A method for preparing amide compounds by heterogeneous catalysis of olefins and amines

Abstract

The present invention belongs to the field of multiphase catalytic reaction processes, and particularly relates to a method for preparing amide compounds by using a solid multiphase catalyst to catalyze olefins and amines. It is characterized in that the method uses a solid multiphase catalyst, which is composed of a metal component and an organic ligand polymer. Among them, the metal component is one or more of metals Co, Fe, Ru, Ir, Rh, Pd, Ni, Mo or Cu, and the organic ligand polymer is a polymer with a large specific surface area and a hierarchical pore structure generated by solvothermal copolymerization of a vinyl-functionalized phosphine ligand monomer and a vinyl-containing acidic organic monomer. In the presence of the solid multiphase catalyst, olefins and amines are used to carry out the reaction of synthesizing amide compounds in a reactor.

Description

Technical Field

[0001] The present invention belongs to the field of multiphase catalytic reaction processes, and particularly relates to a method for using a solid multiphase catalyst in the reaction of olefins and amines to prepare amide compounds. Background Art

[0002] The reaction of preparing amide compounds by catalytically reacting amines, olefins and CO with a catalyst is called hydroaminocarbonylation. One of the reaction products, propionamide, is commonly used in the fields of organic synthesis and pharmaceutical synthesis, such as the synthesis of medemycin. Isobutyramide is an important organic synthesis monomer and can be used as an intermediate for pharmaceuticals and organic pigments. Isobutyramide is also an important intermediate for the synthesis of the anti-AIDS drug ritonavir and an important intermediate for thioisobutyramide. 1-Hexanamide prepared by hydroaminocarbonylation of pentene and ammonia is also an important intermediate widely used in organic synthesis and the pharmaceutical industry. In addition, one of the main products of such reactions, N,N-dimethylpropionamide, as a non-protic solvent and chemical intermediate with low toxicity, high boiling point and high polarity, has a wide range of applications in the fields of synthetic materials, pharmaceuticals, pesticides, chemical fibers, petroleum processing and organic pigments. In short, the products of the hydroaminocarbonylation reaction of amines and olefins have very wide industrial and commercial uses.

[0003] In the past few decades, for the hydroaminocarbonylation reaction of carbon monoxide, amines and olefins, many researchers have developed many catalytic systems based on Co, Ni, Rh, Ru, or Pd. However, these traditional reaction technologies are generally limited to reaction systems with aromatic amines as substrates. Aliphatic amines inhibit the reaction due to their strong basicity. Nevertheless, in the traditional hydroaminocarbonylation reaction process with aromatic amines as reaction substrates, acidic additives such as p-toluenesulfonic acid still need to be added to promote the reaction. The latest research reports indicate that alkylamine hydrochloride can be used as the amine source for the hydroaminocarbonylation reaction. This method has high reaction yield and high regioselectivity. Alkylamine hydrochloride is an amine source without strong basicity and has the effective ability to form palladium hydride species to ensure that olefins can be adsorbed and dissociated in the reaction system. However, the catalytic system of this new reaction route is a homogeneous system, and it is very difficult to separate the catalyst from the reaction system. Moreover, alkylamine hydrochloride has certain corrosiveness. Therefore, such catalysts cannot solve the problems of Pd loss, recycling activity and acid corrosion.

[0004] It is not difficult to see that the existing hydroaminocarbonylation reaction systems are mostly homogeneous systems, and it is difficult to separate the catalyst from the reaction solution. For the above reasons, it is necessary to develop a new and efficient heterogeneous reaction method for the hydroaminocarbonylation reaction of olefins.

[0005] In summary, for the hydroaminocarbonylation reaction in practical industrial applications, developing highly efficient and recyclable catalysts and thus developing a highly efficient and stable reaction process suitable for large-scale production is the main research direction in this field. Summary of the Invention

[0006] Aiming at the deficiencies existing in the prior art, the purpose of the present invention is to provide a reaction process for preparing amide compounds from olefins and amines using a solid heterogeneous catalyst with excellent reaction activity and stability, which can be easily realized industrially.

[0007] To this end, the present invention provides a method for the reaction of olefins and amines to prepare amide compounds, which is characterized in that the method uses a solid heterogeneous catalyst composed of a metal component and an organic ligand polymer, wherein the metal component is one or more of metals Co, Fe, Ru, Ir, Rh, Pd, Ni, Mo or Cu, and the organic ligand polymer is a polymer with a large specific surface area and a hierarchical pore structure generated by solvothermal copolymerization of a vinyl-functionalized phosphine ligand monomer and a vinyl-containing acidic organic monomer. The metal component forms a coordination bond with the P atom in the organic ligand polymer backbone and exists highly dispersed and stably on the organic ligand polymer support. The method includes carrying out the reaction of synthesizing amide compounds between olefins and amines in a reactor in the presence of the solid heterogeneous catalyst.

[0008] In a preferred embodiment, the amines are selected from:

[0009] ammonia, methylamine, dimethylamine, ethylamine, diethylamine, ethylenediamine, n-propylamine, isopropylamine, propanediamine, n-butylamine, isobutylamine, 1,4-butanediamine, n-pentylamine, n-hexylamine, 1,6-hexanediamine, aniline, benzylamine, phenethylamine, 1-naphthylamine and 2-naphthylamine.

[0010] In a preferred embodiment, the molar ratio of the olefin raw material to the amine raw material is 1:1 - 1:100, and the molar ratio of the olefin raw material to the CO raw material is 1:1 - 1:50.

[0011] In a preferred embodiment, the amine raw material is pumped into the reaction system by a high-pressure pump, and the liquid hourly space velocity is 0.01 - 5 h -1 ; the olefin and CO raw materials are fed in gas form with a gas hourly space velocity of 500 - 20000 h -1 .

[0012] In a preferred embodiment, the reactor is a trickle bed or a stirred tank reactor.

[0013] In a preferred embodiment, the reaction of amines and olefins to prepare amide compounds is carried out in a continuous or batch manner.

[0014] In a preferred embodiment, the reaction temperature for the reaction of the amine and the olefin to form the amide compound is 30 - 300 °C, and the reaction pressure is 0.05 - 10 MPa.

[0015] In a preferred embodiment, the metal component accounts for 0.01 - 20.0% of the total weight of the solid heterogeneous catalyst.

[0016] In a preferred embodiment, the vinyl-functionalized phosphine ligand-containing is one or more selected from the following:

[0017]

[0018] In a preferred embodiment, the vinyl-containing acidic organic monomer is one or more selected from the following:

[0019]

[0020] In a preferred embodiment, the specific surface area of the organic ligand polymer is 100 - 3000 m 2 / g, the pore volume is 0.1 - 5.0 cm 3 / g, and the pore size distribution is in the range of 0.1 - 100.0 nm.

[0021] In a preferred embodiment, the inert gas atmosphere during the synthesis of the organic ligand polymer is one or more of argon, helium, and nitrogen.

[0022] In a preferred embodiment, when the reactor is a trickle bed, the reaction of the olefin and the amine to form the amide compound proceeds continuously on the solid heterogeneous catalyst, and the generated liquid product continuously flows out of the reactor and is collected at a temperature of -20 - 25 °C through a product collection tank; when the reactor is a batch reactor, the reaction of the amine and the olefin to form the amide compound proceeds intermittently, and the generated liquid product is obtained by separation from the solid heterogeneous catalyst through filtration, and the obtained liquid product is further processed by distillation or flash evaporation to obtain a high-purity amide product.

[0023] The beneficial effects of the present invention include but are not limited to the following aspects: Compared with the prior art, the reaction technology of the amine and the olefin to form the amide compound in the present invention uses a novel solid heterogeneous catalyst, the reaction process and device are simple, the catalyst has excellent reaction activity and stability, reduces the separation cost of the catalyst from the reactants and products, effectively improves the economic benefits of the reaction process of the amine and the olefin to form the amide compound, and has broad industrial application prospects. Description of the Drawings

[0024] Figure 1Schematic diagram of the reaction process flow for the continuous reaction of amines and olefins to form amide compounds.

[0025] Figure 2 Schematic diagram of the reaction process flow for the batch reaction of amines and olefins to form amide compounds. Detailed implementation mode

[0026] In order to better illustrate the preparation method of the catalyst and its application in the reaction of amines and olefins to form amide compounds, the following are some examples of the preparation of catalyst samples and their application in the reaction process. However, the present invention is not limited to the listed examples. Unless otherwise specifically stated, the contents and percentages in this application are calculated by "mass".

[0027] Example 1

[0028] Under the atmosphere of 298K and argon protection, 8.0 g of tris(4-vinylphenyl)phosphine was dissolved in 100 ml of tetrahydrofuran solvent. 0.25 g of the free radical initiator azobisisobutyronitrile was added to the above solution, and then 2.0 g of 3-fluoro-4-vinyl-benzenesulfonic acid was added, and the mixture was stirred for 0.5 hour. The stirred solution was transferred to a hydrothermal autoclave and polymerized by solvothermal method for 24 h under the atmosphere of 373K and inert gas argon protection. After the above polymerization, the solvent was removed by vacuum pumping at a temperature of 333K, and a porous organic polymer containing triphenylphosphine and sulfonic acid groups was obtained. The specific surface area of this polymer was 736 m 2 / g, the pore volume was 2.38 cm 3 / g, and the pore size distribution was in the range of 7.6 - 64.3 nm. Under the atmosphere of 298K and inert gas argon protection, 0.0146 g of palladium(II) acetate was dissolved in 50 ml of tetrahydrofuran solvent, and 1.0 g of the above-prepared porous organic polymer was added, and the mixture was stirred for 24 hours. Subsequently, the solvent was removed by vacuum pumping at a temperature of 333K, and a solid heterogeneous catalyst with 0.7 wt% of metal component supported by the organic ligand polymer was obtained.

[0029] The above-prepared solid heterogeneous catalyst was added to a trickle-bed reactor, and a mixed gas of ethylene and CO (ethylene:CO = 1:2, molar ratio) was introduced. The liquid ammonia raw material solution was pumped into the reactor by a high-pressure metering pump to start the reaction. The reaction temperature for the production of propionamide from ethylene and ammonia was 90 °C, the reaction pressure was 3 MPa, the liquid hourly space velocity of liquid ammonia was 0.1 h -1 , and the CO / liquid ammonia molar ratio was 50. The liquid product propionamide was collected in a cold trap collection tank. The liquid product was analyzed by HP-7890N gas chromatography equipped with an HP-5 capillary column and an FID detector, and toluene was used as the internal standard. The reaction tail gas was analyzed online by HP-7890N gas chromatography equipped with a Porapak-QS column and a TCD detector. The reaction process flow of a continuous reaction of amines and olefins to form amide compounds of the present invention is shown inFigure 1 。The specific reaction results are shown in Table 1.

[0030] Example 2

[0031] The preparation process of the catalyst is the same as that in Example 1, except that 0.21 g of ruthenium chloride is used instead of 0.0146 g of palladium(II) acetate in the catalyst preparation. The other processes of catalyst preparation are the same as those in Example 1.

[0032] The reaction process for catalyst evaluation is the same as that in Example 1. The specific reaction results are shown in Table 1.

[0033] Example 3

[0034] The preparation process of the catalyst is the same as that in Example 1.

[0035] The prepared solid heterogeneous catalyst is added to a trickle-bed reactor, and a mixed gas of ethylene and CO (ethylene:CO = 1:2) is introduced. The liquid ammonia solution raw material is pumped into the reactor by a high-pressure metering pump to start the reaction. The reaction temperature for the synthesis of propionamide from ethylene and liquid ammonia is 100 °C, the reaction pressure is 3 MPa, and the liquid hourly space velocity of liquid ammonia is 0.15 h -1 −1, and the CO / ammonia molar ratio is 75. The liquid product, propionamide, is collected in a cold trap collection tank. The liquid product is analyzed by HP-7890N gas chromatography equipped with an HP-5 capillary column and an FID detector, using toluene as the internal standard. The reaction tail gas is analyzed online by HP-7890N gas chromatography equipped with a Porapak-QS column and a TCD detector. The specific reaction results are shown in Table 1.

[0036] Example 4

[0037] The preparation process of the catalyst is the same as that in Example 1.

[0038] The prepared solid heterogeneous catalyst is added to a trickle-bed reactor, and a mixed gas of ethylene and CO (ethylene:CO = 1:2) is introduced. The liquid ammonia raw material is pumped into the reactor by a high-pressure metering pump to start the reaction. The reaction temperature for the synthesis of propionamide from ethylene and liquid ammonia is 110 °C, the reaction pressure is 3 MPa, and the liquid hourly space velocity of liquid ammonia is 0.2 h -1 −1, and the CO / liquid ammonia molar ratio is 75. The liquid product, propionamide, is collected in a cold trap collection tank. The liquid product is analyzed by HP-7890N gas chromatography equipped with an HP-5 capillary column and an FID detector, using toluene as the internal standard. The reaction tail gas is analyzed online by HP-7890N gas chromatography equipped with a Porapak-QS column and a TCD detector. The specific reaction results are shown in Table 1.

[0039] Example 5

[0040] The preparation process of the catalyst is the same as that in Example 1.

[0041] The solid heterogeneous catalyst prepared above was added to a kettle reactor, and the liquid ammonia (5g) raw material was added to the reactor at one time, ethylene 0.46MPa (ethylene 6mmol) was introduced, and then CO gas 1.54MPa was introduced to start the reaction. The reaction temperature of ethylene and ammonia to propionamide was 100°C and the reaction pressure was 2MPa. After the reaction was completed, ethanol was charged at room temperature to collect the product propionamide. The liquid product was analyzed using an HP-7890N gas chromatograph equipped with an HP-5 capillary column and an FID detector, using toluene as an internal standard. The reaction tail gas was analyzed online using an HP-7890N gas chromatograph equipped with a Porapak-QS column and a TCD detector. For specific reaction results, refer to Table 1.

[0042] Example 6

[0043] The preparation process of the catalyst is the same as that of Example 1.

[0044] The solid heterogeneous catalyst prepared above was added to a trickle bed reactor, and a mixture of propylene and CO (propylene:CO=1:2) was introduced. The raw liquid ammonia was pumped into the reactor through a high-pressure metering pump to start the reaction. The reaction temperature for preparing butyramide from propylene and liquid ammonia was 90°C, the reaction pressure was 3 MPa, and the liquid ammonia hourly space velocity was 0.1 h -1 , CO / liquid ammonia molar ratio 50. The liquid product was collected in a cold trap collection tank. The liquid product was analyzed using a HP-7890N gas chromatograph equipped with an HP-5 capillary column and an FID detector, using toluene as an internal standard. The reaction tail gas was analyzed online using a HP-7890N gas chromatograph equipped with a Porapak-QS column and a TCD detector. For specific reaction results, refer to Table 1.

[0045] Example 7

[0046] The preparation process of the catalyst is the same as that of Example 1.

[0047] The solid heterogeneous catalyst prepared above was added to a kettle reactor, and the liquid ammonia (5g) raw material was added to the reactor at one time, propylene 0.43MPa (propylene 6mmol) was introduced, and then CO gas 1.57MPa was introduced to start the reaction. The reaction temperature of propylene and ammonia to butanamide was 100°C and the reaction pressure was 2MPa. After the reaction was completed, ethanol was added at room temperature to collect the product butanamide. The liquid product was analyzed by HP-7890N gas chromatography equipped with HP-5 capillary column and FID detector, and toluene was used as internal standard. The reaction tail gas was analyzed online using HP-7890N gas chromatograph equipped with Porapak-QS column and TCD detector. For specific reaction results, refer to Table 1.

[0048] Example 8

[0049] The preparation process of the catalyst is the same as that of Example 1.

[0050] The solid heterogeneous catalyst prepared above was added to a trickle-bed reactor, and a mixed gas of 1-butene and CO (1-butene:CO = 1:5) was introduced. The liquid ammonia raw material was pumped into the reactor by a high-pressure metering pump to start the reaction. The reaction temperature for the production of pentanamide from 1-butene and liquid ammonia was 90 °C, the reaction pressure was 3 MPa, and the liquid hourly space velocity of liquid ammonia was 0.1 h -1

[0050]

[0051] Example 9

[0052] The preparation process of the catalyst was the same as that of Example 1.

[0053] The solid heterogeneous catalyst prepared above was added to a trickle-bed reactor, and pure CO gas was introduced. The raw materials of ethylene and dimethylamine solution were respectively pumped into the reactor by a high-pressure metering pump to start the reaction. The reaction temperature for the production of N,N-dimethylpropanamide from ethylene and dimethylamine was 90 °C, the reaction pressure was 3 MPa, and the liquid hourly space velocities of ethylene and dimethylamine were both 0.1 h -1

[0050]

[0054] Example 10

[0055] The preparation process of the catalyst was the same as that of Example 1.

[0056] The solid heterogeneous catalyst prepared above was added to a trickle-bed reactor, and pure CO gas was introduced. The raw materials of propylene and dimethylamine solution were respectively pumped into the reactor by a high-pressure metering pump to start the reaction. The reaction temperature for the production of N,N-dimethylbutyramide from propylene and dimethylamine was 100 °C, the reaction pressure was 3 MPa, and the liquid hourly space velocities of propylene and dimethylamine were both 0.1 h -1

[0050]

[0057] Example 11

[0058] The preparation process of the catalyst is the same as that of Example 1.

[0059] The above-prepared solid heterogeneous catalyst was added to a trickle-bed reactor, and a mixed gas of ethylene and CO (ethylene:CO = 1:2) was introduced. The ethanol raw material solution was pumped into the reactor by a high-pressure metering pump to start the reaction. The reaction temperature for the production of phenylpropanamide from ethylene and aniline was 90 °C, the reaction pressure was 3 MPa, the liquid hourly space velocity of aniline was 0.1 h -1 , and the CO / aniline molar ratio was 50. The liquid product, phenylpropanamide, was collected in a cold trap collection tank. The liquid product was analyzed by HP-7890N gas chromatography equipped with an HP-5 capillary column and an FID detector, using toluene as the internal standard. The reaction tail gas was analyzed online by HP-7890N gas chromatography equipped with a Porapak-QS column and a TCD detector. The specific reaction results are shown in Table 1.

[0060] Example 12

[0061] The preparation process of the catalyst is the same as that of Example 1.

[0062] The above-prepared solid heterogeneous catalyst was added to a trickle-bed reactor, and a mixed gas of propylene and CO (propylene:CO = 1:2) was introduced. The aniline raw material solution was pumped into the reactor by a high-pressure metering pump to start the reaction. The reaction temperature for the production of phenylbutyramide from propylene and aniline was 100 °C, the reaction pressure was 3 MPa, the liquid hourly space velocity of aniline was 0.1 h -1 , and the CO / aniline molar ratio was 50. The liquid product was collected in a cold trap collection tank. The liquid product was analyzed by HP-7890N gas chromatography equipped with an HP-5 capillary column and an FID detector, using toluene as the internal standard. The reaction tail gas was analyzed online by HP-7890N gas chromatography equipped with a Porapak-QS column and a TCD detector. The specific reaction results are shown in Table 1.

[0063] Comparative Example 1

[0064] Under the atmosphere of 298 K and argon protection, 8.0 g of tris(4-vinylphenyl)phosphine was dissolved in 100 ml of tetrahydrofuran solvent. 0.25 g of the radical initiator azobisisobutyronitrile was added to the above solution and stirred for 0.5 h. The stirred solution was transferred to a hydrothermal autoclave and polymerized by solvothermal method for 24 h under the atmosphere of 373 K and inert gas argon protection. After the above polymerization, the solvent was removed by vacuum pumping at a temperature of 333 K, and a porous organic polymer of self-polymerized triphenylphosphine was obtained. The specific surface area of this polymer was 1196 m 2 / g, and the pore volume was 2.98 cm 3 / g, with a pore size distribution in the range of 7.8 - 69.3 nm. Under the protection of inert gas argon at 298 K, 0.0146 g of palladium (II) acetate was dissolved in 50 ml of tetrahydrofuran solvent, and 1.0 g of the above-prepared porous organic polymer was added and stirred for 24 hours. Subsequently, the solvent was removed by vacuum pumping at 333 K, and a solid heterogeneous catalyst with 0.7 wt% of metal component supported by the organic ligand polymer was obtained.

[0065] The evaluation reaction process of this catalyst is the same as that in Example 1. The specific reaction results are shown in Table 1 for reference.

[0066] The present invention has been described in detail above, but the present invention is not limited to the specific embodiments described herein. Those skilled in the art understand that other changes and modifications can be made without departing from the scope of the present invention. The scope of the present invention is defined by the appended claims.

[0067] Table 1. Reaction results of preparing amide compounds from amines and olefins

[0068]

[0069]

[0070] Note: There is no isomeric amide product in the hydroaminocarbonylation reaction of ethylene.

[0071] It can be seen from the results of the examples and comparative examples that olefins with lower carbon numbers have higher reaction activities; the catalyst with active metal Pd supported by the same acid-containing copolymer has higher activity than the catalyst with active metal Ru supported in the hydroaminocarbonylation reaction; compared with the trickle-bed reaction process, the olefin conversion rate is higher in the batch reaction process, which is directly related to the residence time of olefins in the reaction device; by comparing with the self-polymer supported transition metal catalyst without adding acidic monomers, it can be seen that the self-polymer catalyst without acidic groups has no reaction effect, which is in line with the mechanism of the hydroaminocarbonylation reaction of olefins, that is, the reaction needs to be carried out in an environment with external protons.

Claims

1. A method for preparing amide compounds by heterogeneous catalysis of olefins and amines, characterized in that, A solid heterogeneous catalyst is used, which is a supported catalyst composed of a metal component supported on an organic ligand polymer. The metal component is one or more of metals Co, Fe, Ru, Ir, Rh, Pd, Ni, Mo, or Cu, and the organic ligand polymer is a polymer generated by solvothermal copolymerization of a vinyl-functionalized phosphine ligand monomer and a vinyl-containing acidic organic monomer; The vinyl-functionalized phosphine ligand monomer is one or several selected from the following: ； The vinyl-containing acidic organic monomer is one or several selected from the following: 。 2. The method according to claim 1, wherein The molar ratio of the monodentate organic phosphine ligand to the vinyl-containing acidic organic monomer is 0.01:1 to 20:

1.

3. The method according to claim 2, wherein The molar ratio of the monodentate organic phosphine ligand to the vinyl-containing acidic organic monomer is 0.5:1 to 10:

1.

4. The method according to claim 3, wherein The molar ratio of the monodentate organic phosphine ligand to the vinyl-containing acidic organic monomer is 1:1 to 5:

1.

5. The method according to claim 1, wherein The amines are selected from one or more of the following: ammonia, methylamine, dimethylamine, ethylamine, diethylamine, ethylenediamine, n-propylamine, isopropylamine, propylenediamine, n-butylamine, isobutylamine, 1,4-butanediamine, n-pentylamine, n-hexylamine, 1,6-hexanediamine, aniline, benzylamine, phenethylamine, 1-naphthylamine, and 2-naphthylamine; the olefins are selected from one or more of the following: ethylene, propylene, isobutene, n-butene, isopentene, n-pentene, isohexene, n-hexene, isoheptene, n-heptene, isooctene, n-octene, isononene, n-nonene,isodecene, n-decene, isoundecene, n-undecene, isododecene, n-dodecene.

6. The method according to claim 1, wherein The reaction is carried out in the presence of CO. The molar ratio of the olefin to the amines is 1:1 to 1:100, and the molar ratio of the olefin to CO is 1:1 to 1:

50.

7. The method according to claim 6, wherein The molar ratio of the olefin to the amines is 1:1 to 1:10, and the molar ratio of the olefin to CO is 1:1 to 1:

20.

8. The method according to claim 1, characterized in that, The reaction temperature for the reaction of amines and olefins to prepare amide compounds is 30 - 300 °C, and the total pressure of olefins, amines, and CO during the reaction process is 0.05 - 20 MPa.

9. The method according to claim 8, characterized in that, The reaction temperature for the reaction of amines and olefins to prepare amide compounds is 70 - 180 °C, and the total pressure of olefins, amines, and CO during the reaction process is 1 - 10 MPa.

10. The method according to claim 6 or 8, characterized in that The reaction is carried out continuously in a trickle bed or intermittently in a batch reactor; When the reactor is a trickle bed, the reaction of amines and olefins to form amide compounds proceeds continuously on the solid heterogeneous catalyst, and the resulting liquid product continuously flows out of the reactor and is collected in a product collection tank at a temperature of -20 - 25°C; the space velocity of gaseous olefins is 500 - 20000 h -1 , and the space velocity of liquid olefins is 0.01 - 10 h -1 ; When the reactor is a batch reactor, the reaction of amines and olefins to prepare amide compounds is carried out intermittently. The generated liquid product is separated from the solid heterogeneous catalyst by filtration, and the obtained liquid product is further processed by distillation or flash evaporation to obtain a high-purity amide compound product.

11. The method according to claim 1 or 2 or 3 or 4, characterized in that, The metal component accounts for 0.01 - 30.0% of the total weight of the solid heterogeneous catalyst.

12. The method according to claim 11, wherein The metal component accounts for 0.05 - 10.0% of the total weight of the solid heterogeneous catalyst.

13. The method according to claim 12, characterized in that, The metal component accounts for 0.1 - 2.0% of the total weight of the solid heterogeneous catalyst.

14. The method according to claim 1, characterized in that, The process of ligand solvothermal polymerization: a) In an inert gas atmosphere at 333 - 473 K, in an organic solvent, a monodentate organic phosphine ligand is added, an acidic organic monomer containing vinyl is added, a crosslinking agent is added or not added, and then a radical initiator is added. After mixing, the mixture is stirred for 0.1 - 100 hours; b) The mixed solution obtained in step a) is transferred to a synthesis autoclave. Under an inert gas atmosphere at 273K - 473K, a solvothermal polymerization method is used, and it is left standing for 1 - 80 hours for a polymerization reaction to obtain a phosphine-containing porous organic polymer; c) The polymer obtained in step b) is subjected to vacuum solvent extraction to obtain an organic polymer containing exposed P with a hierarchical pore structure, which is the carrier of the heterogeneous catalyst; Among them, the organic solvent described in step a) is one or more of benzene, toluene, tetrahydrofuran, dichloromethane, or chloroform; the crosslinking agent is one or more of styrene, ethylene, propylene, divinylbenzene, dimethoxymethane, diiodomethane, paraformaldehyde, or 1,3,5 - triethynylbenzene; the radical initiator is one or more of cyclohexanone peroxide, benzoyl peroxide, tert - butyl hydroperoxide, azobisisobutyronitrile, or azodiisooctanenitrile; In step a), when a crosslinking agent is added, the molar ratio of the monodentate organic phosphine ligand to the acidic organic monomer containing vinyl is 0.01:1 - 20:1, the molar ratio of the monodentate organic phosphine ligand to the crosslinking agent is 0.01:1 - 20:1, and the molar ratio of the monodentate organic phosphine ligand to the radical initiator is 300:1 - 5:1; before polymerizing into an organic polymer, the concentration range of the monodentate organic phosphine ligand in the organic solvent is 0.01 - 1000 g / L.

15. The method according to claim 14, wherein Ligand solvothermal polymerization process: In step a), the stirring time of the mixture is 0.1 - 2 hours.

16. The method according to claim 14, wherein: The specific surface area of the organic ligand polymer is 100 - 3000 m 2 / g, the pore volume is 0.1 - 5.0 cm 3 / g, and the pore size distribution is in the range of 0.1 - 100.0 nm.

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