydrogenation.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of noble metal catalysts, and particularly relates to a nitrogen-doped spherical activated carbon supported platinum-cerium catalyst and a preparation and application thereof. BACKGROUND

[0002] Aminoanthraquinone is an important intermediate for synthesizing anthraquinone series dyes, is a raw material for producing bromoamino acid, disperse red RLZ, disperse brilliant red ERLN, and reactive brilliant blue X-BR, and can be used for producing inks, coatings and pigments, and in recent years, has also been used for liquid crystal dyes, photosensitizers for photodegradation of polyesters, catalysts for electrocatalytic reduction of H2O2, photosensitive dyes for dye-sensitized solar cells, and synthesis of electrode materials.

[0003] In the industrial production technology, 1-nitroanthraquinone is mainly used as a raw material, and 1-aminoanthraquinone is obtained through reduction by sodium sulfide and sodium sulfite and then oxidation. However, this process has a serious environmental pollution problem, and a large amount of three wastes is generated in the production process, and the pressure for hazardous waste treatment is large. Compared with the traditional process, the catalytic hydrogenation reduction process has high product yield, generates less three wastes in the production process, and only a small amount of wastewater, which is one of the better alternative processes.

[0004] The superparamagnetic nanoparticle supported carbonyl nickel catalyst disclosed in Chinese Patent CN113045440B is used for 1-nitroanthraquinone hydrogenation, and has high selectivity, but the disadvantages of the tank type hydrogenation process are that the reaction time is relatively long, the catalyst life is relatively short, the production efficiency is low, and the cost is relatively high. Compared with the tank type hydrogenation process, the fixed bed hydrogenation process has the advantages of simple structure, stable operation, short reaction time, and easy control, and most importantly, it can be used for continuous production, improves the production efficiency, and reduces the production cost. The continuous preparation of 1-aminoanthraquinone by using a fixed bed disclosed in Chinese Patent CN105017039B uses a Pd / C catalyst with high selectivity, but the catalyst life is not mentioned. In fact, the fixed bed hydrogenation process not only has high selectivity requirements for the catalyst, but also has high requirements for the catalyst life, so as to truly reflect the advantages of continuous flow process in improving production efficiency and saving cost.

[0005] Therefore, it is urgent to provide a long-life, efficient, safe and stable catalyst for 1-nitroanthraquinone fixed bed continuous flow hydrogenation. SUMMARY

[0006] The purpose of the present application is to provide a preparation method and application of a long-life catalyst for fixed bed continuous hydrogenation, and particularly to provide a nitrogen-doped spherical activated carbon supported platinum-cerium catalyst for 1-nitroanthraquinone fixed bed continuous flow hydrogenation to prepare 1-aminoanthraquinone.

[0007] To achieve the above-mentioned purpose, the technical scheme adopted by the present application is as follows:

[0008] A nitrogen-doped spherical activated carbon supported platinum-cerium catalyst, the catalyst (Pt-Ce / N-SAC) is supported with platinum nanoparticles and cerium oxide nanoparticles on a nitrogen-doped spherical activated carbon carrier; wherein the loading amount of platinum nanoparticles is 1-5% of the mass of the carrier, preferably the loading amount of platinum nanoparticles is 3% of the mass of the carrier; the loading amount of cerium oxide nanoparticles is 0.1-0.5% of the mass of the carrier.

[0009] The nitrogen content in the nitrogen-doped spherical activated carbon is 0.8-3.2%, wherein the pyridine-type nitrogen accounts for more than 65% of the total nitrogen.

[0010] A preparation method of the nitrogen-doped spherical activated carbon supported platinum-cerium catalyst, characterized in that: a nitrogen-doped spherical activated carbon is used as a carrier, impregnated in a cerium solution, and then calcined to obtain a cerium oxide nanoparticle supported nitrogen-doped spherical activated carbon, and then the cerium oxide nanoparticle supported nitrogen-doped spherical activated carbon is mixed and impregnated with a platinum precursor solution, reduced with sodium borohydride, to obtain the nitrogen-doped spherical activated carbon supported platinum-cerium catalyst Pt-Ce / N-SAC.

[0011] The preparation method of the nitrogen-doped spherical activated carbon is: first, hydrogen peroxide is used to pretreat the spherical activated carbon, then the pretreated spherical activated carbon is impregnated in a nitrogen-containing solution, an additive is added, ultrasonic treatment is carried out at 50-70℃ for 10-30min, water is removed by reduced pressure distillation, then drying is carried out at 60-80℃ for 8-10h, and finally calcination is carried out under a nitrogen atmosphere to obtain the nitrogen-doped spherical activated carbon carrier.

[0012] The additive is at least one of ZnCl2, FeCl3 and NiCl2; the calcination temperature is 600-800℃, the heating rate is 15-20℃ / min, and the calcination time is 2-4h.

[0013] Under stirring conditions, the nitrogen-doped spherical activated carbon carrier is impregnated in a cerium nitrate aqueous solution, filtered, and then calcined to obtain the cerium oxide nanoparticle supported nitrogen-doped spherical activated carbon.

[0014] The concentration of the cerium nitrate aqueous solution is 0.001-0.005g / mL, the impregnation temperature is 20-50℃, the impregnation time is 1-3h, the calcination temperature is 200-400℃, the heating rate is 6-12℃ / min, and the calcination time is 2-6h.

[0015] The cerium oxide nanoparticle supported nitrogen-doped spherical activated carbon is placed in a container and vacuumed, then a platinum precursor solution is added, the temperature is raised to 40-60℃, stirring impregnation is carried out for 30-60min, the temperature is lowered to room temperature, and then sodium borohydride aqueous solution is slowly dripped for reduction, to obtain the nitrogen-doped spherical activated carbon supported platinum-cerium catalyst Pt-Ce / N-SAC.

[0016] The platinum precursor solution is at least one of platinum nitrate, platinum chloride, and an aqueous solution of chloroplatinic acid, and the pH of the platinum precursor solution is 4.5-6.0.

[0017] The hydrogen peroxide pretreatment of the spherical activated carbon is mixing the spherical activated carbon with a hydrogen peroxide solution with a concentration of 10-30%, stirring at 40-70 DEG C for 3-5 hours, filtering and washing, and drying in a vacuum oven at 70 DEG C for 8 hours.

[0018] The nitrogen source of the nitrogen-containing solution is at least one of urea and melamine; the mass ratio of the nitrogen source to the pretreated spherical activated carbon is 0.3-0.75:1; the mass ratio of the nitrogen source to the auxiliary agent is 30:1; the nitrogen-containing solution is an ethanol aqueous solution with a volume ratio of 1:1; and the usage ratio of the pretreated spherical activated carbon to the nitrogen-containing solution is 1g:3-6mL.

[0019] The application of the nitrogen-doped spherical activated carbon loaded platinum-cerium catalyst, and the application of the catalyst in the reaction of preparing 1-aminoanthraquinone by hydrogenating 1-nitroanthraquinone.

[0020] A method for preparing 1-aminoanthraquinone, which is prepared by catalytic hydrogenation reaction of 1-nitroanthraquinone as a raw material through the catalyst, specifically comprising the following steps:

[0021] 1-nitroanthraquinone is dissolved in N,N-dimethylformamide, preheated by heating, and hydrogen is introduced into a fixed bed filled with the nitrogen-doped spherical activated carbon loaded platinum-cerium catalyst Pt-Ce / N-SAC of claim 1 to perform hydrogenation reaction, after passing through a gas-liquid separator, the separated liquid phase is introduced into a gas-liquid micro-mixer with oxygen to perform oxidation reaction, and 1-aminoanthraquinone is obtained after cooling and crystallization.

[0022] The mass ratio of 1-nitroanthraquinone to N,N-dimethylformamide is 1:8-15, the preheating temperature is 40-65 DEG C, the hydrogenation reaction temperature is 65-85 DEG C, the hydrogenation reaction pressure is 0.8-1.5 MPa, the hydrogenation reaction liquid residence time is 35-75 s, the oxidation reaction time is 50-80 s, and the oxidation reaction temperature is 25-30 DEG C.

[0023] Compared with the prior art, the nitrogen-doped spherical activated carbon loaded platinum-cerium catalyst Pt-Ce / N-SAC has the following beneficial effects:

[0024] The nitrogen-doped spherical activated carbon loaded platinum-cerium catalyst Pt-Ce / N-SAC has the following beneficial effects:

[0025] 1. The spherical activated carbon as a catalyst carrier has high strength, can maintain stable structure during catalytic reaction, reduces catalyst abrasion and crushing, the spherical structure makes it have excellent flow performance in the fixed bed reactor, fully contacts with the reaction liquid, thereby improving the reaction efficiency.

[0026] 2. The activated carbon carrier is doped with nitrogen, so that the activated carbon has larger specific surface area and stronger adsorption capacity, which is beneficial to the dispersion of metal active components, in addition, the anchoring effect of nitrogen atoms on metals enhances the interaction between the metal active components and the carrier, improves the hydrogenation activity and stability of the catalyst.

[0027] 3. In the form of nitrogen doping, mainly in the form of pyridine nitrogen, the increase of the proportion of pyridine nitrogen is beneficial to improve the nitrogen defect site, and more conducive to the formation of stronger interaction between Pt-N, and improve the catalytic hydrogenation activity. At the same time, the preparation of nitrogen-doped spherical activated carbon uses rapid heating method, the heating rate is 15-20℃ / min, reduces the structure rearrangement during slow pyrolysis of the precursor, retains more edge defects, forms more pyridine nitrogen, and the proportion of pyridine nitrogen in total nitrogen is greater than 65%, and the addition of additives stabilizes the pyridine nitrogen through coordination.

[0028] 4. The surface of cerium oxide in the form of nanoparticles has rich oxygen vacancies, which can be used as adsorption and dissociation sites of hydrogen molecules, significantly reduces the hydrogen dissociation energy barrier, generates high-activity hydrogen atoms, thereby improves the hydrogenation reaction rate, and the defect sites on the surface can better anchor platinum metal particles, inhibit the sintering of metal particles in high-temperature reaction. At the same time, the unique metal valence change of cerium oxide can oxidize the adsorbed carbon precursor in the reaction, prevent it from covering the metal active sites, has certain anti-coking ability, thereby prolongs the service life of the catalyst. BRIEF DESCRIPTION OF DRAWINGS

[0029] Figure 1 The Pt-Ce / N-SAC catalyst provided by the embodiment of the present application is shown in the figure. DETAILED DESCRIPTION

[0030] The present application is described in detail below by means of the drawings and specific embodiments, but does not limit the protection scope of the present application.

[0031] The catalyst Pt-Ce / N-SAC of the application takes nitrogen-doped spherical activated carbon as a carrier, loads platinum and cerium oxide nanoparticles, and dopes nitrogen in the activated carbon carrier. In the nitrogen existing form, the increase of pyridine type nitrogen provides more defect sites, is beneficial to the dispersion of metal active components, promotes the anchoring effect of N atoms on metals, thereby enhancing the interaction between the metal active components and the carrier, improving the hydrogenation activity and stability of the catalyst. The loaded cerium oxide nanoparticles can inhibit the sintering of platinum metal particles in high-temperature reactions and have certain anti-carbon deposition capacity, so that the catalyst has a longer service life. The application of the catalyst to fixed-bed continuous flow hydrogenation reaction has the advantages of high activity, high selectivity, safety and stability, high efficiency and economy.

[0032] Example 1

[0033] (1) Preparation of nitrogen-doped spherical activated carbon: first, pretreat the spherical activated carbon, weigh 10 g of spherical activated carbon into a single-necked flask, add 35 mL of 20% hydrogen peroxide solution, heat to 50℃ in a water bath, and magnetically stir for 4 h, then wash and filter with a small amount of deionized water, and dry in a 70℃ vacuum drying oven for 8 h to obtain pretreated spherical activated carbon. Take 25 mL of ethanol and 25 mL of deionized water, stir uniformly, then add 6 g of melamine, 0.2 g of ZnCl2 and 10 g of pretreated spherical activated carbon, ultrasonically stir at 60℃ for 30 min, remove most of the water by vacuum distillation, then dry in a 70℃ vacuum drying oven for 8 h, and then place in a tube furnace and calcine under a nitrogen atmosphere, with a heating rate of 20℃ / min, a calcination temperature of 750℃ and a calcination time of 2 h. After cooling to room temperature, remove and obtain nitrogen-doped spherical activated carbon, with a nitrogen content of about 2.4% and pyridine type nitrogen accounting for 66.5% of the total nitrogen.

[0034] (2) Preparation of cerium oxide-loaded nitrogen-doped activated carbon: take 0.077 g of Ce(NO3)3·H2O and dissolve in 25 mL of deionized water to prepare a cerium nitrate aqueous solution, immerse the nitrogen-doped spherical activated carbon carrier in the cerium nitrate aqueous solution, magnetically stir at 50℃ for 2 h, filter, and then place in a muffle furnace and calcine, with a heating rate of 8℃ / min in the muffle furnace, a calcination temperature of 350℃ and a calcination time of 4 h. After cooling to room temperature, remove and obtain cerium oxide nanoparticle-loaded nitrogen-doped activated carbon, with a cerium oxide nanoparticle loading of about 0.3%.

[0035] (3) Preparation of platinum-cerium supported nitrogen-doped activated carbon catalyst: 0.83 g of H2PtCl6·6H2O was weighed and dissolved in 25 mL of deionized water, and a platinum precursor solution was obtained by slowly adjusting the pH to 5.0 with a 0.1 mol / L sodium carbonate solution. The cerium oxide nanoparticle supported nitrogen-doped spherical activated carbon was placed in a pressure-resistant flask and vacuumed, and then the platinum precursor solution was slowly dropped into it. After the dropping was completed, the vacuum device was removed, and the temperature was increased to 50°C for 60 min of stirring and impregnation. After the temperature was reduced to room temperature, 0.6 g of sodium borohydride was dissolved in 40 mL of deionized water, and the sodium borohydride aqueous solution was slowly dropped into it. After stirring for 90 min, it was washed and filtered with deionized water to obtain a platinum-cerium catalyst supported by nitrogen-doped spherical activated carbon, Pt-Ce / N-SAC. The platinum nanoparticle loading was about 3%, and the catalyst was named C1.

[0036] Example 2

[0037] (1) The preparation steps of the nitrogen-doped spherical activated carbon were different from those of Example 1 in that the amount of melamine added was 7.5 g, and the amount of ZnCl2 was 0.25. The nitrogen content was about 3.0%, and the pyridine-type nitrogen accounted for 67.2% of the total nitrogen content.

[0038] (2) The preparation method of the cerium oxide supported nitrogen-doped activated carbon was the same as that of Example 1.

[0039] (3) The preparation method of the platinum-cerium supported nitrogen-doped activated carbon catalyst was the same as that of Example 1, and the catalyst was named C2.

[0040] Example 3

[0041] (1) The preparation steps of the nitrogen-doped spherical activated carbon were different from those of Example 1 in that the amount of melamine added was 3.0 g, and the amount of ZnCl2 was 0.1 g. The nitrogen content was about 1.2%, and the pyridine-type nitrogen accounted for 65.9% of the total nitrogen content.

[0042] (2) The preparation method of the cerium oxide supported nitrogen-doped activated carbon was the same as that of Example 1.

[0043] (3) The preparation method of the platinum-cerium supported nitrogen-doped activated carbon catalyst was the same as that of Example 1, and the catalyst was named C3.

[0044] Example 4

[0045] (1) The preparation steps of the nitrogen-doped spherical activated carbon were the same as those of Example 1.

[0046] (2) The preparation method of the cerium oxide supported nitrogen-doped activated carbon was different from that of Example 1 in that the amount of Ce(NO3)3·H2O added was 0.128 g, and the content of cerium oxide nanoparticles was about 0.3%.

[0047] (3) The preparation method of platinum and cerium supported nitrogen-doped activated carbon catalyst is the same as that of Example 1, and the catalyst is named as C4.

[0048] Example 5

[0049] (1) The preparation steps of nitrogen-doped spherical activated carbon are the same as those of Example 1.

[0050] (2) The preparation method of cerium oxide supported nitrogen-doped activated carbon is different from that of Example 1 in that the addition amount of Ce(N03)3-H20 is 0.026 g, and the content of cerium oxide nanoparticles is about 0.1%.

[0051] (3) The preparation method of platinum and cerium supported nitrogen-doped activated carbon catalyst is the same as that of Example 1, and the catalyst is named as C5.

[0052] Example 6

[0053] (1) The preparation steps of nitrogen-doped spherical activated carbon are the same as those of Example 1.

[0054] (2) The preparation method of cerium oxide supported nitrogen-doped activated carbon is the same as that of Example 1.

[0055] (3) The preparation method of platinum and cerium supported nitrogen-doped activated carbon catalyst is different from that of Example 1 in that the platinum precursor solution is 0.028 g of H2PtCl6-6H20 dissolved in 25 mL of deionized water, the reducing agent sodium borohydride is 0.2 g dissolved in 40 mL of deionized water, the content of platinum nanoparticles is about 1%, and the catalyst is named as C6.

[0056] Example 7

[0057] (1) The preparation steps of nitrogen-doped spherical activated carbon are the same as those of Example 1.

[0058] (2) The preparation method of cerium oxide supported nitrogen-doped activated carbon is the same as that of Example 1.

[0059] (3) The preparation method of platinum and cerium supported nitrogen-doped activated carbon catalyst is different from that of Example 1 in that the platinum precursor solution is 0.138 g of H2PtCl6-6H20 dissolved in 25 mL of deionized water, the reducing agent sodium borohydride is 1.0 g dissolved in 40 mL of deionized water, the content of platinum nanoparticles is about 5%, and the catalyst is named as C7.

[0060] Comparative Example 1

[0061] Preparation of platinum supported spherical activated carbon catalyst (Pt / SAC): different from Example 1 is that the spherical activated carbon is not modified by nitrogen doping, and no cerium oxide is supported, only platinum is supported, and the other preparation methods are the same as those of Example 1, and the catalyst is named as C8.

[0062] Comparative Example 2

[0063] Preparation of platinum-loaded nitrogen-doped spherical activated carbon catalyst (Pt / N-SAC): The difference from Example 1 is that cerium oxide is not loaded, only platinum is loaded, and other preparation methods are the same as those of Example 1, and the catalyst is named C9.

[0064] Comparative Example 3

[0065] Preparation of platinum-cerium-loaded spherical activated carbon catalyst (Pt-Ce / SAC): The difference from Example 1 is that the spherical activated carbon is not modified by nitrogen doping, and cerium oxide and platinum are loaded, and other preparation methods are the same as those of Example 1, and the catalyst is named C10.

[0066] Comparative Example 4

[0067] The preparation steps of the nitrogen-doped spherical activated carbon are different from those of Example 1 in that the tube furnace heating rate is 5°C / min during the preparation of the nitrogen-doped spherical activated carbon, and other conditions are the same as those of Example 1, the nitrogen content of the nitrogen-doped spherical activated carbon is 2.4%, and the pyridine-type nitrogen accounts for 48.6% of the total nitrogen, and the catalyst is named C11.

[0068] The catalysts prepared in the above examples and comparative examples were applied to a fixed-bed continuous flow hydrogenation reaction to prepare 1-aminoanthraquinone from 1-nitroanthraquinone.

[0069] The evaluation method is as follows: The fixed-bed reactor is filled with the catalyst prepared above. 80g of 1-nitroanthraquinone is added to 960g of N,N-dimethylformamide (DMF), heated to 60°C, dissolved and kept at temperature with stirring, to form a DMF mixture of 1-nitroanthraquinone, pumped into a 70°C preheater at a flow rate of 2.0mL / min, then mixed with 6.0mL / min of hydrogen gas in a 75°C fixed-bed reactor, the back pressure valve pressure is 1.5MPa, and the residence time of the reaction liquid is 40s. The hydrogenation reaction liquid passes through a gas-liquid separator, the separated liquid phase is cooled to 25°C through a heat exchanger, and 10mL / min of oxygen gas is introduced into a gas-liquid micro-mixer for oxidation reaction, and the residence time in the tubular reactor is 60s. The oxidized reaction liquid is collected, filtered and washed after cooling and crystallization to obtain 1-aminoanthraquinone, which is analyzed by liquid chromatography and the yield is calculated.

[0070] The results of catalyst evaluation are shown in the following table:

[0071] Catalyst number 1-aminoanthraquinone purity / % 1-aminoanthraquinone yield / % Run time / h ① ]] C1 99.82 97.5 120 C2 99.15 96.8 102 C3 98.76 96.6 96 C4 99.15 96.7 115 C5 99.06 96.7 110 C6 99.30 96.9 80 C7 99.35 97.0 75 C8 97.65 95.2 15 C9 98.55 96.3 18 C10 98.78 96.4 64 C11 98.83 96.4 48

[0072] ①The investigation standard is that the real-time monitoring of 1-nitroanthraquinone conversion rate is reduced to below 99.5%, and the total continuous hydrogenation running time is counted.

[0073] From the catalyst evaluation results of the above examples, the nitrogen-doped spherical activated carbon supported platinum-cerium catalyst of the present application has excellent selectivity and longer service life, and the yield of 1-aminoanthraquinone is as high as 97.5%.

[0074] In summary, the appropriate content of nitrogen and cerium oxide in the nitrogen-doped spherical activated carbon support of the present application is beneficial to improve the hydrogenation reaction activity of platinum and prolong the service life of the catalyst, and excessive doping will cause the pore channel of the activated carbon support to be blocked due to agglomeration, which will have a negative effect. Compared with the catalyst without nitrogen and cerium oxide doping, the service life of the catalyst of the present application is increased by 8 times, thanks to the unique metal valence change of cerium oxide, which can oxidize the adsorbed carbon precursor in the reaction and prevent it from covering the metal active sites, making it have the ability to resist carbon deposition. In addition, the use of rapid heating method and the addition of additives improves the proportion of pyridine-type nitrogen in the nitrogen-doped form, increases the nitrogen defect site, and is more conducive to the formation of stronger interaction between Pt-N, which improves the catalytic hydrogenation activity.

[0075] The platinum metal loading has a greater impact on the performance of the catalyst, and low loading leads to fewer effective catalytic active sites, resulting in shorter catalyst life; although high loading significantly increases the catalytic active sites, it will cause uneven dispersion of platinum metal particles in the carrier, which is easy to form agglomeration, which will cause sintering to occur more easily during the reaction, resulting in a decrease in activity and poor stability. Therefore, the platinum metal loading of the catalyst of the present application is 3%, which has the best reaction activity and stability.

[0076] The catalyst of the present application is applied to 1-nitroanthraquinone fixed-bed continuous flow hydrogenation, compared with the traditional tank hydrogenation process, the reaction time is shortened from several hours to tens of seconds, and the product has higher purity and yield, which is due to the high reaction activity, selectivity and long service life of the catalyst. In addition, the micro-channel reactor can accurately control the reaction temperature, reduce the generation of by-products, greatly improve the reaction rate, and has the advantages of safety, stability, high efficiency and economy.

Claims

1. A nitrogen-doped spherical activated carbon-supported platinum-cerium catalyst, characterized in that: The catalyst (Pt-Ce / N-SAC) uses nitrogen-doped spherical activated carbon as a carrier and loads platinum nanoparticles and cerium oxide nanoparticles; the loading amount of the platinum nanoparticles is 1-5% of the carrier mass, and the loading amount of the cerium oxide nanoparticles is 0.1-0.5% of the carrier mass.

2. The nitrogen-doped spherical activated carbon-supported platinum-cerium catalyst according to claim 1, characterized in that: The nitrogen content in nitrogen-doped spherical activated carbon is 0.8-3.2%.

3. A method for preparing the nitrogen-doped spherical activated carbon-supported platinum-cerium catalyst according to claim 1, characterized in that: Nitrogen-doped spherical activated carbon was used as a carrier, which was impregnated in a cerium solution and then calcined to obtain nitrogen-doped spherical activated carbon supported by cerium oxide nanoparticles. The nitrogen-doped spherical activated carbon supported by cerium oxide nanoparticles was then mixed with a platinum precursor solution and impregnated, and reduced with sodium borohydride to obtain a nitrogen-doped spherical activated carbon supported platinum-cerium catalyst Pt-Ce / N-SAC.

4. The method for preparing the nitrogen-doped spherical activated carbon-supported platinum-cerium catalyst according to claim 3, wherein: The preparation method of nitrogen-doped spherical activated carbon comprises: first pre-treating the spherical activated carbon with hydrogen peroxide, then immersing the pre-treated spherical activated carbon in a nitrogen-containing solution, adding an auxiliary agent, ultrasonically treating the spherical activated carbon at 50-70°C for 10-30 minutes, removing water by vacuum distillation, then drying the spherical activated carbon at 60-80°C for 8-10 hours, and finally calcining the spherical activated carbon under a nitrogen atmosphere to obtain a nitrogen-doped spherical activated carbon carrier; The auxiliary agent is at least one of ZnCl2, FeCl3, and NiCl2; the calcination temperature is 600-800°C, the heating rate is 15-20°C / min, and the calcination time is 2-4h.

5. The method for preparing the nitrogen-doped spherical activated carbon-supported platinum-cerium catalyst according to claim 3, wherein: Under stirring conditions, the nitrogen-doped spherical activated carbon support is impregnated with a cerium nitrate aqueous solution, filtered, and then calcined to obtain nitrogen-doped spherical activated carbon supported by cerium oxide nanoparticles; The concentration of the cerium nitrate aqueous solution is 0.001-0.005 g / mL, the immersion temperature is 20-50° C., the immersion time is 1-3 hours, the calcination temperature is 200-400° C., the heating rate is 6-12° C. / min, and the calcination time is 2-6 hours.

6. The method for preparing the nitrogen-doped spherical activated carbon-supported platinum-cerium catalyst according to claim 3, wherein: The nitrogen-doped spherical activated carbon supported by cerium oxide nanoparticles is placed in a vacuum container, and then a platinum precursor solution is added. The temperature is raised to 40-60°C, stirred and immersed for 30-60 minutes. After cooling to room temperature, a sodium borohydride aqueous solution is slowly added dropwise for reduction to obtain a nitrogen-doped spherical activated carbon supported platinum-cerium catalyst Pt-Ce / N-SAC. The platinum precursor solution is at least one of platinum nitrate, platinum chloride, and chloroplatinic acid aqueous solution, and the pH of the platinum precursor solution is 4.5-6.

0.

7. The nitrogen-doped spherical activated carbon-supported platinum-cerium catalyst according to claim 4, characterized in that: The spherical activated carbon is pretreated with hydrogen peroxide by mixing the spherical activated carbon with a 10-30% hydrogen peroxide solution, stirring at 40-70° C. for 3-5 hours, filtering and washing, and then drying in a vacuum oven at 70° C. for 8 hours.

8. The method for preparing the nitrogen-doped spherical activated carbon-supported platinum-cerium catalyst according to claim 4, wherein: The nitrogen source of the nitrogen-containing solution is at least one of urea and melamine; the mass ratio of the nitrogen source to the pretreated spherical activated carbon is 0.3-0.75:1; the mass ratio of the nitrogen source to the auxiliary agent is 30:1; the nitrogen-containing solution is an ethanol-water solution with a volume ratio of 1:1, and the dosage ratio of the pretreated spherical activated carbon to the nitrogen-containing solution is 1 g: 3-6 mL.

9. Use of the nitrogen-doped spherical activated carbon-supported platinum-cerium catalyst according to claim 1, characterized in that: The catalyst is used in the reaction of preparing 1-aminoanthraquinone by hydrogenation of 1-nitroanthraquinone.

10. A method for preparing 1-aminoanthraquinone, characterized in that: The method is prepared by using 1-nitroanthraquinone as a raw material and carrying out a catalytic hydrogenation reaction using the catalyst according to claim 1, specifically: 1-nitroanthraquinone is dissolved in N,N-dimethylformamide, preheated, and introduced together with hydrogen into a fixed bed filled with the nitrogen-doped spherical activated carbon-supported platinum-cerium catalyst Pt-Ce / N-SAC of claim 1 for hydrogenation reaction. After passing through a gas-liquid separator, the separated liquid phase and oxygen are introduced into a gas-liquid micromixer for oxidation reaction, and 1-aminoanthraquinone is obtained after cooling and crystallization. The mass ratio of 1-nitroanthraquinone to N,N-dimethylformamide is 1:8-15, the preheating temperature is 40-65°C, the hydrogenation reaction temperature is 65-85°C, the hydrogenation reaction pressure is 0.8-1.5 MPa, the residence time of the hydrogenation reaction liquid is 35-75s, the oxidation reaction time is 50-80s, and the oxidation reaction temperature is 25-30°C.

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