Cobalt-chromium bimetallic phosphine-containing ligand MOF-based catalyst, and preparation method and application thereof

Abstract

The invention provides a cobalt-chromium bimetallic phosphine-containing ligand MOF-based catalyst as well as a preparation method and application thereof, and belongs to the technical field of heterogeneous catalysis and fine chemical engineering. The catalyst is an MOF-based supported catalyst and is composed of a catalytic active component, a metal auxiliary agent and a carrier, the catalytic active component is Co, the metal auxiliary agent is Cr, the loading amount of a phosphine ligand in the catalyst is 0.5-2.0%, the catalyst has high activity and stability, and a feasible scheme is provided for efficient conversion of 1-butene.

Description

Technical Field

[0001] The present invention relates to the technical fields of heterogeneous catalysis and fine chemicals, and particularly relates to a cobalt-chromium bimetallic phosphine ligand MOF-based catalyst, a preparation method thereof, and an application thereof. Background Art

[0002] The hydroformylation reaction was first proposed by German scientist Otto Roelen (1897−1993) in 1938. During the process of Fischer-Tropsch synthesis, he accidentally discovered that ethylene, CO, and H2 reacted to form diethyl ketone and propionaldehyde under the catalysis of a cobalt complex. Due to its simple reaction pathway and high atom economy, the hydroformylation reaction has been widely used in the field of olefin functionalization. The aldehyde products generated by the hydroformylation reaction have important industrial application values. First, these aldehyde products can be further hydrogenated to form long-chain alcohols, which are used in the production of daily chemicals and industrial raw materials such as detergents, emulsifiers, and plasticizers. Second, branched aldehydes and their derivatives also play important roles in the production of flavors and fragrances, pharmaceutical intermediates, and other high-value-added fine chemicals. In addition, due to its high selectivity and high reaction efficiency, the hydroformylation reaction has been widely applied in continuous flow processes, significantly reducing energy consumption and raw material waste, and providing reliable support for green and efficient chemical production.

[0003] Currently, homogeneous catalysts such as cobalt-phosphine complexes are still the main catalysts for olefin hydroformylation. Homogeneous catalysts have a clear active center structure and can exhibit significant catalytic activity and chemical / regioselectivity under mild reaction conditions. However, such catalysts still have some deficiencies, such as the problems of metal and ligand loss, poor thermal stability, and difficulty in catalyst separation and recovery, which to a certain extent limit their promotion in large-scale industrial applications. Compared with homogeneous catalysis, heterogeneous catalytic systems have gradually become the mainstream direction of industrial catalysis due to their advantages of easy separation and recovery. CRilliam et al. prepared a CoCo3 / SBA-15 bimetallic catalyst by the wet impregnation method and used ethylene as the reaction olefin. The yield of the C3 product reached 50%, which was 3.1 times that of Co / SBA-15, indicating that the synergistic effect between Co and Co significantly enhanced the catalytic performance (J. Catal. 2024, 438, 115733). Although these studies have solved the problem of insufficient activity in heterogeneous catalytic systems by introducing new active metals, the accumulation of CO on the surface of the active components still hinders the adsorption of hydrogen and olefins, thus limiting the further improvement of catalytic activity. Therefore, it is particularly important to design a reasonable catalytic structure and reduce the adsorption strength of the active metal Co for CO.

[0004] Bimetallic catalysis regulates the local electronic environment of active metals without changing the nature of active sites by introducing metal promoters with variable valence states and strong electron transfer capabilities. This strategy effectively weakens the interaction between the active metal Co and CO, promotes the conversion of surface CO by the metal promoter, thus significantly reducing the concentration of surface CO, optimizing the subsequent coordination process of olefins and CO, and significantly improving the catalytic performance. For example, Ro et al. prepared a Co-ReOx / Al2O3 bimetallic catalyst by the conventional impregnation method, which showed excellent performance in the hydroformylation of ethylene, with the selectivity of propionaldehyde reaching 40% and the yield being 0.06 (mol propionaldehyde·molCo-1·min-1) (Nature, 2022, 609(7926), 287).

[0005] Currently, there is little research on catalysts for the hydroformylation of 1-butene. Therefore, based on the construction strategy of the bimetallic catalytic system, it is of great practical significance to provide a catalyst with high activity and stability. Summary of the Invention

[0006] The purpose of the present invention is to provide a cobalt-chromium bimetallic phosphine ligand MOF-based catalyst, its preparation method and application, aiming to solve the technical problem of the lack of bimetallic catalysts for the hydroformylation of 1-butene in the prior art.

[0007] To achieve the above invention purpose, the present invention provides the following technical solutions:

[0008] The present invention provides a preparation method of a cobalt-chromium bimetallic phosphine ligand MOF-based catalyst, including the following steps:

[0009] Mix a cobalt salt with acetone to obtain a cobalt salt solution;

[0010] Mix a chromium salt with water to obtain a chromium salt solution;

[0011] Dissolve a zinc salt, triphenylphosphine and an organic ligand in N,N-dimethylformamide, stir, filter, wash and dry to obtain a solid powder MOF-74@P;

[0012] Dissolve the solid powder MOF-74@P in an acetonitrile solution, add the cobalt salt solution and the chromium salt solution for soaking treatment, and finally perform a calcination treatment to obtain the cobalt-chromium bimetallic phosphine ligand MOF-based catalyst.

[0013] Further, the cobalt salt is one or more of cobalt chloride, cobalt nitrate, cobalt sulfate, cobalt acetate, cobalt citrate or cobalt acetylacetonate; the chromium salt is one or more of chromium nitrate, ammonium chromate, chromium citrate or chromium diethyl ester.

[0014] Further, the concentration of the cobalt salt in the cobalt salt solution is 50 - 250 mg / mL; the concentration of the chromium salt in the chromium salt solution is 50 - 250 mg / mL.

[0015] Further, the zinc salt is one or more of zinc nitrate hexahydrate, zinc acetate, zinc carbonate, zinc chloride, or zinc acetylacetonate; the organic ligand is 2,5-dihydroxyterephthalic acid.

[0016] Further, the ratio of the zinc salt, triphenylphosphine, and the organic ligand is 12:2:3.

[0017] Further, the stirring is carried out at room temperature; the time is 4 - 8 h.

[0018] Further, the calcination temperature is 200 - 400 °C, the time is 2 - 6 h, and the heating rate is 2 - 8 °C / min.

[0019] The present invention also provides a cobalt-chromium bimetallic phosphine ligand MOF-based catalyst obtained by the preparation method of the cobalt-chromium bimetallic phosphine ligand MOF-based catalyst described in the above technical solution.

[0020] The present invention also provides the application of the cobalt-chromium bimetallic phosphine ligand MOF-based catalyst described in the above technical solution in the hydroformylation of olefins to aldehydes. The specific application is as follows:

[0021] Mix the cobalt-chromium bimetallic phosphine ligand MOF-based catalyst, the solvent, and the reaction olefin to obtain a first mixture;

[0022] Heat up and increase the pressure of the first mixture for reaction. After the reaction is completed, cool it to room temperature in a bath, release the pressure, and collect the product.

[0023] Further, the dosage ratio of the cobalt-chromium bimetallic phosphine ligand MOF-based catalyst, the solvent, and the olefin is 50 - 100 mg: 5 - 15 mL: 5 - 15 mmol; the heating up and increasing the pressure specifically involves introducing syngas to increase the pressure to 4 - 6 MPa and heating up to 80 - 100 °C. The syngas is a mixture of H2 and CO, and the volume ratio of H2 and CO is 1:1 - 1:3.

[0024] Compared with the prior art, the technical solution of the present invention has the following beneficial effects:

[0025] Based on the construction strategy of a bimetallic catalytic system, the present invention designs and prepares a catalyst Co-CROx / MOF-74@P. The catalyst is a MOF-based supported catalyst, which consists of a catalytic active component, a metal promoter, and a support. Among them, the catalytic active component is Co, the metal promoter is Cr, and the loading amount of the phosphine ligand in the catalyst is 0.5-2.0%. The catalyst of the present invention has high activity and stability, providing a feasible solution for the efficient conversion of 1-butene. Description of the Drawings

[0026] Figure 1 XRD pattern of the catalyst 1.0Co-5.0Cr / MOF-74@0.5P obtained in Example 1 of the present invention. Detailed Embodiments

[0027] The present invention provides a method for preparing a cobalt-chromium bimetallic phosphine-ligand-containing MOF-based catalyst, which includes the following steps:

[0028] Mix a cobalt salt with acetone to obtain a cobalt salt solution;

[0029] Mix a chromium salt with water to obtain a chromium salt solution;

[0030] Dissolve a zinc salt, triphenylphosphine, and an organic ligand in N,N-dimethylformamide, stir, filter, wash, and dry to obtain a solid powder MOF-74@P;

[0031] Dissolve the solid powder MOF-74@P in an acetonitrile solution, add the cobalt salt solution and the chromium salt solution for soaking treatment, and finally perform a calcination treatment to obtain the cobalt-chromium bimetallic phosphine-ligand-containing MOF-based catalyst.

[0032] Mix a cobalt salt with acetone to obtain a cobalt salt solution; mix a chromium salt with water to obtain a chromium salt solution;

[0033] In the present invention, the cobalt salt is preferably one or more of cobalt chloride, cobalt nitrate, cobalt sulfate, cobalt acetate, cobalt citrate, or cobalt acetylacetonate; the chromium salt is preferably one or more of chromium nitrate, ammonium chromate, chromium citrate, or chromyl diethyl ester.

[0034] In the present invention, the concentration of the cobalt salt in the cobalt salt solution is preferably 50-250 mg / mL, more preferably 100-250 mg / mL; the concentration of the chromium salt in the chromium salt solution is preferably 50-250 mg / mL, more preferably 100-250 mg / mL.

[0035] Dissolve a zinc salt, triphenylphosphine, and an organic ligand in N,N-dimethylformamide, heat and stir, filter, wash, and dry to obtain a solid powder MOF-74@P;

[0036] In the present invention, the zinc salt is preferably one or more of zinc nitrate hexahydrate, zinc acetate, zinc carbonate, zinc chloride or zinc acetylacetonate; the organic ligand is preferably 2,5-dihydroxyterephthalic acid.

[0037] In the present invention, the ratio of the zinc salt, triphenylphosphine to the organic ligand is preferably 12:2:3.

[0038] In the present invention, the stirring is carried out at room temperature; the time is 4 to 8 h.

[0039] Dissolve the solid powder MOF-74@P in an acetonitrile solution, add a cobalt salt solution and a chromium salt solution for soaking treatment, and finally carry out a calcination treatment to obtain the cobalt-chromium bimetallic phosphine ligand MOF-based catalyst.

[0040] In the present invention, the dosage ratio of the solid powder MOF-74@P to the acetonitrile solution is 0.5 g:30 mL, and the volume ratio of the cobalt salt solution to the chromium salt solution is 22:61.

[0041] Dissolve the solid powder MOF-74@P in an acetonitrile solution, add a cobalt salt solution and a chromium salt solution for soaking treatment, and finally carry out a calcination treatment to obtain the cobalt-chromium bimetallic phosphine ligand MOF-based catalyst.

[0042] In the present invention, the solid powder obtained by soaking is subjected to a calcination treatment in an air atmosphere.

[0043] In the present invention, the calcination temperature is preferably 200 to 400 °C, more preferably 250 to 400 °C; the time is preferably 2 to 6 h, more preferably 2 to 4 h; the heating rate is preferably 2 to 8 °C / min, more preferably 5 to 8 °C.

[0044] The present invention also provides a cobalt-chromium bimetallic phosphine ligand MOF-based catalyst obtained by the preparation method of the cobalt-chromium bimetallic phosphine ligand MOF-based catalyst described in the above technical solution.

[0045] The catalyst of the present invention is a MOF-based supported catalyst, which is composed of a catalytic active component, a metal promoter and a carrier. The catalytic active component is Co, the metal promoter is Cr, and the phosphine ligand loading amount in the catalyst is 0.5-2.0%. The catalyst of the present invention has high activity and stability, providing a feasible solution for the efficient conversion of 1-butene.

[0046] The present invention also provides the application of the cobalt-chromium bimetallic phosphine ligand MOF-based catalyst described in the above technical solution in the hydroformylation of olefins to aldehydes. The specific application is as follows:

[0047] Mix the cobalt-chromium bimetallic phosphine ligand MOF-based catalyst, a solvent and a reaction olefin to obtain a first mixture;

[0048] Heat up and increase the pressure of the first mixture, carry out the reaction. After the reaction is completed, cool it to room temperature in a bath, release the pressure, and collect the product.

[0049] In the present invention, the dosage ratio of the cobalt-chromium bimetallic phosphine ligand MOF-based catalyst, solvent and olefin is 50-100 mg: 5-15 mL: 5-15 mmol; specifically, synthesis gas is introduced to increase the pressure during the heating and pressure increase, the pressure is increased to 4-6 MPa, and the temperature is increased to 80-100 °C. The synthesis gas is a mixed gas of H2 and CO, and the volume ratio of H2 and CO is 1:1-1:3.

[0050] In the present invention, unless otherwise specified, the raw materials required for preparation are all commercially available products well-known to those skilled in the art.

[0051] The technical solutions provided by the present invention will be described in detail below in conjunction with the embodiments, but they cannot be understood as limiting the protection scope of the present invention.

[0052] Example 1

[0053] (1) Mix 1.00 g of cobalt acetylacetonate with 10 mL of acetone to prepare a cobalt salt solution; mix 1.00 g of ammonium chromate with 10 mL of water to prepare a chromium salt solution.

[0054] (2) Dissolve 2.67 g of zinc nitrate hexahydrate, 0.20 g of triphenylphosphine and 0.45 g of 2,5-dihydroxyterephthalic acid (the molar ratio of zinc salt to organic ligand is 4:1) in 50 mL of N,N-dimethylformamide solution, stir at room temperature for 4 h, filter, wash and dry to obtain a solid powder MOF-74@P.

[0055] (3) Dissolve 0.50 g of MOF-74@P powder in 30 mL of acetonitrile solution, add 220 μL of the cobalt salt solution and 610 μL of the chromium salt solution, stir at room temperature for 24 h, and calcine the obtained powder in an air atmosphere to prepare the catalyst 1.0Co-5.0Cr / MOF-74@0.5P; the calcination temperature is 250 °C, the calcination time is 4 h, and the heating rate is 5 °C / min.

[0056] Example 2

[0057] (1) Mix 1.00 g of cobalt acetylacetonate with 10 mL of acetone to prepare a cobalt salt solution; mix 1.00 g of ammonium chromate with 10 mL of water to prepare a chromium salt solution.

[0058] (2) Dissolve 2.67 g of zinc nitrate hexahydrate, 0.40 g of triphenylphosphine, and 0.45 g of 2,5-dihydroxyterephthalic acid (the molar ratio of zinc salt to organic ligand is 4:1) in 50 mL of N,N-dimethylformamide solution, stir at room temperature for 4 h, filter, wash, and dry to obtain a solid powder MOF-74@P;

[0059] (3) Dissolve 0.50 g of MOF-74@P powder in 30 mL of acetonitrile solution, add 220 μL of cobalt salt solution and 610 μL of cobalt salt solution, stir at room temperature for 24 h, and calcine the obtained powder in an air atmosphere to prepare the catalyst 1.0Co-5.0Cr / MOF-74@1.0P; the calcination temperature is 250 °C, the calcination time is 4 h, and the heating rate is 5 °C / min.

[0060] Example 3

[0061] (1) Mix 1.00 g of cobalt acetylacetonate with 10 mL of acetone to prepare a cobalt salt solution; mix 1.00 g of ammonium chromate with 10 mL of water to prepare a chromium salt solution;

[0062] (2) Dissolve 2.67 g of zinc nitrate hexahydrate, 0.60 g of triphenylphosphine, and 0.45 g of 2,5-dihydroxyterephthalic acid (the molar ratio of zinc salt to organic ligand is 4:1) in 50 mL of N,N-dimethylformamide solution, stir at room temperature for 4 h, filter, wash, and dry to obtain a solid powder MOF-74@P;

[0063] (3) Dissolve 0.50 g of MOF-74@P powder in 30 mL of acetonitrile solution, add 220 μL of cobalt salt solution and 610 μL of chromium salt solution, stir at room temperature for 24 h, and calcine the obtained powder in an air atmosphere to prepare the catalyst 1.0Co-5.0Cr / MOF-74@1.5P; the calcination temperature is 250 °C, the calcination time is 4 h, and the heating rate is 5 °C / min.

[0064] Example 4

[0065] (1) Mix 1.00 g of cobalt acetylacetonate with 10 mL of acetone to prepare a cobalt salt solution; mix 1.00 g of ammonium chromate with 10 mL of water to prepare a chromium salt solution;

[0066] (2) Dissolve 2.67 g of zinc nitrate hexahydrate, 0.80 g of triphenylphosphine, and 0.45 g of 2,5-dihydroxyterephthalic acid (the molar ratio of zinc salt to organic ligand is 4:1) in 50 mL of N,N-dimethylformamide solution, stir at room temperature for 4 h, filter, wash, and dry to obtain a solid powder MOF-74@P;

[0067] (3) Dissolve 0.50 g of MOF-74@P powder in 30 mL of acetonitrile solution, add 220 μL of cobalt salt solution and 610 μL of chromium salt solution, stir at room temperature for 24 h, and calcine the obtained powder in an air atmosphere to obtain the catalyst 1.0Co-5.0Cr / MOF-74@2.0P; the calcination temperature is 250 °C, the calcination time is 4 h, and the heating rate is 5 °C / min.

[0068] Application Example 1

[0069] (1) Add 0.10 g of the catalyst prepared in Example 1, 1.0 g of 1-butene and 10 mL of toluene to a high-pressure reaction kettle;

[0070] (2) Introduce syngas to 4 MPa, heat up to 80 °C, and start the reaction;

[0071] (3) After reacting for 4 h, cool the high-pressure kettle to room temperature with a cold water bath, slowly release the pressure, and collect the product;

[0072] (4) Analyze the product by liquid chromatography and gas chromatography: the olefin conversion rate is 47.28%, the aldehyde selectivity is 98.42%, and the aldehyde yield is 46.53%.

[0073] Application Example 2

[0074] (1) Add 0.10 g of the catalyst prepared in Example 2, 1.0 g of 1-butene and 10 mL of toluene to a high-pressure reaction kettle, and then introduce 0.60 g of 1-butene;

[0075] (2) Introduce syngas to 4 MPa, heat up to 80 °C, and start the reaction;

[0076] (3) After reacting for 4 h, cool the high-pressure kettle to room temperature with a cold water bath, slowly release the pressure, and collect the product;

[0077] (4) Analyze the product by liquid chromatography and gas chromatography: the olefin conversion rate is 53.25%, the aldehyde selectivity is 98.66%, and the aldehyde yield is 52.54%.

[0078] Application Example 3

[0079] (1) Add 0.10 g of the catalyst prepared in Example 3, 1.0 g of 1-butene and 10 mL of toluene to a high-pressure reaction kettle, and then introduce 0.60 g of 1-butene;

[0080] (2) Introduce syngas to 4 MPa, heat up to 80 °C, and start the reaction;

[0081] (3) After reacting for 4 h, cool the high-pressure kettle to room temperature with a cold water bath, slowly release the pressure, and collect the product;

[0082] (4) Analyze the product using liquid chromatography and gas chromatography: the olefin conversion rate is 67.81%, the aldehyde selectivity is 98.24%, and the aldehyde yield is 66.62%.

[0083] Application Example 4

[0084] (1) Add 0.10 g of the catalyst prepared in Example 4, 1.0 g of 1-butene, and 10 mL of toluene to a high-pressure reaction kettle, and then introduce 0.60 g of 1-butene;

[0085] (2) Introduce syngas to 4 MPa, heat up to 80 °C, and start the reaction;

[0086] (3) After reacting for 4 h, cool the high-pressure kettle to room temperature with a cold water bath, slowly release the pressure, and collect the product;

[0087] (4) Analyze the product using liquid chromatography and gas chromatography: the olefin conversion rate is 54.24%, the aldehyde selectivity is 98.35%, and the aldehyde yield is 53.35%.

[0088] Application Example 5

[0089] (1) Add 0.10 g of the catalyst prepared in Example 3, 1.0 g of 1-butene, and 10 mL of toluene to a high-pressure reaction kettle, and then introduce 0.60 g of 1-butene;

[0090] (2) Introduce syngas to 4 MPa, heat up to 90 °C, and start the reaction;

[0091] (3) After reacting for 4 h, cool the high-pressure kettle to room temperature with a cold water bath, slowly release the pressure, and collect the product;

[0092] (4) Analyze the product using liquid chromatography and gas chromatography: the olefin conversion rate is 79.45%, the aldehyde selectivity is 98.89%, and the aldehyde yield is 78.57%.

[0093] Application Example 6

[0094] (1) Add 0.10 g of the catalyst prepared in Example 3, 1.0 g of 1-butene, and 10 mL of toluene to a high-pressure reaction kettle, and then introduce 0.60 g of 1-butene;

[0095] (2) Introduce syngas to 4 MPa, heat up to 100 °C, and start the reaction;

[0096] (3) After reacting for 4 h, cool the high-pressure kettle to room temperature with a cold water bath, slowly release the pressure, and collect the product;

[0097] (4)Analyze the product using liquid chromatography and gas chromatography: the olefin conversion rate is 78.32%, the aldehyde selectivity is 99.25%, and the aldehyde yield is 77.73%.

[0098] Application Example 7

[0099] (1)Add 0.10 g of the catalyst prepared in Example 3, 1.0 g of 1-butene, and 10 mL of toluene to a high-pressure reactor, and then introduce 0.60 g of 1-butene;

[0100] (2)Introduce syngas to 5 MPa, heat up to 90 °C, and start the reaction;

[0101] (3)After reacting for 4 h, cool the high-pressure reactor to room temperature with a cold water bath, slowly release the pressure, and collect the product;

[0102] (4)Analyze the product using liquid chromatography and gas chromatography: the olefin conversion rate is 90.76%, the aldehyde selectivity is 99.67%, and the aldehyde yield is 90.45%.

[0103] Application Example 8

[0104] (1)Add 0.10 g of the catalyst prepared in Example 3, 1.0 g of 1-butene, and 10 mL of toluene to a high-pressure reactor, and then introduce 0.60 g of 1-butene;

[0105] (2)Introduce syngas to 6 MPa, heat up to 90 °C, and start the reaction;

[0106] (3)After reacting for 4 h, cool the high-pressure reactor to room temperature with a cold water bath, slowly release the pressure, and collect the product.

[0107] (4)Analyze the product using liquid chromatography and gas chromatography: the olefin conversion rate is 87.84%, the aldehyde selectivity is 99.07%, and the aldehyde yield is 87.04%.

[0108] Application Example 9

[0109] (1)Add 0.10 g of the catalyst prepared in Example 3, 1.0 g of 1-butene, and 10 mL of toluene to a high-pressure reactor, and then introduce 0.60 g of 1-butene;

[0110] (2)Introduce syngas to 5 MPa, heat up to 90 °C, and start the reaction;

[0111] (3)After reacting for 5 h, cool the high-pressure reactor to room temperature with a cold water bath, slowly release the pressure, and collect the product;

[0112] (4)Analysis of the product by liquid chromatography and gas chromatography: The olefin conversion rate is 90.57%, the aldehyde selectivity is 99.26%, and the aldehyde yield is 89.90%.

[0113] Application Example 10

[0114] (1)Add 0.10 g of the catalyst prepared in Example 3, 1.0 g of 1-butene, and 10 mL of toluene to a high-pressure reactor, and then introduce 0.60 g of 1-butene;

[0115] (2)Introduce syngas to 6 MPa, heat up to 90 °C, and start the reaction;

[0116] (3)After reacting for 6 h, cool the high-pressure reactor to room temperature with a cold water bath, slowly release the pressure, and collect the product;

[0117] (4)Analysis of the product by liquid chromatography and gas chromatography: The olefin conversion rate is 91.37%, the aldehyde selectivity is 99.57%, and the aldehyde yield is 90.98%.

[0118] Application Example 11

[0119] Select the catalyst prepared in Example 3 for a recyclability test. The reaction conditions are 5 MPa, 90 °C, and 5 h. The research results show that after 6 cycles, the aldehyde yield retains 80% of the initial yield.

[0120] The experimental results of the application examples are shown in Tables 1 to 3. Table 1 is the data table of the influence of different phosphine ligand contents on the hydroformylation performance of the catalyst; Table 2 is the data table of the influence of process conditions on the hydroformylation performance of the catalyst 1.0Co-5.0Cr / MOF-74@1.5P; Table 3 is the data table of the recyclability test results described in Application Example 11;

[0121] Table 1 Data table of the influence of different phosphine ligand contents on the hydroformylation performance of the catalyst

[0122]

[0123] Table 2 Data table of the influence of process conditions on the hydroformylation performance of the catalyst 1.0Co-5.0Cr / MOF-74@1.5P

[0124]

[0125] Table 3 Data table of the recyclability test results described in Application Example 11

[0126]

[0127] As can be seen from Tables 1 to 3, the catalyst prepared by the present invention enables the conversion rate of 1-butene to reach up to 90.76%, and after multiple cycles, 1-butene can still have a relatively high conversion rate.

[0128] The catalyst obtained in Example 1 was characterized by XRD images, and the results are as Figure 1 shown.

[0129] The above are only the preferred embodiments of the present invention. It should be noted that for those of ordinary skill in the art, without departing from the principle of the present invention, several improvements and refinements can be made, and these improvements and refinements should also be regarded as the protection scope of the present invention.

Claims

1. A method for preparing a cobalt-chromium bimetallic phosphine-containing ligand MOF-based catalyst, characterized in that: The steps include: mixing the cobalt salt with acetone to obtain a cobalt salt solution; mixing a chromium salt with water to obtain a chromium salt solution; The zinc salt, triphenylphosphine and organic ligand are dissolved in N,N-dimethylformamide, and then filtered, washed and dried after stirring to obtain a solid powder MOF-74@P; The solid powder MOF-74@P is dissolved in an acetonitrile solution, a cobalt salt solution and a chromium salt solution are added for soaking, and finally a calcination treatment is performed to obtain the cobalt-chromium bimetallic phosphine-containing ligand MOF-based catalyst.

2. The method for preparing the cobalt-chromium bimetallic phosphine-containing ligand MOF-based catalyst according to claim 1, characterized in that: The cobalt salt is one or more of cobalt chloride, cobalt nitrate, cobalt sulfate, cobalt acetate, cobalt citrate or cobalt acetylacetonate; the chromium salt is one or more of chromium nitrate, ammonium chromate, chromium citrate or diethyl chromate.

3. The method for preparing the cobalt-chromium bimetallic phosphine-containing ligand MOF-based catalyst according to claim 1, characterized in that: The concentration of the cobalt salt in the cobalt salt solution is 50-250 mg / mL; the concentration of the chromium salt in the chromium salt solution is 50-250 mg / mL.

4. The method for preparing the cobalt-chromium bimetallic phosphine-containing ligand MOF-based catalyst according to claim 1, characterized in that: The zinc salt is one or more of zinc nitrate hexahydrate, zinc acetate, zinc carbonate, zinc chloride or zinc acetylacetonate; and the organic ligand is 2,5-dihydroxyterephthalic acid.

5. The method for preparing the cobalt-chromium bimetallic phosphine-containing ligand MOF-based catalyst according to claim 1, characterized in that: The ratio of the zinc salt, triphenylphosphine and organic ligand is 12:2:

3.

6. The method for preparing the cobalt-chromium bimetallic phosphine-containing ligand MOF-based catalyst according to claim 1, characterized in that: The stirring is carried out at room temperature for 4 to 8 hours.

7. The method for preparing the cobalt-chromium bimetallic phosphine-containing ligand MOF-based catalyst according to claim 1, characterized in that: The calcination temperature is 200-400° C., the calcination time is 2-6 hours, and the heating rate is 2-8° C. / min.

8. The cobalt-chromium bimetallic phosphine-containing ligand MOF-based catalyst obtained by the preparation method of the cobalt-chromium bimetallic phosphine-containing ligand MOF-based catalyst according to any one of claims 1 to 7.

9. Use of the cobalt-chromium bimetallic phosphine-containing ligand MOF-based catalyst according to claim 8 in olefin hydroformylation to produce aldehydes, characterized in that: The application is specifically: Mixing a cobalt-chromium bimetallic phosphine-containing ligand MOF-based catalyst, a solvent and a reaction olefin to obtain a first mixture; The first mixture is heated and pressurized to react, and after the reaction is completed, the mixture is cooled to room temperature and the product is collected after the pressure is released.

10. Use of the cobalt-chromium bimetallic phosphine-containing ligand MOF-based catalyst in olefin hydroformylation to aldehyde according to claim 9, characterized in that: The dosage ratio of the cobalt-chromium bimetallic phosphine-containing ligand MOF-based catalyst, solvent and olefin is 50~100mg:5~15mL:5~15mmoL; the temperature and pressure increase specifically introduces synthesis gas to increase the pressure to 4~6MPa, and the temperature is increased to 80~100°C. The synthesis gas is a mixture of H2 and CO, and the volume ratio of H2 and CO is 1:1~1:3.

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