Catalyst for selective hydrogenation reaction and method for preparing and using the same

Abstract

The application discloses a catalyst for selective hydrogenation reaction, which is a carbon fiber loaded Cu@ZIF-8 catalyst, and the catalyst is prepared by taking a calcined nano carbon fiber membrane as a carrier and loading Cu@ZIF-8 particles with a core-shell structure, wherein the ZIF-8 after carbonization is used as the shell, and Cu is used as the core. The catalyst has the advantages of high activity, high selectivity, high stability, simple operation and the like. When the catalyst is applied to the reaction of preparing olefins by catalytic hydrogenation of alkynes, the problem of excessive hydrogenation of the olefins caused by the prolongation of the reaction time can be effectively inhibited.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of catalysts, in particular to a catalyst for selective hydrogenation reaction and a preparation method thereof, and application of the catalyst in an alkyne hydrogenation reaction for preparing olefins. BACKGROUND

[0002] Olefins have important application significance in the synthesis of high molecular materials, resins, drugs, pesticides and various active intermediates, etc. The reaction of semi-hydrogenation of alkyne to generate olefins as a means of olefin preparation has attracted more and more attention from the industry and academia, and the main challenge of selective semi-hydrogenation of alkyne is to design and develop an effective catalyst to inhibit the over-hydrogenation process.

[0003] At present, the research on alkyne hydrogenation is focused on supported palladium catalysts, however, Pd catalysts are high in cost and are prone to deactivation after a period of use. For example, the representative Lindlar catalyst is widely used in the synthesis of various olefins, but it has problems such as over-hydrogenation of ethylene to ethane at low temperature (<50℃) and production of "green oil" to deactivate the catalyst. In order to inhibit over-hydrogenation, the active hydrogenation performance of platinum group metal catalysts is partially limited to improve the chemical selectivity, and the commonly used method is to rely on the addition of ligands such as nitrogen, phosphorus, sulfur or the addition of a second metal with lower activity, but the results are not satisfactory. Therefore, developing a catalyst with high activity and high selectivity in alkyne semi-hydrogenation reaction, and being green, economical, environmentally friendly and sustainable, is still the research focus of alkyne hydrogenation catalysts. SUMMARY

[0004] In order to solve the problems existing in the prior art, the present application provides a catalyst for selective hydrogenation reaction, which wraps Cu in the carbonized ZIF-8 shell and then loads it on carbon fibers for full dispersion. The catalyst can effectively inhibit the problem of over-hydrogenation caused by the prolongation of reaction time when applied to hydrogenation reaction, and has the advantages of high activity, high selectivity, high stability and simple operation.

[0005] To achieve the above purpose, the catalyst for selective hydrogenation reaction provided by the present application is a carbon fiber loaded Cu@ZIF-8 catalyst, which uses a calcined nano-carbon fiber membrane as a carrier, and loads Cu@ZIF-8 particles with a core-shell structure, in which carbonized ZIF-8 is the shell and Cu is the core.

[0006] The catalyst of the present application takes Cu as the catalytic active center with low price and long service life, forms a core-shell structure by wrapping Cu in the shell of carbonized ZIF-8, and is further loaded on a carbon fiber membrane; the hydrogenation reactivity is improved by the dispersion of the carbon fiber, the hydrogenation selectivity is improved by the interaction between Cu and carbonized ZIF-8 and the ZIF-8 confinement effect, so that the problem of excessive hydrogenation due to long reaction time in the hydrogenation reaction process can be effectively inhibited, and the demand for preparing olefins by hydrogenating acetylenes can be met.

[0007] As a limitation of the above technical solution, the loading of the Cu@ZIF-8 particles is that the nanometer carbon fiber membrane is placed in a methanol solution containing Cu precursor, zinc nitrate and dimethyl imidazole to be synthesized by a hydrothermal one-step method, that is, hydrothermal reaction at 120-180℃ for 6-12h, alcohol washing, drying, and finally calcination at 800-1000℃ for 1-12h.

[0008] As a limitation of the above technical solution, the Cu precursor is selected from at least one of copper acetylacetonate, copper chloride, copper nitrate and copper sulfate.

[0009] As a limitation of the above technical solution, in the methanol solution, the amount of methanol is 20-1000ml, the content of Cu precursor is 0.1-5g, the content of zinc nitrate is 1-10g, the content of dimethyl imidazole is 1-10g, and the addition amount of nanometer carbon fiber membrane is 0.5-20g.

[0010] As a limitation of the above technical solution, the carrier nanometer carbon fiber membrane is prepared by calcination treatment at 800-1000℃ for 1-12h after obtaining a nanometer spinning membrane by electrospinning through a spinning solution configured by polyacrylonitrile and polyvinylpyrrolidone.

[0011] As a limitation of the above technical solution, the mass concentration of polyacrylonitrile in the spinning solution is 0.10-0.15g / mL, the mass concentration of polyvinylpyrrolidone is 0.03-0.05g / mL, and the solvent of the spinning solution is selected from N,N-dimethylformamide or N,N-dimethylacetamide.

[0012] By limiting the preparation conditions of the catalyst, including the amount of each reaction raw material, hydrothermal and calcination conditions, etc., the microstructure of the catalyst is effectively controlled, especially the size and electronic structure of the active center Cu, so as to effectively control the substrate reaction kinetics, thereby obtaining high selectivity and high conversion rate of hydrogenation reaction.

[0013] The present application also provides a preparation method of the catalyst for selective hydrogenation reaction as described above, which comprises the following preparation steps:

[0014] a. Polyacrylonitrile and polyvinylpyrrolidone are dissolved in a spinning solution solvent to prepare a spinning solution, and a nanometer spinning film is prepared by using coaxial electrospinning technology; the nanometer spinning film is calcined at 800-1000 DEG C for 1-12 h to obtain a nanometer carbon fiber film;

[0015] b. The nanometer carbon fiber film obtained in step a is placed in a methanol solution containing Cu precursor, zinc nitrate and dimethyl imidazole, and is subjected to hydrothermal reaction at 120-180 DEG C for 6-12 h, alcohol washing, drying and calcination at 800-1000 DEG C for 1-12 h to synthesize a carbon fiber supported Cu@ZIF-8 catalyst.

[0016] The carbon fiber supported Cu@ZIF-8 catalyst is prepared by using coaxial electrospinning technology, and the reduction ability of the catalyst is treated in a mild manner, so that the catalyst exhibits excellent catalytic activity and selectivity for catalytic hydrogenation reaction.

[0017] As a limitation of the above technical solution, the spinning solution in step a is stirred at 55-60 DEG C for 10-12 h before coaxial electrospinning is performed to prepare a nanometer spinning film; the electrostatic voltage of the coaxial electrospinning is 14-20 KV, and the flow rate is 0.2-1.0 mL / h.

[0018] The spinning conditions are further controlled to better realize the regulation of the mild treatment structure of the catalyst.

[0019] The application also provides a use method of the catalyst for selective hydrogenation reaction as described above, i.e. the carbon fiber supported Cu@ZIF-8 catalyst is used for catalyzing the reaction of preparing olefin from alkyne, the reaction is carried out in methanol as a solvent, ammonia borane is used as a reducing agent, alkyne and the carbon fiber supported Cu@ZIF-8 catalyst are added, and stirring reaction is carried out at 40-80 DEG C.

[0020] As a limitation of the above technical solution, the conversion rate of alkyne in the reaction of preparing olefin from alkyne is not less than 99%, the selectivity is not less than 95%, and the recovery and reuse rate is not less than 90%.

[0021] The catalyst can convert alkyne into cis-olefin through a mild reaction under normal pressure without using H2, which not only realizes high conversion rate and high selectivity of the reaction, but also effectively inhibits the excessive hydrogenation conversion of the product olefin with the extension of reaction time, achieves high stability, and meets the demand of preparing olefin from alkyne under normal pressure green and environmentally friendly reaction conditions. In addition, the carbon fiber supported Cu@ZIF-8 catalyst is convenient to recover and reuse, greatly reduces the cost of the catalyst, promotes the green development of hydrogenation reaction, and promotes the green development of chemical synthesis and pharmaceutical field.

[0022] In summary, the present application takes Cu as a catalytically active center, forms a core-shell structure by wrapping Cu in the ZIF-8 shell after carbonization, and further loads it on the carbon fiber membrane prepared by electrospinning technology to regulate the microstructure of the catalyst, so as to obtain a catalyst with high activity, high selectivity and high stability for hydrogenation reaction, solve the problem of excessive hydrogenation in the hydrogenation reaction process, meet the demand of preparing olefins from alkynes by hydrogenation, and enable the high conversion of alkynes to cis-olefins under normal pressure and green and environmentally friendly reaction conditions. In addition, the carbon fiber loaded Cu@ZIF-8 catalyst of the present application not only has a convenient preparation process, but also is easy to recover and reuse after application, greatly reduces the cost of the catalyst, and can significantly promote the green development of chemical synthesis and pharmaceutical field. BRIEF DESCRIPTION OF DRAWINGS

[0023] Figure 1 , scanning electron microscope image of the nanofiber membrane of Example 1 of the present application;

[0024] Figure 2 , scanning electron microscope image of the carbon fiber loaded Cu@ZIF-8 catalyst obtained in Example 1 of the present application;

[0025] Figure 3 , transmission electron microscope image of the carbon fiber loaded Cu@ZIF-8 catalyst obtained in Example 1 of the present application;

[0026] Figure 4 , spherical aberration electron microscope image of the carbon fiber loaded Cu@ZIF-8 catalyst obtained in Example 1 of the present application;

[0027] Figure 5 , X-ray diffraction (XRD) pattern of the carbon fiber loaded Cu@ZIF-8 catalyst obtained in Example 1 of the present application;

[0028] Figure 6 , X-ray photoelectron spectroscopy (XPS) pattern of the carbon fiber loaded Cu@ZIF-8 catalyst obtained in Example 1 of the present application;

[0029] Figure 7 , scanning electron microscope image of the microstructure of the carbon fiber loaded Cu@ZIF-8 catalyst obtained in Example 1 of the present application after recycling.

[0030] Figure 8 , scanning electron microscope image of the Cu@ZIF-8 catalyst obtained in Comparative Example 1. DETAILED DESCRIPTION

[0031] The technical solutions of the present application will be clearly and completely described below in combination with the embodiments. Obviously, the described embodiments are only some of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative work fall within the protection scope of the present application.

[0032] The chemical raw materials involved in the following examples and comparative examples are typical products purchased in the market.

[0033] The following examples relate to the preparation of carbon fiber supported Cu@ZIF-8 catalyst.

[0034] Example 1

[0035] a, 1g of polyacrylonitrile (PAN) was dissolved in 10mL of N,N-dimethylformamide (DMF) solution, 0.3g of polyvinylpyrrolidone (PVP) was added, stirring at 60℃ for 10h as a spinning solution; then electrospinning was carried out, using 14KV static voltage, 0.4mL / h flow rate spinning, the distance between the needle and the receiving paper was 15cm.

[0036] b, the nanospun membrane was vacuum dried at 60℃ (according to the conventional vacuum drying operation), and then calcined in a tube furnace, calcined at 900℃ for 2h to obtain a nanocarbon fiber membrane, the microstructure of the carbon fiber membrane was observed, see the scanning electron microscope graph of the carbon fiber membrane in Figure 1

[0037] c, 1g of nanocarbon fiber membrane was placed in 100ml of methanol, 0.5g of copper acetylacetonate, 2.3g of Zn(NO3)2·6H2O, and 3.6g of 2-methylimidazole were added, and hydrothermal reaction was carried out at 120℃ for 6h, ethanol washing, drying, and calcining at 900℃ for 2h to obtain a carbon fiber supported Cu@ZIF-8 catalyst.

[0038] The carbon fiber supported Cu@ZIF-8 catalyst obtained in Example 1 was respectively characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), spherical aberration electron microscopy, X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS) to characterize the microstructure of the catalyst, see the SEM graph of the catalyst in Figure 2 , the TEM graph of the catalyst in Figure 3 , the spherical aberration electron microscopy graph of the catalyst in Figure 4 , the XRD graph of the catalyst in Figure 5 , and the XPS graph of the catalyst in Figure 6 . The above characterization shows the successful preparation of the carbon fiber supported Cu@ZIF-8 catalyst, in which Cu exists in the form of atomic clusters.

[0039] Example 2

[0040] ​a, 1 g of PAN was dissolved in 10 mL of DMF solution, 0.5 g of PVP was added, and stirred at 60°C for 10 h as a spinning solution; then electrospinning was carried out, and the spinning was carried out at a voltage of 14 KV and a flow rate of 0.8 mL / h, and the distance between the needle and the receiving paper was 15 cm.

[0041] b, the nanospinning film was vacuum dried at 60°C, and then calcined in a tube furnace, and calcined at 900°C for 2 h to obtain a nanocarbon fiber film.

[0042] c, 1 g of the nanocarbon fiber film was placed in 100 ml of methanol, 0.5 g of copper acetylacetonate, 2.3 g of Zn(NO3)2·6H2O, and 3.6 g of 2-methylimidazole were added, and hydrothermal reaction was carried out at 120°C for 6 h, and then washed with ethanol, dried, and calcined at 900°C for 2 h to obtain a carbon fiber supported Cu@ZIF-8 catalyst.

[0043] Example 3

[0044] a, 1 g of PAN was dissolved in 10 mL of DMF solution, 0.3 g of PVP was added, and stirred at 60°C for 10 h as a spinning solution; then electrospinning was carried out, and the spinning was carried out at a voltage of 14 KV and a flow rate of 0.4 mL / h, and the distance between the needle and the receiving paper was 15 cm.

[0045] b, the nanospinning film was vacuum dried at 60°C, and then calcined in a tube furnace, and calcined at 900°C for 2 h to obtain a nanocarbon fiber film.

[0046] c, 1 g of the nanocarbon fiber film was placed in 100 ml of methanol, 0.25 g of copper acetylacetonate, 2.3 g of Zn(NO3)2·6H2O, and 3.6 g of 2-methylimidazole were added, and hydrothermal reaction was carried out at 130°C for 6 h, and then washed with ethanol, dried, and calcined at 900°C for 2 h to obtain a carbon fiber supported Cu@ZIF-8 catalyst.

[0047] Example 4

[0048] a, 1 g of PAN was dissolved in 10 mL of DMF solution, 0.3 g of PVP was added, and stirred at 60°C for 10 h as a spinning solution; then electrospinning was carried out, and the spinning was carried out at a voltage of 14 KV and a flow rate of 0.4 mL / h, and the distance between the needle and the receiving paper was 15 cm.

[0049] b, the nanospinning film was vacuum dried at 60°C, and then calcined in a tube furnace, and calcined at 900°C for 2 h to obtain a nanocarbon fiber film.

[0050] c. 1 g of nanometer carbon fiber membrane was placed in 100 ml of methanol, 1 g of copper acetate, 3 g of Zn(NO3)2·6H2O, and 4.5 g of 2-methylimidazole were added, and hydrothermal reaction was carried out at 120℃ for 6 h, ethanol washing, drying, and calcination at 900℃ for 2 h to obtain a carbon fiber supported Cu@ZIF-8 catalyst.

[0051] Example 5

[0052] a. 1 g of PAN was dissolved in 10 mL of DMF solution, 0.4 g of PVP was added, and stirring was carried out at 60℃ for 10 h as a spinning solution; then electrospinning was carried out at an electrostatic voltage of 16 KV and a flow rate of 0.5 mL / h, and the distance between the needle and the receiving paper was 15 cm.

[0053] b. The nanometer spinning membrane was dried at 60℃ under vacuum, and then calcination was carried out in a tube furnace, and calcination was carried out at 900℃ for 2 h to obtain a nanometer carbon fiber membrane.

[0054] c. 1 g of nanometer carbon fiber membrane was placed in 100 ml of methanol, 0.25 g of copper acetylacetone, 1.2 g of Zn(NO3)2·6H2O, and 1.8 g of 2-methylimidazole were added, and hydrothermal reaction was carried out at 120℃ for 6 h, ethanol washing, drying, and calcination at 1000℃ for 3 h to obtain a carbon fiber supported Cu@ZIF-8 catalyst.

[0055] The catalysts prepared in Examples 1-5 were subjected to phenylacetylene hydrogenation test and result analysis.

[0056] Phenylacetylene hydrogenation test: 10 mg of the catalyst prepared in each of Examples 1-5 was respectively placed in 5 10 mL round-bottomed flasks, 5 mL of methanol was respectively added to each flask as a solvent, 22 μL of phenylacetylene was respectively added to each flask as a substrate, and 30 mg of ammonia borane was respectively added to each flask as a hydrogen source. Reaction was carried out at 40℃ under normal pressure for 90 min, and the product was analyzed by gas chromatography. The experimental results are shown in the following table:

[0057] Catalyst Example 1 Example 2 Example 3 Example 4 Example 5 Phenylacetylene conversion (%) 99.9 99.9 99.9 99.9 97.9 Styrene selectivity (%) 97.2 94.0 96.5 92.1 96.4 Phenylmethane selectivity (%) 2.8 6.0 3.5 7.9 3.6 Reaction time (min) 90 90 180 90 90

[0058] As can be seen from the above table data, the catalysts of the present application have obvious advantages in phenylacetylene conversion rate and selectivity. Although the Cu content of Example 3 is reduced, the conversion rate and selectivity can be improved by prolonging the reaction time, and prolonging the reaction time does not cause excessive hydrogenation. By changing the synthesis conditions, the reaction activity and selectivity of the other examples are adjusted.

[0059] In addition, the catalyst of Example 1 was subjected to a cycle experiment, i.e. after completing the catalytic phenylacetylene hydrogenation test, the catalyst was recovered and subjected to phenylacetylene hydrogenation test again. The cycle experiment was repeated for 6 times, and the results are shown in the following table.

[0060] Number of cycle experiments 1 2 3 4 5 6 Phenylacetylene conversion (%) 99.9 99.9 99.9 99.9 99.3 98.9 Styrene selectivity (%) 95.2 96.8 95.4 97.1 97.5 96.4 Phenylmethane selectivity (%) 4.8 3.2 4.6 2.9 2.5 3.6

[0061] From the results of the above table, it can be seen that the carbon fiber loaded Cu@ZIF-8 catalyst of the present application has good stability in sequential use, and the microstructure of the recovered catalyst is shown in the scanning electron microscope image of the catalyst in FIG. 1. Figure 7 .

[0062] Comparative Example 1

[0063] The catalyst of the present comparative example is a Cu@ZIF-8 catalyst, and the specific preparation process is as follows:

[0064] In 100 ml of methanol, 0.5 g of copper acetylacetonate, 2.3 g of Zn(NO3)2·6H2O, and 3.6 g of 2-methylimidazole were added, and hydrothermal reaction was performed at 120°C for 6 h. After ethanol washing and drying, calcination was performed in a tube furnace at 900°C for 2 h to obtain a Cu@ZIF-8 catalyst. The microstructure of the catalyst was observed, and the scanning electron microscope image of the catalyst is shown in FIG. 1. Figure 8

[0065] Comparative Example 2

[0066] The catalyst of the present comparative example is a Cu / ZIF-8 catalyst supported on ZIF-8, and the specific preparation process is as follows:

[0067] 2.3 g of Zn(NO3)2·6H2O was dissolved in 100 mL of methanol, and 3.6 g of 2-methylimidazole was dissolved in 40 mL of methanol. The two methanol solutions were mixed, and stirring was performed at room temperature for 24 h. Then, 0.5 g of copper acetylacetonate was added, and stirring was continued for 12 h. After centrifugation, the mixture was washed with methanol three times, and vacuum drying was performed at 60°C. Then, calcination was performed in a tube furnace at 900°C under N2atmosphere for 2 h to obtain a Cu / ZIF-8 catalyst supported on ZIF-8.

[0068] Comparative Example 3

[0069] The catalyst of the present comparative example is a carbon fiber supported Cu catalyst, and the specific preparation process is as follows:

[0070] 1 g of a nanometer carbon fiber membrane (the preparation of the nanometer carbon fiber membrane is the same as in Example 1) was placed in 100 ml of methanol, and 0.5 g of copper acetylacetonate was added. Calcination was performed at 900°C for 2 h to obtain a carbon fiber supported Cu catalyst.

[0071] The catalysts obtained in Comparative Examples 1 to 3 were subjected to phenylacetylene hydrogenation tests, and the operation of the phenylacetylene hydrogenation test was the same as above. The experimental results are shown in the following table:

[0072] Catalyst Comparative Example 1 Comparative Example 2 Comparative Example 3 Phenylacetylene conversion (%) 70.1 99.9 99.9 Styrene selectivity (%) 95.2 81.1 80.6 Phenylmethane selectivity (%) 4.8 18.9 19.4 Reaction time (min) 90 90 90

[0073] ​As shown in the above table, the conversion rate and conversion activity and selectivity of each comparative example are obviously insufficient compared with the examples. The analysis shows that the low conversion activity of the catalyst of comparative example 1 is because the Cu@ZIF-8 particles are easy to agglomerate, which is not conducive to the full activity of the catalytic process. The low selectivity of the catalysts of comparative examples 2 and 3 is because the carbonized ZIF-8 does not have a limiting effect on Cu, causing the catalytic selectivity of Cu to not meet the high selectivity requirement of the alkyne preparation olefin reaction.

[0074] In summary, the carbon fiber loaded Cu@ZIF-8 catalyst of the present application has higher activity and selectivity compared with the traditional selective hydrogenation catalyst of phenylacetylene. The combination of carbon fiber structure and core-shell structure significantly improves the catalyst performance, reduces the production cost of the catalyst, and has higher economic benefits and practical significance.

Claims

1. A catalyst for selective hydrogenation reactions, characterized in that: The catalyst is a carbon fiber supported Cu@ZIF-8 catalyst, a calcined nano carbon fiber membrane is used as a carrier, and a Cu@ZIF-8 particle with a core-shell structure and a calcined ZIF-8 shell and a Cu core is loaded; The Cu@ZIF-8 particle is loaded by placing the nano carbon fiber membrane in a methanol solution containing a Cu precursor, zinc nitrate and dimethyl imidazole to synthesize by a hydrothermal one-step method, that is, hydrothermal reaction at 120-180 ℃ for 6-12 h, alcohol washing, drying, and finally calcination at 800-1000 ℃ for 1-12 h.

2. The catalyst for selective hydrogenation reaction according to claim 1, wherein: The Cu precursor is at least one of copper acetylacetonate, copper chloride, copper nitrate and copper sulfate.

3. The catalyst for selective hydrogenation reaction according to claim 1, wherein: In the methanol solution, the amount of methanol is 20-1000 ml, the content of the Cu precursor is 0.1-5 g, the content of zinc nitrate is 1-10 g, the content of dimethyl imidazole is 1-10 g, and the added amount of the nano carbon fiber membrane is 0.5-20 g.

4. The catalyst for selective hydrogenation reaction according to claim 1, wherein: The carrier nano carbon fiber membrane is prepared by electrospinning a spinning solution of polyacrylonitrile and polyvinylpyrrolidone, and then calcining at 800-1000 ℃ for 1-12 h.

5. The catalyst for selective hydrogenation reaction according to claim 4, wherein: The mass concentration of polyacrylonitrile in the spinning solution is 0.10-0.15 g / mL, the mass concentration of polyvinylpyrrolidone is 0.03-0.05 g / mL, and the solvent of the spinning solution is selected from N,N-dimethylformamide or N,N-dimethylacetamide.

6. A method for producing a catalyst for selective hydrogenation reaction according to any one of claims 1 to 5, characterized by, The following preparation steps are included: a. Dissolve polyacrylonitrile and polyvinylpyrrolidone in a spinning solution solvent to prepare a spinning solution, and prepare a nano spinning membrane by coaxial electrospinning technology, and calcine the nano spinning membrane at 800-1000 ℃ for 1-12 h to obtain a nano carbon fiber membrane; b. Place the nano carbon fiber membrane obtained in step a in a methanol solution containing a Cu precursor, zinc nitrate and dimethyl imidazole, hydrothermal reaction at 120-180 ℃ for 6-12 h, alcohol washing, drying, and calcination at 800-1000 ℃ for 1-12 h to synthesize a carbon fiber supported Cu@ZIF-8 catalyst.

7. The method for preparing a catalyst for selective hydrogenation reaction according to claim 6, wherein: The spinning solution in step a needs to be stirred at 55-60 ℃ for 10-12 h before coaxial electrospinning to prepare a nano spinning membrane; the electrostatic voltage of the coaxial electrospinning is 14-20 KV, and the flow rate is 0.2-1.0 mL / h.

8. The method of using a catalyst for selective hydrogenation reactions according to any one of claims 1 to 5, wherein: The carbon fiber supported Cu@ZIF-8 catalyst is used to catalyze the reaction of hydrolysis of alkyne to prepare olefin, the reaction uses methanol as a solvent, ammonia borane as a reducing agent, and after adding alkyne and carbon fiber supported Cu@ZIF-8 catalyst, stirring is carried out at 40-80 ℃.

9. The method of using a catalyst for selective hydrogenation reactions according to claim 8, wherein: In the reaction of hydrolysis of alkyne to prepare olefin, the conversion rate of alkyne is not less than 99%, the selectivity is not less than 95%, and the recovery and reuse rate is not less than 90%.

Images