Method for preparing aldehyde through hydroformylation of Fischer-Tropsch product

Abstract

The invention relates to the field of organic synthesis, and discloses a method for preparing aldehyde through hydroformylation of a Fischer-Tropsch product. The method comprises the following steps: under the action of a catalyst, carrying out hydroformylation reaction on a Fischer-Tropsch product and synthesis gas to prepare aldehyde; the catalyst is prepared based on a rhodium compound, a monophosphine ligand and a polyphosphine ligand. The catalyst is prepared by simultaneously adding the monophosphine ligand and the polyphosphine ligand, so that when aldehyde is prepared through hydroformylation reaction, the production cost of the aldehyde can be reduced while the normal / isomeric ratio of the product aldehyde is increased.

Description

Method for preparing aldehydes by hydroformylation of Fischer-Tropsch products Technical Field

[0001] This invention relates to the field of organic synthesis technology, and more specifically to a method for preparing aldehydes by hydroformylation of Fischer-Tropsch products. Background Technology

[0002] Hydroformylation, also known as the OXO reaction, is a reaction in which carbon monoxide and hydrogen are added to an alkene in one step under the action of a catalyst to produce an aldehyde with one more carbon atom than the original alkene. The aldehydes produced by hydroformylation include linear aldehydes and branched aldehydes, which can be further converted into alcohols through hydrogenation reduction. This is a common method used industrially to produce plasticizer alcohols and surfactant alcohols.

[0003] Linear α-olefins are important raw materials for hydroformylation reactions. Initially, linear α-olefins were produced via paraffin thermal cracking or the dehydration of α-alkanols. However, these two methods require extremely harsh reaction conditions. Therefore, Shell's High Olefins Process (SHOP) was adopted to generate linear α-olefins through ethylene oligomerization. However, SHOP is based on ethylene oligomerization, thus only providing α-olefins with even-numbered carbon chain lengths, and struggling to provide α-olefins with odd-numbered carbon chain lengths (excluding propylene). To further meet the demand for α-olefins with odd-numbered carbon chain lengths, attention turned to coal-based Fischer-Tropsch synthesis. Olefins obtained through coal-based Fischer-Tropsch synthesis have advantages such as high content of straight-chain α-olefins and a wide carbon chain distribution.

[0004] Currently, when preparing aldehydes through hydroformylation of olefins obtained from coal-based Fischer-Tropsch synthesis, single-phosphorus ligand catalysts or polyphosphorus ligand catalysts are commonly used. However, using single-phosphorus ligand catalysts results in a low positive-to-negative ratio of the aldehyde product, while using polyphosphorus ligand catalysts leads to higher costs, making it difficult to balance the positive-to-negative ratio of the aldehyde product with the aldehyde production cost. Summary of the Invention

[0005] The purpose of this invention is to overcome the problem in the prior art that it is difficult to balance the positive-to-iso ratio of aldehydes and the production cost of aldehydes when performing hydroformylation reactions on olefins obtained from coal-based Fischer-Tropsch synthesis, and to provide a method for preparing aldehydes by hydroformylation of Fischer-Tropsch products.

[0006] The method for preparing aldehydes by hydroformylation of Fischer-Tropsch products includes: preparing aldehydes by hydroformylation of Fischer-Tropsch products and syngas under the action of a catalyst; wherein the catalyst is prepared based on rhodium compounds, monophosphorus ligands and polyphosphine ligands.

[0007] In the embodiments of this application, the catalyst is a coordination catalyst formed by a rhodium compound, a monophosphorus ligand, and a polyphosphorus ligand.

[0008] In the embodiments of this application, the rhodium compound is Rh(acac)(CO)2, and the catalyst is HRh(CO)(A)2(B), wherein A is a monophosphorus ligand and B is a polyphosphorus ligand.

[0009] In the embodiments of this application, the polyphosphine ligand is a tetraphosphine ligand.

[0010] In the embodiments of this application, the monophosphorus ligand and the tetraphosphine ligand are sulfonated and then used to react with rhodium compounds to prepare a catalyst.

[0011] In this embodiment, the structural formula of the sulfonated monophosphorus ligand is shown below:

[0012] The structural formula of the sulfonated tetraphosphine ligand is shown below: .

[0013] In the embodiments of this application, when preparing the catalyst, the molar ratio of the rhodium compound, the monophosphorus ligand and the polyphosphine ligand is 1:(10-70):(1-2.1).

[0014] In the embodiments of this application, the molar ratio of rhodium compound, monophosphorus ligand, polyphosphorus ligand and olefin is 1:(10-70):(1-2.1):(8000-8500), and the olefin is 1-olefin in the C5-C11 fraction of Fischer-Tropsch product.

[0015] In the embodiments of this application, when preparing aldehydes by hydroformylation reaction using Fischer-Tropsch products and syngas under the action of a catalyst, an auxiliary agent is also added, which is glycerol or isopropanol.

[0016] In the embodiments of this application, the reaction pressure of the hydroformylation reaction is 1~7MPa, the reaction temperature of the hydroformylation reaction is 70~110℃, the hydroformylation reaction is carried out under stirring conditions, the stirring rate is 400-600rpm, and the reaction time is 1-8h.

[0017] The method for preparing aldehydes by hydroformylation of Fischer-Tropsch products based on the above technical solution includes: preparing aldehydes by hydroformylation of Fischer-Tropsch products and syngas under the action of a catalyst; wherein the catalyst is prepared based on a rhodium compound, a monophosphorus ligand, and a polyphosphine ligand. By simultaneously adding monophosphorus ligands and polyphosphine ligands to prepare the catalyst, the production cost of aldehydes can be reduced while increasing the positive-to-isophosphine ratio of the aldehyde product during the hydroformylation reaction.

[0018] Other features and advantages of the embodiments of this application will be described in detail in the following detailed description section. Attached Figure Description

[0019] The accompanying drawings are provided to further illustrate the embodiments of this application and constitute a part of the specification. They are used together with the following detailed description to explain the embodiments of this application, but do not constitute a limitation on the embodiments of this application. In the drawings: Figure 1 schematically illustrates a process flow diagram of a method for preparing aldehydes by hydroformylation of Fischer-Tropsch products according to an embodiment of this application. Detailed Implementation

[0020] To make the objectives, technical solutions, and advantages of the embodiments of this application clearer, the technical solutions of the embodiments of this application will be clearly and completely described below with reference to the accompanying drawings. It should be understood that the specific embodiments described herein are only for illustration and explanation of the embodiments of this application and are not intended to limit the embodiments of this application. All other embodiments obtained by those skilled in the art based on the embodiments of this application without creative effort are within the scope of protection of this application.

[0021] If the embodiments of this application involve descriptions such as "first" or "second," such descriptions are for descriptive purposes only and should not be construed as indicating or implying their relative importance or implicitly specifying the number of technical features indicated. Furthermore, the technical solutions of various embodiments can be combined with each other, but this must be based on the ability of those skilled in the art to implement them. When the combination of technical solutions is contradictory or impossible to implement, it should be considered that such a combination of technical solutions does not exist and is not within the scope of protection claimed in this application.

[0022] As described in the background section, currently, when using olefins obtained from coal-based Fischer-Tropsch synthesis for hydroformylation to prepare aldehydes, single-phosphorus ligand catalysts or polyphosphine ligand catalysts are commonly employed. However, using single-phosphorus ligand catalysts results in a low n-to-isotropic ratio of the product aldehyde; while using polyphosphine ligand catalysts can improve the n-to-isotropic ratio of the product aldehyde, the cost of polyphosphine ligands is often higher, leading to higher aldehyde production costs. Therefore, it is currently difficult to balance the n-to-isotropic ratio of the product aldehyde and the aldehyde production cost when using olefins obtained from coal-based Fischer-Tropsch synthesis for hydroformylation to prepare aldehydes; that is, it is impossible to achieve a high n-to-isotropic ratio while simultaneously achieving low production costs.

[0023] To address this, this application provides a method for preparing aldehydes by hydroformylation of Fischer-Tropsch products. The method includes: preparing aldehydes by hydroformylation of Fischer-Tropsch products and syngas under the action of a catalyst; wherein the catalyst is prepared based on a rhodium compound, a monophosphorus ligand, and a polyphosphine ligand.

[0024] In the embodiments of this application, the catalyst is prepared based on a rhodium compound, a monophosphorus ligand, and a polyphosphine ligand. This can be understood as follows: when preparing the catalyst, a rhodium compound, a monophosphorus ligand, and a polyphosphine ligand are simultaneously added as raw materials. In specific implementations, the molar ratio of the rhodium compound, the monophosphorus ligand, and the polyphosphine ligand can be 1:(10-70):(1-2.1).

[0025] More specifically, the catalyst comprises a coordination catalyst formed by a rhodium compound, a monophosphorus ligand, and a polyphosphorus ligand; that is, the catalyst is obtained by simultaneously combining a rhodium compound with a monophosphorus ligand and a polyphosphorus ligand. In a specific implementation, the rhodium compound may be Rh(acac)(CO)2, and the catalyst may be HRh(CO)(A)2(B), wherein A is a monophosphorus ligand and B is a polyphosphorus ligand.

[0026] To improve the positive-to-negative ratio of the aldehyde product, preferably, the monophosphorus ligand can be triphenylphosphine, with the structural formula shown in Formula I, and the polyphosphorus ligand can be a polyphosphoxy-substituted hydroquinone derivative, preferably a tetraphosphine ligand, specifically a tetraphosphoxy-substituted hydroquinone derivative among polyphosphoxy-substituted hydroquinone derivatives, with the structural formula shown in Formula II.

[0027]

[0028] Formula I

[0029] In practical applications, the preparation process of tetraphosphoxy-substituted hydroquinone derivatives of Formula II can be as follows: Hydroquinone (1 mol) and excess diphenylphosphine chloride (usually 4.5~5 mol, to ensure complete reaction of the four hydroxyl groups) are dissolved in anhydrous dichloromethane (DCM) or tetrahydrofuran (THF); under the protection of an inert gas (such as argon or nitrogen), an organic base (such as triethylamine, pyridine or 4-dimethylaminopyridine (DMAP)) is slowly added as an acid-binding agent, and the reaction is stirred at 0℃ to room temperature for 4~8 hours to allow the hydroxyl groups to undergo nucleophilic substitution with the phosphoryl chloride, and the HCl generated in the substitution reaction is neutralized by the base; after the reaction is completed, the reaction solution is washed with dilute hydrochloric acid or saturated brine, the organic phase is separated, dried with anhydrous magnesium sulfate, and the solvent is removed by rotary evaporation to obtain the crude product; then, the tetraphosphoxy-substituted hydroquinone derivative is obtained by column chromatography (silica gel, eluent can be a mixture of petroleum ether or ethyl acetate) or recrystallization (such as dichloromethane / diethyl ether system).

[0030] To improve the hydrophilicity of the catalyst and ensure smooth separation of the product phase (which can be further sampled for gas chromatography analysis to determine its composition) and the catalyst phase (which can be further recycled) after the hydroformylation reaction, the monophosphorus ligand and polyphosphine ligand can be sulfonated before being used to coordinate with a rhodium compound to form a coordination catalyst. In other words, the monophosphorus ligand and polyphosphine ligand are first sulfonated, and then the catalyst is prepared based on the rhodium compound, the sulfonated monophosphorus ligand, and the sulfonated polyphosphine ligand. It is understood that A specifically refers to the sulfonated monophosphorus ligand, and B specifically refers to the sulfonated polyphosphine ligand.

[0031] In practical applications, the sulfonation process can be as follows: Under nitrogen protection, the phosphine ligand is dissolved in concentrated sulfuric acid, and then 50% fuming sulfuric acid is added dropwise at a temperature of 0-10℃. The temperature is then raised to 20-22℃ and stirred for 40-50 hours. Subsequently, the reaction solution is diluted with water and neutralized to pH 8-9 by adding 1N NaOH aqueous solution. The solution is filtered, and the filtrate is concentrated. Then, ethanol is added to remove sodium sulfate, and the mother liquor is evaporated to dryness and vacuum dried at 55-65℃ to obtain the sulfonated phosphine ligand.

[0032] It is understandable that the sulfonation process for both monophosphorus ligands and polyphosphorus ligands can be carried out in accordance with the above method.

[0033] Taking a hydroquinone derivative with triphenylphosphine as the monophosphine ligand and tetraphosphooxy-substituted polyphosphine ligand as an example, the structural formula of the sulfonated triphenylphosphine is shown in Formula III, and the structural formula of the sulfonated tetraphosphooxy-substituted hydroquinone derivative is shown in Formula IV:

[0034] Formula III

[0035] In the embodiments of this application, Formula IV refers to the Fischer-Tropsch product used for hydroformylation with syngas, specifically the C5-C11 fraction of a coal-based Fischer-Tropsch product. The composition of the C5-C11 fraction in the coal-based Fischer-Tropsch product is generally as follows: 2-5 wt% 1-pentene, 10-15 wt% 1-hexene, 15-20 wt% 1-heptene, 18-20 wt% 1-octene, 19-20 wt% 1-nonene, 0.1-1 wt% 1-decene, 0.1-1 wt% 1-undecene, 26.5-30 wt% mixed C5-C11 alkanes, 1-2 wt% mixed C5-C11 isoolefins, and 4-5 wt% oxygen-containing compounds. For example, the composition of the C5-C11 fraction in a certain coal-based Fischer-Tropsch product may be as shown in Table 1.

[0036] Table 1. Composition of C5-C11 fractions in coal-based Fischer-Tropsch products

[0037] By using the C5-C11 fraction of coal-based Fischer-Tropsch products as the Fischer-Tropsch products for hydroformylation with syngas in this application, the 1-olefins in the C5-C11 fraction can be used as olefin feedstocks for hydroformylation, thereby providing α-olefins with odd-numbered carbon chain lengths, which can improve the positive-to-iso ratio of the aldehydes in the product and broaden the product range.

[0038] In the embodiments of this application, the synthesis gas is a synthesis gas of carbon monoxide and hydrogen, and the molar ratio of carbon monoxide and hydrogen in the synthesis gas can be (0.5~1):1, more preferably 1:1.

[0039] The molar ratio of rhodium compound, monophosphorus ligand, polyphosphorus ligand and olefin in the reaction system can be 1:(10-70):(1-2.1):(8000-8500); wherein the olefin is 1-olefin in the C5-C11 fraction of coal-based Fischer-Tropsch products.

[0040] In practical applications, as shown in Figure 1, the process of preparing aldehydes by hydroformylation reaction using Fischer-Tropsch products and syngas under the action of a catalyst may include steps 101 and 102, as follows: Step 101, adding rhodium compound, monophosphorus ligand, polyphosphine ligand and Fischer-Tropsch products into a high-pressure reactor.

[0041] Step 102: Replace the air in the high-pressure reactor with syngas. After replacement, introduce syngas at a specified pressure to carry out the hydroformylation reaction.

[0042] The reaction pressure (i.e., the specified pressure) of the hydroformylation reaction can be 1~7 MPa, more preferably 2~3 MPa; the reaction temperature of the hydroformylation reaction can be 70~110℃, more preferably 100~110℃. The hydroformylation reaction is carried out under stirring conditions, the stirring rate can be 400-600 rpm, and the reaction time can be 1-8 h.

[0043] In this application, the rhodium compound, monophosphorus ligand, and polyphosphine ligand can be fed together with the Fischer-Tropsch product. That is, the reaction conditions for preparing the catalyst from the rhodium compound, monophosphorus ligand, and polyphosphine ligand can be: a reaction pressure of 1-7 MPa, more preferably 2-3 MPa; a reaction temperature of 70-110°C, more preferably 100-110°C; and the reaction is carried out in a syngas atmosphere, wherein the molar ratio of carbon monoxide to hydrogen in the syngas is (0.5-1):1, more preferably 1:1.

[0044] In practical applications, when preparing aldehydes via hydroformylation using Fischer-Tropsch products and syngas under the action of a catalyst, an auxiliary agent can be added. This auxiliary agent can be glycerol or isopropanol, which can be used to promote the fusion of the catalyst and the oil phase and improve mass transfer. The molar ratio of rhodium compounds, monophosphorus ligands, polyphosphorus ligands, olefins, and auxiliary agents in the reaction system can be 1:(10-70):(1-2.1):(8000-8500):(8300-8800).

[0045] It is understood that the method for preparing aldehydes by hydroformylation of Fischer-Tropsch products provided in the embodiments of this application includes: preparing aldehydes by hydroformylation of Fischer-Tropsch products and syngas under the action of a catalyst; wherein the catalyst is prepared based on a rhodium compound, a monophosphorus ligand, and a polyphosphine ligand. By simultaneously adding monophosphorus ligands and polyphosphine ligands to prepare the catalyst, the production cost of aldehydes can be reduced while increasing the positive-to-isophosphine ratio of the aldehyde product during the hydroformylation reaction.

[0046] In other words, by combining monophosphorus ligands and polyphosphorus ligands with rhodium compounds, the addition of polyphosphorus ligands can increase the positive-to-negative ratio of the product aldehyde. Furthermore, compared to the existing technology that only uses polyphosphorus ligand catalysts, the amount of polyphosphorus ligands used is greatly reduced, thus lowering the production cost of aldehydes and improving economic efficiency.

[0047] The solutions provided by the embodiments of this application are described below with reference to specific examples and comparative examples. It should be understood that the following embodiments are merely some specific implementation methods and do not imply an improper limitation on the solutions of this application.

[0048] In a nitrogen-protected 50 ml three-necked flask, 1 mmol of triphenylphosphine was dissolved in 5 ml of concentrated sulfuric acid. Then, 20 ml of 50% fuming sulfuric acid was added dropwise at 10 °C. The temperature was then raised to 20 °C and stirred for 48 hours. Subsequently, the reaction solution was diluted with 100 ml of water and neutralized to pH 8 by adding 1N NaOH aqueous solution. The solution was filtered, and the filtrate was concentrated to 20 ml. Then, 10 ml of ethanol was added to remove sodium sulfate. The mother liquor was evaporated to dryness and dried under vacuum at 60 °C to obtain sulfonated triphenylphosphine.

[0049] In a nitrogen-protected 50 ml three-necked flask, 1 mmol of a tetraphosphoxy-substituted hydroquinone derivative was dissolved in 5 ml of concentrated sulfuric acid. Then, 20 ml of 50% fuming sulfuric acid was added dropwise at 10 °C. The temperature was then raised to 20 °C and stirred for 48 hours. Subsequently, the reaction solution was diluted with 100 ml of water and neutralized to pH 8 by adding 1N NaOH aqueous solution. The solution was filtered, and the filtrate was concentrated to 20 ml. Then, 10 ml of ethanol was added to remove sodium sulfate. The mother liquor was evaporated to dryness and dried under vacuum at 60 °C to obtain the sulfonated tetraphosphoxy-substituted hydroquinone derivative.

[0050] Example 1: 8.5 mg of Rh(acac)(CO)2, 0.37 g of sulfonated triphenylphosphine, 0.05 g of sulfonated tetraphosphoxy-substituted hydroquinone derivative, 41.6 mL of glycerol, and 41.6 mL of Fischer-Tropsch product (composition as shown in Table 1) were added to a high-pressure reactor equipped with a temperature controller and a magnetic stirrer. P was introduced into the reactor. H2 :P CO Syngas with a molar ratio of 1:1 was used to replace air three times. Then, syngas was added to the reactor to bring the system pressure to 2 MPa. The reaction was carried out at 100°C and 500 rpm for 5 hours. The reaction was then stopped. After the reactor temperature dropped to room temperature, the pressure was released and the reactor was opened. After separation, the upper product phase was sampled for gas chromatography analysis. The analysis results are shown in Table 2.

[0051] In Example 2, 8.5 mg of Rh(acac)(CO)2, 0.66 g of sulfonated triphenylphosphine, 0.05 g of sulfonated tetraphosphoxy-substituted hydroquinone derivative, 41.6 mL of glycerol, and 41.6 mL of Fischer-Tropsch product (composition as shown in Table 1) were added to a high-pressure reactor equipped with a temperature controller and a magnetic stirrer. P was introduced into the reactor. H2 :P CO Syngas with a molar ratio of 1:1 was used to replace air three times. Then, syngas was added to the reactor to bring the system pressure to 2 MPa. The reaction was carried out at 100°C and 500 rpm for 5 hours. The reaction was then stopped. After the reactor temperature dropped to room temperature, the pressure was released and the reactor was opened. After separation, the upper product phase was sampled for gas chromatography analysis. The analysis results are shown in Table 2.

[0052] In Example 3, 8.5 mg of Rh(acac)(CO)2, 0.94 g of sulfonated triphenylphosphine, 0.05 g of sulfonated tetraphosphoxy-substituted hydroquinone derivative, 41.6 mL of glycerol, and 41.6 mL of Fischer-Tropsch product (composition as shown in Table 1) were added to a high-pressure reactor equipped with a temperature controller and a magnetic stirrer. P was introduced into the reactor. H2 :P COSyngas with a molar ratio of 1:1 was used to replace air three times. Then, syngas was added to the reactor to bring the system pressure to 2 MPa. The reaction was carried out at 100°C and 500 rpm for 5 hours. The reaction was then stopped. After the reactor temperature dropped to room temperature, the pressure was released and the reactor was opened. After separation, the upper product phase was sampled for gas chromatography analysis. The analysis results are shown in Table 2.

[0053] In Example 4, 8.5 mg of Rh(acac)(CO)2, 1.12 g of sulfonated triphenylphosphine, 0.05 g of sulfonated tetraphosphoxy-substituted hydroquinone derivative, 41.6 mL of glycerol, and 41.6 mL of Fischer-Tropsch product (composition as shown in Table 1) were added to a high-pressure reactor equipped with a temperature controller and a magnetic stirrer. P was introduced into the reactor. H2 :P CO Syngas with a molar ratio of 1:1 was used to replace air three times. Then, syngas was added to the reactor to bring the system pressure to 2 MPa. The reaction was carried out at 100°C and 500 rpm for 5 hours. The reaction was then stopped. After the reactor temperature dropped to room temperature, the pressure was released and the reactor was opened. After separation, the upper product phase was sampled for gas chromatography analysis. The analysis results are shown in Table 2.

[0054] In Example 5, 8.5 mg of Rh(acac)(CO)2, 0.94 g of sulfonated triphenylphosphine, 0.03 g of sulfonated tetraphosphoxy-substituted hydroquinone derivative, 41.6 mL of glycerol, and 41.6 mL of Fischer-Tropsch product (composition as shown in Table 1) were added to a high-pressure reactor equipped with a temperature controller and a magnetic stirrer. P was introduced into the reactor. H2 :P CO Syngas with a molar ratio of 1:1 was used to replace air three times. Then, syngas was added to the reactor to bring the system pressure to 2 MPa. The reaction was carried out at 100°C and 500 rpm for 5 hours. The reaction was then stopped. After the reactor temperature dropped to room temperature, the pressure was released and the reactor was opened. After separation, the upper product phase was sampled for gas chromatography analysis. The analysis results are shown in Table 2.

[0055] In Example 6, 8.5 mg of Rh(acac)(CO)2, 0.94 g of sulfonated triphenylphosphine, 0.05 g of sulfonated tetraphosphoxy-substituted hydroquinone derivative, 41.6 mL of glycerol, and 41.6 mL of Fischer-Tropsch product (composition as shown in Table 1) were added to a high-pressure reactor equipped with a temperature controller and a magnetic stirrer. P was introduced into the reactor. H2 :P COSyngas with a molar ratio of 1:1 was used to replace air three times. Then, syngas was added to the reactor to bring the system pressure to 2 MPa. The reaction was carried out at 100°C and 500 rpm for 5 hours. The reaction was then stopped. After the reactor temperature dropped to room temperature, the pressure was released and the reactor was opened. After separation, the upper product phase was sampled for gas chromatography analysis. The analysis results are shown in Table 2.

[0056] In Example 7, 8.5 mg of Rh(acac)(CO)2, 0.94 g of sulfonated triphenylphosphine, 0.06 g of sulfonated tetraphosphoxy-substituted hydroquinone derivative, 41.6 mL of glycerol, and 41.6 mL of Fischer-Tropsch product (composition as shown in Table 1) were added to a high-pressure reactor equipped with a temperature controller and a magnetic stirrer. P was introduced into the reactor. H2 :P CO Syngas with a molar ratio of 1:1 was used to replace air three times. Then, syngas was added to the reactor to bring the system pressure to 2 MPa. The reaction was carried out at 100°C and 500 rpm for 5 hours. The reaction was then stopped. After the reactor temperature dropped to room temperature, the pressure was released and the reactor was opened. After separation, the upper product phase was sampled for gas chromatography analysis. The analysis results are shown in Table 2.

[0057] In Example 8, 8.5 mg of Rh(acac)(CO)2, 0.94 g of sulfonated triphenylphosphine, 0.05 g of sulfonated tetraphosphoxy-substituted hydroquinone derivative, 41.6 mL of glycerol, and 41.6 mL of Fischer-Tropsch product (composition as shown in Table 1) were added to a high-pressure reactor equipped with a temperature controller and a magnetic stirrer. P was introduced into the reactor. H2 :P CO Syngas with a molar ratio of 1:1 was used to replace air three times. Then, syngas was added to the reactor to make the system pressure 2 MPa. The reaction was carried out at 80℃ and 500 rpm for 5 hours. The reaction was then stopped. After the reactor temperature dropped to room temperature, the pressure was released and the reactor was opened. After separation, the upper product phase was sampled for gas chromatography analysis. The analysis results are shown in Table 2.

[0058] In Example 9, 8.5 mg of Rh(acac)(CO)2, 0.94 g of sulfonated triphenylphosphine, 0.05 g of sulfonated tetraphosphoxy-substituted hydroquinone derivative, 41.6 mL of glycerol, and 41.6 mL of Fischer-Tropsch product (composition as shown in Table 1) were added to a high-pressure reactor equipped with a temperature controller and a magnetic stirrer. P was introduced into the reactor. H2 :P COSyngas with a molar ratio of 1:1 was used to replace air three times. Then, syngas was added to the reactor to make the system pressure 2 MPa. The reaction was carried out at 110℃ and 500 rpm for 5 hours. The reaction was then stopped. After the reactor temperature dropped to room temperature, the pressure was released and the reactor was opened. After separation, the upper product phase was sampled for gas chromatography analysis. The analysis results are shown in Table 2.

[0059] Example 10: 8.5 mg of Rh(acac)(CO)2, 0.94 g of sulfonated triphenylphosphine, 0.05 g of sulfonated tetraphosphoxy-substituted hydroquinone derivative, 41.6 mL of glycerol, and 41.6 mL of Fischer-Tropsch product (composition as shown in Table 1) were added to a high-pressure reactor equipped with a temperature controller and a magnetic stirrer. P was introduced into the reactor. H2 :P CO Syngas with a molar ratio of 1:1 was used to replace air three times. Then, syngas was added to the reactor to make the system pressure 1 MPa. The reaction was carried out at 100℃ and 500 rpm for 5 hours. The reaction was then stopped. After the reactor temperature dropped to room temperature, the pressure was released and the reactor was opened. After separation, the upper product phase was sampled for gas chromatography analysis. The analysis results are shown in Table 2.

[0060] Example 11: 8.5 mg of Rh(acac)(CO)2, 0.94 g of sulfonated triphenylphosphine, 0.05 g of sulfonated tetraphosphoxy-substituted hydroquinone derivative, 41.6 mL of glycerol, and 41.6 mL of Fischer-Tropsch product (composition as shown in Table 1) were added to a high-pressure reactor equipped with a temperature controller and a magnetic stirrer. P was introduced into the reactor. H2 :P CO Syngas with a molar ratio of 1:1 was used to replace air three times. Then, syngas was added to the reactor to make the system pressure 3 MPa. The reaction was carried out at 100℃ and 500 rpm for 5 hours. The reaction was then stopped. After the reactor temperature dropped to room temperature, the pressure was released and the reactor was opened. After separation, the upper product phase was sampled for gas chromatography analysis. The analysis results are shown in Table 2.

[0061] Example 12: 8.5 mg of Rh(acac)(CO)2, 0.94 g of sulfonated triphenylphosphine, 0.05 g of sulfonated tetraphosphoxy-substituted hydroquinone derivative, 41.6 mL of glycerol, and 41.6 mL of Fischer-Tropsch product (composition as shown in Table 1) were added to a high-pressure reactor equipped with a temperature controller and a magnetic stirrer. P was introduced into the reactor. H2 :P COSyngas with a molar ratio of 1:1 was used to replace air three times. Then, syngas was added to the reactor to make the system pressure 2 MPa. The reaction was carried out at 100℃ and 500 rpm for 3 hours. The reaction was then stopped. After the reactor temperature dropped to room temperature, the pressure was released and the reactor was opened. After separation, the upper product phase was sampled for gas chromatography analysis. The analysis results are shown in Table 2.

[0062] Example 13: 8.5 mg of Rh(acac)(CO)2, 0.94 g of sulfonated triphenylphosphine, 0.05 g of sulfonated tetraphosphoxy-substituted hydroquinone derivative, 41.6 mL of glycerol, and 41.6 mL of Fischer-Tropsch product (composition as shown in Table 1) were added to a high-pressure reactor equipped with a temperature controller and a magnetic stirrer. P was introduced into the reactor. H2 :P CO Syngas with a molar ratio of 1:1 was used to replace air three times. Then, syngas was added to the reactor to make the system pressure 2 MPa. The reaction was carried out at 100℃ and 500 rpm for 7 hours. The reaction was then stopped. After the reactor temperature dropped to room temperature, the pressure was released and the reactor was opened. After separation, the upper product phase was sampled for gas chromatography analysis. The analysis results are shown in Table 2.

[0063] Example 14 (Cyclic Test): After removing the upper product phase from the reaction product obtained in Example 6 using a separatory funnel, the lower catalyst phase was transferred to a high-pressure reactor. 41.6 mL of the Fischer-Tropsch product (composition as shown in Table 1) was added, and P was introduced into the reactor. H2 :P CO Syngas was added at a ratio of 1:1, and air was replaced three times. Then, 2 MPa of syngas was added to the reactor. The reaction was carried out at 100℃ and 500 rpm for 5 hours. The reaction was then stopped. After the reactor temperature dropped to room temperature, the pressure was released and the reactor was opened. After separation, the upper product phase was sampled for gas chromatography analysis. This operation was repeated 7 times. The analysis results are shown in Table 2.

[0064] Comparative Example 1: 8.5 mg of Rh(acac)(CO)2, 0.94 g of sulfonated triphenylphosphine, 41.6 mL of glycerol, and 41.6 mL of Fischer-Tropsch product (composition as shown in Table 1) were added to a high-pressure reactor equipped with a temperature controller and a magnetic stirrer. P was introduced into the reactor. H2 :P CO Syngas with a molar ratio of 1:1 was used to replace air three times. Then, syngas was added to the reactor to make the system pressure 1 MPa. The reaction was carried out at 100℃ and 500 rpm for 5 hours. The reaction was then stopped. After the reactor temperature dropped to room temperature, the pressure was released and the reactor was opened. After separation, the upper product phase was sampled for gas chromatography analysis. The analysis results are shown in Table 2.

[0065] Comparative Example 2: 8.5 mg of Rh(acac)(CO)2, 0.05 g of sulfonated tetraphosphoxy-substituted hydroquinone derivative, 41.6 mL of glycerol, and 41.6 mL of Fischer-Tropsch product (composition as shown in Table 1) were added to a high-pressure reactor equipped with a temperature controller and a magnetic stirrer. P was introduced into the reactor. H2 :P CO Syngas with a molar ratio of 1:1 was used to replace air three times. Then, syngas was added to the reactor to make the system pressure 1 MPa. The reaction was carried out at 100℃ and 500 rpm for 5 hours. The reaction was then stopped. After the reactor temperature dropped to room temperature, the pressure was released and the reactor was opened. After separation, the upper product phase was sampled for gas chromatography analysis. The analysis results are shown in Table 2.

[0066] Table 2 Analysis Results

[0067] The results of Examples 1, 2, 3, and 4 show that the yield of the aldehyde product is higher when the mass ratio of sulfonated triphenylphosphine to Rh(acac)(CO)2 is 110.6. The results of Examples 5, 6, and 7 show that the yield of the aldehyde product is higher when the mass ratio of sulfonated tetraphosphoxy-substituted hydroquinone derivative to Rh(acac)(CO)2 is 5.9. However, when the mass ratio of sulfonated tetraphosphoxy-substituted hydroquinone derivative to Rh(acac)(CO)2 is 3.5 (Example 5), the normal-to-isotropic ratio of the aldehyde product is only 15.3. The results of Examples 6, 8, and 9 show that the yield of the aldehyde product is higher at a temperature of 110°C, indicating that a reaction temperature of 110°C is favorable for the reaction of olefins. However, at this temperature, the catalyst phase is darker in color (severe oxidation), which is not conducive to catalyst recovery. The results of Examples 6, 10, and 11 show that the yield of the aldehyde product is higher at a pressure of 2 MPa. The results from Examples 6, 12, and 13 show that increasing the reaction time increases the olefin conversion rate, but decreases the selectivity; the yield is actually higher after 5 hours of reaction. The results from Example 14 show that the catalyst has good reproducibility and can be recycled with minimal rhodium loss during recycling. Furthermore, compared to the separation method using homogeneous catalysts, the separation method using this aqueous catalyst is simpler and more economical. The results from Comparative Example 1 show that the N / I ratio of triphenylphosphine alone is only 2.5. The results from Comparative Example 2 show that the yield of the aldehyde product from the tetraphosphoxy-substituted hydroquinone derivative alone is only 51.4%. Therefore, the effect of using triphenylphosphine alone or the tetraphosphoxy-substituted hydroquinone derivative alone is not as good as using them together. Moreover, the raw materials for synthesizing the tetraphosphoxy-substituted hydroquinone derivative are difficult to synthesize and expensive, while the raw materials for synthesizing triphenylphosphine are commercially available, inexpensive, and readily available. Adding a small amount of the tetraphosphoxy-substituted hydroquinone derivative can achieve better results (N / I ratio > 25). Therefore, this method has certain economic and high efficiency.

[0068] It should also be noted that 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.

[0069] The terms “comprising,” “including,” or any other variations thereof are intended to cover non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements includes not only those elements but also other elements not expressly listed, or elements inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase “comprising one…” does not exclude the presence of other identical elements in the process, method, article, or apparatus that includes that element.

[0070] The above are merely embodiments of this application and are not intended to limit the scope of this application. Various modifications and variations can be made to this application by those skilled in the art. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of this application should be included within the scope of the claims of this application.

Claims

1. A method for preparing aldehydes by hydroformylation of Fischer-Tropsch products, characterized in that, The method includes: preparing aldehydes by hydroformylation of Fischer-Tropsch products and syngas under the action of a catalyst; wherein the catalyst is prepared based on rhodium compounds, monophosphorus ligands and polyphosphine ligands.

2. The method for preparing aldehydes by hydroformylation of Fischer-Tropsch products according to claim 1, characterized in that, The catalyst is a coordination catalyst formed by a rhodium compound, a single phosphorus ligand, and a polyphosphine ligand.

3. The method for preparing aldehydes by hydroformylation of Fischer-Tropsch products according to claim 2, characterized in that, The rhodium compound is Rh(acac)(CO)2, and the catalyst is HRh(CO)(A)2(B), wherein A is a monophosphorus ligand and B is a polyphosphorus ligand.

4. The method for preparing aldehydes by hydroformylation of Fischer-Tropsch products according to claim 1, characterized in that, The polyphosphine ligand is a tetraphosphine ligand.

5. The method for preparing aldehydes by hydroformylation of Fischer-Tropsch products according to claim 4, characterized in that, The monophosphorus ligand and the tetraphosphine ligand are sulfonated and then reacted with rhodium compounds to prepare a catalyst.

6. The method for preparing aldehydes by hydroformylation of Fischer-Tropsch products according to claim 5, characterized in that, The structural formula of the sulfonated monophosphorus ligand is shown below: The structural formula of the sulfonated tetraphosphine ligand is shown below: 。 7. The method for preparing aldehydes by hydroformylation of Fischer-Tropsch products according to claim 1, characterized in that, In preparing the catalyst, the molar ratio of the rhodium compound, the monophosphorus ligand, and the polyphosphorus ligand is 1:(10-70):(1-2.1).

8. The method for preparing aldehydes by hydroformylation of Fischer-Tropsch products according to claim 1, characterized in that, The molar ratio of rhodium compound, monophosphorus ligand, polyphosphorus ligand and olefin is 1:(10-70):(1-2.1):(8000-8500), wherein the olefin is 1-olefin in the C5-C11 fraction of the Fischer-Tropsch product.

9. The method for preparing aldehydes by hydroformylation of Fischer-Tropsch products according to claim 1, characterized in that, In the preparation of aldehydes by hydroformylation reaction using Fischer-Tropsch products and syngas under the action of a catalyst, an auxiliary agent is also added, namely glycerol or isopropanol.

10. The method for preparing aldehydes by hydroformylation of Fischer-Tropsch products according to claim 1, characterized in that, The hydroformylation reaction is carried out at a pressure of 1-7 MPa and a temperature of 70-110 °C. The hydroformylation reaction is carried out under stirring conditions at a stirring rate of 400-600 rpm and a reaction time of 1-8 h.

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