Preparation and application of high selectivity heterogeneous catalyst for hydroformylation of fischer-tropsch by-product olefins

Abstract

The present application relates to a kind of novel solid heterogeneous catalyst and its preparation method, specifically relates to a kind of high selectivity heterogeneous catalyst applied to Fischer-Tropsch by-product olefin hydroformylation, by one or two of metal components Rh or Co, and P, N polymer carrier with acidity composition.Wherein, P, N organic ligand with acid comonomer containing vinyl group is copolymerized by solvothermal to generate polymer with large specific surface area and multistage pore structure.P, N organic ligand with acid comonomer containing vinyl group is copolymerized by solvothermal to generate polymer with large specific surface area and multistage pore structure.The present application catalyst in Fischer-Tropsch by-product olefin heterogeneous hydroformylation reaction, not only reaction activity is excellent, also has higher straight-chain aldehyde selectivity, effectively realizes the unity of high carbon olefin heterogeneous hydroformylation reaction activity and straight-chain aldehyde selectivity.

Description

TECHNICAL FIELD

[0001] The present application relates to a kind of preparation and application of high selectivity heterogeneous catalyst for Fischer-Tropsch by-product olefin hydroformylation, belong to heterogeneous catalysis technical field. BACKGROUND

[0002] At present, the product of high-temperature iron-based slurry bed coal indirect liquefaction (medium-temperature Fischer-Tropsch) is rich in a large number of olefins (about 65%) in gasoline and diesel fraction section, how to convert this part of olefins into high value-added aldehydes, alcohols, ketones and esters, etc. is one of the technical selectivity to improve the economic efficiency of indirect liquefaction technology. By hydroformylation reaction, Fischer-Tropsch product containing more olefins is converted into oxygen-containing high-value chemicals, which can effectively improve the economic efficiency of coal indirect liquefaction.

[0003] Hydroformylation reaction is the reaction of olefins and synthesis gas to generate aldehyde which has one more carbon than the raw material olefins, and it is one of the most important industrial homogeneous catalytic reactions. Hydroformylation reaction is a typical atom economy reaction, and the research on its catalytic process and catalyst has a history of nearly 60 years. At present, more than 12 million tons of aldehydes and alcohols are produced worldwide each year using olefin hydroformylation technology. This reaction can make the raw material olefins generate aldehyde under not too harsh conditions, and the product aldehyde can be further hydrogenated to alcohol. Homogeneous catalytic system has high catalytic activity and selectivity of target product under mild reaction conditions, but the separation of catalyst from reaction materials is difficult, which hinders the large-scale industrial application of homogeneous catalytic system. The biggest advantage of heterogeneous catalysis compared with homogeneous catalysis is that the catalyst and reaction materials are easy to separate, and the main problems are harsh reaction conditions and relatively low reaction activity. At present, the main research focus of hydroformylation is to develop a new type of heterogeneous catalyst, which has the advantages of easy separation of heterogeneous catalyst and reaction materials, and high reaction activity and mild reaction conditions of homogeneous catalyst.

[0004] CN102281948A reports a kind of polymer-supported transition metal catalyst complex and use method, and a soluble polymer-supported Rh catalyst with relatively narrow molecular weight distribution is prepared. However, the catalyst preparation, catalytic reaction and catalyst separation process are complex. The catalyst preparation needs to control the functional monomer and styrene to synthesize soluble polymer first, then introduce ligand, and finally load Rh catalyst. Compressed gas needs to be added during the catalytic reaction process. The catalyst is separated from the reaction mixture by nanofiltration, and the reaction result is not ideal.

[0005] US6184413, which is a patent applied by California Institute of Technology, reports a supported phase catalyst, the supported phase of which is strong polarity, such as ethylene glycol or glycerol; and the metal center thereof is chiral sulfonated 2,2-bis(diphenylphosphino)-1,1-binaphthyl metal complex, which is soluble in the supported phase, and such a catalytic system can be used for asymmetric synthesis with optical activity.

[0006] Kausik Mukhopadhyay et al. (Chem Mater, 2003, 15: 1766-1777) first passivated the outer surface of MCM-41 and MCM-48 molecular sieves with diphenyldichlorosilane, and then modified the inner surface of the molecular sieves with 3-aminopropyltrimethoxysilane, so as to selectively immobilize HRh(CO)(PPh3)3 on the inner surface of the molecular sieves. In the research work, the authors creatively selectively immobilized HRh(CO)(PPh3)3 on the inner surface of MCM-41 and MCM-48 molecular sieves, but from the reaction effect of the catalyst, the reaction activity of such a heterogeneous catalytic system is low, and the recycling experiment shows that the reusability of the catalyst is poor, and the metal loss is serious.

[0007] US4252678 discloses the preparation of a colloidal dispersion containing transition metals such as Rh, wherein the transition metal component is in a colloidal dispersion of 1.0 to 20.0 nanometers, and a catalyst system composed of a hydroxyl-terminated (styrene / butadiene) functional copolymer is applied to the hydroformylation of 1-octene. The catalyst prepared by this method cannot be applied to fixed bed and trickle bed reactors, and the catalyst is difficult to separate from the product.

[0008] In summary, the biggest bottleneck of restricting the homogeneous immobilization of hydroformylation is the loss of homogeneous catalysts and the problem of activity reduction of homogeneous catalysts immobilized on the carrier. SUMMARY

[0009] The purpose of the present application is to provide a solid heterogeneous catalyst for the hydroformylation of Fischer-Tropsch by-product olefins, which can be used to prepare oxygen-containing high-value chemicals by the heterogeneous hydroformylation of Fischer-Tropsch by-product olefins, thereby effectively improving the economic efficiency of Fischer-Tropsch synthesis reaction.

[0010] To this end, the present application provides a heterogeneous catalyst for the hydroformylation of Fischer-Tropsch by-product olefins, which is composed of one or both of metal components Rh or Co, and a P, N polymer carrier with acidity; wherein the P, N polymer carrier with acidity is a polymer generated by solvothermal copolymerization of a vinyl group-containing P, N organic ligand and an acidic comonomer; the mass ratio of the vinyl group-containing P, N organic ligand and the acidic comonomer is 1000:1-1:1, preferably 500:1-2:1, and more preferably 100:1-5:1.

[0011] In a preferred embodiment, the P, N organic ligand containing vinyl group is selected from one or more of the following:

[0012]

[0013] In a preferred embodiment, the acid co-monomer containing vinyl group is selected from one or more of the following:

[0014]

[0015] In a preferred embodiment, the metal component is 0.05% to 20% (preferably 0.08% to 5%, more preferably 0.12% to 3%) of the total weight of the solid heterogeneous catalyst.

[0016] In a preferred embodiment, the specific surface area of the solid heterogeneous catalyst is 500 to 2000 m 2 / g, the pore volume is 0.5 to 4 cm 3 / g, and the pore size distribution is 0.1 to 200.0 nm.

[0017] In a preferred embodiment, the method comprises: a) adding a free radical initiator into a solvent containing P, N organic ligand with vinyl functional group and acid co-monomer containing vinyl group, stirring for 0.5 to 20 h (preferably 2 to 10 h) at 0 to 200 °C (preferably 20 to 150 °C) under Ar atmosphere; b) placing the solution of step a) in an autoclave for hydrothermal polymerization at 0 to 200 °C (preferably 20 to 150 °C) under Ar atmosphere for 0.5 to 50 h (preferably 5 to 40 h); c) removing the solvent under vacuum at 0 to 200 °C (preferably 20 to 150 °C) after step b) to obtain a P, N polymer carrier; d) placing the P, N polymer carrier in a solvent containing an active metal component, stirring for 0.5 to 50 h (preferably 5 to 40 h) at 0 to 200 °C (preferably 20 to 150 °C) under Ar atmosphere, and then removing the solvent under vacuum at 0 to 200 °C (preferably 20 to 150 °C) to obtain a solid heterogeneous catalyst with the active metal component supported on the P, N polymer.

[0018] In a preferred embodiment, the weight ratio of the free radical initiator to the P, N ligand is 1:500 to 1:5 (preferably 1:400 to 1:10).

[0019] In a preferred embodiment, the solid heterogeneous catalyst is used in the hydroformylation reaction of the by-product olefins from Fischer-Tropsch synthesis. The hydroformylation reaction is carried out in a fixed bed, a trickle bed, a slurry bed or a tank reactor with the Fischer-Tropsch product feedstock and a CO / H2mixed gas in the presence of the solid heterogeneous catalyst, wherein the reaction temperature is 20-300°C (preferably 50-250°C), the reaction pressure is 0.5-10 MPa (preferably 1-5 MPa), the liquid hourly space velocity is 0.1-5 h -1 (optimally 0.3-3 h -1 ), the gas hourly space velocity is 500-5000 h -1 (optimally 1000-4000 h -1 ); the by-product olefin feedstock is C2-C 30 hydrocarbons and oxygen-containing compounds, and the C2-C 30 hydrocarbons contain olefins, and the olefins account for 5%-90% of the total weight of the Fischer-Tropsch product feedstock.

[0020] The beneficial effects of the present application include, but are not limited to, the following: compared with the existing industrial application of the hydroformylation reaction technology, the use of the solid heterogeneous catalyst reduces the cost of separation of the catalyst from the reactants and products, and is suitable for large-scale industrial production; the catalyst of the present application has excellent reaction activity and straight-chain aldehyde selectivity, and good long-period stability in continuous reaction. The use of the catalyst of the present application can prepare high-value chemicals by the hydroformylation reaction of the by-product olefins from Fischer-Tropsch synthesis, and effectively improve the economy of the Fischer-Tropsch synthesis reaction.

[0021] The catalyst of the present application not only has excellent reaction activity in the heterogeneous hydroformylation reaction of the by-product olefins from Fischer-Tropsch synthesis, but also has high straight-chain aldehyde selectivity, effectively realizing the unity of the reaction activity and the straight-chain aldehyde selectivity in the heterogeneous hydroformylation reaction of high-carbon olefins. DETAILED DESCRIPTION

[0022] In order to better illustrate the preparation method of the catalyst and its application in the heterogeneous hydroformylation reaction of the by-product olefins from Fischer-Tropsch synthesis, some examples of the preparation of catalyst samples and their application in the reaction process are given below, but the present application is not limited to the listed examples. Unless otherwise specified, the content and percentage in this application are calculated by "mass".

[0023] Example 1

[0024] In an Ar atmosphere at 25°C, 8 g of P, N organic ligand L1 and 2 g of acidic co-monomer AL1 were dissolved in 100 ml of tetrahydrofuran solvent, 0.5 g of free radical initiator azobisisobutyronitrile was added to the above solution, and stirred for 0.5 h. The stirred solution was transferred to an autoclave, and solvent-thermal polymerization was carried out at 100°C for 24 h. After the above polymerization, the solution was cooled to room temperature, and the solvent was removed at 65°C under vacuum to obtain a P, N ligand polymer carrier containing an acid. In an Ar atmosphere at 25°C, 0.0627 g of Rh(acac)(CO)2 was dissolved in 100 ml of tetrahydrofuran solvent, 10.0 g of the above prepared polymer carrier was added, and stirred for 24 h. Subsequently, the solvent was removed at 65°C under vacuum to obtain a P, N ligand polymer supported metal component heterogeneous catalyst containing an acid.

[0025] The above prepared heterogeneous catalyst was loaded into a fixed bed reactor, and quartz sand was loaded at both ends. Synthetic gas (H2:CO = 1:1) and Fischer-Tropsch product naphtha raw material (C4-C 12 hydrocarbons and oxygen-containing compounds, olefin content about 70%), and the naphtha raw material was fed into the reaction system by a high-pressure pump, and the synthetic gas was directly fed in the form of a gas. The hydroformylation reaction was carried out at 110°C, 3 MPa, naphtha liquid hourly space velocity 2.5 h -1 , and synthetic gas gas hourly space velocity 1000 h -1 . The reaction product was collected in a collection tank equipped with a circulating cooler at 2.5°C. The obtained liquid phase product was analyzed by HP-7890N gas chromatography, and the normalization method was used for calculation. The reaction results are shown in Table 1.

[0026] Example 2

[0027] In Example 2, except that 8 g of P, N organic ligand L2 was weighed instead of 8 g of P, N organic ligand L1 dissolved in 100 ml of tetrahydrofuran solvent, the other processes were the same as Example 1. The reaction results are shown in Table 1.

[0028] Example 3

[0029] In Example 3, except that 8 g of P, N organic ligand L3 was weighed instead of 8 g of P, N organic ligand L1 dissolved in 100 ml of tetrahydrofuran solvent, the other processes were the same as Example 1. The reaction results are shown in Table 1.

[0030] Example 4

[0031] In Example 4, except that 2 g of acidic co-monomer AL2 was weighed instead of 2 g of acidic co-monomer AL1 dissolved in 100 ml of tetrahydrofuran solvent, the other processes were the same as Example 1. The reaction results are shown in Table 1.

[0032] Example 5

[0033] In Example 5, except that 2 g of acidic co-monomer AL3 was weighed instead of 2 g of acidic co-monomer AL1 and dissolved in 100 ml of tetrahydrofuran solvent, the other processes were the same as Example 1. The reaction results are listed in Table 1.

[0034] Example 6

[0035] In Example 6, except that 2 g of acidic co-monomer AL4 was weighed instead of 2 g of acidic co-monomer AL1 and dissolved in 100 ml of tetrahydrofuran solvent, the other processes were the same as Example 1. The reaction results are listed in Table 1.

[0036] Example 7

[0037] In Example 7, except that 5 g of P, N organic ligand L1 and 5 g of acidic co-monomer AL1 were weighed instead of 8 g of P, N organic ligand L1 and 2 g of acidic co-monomer AL1 and dissolved in 100 ml of tetrahydrofuran solvent, the other processes were the same as Example 1. The reaction results are listed in Table 1.

[0038] Example 8

[0039] In Example 8, except that 6 g of P, N organic ligand L1 and 4 g of acidic co-monomer AL1 were weighed instead of 8 g of P, N organic ligand L1 and 2 g of acidic co-monomer AL1 and dissolved in 100 ml of tetrahydrofuran solvent, the other processes were the same as Example 1. The reaction results are listed in Table 1.

[0040] Example 9

[0041] In Example 9, except that 7 g of P, N organic ligand L1 and 3 g of acidic co-monomer AL1 were weighed instead of 8 g of P, N organic ligand L1 and 2 g of acidic co-monomer AL1 and dissolved in 100 ml of tetrahydrofuran solvent, the other processes were the same as Example 1. The reaction results are listed in Table 1.

[0042] Example 10

[0043] In Example 10, except that 9 g of P, N organic ligand L1 and 1 g of acidic co-monomer AL1 were weighed instead of 8 g of P, N organic ligand L1 and 2 g of acidic co-monomer AL1 and dissolved in 100 ml of tetrahydrofuran solvent, the other processes were the same as Example 1. The reaction results are listed in Table 1.

[0044] Comparative Example 1

[0045] In Comparative Example 1, except that P, N porous polymer carrier containing P (PPh3) was used instead of P, N porous polymer carrier for catalyst preparation and subsequent evaluation of heterogeneous hydroformylation reaction, the other processes were the same as Example 3. The reaction results are listed in Table 1.

[0046] Comparative Example 2

[0047] In Comparative Example 2, the process was the same as Example 3 except that the porous organic polymer containing phosphine ligand was replaced by SiO2 support for catalyst preparation and its subsequent evaluation in heterogeneous hydroformylation reaction. The reaction results are listed in Table 1.

[0048] Comparative Example 3

[0049] In Comparative Example 3, the process was the same as Example 3 except that the porous organic polymer containing phosphine ligand was replaced by molecular sieve SBA-15 support for catalyst preparation and its subsequent evaluation in heterogeneous hydroformylation reaction. The reaction results are listed in Table 1.

[0050] Comparative Example 4

[0051] In Comparative Example 4, the process was the same as Example 3 except that the porous organic polymer containing phosphine ligand was replaced by activated carbon support for catalyst preparation and its subsequent evaluation in heterogeneous hydroformylation reaction. The reaction results are listed in Table 1.

[0052] Table 1. Results of heterogeneous hydroformylation of Fischer-Tropsch by-product olefins

[0053]

[0054] From the reaction data results of Examples 1-10 and Comparative Examples 1-4 above, it can be seen that the solid heterogeneous catalyst provided by the present application is used for the hydroformylation of Fischer-Tropsch by-product olefins, and the reaction activity and selectivity are excellent for the heterogeneous hydroformylation process method designed and developed for specific Fischer-Tropsch products, the normal-isomer ratio of the product aldehyde is high, and the reaction stability is good; since the solid heterogeneous catalyst is used, the separation cost of the catalyst from the reactants and products is reduced. The Fischer-Tropsch by-product olefins can be converted into high-value chemicals by the hydroformylation reaction using the catalyst of the present application, and the economic efficiency of the Fischer-Tropsch synthesis reaction is effectively improved.

[0055] The present application has been described in detail by the foregoing, but the present application 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 application. The scope of the present application is defined by the appended claims.

Claims

1. Use of a solid heterogeneous catalyst in the hydroformylation of a by-product olefin from a Fischer-Tropsch process, characterised in that, The solid heterogeneous catalyst is composed of a metal component Rh and a P, N polymer carrier with acidity; wherein the P, N polymer carrier with acidity is a polymer generated by solvothermal copolymerization of a P, N organic ligand containing a vinyl group and an acidic comonomer; the mass ratio of the P, N organic ligand containing a vinyl group to the acidic comonomer is 1000:1-1:1, and the P, N organic ligand containing a vinyl group is selected from one or two or more of the following: ， The acidic comonomer containing a vinyl group is selected from one or two or more of the following: 。 2. Use according to claim 1, characterized in that, The mass ratio of the P, N organic ligand containing a vinyl group to the acidic comonomer is 500:1-2:

1.

3. Use according to claim 1, characterized in that, The metal component accounts for 0.05%-20% of the total weight of the solid heterogeneous catalyst.

4. Use according to claim 3, characterized in that, The metal component accounts for 0.08%-5% of the total weight of the solid heterogeneous catalyst.

5. Use according to claim 1, characterized in that, The solid heterogeneous catalyst has a specific surface area of 500-2000 m 2 / g, a pore volume of 0.5-4 cm 3 / g, and a pore size distribution of 0.1-200.0 nm.

6. Use according to any one of claims 1 to 5, wherein the process for the preparation of the solid heterogeneous catalyst comprises: a) adding a free radical initiator in a P, N organic ligand containing a vinyl group and an acidic comonomer containing a vinyl group solvent under an Ar atmosphere at 20-200℃ and stirring for 0.5-20 h; b) placing the solution of step a) in a hydrothermal autoclave under an Ar atmosphere at 20-200℃ and standing for 0.5-50 h to perform a solvothermal polymerization reaction; c) removing the solvent under vacuum at a temperature of 20-200℃ after step b) is completed, to obtain a P, N polymer carrier; d) placing the P, N polymer carrier in a solvent containing an active metal component, stirring at 20-200℃ and under an Ar atmosphere for 0.5-50 h, and then removing the solvent under vacuum at 20-200℃, to obtain a solid heterogeneous catalyst with the P, N polymer loaded with the active metal component.

7. Use according to claim 6, characterized in that, The solvent used in steps a) and d) is one or several of benzene, toluene, tetrahydrofuran, methanol, ethanol, dichloromethane, dichloroethane or deionized water; and the free radical initiator used in step a) is one or several of cyclohexanone peroxide, dibenzoyl peroxide, tert-butyl hydroperoxide, azobisisobutyronitrile or azobisisoheptyl nitrile.

8. Use according to claim 7, characterized in that, The weight ratio of the free radical initiator to the P, N organic ligand containing a vinyl group is 1:500-1:

5.

9. Use according to claim 8, characterized in that, The weight ratio of the free radical initiator to the P, N organic ligand containing a vinyl group is 1:400-1:

10.

10. Use according to claim 1, characterized in that, The hydroformylation reaction is carried out in a fixed bed, a trickle bed, a slurry bed or a tank reactor in the presence of the solid heterogeneous catalyst, wherein the reaction temperature is 20-300°C, the reaction pressure is 0.5-10 MPa, the liquid hourly space velocity is 0.1-5 h -1 , and the gas hourly space velocity is 500-5000 h -1 ; the by-product olefin raw material is C2-C 30 hydrocarbons and oxygen-containing compounds, and the C2-C 30 hydrocarbons contain olefins, and the olefins account for 5%-90% of the total weight of the Fischer-Tropsch product raw material.

11. Use according to claim 10, characterized in that, The hydroformylation reaction is carried out in a fixed bed, a trickle bed, a slurry bed or a tank reactor in the presence of the solid heterogeneous catalyst, with a CO / H2mixture as the feedstock, at a reaction temperature of 50-250°C, a reaction pressure of 1-5 MPa, a liquid hourly space velocity of 0.3-3 h -1 , and a gas hourly space velocity of 1000-4000 h -1 .

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