Method for hydroformylation of 2, 5-dihydrofuran

Abstract

The invention discloses a method for efficiently preparing 3-furaldehyde from a substrate 2, 5-dihydrofuran (2, 5-DHF) which is difficult to react through hydroformylation reaction, a catalyst takes one, two or more than two of metals Rh, Co, Ir, Ru, Pt, Pd and Fe as active components, and a carrier is formed by introducing a substance containing S and / or N atoms into a phosphine-containing polymer skeleton. The heteroatom-containing heterogeneous catalyst provided by the invention has good performance in a hydroformylation process of 2, 5-dihydrofuran, an active central component is coordinated with P in a carrier framework and is also coordinated with a heteroatom (S and / or N atoms), and compared with a single-coordination (only coordinated with P) mode, the specific active central component of the catalyst is increased, so that the specific active central component of the catalyst is increased, and the yield of the catalyst is increased. Therefore, the conversion rate and selectivity of the reaction are increased, the final effect is that the conversion rate is increased by 10-100%, and the selectivity of the 3-furaldehyde is increased by 10-100%.

Description

Technical Field

[0001] The invention belongs to the field of heterogeneous catalysis and fine chemical industry, and specifically relates to a method for carrying out 2,5-dihydrofuran hydroformylation reaction using a phosphine ligand polymer-supported catalyst containing heteroatoms. Background Art

[0002] The reaction of furan compounds has high application value in industry and is widely used in the fields of medicine, coatings, pesticides, fragrances, etc. Among them, the preparation of dinotefuran from 3-furancarboxaldehyde is an extremely important process in pesticide production and is widely used. However, in this reaction, the preparation of the raw material 3-furancarboxaldehyde is relatively difficult, and it is mainly prepared by hydroformylation of 2,5-dihydrofuran. Although the hydroformylation reaction is an important way to produce aldehyde and alcohol products with high added value, it is a green and economical reaction, a typical example of homogeneous catalytic industrialization, and the industrial technology is relatively mature. However, in the process of 2,5-dihydrofuran hydroformylation, the low activity of the reaction raw materials, low selectivity, and difficult substrate conversion all limit its production and application.

[0003] In the early research on 2,5-dihydrofuran, Rh-loaded homogeneous catalysts were often used, which consumed a large amount of precious metals and had high production costs. With the research on heterogeneous catalysts, the consumption of precious metal Rh has been reduced to a certain extent, but due to its difficult reaction, a large amount of heterogeneous Rh-based catalysts are still required, which greatly limits the efficiency optimization of the factory. At the same time, people considered replacing Rh metal with Co metal. Although it can reduce production costs, the Co-P coordination is weak, the product is easy to lose, and the activity is somewhat lower than that of Rh-based catalysts. Summary of the invention

[0004] In order to solve the above problems, the purpose of the present invention is to provide a heteroatom-containing phosphine ligand polymer-supported catalyst for use in the hydroformylation reaction of 2,5-dihydrofuran to generate 3-furancarboxaldehyde.

[0005] The technical solution of the present invention is:

[0006] A method for hydroformylation of 2,5-dihydrofuran using a heteroatom-containing phosphine ligand supported catalyst, characterized in that:

[0007] In the presence of a phosphine ligand-supported catalyst containing a heteroatom, a reaction solution containing 2,5-dihydrofuran is added, and synthesis gas is introduced to carry out a hydroformylation reaction;

[0008] The catalyst uses one, two or more of the metals Rh, Co, Ir, Ru, Pt, Cu, Pd and Fe as active components, and the carrier is formed by introducing a substance containing S and / or N into a phosphine-containing polymer skeleton;

[0009] The catalyst carrier is prepared by copolymerization of a phosphine ligand and a second component containing S and / or N, wherein both components contain olefin groups; the phosphine ligand used in the polymerization comprises one or more of all phosphine ligands having olefin groups, and the olefin groups are preferably vinyl groups; including but not limited to one or more of the following structures:

[0010]

[0011]

[0012]

[0013]

[0014] Wherein L1-L18 are secondary phosphine oxide ligands, B1-B15 are multidentate phosphine ligands, and P1-P17 are monophosphine ligands;

[0015] The olefinic group in the second component containing S and / or N containing an olefinic group is preferably a vinyl group, including but not limited to one or more of the following structures:

[0016]

[0017]

[0018] The ligands used in the polymerization and the substances containing heteroatoms (S and / or N atoms) all contain olefin groups, wherein the olefin groups are preferably vinyl functional groups.

[0019] The reaction process is as follows: the prepared catalyst is loaded into a reactor, and a raw material mixed gas is introduced, wherein the main components of the mixed gas are H2 and CO, the volume content of H2+CO is 30-100% (preferably 50-100%), the volume ratio of H2 / CO is 0.5-5.0 (preferably 0.5-2.0), and the remaining gas components are one or more of CO2, N2, He, and Ar gas; the purity of the raw material 2,5-dihydrofuran is 20-100% (preferably 40-100%), and the remaining liquid components are one or more of toluene, tetrahydrofuran, dioxane, and cyclohexane; the reaction temperature is 330-460K (preferably 350-430K), the reaction pressure is 0.1-8MPa (preferably 2-6MPa), and the synthesis gas space velocity is 100-10000h -1 (Preferably 500 to 5000 hours -1 ), the hydroformylation reaction is carried out under the above conditions, and the reactor is a fixed bed, slurry bed, trickle bed or kettle reactor.

[0020] The loading amount of the metal active component in the catalyst is in the range of 0.01-20wt%, preferably 0.5-10wt%.

[0021] The heteroatom-containing phosphine ligand has a multi-level pore structure with a specific surface area of ​​10-3000m 2 / g, preferably in the range of 200-1000m 2 / g, pore volume is 0.1-8cm 3 / g, preferably 0.5-3cm 3 / g, pore size distribution is 0.01-100.0nm, preferably 0.5-20nm;

[0022] The active component metal loading in the catalyst ranges from 0.01 to 20 wt%, preferably from 0.5 to 5 wt%. The preparation process of the heteroatom-containing phosphine ligand is as follows:

[0023] After dissolving one or more phosphine ligands containing olefin groups and one or more second components containing heteroatoms, a polymerization reaction is initiated by a free radical initiator to generate a heteroatom-containing phosphine ligand having a multi-level pore structure;

[0024] The preparation process of the heteroatom-containing phosphine ligand supported catalyst is as follows: the precursor of the active metal component and the heteroatom-containing phosphine ligand are fully stirred and coordinated in a solvent, the active metal component forms a strong chemical bond with the exposed P, N, and S in the heteroatom-containing phosphine ligand, and after evaporating the solvent, the heteroatom-containing phosphine ligand supported catalyst is obtained.

[0025] The specific preparation steps of the heteroatom-containing phosphine ligand supported catalyst are:

[0026] a) adding a phosphine ligand containing an olefin group and a second component containing S and / or N of an olefin group to a solvent under an inert gas atmosphere at 273-473K (preferably 303-433K) to dissolve the phosphine ligand containing an olefin group and / or a second component containing S and / or N of an olefin group, and then adding a free radical initiator, and stirring the mixture for 0.1-100 hours to obtain a prepolymer solution, preferably in the range of 0.5-24 hours;

[0027] b) transferring the prepolymer mixed solution obtained in step a) to a polymerization reactor, and performing polymerization reaction by one or more of bulk polymerization, solution polymerization, suspension polymerization and emulsion polymerization for a polymerization time of 1-100 hours to obtain a polymer containing heteroatom phosphine ligands;

[0028] c) removing the solvent from the heteroatom phosphine ligand polymer obtained in step b) at 273-430K to obtain a heteroatom phosphine ligand polymer having a multi-level pore structure, i.e., a carrier of a heteroatom phosphine ligand polymer-supported catalyst;

[0029] d) adding the heteroatom phosphine ligand polymer carrier obtained in step c) to a solvent containing an active metal component precursor under an inert gas atmosphere of 273-473K (preferably 298-403K), stirring for 0.1-100 hours, preferably 0.5-24 hours, and after stirring, removing the solvent at 273-473K (preferably 303-433K) to obtain a heteroatom phosphine ligand polymer supported catalyst; the concentration of the active metal in the precursor solution is in the range of 0.001-3 mol / L (preferably 0.01-3 mol / L). The solvents described in steps a) and d) are one or more of methanol, ethanol, dichloromethane, chloroform, benzene, toluene, xylene, water or tetrahydrofuran;

[0030] The free radical initiator described in step a) is one or more of tert-butyl hydroperoxide, azobisisobutyronitrile, azobisisoheptanenitrile, cyclohexanone peroxide or dibenzoyl peroxide.

[0031] In step a), the molar ratio of the phosphine ligand containing an olefin group to the S and / or N second component containing an olefin group is 0.01:1-100:1, preferably 1:1-20:1, and the molar ratio of the phosphine ligand containing an olefin group to the free radical initiator is 500:1-10:1, preferably 100:1-10:1. Before polymerizing into an organic polymer, the concentration of the phosphine ligand containing an olefin group in the solvent ranges from 0.01-1000 g / L, preferably 0.2-20 g / L; the inert gas in steps a), b) and d) is selected from one or more of Ar, He, N2 and CO2.

[0032] The active component is one or more of Rh, Co, Ir, Ru, Pt, Pd or Fe, wherein the precursor of Rh is one or more of RhH(CO)(PPh3)3, Rh(CO)2(acac), RhCl3, and Rh(CH3COO)2; the precursor of Co is one or more of Co(CH3COO)2, Co(CO)2(acac), Co(acac)2, and CoCl2; the precursor of Ir is one or more of Ir(CO)3(acac), Ir(CH3COO)3, Ir(acac)3, and IrCl4; the precursor of Ru is dichloro(cyclooctyl-1,5-diene)ruthenium(II), RuCl3, Ru(acac)3, triruthenium dodecacarbonyl,

[0033] [RuAr2(benzene)]2, [RuAr2(p-cymene)]2,[RuAr2(mesitylene)]2,

[0034] [(π-ally)Ru(cod)]2, [(π-ally)Ru(nbd)]2; the precursor of Pt is one or more of Pt(acac)2, PtCl4, PtCl2(NH3)2; the precursor of Pd is one or more of Pd(CH3COO)2, Pd(acac)2, PdCl2, Pd(PPh3)4, PdCl2(CH3CN)2; the precursor of Fe is one or more of Fe(acac)3, FeCl3, FeCl2, FeS, ferrocene, nonacarbonyl iron, and the metal loading in the catalyst is 0.01-20wt%, preferably 0.5-10wt%.

[0035] The inventive principle of the present invention:

[0036] The present invention creatively introduces heteroatom S and / or N into the phosphine ligand polymer skeleton, utilizes the olefin group on the monomer molecule to carry out polymerization, and prepares a polymer carrier with developed pores. The P, N or S in the carrier can form a high-performance catalyst suitable for the hydroformylation reaction of 2,5-dihydrofuran after coordination with the metal. Thanks to the unique electronic effect and stereo effect in the heteroatom-containing phosphine ligand, the phosphine ligand is cross-linked with the heteroatom-containing ligand, and cheap metals such as Co and Fe are loaded, and the catalyst performs well in the hydroformylation reaction of 2,5-dihydrofuran. The selectivity of 3-furan carboxaldehyde can reach 95%. When noble metals such as Rh, Ir, Ru, Pt, and Pd are loaded, the TOF value in 2,5-dihydrofuran can reach 80h. -1 , the selectivity of 3-furan carboxaldehyde is up to 100%. The ratio of product aldehydes is flexible and adjustable, and the active metal components can be dispersed in the heteroatom-containing phosphine skeleton in the form of single atoms or ions, which greatly improves the utilization rate of the metal. In the prepared catalyst, in addition to a high concentration of P, it also contains a certain concentration of S or N atoms, which changes the coordination environment of the loaded metal, thereby forming active centers such as metal-P, metal-S, and metal-N. The multiple coordination centers have stronger bonding ability, which improves the reaction activity, makes the active components more stable and not easy to lose, and are suitable for industrial applications.

[0037] The beneficial effects of the present invention are:

[0038] The multiphase catalyst provided by the present invention has a good performance in the hydroformylation reaction of 2,5-dihydrofuran. Compared with the non-precious metal Co, Fe and other cheap metals, the reaction activity is only 1%-10% different from the activity of the unregulated ligand loaded with precious metals when loaded, which greatly reduces the production cost. And the supported catalyst has good stability, and the separation of the catalyst from the reactants and products is simple and efficient. Such supported catalysts are suitable for fixed beds, slurry beds, kettle reactors and trickle beds. The method for hydroformylation of 2,5-dihydrofuran based on the heteroatom-containing phosphine ligand supported catalyst involved in this patent is green and environmentally friendly, with less pollutant emissions. At the same time, the catalyst and method provided by this patent can solve the problems of poor stability, selectivity, activity, and serious loss of metal components of difficult-to-react substrates in the multiphase process of hydroformylation. The cost of industrial production of 2,5-dihydrofuran hydroformylation is reduced, the catalyst has good stability, and the separation of reactants and products from the catalyst is simple and efficient, providing a new industrial technology for the production of 3-furancarboxaldehyde by 2,5-dihydrofuran hydroformylation.

[0039] The heterogeneous catalyst containing heteroatoms provided by the present invention has good performance in the hydroformylation process of 2,5-dihydrofuran. The active center component is not only coordinated with P in the carrier skeleton, but also coordinated with heteroatoms (S and / or N atoms). Compared with the single coordination (only coordinated with P) mode, the specific active center component of the catalyst is increased, thereby increasing the conversion rate and selectivity of the reaction, and the final effect is that the conversion rate is increased by 10%-100%, and the selectivity of 3-furan carboxaldehyde is increased by 10-100%. This type of supported catalyst is suitable for fixed bed, slurry bed, kettle reactor and trickle bed reactor. It is worth noting that when the modified heteroatom catalyst is loaded with one or two of the cheap metals such as non-precious metals Co, Fe, etc., the reaction activity is only 1%-20% different from the activity when triphenylphosphine is used as a ligand to load precious metals such as Rh. The non-precious metal has an activity comparable to that of the precious metal, which greatly reduces the cost of the catalyst, thereby reducing the production cost of 3-furan carboxaldehyde. The separation of the heteroatom-containing polymer-supported catalyst from reactants and products provided by this patent is simple and efficient. The catalyst is stable to air and moisture, and the operating conditions do not need to be too harsh, providing a new industrial technology for the hydroformylation of difficult-to-react substrates. The method for hydroformylation of 2,5-dihydrofuran based on the heteroatom-containing polymer-supported catalyst involved in this patent is green and environmentally friendly, with low pollutant emissions. The technical solution for producing 3-furan carboxaldehyde provided by this patent has significant cost advantages. DETAILED DESCRIPTION

[0040] The following embodiments are provided to better illustrate the present invention, but are not intended to limit the scope of the present invention.

[0041] Example 1

[0042] The preparation method of the heteroatom-containing phosphine ligand polymer carrier is as follows: 100 g of monomer P1 (synthesis process is described in reference) is reacted at 285 K under an inert gas N2 atmosphere.

[0043] Chem. Commun. 2014, 50, 11844-11847) and 40.0g of the second component A are dissolved in 700.0ml of tetrahydrofuran solvent, 2.0g of azobisisobutyronitrile as a free radical initiator is added to the above solution, and stirred for 2.0 hours to obtain a prepolymer. The prepolymer is transferred to an autoclave and polymerized by solvent thermal polymerization at 383K and inert gas N2 gas protection atmosphere for 24 hours. After the polymerization autoclave is cooled to room temperature, the solvent is vacuumed off at 333K to obtain an organic polymer containing heteroatom phosphine ligands, which can be used as a carrier for subsequent preparation of solid catalysts.

[0044] The preparation method of the self-supported catalyst containing heteroatom phosphine ligand is as follows: 0.25 g of acetylacetonato carbonyl rhodium is weighed and dissolved in 500.0 ml of tetrahydrofuran solvent, 10.0 g of the above-prepared phosphine-containing organic polymer is added, the mixture is stirred for 24 hours under an inert gas N2 protective atmosphere at 323 K, and the solvent is removed under vacuum at 373 K to obtain a catalyst, wherein the Rh metal mass loading of the catalyst is 1.0%, and the pore volume of the catalyst carrier is 2.03 cm 3 / g, pore size distribution 0.1-20nm, specific surface area 907m 2 / g.

[0045] Example 2

[0046] In Example 2, in the polymer support preparation step, except that 40.0 g of the second component D was weighed to replace 40.0 g of the second component A, the rest of the catalyst synthesis process and conditions were the same as in Example 1. The Rh metal loading of the obtained catalyst was 1.0%, and the pore volume of the catalyst support was 1.98 cm 3 / g, pore size distribution 0.1-20nm, specific surface area 873m 2 / g.

[0047] Example 3

[0048] In Example 3, in the polymer support preparation step, except that 40.0 g of the second component E was weighed to replace 40.0 g of the second component A, the rest of the catalyst synthesis process and conditions were the same as in Example 1. The Rh metal loading of the obtained catalyst was 1.0%, and the pore volume of the catalyst support was 2.14 cm 3 / g, pore size distribution 0.1-20nm, specific surface area 887m 2 / g.

[0049] Example 4

[0050] In Example 4, in the polymer support preparation step, except that 40.0 g of the second component G was weighed to replace 40.0 g of the second component A, the rest of the catalyst synthesis process and conditions were the same as in Example 1. The Rh metal loading of the obtained catalyst was 1.0%, and the pore volume of the catalyst support was 1.98 cm 3 / g, pore size distribution 0.1-20nm, specific surface area 873m 2 / g.

[0051] Example 5

[0052] In Example 5, in the polymer support preparation step, except that 40.0 g of the second component J was weighed to replace 40.0 g of the second component A, the rest of the catalyst synthesis process and conditions were the same as in Example 1. The Rh metal loading of the obtained catalyst was 1.0%, and the pore volume of the catalyst support was 2.05 cm 3 / g, pore size distribution 0.1-20nm, specific surface area 902m 2 / g.

[0053] Example 6

[0054] In Example 6, in the polymer support preparation step, except that 40.0 g of the second component L was weighed to replace 40.0 g of the second component A, the rest of the catalyst synthesis process and conditions were the same as in Example 1. The Rh metal loading of the obtained catalyst was 1.0%, and the pore volume of the catalyst support was 1.91 cm 3 / g, pore size distribution 0.1-20nm, specific surface area 888m 2 / g.

[0055] Example 7

[0056] In Example 7, in the polymer support preparation step, except that 20.0 g of the second component L and 20.0 g of N were weighed to replace 40.0 g of the second component A, the rest of the catalyst synthesis process and conditions were the same as in Example 1. The Rh metal loading of the obtained catalyst was 1.0%, and the pore volume of the catalyst support was 1.93 cm 3 / g, pore size distribution 0.1-20nm, specific surface area 886m 2 / g.

[0057] Example 8

[0058] In Example 8, except that the same number of moles of iridium acetylacetonate tricarbonyl was weighed to replace rhodium acetylacetonate carbonyl, the rest of the catalyst synthesis process and conditions were the same as in Example 1. The Ir metal loading of the obtained catalyst was 1.9%.

[0059] Example 9

[0060] In Example 9, except that the same number of moles of palladium dichloride was used to replace acetylacetonato carbonyl rhodium, the rest of the catalyst synthesis process and conditions were the same as in Example 1. The Pd metal loading of the obtained catalyst was 1.0%.

[0061] Example 10

[0062] In Example 10, except that 0.25 g of acetylacetonato carbonyl rhodium was replaced with 0.58 g of dicobalt octacarbonyl, the rest of the catalyst synthesis process and conditions were the same as in Example 1. The Co metal loading of the catalyst was 2.0%, and the pore volume of the catalyst carrier was 2.03 cm 3 / g, pore size distribution 0.1-20nm, specific surface area 907m 2 / g.

[0063] Embodiment 11

[0064] In Example 11, except for weighing the same mole of ferric chloride to replace dicobalt octacarbonyl, the rest of the catalyst synthesis process and conditions were the same as those in Example 10. The Fe metal loading of the obtained catalyst was 1.9%.

[0065] Example 12

[0066] In Example 12, except that 100.0 g of L7 was used instead of 100.0 g of P1 as the first component, the rest of the catalyst synthesis process and conditions were the same as those in Example 1. The Rh metal loading of the obtained catalyst was 1.0%, and the pore volume of the catalyst carrier was 2.010 cm 3 / g, pore size distribution 0.1-20nm, specific surface area 937m 2 / g.

[0067] Embodiment 13

[0068] In Example 13, except that 100.0 g of P9 was used instead of 100.0 g of P1 as the first component, the rest of the catalyst synthesis process and conditions were the same as those in Example 1. The Rh metal loading of the obtained catalyst was 1.0%, and the pore volume of the catalyst carrier was 1.830 cm 3 / g, pore size distribution 0.1-20nm, specific surface area 867m 2 / g.

[0069] Embodiment 14

[0070] In Example 14, except that 100.0 g of L1 was used instead of 100.0 g of P1, the rest of the catalyst synthesis process and conditions were the same as those in Example 1. The Rh metal loading of the obtained catalyst was 1.0%, and the pore volume of the catalyst carrier was 1.990 cm 3 / g, pore size distribution 0.1-20nm, specific surface area 931m 2 / g.

[0071] Embodiment 15

[0072] In Example 15, in the polymer support preparation step, except that 100.0 g of monomer B2 (synthesis process see patent ZL 201410805880.X) was weighed to replace 100.0 g of monomer P1, the rest of the catalyst synthesis process and conditions were the same as in Example 1. The Rh metal loading of the obtained catalyst was 1.0%, and the pore volume of the catalyst support was 1.86 cm 3 / g, pore size distribution 0.1-20nm, specific surface area 867m 2 / g.

[0073] Example 16

[0074] In Example 16, except that 100.0 g of B5 was used instead of 100.0 g of P1 as the first component, the rest of the catalyst synthesis process and conditions were the same as those in Example 1. The Rh metal loading of the obtained catalyst was 1.0%, and the pore volume of the catalyst carrier was 2.010 cm 3 / g, pore size distribution 0.1-20nm, specific surface area 937m 2 / g.

[0075] Embodiment 17

[0076] In Example 17, except that 100.0 g of B7 was used instead of 100.0 g of P1 as the first component, the rest of the catalyst synthesis process and conditions were the same as those in Example 1. The Rh metal loading of the obtained catalyst was 1.0%, and the pore volume of the catalyst carrier was 2.010 cm 3 / g, pore size distribution 0.1-20nm, specific surface area 937m 2 / g.

[0077] 1g of the catalyst prepared in Examples 1-9 and 11-17 was added to a 50ml reactor, and the substrate 2,5-dihydrofuran was added according to S / C=400. The reaction mixture (H2:CO=1:1, V / V) was introduced, and the hydroformylation reaction was carried out under the conditions of reaction temperature of 373K, pressure of 3.0MPa, and reaction time of 20h. In Examples 10 and 11, except for the reaction temperature of 400K, pressure of 6.0MPa, and reaction time of 30h, the other conditions were the same as the above conditions. After the reaction, an internal standard was added, and then centrifuged at 4000r / min to take the supernatant. The obtained supernatant solution was analyzed by HP-7890N liquid chromatography equipped with HP-5 capillary column and FID detector, and dioxane was used as internal standard. The reaction results are listed in Table 1.

[0078] Table 1. Catalysts for 2,5-dihydrofuran hydroformylation

[0079]

[0080] The metals used in Examples 8, 9, 10, and 11 are Ir, Pd, Co, and Fe, and the reaction effect is lower than that of Rh metal. As can be seen from the data in the table, when copolymerizing with the second component containing heteroatoms, when Rh is used as the active metal, the conversion rate of 2,5-dihydrofuran exceeds 90%, and the selectivity of the product 3-furancarboxaldehyde also exceeds 90%. Among them, the ligands used in Examples 15, 16, and 17 are bidentate phosphine ligands, and the ratio of 3-furancarboxaldehyde to 2-furancarboxaldehyde can reach more than 30, mainly because it has a strong steric hindrance effect.

[0081] Comparative Example 1

[0082] In Comparative Example 1, except that the second component A was not added, the rest of the catalyst synthesis process and conditions were the same as those in Example 1. The Rh metal loading was 1.0%, and the pore volume of the catalyst carrier was 1.925 cm 3 / g, pore size distribution 0.1-20nm, specific surface area 1027m 2 / g.

[0083] Comparative Example 2

[0084] In Comparative Example 2, in addition to using Except for replacing the second component A, the rest of the catalyst synthesis process and conditions were the same as those in Example 1. The Rh metal loading of the obtained catalyst was 1.0%, and the pore volume of the catalyst carrier was 1.520 cm 3 / g, pore size distribution 0.1-20nm, specific surface area 767m 2 / g.

[0085] Comparative Example 3

[0086] In Comparative Example 3, in addition to using Except for replacing the second component A, the rest of the catalyst synthesis process and conditions were the same as those in Example 1. The Rh metal loading of the obtained catalyst was 1.0%, and the pore volume of the catalyst carrier was 1.720 cm 3 / g, pore size distribution 0.1-20nm, specific surface area 869m 2 / g.

[0087] Comparative Example 4

[0088] In Comparative Example 4, in addition to using Except for replacing the second component A, the rest of the catalyst synthesis process and conditions were the same as those in Example 1. The Rh metal loading of the obtained catalyst was 1.0%, and the pore volume of the catalyst carrier was 1.920 cm 3 / g, pore size distribution 0.1-20nm, specific surface area 902m 2 / g.

[0089] Comparative Example 5

[0090] In Comparative Example 5, except that the second component A was not added, the rest of the catalyst synthesis process and conditions were the same as those of Example 10. The Co metal loading of the catalyst was 2.0%, and the pore volume of the catalyst carrier was 2.03 cm 3 / g, pore size distribution 0.1-20nm, specific surface area 907m 2 / g.

[0091] Comparative Example 6

[0092] In Comparative Example 6, in addition to using Except for replacing the second component A, the rest of the catalyst synthesis process and conditions were the same as those in Example 10. The Co metal loading of the catalyst was 2.0%, and the pore volume of the catalyst carrier was 1.53 cm 3 / g, pore size distribution 0.1-20nm, specific surface area 707m 2 / g.

[0093] Comparative Example 7

[0094] In Comparative Example 7, 1 g of the catalyst prepared in Comparative Examples 1-4 was added to a 50 ml reactor, and the substrate 2,5-dihydrofuran was added according to S / C=400. A reaction mixture (H2:CO=1:1, V / V) was introduced, and the hydroformylation reaction was carried out under the conditions of reaction temperature of 373K, pressure of 3.0 MPa, and reaction time of 20 h. For Comparative Examples 5 and 6, except for the reaction temperature of 400K, pressure of 6.0 MPa, and reaction time of 30 h, the other conditions were the same as the above conditions. After the reaction, an internal standard was added, and then centrifuged at 4000 r / min to take the supernatant. The obtained supernatant solution was analyzed by HP-7890N liquid chromatography equipped with an HP-5 capillary column and an FID detector, and dioxane was used as the internal standard.

[0095] The reaction results are listed in Table 1

[0096] Table 2. Catalysts for 2,5-dihydrofuran hydroformylation

[0097]

[0098] As can be seen in Table 2, by comparing Comparative Example 1 with Example 1, it can be seen that with the addition of heteroatoms containing olefins, the conversion rate of 2,5-dihydrofuran is increased by more than 20%. By comparing Comparative Example 1 with Example 10, it can be seen that when the cheap metal is coordinated with the ligand containing heteroatoms, the activity of the catalyst prepared by the coordination of the noble metal with no heteroatoms is only 10%-20%, which greatly improves the reaction activity. By comparing Comparative Examples 2-6 with Examples 1 / and Example 10, the promoting effect of heteroatoms on the reaction can be further reflected.

Claims

1. A method for the hydroformylation of 2,5-dihydrofuran, characterized in that: In the presence of a heteroatom polymer supported catalyst, a reaction solution containing 2,5-dihydrofuran is added, and synthesis gas is introduced to carry out a hydroformylation reaction; The catalyst uses one, two or more of metals Rh, Co, Ir, Ru, Pt, Cu, Pd and Fe as active components, and the carrier is a phosphine-containing polymer; The catalyst carrier containing phosphine polymer is prepared by copolymerizing a phosphine ligand containing olefin groups and a second component containing S and / or N with olefin groups.

2. The method according to claim 1, characterized in that: The ligands used in the polymerization and the substances containing heteroatoms (S and / or N atoms) all contain olefin groups, wherein the olefin groups are preferably vinyl functional groups; the phosphine ligands include all phosphine ligands containing olefin groups, and the second component includes all substances containing S and / or N with olefin groups; The phosphine ligands containing olefin groups used in the polymerization include, but are not limited to, one or more of the following structures: The olefinic group in the second component containing S and / or N containing an olefinic group is preferably a vinyl group, including but not limited to one or more of the following structures:

3. The method according to claim 1, wherein the reaction process is as follows: loading the catalyst into a reactor, adding a reaction solution, and introducing a raw mixed gas, wherein the main components of the mixed gas are H2 and CO, the volume content of H2 + CO is 30-100% (preferably 50-100%), the volume ratio of H2 to CO is 0.5-5.0 (preferably 0.5-2.0), and the remaining gas components are one or more of CO2, N2, He, and Ar gases; the mass concentration of the reaction solution raw material 2,5-dihydrofuran is 20-100% (preferably 40-100%), and the remaining liquid components are one or more of toluene, tetrahydrofuran, dioxane, and cyclohexane; the reaction temperature is 330-460K (preferably 350-430K), the reaction pressure is 0.1-8MPa (preferably 2-6MPa), and the synthesis gas space velocity is 100-10000h -1 (Preferably 500 to 5000 hours -1 ), the hydroformylation reaction is carried out under the above conditions, and the reactor is a fixed bed, slurry bed, trickle bed or kettle reactor.

4. The method according to claim 1, characterized in that: The loading amount of the metal active component in the catalyst is in the range of 0.01-20wt%, preferably 0.5-10wt%, more preferably 0.5-5wt%.

5. The method according to claim 1, characterized in that: The heteroatom-containing polymer carrier has a multi-level pore structure and a specific surface area of ​​10-3000m 2 / g, preferably in the range of 200-1000m 2 / g, pore volume is 0.1-8cm 3 / g, preferably 0.5-3cm 3 / g, and the pore size distribution is 0.01-100.0nm, preferably 0.5-20nm.

6. The method according to any one of claims 1 to 5, characterized in that: The preparation process of heteroatom-containing phosphine ligands is as follows: After dissolving one or more phosphine ligands containing olefin groups and one or more S and / or N substances in the second component containing olefin groups, a polymerization reaction is initiated by an initiator to generate a heteroatom-containing phosphine ligand having a multi-level pore structure; wherein the initiator is preferably a free radical initiator; The preparation process of the heteroatom-containing phosphine ligand supported catalyst is as follows: The precursor of the active metal component and the heteroatom-containing phosphine ligand polymer are fully stirred and coordinated in a solvent, and the active metal component forms a strong chemical bond with the exposed P, N, and S in the heteroatom-containing phosphine ligand. After evaporating the solvent, a heteroatom-containing phosphine ligand polymer-supported catalyst is obtained.

7. The method for hydroformylation of 2,5-dihydrofuran according to claim 1, characterized in that: The specific preparation steps of the heteroatom phosphine ligand-containing supported catalyst are as follows: a) adding a phosphine ligand containing an olefin group and a second component containing S and / or N of an olefin group to a solvent under an inert gas atmosphere at 273-473K (preferably 303-433K) to dissolve the phosphine ligand containing an olefin group and / or a second component containing S and / or N of an olefin group, and then adding a free radical initiator, and stirring the mixture for 0.1-100 hours to obtain a prepolymer solution, preferably in the range of 0.5-24 hours; b) transferring the prepolymer mixed solution obtained in step a) to a polymerization reactor, and performing polymerization reaction by one or more methods selected from bulk polymerization, solution polymerization, suspension polymerization and emulsion polymerization for a polymerization time of 1-100 hours to obtain a polymer containing heteroatom phosphine ligands; c) removing the solvent from the heteroatom phosphine ligand polymer obtained in step b) at 273-430K to obtain a heteroatom phosphine ligand having a multi-level pore structure, i.e., a carrier of a heteroatom phosphine ligand supported catalyst; d) adding the carrier obtained in step c) to a solvent containing an active metal component precursor under an inert gas atmosphere at 273-473K (preferably 298-403K), stirring for 0.1-100 hours, preferably 0.5-24 hours, and after stirring, removing the solvent at 273-473K (preferably 303-433K) to obtain a supported catalyst containing a heteroatom phosphine ligand; the concentration of the active metal in the precursor solution is in the range of 0.001-3 mol / L (preferably 0.01-3 mol / L).

8. The method according to claim 7, characterized in that: The solvent described in steps a) and d) is one or more of methanol, ethanol, dichloromethane, chloroform, benzene, toluene, xylene, water or tetrahydrofuran; The free radical initiator described in step a) is one or more of tert-butyl hydroperoxide, azobisisobutyronitrile, azobisisoheptanenitrile, cyclohexanone peroxide or dibenzoyl peroxide.

9. The method according to claim 7, characterized in that: In step a), the molar ratio of the phosphine ligand containing an olefin group to the second component of S and / or N containing an olefin group is 0.01:1-100:1, preferably 1:1-20:1, and the molar ratio of the phosphine ligand containing an olefin group to the free radical initiator is 500:1-10:1, preferably 100:1-10:

1. Before polymerizing into an organic polymer, the concentration of the phosphine ligand containing an olefin group in the solvent ranges from 0.01-1000 g / L, preferably 0.2-20 g / L; the inert gas in steps a), b) and d) is selected from one or more of Ar, He, N2 and CO2.

10. The method according to claim 7, characterized in that: The active component is one or more of Rh, Co, Ir, Ru, Pt, Pd or Fe, wherein the precursor of Rh is one or more of RhH(CO)(PPh3)3, Rh(CO)2(acac), RhCl3, and Rh(CH3COO)2; the precursor of Co is one or more of Co(CH3COO)2, Co(CO)2(acac), Co(acac)2, and CoCl2; the precursor of Ir is one or more of Ir(CO)3(acac), Ir(CH3COO)3, Ir(acac), and IrCl4; the precursor of Ru is dichloro(cyclooctyl-1,5-diene)ruthenium(II), RuCl3, Ru(acac), dodecachloro(II), and tetrachloro(III). Carbonyltriruthenium, [RuAr2(benzene)]2, [RuAr2(p-cymene)]2, [RuAr2(mesitylene)]2, [(π-ally)Ru(cod)]2, [(π-ally)Ru(nbd)]2; the precursor of Pt is one or more of Pt(acac)2, PtCl4, PtCl2(NH3)2; the precursor of Pd is one or more of Pd(CH3COO)2, Pd(acac)2, PdCl2, Pd(PPh3)4, PdCl2(CH3CN)2; the precursor of Fe is one or more of Fe(acac)3, FeCl3, FeCl2, FeS, ferrocene, nonacarbonyldiiron.

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