Application of Ni-based reverse catalyst in catalytic hydrogenation reaction of nitro compound

Abstract

The invention discloses application of a Ni-based reverse-phase catalyst in catalytic hydrogenation reaction of a nitro compound, nitro in the nitro compound is hydrogenated to reduce amino, the Ni-based reverse-phase catalyst is of an M / Ni reverse-phase structure, metal Ni for dissociating hydrogen serves as a carrier, nano metal M oxide is loaded on the carrier to serve as a loading phase, and reverse-phase interface active sites are constructed; wherein the metal M is one or two of Ce, Zr, Al, Y and Mg, and the mole fraction of the load phase metal M is 5-50% based on the mole fraction of all the metals in the catalyst being 100%. The preparation method of the catalyst is simple and easy to implement, the catalyst has a non-traditional supported reversed-phase structure, the activity of the catalyst is more excellent than that of a traditional supported catalyst when the catalyst is applied to the nitro-compound hydrogenation process, a traditional Raney nickel catalyst can be effectively replaced, a reaction system is clean and safe, repeatability is good, effective recycling can be achieved, and the catalyst is suitable for industrial production. The method is suitable for industrial production and has a good application prospect.

Description

Technical Field

[0001] The invention relates to application of a Ni-based reverse phase catalyst in catalytic hydrogenation reaction of nitro compounds. Background Art

[0002] o-Toluidine is an important raw material for organic synthesis, widely used in key industries such as dyes, pesticides, and pharmaceuticals. The dye industry, a traditional consumer of o-toluidine, accounts for a significant share of the market due to continued demand for textiles both domestically and internationally. Common methods for reducing o-toluidine include chemical reduction, catalytic hydrogenation, and electrolytic reduction. Chemical reduction, the earliest of these methods, utilizes iron powder as a reducing agent. However, this method suffers from disadvantages such as poor operating conditions, high costs, and the consumption of large amounts of refined iron powder. Furthermore, the reaction generates a large amount of pollutants that must be treated to prevent severe environmental pollution, and is now prohibited by national regulations. To address these shortcomings, hydrogenation and electrolytic reduction methods have been developed. Electrolytic reduction is a clean, pollution-free reaction, but due to limitations in energy, technical requirements, and equipment, its development has lagged behind catalytic hydrogenation. Compared to traditional chemical reduction methods, the new catalytic hydrogenation process offers significant improvements in product quality and yield, while also offering significant environmental benefits. Catalytic hydrogenation can be categorized as gas-phase hydrogenation or liquid-phase hydrogenation.

[0003] With the further development of green chemistry, the transfer hydrogenation of aromatic nitro compounds has gradually become an important method for preparing aromatic amines. Currently, commonly used catalysts include nickel catalysts, noble metal supported catalysts, copper-silica gel supported catalysts, etc. Generally, noble metal catalysts show good catalytic hydrogenation activity, but due to reasons such as high cost, they are not suitable for large-scale application. In addition, as the most common nickel-based catalyst, the main disadvantages of Raney nickel catalyst include active chemical properties, unstable physical state, strict storage and use conditions, environmental pollution problems and safety hazards. Traditional copper-silica gel catalysts have poor thermal stability, easy carbon deposition, easy crushing and low selectivity. Invention patent CN112536033 discloses a modified copper-silica gel catalyst that overcomes the shortcomings of traditional copper-silica gel catalysts, but it requires a relatively high temperature to be realized.

[0004] Therefore, the present invention provides a low-temperature, high-activity, and high-selectivity Ni-based catalyst for hydrogenation of nitro compounds, which is expected to be used for large-scale application of the catalyst. Summary of the Invention

[0005] In response to the problems encountered during the hydrogenation reaction of nitro compounds, the present invention aims to provide a new type of reversed-phase catalyst with low temperature, high activity and high selectivity, as well as its preparation method and application in the hydrogenation reaction of nitro compounds. Metal Ni, which dissociates hydrogen, is used as a carrier, and nano-oxides are loaded on it to construct reversed-phase interface active sites, which can achieve low-temperature, high conversion rate, high selectivity and high stability for the hydrogenation of nitro compounds.

[0006] The technical solutions of the present invention are as follows:

[0007] A Ni-based reversed-phase catalyst is a composite oxide with an M / Ni reversed-phase structure. The catalyst uses metal Ni, which dissociates hydrogen, as a carrier, on which nano-metal M oxide is loaded as a loading phase, thereby constructing reversed-phase interface active sites. The metal M is one or two of Ce, Zr, Al, Y, and Mg, and the molar fraction of the loaded phase metal M is 5-50%, based on the molar fraction of all metals in the catalyst being 100%.

[0008] Furthermore, based on the molar fraction of all metals in the catalyst being 100%, the molar fraction of the supported phase metal M is in the range of 10-23%.

[0009] Furthermore, the metal M includes two active metals, and the combination of the two active metals is Ce-Zr, Zr-Al, Zr-Y, Mg-Al and Ce-Al, and their molar ratio is 0.5-2:1, preferably 1-1.2:1.

[0010] Furthermore, the preparation method of the catalyst comprises the following steps:

[0011] (1) Add the precursor salt corresponding to the metal Ni and the precursor salt of the supported phase M oxide to the solvent at the same time and stir until completely dissolved;

[0012] (2) adding the precipitant dropwise to the solution of step (1) under continuous stirring, stirring at room temperature and 400-800 rpm for 2-5 hours, centrifuging, washing, drying, and grinding into powder;

[0013] (3) calcining the solid powder obtained in step (2) in a muffle furnace, and reducing it in a hydrogen atmosphere after calcination to finally obtain the Ni-based reverse phase catalyst.

[0014] Furthermore, in step (1), the metal Ni precursor salt is selected from one of nickel nitrate and nickel chloride salts; the precursor salt of the supported phase M oxide is selected from one or more of the nitrate, chloride, oxychloride, acetylacetonate, and sulfate of metal M, specifically selected from one or more of aluminum nitrate, aluminum chloride, cerium nitrate, cerium chloride, zirconium nitrate, zirconium chloride, zirconium oxychloride, yttrium nitrate, yttrium chloride, yttrium acetylacetonate, magnesium nitrate, magnesium sulfate, and magnesium chloride.

[0015] Furthermore, in step (2), the precipitant is selected from one of urea, ammonium fluoride, ammonium chloride, ammonium oxalate, and oxalic acid, and the amount of the precipitant is 2-4 times, preferably 2-3 times, the total molar amount of the loaded phase metal M and metal Ni; and the solvent used to dissolve the oxide precursor salt and the precipitant is selected from one or more of water, ethanol, butanol, and ethylene glycol.

[0016] Furthermore, in step (3), the calcination temperature in the muffle furnace is 300-500° C., and the calcination time is 1-5 hours.

[0017] Furthermore, the reduction temperature in step (3) is 300-400° C., and the time is 1-4 hours; the hydrogen concentration in the reducing atmosphere is in the range of 10-20%.

[0018] The present invention discloses an application of a Ni-based reverse-phase catalyst in a catalytic hydrogenation reaction of a nitro compound, so that the nitro group in the nitro compound is hydrogenated to reduce the amino group. The application process comprises the following steps: adding the nitro compound, a solvent, and the Ni-based reverse-phase catalyst into a high-pressure reactor, reacting for 2 to 4 hours at 40 to 80° C. and a hydrogen pressure of 0.1 to 1.5 MPa. After the reaction is completed, the reactor is rapidly cooled to room temperature to release the remaining hydrogen in the reactor. Finally, the reaction liquid and the catalyst are separated, and the catalyst is recovered to obtain a target product.

[0019] The amount of the catalyst is 5-20 g / mol, preferably 10-15 g / mol, based on the amount of the nitro compound; the amount of the solvent is 500-5000 mL / mol, preferably 1500-2000 mL / mol, based on the amount of the nitro compound.

[0020] Furthermore, the solvent is selected from one of n-hexane, cyclohexane, water, and methanol, preferably n-hexane or cyclohexane, the catalytic reaction temperature is 60-80° C., and the hydrogen pressure is 1-1.5 MPa.

[0021] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0022] 1) This invention uses metallic nickel as a substrate to construct an in-situ reversed-phase interface active site catalyst. This results in a higher nitro compound conversion rate than when using a conventional oxide as a support at the same temperature. Under conditions of 1 MPa H₂ and 60°C to 80°C, the substrate conversion rate and product selectivity are 100%. The reversed structure of the oxide specifically dispersed on the surface of the nickel particles significantly enhances the activity of the supported oxide on the nickel particles, breaking through the limitations of traditional catalyst design and preparation structures.

[0023] 2) The reversed-phase Ni-based catalyst prepared by the method of the present invention is applied to the hydrogenation reaction of nitrobenzene. The catalyst preparation method is simple, the preparation process conditions are easy to achieve, the catalyst preparation cost can be reduced, and it can effectively replace the traditional Raney nickel catalyst, and is suitable for large-scale promotion and use. DETAILED DESCRIPTION

[0024] The present invention will be further described below with reference to the embodiments, but the scope of protection of the present invention is not limited to the described scope.

[0025] Example 1

[0026] Catalyst preparation: First, weigh 2.529873g nickel nitrate hexahydrate (8.7mmol), 0.282243g cerium nitrate hexahydrate (0.65mmol), and 0.279058g zirconium nitrate pentahydrate (0.65mmol) and dissolve them in 100mL of ethanol. Stir until completely dissolved, and then stir at 25°C and 600rpm for 4h. Then, 2.7g anhydrous oxalic acid (30mmol) was dissolved in 100ml of ethanol and added dropwise to the mixed solution at a constant speed of 1ml / min as a precipitant. Stir for 2h, centrifuge, and wash three times with ethanol. Dry it in an oven at 80°C for 12 hours, then grind it into powder and calcine it in a muffle furnace at 400°C for 4h. The powder was recorded as unreduced CeZrO before the reaction. x The above sample was placed in a U-shaped reactor and reduced at 400°C for 3 hours in a mixture of H2 and N2 containing 15 vol% H2. The product was recorded as the reduced CeZrO before the reaction. x Based on the molar fraction of all metals in the catalyst being 100%, the molar fraction of the supported metal Ce-Zr is 13%.

[0027] Testing Procedure: Selective hydrogenation experiments were conducted using the prepared catalyst. The reaction was conducted in an autoclave with 1.2 g of o-nitrotoluene as the substrate, 15 mL of n-hexane as the solvent, and 0.12 g of the catalyst. The H2 pressure was set at 1.0 MPa, the reaction temperature was 60°C, and the stirring speed was 800 rpm / min. After the reaction, the catalyst was separated from the reaction liquid by filtration. The conversion of the raw material and the selectivity of the target product, o-toluidine, were analyzed using an Agilent 8860 gas chromatograph. The experimental results are shown in Table 1.

[0028] In addition, CeZrO x The cyclic test of the / Ni catalyst was carried out. After each catalytic reaction, the catalyst was separated from the reaction liquid by filtration, and the recovered catalyst was used in the next reaction. According to this method, the cyclic test results of the repeated use of the catalyst are shown in Table 2.

[0029] Examples 2-5

[0030] The preparation steps of the catalysts of Examples 2-5 were repeated in Example 1, and the molar ratio of cerium nitrate hexahydrate to zirconium nitrate pentahydrate was maintained unchanged at 1:1. The only difference from Example 1 was that the amounts of "cerium nitrate hexahydrate and zirconium nitrate pentahydrate" were adjusted so that the molar fractions of the supported phase metal Ce-Zr in the catalyst to the total metal were 23 mol%, 37 mol%, 50 mol%, and 7 mol%, respectively, and the molar fraction of all metals in the catalyst was 100%.

[0031] The catalysts of Examples 2-5 were used in catalytic hydrogenation reactions, and the reaction conditions were the same as those of Example 1.

[0032] Examples 6-7

[0033] When the catalyst was used in the selective hydrogenation experiment, the reaction temperature was the same as in Example 1 except that the reaction temperature was 40° C. and 80° C. during the catalytic application test.

[0034] Implementation columns 8-10

[0035] When the catalyst was used in the selective hydrogenation experiment, the catalyst was the same as in Example 1 except that the solvents selected in the catalytic application test were methanol, cyclohexane, and water (the solvent volume was kept constant at 15 mL).

[0036] Example 11

[0037] In addition to the metal oxide selected for the catalyst preparation, ZrAlO x Except that the added oxide precursor salt was replaced by "cerium nitrate hexahydrate (0.65 mmol) and zirconium nitrate pentahydrate (0.65 mmol)" with "zirconium nitrate pentahydrate (0.65 mmol) and aluminum nitrate nonahydrate (0.65 mmol)", the rest was the same as Example 1.

[0038] Example 12

[0039] In addition to the metal oxide selected for the catalyst preparation, ZrYO x , except that the added metal oxide precursor salt was replaced by "cerium nitrate hexahydrate (0.65 mmol), zirconium nitrate pentahydrate (0.65 mmol)" with "zirconium nitrate pentahydrate (0.65 mmol), yttrium nitrate tetrahydrate (0.65 mmol)", the rest were the same as in Example 1.

[0040] Example 13

[0041] In addition to the metal oxide selected for the catalyst preparation, MgAlO x, except that the added metal oxide precursor salt was replaced by 0.65 mmol of magnesium nitrate hexahydrate and 0.65 mmol of aluminum nitrate nonahydrate, the rest were the same as in Example 1.

[0042] Example 14

[0043] In addition to the metal oxide selected for the catalyst preparation, CeAlO x The addition of metal oxide precursor salts was 0.65 mmol of cerium nitrate hexahydrate and 0.65 mmol of aluminum nitrate tetrahydrate, and the rest was the same as in Example 1.

[0044] Example 15

[0045] Except that the metal oxide selected for the catalyst preparation is CeO2 and the added metal oxide precursor salt is 1.3 mmol of cerium nitrate hexahydrate, the rest is the same as Example 1.

[0046] Example 16

[0047] Except that the metal oxide selected for the catalyst preparation is ZrO2 and the added metal oxide precursor salt is 1.3 mmol zirconium nitrate hexahydrate, the rest is the same as Example 1.

[0048] Example 17

[0049] Except that the metal oxide selected for the catalyst preparation is Al2O3 and the added metal oxide precursor salt is 1.3 mmol aluminum nitrate nonahydrate, the rest is the same as Example 1.

[0050] Example 18

[0051] Except that the metal oxide selected for the catalyst preparation is Y2O3 and the added metal oxide precursor salt is 1.3 mmol yttrium nitrate tetrahydrate, the rest is the same as Example 1.

[0052] Example 19

[0053] Except that the metal oxide selected for the catalyst preparation is MgO and the metal oxide precursor salt added is 1.3 mmol magnesium nitrate hexahydrate, the rest is the same as Example 1.

[0054] Examples 20-21

[0055] When the catalyst was used in the selective hydrogenation experiment, the reaction pressures during the catalytic application test were the same as in Example 1, except that the reaction pressures were 0.5 MPa and 1.5 MPa, respectively.

[0056] Example 22

[0057] The preparation method of the catalyst was repeated in Example 1, except that the amount of cerium nitrate hexahydrate was replaced by 0.433 mmol, and the molar amount of zirconium nitrate pentahydrate was replaced by 0.867 mmol. Other conditions remained unchanged, and the catalyst was finally prepared.

[0058] Example 23

[0059] The catalyst preparation method was repeated in Example 1, except that the amount of cerium nitrate hexahydrate was replaced by 0.867 mmol, and the molar amount of zirconium nitrate pentahydrate was replaced by 0.433 mmol. Other conditions remained unchanged, and the catalyst was finally prepared.

[0060] The catalysts of Examples 11-23 were used in catalytic hydrogenation reactions, and the reaction conditions were the same as those of Example 1.

[0061] Comparative Example 1

[0062] Catalyst preparation: Nickel nitrate hexahydrate was used as the nickel source of the catalyst, and a normal-phase nickel-based catalyst was prepared by coprecipitation method. The method was as follows: 0.8723 g of nickel nitrate hexahydrate, 1.5197 g of cerium nitrate hexahydrate, 1.5026 g of zirconium nitrate pentahydrate and 100 mL of anhydrous ethanol were added to a beaker. 100 mL of anhydrous ethanol was added to 2.7 g of anhydrous oxalic acid. The two prepared solutions were placed on a six-paddle stirrer and stirred evenly. The oxalic acid solution was added dropwise to the metal salt solution using a syringe pump at a flow rate of 60 mL / h. After the addition was completed, the metal salt solution was continued to be stirred on the six-paddle stirrer for 2 h to completely precipitate the metal salt. The precipitated metal salt solution was vacuum filtered and washed with anhydrous ethanol to obtain a filter cake, which was dried in an oven at 80°C overnight. The dried solid was ground into powder in a mortar and finally calcined in a muffle furnace at 400°C for 3 h to obtain Ni / CeZrO x Powder catalyst.

[0063] Testing Procedure: A selective hydrogenation experiment was conducted using the prepared catalyst. The reaction was conducted in an autoclave with 1.2 g of o-nitrotoluene as substrate, 15 mL of n-hexane as solvent, and 0.12 g of catalyst. The H2 pressure was set at 1.0 MPa, the reaction temperature was 60°C, and the stirring speed was 800 rpm / min. After the reaction, the catalyst was separated from the reaction liquid by filtration. The conversion of the raw material and the selectivity of the target product, o-toluidine, were analyzed using an Agilent 8860 gas chromatograph. The experimental results are shown in Table 1.

[0064] Comparative Example 2

[0065] Except that the metal oxide selected for the catalyst preparation is CeO2 and the added metal oxide precursor salt is 3.778 g of cerium nitrate hexahydrate, the rest is the same as Comparative Example 1.

[0066] Comparative Example 3

[0067] Except that the metal oxide selected for the catalyst preparation is ZrO2 and the added metal oxide precursor salt is 3.735 g of zirconium nitrate hexahydrate, the rest is the same as Comparative Example 1.

[0068] Comparative Example 4

[0069] Except that the metal oxide selected for the catalyst preparation is Al2O3 and the added metal oxide precursor salt is 3.264g of aluminum nitrate nonahydrate, the rest is the same as Comparative Example 1.

[0070] Comparative Example 5

[0071] Except that the metal oxide selected for the catalyst preparation is Y2O3 and the added metal oxide precursor salt is 3.019 g of yttrium nitrate tetrahydrate, the rest is the same as Comparative Example 1.

[0072] Comparative Example 6

[0073] Except that the metal oxide selected for the catalyst preparation is MgO and the added metal oxide precursor salt is 2.231 g of magnesium nitrate hexahydrate, the rest is the same as Comparative Example 1.

[0074] Comparative Example 7

[0075] Except that the catalyst in the catalyst preparation is Raney nickel, the rest is the same as that in Comparative Example 1.

[0076] The catalysts of Comparative Examples 1-7 were used in catalytic hydrogenation reactions, and the reaction conditions were the same as those of Example 1.

[0077] Table 1 Product analysis results of each catalyst for o-nitrotoluene hydrogenation reaction

[0078]

[0079] Compared with Comparative Examples 1 to 6, Examples 1 to 21 in Table 1 showed higher o-nitrotoluene hydrogenation activity, reflecting the superiority of reverse metal oxide catalysts over traditional forward metal oxide catalysts in the selective hydrogenation of nitro compounds.

[0080] Compared with Comparative Example 7, Example 1 in Table 1 shows higher o-nitrotoluene hydrogenation activity, which demonstrates the superiority of the reversed metal oxide catalyst over the traditional Raney nickel catalyst in the selective hydrogenation of nitro compounds.

[0081] From Examples 1, 11 to 19, it can be seen that the conversion rate of o-nitrotoluene and the selectivity of o-toluidine under the conditions of 60°C, 2h, 1Mpa H2 nickel deposition of different metal oxides are the preferred metal oxides. x .

[0082] From Examples 1 to 5, it can be seen that the conversion rate of o-nitrotoluene and the selectivity of o-toluidine under the conditions of 60° C., 2 h, 1 MPa H2 with different metal oxide contents are preferably 13 mol %.

[0083] From Example 1, Example 6-Example 7, it can be seen that at 2h, 1Mpa H2, and different reaction temperatures, the o-nitrotoluene conversion rate and o-toluidine selectivity all reach 100% in the range of 60°C-80°C.

[0084] From Examples 1 and 8 to 11, it can be seen that the conversion rate of o-nitrotoluene and the selectivity of o-toluidine under different solvent conditions of 60° C., 2 h, and 1 MPa H2 are preferably n-hexane.

[0085] From Example 1, Example 20-Example 21, it can be seen that the o-nitrotoluene conversion rate and o-toluidine selectivity under different reaction pressure conditions of 60°C and 2h, the o-nitrotoluene conversion rate reaches 100% in the range of 1 MPa-1.5 MPa.

[0086] From Example 1, Example 22-Example 23, it can be seen that the conversion rate of o-nitrotoluene and the selectivity of o-toluidine under the conditions of different ratios of Ce:Zr deposited by H2 metal nickel at 60°C, 2h, 1Mpa, the preferred metal ratio is 1:1.

[0087] Table 2 Cyclic test of o-nitrotoluene hydrogenation reaction

[0088] o-Nitrotoluene conversion rate (%) Selectivity of o-toluidine (%) Cycle test 1 time 100 100 Cycle test 2 times 100 100 Cycle test 3 times 100 100 Cycle test 4 times 100 100 Cycle test 5 times 100 100

[0089] As shown in Table 2, high conversion rate and high selectivity can be maintained during the five cycles, which lays the foundation for the future large-scale promotion and use of this catalyst.

[0090] Example 24

[0091] A selective hydrogenation experiment was carried out using the catalyst prepared in Example 1, comprising the following steps:

[0092] 1) Preparation of substrate solution: o-nitrotoluene was dissolved in ethyl acetate solution to a substrate concentration of 1 mol / L;

[0093] 2) Catalytic reaction: 10 g of catalyst was filled in a micro-reactor continuous flow reactor, and the substrate solution of step 1) was continuously introduced into the reactor. H2 was also introduced at the same time, and the H2 equivalent was controlled to be 3-6, that is, the molar flow rate of H2 introduced was 3-6 times the molar flow rate of the substrate. The reaction temperature was controlled to be 25° C. and the reaction pressure was controlled to be 1 MPa (that is, the total pressure of the reaction system after gas-liquid mixing was 1 MPa).

[0094] According to the above experimental process, the reaction liquid was collected after the reaction reached stability and analyzed using an Agilent 8860 gas chromatograph to obtain the conversion rate of the raw material and the selectivity of the target product. The target product was o-toluidine. The experimental results of the reaction residence time and the yield of the target product under the experimental conditions of different H2 equivalents are shown in Table 3.

[0095] Comparative Example 8

[0096] Test process: Selective hydrogenation experiments were conducted using a Raney nickel catalyst. The reaction was carried out in a microreactor continuous flow reactor. The substrate, o-nitrotoluene, was dissolved in an ethyl acetate solution to form a substrate solution with a substrate concentration of 0.291 mol / L. The reactor was filled with 10 g of catalyst. The substrate solution was continuously introduced into the reactor, while H2 was introduced simultaneously. The H2 equivalent was controlled to be 5-8, that is, the molar flow rate of the H2 introduced was 5-8-6 times the molar flow rate of the substrate. The reaction temperature was controlled at 25°C, and the reaction pressure was 1 MPa (i.e., the total pressure of the reaction system after gas-liquid mixing was 1 MPa).

[0097] According to the above experimental process, the reaction liquid was collected after the reaction reached stability and analyzed using an Agilent 8860 gas chromatograph to obtain the conversion rate of the raw material and the selectivity of the target product. The target product was o-toluidine. The experimental results of the reaction residence time and the yield of the target product under the experimental conditions of different H2 equivalents are shown in Table 4.

[0098] Table 3 CeZrO x Reaction results of o-nitrotoluene hydrogenation using Ni / Ni catalyst in mobile phase

[0099]

[0100] Table 4 Raney nickel catalyst for o-nitrotoluene hydrogenation reaction results in the mobile phase

[0101]

[0102] From Table 3 and Table 4, we know that under the same temperature and pressure, the reverse phase CeZrO x The / Ni catalyst has a higher substrate concentration, requires a lower H2 equivalent, and has a shorter residence time, which shows that the reversed metal oxide catalyst is more active than the Raney nickel catalyst in the selective hydrogenation of nitro compounds.

[0103] The above description is only a preferred embodiment of the present application and is not intended to limit the present application. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principles of the present application shall be included in the scope of protection of the present application.

Claims

1. Application of a Ni-based reverse phase catalyst in the catalytic hydrogenation reaction of a nitro compound to reduce the nitro group in the nitro compound to an amino group by hydrogenation, characterized in that The Ni-based reversed-phase catalyst has an M / Ni reversed-phase structure, which uses metal Ni that dissociates hydrogen as a carrier, and loads nano-metal M oxide as a supporting phase on it to construct reversed-phase interfacial active sites; wherein the metal M is one or two of Ce, Zr, Al, Y, and Mg, and the molar fraction of the supported phase metal M is 5-50% based on the molar fraction of all metals in the catalyst as 100%.

2. The use according to claim 1, characterized in that Taking the molar fraction of all metals in the catalyst as 100%, the molar fraction of the supported phase metal M is in the range of 10-23%.

3. The use according to claim 1, characterized in that The metal M includes two active metals. The combination of the two active metals is Ce-Zr, Zr-Al, Zr-Y, Mg-Al and Ce-Al. The molar ratio of the two active metals is 0.5-2:1, preferably 1-1.2:

1.

4. A use according to claim 1, characterized in that The preparation method of the catalyst comprises the following steps: (1) Add the precursor salt corresponding to the metal Ni and the precursor salt of the supported phase M oxide to the solvent at the same time and stir until they are completely dissolved; (2) Add the precipitant dropwise to the solution of step (1) under continuous stirring. After the addition is complete, stir at room temperature and 400-800 rpm for 2-5 h, centrifuge, wash, dry, and grind into powder; (3) The solid powder obtained in step (2) is calcined in a muffle furnace, and then reduced in a hydrogen atmosphere after calcination to finally obtain the Ni-based reverse phase catalyst.

5. The use according to claim 4, characterized in that In step (1), the metal Ni precursor salt is selected from one of nickel nitrate and nickel chloride salts; the precursor salt of the supported phase M oxide is selected from one or more of the nitrate, chloride, oxychloride, acetylacetonate and sulfate of metal M.

6. The use according to claim 4, characterized in that In step (2), the precipitant is selected from one of urea, ammonium fluoride, ammonium chloride, ammonium oxalate, and oxalic acid. The amount of the precipitant is 2-4 times, preferably 2-3 times, the total molar amount of the loaded phase metal M and metal Ni. The solvent used to dissolve the oxide precursor salt and the precipitant is selected from one or more of water, ethanol, butanol, and ethylene glycol.

7. The use according to claim 4, characterized in that Step (3) The calcination temperature in the muffle furnace is 300-500°C, and the calcination time is 1-5 h.

8. The use according to claim 4, characterized in that The reduction temperature in step (3) is 300-400°C, and the time is 1-4 hours; the hydrogen concentration in the reducing atmosphere is in the range of 10-20%.

9. The use according to claim 1, wherein The application process is as follows: adding a nitro compound, a solvent, and a Ni-based reverse-phase catalyst to a high-pressure reactor, reacting for 2 to 4 hours at 40 to 80° C. and a hydrogen pressure of 0.1 to 1.5 MPa; after the reaction is completed, rapidly cooling the reactor to room temperature to release the remaining hydrogen in the reactor; and finally separating the reaction liquid from the catalyst, recovering the catalyst, and obtaining the target product. The amount of the catalyst is 5-20 g / mol, preferably 10-15 g / mol, based on the amount of the nitro compound; the amount of the solvent is 500-5000 mL / mol, preferably 1500-2000 mL / mol, based on the amount of the nitro compound.

10. The use according to claim 9, characterized in that The solvent is selected from one of n-hexane, cyclohexane, water and methanol, preferably n-hexane or cyclohexane. The catalytic reaction temperature is 60-80° C., and the hydrogen pressure is 1-1.5 MPa.

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