A porous catalyst, a method for preparing the same and an application thereof

Abstract

The application discloses a porous catalyst and a preparation method and application thereof, and belongs to the technical field of catalysts. The porous catalyst is prepared by using specific borate-containing raw materials and bromine-containing raw materials as raw materials for polymerization, and loading cobalt metal active sites into the porous polymer, and through the reaction between different functional groups, a solid porous catalyst with nanoscale pores is generated, and the catalyst has high thermal stability, chemical stability and catalytic performance. The porous catalyst is used for preparing high-carbon alcohols, and the yield of the high-carbon alcohols can be improved.

Description

Technical Field

[0001] This application relates to the field of catalyst technology, specifically to a porous catalyst, its preparation method, and its application. Background Technology

[0002] The production of higher alcohols abroad began in the 18th century, primarily through the extraction of animal fats and oils. In the early 19th century, the oxidation of n-alkane to produce higher alcohols was developed. In the 1940s, Germany successfully produced higher alcohols using carbonyl synthesis. In 1961, the United States developed the Ziegler process, a new route for alcohol production. There are three main routes for producing higher alcohols: fat hydrogenation, alkylaluminum synthesis, and carbonyl synthesis.

[0003] my country's fatty alcohol industry has developed rapidly, and the applications of alcohol-based surfactants are becoming increasingly widespread. Currently, the main types of fatty alcohols in my country include: natural oil and fat higher alcohols and synthetic higher alcohols, including carbonyl synthetic alcohols, paraffin oxidation to synthesize fatty acid methyl esters and hydrogenate alcohols, liquid wax oxidation to produce secondary alcohols, and alcohols recovered from secondary unsaponifiable matter. Alcohol-based nonionic surfactants include saturated alcohols, unsaturated alcohols, lanolin alcohols, and polyoxyethylene sulfate ethers.

[0004] Therefore, the most critical step in the process route for the preparation of higher alcohols from olefins via hydroformylation and hydrogenation is the hydroformylation reaction. Homogeneous catalysts are predominantly used for hydroformylation to prepare higher alcohols. Homogeneous catalytic systems exhibit high catalytic activity and selectivity for the target product under mild reaction conditions. However, the difficulty in separating the catalyst from the reactants hinders the large-scale industrial application of homogeneous catalytic systems. The biggest advantage of heterogeneous catalysis compared to homogeneous catalysis is the ease of separating the catalyst from the reactants. The main problems are harsh reaction conditions and relatively lower reaction activity. Therefore, developing catalysts that combine the advantages of both homogeneous and heterogeneous catalysis is currently a major research challenge. Summary of the Invention

[0005] The purpose of this invention is to overcome the shortcomings of the prior art and to provide a porous catalyst, its preparation method and application; the catalyst has the advantages of large metal loading, high thermal stability and good catalytic effect.

[0006] To achieve the above objectives, the technical solution adopted by the present invention is as follows: a method for preparing a porous catalyst, comprising the following steps:

[0007] A boric acid-containing raw material, a bromine-containing raw material, an alkaline auxiliary agent, a catalyst, and a solvent are mixed and subjected to a Suzuki reaction at 80-140°C to obtain a support. The obtained support is then immersed in a cobalt-containing raw material solution, and the resulting mixture is dried to obtain a porous catalyst. The boric acid-containing raw material is 4,4,4-triphenylbenzene triboronic acid, and the bromine-containing raw material is 2,5-dibromophenol.

[0008] The structural formula of 4,4,4-triboronic acid triphenylbenzene is: ;

[0009] The structural formula of 2,5-dibromophenol is: .

[0010] This application uses specific boric acid and bromine-containing raw materials to prepare porous polymers through polymerization reactions. Cobalt metal active sites are loaded into the porous polymers, and through the reaction between different functional groups, a solid porous catalyst with nanoscale pores is generated. The nanoscale pores are beneficial to increasing the specific surface area of ​​the porous catalyst, allowing more catalytic sites to be exposed in the catalytic system, thereby improving the catalytic performance of the porous catalyst. At the same time, the porous catalyst contains a large number of hydroxyl groups, which anchor the metal catalytic active sites to the pore walls through coordination and electrostatic interactions. The presence of hydroxyl groups improves the selectivity of the catalyst and the yield of the product.

[0011] Furthermore, this application uses polymer monomers containing benzene rings as building groups, giving the resulting porous catalyst a rigid structure and improving its mechanical strength. At the same time, the polymeric components are interconnected by chemical bonds, further improving the thermal and chemical stability of the porous catalyst. Even after prolonged immersion in organic solvents, the structure of the porous catalyst remains intact.

[0012] The porous catalyst of this application is a solid material containing hydroxyl groups, and its structure is an amorphous nanostructure with a smooth surface; furthermore, the porous catalyst of this application has a specific surface area of ​​50-100 m². 2 / cm 3 .

[0013] In one embodiment, the cobalt-containing raw material is at least one selected from cobalt octacarbonyl, cobalt dicarbonylcyclopentadiene, cobalt tricarbonylnitrosyl, cobalt(II) chloride hexahydrate, and cobalt acetate tetrahydrate.

[0014] In this application, the cobalt-containing raw material can affect the catalytic performance of the catalyst. Different cobalt-containing raw materials have different interactions with the support. When at least one of dicarbonylcyclopentadiene cobalt or tricarbonylnitrosyl cobalt is used, the interaction between the cobalt active sites and the support is enhanced, resulting in a porous catalyst with a higher specific surface area and stability, thereby improving the catalytic performance of the porous catalyst. In this application, the cobalt-containing raw material is preferably dicarbonylcyclopentadiene cobalt to further improve the catalytic performance of the porous catalyst.

[0015] In this application, during the Suzuki polymerization reaction, it is necessary to control the amount of each raw material to obtain a porous polymer with better performance. For example, in one embodiment, the molar ratio of the boric acid-containing raw material to the bromine-containing raw material is 1:1 to 1:2, preferably 1:1.2 to 1:1.8, and more preferably 1:1.4 to 1:1.6;

[0016] And / or, in one embodiment, the mass ratio of the catalyst to the total molar ratio of the boric acid feedstock and the bromine feedstock is 0.8 g: 1-2.5 mmol.

[0017] In one embodiment, the catalyst is tetraphenylphosphine palladium and triphenylphosphine.

[0018] In one embodiment, the molar ratio of tetraphenylphosphine palladium to triphenylphosphine is 1:1 to 1:1.5; preferably 1:1.2 to 1:1.5, and more preferably 1:1.4 to 1:1.5.

[0019] In the Suzuki polymerization process, the type of catalyst affects the polymerization of monomers and the reaction efficiency. In this application, the preferred catalyst is tetrakis(triphenylphosphine)palladium and triphenylphosphine to improve the purity and performance of the porous polymer. Based on this, the molar ratio of tetrakis(triphenylphosphine)palladium and triphenylphosphine is optimized to increase the specific surface area of ​​the porous polymer, thereby improving the catalytic performance and stability of the porous catalyst.

[0020] In one embodiment, the ratio of the carrier to the cobalt-containing raw material solution is 1 mg: 50-100 mL; preferably 1 mg: 70 mL to 1 mg: 100 mL, and more preferably 1 mg: 90 mL to 1 mg: 100 mL.

[0021] In one embodiment, the concentration of the cobalt-containing raw material solution is 5-10 mmol / L, preferably 6-8 mmol / L, and more preferably 7-8 mmol / L.

[0022] In this application, the active component is loaded onto the support by impregnation. The preferred ratio of the support to the cobalt-containing raw material solution and the concentration of the cobalt-containing raw material solution are to further increase the content of the active component in the porous catalyst, thereby improving the catalytic performance of the porous catalyst.

[0023] The solvent in the cobalt-containing raw material solution described in this application only needs to be able to dissolve the cobalt-containing raw material. It can be a solvent known in the art, such as at least one of ethanol, n-propanol, dichloromethane, n-butanol, acetone, n-hexane, tetrahydrofuran, and water, preferably at least one of n-propanol, dichloromethane, n-butanol, and acetone, and more preferably dichloromethane. The specific solvents exemplified in this application should not be construed as limiting the invention by those skilled in the art.

[0024] In one embodiment, the parameters of the Suzuki reaction include: a temperature of 80~140°C and a time of 20~50h; preferably, the parameters of the Suzuki reaction include: a temperature of 90~130°C and a time of 30~40h; more preferably, the parameters of the Suzuki reaction include: a temperature of 100~110°C and a time of 35~40h.

[0025] Under the above reaction parameters, porous polymers with better performance can be obtained.

[0026] In one embodiment, the solvent used in the polymerization reaction of this application can be any solvent capable of dissolving boric acid-containing raw materials, bromine-containing raw materials, and catalysts. It can be a solvent known in the art, such as at least one of chloroform, ether, benzene, methyl acetate, tetrahydrofuran, acetone, methanol, petroleum, chlorophenol, dichloroethylene, and carbon tetrachloride, preferably tetrahydrofuran. The specific solvents exemplified in this application should not be construed as limiting the invention by those skilled in the art.

[0027] In one embodiment, the alkaline auxiliary is one or more of potassium carbonate, sodium carbonate, and sodium bicarbonate, and the mass ratio of tetraphenylphosphine palladium to the alkaline auxiliary is 1:0.8 to 1:1.2.

[0028] Another objective of this application is to provide a porous catalyst, which is prepared by the above-described method for preparing porous catalysts.

[0029] Another object of this application is to provide the application of the porous catalyst in the preparation of higher alcohols, characterized by comprising the following steps:

[0030] In a syngas environment, a porous catalyst solution and an olefin are subjected to a hydroformylation reaction to obtain a high carbon aldehyde with ≥10 carbon atoms.

[0031] In a hydrogen atmosphere, a high carbon aldehyde and a hydrogenation catalyst solution undergo a hydrogenation reaction to obtain a high carbon alcohol, wherein the high carbon alcohol has ≥10 carbon atoms.

[0032] The porous catalyst described in this application is used in the hydroformylation reaction of higher alcohols to improve the conversion rate of olefins and thus increase the yield of higher alcohols.

[0033] This application does not impose any particular restrictions on the reactors used for hydroformylation and hydrogenation reactions, as long as the temperature of the hydroformylation and hydrogenation reactions can be freely controlled.

[0034] In one embodiment, the synthesis gas is carbon monoxide and hydrogen;

[0035] And / or, the molar ratio of carbon monoxide to hydrogen is 1:0.5 to 1:2;

[0036] And / or, the olefin is a C10 to C16 olefin;

[0037] And / or, the amount of the olefin used is 1 to 3 mol;

[0038] And / or, the amount of the porous catalyst used is 10–50 mg;

[0039] And / or, the parameters of the hydroformylation reaction include: pressure of 10-50 MPa, temperature of 100-150℃, and time of 6-10 h;

[0040] And / or, the hydrogenation catalyst is palladium on carbon;

[0041] And / or, the parameters of the hydrogenation reaction include: pressure of 1-2 MPa, temperature of 150-200°C, and time of 1-2 h.

[0042] The endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0043] Compared with existing technologies, the beneficial effects of this invention are as follows: This application uses specific boric acid and bromine-containing raw materials to prepare porous polymers through polymerization reactions, and loads cobalt metal active sites into the porous polymers. Through the reaction between different functional groups, a solid porous catalyst with nanoscale pores is generated. This catalyst has high thermal stability, chemical stability, and catalytic performance. Using the porous catalyst to prepare higher alcohols can improve the yield of higher alcohols. Attached Figure Description

[0044] Figure 1 Specific surface area diagrams of the porous catalysts obtained in Examples 1-5;

[0045] Figure 2 The graphs show the adsorption amounts of high-carbon olefins by the porous catalysts obtained in Examples 1-5.

[0046] Figure 3 The yield graphs are for the higher alcohols obtained in Examples 1-5. Detailed Implementation

[0047] To better illustrate the purpose, technical solution, and advantages of this invention, the invention will be further described below with reference to specific embodiments and comparative examples. The purpose of this description is to provide a detailed understanding of the invention, not to limit its scope. All other embodiments obtained by those skilled in the art without inventive effort are within the protection scope of this invention. Unless otherwise specified, the experimental reagents and instruments involved in the implementation of this invention are commonly used reagents and instruments.

[0048] Example 1

[0049] Preparation of porous catalysts

[0050] 4.3 g of 4,4,4-triphenylbenzene 4,4,4-triboronic acid, 3.7 g of 2,5-dibromophenol, and 0.1 g of potassium carbonate were added to a round-bottom flask. After evacuating the flask, nitrogen gas was introduced, followed by the injection of tetrahydrofuran. Then, 0.08 g of tetratriphenylphosphine palladium and 0.018 g of triphenylphosphine were added to the flask. The mixture was heated to 100 °C with stirring and reacted for 40 h. After the reaction was completed, the mixture was cooled to room temperature, and the resulting product was filtered. The crude product obtained by filtration was washed with 1.5 mol / L HCl solution. The washed product was then subjected to Soxhlet extraction with dichloromethane, tetrahydrofuran, and petroleum ether to obtain a porous polymer.

[0051] 10 mg of the obtained porous polymer was added to 1000 mL of 8 mmol / L octacarbonyldicobalt dichloromethane solution, stirred for 5 h, and then filtered. The filtered product was washed three times with dichloromethane, and the washed product was dried in a vacuum environment at 80 °C for 20 h to obtain the porous catalyst.

[0052] Preparation of higher alcohols

[0053] Hydroformylation reaction: 1 mol of olefin and 10 mg of the porous catalyst prepared above were added to the reactor. The reactor was purged with nitrogen three times, the temperature was raised to 140℃, carbon monoxide and hydrogen were introduced and the pressure was raised to 20 MPa. The reaction was started by stirring and the reaction time was 8 h. High carbon aldehyde was obtained. The molar ratio of hydrogen to carbon monoxide was 1:1.

[0054] Hydrogenation reaction: 0.5 mol of the obtained higher carbon aldehyde and 20 mg of palladium on carbon were added to the reactor, hydrogen gas was introduced at 1 MPa, and the reaction was stirred for 1 h to obtain higher carbon alcohol with a yield of 76%.

[0055] Example 2

[0056] Preparation of porous catalysts

[0057] 4.3 g of 4,4,4-triphenylbenzene 4,4,4-triboronic acid, 3.7 g of 2,5-dibromophenol, and 0.1 g of potassium carbonate were added to a round-bottom flask. After evacuating the flask, nitrogen gas was introduced, followed by the injection of tetrahydrofuran. Then, 0.08 g of tetratriphenylphosphine palladium and 0.018 g of triphenylphosphine were added to the flask. The mixture was heated to 100 °C with stirring and reacted for 40 h. After the reaction was completed, the mixture was cooled to room temperature, and the resulting product was filtered. The crude product obtained by filtration was washed with 1.5 mol / L HCl solution. The washed product was then subjected to Soxhlet extraction with dichloromethane, tetrahydrofuran, and petroleum ether to obtain a porous polymer.

[0058] 10 mg of the obtained porous polymer was added to 1000 mL of a dicarbonylcyclopentadiene cobalt dichloromethane solution with a concentration of 8 mmol / L. After stirring for 5 h, the mixture was filtered. The filtered product was washed three times with dichloromethane. The washed product was dried in a vacuum environment at 80 °C for 20 h to obtain the porous catalyst.

[0059] Preparation of higher alcohols

[0060] Hydroformylation reaction: 1 mol of olefin and 10 mg of the porous catalyst prepared above were added to the reactor. The reactor was purged with nitrogen three times, the temperature was raised to 140℃, carbon monoxide and hydrogen were introduced and the pressure was raised to 20 MPa. The reaction was started by stirring and the reaction time was 8 h. High carbon aldehyde was obtained. The molar ratio of hydrogen to carbon monoxide was 1:1.

[0061] Hydrogenation reaction: 0.5 mol of the obtained high carbon aldehyde and 20 mg of palladium on carbon were added to the reactor, hydrogen gas was introduced at 1 MPa, and the reaction was stirred for 1 h to obtain high carbon alcohol with a yield of 98%.

[0062] Example 3

[0063] Preparation of porous catalysts

[0064] 4.3 g of 4,4,4-triphenylbenzene 4,4,4-triboronic acid, 3.7 g of 2,5-dibromophenol, and 0.1 g of potassium carbonate were added to a round-bottom flask. After evacuating the flask, nitrogen gas was introduced, followed by the injection of tetrahydrofuran. Then, 0.08 g of tetratriphenylphosphine palladium and 0.018 g of triphenylphosphine were added to the flask. The mixture was heated to 100 °C with stirring and reacted for 40 h. After the reaction was completed, the mixture was cooled to room temperature, and the resulting product was filtered. The crude product obtained by filtration was washed with 1.5 mol / L HCl solution. The washed product was then subjected to Soxhlet extraction with dichloromethane, tetrahydrofuran, and petroleum ether to obtain a porous polymer.

[0065] 10 mg of the obtained porous polymer was added to 1000 mL of a tricarbonylnitrosylcobalt dichloromethane solution with a concentration of 8 mmol / L. After stirring for 5 h, the mixture was filtered. The filtered product was washed three times with dichloromethane. The washed product was dried in a vacuum environment at 80 °C for 20 h to obtain the porous catalyst.

[0066] Preparation of higher alcohols

[0067] Hydroformylation reaction: 1 mol of olefin and 10 mg of the porous catalyst prepared above were added to the reactor. The reactor was purged with nitrogen three times, the temperature was raised to 140℃, carbon monoxide and hydrogen were introduced and the pressure was raised to 20 MPa. The reaction was started by stirring and the reaction time was 8 h. High carbon aldehyde was obtained. The molar ratio of hydrogen to carbon monoxide was 1:1.

[0068] Hydrogenation reaction: 0.5 mol of the obtained higher carbon aldehyde and 20 mg of palladium on carbon were added to the reactor, hydrogen gas was introduced at 1 MPa, and the reaction was stirred for 1 h to obtain higher carbon alcohol with a yield of 84%.

[0069] Example 4

[0070] Preparation of porous catalysts

[0071] 4.3 g of 4,4,4-triphenylbenzene 4,4,4-triboronic acid, 3.7 g of 2,5-dibromophenol, and 0.1 g of potassium carbonate were added to a round-bottom flask. After evacuating the flask, nitrogen gas was introduced, followed by the injection of tetrahydrofuran. Then, 0.08 g of tetratriphenylphosphine palladium and 0.018 g of triphenylphosphine were added to the flask. The mixture was heated to 100 °C with stirring and reacted for 40 h. After the reaction was completed, the mixture was cooled to room temperature, and the resulting product was filtered. The crude product obtained by filtration was washed with 1.5 mol / L HCl solution. The washed product was then subjected to Soxhlet extraction with dichloromethane, tetrahydrofuran, and petroleum ether to obtain a porous polymer.

[0072] 10 mg of the obtained porous polymer was added to 1000 mL of a solution of cobalt chloride hexahydrate in dichloromethane with a concentration of 8 mmol / L. After stirring for 5 h, the mixture was filtered. The filtered product was washed three times with dichloromethane. The washed product was dried in a vacuum environment at 80 °C for 20 h to obtain the porous catalyst.

[0073] Preparation of higher alcohols

[0074] Hydroformylation reaction: 1 mol of olefin and 10 mg of the porous catalyst prepared above were added to the reactor. The reactor was purged with nitrogen three times, the temperature was raised to 140℃, carbon monoxide and hydrogen were introduced and the pressure was raised to 20 MPa. The reaction was started by stirring and the reaction time was 8 h. High carbon aldehyde was obtained. The molar ratio of hydrogen to carbon monoxide was 1:1.

[0075] Hydrogenation reaction: 0.5 mol of the obtained high carbon aldehyde and 20 mg of palladium on carbon were added to the reactor, hydrogen gas was introduced at 1 MPa, and the reaction was stirred for 1 h to obtain high carbon alcohol with a yield of 55%.

[0076] Example 5

[0077] Preparation of porous catalysts

[0078] 4.3 g of 4,4,4-triphenylbenzene 4,4,4-triboronic acid, 3.7 g of 2,5-dibromophenol, and 0.1 g of potassium carbonate were added to a round-bottom flask. After evacuating the flask, nitrogen gas was introduced, followed by the injection of tetrahydrofuran. Then, 0.08 g of tetratriphenylphosphine palladium and 0.018 g of triphenylphosphine were added to the flask. The mixture was heated to 100 °C with stirring and reacted for 40 h. After the reaction was completed, the mixture was cooled to room temperature, and the resulting product was filtered. The crude product obtained by filtration was washed with 1.5 mol / L HCl solution. The washed product was then subjected to Soxhlet extraction with dichloromethane, tetrahydrofuran, and petroleum ether to obtain a porous polymer.

[0079] 10 mg of the obtained porous polymer was added to 1000 mL of a cobalt acetate tetrahydrate dichloromethane solution with a concentration of 8 mmol / L. After stirring for 5 h, the mixture was filtered. The filtered product was washed three times with dichloromethane. The washed product was dried in a vacuum environment at 80 °C for 20 h to obtain the porous catalyst.

[0080] Preparation of higher alcohols

[0081] Hydroformylation reaction: 1 mol of olefin and 10 mg of the porous catalyst prepared above were added to the reactor. The reactor was purged with nitrogen three times, the temperature was raised to 140℃, carbon monoxide and hydrogen were introduced and the pressure was raised to 20 MPa. The reaction was started by stirring and the reaction time was 8 h. High carbon aldehyde was obtained. The molar ratio of hydrogen to carbon monoxide was 1:1.

[0082] Hydrogenation reaction: 0.5 mol of the obtained higher carbon aldehyde and 20 mg of palladium on carbon were added to the reactor, hydrogen gas was introduced at 1 MPa, and the reaction was stirred for 1 h to obtain higher carbon alcohol with a yield of 79%.

[0083] Example 6

[0084] Preparation of porous catalysts

[0085] 4.3 g of triphenylbenzene 4,4,4-triboronic acid, 2.9 g of 2,5-dibromophenol, and 0.1 g of potassium carbonate were added to a round-bottom flask. The flask was evacuated, and nitrogen gas was introduced. Tetrahydrofuran was then injected, followed by 0.08 g of tetraphenylphosphine palladium and 0.027 g of triphenylphosphine. The mixture was heated to 80 °C with stirring and reacted for 50 h. After the reaction was complete, the mixture was cooled to room temperature, and the resulting product was filtered. The crude product was washed with 1.5 mol / L HCl solution, and the washing product was successively subjected to Soxhlet extraction with dichloromethane, tetrahydrofuran, and petroleum ether to obtain a porous polymer with a specific surface area of ​​48 m². 2 / g, with an adsorption capacity of 25mg / g for high-carbon olefins;

[0086] 10 mg of the obtained porous polymer was added to 500 mL of a 10 mmol / L solution of octacarbonyldicobalt dichloromethane. After stirring for 5 h, the mixture was filtered. The filtered product was washed three times with dichloromethane. The washed product was dried in a vacuum environment at 80 °C for 20 h to obtain the porous catalyst.

[0087] Preparation of higher alcohols

[0088] Hydroformylation reaction: 1 mol of olefin and 10 mg of the porous catalyst prepared above were added to the reactor. The reactor was purged with nitrogen three times, the temperature was raised to 140℃, carbon monoxide and hydrogen were introduced and the pressure was raised to 20 MPa. The reaction was started by stirring and the reaction time was 8 h. High carbon aldehyde was obtained. The molar ratio of hydrogen to carbon monoxide was 1:1.

[0089] Hydrogenation reaction: 0.5 mol of the obtained high carbon aldehyde and 20 mg of palladium on carbon were added to the reactor, hydrogen gas was introduced at 1 MPa, and the reaction was stirred for 1 h to obtain high carbon alcohol with a yield of 38%.

[0090] Example 7

[0091] Preparation of porous catalysts

[0092] 4.3 g of triphenylbenzene 4,4,4-triboronic acid, 5.7 g of 2,5-dibromophenol, and 0.1 g of potassium carbonate were added to a round-bottom flask. The flask was evacuated, and nitrogen gas was introduced. Tetrahydrofuran was then injected, followed by 0.08 g of tetraphenylphosphine palladium and 0.023 g of triphenylphosphine. The mixture was heated to 140 °C with stirring and reacted for 20 h. After the reaction was complete, the mixture was cooled to room temperature, and the resulting product was filtered. The crude product was washed with 1.5 mol / L HCl solution, and the washing product was successively subjected to Soxhlet extraction with dichloromethane, tetrahydrofuran, and petroleum ether to obtain a porous polymer with a specific surface area of ​​43 m². 2 / g, the adsorption capacity for high carbon olefins is 24mg / g;

[0093] 10 mg of the obtained porous polymer was added to 700 mL of a 5 mmol / L solution of octacarbonyldicobalt dichloromethane, stirred for 5 h, and then filtered. The filtered product was washed three times with dichloromethane, and the washed product was dried in a vacuum environment at 80 °C for 20 h to obtain the porous catalyst.

[0094] Preparation of higher alcohols

[0095] Hydroformylation reaction: 1 mol of olefin and 10 mg of the porous catalyst prepared above were added to the reactor. The reactor was purged with nitrogen three times, the temperature was raised to 140℃, carbon monoxide and hydrogen were introduced and the pressure was raised to 20 MPa. The reaction was started by stirring and the reaction time was 8 h. High carbon aldehyde was obtained. The molar ratio of hydrogen to carbon monoxide was 1:1.

[0096] Hydrogenation reaction: 0.5 mol of the obtained high carbon aldehyde and 20 mg of palladium on carbon were added to the reactor, hydrogen gas was introduced at 1 MPa, and the reaction was stirred for 1 h to obtain high carbon alcohol with a yield of 37%.

[0097] Performance testing

[0098] The specific surface area, adsorption capacity of higher olefins, and yield of higher alcohols of the porous catalysts obtained in each embodiment were tested.

[0099] Specific surface area: Nova 600 BET specific surface area and pore size analyzer.

[0100] Adsorption capacity of high carbon olefins: UV-Vis spectrophotometer UV5.

[0101] Yields of higher alcohols: The obtained liquid products were analyzed by HP-7890N gas chromatography, and n-propanol was used as an internal standard for analysis and calculation.

[0102] The results are as follows Figures 1-3 As shown, Figure 1 Specific surface area diagrams of the porous catalysts obtained in Examples 1-5; Figure 2 The graphs show the adsorption amounts of high-carbon olefins by the porous catalysts obtained in Examples 1-5. Figure 3 This is a yield graph of the higher alcohols obtained in Examples 1-5. From... Figures 1-3 As can be seen, the porous catalyst prepared in this application has a high specific surface area and excellent adsorption performance for higher carbon olefins. The adsorption of higher carbon olefins by the porous catalyst increases the contact probability between the catalytic sites and higher carbon olefins, thereby improving the catalytic performance of the porous catalyst. The yield of higher carbon alcohols in this application exceeds 35%, indicating that the porous catalyst of this application can improve the yield of higher carbon alcohols.

[0103] Finally, it should be noted that the above embodiments are used to illustrate the technical solutions of the present invention and not to limit the scope of protection of the present invention. Although the present invention has been described in detail with reference to preferred embodiments, those skilled in the art should understand that modifications or equivalent substitutions can be made to the technical solutions of the present invention without departing from the essence and scope of the technical solutions of the present invention.

Claims

1. A method for preparing a porous catalyst for higher alcohols, characterized in that, Includes the following steps: A boric acid-containing raw material, a bromine-containing raw material, an alkaline auxiliary agent, a catalyst, and a solvent are mixed and subjected to a Suzuki reaction at 80-140°C to obtain a support; the obtained support is immersed in a cobalt-containing raw material solution, and the resulting mixture is dried to obtain a porous catalyst; the boric acid-containing raw material is 4,4,4-triphenylbenzene triboronic acid; the bromine-containing raw material is 2,5-dibromophenol. The molar ratio of the boric acid-containing raw material to the bromine-containing raw material is 1:1 to 1:2; The mass ratio of the catalyst to the total molar ratio of the boric acid-containing raw material and the bromine-containing raw material is 0.8 g: 1-2.5 mmol; The catalyst is tetra(triphenylphosphine)palladium and triphenylphosphine; The ratio of the carrier to the cobalt-containing raw material solution is 1g: 50~100mL; The parameters of the Suzuki reaction include: temperature of 80~140℃ and time of 20~50 h.

2. The preparation method according to claim 1, characterized in that, The cobalt-containing raw material is at least one of cobalt octacarbonyl, cobalt dicarbonylcyclopentadiene, cobalt tricarbonylnitrosyl, cobalt(II) chloride hexahydrate, and cobalt acetate tetrahydrate.

3. The preparation method according to claim 1, characterized in that, The molar ratio of the boric acid raw material to the bromine-containing raw material is 1:1.2 to 1:1.

8.

4. The preparation method according to claim 3, characterized in that, The molar ratio of the boric acid raw material to the bromine-containing raw material is 1:1.4 to 1:1.

6.

5. The preparation method according to claim 1, characterized in that, The molar ratio of tetra(triphenylphosphine)palladium to triphenylphosphine is 1:1 to 1:1.

5.

6. The preparation method according to claim 5, characterized in that, The molar ratio of tetra(triphenylphosphine)palladium to triphenylphosphine is 1:1.2 to 1:1.

5.

7. The preparation method according to claim 6, characterized in that, The molar ratio of tetra(triphenylphosphine)palladium to triphenylphosphine is 1:1.4 to 1:1.

5.

8. The preparation method according to claim 1, characterized in that, The ratio of the carrier to the cobalt-containing raw material solution is 1 g: 70~100 mL.

9. The preparation method according to claim 8, characterized in that, The ratio of the carrier to the cobalt-containing raw material solution is 1 g: 90~100 mL.

10. The preparation method according to claim 1, characterized in that, The concentration of the cobalt-containing raw material solution is 5~10 mmol / L.

11. The preparation method according to claim 10, characterized in that, The concentration of the cobalt-containing raw material solution is 6~8 mmol / L.

12. The preparation method according to claim 11, characterized in that, The concentration of the cobalt-containing raw material solution is 7~8 mmol / L.

13. The preparation method according to claim 1, characterized in that, The parameters of the Suzuki reaction include: temperature of 90~130℃ and time of 30~40 h.

14. The preparation method according to claim 13, characterized in that, The parameters of the Suzuki reaction include: temperature of 100~110℃ and time of 35~40 h.

15. A porous catalyst, characterized in that, The porous catalyst is prepared by the method described in any one of claims 1-14.

16. The application of the porous catalyst as described in claim 15 in the preparation of higher alcohols, characterized in that... Includes the following steps: In a syngas environment, a porous catalyst solution and an olefin are subjected to a hydroformylation reaction to obtain a high carbon aldehyde with ≥10 carbon atoms. In a hydrogen atmosphere, a high carbon aldehyde and a hydrogenation catalyst solution undergo a hydrogenation reaction to obtain a high carbon alcohol, wherein the high carbon alcohol has ≥10 carbon atoms.

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