Method and product for preparing aldehydes by hydroformylation of Fischer-Tropsch oil

Abstract

The present invention provides a method and product for preparing aldehyde by hydroformylation reaction of Fischer-Tropsch oil. The method includes: under the action of a catalyst and a nonionic surfactant, in a synthesis gas environment, using normal olefins as raw materials, and carrying out hydroformylation reaction in a solvent to prepare aldehyde, wherein the catalyst includes a rhodium compound and a bisphosphine ligand, the solvent includes water, and the carbon number of the normal olefin is 8-12. The nonionic surfactant used in the present application not only improves the solubility of olefins in water, increases the two-phase mass transfer rate, but also increases the coordination of olefins and catalytically active substances; using bisphosphine as a phosphine ligand, by adding a mixed nonionic surfactant, the catalyst can be well fixed in the water phase, so that the catalyst has good recycling performance; the nonionic surfactant of the present application is matched with a rhodium catalyst and a bisphosphine ligand, and is used in the hydroformylation reaction of Fischer-Tropsch oil, and has the characteristics of high conversion rate, good selectivity, and high number of catalyst recycling times.

Description

Technical Field

[0001] The invention relates to the technical field of preparation of higher carbon alcohols, and in particular to a method and product for preparing aldehydes by hydroformylation of Fischer-Tropsch oil. Background Art

[0002] Fischer-Tropsch oil has a high olefin content, a complete and continuous carbon number distribution, a high content of straight-chain alkanes, and extremely low sulfur, nitrogen and diolefins. It is a high-quality raw material for the development of the downstream industry of α-olefins, especially high-carbon olefins. At present, the market demand for synthetic detergent alcohol products in my country is large and has broad development prospects. Converting Fischer-Tropsch oil into high-carbon aldehyde products through hydroformylation can not only improve the economic benefits of Fischer-Tropsch oil, but also increase product diversification.

[0003] At present, in industry, the hydroformylation reaction process of high carbon olefins is mainly divided into homogeneous catalysis and two-phase catalysis. The Chinese patent application with application number 202010585946.4 provides a method for the hydroformylation of high carbon olefins with a carbon number ≥ 8. By adding formamide, N-methylformamide, N,N-dimethylformamide, etc. as solvents, a water-soluble phosphine ligand and a rhodium catalyst form a catalytic system, which improves the conversion rate and selectivity of the reaction, but there is still a problem of large amount of solubilizer used.

[0004] The patent application with application number 202010362103.8 provides a composition and method for preparing aldehydes by two-phase catalytic hydroformylation. By adding a new cationic phosphine ligand, the hydroformylation reaction of olefins is catalyzed. Although the solubility of olefins in water is improved and the activity of the catalyst is increased, the reaction process of synthesizing the ligand is complicated and costly, which is not conducive to industrial production.

[0005] The Chinese patent application No. 202110038259.5 provides a method for preparing aldehyde compounds by two-phase hydroformylation of olefins. The use of asymmetric quaternary ammonium salt-type gemini surfactants for two-phase catalytic hydroformylation to prepare aldehydes can significantly improve the conversion rate of olefins and the selectivity of aldehydes, but the synthesis process of asymmetric quaternary ammonium salt-type gemini surfactants is complicated and has poor economic efficiency.

[0006] Chinese patent application No. 200810045977.X provides a method for preparing aldehydes by hydroformylation of olefins, using a di-long chain surfactant and a water-soluble rhodium phosphine catalyst to carry out hydroformylation of butene. After the reaction, no emulsion layer will appear between the product and the catalyst, but it is only applicable to low-carbon olefins.

[0007] Although homogeneous catalysis has the advantages of fast reaction rate and high activity, it is difficult to separate the catalyst and the product, and the distillation method used for separation can easily deactivate the catalyst, making it difficult to achieve the recycling of the catalyst. In order to overcome the shortcomings of homogeneous reactions, two-phase catalysis has been developed. In the two-phase catalytic system, the olefin hydroformylation reaction catalyzed by water-soluble rhodium phosphine complexes in the water / organic two-phase system has attracted widespread attention due to its advantages such as environmental friendliness and easy separation of the catalyst. Among them, the water-soluble catalyst system has been used for the industrial production of butyraldehyde by propylene hydroformylation reaction. However, for the hydroformylation reaction of high-carbon olefins, the reaction rate of the system is low due to the low solubility of olefins in water in the two-phase catalyst. In order to increase the reaction rate, researchers added cationic surfactants, anionic surfactants, additives, new phosphine ligands, etc. to the system. Although the mass transfer problem of high-carbon olefins in water can be solved, there are still shortcomings such as emulsification leading to difficult separation, catalysts are not easy to recycle, and high cost. Therefore, it is necessary to improve the types of additives to solve the limitations of the industrial production of high-carbon olefin hydroformylation reaction in the water / organic two-phase system. Summary of the invention

[0008] The main purpose of the present invention is to provide a method and product for preparing aldehydes by hydroformylation of Fischer-Tropsch oil, so as to solve the problems of low reaction rate and high cost in preparing aldehydes by high carbon olefins in the prior art.

[0009] In order to achieve the above-mentioned object, according to one aspect of the present invention, a method for preparing aldehyde by hydroformylation reaction of Fischer-Tropsch oil is provided, the method comprising: in the presence of a catalyst and a non-ionic surfactant, in a synthesis gas environment, using normal olefins as raw materials, and carrying out a hydroformylation reaction in a solvent to prepare aldehyde, wherein the catalyst comprises a rhodium compound and a diphosphine ligand, the solvent comprises water, and the number of carbon atoms of the normal olefins is 8-12.

[0010] Furthermore, the nonionic surfactant is a mixed nonionic surfactant, and preferably the mixed nonionic surfactant includes any one or more of polyethylene glycol 200, ethylene glycol, polyethylene glycol 400, polyethylene glycol 600, glycerol, polyethylene glycol 800, fatty alcohol polyoxyethylene ether, polypropylene glycol and diethylene glycol; preferably, the volume ratio of the nonionic surfactant to the solvent is 10:1-1:4.

[0011] Furthermore, an inorganic salt demulsifier is added to the nonionic surfactant, and preferably the inorganic salt demulsifier includes any one or more of sodium sulfite, sodium sulfate and sodium chloride;

[0012] Preferably, the addition amount of the inorganic salt demulsifier is 0.01-0.15 wt % of the nonionic surfactant.

[0013] Further, the bisphosphine ligand includes any one or more of Xantphos, NORBOS and BINAS;

[0014] Preferably, the bisphosphine ligand is sulfonated with oleum before being used in the hydroformylation reaction.

[0015] Further, the rhodium compound is selected from any one or more of hydrated rhodium trichloride, dicarbonyl rhodium acetylacetonate, tris(sodium triphenylphosphine tris-metasulfonate) carbonyl rhodium hydride and divinyl rhodium acetylacetonate;

[0016] Preferably, the molar ratio of the rhodium compound to the phosphine ligand is 1:5-1:20;

[0017] Preferably, the molar ratio of normal olefin to rhodium compound is 500-1000:1;

[0018] Preferably, the concentration of the rhodium compound in the aqueous phase is 150-350 ppm.

[0019] Furthermore, the raw material is Fischer-Tropsch oil, preferably the raw material is Fischer-Tropsch oil in the C8-C12 fraction, preferably, the Fischer-Tropsch oil is deacidified, and more preferably the acid value of the Fischer-Tropsch oil is ≤0.03 mg KOH / g.

[0020] Furthermore, the volume ratio of the Fischer-Tropsch oil to the solvent is 1:1-1:10.

[0021] Furthermore, the volume ratio of CO and H2 in the synthesis gas is 0.5-1:1.

[0022] Furthermore, the reaction temperature of the hydroformylation reaction is 85-120° C., the reaction pressure of the hydroformylation reaction is preferably 1-5 MPa, and the reaction time of the hydroformylation reaction is preferably 2-10 h.

[0023] According to another aspect of the present invention, an aldehyde product is provided. The aldehyde product is prepared by any one of the above preparation methods.

[0024] The technical scheme of the present invention is applied, and the nonionic surfactant is used to not only improve the solubility of olefins in water, increase the two-phase mass transfer rate, but also increase the coordination of olefins and catalytic active substances; using diphosphine as a phosphine ligand, by adding a mixed nonionic surfactant, the catalyst can be well fixed in the water phase, so that the catalyst has a good recycling performance; further, the nonionic surfactant of the present application is matched with a rhodium catalyst and a diphosphine ligand, and applied to the hydroformylation reaction of Fischer-Tropsch oil, which has the characteristics of high conversion rate, good selectivity, and high number of catalyst recycling, and the nonionic surfactant is not only low in usage, cheap and easy to obtain, and green and environmentally friendly. Especially when the normal olefins in Fischer-Tropsch oil are used as the reaction raw materials, the normal olefins in Fischer-Tropsch oil are obtained by the hydroformylation reaction to obtain the corresponding aldehydes through the method of the present application, and then separated from the system, so that the separation from isoolefins and alkanes becomes simple, which is conducive to improving the application value of Fischer-Tropsch oil and reducing costs. DETAILED DESCRIPTION

[0025] It should be noted that, in the absence of conflict, the embodiments and features in the embodiments of the present application can be combined with each other. The present invention will be described in detail below in conjunction with the embodiments.

[0026] As analyzed in the background technology of the present application, the prior art has the problems of low reaction rate and high cost in preparing aldehydes by high-carbon olefins. In order to solve this problem, the present application provides a method and product for preparing aldehydes by hydroformylation reaction of Fischer-Tropsch oil.

[0027] According to a typical embodiment of the present application, a method for preparing aldehydes by hydroformylation of Fischer-Tropsch oil is provided, the method comprising: carrying out a hydroformylation reaction in a solvent to prepare aldehydes with normal olefins as raw materials in the presence of a catalyst and a non-ionic surfactant in a synthesis gas environment, wherein the catalyst comprises a rhodium compound and a diphosphine ligand, the solvent comprises water, and the number of carbon atoms of the normal olefins is 8-12.

[0028] The application adopts nonionic surfactants to not only improve the solubility of olefins in water, increase the two-phase mass transfer rate, but also increase the coordination of olefins and catalytic active substances; using diphosphine as a phosphine ligand, by adding mixed nonionic surfactants, the catalyst can be well fixed in the water phase, so that the catalyst has good recycling performance; further, the nonionic surfactant of the application of the application is matched with a rhodium catalyst and a diphosphine ligand, and applied to the hydroformylation reaction of Fischer-Tropsch oil, with high conversion rate, good selectivity, high number of catalyst recycling, and nonionic surfactants are not only low in usage, cheap and easy to obtain, green and environmentally friendly. Especially when the normal olefins in Fischer-Tropsch oil are used as reaction raw materials, the normal olefins in Fischer-Tropsch oil are obtained by hydroformylation reaction to obtain corresponding aldehydes by the method of the application, and then separated from the system, so that the separation from isoolefins and alkanes becomes simple, which is conducive to improving the application value of Fischer-Tropsch oil and reducing costs.

[0029] In some typical embodiments of the present application, the above-mentioned non-ionic surfactant is a mixed non-ionic surfactant, that is, the reaction system contains two or more non-ionic surfactants. The researchers of the present application found in their studies that the use of mixed non-ionic surfactants not only further improves the solubility of olefins in water and increases the two-phase mass transfer rate, but also significantly increases the coordination of olefins and catalytically active species, thereby significantly improving the selectivity of the target product and the conversion rate of olefins in Fischer-Tropsch oil, and also has a relatively obvious improvement in the recyclability of the catalyst.

[0030] In the above-mentioned mixed nonionic surfactants, there is no special requirement for the content of one of the nonionic surfactants. In some embodiments of the present application, the volume content of a single nonionic surfactant is 1% to 95%; in some embodiments of the present application, the volume content of a single nonionic surfactant is 5% to 90%, and the effect is more obvious. In some embodiments of the present application, the volume content of a single nonionic surfactant is 5% to 85%. In some embodiments of the present application, the volume content of a single nonionic surfactant is 1% to 80%. In some embodiments of the present application, the volume content of a single nonionic surfactant is 1% to 70%. In some embodiments of the present application, the volume content of a single nonionic surfactant is 1% to 65%. In some embodiments of the present application, the volume content of a single nonionic surfactant is 1% to 60%.

[0031] The mixed nonionic surfactant is used for the hydroformylation reaction of Fischer-Tropsch oil, which has the characteristics of high conversion rate, good selectivity, and high catalyst recycling times. In some embodiments of the present application, the conversion rate of normal olefins in Fischer-Tropsch oil reaches 85%, the aldehyde selectivity reaches about 95%, and the catalyst can be recycled more than 40 times. Among them, normal olefins refer to olefins without branches, and correspondingly, isoolefins are olefins with branches.

[0032] The above-mentioned nonionic surfactant can be selected from the prior art without special requirements. In some preferred embodiments of the present application, the above-mentioned mixed nonionic surfactant includes any one or more of polyethylene glycol 200, ethylene glycol, polyethylene glycol 400, polyethylene glycol 600, glycerol, polyethylene glycol 800, fatty alcohol polyoxyethylene ether, polypropylene glycol and diethylene glycol, especially when two or more of the above-mentioned nonionic surfactants are included, the promoting effect on the reaction effect is more significant.

[0033] In some embodiments of the present application, the volume ratio of the nonionic surfactant to the solvent is 10:1-1:4, which has a more obvious promoting effect on the hydroformylation reaction.

[0034] In order to prevent the organic phase and the aqueous phase in the system from emulsifying, increase the difficulty of separating the two phases, and affect the recycling of the catalyst, in some embodiments of the present application, an inorganic salt demulsifier is added to the non-ionic surfactant, which can effectively solve the above problems. The inorganic salt demulsifier can be selected from the prior art, such as any one or more of sodium sulfite, sodium sulfate and sodium chloride. Preferably, the addition amount of the inorganic salt demulsifier is 0.01-0.15wt% of the non-ionic surfactant, and the demulsification effect is good, which can facilitate the separation of the two phases and reduce the catalyst loss.

[0035] In some typical embodiments of the present application, the above-mentioned bisphosphine ligand includes any one or more of Xantphos, NORBOS and BINAS, as shown in formulas (1), (2) and (3), respectively. The use of the above-mentioned bisphosphine ligand can significantly improve the selectivity of the catalyst and the conversion rate of the raw materials, and improve the yield of the target aldehydes.

[0036]

[0037] In some embodiments of the present application, the diphosphine ligand is sulfonated with oleum before being used in the hydroformylation reaction, which can improve the reaction activity of the ligand and further improve the efficiency of the hydroformylation reaction.

[0038] The above-mentioned rhodium compound can be selected in the prior art. In some preferred embodiments of the present application, the rhodium compound is selected from any one or more of hydrated rhodium trichloride, dicarbonyl rhodium acetylacetonate, tris(sodium triphenylphosphine tris-sulfonate) carbonyl hydrogenated rhodium and divinyl rhodium acetylacetonate, which can better play a synergistic role with the above-mentioned phosphorus ligands, further improving the selectivity of the hydroformylation reaction and the conversion rate of the Fischer-Tropsch oil raw material. Preferably, the molar ratio of the rhodium compound to the phosphine ligand is 1:5-1:20, which has a good catalytic effect and further improves the yield and reaction rate of the target product. Preferably, the molar ratio of normal olefins to rhodium compounds is 500-1000:1; preferably, the concentration of the rhodium compound in the aqueous phase is 150-350ppm, that is, the weight of the rhodium compound per kg of aqueous phase liquid is 0.15-0.35g.

[0039] In some typical embodiments of the present application, the above-mentioned normal olefins are normal olefins in Fischer-Tropsch oil, that is, Fischer-Tropsch oil is directly used as the raw material for the reaction, preferably Fischer-Tropsch oil of the C8-C12 fraction, with a high conversion rate of normal olefins with this number of carbon atoms, and good reaction selectivity, and the target product has good application value. In some embodiments of the present application, the content of normal alkanes in Fischer-Tropsch oil is 25-40%, the content of normal olefins is 25-60%, the content of isoolefins is 10-25%, and the content of oxygen-containing compounds is 1-5%.

[0040] In order to facilitate the separation and purification of the reaction product at room temperature, in some embodiments of the present application, the Fischer-Tropsch oil is deacidified, and the deacidification method can be selected from the prior art, such as alkaline solution washing. Preferably, the acid value of the Fischer-Tropsch oil used as the reaction raw material is ≤0.03mg KOH / g.

[0041] In some embodiments of the present application, in order to further improve the reaction rate and the yield of the target aldehydes, the volume ratio of the raw material Fischer-Tropsch oil to the solvent is 1:1-1:10. The above-mentioned synthesis gas can be selected from the prior art, and the volume ratio of CO and H2 in the synthesis gas is preferably 0.5-1:1, which helps to further improve the selectivity.

[0042] In some typical embodiments of the present application, the reaction temperature of the hydroformylation reaction is 85-120° C., with a high normal olefin conversion rate and aldehyde yield. Preferably, the reaction pressure of the hydroformylation reaction is 1-5 MPa, and the reaction time of the hydroformylation reaction is 2-10 h.

[0043] According to another typical embodiment of the present application, an aldehyde product is provided, and the aldehyde product is prepared by any of the above-mentioned preparation methods. The present application adopts nonionic surfactants to not only improve the solubility of olefins in water, increase the two-phase mass transfer rate, but also increase the coordination of olefins and catalytic active substances; using diphosphine as a phosphine ligand, by adding mixed nonionic surfactants, the catalyst can be well fixed in the water phase, so that the catalyst has good recycling performance; further, the nonionic surfactant of the present application of the present application is matched with a rhodium catalyst and a diphosphine ligand, and applied to the hydroformylation reaction of Fischer-Tropsch oil, which has the characteristics of high conversion rate, good selectivity, and high number of catalyst recycling, and the nonionic surfactant is not only low in usage, cheap and easy to obtain, but also green and environmentally friendly. Especially when the normal olefins in Fischer-Tropsch oil are used as the reaction raw materials, the normal olefins in Fischer-Tropsch oil are obtained by hydroformylation reaction to obtain the corresponding aldehydes, and then separated from the system, so that the separation from isoolefins and alkanes becomes simple, which is conducive to improving the application value of Fischer-Tropsch oil and reducing costs.

[0044] The beneficial effects that can be achieved by the present application will be further illustrated below in combination with embodiments and comparative examples.

[0045] Example 1

[0046] Acetylacetonato dicarbonyl rhodium, sulfonated phosphine ligand Xantphos (Formula 1), a mixed nonionic surfactant (PEG400 and PEG600, the volume ratio of PEG400 and PEG600 is 1:1, 0.05g sodium sulfite, accounting for 1 / 800 of the weight ratio of the mixed nonionic surfactant), water as a solvent, and deacidified C10-C12 fraction (acid value 0.021mg KOH / g, normal olefins 43.6%, isoolefins 15.8%, alkanes 33.8%) Fischer-Tropsch oil in a volume ratio of 1:1 (volume ratio of water phase to oil phase) are placed in a high-pressure reactor, wherein the molar ratio of rhodium catalyst:phosphine ligand is 1:7, the volume ratio of the mixed nonionic surfactant to water is 8:2, and the molar ratio of the rhodium catalyst to the normal olefins in the raw material Fischer-Tropsch oil is 1:650. Synthesis gas (CO:H2=1:1) was introduced to replace the air in the kettle, and then synthesis gas was introduced to maintain the pressure in the kettle at 2MPa. The temperature was raised to 100°C, and the reaction was stirred at constant temperature and pressure for 5 hours. The reaction was stopped, cooled to room temperature, the pressure was released, the mixture was taken out, the upper layer was separated and measured by gas chromatography. After the measurement, the normal olefin conversion rate was 93.35%, the selectivity was 95.31%, the yield was 88.97%, and the catalyst loss was 0.03ppm.

[0047] Example 2

[0048] Acetylacetonate dicarbonyl rhodium, sulfonated phosphine ligand Xantphos, a mixed nonionic surfactant (PEG400 and glycerol in a volume ratio of 1:1, 0.05g sodium chloride, accounting for 1 / 800 of the weight ratio of the mixed nonionic surfactant), water as a solvent, and the Fischer-Tropsch oil of the C10-C12 fraction after deacidification (the same as in Example 1) are added into a high-pressure reactor in a volume ratio of 1:1, wherein the molar ratio of rhodium catalyst: phosphine ligand is 1:7, PEG400 and glycerol are 2:1, the volume ratio of the mixed nonionic surfactant to water is 7:3, and the molar ratio of the rhodium catalyst to the normal olefins in the raw Fischer-Tropsch oil is 1:650. Synthesis gas (CO:H2=1:1) was introduced to replace the air in the kettle, and then synthesis gas was introduced to maintain the pressure in the kettle at 2MPa. The temperature was raised to 100°C, and the reaction was stirred at constant temperature and pressure for 5 hours. The reaction was stopped, cooled to room temperature, the pressure was released, the mixture was taken out, the upper layer was separated and measured by gas chromatography. After the measurement, the normal olefin conversion rate was 85.62%, the selectivity was 97.08%, the yield was 83.12%, and the catalyst loss was 0.09ppm.

[0049] Example 3

[0050] Acetylacetonate dicarbonyl rhodium, sulfonated phosphine ligand BINAS, a mixed non-ionic surfactant (AEO-9 and ethylene glycol in a volume ratio of 1:1, 0.05 g sodium sulfite, accounting for 1 / 800 of the weight ratio of the mixed non-ionic surfactant), water as a solvent, and the Fischer-Tropsch oil of the C10-C12 fraction after deacidification (the same as in Example 1) are added into a high-pressure reactor in a volume ratio of 1:1, wherein the molar ratio of rhodium catalyst: phosphine ligand is 1:7, AEO-9 and ethylene glycol are 1:1, the volume ratio of the mixed non-ionic surfactant to water is 8:2, and the molar ratio of the rhodium catalyst to the normal olefins in the raw Fischer-Tropsch oil is 1:780. Synthesis gas (CO:H2=1:1) was introduced to replace the air in the kettle, and then synthesis gas was introduced to maintain the pressure in the kettle at 1MPa. The temperature was raised to 100°C, and the reaction was stirred at constant temperature and pressure for 5 hours. The reaction was stopped, cooled to room temperature, the pressure was released, the mixture was taken out, the upper layer was separated and measured by gas chromatography. After the measurement, the normal olefin conversion rate was 85.68%, the selectivity was 93.84%, the yield was 88.97%, and the catalyst loss was 0.03ppm.

[0051] Example 4

[0052] Acetylacetonato dicarbonyl rhodium, sulfonated phosphine ligand Xantphos, a mixed nonionic surfactant (PEG400 and PEG600 in a volume ratio of 1:1, 0.05 g sodium sulfite, accounting for 1 / 800 of the weight ratio of the mixed nonionic surfactant), and water as a solvent are added to a high-pressure reactor with a volume ratio of 1:1 with the Fischer-Tropsch oil of the C10-C12 fraction after deacidification (the same as in Example 1), wherein the molar ratio of rhodium catalyst: phosphine ligand is 1:10, the molar ratio of PEG400 and PEG600 is 1:1, the volume ratio of the mixed nonionic surfactant to water is 8:2, and the molar ratio of the rhodium catalyst to the normal olefins in the raw Fischer-Tropsch oil is 1:650. Synthesis gas (CO:H2=1:1) was introduced to replace the air in the kettle, and then synthesis gas was introduced to maintain the pressure in the kettle at 1MPa. The temperature was raised to 105°C, and the reaction was stirred at constant temperature and pressure for 4 hours. The reaction was stopped, cooled to room temperature, the pressure was released, the mixture was taken out, the upper layer was separated and measured by gas chromatography. After the measurement, the normal olefin conversion rate was 98.5%, the selectivity was 69%, the yield was 68%, and the catalyst loss was 0.02ppm.

[0053] Example 5

[0054] Hydrated rhodium trichloride, sulfonated phosphine ligand NORBOS, a mixed nonionic surfactant (PEG800 and ethylene glycol in a volume ratio of 1:1, 0.05g sodium sulfite, accounting for 1 / 800 of the weight ratio of the mixed nonionic surfactant), water as a solvent, and Fischer-Tropsch oil of the C8-C10 fraction after deacidification (acid value 0.079mg KOH / g, 52.44% normal olefins, 15.9% isoolefins, 24.07% alkanes) are added into a high-pressure reactor in a volume ratio of 1:1, wherein the molar ratio of rhodium catalyst:phosphine ligand is 1:10, PEG800 and ethylene glycol are 1:1, the volume ratio of the mixed nonionic surfactant to water is 6:4, and the molar ratio of the rhodium catalyst to the normal olefins in the raw Fischer-Tropsch oil is 1:840. Synthesis gas (CO:H2=1:1) was introduced to replace the air in the kettle, and then synthesis gas was introduced to maintain the pressure in the kettle at 1MPa. The temperature was raised to 100°C, and the reaction was stirred at constant temperature and pressure for 7 hours. The reaction was stopped, cooled to room temperature, the pressure was released, the mixture was taken out, the upper layer was separated and measured by gas chromatography. After the measurement, the normal olefin conversion rate was 84.27%, the selectivity was 95.33%, the yield was 80.43%, and the catalyst loss was 0.07ppm.

[0055] Example 6

[0056] Hydrated rhodium trichloride, sulfonated phosphine ligand Xantphos, a mixed nonionic surfactant (PEG200 and AEO-9 in a volume ratio of 1:1, 0.05 g sodium sulfite, accounting for 1 / 800 of the weight ratio of the mixed nonionic surfactant), water as a solvent, and the Fischer-Tropsch oil of the C8-C10 fraction after deacidification (same as Example 5) are added into a high-pressure reactor in a volume ratio of 1:1, wherein the molar ratio of rhodium catalyst: phosphine ligand is 1:7, PEG200 and AEO-9 is 2:1, the volume ratio of the mixed nonionic surfactant to water is 5:5, and the molar ratio of normal olefins in the raw Fischer-Tropsch oil to the rhodium catalyst is 1:650. Synthesis gas (CO:H2=1:1) was introduced to replace the air in the kettle, and then synthesis gas was introduced to maintain the pressure in the kettle at 2MPa. The temperature was raised to 105°C, and the reaction was stirred at constant temperature and pressure for 4 hours. The reaction was stopped, cooled to room temperature, the pressure was released, the mixture was taken out, the upper layer was separated and measured by gas chromatography. After the measurement, the normal olefin conversion rate was 86.37%, the selectivity was 91.62%, the yield was 79.13%, and the catalyst loss was 0.05ppm.

[0057] Example 7

[0058] Acetylacetonato dicarbonyl rhodium, sulfonated phosphine ligand BINAS, a mixed nonionic surfactant (diethylene glycol and PEG600 in a volume ratio of 1:1, 0.05 g sodium sulfate, accounting for 1 / 800 of the weight ratio of the mixed nonionic surfactant), water as a solvent, and the Fischer-Tropsch oil of the C8-C10 fraction after deacidification (same as Example 5) are added into a high-pressure reactor in a volume ratio of 1:1, wherein the molar ratio of rhodium catalyst:phosphine ligand is 1:7, the molar ratio of diethylene glycol and PEG600 is 1:3, and the mixed nonionic surfactant is 1:1. The volume ratio of the catalyst to water is 7:3, and the molar ratio of the rhodium catalyst to the normal olefins in the raw material Fischer-Tropsch oil is 1:540. Synthesis gas (CO:H2=1:1) is introduced to replace the air in the kettle, and then synthesis gas is introduced to maintain the pressure in the kettle at 3MPa. The temperature is raised to 95°C, and the reaction is stirred at constant temperature and pressure for 3 hours. The reaction is stopped, cooled to room temperature, the pressure is released, the mixture is taken out, the upper layer is separated and measured by gas chromatography. After the measurement, the normal olefin conversion rate is 85.92%, the selectivity is 92.55%, the yield is 79.52%, and the catalyst loss is 0.08ppm.

[0059] Example 8

[0060] Acetylacetonate dicarbonyl rhodium, sulfonated phosphine ligand BINAS, a mixed non-ionic surfactant (polypropylene glycol and glycerol in a volume ratio of 1:1, 0.05g sodium chloride, accounting for 1 / 800 of the weight ratio of the mixed non-ionic surfactant), water as a solvent, and the Fischer-Tropsch oil of the C8-C10 fraction after deacidification (same as Example 5) are added into a high-pressure reactor in a volume ratio of 1:1, wherein the molar ratio of rhodium catalyst: phosphine ligand is 1:7, the molar ratio of polypropylene glycol and glycerol is 1:1, the volume ratio of the mixed non-ionic surfactant to water is 5:5, and the molar ratio of the rhodium catalyst to the normal olefins in the raw Fischer-Tropsch oil is 1:540. Synthesis gas (CO:H2=1:1) was introduced to replace the air in the kettle, and then synthesis gas was introduced to maintain the pressure in the kettle at 1MPa. The temperature was raised to 105°C, and the reaction was stirred at constant temperature and pressure for 8 hours. The reaction was stopped, cooled to room temperature, the pressure was released, the mixture was taken out, the upper layer was separated and measured by gas chromatography. After the measurement, the normal olefin conversion rate was 87.27%, the aldehyde selectivity was 86.76%, the yield was 75.72%, and the catalyst loss was 0.17ppm.

[0061] Example 9

[0062] Acetylacetonato dicarbonyl rhodium, sulfonated phosphine ligand NORBOS, a mixed nonionic surfactant (PEG400 and PEG600 in a volume ratio of 1:1, 0.05g sodium sulfite, accounting for 1 / 800 of the weight ratio of the mixed nonionic surfactant), water as a solvent, and Fischer-Tropsch oil of the C11-C12 fraction after deacidification (acid value 0.019mg KOH / g, normal olefins 44.57%, isoolefins 15.18%, alkanes 33.85%) are added into a high-pressure reactor in a volume ratio of 1:1, wherein the molar ratio of rhodium catalyst:phosphine ligand is 1:15, PEG400 and PEG600 is 1:2, the volume ratio of the mixed nonionic surfactant to water is 7:3, synthesis gas (CO:H2=1:1) is introduced to replace the air in the reactor, and the molar ratio of rhodium catalyst to normal olefins in the raw material Fischer-Tropsch oil is 1:720. Then, synthesis gas was introduced to maintain the pressure in the kettle at 1 MPa, and the temperature was raised to 95°C. The reaction was stirred at constant temperature and pressure for 8 hours, the reaction was stopped, cooled to room temperature, the pressure was released, the mixture was taken out, the upper layer was separated and measured by gas chromatography. After the measurement, the normal olefin conversion rate was 87.82%, the aldehyde selectivity was 93.26, the yield was 81.90%, and the catalyst loss was 0.12 ppm.

[0063] Example 10

[0064] Acetylacetonate dicarbonyl rhodium, sulfonated phosphine ligand NORBOS, a mixed nonionic surfactant (AEO-9 and glycerol in a volume ratio of 1:1, 0.05 g sodium sulfate, accounting for 1 / 800 of the weight ratio of the mixed nonionic surfactant), water as a solvent, and the Fischer-Tropsch oil of the C11-C12 fraction after deacidification (same as Example 9) are added into a high-pressure reactor in a volume ratio of 1:1, wherein the molar ratio of rhodium catalyst: phosphine ligand is 1:7, AEO-9 and glycerol are 2:1, the volume ratio of the mixed nonionic surfactant to water is 9:1, and the molar ratio of the rhodium catalyst to the normal olefins in the raw Fischer-Tropsch oil is 1:635. Synthesis gas (CO:H2=1:1) was introduced to replace the air in the kettle, and then synthesis gas was introduced to maintain the pressure in the kettle at 2MPa. The temperature was raised to 90°C, and the reaction was stirred at constant temperature and pressure for 10 hours. The reaction was stopped, cooled to room temperature, the pressure was released, the mixture was taken out, the upper layer was separated and measured by gas chromatography. After the measurement, the normal olefin conversion rate was 84.41%, the selectivity was 91.90%, the yield was 77.57%, and the catalyst loss was 0.06ppm.

[0065] Embodiment 11

[0066] The only difference from Example 1 is that a nonionic surfactant PEG400 is used, and its amount is the same as that of the mixed nonionic surfactant in Example 1.

[0067] After the reaction, the normal olefin conversion rate was 71.5%, the selectivity was 75.65%, the yield was 54.09%, and the catalyst loss was 0.14 ppm.

[0068] Example 12

[0069] The only difference from Example 1 is that the ratio of the mixed nonionic surfactant to water is 1:4.

[0070] After the reaction, the normal olefin conversion rate was 62.91%, the selectivity was 81.04%, the yield was 50.98%, and the catalyst loss was 0.68 ppm.

[0071] Example 13

[0072] The only difference from Example 1 is that the ratio of the mixed nonionic surfactant to water is 12:1.

[0073] After the reaction, the normal olefin conversion rate was 77.13%, the selectivity was 94.89%, the yield was 73.19%, and the catalyst loss was 0.48 ppm.

[0074] Embodiment 14

[0075] The only difference from Example 1 is that the phosphine ligand is triphenyl phosphite.

[0076] After the reaction, it was determined that the normal olefin conversion rate was 67.61%, the selectivity was 7.67%, the yield was 11.58%, and the catalyst loss was 0.19 ppm.

[0077] Embodiment 15

[0078] The only difference from Example 1 is that the molar ratio of the phosphine ligand to the rhodium catalyst is 2:1.

[0079] After the reaction, the normal olefin conversion rate was 38.85%, the selectivity was 90.2%, the yield was 35.05%, and the catalyst loss was 0.29 ppm.

[0080] Example 16

[0081] The only difference from Example 1 is that no demulsifier sodium sulfite is added in the reaction. After the reaction is completed, the two phases are difficult to separate and the emulsification phenomenon is serious.

[0082] After the reaction, the normal olefin conversion rate was 58.06%, the selectivity was 96.03%, the yield was 55.76%, and the catalyst loss was 4.2 ppm.

[0083] Embodiment 17

[0084] The only difference from Example 1 is that PEG400 and PEG600 are replaced by ethylene glycol and glycerol in a volume ratio of 1:1.

[0085] After the reaction, the normal olefin conversion rate was 55.04%, the selectivity was 89.46%, the yield was 49.24%, and the catalyst loss was 0.28 ppm.

[0086] Embodiment 18

[0087] Acetylacetonato dicarbonyl rhodium, sulfonated phosphine ligand Xantphos (Formula 1), mixed nonionic surfactant (PEG400 and PEG600, PEG400 and PEG600 are 1:1, 0.05g sodium sulfite), water as solvent, 1-decene is added into a high pressure reactor at a volume ratio of 1:1 (volume ratio of water phase and oil phase), wherein the molar ratio of rhodium catalyst:phosphine ligand is 1:7, the ratio of mixed nonionic surfactant to water is 8:2, and the molar ratio of rhodium catalyst to olefin is 1:560. Synthesis gas (CO:H2=1:1) is introduced to replace the air in the reactor, and then synthesis gas is introduced to maintain the pressure in the reactor at 2MPa, the temperature is raised to 100°C, the reaction is stirred at constant temperature and pressure for 5h, the reaction is stopped, the room temperature is cooled, the pressure is released to take out the mixture, the upper layer is separated and taken out for gas chromatography, and after the measurement, the normal olefin conversion rate is 80.52%, the selectivity is 94.31%, the yield is 75.93%, and the catalyst loss is 0.12ppm.

[0088] Comparative Example 1

[0089] Acetylacetonato dicarbonyl rhodium, sulfonated phosphine ligand Xantphos (Formula 1), water as solvent, and deacidified C10-C12 fraction (acid value 0.021 mg KOH / g, normal olefins 43.6%, isoolefins 15.8%, alkanes 33.8%) Fischer-Tropsch oil are placed in a high-pressure reactor in a volume ratio of 1:1 (volume ratio of water phase to oil phase), wherein the molar ratio of rhodium catalyst:phosphine ligand is 1:7, and the molar ratio of rhodium catalyst to normal olefins in the raw material Fischer-Tropsch oil is 1:650. Synthesis gas (CO:H2=1:1) was introduced to replace the air in the kettle, and then synthesis gas was introduced to maintain the pressure in the kettle at 2MPa. The temperature was raised to 100°C, and the reaction was stirred at constant temperature and pressure for 5 hours. The reaction was stopped, cooled to room temperature, the pressure was released, the mixture was taken out, the upper layer was separated and measured by gas chromatography. After the measurement, the normal olefin conversion rate was 32.3%, the selectivity was 58.4%, the yield was 18.86%, and the catalyst loss was 0.06ppm.

[0090] Comparative Example 2

[0091] The difference from Example 1 is that the mixed nonionic surfactant (PEG400 and PEG600) is replaced by the same volume of hexadecyltrimethylammonium bromide.

[0092] After the reaction, the normal olefin conversion rate was 70.48%, the selectivity was 95.39%, the yield was 67.23%, and the catalyst loss was 0.28 ppm.

[0093] Application Example 1

[0094] In order to investigate the recycling rate of the catalyst, the lower catalyst of Example 1 was subjected to a recycling experiment. The lower catalyst was added to a high-pressure reactor, and a Fischer-Tropsch oil raw material (the volume ratio of the raw material to the water phase was 1:1) was added at the same time. The molar ratio of the rhodium catalyst to the normal olefins in the raw material Fischer-Tropsch oil was 1:650. Synthesis gas (CO:H2=1:1) was introduced to replace the air in the reactor, and then synthesis gas was introduced to maintain the pressure in the reactor at 2MPa, and the temperature was raised to 100°C. The reaction was stirred at constant temperature and pressure for 5h, the reaction was stopped, the room temperature was cooled, the pressure was released, the mixture was taken out, the upper layer was separated and measured by gas chromatography, and the above operation was repeated 43 times. The test results are shown in Table 1.

[0095] Table 1

[0096]

[0097]

[0098] It can be seen from Table 1 that the selectivity and yield of the lower catalyst in Example 1 remained basically unchanged after 43 cycles, indicating that the catalyst was very stable and the loss of rhodium was less than 0.1 ppm.

[0099] From the above description, it can be seen that the above-mentioned embodiments of the present invention achieve the following technical effects: the application adopts nonionic surfactants not only to improve the solubility of olefins in water, increase the two-phase mass transfer rate, but also increase the coordination of olefins and catalytic active substances; using diphosphine as a phosphine ligand, by adding mixed nonionic surfactants, the catalyst can be well fixed in the water phase, so that the catalyst has good recycling performance; further, the nonionic surfactant of the present application of the present application is matched with rhodium catalyst and diphosphine ligand, and applied to the hydroformylation reaction of Fischer-Tropsch oil, with high conversion rate, good selectivity, high number of catalyst recycling, and nonionic surfactants are not only low in usage, cheap and easy to obtain, green and environmentally friendly. Especially when the normal olefins in Fischer-Tropsch oil are used as reaction raw materials, the normal olefins in Fischer-Tropsch oil are obtained by hydroformylation reaction to obtain corresponding aldehydes by the method of the present application, and then separated from the system, so that the separation from isoolefins and alkanes becomes simple, which is conducive to improving the application value of Fischer-Tropsch oil and reducing costs.

[0100] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. For those skilled in the art, the present invention may have various modifications and variations. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. A method for preparing aldehydes by hydroformylation of Fischer-Tropsch oil, characterized in that: include: Under the action of catalyst and non-ionic surfactant, in the synthesis gas environment, Fischer-Tropsch oil of C8-C12 fraction is used as raw material, and aldehyde is prepared by hydroformylation reaction in solvent. The catalyst is a rhodium compound and a phosphine ligand, the solvent is water; the phosphine ligand is any one or more of Xantphos, NORBOS and BINAS; The nonionic surfactant is a mixed nonionic surfactant, and the mixed nonionic surfactant is any two or more of polyethylene glycol 200, ethylene glycol, polyethylene glycol 400, polyethylene glycol 600, glycerol, polyethylene glycol 800, fatty alcohol polyoxyethylene ether, polypropylene glycol and diethylene glycol; The volume ratio of the nonionic surfactant to the solvent is 10:1-1:4; An inorganic salt demulsifier is added to the nonionic surfactant.

2. The method according to claim 1, characterized in that: The inorganic salt demulsifier is any one or more of sodium sulfite, sodium sulfate and sodium chloride.

3. The method according to claim 1, characterized in that The addition amount of the inorganic salt demulsifier is 0.01-0.15wt% of the non-ionic surfactant.

4. The method according to claim 1, characterized in that: The phosphine ligand is sulfonated with fuming sulfuric acid and then used in the hydroformylation reaction.

5. The method according to claim 1, characterized in that The rhodium compound is selected from any one or more of hydrated rhodium trichloride, dicarbonyl rhodium acetylacetonate, tris(sodium triphenylphosphine tris-metasulfonate) carbonyl rhodium hydride and divinyl rhodium acetylacetonate.

6. The method according to claim 5, characterized in that The molar ratio of the rhodium compound to the phosphine ligand is 1:5-1:

20.

7. The method according to claim 5, characterized in that The molar ratio of the Fischer-Tropsch oil in the C8-C12 fraction to the rhodium compound is 500-1000:

1.

8. The method according to claim 5, characterized in that The concentration of the rhodium compound in the aqueous phase is 150-350 ppm.

9. The method according to claim 1, characterized in that: The Fischer-Tropsch oil is deacidified.

10. The method according to claim 1, characterized in that The acid value of the Fischer-Tropsch oil is ≤0.03 mg KOH / g.

11. The method according to any one of claims 1 to 8, characterized in that: The volume ratio of the Fischer-Tropsch oil to the solvent is 1:1-1:

10.

12. The method according to any one of claims 1 to 8, characterized in that: The volume ratio of CO to H2 in the synthesis gas is 0.5-1:

1.

13. The method according to any one of claims 1 to 8, characterized in that: The reaction temperature of the hydroformylation reaction is 85-120°C.

14. The method according to claim 13, characterized in that The reaction pressure of the hydroformylation reaction is 1-5 MPa.

15. The method according to claim 13, characterized in that The reaction time of the hydroformylation reaction is 2-10 hours.

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