Composition and method for preparing high-carbon aldehyde through two-phase hydroformylation

Abstract

The invention discloses a composition and a method for preparing high-carbon aldehyde through two-phase hydroformylation. The composition comprises a rhodium catalyst, a water-soluble phosphine ligand, a quaternary ammonium salt cationic surfactant and an ampholytic surfactant, the structural formula of the quaternary ammonium salt cationic surfactant is shown in a formula (I), R1, R2, R3, R4 and R5 are independently selected from methyl, ethyl and C3-C18 straight-chain or branched-chain alkane, and X is F, Cl or Br; the molar ratio of the water-soluble phosphine ligand to the rhodium catalyst is (0.1-20): 1; the molar ratio of the quaternary ammonium salt cationic surfactant to the rhodium catalyst is (0.05-100): 1; the molar ratio of the quaternary ammonium salt cationic surfactant to the ampholytic surfactant is (0.1-50): 1. # imgabs0 #

Description

Technical Field

[0001] The invention relates to the field of preparation of high-carbon aldehydes, and in particular to a composition and a method for preparing high-carbon aldehydes by two-phase hydroformylation. Background Art

[0002] Aldehydes above C6 are commonly known as high-carbon aldehydes, which are mainly used to produce high-carbon alcohols. High-carbon alcohols are the main raw materials for preparing plasticizers, detergents and surfactants. With the development of plastic processing, automobile industry, cable industry, construction industry and the improvement of people's living standards, the demand for high-carbon alcohols has increased rapidly.

[0003] Olefins and synthesis gas can produce aldehydes with one more carbon than the raw olefins under the action of catalysts, which is an atom-economic reaction. The current industrial hydroformylation production process is mainly homogeneous catalysis. Like all homogeneous catalytic reactions, one of the main problems encountered in the industrialization of hydroformylation reactions is the separation of products and catalysts. The development of water / oil two-phase systems provides research ideas for the hydroformylation of high-carbon olefins, but the solubility of high-carbon olefins (especially C6 and above) in water is too low, resulting in slow mass transfer, affecting reaction activity, and limiting the application of water / oil two-phase systems in the industrial production of high-carbon olefin hydroformylation. Therefore, it is particularly important to solve the problem of slow mass transfer rate of high-carbon olefins in the water / oil two-phase catalytic process.

[0004] CN1184710A discloses a phosphine ligand with temperature-controlled phase transfer function and its application. The ligand draws on the solubility characteristics of non-ionic surfactants in water with a "cloud point", that is, it is water-soluble at a lower temperature due to the presence of hydrogen bonds, and it is oil-soluble when the temperature rises due to the destruction of hydrogen bonds. The designed and synthesized polyether phosphine ligand and rhodium complex show high catalytic activity in water / oil phases, and the olefin conversion rate and aldehyde selectivity both reach more than 95%, but the selectivity of normal aldehydes is poor, and additional organic solvents such as benzene and toluene are required, which does not meet the requirements of green development. US6452055B1 discloses a method for hydroformylation in microemulsion. Although the mass transfer rate of high-carbon olefins in water is increased, the use of a large amount of emulsifiers leads to difficulties in post-processing separation. CN109894150A discloses a method for promoting the hydroformylation reaction of high-carbon olefins in water / oil phases using betaine cationic surfactants. The addition of surfactants can easily cause solution emulsification, which brings difficulties to the separation of the two phases. CN105777513A discloses a hydroformylation reaction of a polyether pyrrolidino salt ionic liquid. The ionic liquid can form a temperature control system with an organic solvent to achieve the effect of "low-temperature phase separation and high-temperature miscibility". The use of a water-soluble diphosphine ligand and a rhodium complex to catalyze high-carbon olefins has good catalytic activity and normal aldehyde selectivity. However, the synthesis conditions of the ionic liquid itself are harsh, the steps are cumbersome, and it is sensitive to impurities, thereby increasing the production cost.

[0005] Although the above technologies have improved the mass transfer problem caused by the low solubility of high-carbon olefins in water, there are certain problems that hinder their application in actual industrial production. Summary of the invention

[0006] To solve at least one of the above technical problems, the present invention provides a composition and method for preparing high carbon aldehydes by two-phase hydroformylation, which is particularly suitable for preparing high carbon aldehydes above C6 by water / oil two-phase hydroformylation reaction.

[0007] In order to achieve the above purpose, the present invention adopts the following technical solutions:

[0008] In one aspect, the present invention provides a composition for preparing high-carbon aldehydes by two-phase hydroformylation, wherein the composition comprises a rhodium catalyst, a water-soluble phosphine ligand, a quaternary ammonium salt cationic surfactant and an amphoteric surfactant;

[0009] The structural formula (I) of the quaternary ammonium salt cationic surfactant is shown as follows:

[0010]

[0011] In formula (I), R1, R2, R3, R4 and R5 are independently selected from methyl, ethyl, C3-C 18 A straight or branched alkane, X is F, Cl or Br;

[0012] The molar ratio of the water-soluble phosphine ligand to the rhodium catalyst is (0.1-20):1; the molar ratio of the quaternary ammonium salt cationic surfactant to the rhodium catalyst is (0.05-100):1; the molar ratio of the quaternary ammonium salt cationic surfactant to the amphoteric surfactant is (0.1-50):1.

[0013] In some specific embodiments of the present invention, in formula (I), X is Br.

[0014] In some specific embodiments of the present invention, in formula (I), R1 and R2 are independently selected from methyl, ethyl, C3-C6 straight-chain or branched alkane; R3 is selected from C5-C 18 A straight or branched alkane; R4 and R5 are independently selected from a straight or branched alkane of C1 to C5.

[0015] In some specific embodiments of the present invention, in formula (I), R1 and R2 are independently selected from methyl, ethyl, propyl or isopropyl; R3 is selected from C8 to C 16 R4 and R5 are independently selected from C1 to C3 straight chain or branched chain alkanes.

[0016] In some specific embodiments of the present invention, in formula (I), R4 is propyl and R5 is methyl.

[0017] In some specific embodiments of the present invention, the amphoteric surfactant is selected from at least one of a betaine amphoteric surfactant or an imidazoline amphoteric surfactant.

[0018] In some specific embodiments of the present invention, the amphoteric surfactant is selected from lauryl betaine, coconut oil betaine, stearyl betaine, oleyl betaine, C 12 ~C 18 At least one of alkyl dimethyl betaine ammonium salt, lauroyl propyl betaine, cocamidopropyl-2-hydroxy-3-sulfopropyl betaine, 1-hydroxyethyl-2-cocoyl imidazoline acetate, disodium caprylamidoethyl-N-hydroxyethylaminoethoxypropionate, sodium cocamidoethyl-N-hydroxyethylaminopropionate, and sodium stearamidoethyl-N-hydroxyethylaminopropionate.

[0019] In some specific embodiments of the present invention, the rhodium catalyst is a water-soluble rhodium catalyst, selected from at least one of hydrated rhodium trichloride, acetylacetonato dicarbonyl rhodium, and monohydrogen monocarbonyl tris(trisulfonated triphenylphosphine trisodium salt) rhodium.

[0020] In some specific embodiments of the present invention, the water-soluble phosphine ligand is selected from at least one of trisulfonated triphenylphosphine trisodium salt, disulfonated triphenylphosphine disodium salt, monosulfonated triphenylphosphine monosodium salt, sulfonated 2,2'-bis(diphenylphosphinomethylene)-1,1'-biphenyl sodium salt, and 2,7-disulfo-4,5-bis(diphenylphosphino)-9,9-dimethylxanthene disodium salt.

[0021] In some specific embodiments of the present invention, the molar ratio of the water-soluble phosphine ligand to the rhodium catalyst is (1-15):1.

[0022] In some specific embodiments of the present invention, the molar ratio of the water-soluble phosphine ligand to the rhodium catalyst is (3-12):1.

[0023] In some specific embodiments of the present invention, the molar ratio of the quaternary ammonium salt cationic surfactant to the rhodium catalyst is (0.02-30):1.

[0024] In some specific embodiments of the present invention, the molar ratio of the quaternary ammonium salt cationic surfactant to the rhodium catalyst is (0.5-10):1.

[0025] In some specific embodiments of the present invention, the molar ratio of the quaternary ammonium salt cationic surfactant to the amphoteric surfactant is (1-30):1.

[0026] In some specific embodiments of the present invention, the molar ratio of the quaternary ammonium salt cationic surfactant to the amphoteric surfactant is (3-15):1.

[0027] Another aspect of the present invention provides a method for preparing high carbon aldehydes by two-phase hydroformylation, comprising reacting an olefin raw material with synthesis gas in the presence of a solution consisting of any of the above compositions and water to obtain a product high carbon aldehyde; the synthesis gas comprises hydrogen and carbon monoxide.

[0028] In some specific embodiments of the present invention, the olefin raw material is C3-C 18 of olefins.

[0029] In some specific embodiments of the present invention, the olefin raw material is C5-C 18 of olefins.

[0030] In some specific embodiments of the present invention, the olefin raw material is C5-C 14 The terminal olefin.

[0031] In some specific embodiments of the present invention, in the solution, the concentration of rhodium, calculated as rhodium metal atoms, is 0.1 mmol / L to 3 mmol / L.

[0032] In some specific embodiments of the present invention, in the solution, the concentration of rhodium, calculated as rhodium metal atoms, is 0.5 mmol / L to 2.5 mmol / L.

[0033] In some specific embodiments of the present invention, in the solution, the concentration of rhodium, calculated as rhodium metal atoms, is 0.5 mmol / L to 1.5 mmol / L.

[0034] In some specific embodiments of the present invention, the reaction temperature is 50-150°C.

[0035] In some specific embodiments of the present invention, the reaction temperature is 80-120°C.

[0036] In some specific embodiments of the present invention, the reaction pressure is 0.5 MPa to 10 MPa.

[0037] In some specific embodiments of the present invention, the reaction pressure is 2 MPa to 5 MPa.

[0038] In some specific embodiments of the present invention, the reaction time is 0.5h to 12h.

[0039] In some specific embodiments of the present invention, the reaction time is 2 h to 5 h.

[0040] In some specific embodiments of the present invention, the molar ratio of the olefin raw material to the rhodium metal atom of the rhodium catalyst is (500-50000):1.

[0041] In some specific embodiments of the present invention, the molar ratio of the olefin raw material to the rhodium metal atom of the rhodium catalyst is (1000-20000):1.

[0042] In some specific embodiments of the present invention, the molar ratio of the olefin raw material to the rhodium metal atom of the rhodium catalyst is (2000-10000):1.

[0043] In some specific embodiments of the present invention, the molar ratio of hydrogen to carbon monoxide is (0.5-3):1.

[0044] In some specific embodiments of the present invention, the molar ratio of hydrogen to carbon monoxide is (0.9-2):1.

[0045] In some specific embodiments of the present invention, the molar ratio of hydrogen to carbon monoxide is 1:1.

[0046] The water used in the present invention is preferably deionized water.

[0047] The invention adds a small amount of a cationic surfactant and an amphoteric surfactant, especially a composite system of a quaternary ammonium salt cationic surfactant-amphoteric surfactant in a specific ratio and structure. The cationic surfactant and the anionic group in the amphoteric surfactant have an electrostatic effect, thereby improving the reaction rate of the hydroformylation of high-carbon olefins, avoiding severe emulsification after the addition of a high-concentration surfactant, thereby reducing the loss of rhodium catalyst, reducing production costs, and improving the possibility of a water / oil two-phase catalytic process in the industrial production of high-carbon olefin hydroformylation. BRIEF DESCRIPTION OF THE DRAWINGS

[0048] Figure 1 is the surfactant 2a in Example 1 1 H-MNR diagram.

[0049] Figure 2 is the surfactant 2b in Example 2 1 H-MNR diagram.

[0050] Figure 3 is the surfactant 2c in Example 3 1 H-MNR diagram.

[0051] Figure 4 is the surfactant 2a in Example 1 15 N-MNR diagram.

[0052] Figure 5 is the surfactant 2b in Example 2 15 N-MNR diagram.

[0053] Figure 6is the surfactant 2c in Example 3 15 N-MNR diagram. DETAILED DESCRIPTION

[0054] In order to explain the present invention more clearly, the present invention is further described below in conjunction with preferred embodiments. It should be understood by those skilled in the art that the following specific description is illustrative rather than restrictive, and should not be used to limit the scope of protection of the present invention.

[0055] The key to the technical solution of the present invention is that a quaternary ammonium salt cationic surfactant and an amphoteric surfactant are simultaneously added to the rhodium catalyst system for preparing high carbon aldehydes by two-phase hydroformylation, especially the compound use of two surfactants with specific structures and specific ratios. The cationic surfactant interacts with the hydrophilic head groups of the amphoteric surfactant to more easily form micelles, achieving the effect of compounding and enhancing synergy, thereby reducing the amount of surfactant used, and effectively avoiding the problem that the product forms an emulsion after the reaction is completed and is difficult to separate.

[0056] The catalyst composition of the present invention comprises a rhodium catalyst, a water-soluble phosphine ligand, a quaternary ammonium salt cationic surfactant and an amphoteric surfactant; the structural formula (I) of the quaternary ammonium salt cationic surfactant is shown as follows:

[0057]

[0058] In formula (I), R1, R2, R3, R4 and R5 are independently selected from methyl, ethyl, C3-C 18 A straight or branched alkane; X is F, Cl or Br, preferably Br;

[0059] The molar ratio of the water-soluble phosphine ligand to the rhodium catalyst is (0.1-20):1; the molar ratio of the quaternary ammonium salt cationic surfactant to the rhodium catalyst is (0.05-100):1; the molar ratio of the quaternary ammonium salt cationic surfactant to the amphoteric surfactant is (0.1-50):1.

[0060] According to a specific embodiment of the present invention, preferably, in formula (I), R1 and R2 are independently selected from methyl, ethyl, C3-C6 straight-chain or branched alkane; R3 is selected from C5-C 18 R4 and R5 are independently selected from C1 to C5 straight chain or branched chain alkanes. More preferably, R1 and R2 are independently selected from methyl, ethyl, propyl or isopropyl; R3 is selected from C8 to C 16 R4 and R5 are independently selected from C1 to C3 straight chain or branched chain alkanes. Further preferably, R4 is propyl and R5 is methyl.

[0061] According to a specific embodiment of the present invention, preferably, the amphoteric surfactant is selected from at least one of a betaine amphoteric surfactant or an imidazoline amphoteric surfactant. More preferably, the amphoteric surfactant is selected from lauryl betaine, coconut oil betaine, stearyl betaine, oleyl betaine, C 12 ~C 18 At least one of alkyl dimethyl betaine ammonium salt, lauroyl propyl betaine, cocamidopropyl-2-hydroxy-3-sulfopropyl betaine, 1-hydroxyethyl-2-cocoyl imidazoline acetate, disodium caprylamidoethyl-N-hydroxyethylaminoethoxypropionate, sodium cocamidoethyl-N-hydroxyethylaminopropionate, and sodium stearamidoethyl-N-hydroxyethylaminopropionate.

[0062] According to a specific embodiment of the present invention, preferably, the rhodium catalyst is a water-soluble rhodium catalyst, selected from at least one of hydrated rhodium trichloride, acetylacetonato dicarbonyl rhodium, and monohydrogen monocarbonyl tris(trisulfonated triphenylphosphine trisodium salt) rhodium.

[0063] According to a specific embodiment of the present invention, preferably, the water-soluble phosphine ligand is selected from at least one of trisulfonated triphenylphosphine trisodium salt, disulfonated triphenylphosphine disodium salt, monosulfonated triphenylphosphine monosodium salt, sulfonated 2,2'-bis(diphenylphosphinomethylene)-1,1'-biphenyl sodium salt, and 2,7-disulfono-4,5-bis(diphenylphosphino)-9,9-dimethylxanthene disodium salt.

[0064] According to a specific embodiment of the present invention, preferably, the molar ratio of the water-soluble phosphine ligand to the rhodium catalyst is (1-15):1, more preferably (3-12):1.

[0065] According to a specific embodiment of the present invention, preferably, the molar ratio of the quaternary ammonium salt cationic surfactant to the rhodium catalyst is (0.02-30):1, more preferably (0.5-10):1.

[0066] According to a specific embodiment of the present invention, preferably, the molar ratio of the quaternary ammonium salt cationic surfactant to the amphoteric surfactant is (1-30):1, more preferably (3-15):1; further preferably (5-8):1.

[0067] Any of the above catalyst compositions is used in two-phase hydroformylation to prepare high carbon aldehydes, which comprises reacting olefin raw materials with synthesis gas in the presence of a solution consisting of any of the above compositions and water to obtain product high carbon aldehydes; the synthesis gas comprises hydrogen and carbon monoxide.

[0068] According to a specific embodiment of the present invention, preferably, the olefin raw material is C3-C 18 Olefins, more preferably C5 to C 18 Olefins, more preferably C5 to C14 The terminal olefin.

[0069] According to a specific embodiment of the present invention, preferably, the concentration of rhodium, calculated as rhodium metal atoms, is 0.1 mmol / L to 3 mmol / L, more preferably 0.5 mmol / L to 2.5 mmol / L, and further preferably 0.5 mmol / L to 1.5 mmol / L.

[0070] According to a specific embodiment of the present invention, preferably, the reaction temperature is 50-150°C, more preferably 80-120°C.

[0071] According to a specific embodiment of the present invention, preferably, the reaction pressure is 0.5 MPa to 10 MPa, more preferably 2 MPa to 5 MPa.

[0072] According to a specific embodiment of the present invention, preferably, the reaction time is 0.5h to 12h, more preferably 2h to 5h.

[0073] According to a specific embodiment of the present invention, preferably, the molar ratio of the olefin feedstock to the rhodium catalyst (based on the central rhodium metal atom of the rhodium catalyst) is (500-50000):1, more preferably (1000-20000):1, and further preferably (2000-10000):1.

[0074] According to a specific embodiment of the present invention, preferably, the molar ratio of hydrogen to carbon monoxide is (0.5-3):1, more preferably (0.9-2):1, and further preferably 1:1.

[0075] The present invention is described in more detail below with some specific examples. All numerical values ​​specified therein (such as temperature, time, concentration and weight, etc., including the range of each thereof) are usually appropriately changed by (+) or (-) approximate values ​​in increments of 0.1 or 1.0. All numerical values ​​specified are understood to be preceded by the term "about".

[0076] Source of raw materials or equipment:

[0077] Dimethylamine (Aladdin Biochemical Technology Co., Ltd.), diethylamine (Aladdin Biochemical Technology Co., Ltd.), decane bromide (Aladdin Biochemical Technology Co., Ltd.), dodecane bromide (Aladdin Biochemical Technology Co., Ltd.), 1,3-dibromo-2-(bromoethyl)propane (Hubei Nordina Biotechnology Co., Ltd.), anhydrous ethanol (Sinopharm Chemical Reagent Co., Ltd.), isopropanol (Sinopharm Chemical Reagent Co., Ltd.), ethyl acetate (Sinopharm Chemical Reagent Co., Ltd.), sodium hydroxide (Sinopharm Chemical Reagent Co., Ltd.), lauryl betaine (Wa Reagent), 1-octene (Aladdin Biochemical Technology Co., Ltd.), 1-decene (Aladdin Biochemical Technology Co., Ltd.), 1-dodecene (Aladdin Biochemical Technology Co., Ltd.), hexadecyltrimethylammonium bromide (Aladdin Biochemical Technology Co., Ltd.), and synthesis gas (Daqing Petrochemical Company).

[0078] Example 1

[0079] This example synthesizes a quaternary ammonium salt cationic surfactant 2a

[0080] Add 18.04 g (0.4 mol) of dimethylamine, 24.71 g (0.1 mol) of 1-bromodecane and 200 mL of anhydrous ethanol to a reaction flask, and react at 50°C for 48 h under stirring. Cool and evaporate to remove the solvent, vacuum dry at 50°C for 24 h, add petroleum ether and water for separation, extract the aqueous phase with petroleum ether, wash with water, and distill under reduced pressure to obtain N,N-dimethyldecylamine (Compound 1a).

[0081]

[0082] In a round-bottom flask, 14.74 g (0.1 mol) of 1,3-dibromo-2-(bromoethyl)propane was dissolved in 100 mL of isopropanol, 0.3 mol of compound 1a was added, 0.4 g of sodium hydroxide was added as a catalyst, and the mixture was reacted at 80°C for 12 h. A waxy crude solid was obtained. The product was recrystallized three times in a mixed solvent of ethyl acetate / ethanol (20:1) to obtain a white powder compound 2a.

[0083]

[0084] Example 2

[0085] This example synthesizes a quaternary ammonium salt cationic surfactant 2b

[0086] Add 28.83 g (0.4 mol) of diethylamine, 22.02 g (0.1 mol) of 1-bromodecane and 200 mL of anhydrous ethanol to a reaction flask, and react at 60°C for 48 h under stirring. Cool and evaporate to remove the solvent, vacuum dry at 50°C for 24 h, add petroleum ether and water for separation, extract the aqueous phase with petroleum ether, wash with water, and distill under reduced pressure to obtain N,N-diethyldecylamine (Compound 1b).

[0087]

[0088] In a round-bottom flask, 14.74 g (0.05 mol) of 1,3-dibromo-2-(bromoethyl)propane was dissolved in 100 mL of isopropanol, 0.15 mol (32.01 g) of compound 1b was added, and 0.4 g of sodium hydroxide was added as a catalyst, and the mixture was reacted at 80°C for 15 h. A waxy crude solid was obtained. The product was recrystallized three times in a mixed solvent of ethyl acetate / ethanol (20:1) to obtain a white powder compound 2b.

[0089]

[0090] Example 3

[0091] This example synthesizes a quaternary ammonium salt cationic surfactant 2c

[0092] Add 18.04 g (0.4 mol) of dimethylamine, 24.71 g (0.1 mol) of dodecyl bromide and 200 mL of anhydrous ethanol to a reaction flask, and react at 60°C for 48 h under stirring. Cool and evaporate the solvent, vacuum dry at 50°C for 24 h, add petroleum ether and water for separation, extract the aqueous phase with petroleum ether, wash with water, and distill under reduced pressure to obtain N,N-dimethyldodecylamine (Compound 1c).

[0093]

[0094] In a round-bottom flask, 14.74 g (0.05 mol) of 1,3-dibromo-2-(bromoethyl)propane was dissolved in 100 mL of isopropanol, 32.01 g (0.15 mol) of compound 1b was added, 0.4 g of sodium hydroxide was added as a catalyst, and the mixture was reacted at 80°C for 18 h. A waxy crude solid was obtained. The product was recrystallized three times in a mixed solvent of ethyl acetate / ethanol (20:1) to obtain a white powder compound 2c.

[0095]

[0096] The quaternary ammonium salt cationic surfactants 2a to 2c prepared in the above Examples 1 to 3 are 1 H-MNR and 15 N-MNR Figure 1 to Figure 6 .

[0097] Example 4

[0098] In this embodiment, a composite system is prepared using a quaternary ammonium salt cationic surfactant 2a, and is used in the hydroformylation of 1-octene.

[0099] 0.12 g of monohydrogen monocarbonyl tris(trisulfonated triphenylphosphine trisodium salt) rhodium HRh(CO)(TPPTS)3, 0.29 g of trisulfonated triphenylphosphine trisodium salt TPPTS, 34 mg of quaternary ammonium salt cationic surfactant 2a and 2.4 mg of lauryl betaine were dissolved in 20 mL of deionized water and added to a 100 mL stainless steel autoclave with stirring and stirred evenly.

[0100] 10mL 1-octene was added, and the air in the reactor was replaced with synthesis gas (CO:H2=1:1) for 3 times. The pressure was filled to 2MPa, and heating and stirring were turned on. The stirring rate was 100r / min. When the temperature rose to 100°C, the stirring rate was increased to 800r / min, and the timing was started. When the pressure in the reactor dropped, the pressure was replenished to 2MPa in time, and the reaction was carried out for 2 hours. After cooling, the reactants were taken out, and the water and oil phases were separated with a separatory funnel. The composition of the oil phase product was analyzed by gas chromatography, and the Rh loss in the product was determined by ICP-MS. The experimental results are shown in Table 1.

[0101] Example 5

[0102] The experimental method was the same as that of Example 4, except that 1-octene was replaced with an equal volume of 1-decene and other conditions remained unchanged. The experimental results are shown in Table 1.

[0103] Example 6

[0104] The experimental method was the same as that of Example 4, wherein 1-decene was replaced by an equal volume of 1-dodecene, and other conditions remained unchanged. The experimental results are shown in Table 1.

[0105] Example 7

[0106] The experimental method is the same as that of Example 4, wherein the quaternary ammonium salt surfactant is replaced by 2b in an equal amount of substance, and other conditions remain unchanged. The experimental results are shown in Table 1.

[0107] Example 8

[0108] The experimental method is the same as that of Example 4, wherein the quaternary ammonium salt surfactant is replaced by 2c in an equal amount of substance, and other conditions remain unchanged. The experimental results are shown in Table 1.

[0109] Example 9

[0110] The experimental method was the same as that of Example 4, wherein 2.4 mg of lauryl betaine surfactant was replaced by 1.5 mg, and other conditions remained unchanged. The experimental results are shown in Table 1.

[0111] Example 10

[0112] The experimental method was the same as that of Example 4, wherein 2.4 mg of lauryl betaine surfactant was replaced by 3.4 mg of cocamidopropyl-2-hydroxy-3-sulfopropyl betaine, and other conditions remained unchanged. The experimental results are shown in Table 1.

[0113] Embodiment 11

[0114] The experimental method was the same as that of Example 4, wherein 2.4 mg of lauryl betaine surfactant was replaced by 2.7 mg of lauryl amidopropyl betaine, and other conditions remained unchanged. The experimental results are shown in Table 1.

[0115] Example 12

[0116] The experimental method was the same as that of Example 4, wherein 2.4 mg of lauryl betaine surfactant was replaced by 3.0 mg of 1-hydroxyethyl-2-cocoyl imidazoline acetate, and other conditions remained unchanged. The experimental results are shown in Table 1.

[0117] Embodiment 13

[0118] The experimental method was the same as that of Example 4, except that 34 mg of surfactant 2a and 2.4 mg of lauryl betaine were replaced by 17 mg of surfactant 2a and 1.2 mg of lauryl betaine, and other conditions remained unchanged. The experimental results are shown in Table 1.

[0119] Embodiment 14

[0120] The experimental method was the same as that of Example 4, except that 34 mg of surfactant 2a and 2.4 mg of lauryl betaine were replaced by 25.5 mg of surfactant 2a and 1.8 mg of lauryl betaine, and other conditions remained unchanged. The experimental results are shown in Table 1.

[0121] Embodiment 15

[0122] The experimental method was the same as that of Example 4, wherein 34 mg of surfactant 2a and 2.4 mg of lauryl betaine were replaced by 42.5 mg of surfactant 2a and 3.0 mg of lauryl betaine, and other conditions remained unchanged. The experimental results are shown in Table 1.

[0123] Example 16

[0124] The experimental method was the same as in Example 4, wherein 2.4 mg of lauryl betaine surfactant was replaced by 12 mg, and other conditions remained unchanged. The experimental results are shown in Table 1.

[0125] Embodiment 17

[0126] The product after the reaction of Example 4 was taken out and quickly separated after standing. The separated lower catalyst water system was recycled. The recycling effect was evaluated according to the reaction conditions of Example 4. After 20 cycles, the catalytic effect remained basically unchanged. This is because the surfactant added in the invention is low, which can avoid the problem of product separation and catalyst loss caused by emulsification in the reaction system.

[0127] Comparative Example 1

[0128] The experimental method is the same as that of Example 4, wherein no surfactant is added to the system and other conditions remain unchanged. The experimental results are shown in Table 1.

[0129] Comparative Example 2

[0130] Experimental method Example 4, wherein the quaternary ammonium salt surfactant is replaced by an equal amount of cetyltrimethylammonium bromide (CTAB), the experimental results are shown in Table 1.

[0131] Comparative Example 3

[0132] Experimental method Example 4, wherein only 34 mg of cationic surfactant 2a was added as surfactant, and the experimental results are shown in Table 1.

[0133] Table 1

[0134]

[0135] From Comparative Examples 1 to 3, it can be seen that the addition of surfactants helps to improve the reactivity of the water-oil two-phase system. This is because the surfactants form micelles in water, which increases the solubility of olefins in the water phase, improves the mass transfer between the water and oil phases, and improves the catalytic activity of the catalytic system. Moreover, the quaternary ammonium salt cationic surfactant 2a containing three hydrophilic head groups is significantly better than the single head group CTAB under the condition of adding the same amount of substance.

[0136] From Comparative Example 3 and Example 4, it can be seen that after adding amphoteric surfactants to a quaternary ammonium salt cationic surfactant containing three hydrophilic head groups for compounding, the catalyst activity is better than that of a quaternary ammonium salt cationic surfactant containing three hydrophilic head groups alone. This is because the amphoteric surfactant carries an anionic group, which can increase the interaction with the cationic surfactant to improve the surface activity, making it easier for the surfactant molecules to form micelles. From Examples 4, 9, and 16, it can be seen that the amphoteric surfactant and the cationic surfactant can achieve the optimal effect within a certain range. This is because when the amount of the amphoteric surfactant added is too large, the interaction between the cation and the anion in the amphoteric surfactant is too strong, which reduces its surface activity.

[0137] The composition provided by the present invention can significantly improve the conversion rate of olefins when used for preparing high-carbon aldehydes by two-phase catalytic hydroformylation. This is because the cationic surfactant and the hydrophilic head group of the amphoteric surfactant interact with each other to form micelles more easily, achieving the effect of compounding and enhancing synergy, thereby reducing the amount of surfactant used, and effectively avoiding the problem that the product forms an emulsion after the reaction is completed and is difficult to separate.

[0138] Embodiment 18

[0139] In order to further verify the effect of the composition of the invention, the reaction effect was studied under different experimental conditions. The reaction conditions and experimental results are shown in Table 2. The conditions not specifically marked are the same as those in Example 4.

[0140] Table 2

[0141]

[0142] Obviously, the above embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not limitations on the implementation methods of the present invention. For ordinary technicians in the relevant field, other different forms of changes or modifications can be made based on the above description. It is impossible to list all the implementation methods here. All obvious changes or modifications derived from the technical solution of the present invention are still within the protection scope of the present invention.

Claims

1. A composition for preparing high carbon aldehydes by two-phase hydroformylation, wherein: The composition comprises a rhodium catalyst, a water-soluble phosphine ligand, a quaternary ammonium salt cationic surfactant and an amphoteric surfactant; The structural formula (I) of the quaternary ammonium salt cationic surfactant is shown as follows: In formula (I), R1, R2, R3, R4 and R5 are independently selected from methyl, ethyl, C3-C 18 A straight or branched alkane, X is F, Cl or Br; The molar ratio of the water-soluble phosphine ligand to the rhodium catalyst is (0.1-20):1; the molar ratio of the quaternary ammonium salt cationic surfactant to the rhodium catalyst is (0.05-100):1; the molar ratio of the quaternary ammonium salt cationic surfactant to the amphoteric surfactant is (0.1-50):

1.

2. The composition according to claim 1, wherein In formula (I), X is Br.

3. The composition according to claim 1, wherein In formula (I), R1 and R2 are independently selected from methyl, ethyl, C3-C6 straight-chain or branched alkane; R3 is selected from C5-C 18 A straight or branched alkane; R4 and R5 are independently selected from a straight or branched alkane of C1 to C5.

4. The composition according to claim 1, wherein In formula (I), R1 and R2 are independently selected from methyl, ethyl, propyl or isopropyl; R3 is selected from C8 to C 16 R4 and R5 are independently selected from C1 to C3 straight chain or branched chain alkanes.

5. The composition according to any one of claims 1 to 4, wherein In formula (I), R4 is a propyl group and R5 is a methyl group.

6. The composition according to claim 1, wherein The amphoteric surfactant is selected from lauryl betaine, coconut oil betaine, stearyl betaine, oleyl betaine, C 12 ~C 18 At least one of alkyl dimethyl betaine ammonium salt, lauroyl propyl betaine, cocamidopropyl-2-hydroxy-3-sulfopropyl betaine, 1-hydroxyethyl-2-cocoyl imidazoline acetate, disodium caprylamidoethyl-N-hydroxyethylaminoethoxypropionate, sodium cocamidoethyl-N-hydroxyethylaminopropionate, and sodium stearamidoethyl-N-hydroxyethylaminopropionate.

7. The composition according to claim 1, wherein The rhodium catalyst is selected from at least one of hydrated rhodium trichloride, acetylacetonato dicarbonyl rhodium, and monohydrogen monocarbonyl tris(trisulfonated triphenylphosphine trisodium salt) rhodium.

8. The composition according to claim 1, wherein The water-soluble phosphine ligand is selected from at least one of trisulfonated triphenylphosphine trisodium salt, disulfonated triphenylphosphine disodium salt, monosulfonated triphenylphosphine monosodium salt, sulfonated 2,2'-bis(diphenylphosphine methylene)-1,1'-biphenyl sodium salt, and 2,7-disulfo-4,5-bis(diphenylphosphine)-9,9-dimethylxanthene disodium salt.

9. The composition according to claim 1, wherein The molar ratio of the water-soluble phosphine ligand to the rhodium catalyst is (1-15):

1.

10. The composition according to claim 1, wherein The molar ratio of the quaternary ammonium salt cationic surfactant to the rhodium catalyst is (0.02-30):

1.

11. The composition according to claim 1, wherein The molar ratio of the quaternary ammonium salt cationic surfactant to the amphoteric surfactant is (1-30):

1.

12. A method for preparing high carbon aldehydes by two-phase hydroformylation, wherein: The method comprises reacting an olefin raw material with synthesis gas in the presence of a solution consisting of the composition according to any one of claims 1 to 11 and water to obtain a product, high-carbon aldehyde; the synthesis gas comprises hydrogen and carbon monoxide.

13. The method according to claim 12, wherein: The olefin raw material is C3~C 18 of olefins.

14. The method according to claim 12, wherein: In the solution, the concentration of rhodium is 0.1 mmol / L to 3 mmol / L, calculated as rhodium metal atoms.

15. The method according to claim 12, wherein: The reaction temperature is 50-150°C.

16. The method according to claim 12, wherein: The reaction pressure is 0.5 MPa to 10 MPa.

17. The method according to claim 12, wherein: The reaction time is 0.5h to 12h.

18. The method according to claim 12, wherein: The molar ratio of the olefin raw material to the rhodium metal atoms of the rhodium catalyst is (500-50000):

1.

19. The method according to claim 12, wherein: The molar ratio of hydrogen to carbon monoxide is (0.5-3):1.

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