Method for preparing amino phenyl acetylene by selectively hydrogenating nitro phenyl acetylene

Abstract

The present application relates to a method for preparing amino phenyl acetylene by selectively hydrogenating nitro phenyl acetylene. The method uses anhydrous ethanol as a solvent, hydrazine hydrate as a hydrogen source, and alpha-Fe2O3, Fe3O4, alpha-Fe2O3 / TiO2, alpha-Fe2O3 / neutral Al2O3 or alpha-Fe2O3 / activated carbon catalyst to catalyze the hydrogenation of nitro phenyl acetylene to prepare amino phenyl acetylene at 80-150 DEG C. The above-mentioned catalyst has high selectivity for hydrogenating the nitro group in nitro phenyl acetylene. When the conversion rate of nitro phenyl acetylene is 100%, the highest selectivity of amino phenyl acetylene can reach 96%. If the reaction time is prolonged, the selectivity of amino phenyl acetylene remains basically unchanged, and there is no accumulation of harmful intermediates such as phenylhydroxylamine during the reaction.

Description

TECHNICAL FIELD

[0001] The present application relates to a method for preparing amino phenyl acetylene by selective hydrogenation of nitro phenyl acetylene. Specifically, the method for preparing amino phenyl acetylene by selective hydrogenation of nitro phenyl acetylene using α-Fe2O3, Fe3O4, α-Fe2O3 / TiO2, α-Fe2O3 / neutral Al2O3 or α-Fe2O3 / activated carbon as catalyst, hydrazine hydrate as hydrogen source in green solvent ethanol. BACKGROUND

[0002] Amino phenyl acetylene is an important intermediate for preparing high-end polymer materials, and is also an important raw material for synthesizing effective anticancer drug erlotinib hydrochloride.

[0003] Catalytic hydrogenation of nitro phenyl acetylene is a relatively clean process for preparing amino phenyl acetylene. Nitro phenyl acetylene contains both nitro and acetylene groups which are easy to be reduced. The catalyst has the performance of preferentially catalyzing hydrogenation of nitro group and being inert to hydrogenation of acetylene group, which is the key to improve the yield of amino phenyl acetylene. CoS xFor the catalyst, 3-nitrophenylacetylene was reacted at 108℃ under 1000psig H2pressure for 0.75h, and the yield of 3-aminophenylacetylene was 86%(Anatoli Onopchenko, et al., J. Org. Chem., 1979). The reaction process produces sulfur-containing byproducts, and the solvent is difficult to reuse, which pollutes the environment. The 3 wt% Co / C prepared by high-temperature pyrolysis catalyzes the hydrogenation of 4-nitrophenylacetylene in tetrahydrofuran, and the yield of 4-aminophenylacetylene is 88% at 110℃ under 50bar H2pressure for 4h(Felix A. Westerhaus, et al., Nat. Chem., 2013). The nitrogen-doped Fe2O3-N / C catalyst prepared by mixing Fe(OAc)2, 1,10-phenanthroline and carbon powder at 800℃ by high-temperature pyrolysis method catalyzes the reaction of 4-nitrophenylacetylene in tetrahydrofuran with hydrazine hydrate as the hydrogen source at 100℃ for 10h, and the reaction is completely converted, and the selectivity of 4-aminophenylacetylene is 96%(Rajenahally V. Jagadeesh, et al., Chem. Commun., 2011); in addition, 60mg Fe2O3-N / C catalyzes the reaction of 0.5mmol 4-nitrophenylacetylene in 1:1 water-tetrahydrofuran solvent at 105℃ under 50bar H2pressure for 26h, and the yield of 4-aminophenylacetylene is 75%(Rajenahally V. Jagadeesh, et al., Science, 2013). Toluene is used as the solvent, 0.2wt% Pt / TiO2 is used as the catalyst, and the hydrogenation of 4-nitrophenylacetylene is catalyzed at 6bar H2and 313K for 5.6h, the conversion rate is 98.9%, and the selectivity of 4-aminophenylacetylene is 90.1%(Corma, et al., J. Am. Chem. Soc., 2008). Pt-Zn / SnO2-Sb2O3 is used as the catalyst, and the conversion rate of 4-nitrophenylacetylene hydrogenation is 100% and the selectivity of 4-aminophenylacetylene is 87.9% in ethanol at 50℃ under 4MPa H2for 20min(CN107216255B). Ammonia borane is used as the hydrogen source, and PtZn / HNCNT catalyzes the hydrogenation of 4-nitrophenylacetylene in a mixture of ethanol and water, and the conversion rate is >99% and the selectivity of 4-aminophenylacetylene is 99% at 40℃ for 4h(Aijuan Han, et al., Nat. Commun., 2019). In the presence of CO and H2, 0.25% Pt / α-MoC is used as the catalyst to catalyze the hydrogenation of 4-nitrophenylacetylene in toluene-water medium, and the conversion rate is 100% and the selectivity of 4-aminophenylacetylene is 99.9% after 4h(Lili Lin, et al., Nat. Nanotech., 2019). PdCd1.13 Catalytic hydrogenation of 4-nitrophenylacetylene with HCOONH4 as hydrogen source in DMF at 60℃ for 3h, the reactant was completely converted, and the selectivity of 4-aminophenylacetylene was 92% (Yonggang Feng, et al., J. Am. Chem. Soc., 2020).

[0004] The use of non-noble metal catalysts to catalyze the hydrogenation of nitrophenylacetylene can significantly reduce the cost of the catalyst. Currently, the process using non-noble metal catalysts has the following main problems: (1) the reaction is carried out in harmful and volatile organic solvents such as tetrahydrofuran, which is easy to pollute the environment. (2) The activity of the above non-noble metal catalysts is low and needs to be further improved. (3) The catalyst is prepared by pyrolysis at 800℃, which is a harsh condition. SUMMARY

[0005] The present application relates to a method for selectively hydrogenating nitrophenylacetylene to prepare aminophenylacetylene using α-Fe2O3, Fe3O4, α-Fe2O3 / TiO2, α-Fe2O3 / neutral Al2O3 or α-Fe2O3 / activated carbon as catalyst, hydrazine hydrate as hydrogen source in green solvent ethanol.

[0006] The technical solution adopted by the present application is: anhydrous ethanol, nitrophenylacetylene, catalyst α-Fe2O3 or Fe3O4 powder or catalyst α-Fe2O3 / TiO2, α-Fe2O3 / neutral Al2O3 or α-Fe2O3 / activated carbon and 80% N2H4·H2O solution are added to the reactor, the mass ratio of anhydrous ethanol to nitrophenylacetylene is (20-120):1, the mass ratio of nitrophenylacetylene to catalyst is (1-20):1, the mass ratio of N2H4·H2O to nitrophenylacetylene is (0.5-1.3):1, the reactor is tightened, high-purity nitrogen is used to purge for 5min at room temperature to exclude air in the reactor, and then the reactor is heated to 80-150℃, and after preheating for 20min, the stirring is turned on, and the reaction is carried out until the reactant is close to or reaches complete conversion to obtain aminophenylacetylene.

[0007] The nitrophenylacetylene is 2-nitrophenylacetylene, 3-nitrophenylacetylene and 4-nitrophenylacetylene.

[0008] The catalyst is prepared by the following method:

[0009] (1) The catalyst α-Fe2O3, Fe3O4 can use commercially available nano α-Fe2O3 and Fe3O4, and the α-Fe2O3 can also be prepared by calcining ferric citrate, ferric ammonium citrate or ferric nitrate in a muffle furnace at 250-500℃ in air atmosphere for 2-10h.

[0010] (2) The mass content of Fe2O3 in the supported catalyst α-Fe2O3 / TiO2, α-Fe2O3 / neutral Al2O3 or α-Fe2O3 / activated carbon is 5% to 45%. A certain amount of ferric nitrate solution or ferric ammonium citrate solution is loaded onto the carrier by using the equal-volume impregnation method; if the loading amount of α-Fe2O3 cannot meet the requirements due to the limitation of ferric salt solubility, a certain amount of α-Fe2O3 is loaded onto the carrier by using the method of excessive solution impregnation and evaporation to remove excessive water. For example, the TiO2 is impregnated with ferric nitrate solution; when the mass content of α-Fe2O3 is less than 15%, the equal-volume impregnation method is used to prepare α-Fe2O3 / TiO2; when the content of α-Fe2O3 is greater than or equal to 15%, the method of excessive solution impregnation and evaporation to remove excessive water is used to prepare α-Fe2O3 / TiO2, and the specific process is as follows: the TiO2 powder is placed in a certain amount of Fe(NO3)3·9H2O solution, stirred for 20 min, and then the solid-liquid mixture is evaporated at 70-80°C. After the sample is dried at 120°C for 12 h, it is ground, sieved, and calcined in a muffle furnace in an air atmosphere.

[0011] (3) The calcination conditions of the preparation process of the catalyst α-Fe2O3 / TiO2 and α-Fe2O3 / neutral Al2O3 are calcination at 250-500°C in an air atmosphere for 2-10 h; the calcination conditions of the preparation process of the catalyst α-Fe2O3 / activated carbon are calcination at 250-350°C in an air atmosphere for 2-5 h.

[0012] The present application has the following advantages:

[0013] (1) Using anhydrous ethanol as the solvent avoids the pollution of harmful solvents such as toluene and tetrahydrofuran to the environment.

[0014] (2) The catalyst has high activity and selectivity for the hydrogenation of the nitro group in nitrophenylacetylene; when the conversion rate is 100%, the selectivity of aminophenylacetylene can be as high as 96%. The catalyst has almost no catalytic activity for the hydrogenation of the acetylene group, so the selectivity of aminophenylacetylene does not decrease basically when the reaction time is prolonged after the complete conversion of the reactant, which reduces the difficulty of controlling the reaction in large-scale production.

[0015] (3) There is no accumulation of harmful intermediates such as phenylhydroxylamine, nitroso compounds and azo compounds in the reaction process.

[0016] In summary, using α-Fe2O3, Fe3O4, α-Fe2O3 / TiO2, α-Fe2O3 / neutral Al2O3 or α-Fe2O3 / activated carbon as the catalyst, using 80% hydrazine hydrate solution as the hydrogen source, and catalyzing the hydrogenation of nitrophenylacetylene to prepare aminophenylacetylene in anhydrous ethanol is a green and efficient process. DETAILED DESCRIPTION

[0017] Example 1 Hydrogenation of 4-nitrophenylacetylene

[0018] Into a reaction kettle equipped with a 30 mL polytetrafluoroethylene liner, 10 mL of ethanol, 0.5 mmol of 4-nitrophenylacetylene, 80% hydrazine hydrate solution containing 0.9 mmol of N2H4·H2O, and 0.05 g of α-Fe2O3 catalyst were added, wherein the catalyst was a commercially available nano-α-Fe2O3. The reaction kettle was tightly closed, purged with high-purity nitrogen for 5 min to exclude air, preheated in an oil bath at 120°C for 20 min, and then the stirring was turned on. The reaction time was 10 min and 30 min, respectively, and the reaction products were analyzed by gas chromatography. After 10 min of reaction, the conversion rate of 4-nitrophenylacetylene was 100%, and the selectivity of 4-aminophenylacetylene was 96.5%. After 30 min of reaction, the conversion rate of 4-nitrophenylacetylene was 100%, and the selectivity of 4-aminophenylacetylene was 96.6%.

[0019] Example 2 Hydrogenation of 4-nitrophenylacetylene

[0020] The catalyst was added in an amount of 0.005 g, and the reaction time was 90 min. The catalyst and other conditions were the same as in Example 1. The conversion rate of 4-nitrophenylacetylene was 99.4%, and the selectivity of 4-aminophenylacetylene was 92.4%.

[0021] Comparative Example 1 Hydrogenation of 4-nitrophenylacetylene

[0022] Preparation of FeO using thermal decomposition method x The specific steps are as follows: a certain amount of Fe(NO3)3·9H2O is added to a certain volume of deionized water, and after complete dissolution, a certain mass of sodium citrate is added. Stirring is carried out at 60°C for 90 min, the temperature is raised to 100°C, and stirring is continued until the solution becomes gel-like. It is placed in an oven and dried at 150°C for 12 h, and then it is transferred to a muffle furnace and pyrolyzed at 250°C for 3 h. The resulting material is sieved through a 120 mesh sieve, and FeO / C catalyst is obtained. x The specific steps are as follows: a certain amount of Fe(NO3)3·9H2O is added to a certain volume of deionized water, and after complete dissolution, a certain mass of sodium citrate is added. Stirring is carried out at 60°C for 90 min, the temperature is raised to 100°C, and stirring is continued until the solution becomes gel-like. It is placed in an oven and dried at 150°C for 12 h, and then it is transferred to a muffle furnace and pyrolyzed at 250°C for 3 h. The resulting material is sieved through a 120 mesh sieve, and FeO / C catalyst is obtained. x The catalyst was added in an amount of 0.005 g, and the reaction time was 90 min. The catalyst and other conditions were the same as in Example 1. The conversion rate of 4-nitrophenylacetylene was 99.4%, and the selectivity of 4-aminophenylacetylene was 92.4%.

[0023] Example 3 Hydrogenation of 4-nitrophenylacetylene

[0024] The catalyst is commercially available nano Fe3O4, and the reaction time is 10 min and 30 min, respectively, and other conditions are the same as in Example 1. The conversion rate of 4-nitrophenylacetylene is 99% and the selectivity of 4-aminophenylacetylene is 93.1% after 10 min of reaction. The conversion rate of 4-nitrophenylacetylene is 99.9% and the selectivity of 4-aminophenylacetylene is 95.1% after 30 min of reaction.

[0025] Example 2 Hydrogenation of 4-nitrophenylacetylene

[0026] The catalyst is commercially available nano γ-Fe2O3, and the reaction time is 10 min and 30 min, respectively, and other conditions are the same as in Example 1. The conversion rate of 4-nitrophenylacetylene is 84.6% and the selectivity of 4-aminophenylacetylene is 89.2% after 10 min of reaction. The conversion rate of 4-nitrophenylacetylene is 100% and the selectivity of 4-aminophenylacetylene is 88.6% after 30 min of reaction.

[0027] Example 3 Hydrogenation of 4-nitrophenylacetylene

[0028] A certain amount of iron nitrate nonahydrate is calcined in a muffle furnace at 250°C for 5 h in an air atmosphere to obtain an α-Fe2O3 catalyst, and the reaction time is 10 min and 30 min, respectively, and other conditions are the same as in Example 1. The conversion rate of 4-nitrophenylacetylene is 100% and the selectivity of 4-aminophenylacetylene is 96.1% after 10 min of reaction. The conversion rate of 4-nitrophenylacetylene is 100% and the selectivity of 4-aminophenylacetylene is 96.7% after 30 min of reaction.

[0029] Example 4 Hydrogenation of 4-nitrophenylacetylene

[0030] A certain amount of iron citrate is calcined in a muffle furnace at 300°C for 3 h in an air atmosphere, and the calcined product is used as a catalyst, and the reaction time is 30 min, and other conditions are the same as in Example 1. The conversion rate of 4-nitrophenylacetylene is 99.8% and the selectivity of 4-aminophenylacetylene is 95.8%.

[0031] Example 5 Hydrogenation of 4-nitrophenylacetylene

[0032] A certain amount of iron ammonium citrate is calcined in a muffle furnace at 425°C for 3 h in an air atmosphere, and the calcined product is used as a catalyst, and the reaction time is 30 min, and other conditions are the same as in Example 1. The conversion rate of 4-nitrophenylacetylene is 99.7% and the selectivity of 4-aminophenylacetylene is 95.8%.

[0033] Example 6 Hydrogenation of 4-nitrophenylacetylene

[0034] A certain amount of Fe(OH)3was calcined in a muffle furnace at 350°C for 3h in air atmosphere, and the calcined product was used as catalyst for 60 min. The conversion of 4-nitrophenylacetylene was 84.3%, and the selectivity of 4-aminophenylacetylene was 70.3%.

[0035] Example 7 Hydrogenation of 4-nitrophenylacetylene

[0036] A 1.34 mol / L iron nitrate solution was prepared, and Fe(NO3)3was loaded on TiO2by equal volume impregnation. After calcination at 300°C for 3h in air atmosphere, 9.76% α-Fe2O3 / TiO2catalyst was obtained. 0.05 g of the catalyst was used, and the reaction temperature was 80°C for 10 min. The conversion of 4-nitrophenylacetylene was 99.6%, and the selectivity of 4-aminophenylacetylene was 95.2%.

[0037] Example 8 Hydrogenation of 4-nitrophenylacetylene

[0038] A 1.34 mol / L iron ammonium citrate (III) solution was prepared, and iron ammonium citrate (III) was loaded on TiO2by equal volume impregnation. After calcination at 350°C for 3h in air atmosphere, 12.6% α-Fe2O3 / TiO2catalyst was obtained. 0.05 g of the catalyst was used, and the reaction time was 30 min. The conversion of 4-nitrophenylacetylene was 100%, and the selectivity of 4-aminophenylacetylene was 93.3%.

[0039] Example 9 Hydrogenation of 4-nitrophenylacetylene

[0040] A 1.88 mol / L iron nitrate solution was prepared, and Fe(NO3)3was loaded on TiO2by equal volume impregnation. After calcination at 250°C for 10h in air atmosphere, 13.7% α-Fe2O3 / TiO2catalyst was obtained. 0.05 g of the catalyst was used, and the reaction time was 10 min. The conversion of 4-nitrophenylacetylene was 100%, and the selectivity of 4-aminophenylacetylene was 96.2%.

[0041] Example 10 Hydrogenation of 4-nitrophenylacetylene

[0042] A 4.92 mol / L iron nitrate solution was prepared, and Fe(NO3)3 was loaded on TiO2 by the method of impregnation with excess solution and evaporation to remove excess water, and was evaporated to a paste in a 75 °C water bath. After calcination in a muffle furnace in air at 300 °C for 3 h, a 39.75% α-Fe2O3 / TiO2 catalyst was obtained. 0.05 g of the catalyst was used, the reaction temperature was 100 °C, and the reaction time was 60 min, and the other conditions were the same as in Example 1. The conversion of 4-nitrophenylacetylene was 100%, and the selectivity was 94.4%.

[0043] Example 11 Hydrogenation of 4-nitrophenylacetylene

[0044] A 1.87 mol / L iron nitrate solution was prepared, and Fe(NO3)3 was loaded on neutral Al2O3 by the method of equal volume impregnation, and a 9.0% α-Fe2O3 / neutral Al2O3 catalyst was obtained after calcination in a muffle furnace in air at 450 °C for 3 h. 0.05 g of the catalyst was used, the reaction time was 30 min, and the other conditions were the same as in Example 1. The conversion of 4-nitrophenylacetylene was 100%, and the selectivity of 4-aminophenylacetylene was 93.6%.

[0045] Example 12 Hydrogenation of 4-nitrophenylacetylene

[0046] A 1.87 mol / L iron nitrate solution was prepared, and Fe(NO3)3 was loaded on activated carbon by the method of equal volume impregnation, and a 24.8% α-Fe2O3 / activated carbon catalyst was obtained after calcination in a muffle furnace in air at 300 °C for 3 h. 0.05 g of the catalyst was used, the reaction time was 10 min, and the other conditions were the same as in Example 1. The conversion of 4-nitrophenylacetylene was 98.9%, and the selectivity of 4-aminophenylacetylene was 93.4%.

[0047] Comparative Example 4 Hydrogenation of 4-nitrophenylacetylene

[0048] A 1.88 mol / L iron nitrate solution was prepared, and Fe(NO3)3 was loaded on γ-Al2O3 by the method of equal volume impregnation, and a 18.37% α-Fe2O3 / γ-Al2O3 catalyst was obtained after calcination in a muffle furnace in air at 450 °C for 3 h. 0.05 g of the catalyst was used, the reaction time was 10 min, and the other conditions were the same as in Example 1. The conversion of 4-nitrophenylacetylene was 100%, and the selectivity of 4-aminophenylacetylene was 86.1%.

[0049] Example 13 Hydrogenation of 3-nitrophenylacetylene

[0050] In a 30 mL high-pressure reactor with polytetrafluoroethylene lining, 10 mL of ethanol, 0.5 mmol of 3-nitrophenylacetylene, 80% hydrazine hydrate solution containing 0.9 mmol of N2H4-H2O, and 0.05 g of commercially available nano α-Fe2O3 catalyst were added. The reactor was tightly closed, purged with high-purity nitrogen for 5 min to remove air. The reactor was preheated in an oil bath at 150°C for 20 min, and then the stirring was started. After 5 min of reaction, the reactor was cooled and opened to take out the reaction product, which was analyzed by gas chromatography. The conversion rate of 3-nitrophenylacetylene was 100%, and the selectivity of 3-aminophenylacetylene was 96.7%.

[0051] Example 14 Hydrogenation of 3-nitrophenylacetylene

[0052] The catalyst was 0.05 g of 9.76% Fe2O3 / TiO2 (prepared according to the method of Example 7), the reactant was 3-nitrophenylacetylene, the reaction time was 10 min, and the other conditions were the same as in Example 1. The conversion rate of 3-nitrophenylacetylene was 100%, and the selectivity of 3-aminophenylacetylene was 94.7%.

[0053] Example 15 Hydrogenation of 2-nitrophenylacetylene

[0054] 0.5 mmol of 2-nitrophenylacetylene was added as the reactant, and the catalyst and other conditions were the same as in Example 13. The conversion rate of 2-nitrophenylacetylene was 99.4%, and the selectivity of 2-aminophenylacetylene was 89.2%.

[0055] Example 16 Hydrogenation of 4-nitrophenylacetylene

[0056] A 1.88 mol / L iron nitrate solution was prepared, and Fe(NO3)3 was loaded on TiO2 by equal-volume impregnation. After calcination in a 250°C muffle furnace in air for 3 h, a 13.7% α-Fe2O3 / TiO2 catalyst was obtained. In a 30 mL high-pressure reactor with polytetrafluoroethylene lining, 10 mL of ethanol, 2 mmol of 4-nitrophenylacetylene, 80% hydrazine hydrate solution containing 3.63 mmol of N2H4-H2O, and 0.05 g of the catalyst were added. The reaction was carried out for 10 min, and the other conditions were the same as in Example 1. The conversion rate of 4-nitrophenylacetylene was 99.9%, and the selectivity of 4-aminophenylacetylene was 89.6%.

[0057] Example 17 Hydrogenation of 4-nitrophenylacetylene in a cycle experiment

[0058] A certain amount of ferric ammonium citrate was calcined at 300℃ for 3h in a muffle furnace under air atmosphere to obtain α-Fe2O3 catalyst. In a 30 mL high-pressure reactor with polytetrafluoroethylene lining, 10 mL of ethanol, 0.5 mmol of 4-nitrophenylacetylene, 0.9 mmol of N2H4·H2O-containing hydrazine hydrate solution, and 0.05 g of the catalyst were added. The reactor was tightly closed, purged with high-purity nitrogen for 5 min to remove air. The reactor was preheated in an oil bath at 120℃ for 20 min, and then the stirring was turned on. After 15 min of reaction, the reaction product was obtained by cooling and opening the reactor. The product and catalyst were separated by centrifugation and filtration. The catalyst was washed with anhydrous ethanol for 5 times and used for the second reaction. The above reaction and separation steps were repeated multiple times. The conversion rate of 4-nitrophenylacetylene was 99.9% and the selectivity of 4-aminophenylacetylene was 96.8% in the first cycle reaction. The conversion rate of 4-nitrophenylacetylene was 96.1% and the selectivity of 4-aminophenylacetylene was 95.6% in the fifth cycle reaction. The conversion rate of 4-nitrophenylacetylene was 92.8% and the selectivity of 4-aminophenylacetylene was 95.2% in the seventh cycle reaction.

Claims

1. A process for the selective hydrogenation of nitrophenylacetylenes to aminophenylacetylenes, characterized in that, The α-Fe2O3, Fe3O4 powder or supported α-Fe2O3 is used as a catalyst, anhydrous ethanol, nitrophenylacetylene, the catalyst pre-calcined and 80% N2H4·H2O solution are added into a reactor, the mass ratio of anhydrous ethanol to nitrophenylacetylene is (20-120):1, the mass ratio of nitrophenylacetylene to catalyst is (1-20):1, the mass ratio of N2H4·H2O to nitrophenylacetylene is (0.5-1.3):1, the reactor is heated to 80-150℃, after preheating for 20 min, the stirring is started, and the reaction is carried out until the conversion rate approaches or reaches 100%; The nitrophenylacetylene is 2-nitrophenylacetylene, 3-nitrophenylacetylene and 4-nitrophenylacetylene; The catalyst α-Fe2O3, Fe3O4 powder is a commercially available nano-powder product, or α-Fe2O3 powder generated by calcining ferric citrate, ammonium citrate ferrite or nine water ferric nitrate in air at 250-500℃ for 2-10h; The supported α-Fe2O3 catalyst is α-Fe2O3 / TiO2, α-Fe2O3 / neutral Al2O3 or α-Fe2O3 / activated carbon; The catalyst α-Fe2O3 / TiO2 or α-Fe2O3 / neutral Al2O3 is calcined in air at 250-500℃ for 2-10h in the preparation process; The catalyst α-Fe2O3 / activated carbon is calcined in air at 250-350℃ for 2-5h in the preparation process.

2. The process for the selective hydrogenation of nitrophenylacetylenes to aminophenylacetylenes according to claim 1, characterized in that, The supported catalyst α-Fe2O3 / TiO2, α-Fe2O3 / neutral Al2O3 or α-Fe2O3 / activated carbon has a mass content of Fe2O3 of 5%-45%; The supported catalyst α-Fe2O3 / TiO2, α-Fe2O3 / neutral Al2O3 or α-Fe2O3 / activated carbon uses ferric nitrate nonahydrate or ammonium citrate ferrite as an iron salt for preparing the catalyst.