A metal complex-derived acetate hydrogenation catalyst, its preparation method and application

Abstract

This invention discloses a metal complex-derived acetate hydrogenation catalyst, comprising a support and an active component. The support is derived from a metal complex through calcination, and the active component is at least one selected from copper, palladium, platinum, and rhodium. The metal complex is formed by coordinating one or two metals selected from Zr, Ce, and Al with a ligand selected from terephthalic acid, trimesic acid, and 2-aminoterephthalic acid. This invention utilizes the metal complex as a support, leveraging the abundant and tunable pore structure of the support metal complex to introduce the active metal component, maximizing the dispersion of the active metal component and improving catalytic reaction performance. The catalyst of this invention enhances the mass transfer process of reactants within the catalyst, enabling the catalytic hydrogenation of acetate to ethanol under mild conditions, improving the conversion rate of acetate and the selectivity of alcohol. The acetate conversion rate reaches over 97%, and the ethanol selectivity is greater than 97%.

Description

Technical Field

[0001] This invention belongs to the field of catalytic materials and relates to a metal complex-derived acetate hydrogenation catalyst, its preparation method and application, particularly to a method for hydrogenating acetate to ethanol under the action of a metal complex-derived supported metal catalyst. Background Technology

[0002] Fatty alcohols, as important chemical products, have wide applications in fuel additives, coatings, daily chemicals, fragrances, pharmaceuticals, and polymers. Currently, the industrial production of alcohols commonly employs olefin hydration and olefin carbonylation hydrogenation methods. When using olefin hydration to prepare the corresponding alcohols, the reaction pressure is high, the monomer conversion rate is low, and the water-to-olefin ratio is high, resulting in large equipment investment and high separation energy consumption. The synthesis of alcohols via olefin carbonylation hydrogenation involves two steps: homogeneous hydroformylation and heterogeneous hydrogenation. The difficulty lies in the homogeneous hydroformylation reaction, which uses a noble metal as a catalyst and requires relatively harsh reaction conditions.

[0003] The route of esterifying olefins with acids to obtain esters, and then further reducing them to prepare alcohols, can effectively solve the shortcomings of the olefin hydration method, such as low reaction conversion rate, high reaction pressure, large raw material loss, or high energy consumption. At the same time, because the raw materials and products are less corrosive, carbon steel can be used, significantly reducing investment and production costs.

[0004] Currently, research on catalysts for the hydrogenation of acetate is extensive. Chinese patent CN104667925A prepared a Cu / MgO-SiO2 catalyst in a fixed-bed continuous flow reactor via ammonia evaporation for the hydrogenation of methyl acetate, achieving a conversion rate of over 85%. Chinese patent CN102327774A reported a copper-based catalyst for the hydrogenation of acetate to ethanol. Its preparation method involves adding silica sol or a soluble aluminum salt to a mixed solution of a soluble copper salt and a soluble metal salt, stirring until homogeneous, then adding the mixture to a precipitant solution. The catalyst is then subjected to aging, filtration, washing, drying, calcination, molding, and reduction to obtain the catalyst. This copper-based catalyst achieved a maximum conversion rate of 85% and a maximum ethanol selectivity of 91% in the acetate hydrogenation reaction. Chinese patent application CN101934228A discloses a copper-based catalyst for the hydrogenation of acetate to ethanol, with alumina or silica as the support and oxides of elements such as zinc, manganese, chromium, calcium, barium, iron, nickel, and magnesium as promoters. The highest acetate conversion rate achieved is only 88%. Chinese patent application CN116803500A discloses a Cu / Zr catalyst prepared by the sol-gel method, achieving a reactant conversion rate of 56.6% and an ethanol selectivity of over 62.3% in the acetate hydrogenation reaction. Chinese patent CN103464157A discloses a Sn, Y, La, and Mo modified Cu / ZrO2 catalyst, achieving an acetate conversion rate greater than 95%.

[0005] It is evident that existing ester hydrogenation catalysts generally use alumina, silica, zinc oxide, etc., as supports, which commonly suffer from drawbacks such as low acetate conversion and ethanol selectivity, cumbersome catalyst preparation methods, and harsh reaction conditions. Furthermore, these supports cannot restrict the particle size and dispersion density of Cu species, which easily agglomerate into large particles during the reaction, significantly reducing the dispersion of active sites and leading to irreversible deactivation, resulting in poor catalyst stability (Chemical Industry Progress, 2018, 38(9), 3393-3400), hindering its further industrial application and development. Therefore, developing hydrogenation catalysts with small active component particle size, high dispersion, and inhibition of active species agglomeration is one of the important research directions in this field.

[0006] In summary, utilizing the abundant pores of metal complexes to load metal active species, thereby improving the nucleation and growth of active components on the catalyst support, and further improving the particle size and distribution of active components on the support, is of great importance in creating a catalyst with high stability, high acetate conversion rate, and high alcohol selectivity. Summary of the Invention

[0007] To address the technical problems of harsh reaction conditions and unsatisfactory stability of current acetate hydrogenation catalysts, this invention proposes a catalyst for the production of alcohols from acetate hydrogenation. This catalyst is a supported metal catalyst derived from a metal-organic complex with highly dispersed active metal sites and abundant pore structure. It can exhibit stable catalytic activity at lower temperatures and pressures, and has high selectivity and high conversion rate in the acetate hydrogenation to alcohol reaction.

[0008] The objective of this invention is achieved through the following technical solution:

[0009] An acetate hydrogenation catalyst derived from a metal complex, the acetate hydrogenation catalyst comprising a support and an active component supported on the support, wherein the support is derived from a metal complex by calcination, and the active component is at least one of copper, palladium, platinum, and rhodium.

[0010] The metal complex-derived acetate hydrogenation catalyst is prepared by the following method: dissolving the metal salt of the active component in a solvent to obtain a metal salt solution; dispersing the metal complex in the metal salt solution, stirring at room temperature, separating the solid and liquid phases to obtain a catalyst precursor; calcining the catalyst precursor in an air atmosphere, and then reducing it with hydrogen to obtain the ester hydrogenation catalyst.

[0011] Another object of the present invention is to provide a method for preparing the acetate hydrogenation catalyst derived from the metal complex, comprising: dissolving the metal salt of the active component in a solvent to obtain a metal salt solution; dispersing the metal complex in the metal salt solution, stirring and diffusing at room temperature for 3-12 h, separating the solid and liquid, washing the solid to obtain a catalyst precursor; calcining the catalyst precursor at 400-800°C for 2-12 h in an air atmosphere, cooling, and then reducing it with hydrogen at 300-500°C for 2-24 h to obtain an ester hydrogenation catalyst with highly dispersed active sites and abundant pore structure.

[0012] The mass ratio of the metal salt to the metal complex is 0.01:1 to 0.4:1, preferably 0.02:1 to 0.2:1.

[0013] The metal salt of the active component is selected from copper acetate, copper nitrate, copper chloride, palladium acetate, palladium chloride, ammonium chloropalladate, ammonium chloroplatinate, platinum nitrate, and rhodium chloride, preferably copper acetate, copper nitrate, or palladium acetate.

[0014] The solvent is one of methanol, ethanol, and DMF. Considering that methanol has a lower boiling point and smaller molecular size than ethanol and DMF, it is easier for methanol to enter the pores of the metal complex. This not only facilitates the exchange of organic solvents already present in the pores of the metal complex, but also allows the active component to be attracted into the pores of the metal complex through capillary action. Therefore, methanol is preferred as the solvent.

[0015] The mass ratio of the metal salt to the solvent is 1:200 to 1:1000, preferably 1:200 to 1:500, and more preferably 1:200 to 1:400.

[0016] The metal complex is a crystal structure formed by coordinating one or two metals selected from Zr, Ce, and Al with a ligand selected from terephthalic acid, trimesic acid, and 2-aminoterephthalic acid.

[0017] Furthermore, the metal complex is one of Ce-UiO-66, Zr-UiO-66, Ce-MOF-808, Zr-MOF-808, Al-MIL-100, Al-CAU-1, Al-CAU-3, Ce-BTC, Ce / Zr-UiO-66 (Ce:Zr molar ratio = 1:4), and Ce / Zr-MOF-808 (Ce:Zr molar ratio = 1:4).

[0018] Most preferably, the metal complex is Ce-UiO-66 or Ce / Zr-UiO-66 (Ce:Zr = 1:4).

[0019] Specifically, the metal complex is dispersed in a metal salt solution by ultrasound, and the active component is loaded into the pores of the metal complex by stirring and diffusion at room temperature for 3 to 12 hours.

[0020] Preferably, the stirring and diffusion time is 3 to 8 hours.

[0021] More preferably, the stirring and diffusion time is 3.4 to 6 hours.

[0022] Solid-liquid separation can be achieved using centrifugation or other conventional solid-liquid separation methods.

[0023] The solid was washed with methanol.

[0024] Preferably, the calcination temperature is 400–600°C and the calcination time is 2–4 hours.

[0025] More preferably, the calcination temperature is 500-600°C and the calcination time is 3-4 hours.

[0026] The metal oxide is reduced to the elemental metal. Preferably, the reduction temperature is 350℃~400℃, and the reduction time is 6~15h.

[0027] Another object of the present invention is to provide the application of the aforementioned metal complex-derived acetate hydrogenation catalyst in the hydrogenation of acetate.

[0028] A method for preparing ethanol by hydrogenation of acetate includes: mixing acetate, the said acetate hydrogenation catalyst and a solvent, reacting under a hydrogen atmosphere and stirring to obtain ethanol, cooling after the reaction is completed, and filtering the reaction solution to separate the acetate hydrogenation catalyst.

[0029] The mass of the acetate hydrogenation catalyst is 1% to 20% of the mass of the acetate, preferably 8% to 12%, and more preferably 10% to 12%.

[0030] The acetate esters mentioned are methyl acetate, ethyl acetate, isopropyl acetate, and cyclohexyl acetate.

[0031] The stirring speed is 300-900 rpm, preferably 500-700 rpm.

[0032] The reaction temperature is 150–350°C, and the reaction pressure is 1.0–4.5 MPa; preferably, the reaction temperature is 220–280°C, and the reaction pressure is 2.0–3.0 MPa.

[0033] The reaction time is 2 to 12 hours, preferably 5 to 7 hours.

[0034] In this invention, all pressures are absolute pressures.

[0035] A method for preparing ethanol by hydrogenation of acetate ester specifically includes: adding acetate ester, the acetate ester hydrogenation catalyst and solvent into a reactor; first replacing the air in the reactor with nitrogen gas, then replacing the nitrogen gas in the reactor with hydrogen gas; turning on the heater; raising the temperature to the reaction temperature; then introducing hydrogen gas to maintain the reaction pressure; carrying out the reaction under stirring; after the reaction is completed, cooling down, opening the reactor, and filtering the reaction liquid to separate the acetate ester hydrogenation catalyst.

[0036] The reactor is a high-pressure autoclave reactor.

[0037] The beneficial effects of this invention are reflected in:

[0038] The catalyst of this invention is a non-precious metal catalyst, which is low in cost and simple to synthesize. It uses a metal complex as a support, and takes advantage of the rich and tunable pore structure of the support metal complex to introduce active metal components, anchor active metal sites, maximize the dispersion of active metal components, and improve catalytic reaction performance.

[0039] The catalyst of this invention has highly dispersed metal active sites and a stable structure with abundant pore structure, which enhances the mass transfer process of reactants within the catalyst. It exhibits good activity, good stability, and environmental friendliness in ester hydrogenation reactions.

[0040] The catalyst of this invention can catalyze the hydrogenation of acetate to produce ethanol under mild conditions, improving the conversion rate of acetate and the selectivity of alcohol during the acetate hydrogenation reaction. The acetate conversion rate reaches more than 97%, and the ethanol selectivity is greater than 97%, which has promising prospects for industrial application. Attached Figure Description

[0041] Figure 1 The image shows the XRD pattern of catalyst 1 before the reaction.

[0042] Figure 2 This is a pore size distribution diagram of catalyst 1 before the reaction.

[0043] Figure 3 The image shows the XRD pattern of catalyst 1 after the reaction.

[0044] Figure 4 This is a pore size distribution diagram of catalyst 1 after the reaction.

[0045] Figure 5 The results of stability tests on the catalyst for the hydrogenation of acetate to ethanol. Detailed Implementation

[0046] The present invention will be further illustrated by the following implementation examples. Experimental methods not specified with specific experimental conditions in the following examples are generally carried out in accordance with known methods in the art.

[0047] Conversion rate = (Amount of raw materials converted / Total amount of raw materials) × 100%

[0048] Selectivity = (Amount of raw materials consumed in conversion to the target product / Amount of raw materials converted) × 100%

[0049] Example 1

[0050] 0.2 g of copper acetate was added to an Erlenmeyer flask, along with 80 g of methanol as a solvent, to prepare a copper acetate solution. Then, 1.0 g of Ce-UiO-66 was added to the copper acetate solution, and the mixture was stirred and diffused at room temperature for 6 hours. The solid was obtained by centrifugation and washed twice with methanol to obtain the catalyst precursor. The methanol used for washing was recovered. The catalyst precursor was calcined at 550 °C for 3.4 h in air, cooled, and then reduced with hydrogen at 380 °C for 12 h to obtain catalyst 1. Its XRD pattern is shown below. Figure 1 See the aperture distribution diagram. Figure 2 .

[0051] Example 2

[0052] Catalyst 2-Catalyst 18 were prepared according to the method of Example 1. During the preparation process, the type of metal complex, the mass ratio of metal salt to solvent, the mass ratio of metal salt to metal complex, the stirring and diffusion time, the calcination temperature and calcination time, and the reduction temperature and reduction time were changed according to Table 1.

[0053] Table 1. Preparation of catalysts 2-18

[0054]

[0055] Note: In Ce / Zr-UiO-66, the Ce:Zr molar ratio is 1:4; in Ce / Zr-MOF-808, the Ce:Zr molar ratio is 1:4.

[0056] Example 3

[0057] 1.76 g of cyclohexyl acetate and 0.176 g of catalyst 1 were added to a 50 mL batch stainless steel high-pressure reactor. The reactor was first purged with nitrogen to replace the air, then purged with hydrogen. Heating was initiated and the temperature was raised to the reaction temperature of 250 °C. Hydrogen was then introduced to raise the pressure inside the reactor to 3 MPa and maintained at 3 MPa during the reaction. The reaction was stirred at 600 rpm for 6 hours. The reaction solution was collected through a sampling tube in the reactor, the catalyst was removed by filtration, and the solution was analyzed by gas chromatography. The conversion rate of cyclohexyl acetate was 99.83%, and the selectivity for ethanol was 98.92%.

[0058] Figure 3 , Figure 4 The XRD pattern and pore size distribution of catalyst 1 after a single activity test under the reaction conditions of this embodiment are shown below, compared with the XRD pattern of catalyst 1 before the reaction. Figure 1 ) and aperture distribution map ( Figure 2 The difference was not significant, indicating that the catalyst still maintained a good structure and the active components were not lost.

[0059] Catalyst repeatability testing. Stability testing of catalyst 1 was conducted according to the reaction conditions of this embodiment, with a total of 5 tests performed. Figure 5 It can be seen that the results of the second to fifth reactions were not significantly different from those of the first reaction, indicating that the catalyst has stable catalytic activity.

[0060] Example 4

[0061] Catalyst performance testing

[0062] 1.76 g of cyclohexyl acetate and the catalyst were added to a 50 mL batch stainless steel high-pressure reactor. First, the air in the reactor was replaced with nitrogen, then the nitrogen was replaced with hydrogen. Heating was started and the temperature was raised to the reaction temperature. Hydrogen was then introduced to raise the pressure inside the reactor to the reaction pressure and maintained at that pressure. The reaction was started with stirring. The reaction pressure, rotation speed, and reaction time are shown in Table 2. After the reaction was completed, the reaction solution was collected through a sampling tube in the reactor. The catalyst was removed by filtration, and the solution was analyzed using gas chromatography. The conversion rate of cyclohexyl acetate and the selectivity of ethanol are shown in Table 2.

[0063] Table 2. Performance test conditions and results of the catalyst

[0064]

[0065]

[0066] Note: Catalyst dosage refers to the percentage of catalyst mass relative to the mass of cyclohexyl acetate.

[0067] Example 5

[0068] 10 mmol of acetate and 10% wt% of catalyst 1 were added to a 50 mL batch stainless steel high-pressure reactor. The reactor was first purged with nitrogen to replace the air, then with hydrogen. Heating was initiated and the temperature was raised to the reaction temperature of 250 °C. Hydrogen was introduced to raise the pressure inside the reactor to 3 MPa and maintained at 3 MPa during the reaction. The reactor was stirred at 600 rpm for 6 hours. The reaction solution was collected through a sampling tube in the reactor, filtered to remove the catalyst, and analyzed using gas chromatography. The results are shown in Table 3.

[0069] Table 3. Catalyst performance test results

[0070]

[0071] Example 6

[0072] Catalyst 19 was prepared according to the method in Example 1. During the preparation process, only 80g of methanol was replaced with 40g of anhydrous ethanol, while other conditions remained unchanged.

[0073] Catalyst 20 was prepared according to the method in Example 1. During the preparation process, only 80g of methanol was replaced with 200g of anhydrous ethanol, while other conditions remained unchanged.

[0074] Catalyst 21 was prepared according to the method of Example 1. During the preparation process, only the metal complex was changed to Zr-MOF-808, while other conditions remained unchanged.

[0075] Catalyst 22 was prepared according to the method of Example 1. During the preparation process, only the metal complex was changed to Al-CAU-1, while other conditions remained unchanged.

[0076] Catalyst 23 was prepared according to the method in Example 1. During the preparation process, only the metal complex was changed to Al-CAU-3, while other conditions remained unchanged.

[0077] Catalyst 24 was prepared according to the method of Example 1. During the preparation process, only the metal complex was changed to Ce-BTC, while other conditions remained unchanged.

[0078] Catalyst 25 was prepared according to the method in Example 1. During the preparation process, only the metal complex was changed to Ce / Zr-MOF-808, while other conditions remained unchanged.

[0079] Catalyst 26 was prepared according to the method of Example 1. During the preparation process, only copper acetate was replaced with palladium chloride, while other conditions remained unchanged.

[0080] Catalyst 27 was prepared according to the method of Example 1. During the preparation process, only copper acetate was replaced with ammonium chloroplatinate, while other conditions remained unchanged.

[0081] Catalyst 28 was prepared according to the method of Example 1. During the preparation process, only copper acetate was replaced with platinum nitrate, while other conditions remained unchanged.

[0082] Catalyst 29 was prepared according to the method in Example 1. During the preparation process, only the calcination time was adjusted to 4 hours, while other conditions remained unchanged.

[0083] Catalyst 30 was prepared according to the method in Example 1. During the preparation process, only the calcination time was adjusted to 8 hours, while other conditions remained unchanged.

[0084] Catalyst 31 was prepared according to the method in Example 1. During the preparation process, only the reduction time was adjusted to 2 hours, while other conditions remained unchanged.

[0085] Catalyst 32 was prepared according to the method in Example 1. During the preparation process, only the reduction time was adjusted to 24 h, while other conditions remained unchanged.

[0086] The activity of catalysts 19-32 was tested according to the conditions of Example 3, and the results are shown in Table 4.

[0087] Table 4. Performance test results of catalysts 19-32

[0088]

[0089]

[0090] Example 7

[0091] Except for adjusting the amount of catalyst 1 to 0.018g, the rest was the same as in Example 3. After the reaction was completed, the gas chromatograph was used for analysis. The conversion rate of cyclohexyl acetate was 97.03%, and the selectivity of ethanol was 97.52%.

[0092] Example 8

[0093] Except for adjusting the amount of catalyst 1 to 0.352g, the rest was the same as in Example 3. After the reaction was completed, the gas chromatograph was used for analysis. The conversion rate of cyclohexyl acetate was 97.89%, and the selectivity of ethanol was 98.52%.

[0094] Example 9

[0095] Except for adjusting the reaction temperature to 200℃, the process was the same as in Example 3. After the reaction was completed, the gas chromatograph was used for analysis. The conversion rate of cyclohexyl acetate was 97.12%, and the selectivity of ethanol was 97.43%.

[0096] Example 10

[0097] Except for adjusting the reaction temperature to 350℃, the process was the same as in Example 3. After the reaction was completed, the gas chromatograph was used for analysis. The conversion rate of cyclohexyl acetate was 99.22%, and the selectivity of ethanol was 97.20%.

[0098] Example 11

[0099] Except for adjusting the reaction pressure to 1.5 MPa, the reaction was the same as in Example 3. After the reaction was completed, the gas chromatograph was used for analysis. The conversion rate of cyclohexyl acetate was 97.93%, and the selectivity of ethanol was 97.66%.

[0100] Example 12

[0101] Except for adjusting the reaction pressure to 4.5 MPa, everything else was the same as in Example 3. After the reaction was completed, the gas chromatograph was used for analysis. The conversion rate of cyclohexyl acetate was 98.31%, and the selectivity of ethanol was 98.12%.

[0102] Example 13

[0103] Except for adjusting the rotation speed to 300 rpm, everything else was the same as in Example 3. After the reaction was completed, the gas chromatograph was used for analysis. The conversion rate of cyclohexyl acetate was 97.11%, and the selectivity of ethanol was 97.62%.

[0104] Example 14

[0105] Except for adjusting the rotation speed to 900 rpm, everything else was the same as in Example 3. After the reaction was completed, the gas chromatograph was used for analysis. The conversion rate of cyclohexyl acetate was 98.12%, and the selectivity of ethanol was 97.93%.

[0106] Example 15

[0107] Except for adjusting the reaction time to 2 hours, the process was the same as in Example 3. After the reaction, the results were analyzed using gas chromatography. The conversion rate of cyclohexyl acetate was 97.21%, and the selectivity of ethanol was 97.73%.

[0108] Comparative Example 1

[0109] 200 mg of copper acetate was added to an Erlenmeyer flask, along with 80 g of methanol as a solvent, to prepare a copper acetate solution. Subsequently, 1.0 g of CeO2 cubes (commercially available) was added to the Erlenmeyer flask, and the mixture was stirred and diffused at room temperature for 6 hours. The solid and solution were separated by centrifugation. The obtained solid was washed twice with methanol to obtain the catalyst precursor, and the washing solvent was recovered. The catalyst precursor was calcined at 550 °C for 3.4 h in air, cooled, and then reduced with hydrogen at 380 °C for 12 h to obtain catalyst 29.

[0110] 1.76 g of cyclohexyl acetate and 176 mg (10% of the mass of cyclohexyl acetate) of catalyst 29 were added to a 50 mL batch stainless steel high-pressure reactor. The reactor was first purged with nitrogen to replace the air, then with hydrogen. Heating was initiated and the temperature was raised to the reaction temperature of 250 °C. Hydrogen was then introduced to increase the pressure inside the reactor to 3 MPa. The reaction was carried out for 6 hours at a stirring speed of 600 rpm. The reaction solution was collected through a sampling tube in the reactor, the catalyst was removed by filtration, and the analysis was performed using gas chromatography. The conversion rate of cyclohexyl acetate was 83.62%, and the selectivity for ethanol was 91.21%. Using catalyst 1, under the same reaction conditions, the conversion rate of cyclohexyl acetate was 99.83%, and the selectivity for ethanol was 98.92% (Example 3).

[0111] Compared with catalyst 1, the catalytic performance of the catalyst prepared with CeO2 cube support is greatly reduced.

Claims

1. A metal complex-derived acetate hydrogenation catalyst, characterized in that: The acetate hydrogenation catalyst comprises a support and an active component. The support is derived from a metal complex through calcination. The active component is at least one of copper, palladium, platinum, and rhodium. The metal complex-derived acetate hydrogenation catalyst is prepared by dissolving a metal salt of the active component in a solvent to obtain a metal salt solution. The metal complex was dispersed in a metal salt solution, stirred at room temperature, and the solid and liquid phases were separated to obtain the catalyst precursor. The catalyst precursor was calcined in air and then reduced with hydrogen to obtain an acetate hydrogenation catalyst. The mass ratio of the metal salt to the metal complex is 0.01:1 to 0.4:

1. The metal complex is one of Ce-UiO-66, Zr-UiO-66, Ce-MOF-808, Zr-MOF-808, Al-MIL-100, Al-CAU-1, Al-CAU-3, Ce-BTC, Ce / Zr-UiO-66, and Ce / Zr-MOF-808.

2. The acetate hydrogenation catalyst derived from the metal complex according to claim 1, characterized in that: The mass ratio of the metal salt to the metal complex is 0.02:1 to 0.2:

1.

3. The acetate hydrogenation catalyst derived from the metal complex according to claim 1, characterized in that: The metal salt of the active component is one of copper acetate, copper nitrate, copper chloride, palladium acetate, palladium chloride, ammonium chloropalladate, ammonium chloroplatinate, platinum nitrate, and rhodium chloride.

4. The acetate hydrogenation catalyst derived from the metal complex according to claim 1 or 3, characterized in that: The metal salts of the active components are copper acetate, copper nitrate, and palladium acetate; The metal complexes are Ce-UiO-66 and Ce / Zr-UiO-66.

5. A method for preparing the acetate hydrogenation catalyst derived from the metal complex according to claim 1, characterized in that: include: The metal salt of the active component is dissolved in a solvent to obtain a metal salt solution; The metal complex was dispersed in a metal salt solution and stirred at room temperature for 3–12 h to diffuse. The solid and liquid were separated, and the solid was washed to obtain the catalyst precursor. The catalyst precursor was calcined at 400–800 °C for 2–12 h in air, and after cooling, it was reduced with hydrogen at 300–500 °C for 2–24 h to obtain an ester hydrogenation catalyst with highly dispersed active sites and abundant pore structure.

6. The method for preparing the acetate hydrogenation catalyst derived from the metal complex according to claim 5, characterized in that: The solvent is one of methanol, ethanol, and DMF; the mass ratio of the metal salt to the solvent is 1:200 to 1:1000.

7. The method for preparing the metal complex-derived acetate hydrogenation catalyst according to claim 6, characterized in that: The solvent is methanol.

8. The method for preparing the acetate hydrogenation catalyst derived from the metal complex according to claim 6, characterized in that: The mass ratio of the metal salt to the solvent is 1:200 to 1:

500.

9. The method for preparing the acetate hydrogenation catalyst derived from the metal complex according to claim 8, characterized in that: The mass ratio of the metal salt to the solvent is 1:200 to 1:

400.

10. The method for preparing the metal complex-derived acetate hydrogenation catalyst according to claim 5, characterized in that: The stirring and diffusion time is 3 to 8 hours.

11. The method for preparing the metal complex-derived acetate hydrogenation catalyst according to claim 10, characterized in that: The stirring and diffusion time is 3.4 to 6 hours.

12. The method for preparing the metal complex-derived acetate hydrogenation catalyst according to claim 5, characterized in that: The calcination temperature is 400–600℃, and the calcination time is 2–4 h; the reduction temperature is 350℃–400℃, and the reduction time is 6–15 h.

13. The method for preparing the acetate hydrogenation catalyst derived from the metal complex according to claim 12, characterized in that: The calcination temperature is 500–600℃, and the calcination time is 3–4 hours.

14. A method for preparing ethanol by hydrogenation of acetate, characterized in that: include: Acetate, the acetate hydrogenation catalyst according to claim 1, and a solvent are mixed and reacted under a hydrogen atmosphere with stirring to obtain ethanol; wherein the mass of the acetate hydrogenation catalyst is 1% to 20% of the mass of acetate; the acetate is methyl acetate, ethyl acetate, isopropyl acetate, or cyclohexyl acetate; the reaction temperature is 150 to 350 °C, and the reaction pressure is 1.0 to 4.5 MPa.

15. The method for preparing ethanol by hydrogenation of acetate according to claim 14, characterized in that: The mass of the acetate hydrogenation catalyst is 8% to 12% of the mass of acetate; the reaction temperature is 220 to 280 °C, and the reaction pressure is 2.0 to 3.0 MPa.

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