A method for the preparation of fatty acids and fatty alcohols from fatty aldehydes

Abstract

The application discloses a method for preparing fatty acid and fatty alcohol from fatty aldehyde, which comprises the following steps: S1: reacting a mixture I containing a first catalyst and fatty aldehyde to obtain a fatty acid ester; S2: reacting a mixture II containing the fatty acid ester obtained in S1 and a second catalyst to obtain a fatty acid and a fatty alcohol; the fatty aldehyde is at least one of C4-C10 fatty aldehyde; the first catalyst is an aluminum catalyst supported by a polystyrene resin containing an amino acid functional group; and the second catalyst is a strong acidic cation exchange resin. The method has the advantages of mild reaction condition, good operation safety, simultaneous preparation of the fatty acid and the fatty alcohol, continuous reaction and high efficiency.

Description

TECHNICAL FIELD

[0001] The application relates to a method for preparing fatty acid and fatty alcohol from fatty aldehyde, and belongs to the technical field of organic chemical industry. BACKGROUND

[0002] Fatty acid is an organic acid composed of C, H and O, and is widely used in the production of chemicals such as cosmetics, detergents, fatty acid salts, paints, varnishes, rubber and soap. Fatty acid usually exists in the form of ester in nature, and fatty acid in free form is rarely seen. Fatty alcohol is an alcohol with a hydroxyl group connected to a fatty hydrocarbon group, and is widely used in the production of chemicals such as detergents, cosmetics and medicines. Fatty acid is mainly prepared by catalytic oxidation of fatty aldehyde, and fatty alcohol is mainly prepared by catalytic hydrogenation of fatty aldehyde. O2, H2 and other gases are needed, and usually high reaction temperature and pressure are needed, which is high in energy consumption and high in operation safety risk. SUMMARY

[0003] In order to solve the problems that O2, H2 and other gases are needed in the production process of fatty acid and fatty alcohol at present, and high reaction temperature and pressure are needed, which is high in energy consumption and high in operation safety risk, the application provides a method for preparing fatty acid and fatty alcohol by hydrolysis after preparing fatty acid ester from fatty aldehyde, which has the advantages of mild reaction conditions, good operation safety, simultaneous preparation of fatty acid and fatty alcohol, continuous reaction and high efficiency.

[0004] According to one aspect of the application, a method for preparing fatty acid and fatty alcohol from fatty aldehyde is provided, the method comprising the following steps:

[0005] S1: reacting a mixture I containing a first catalyst and fatty aldehyde to obtain a fatty acid ester;

[0006] S2: reacting a mixture II containing the fatty acid ester obtained in S1 and a second catalyst to obtain a fatty acid and a fatty alcohol;

[0007] The fatty aldehyde is at least one of C4-C10 fatty aldehyde;

[0008] The first catalyst is an aluminum catalyst supported by a polystyrene resin containing an amino acid functional group;

[0009] The second catalyst is a strong acid cation exchange resin.

[0010] Optionally, the aluminum catalyst supported by the polystyrene resin containing an amino acid functional group is prepared from a polystyrene resin containing an amino acid functional group and an aluminum salt as raw materials.

[0011] Optionally, the preparation method of the aluminum catalyst supported by the polystyrene resin containing an amino acid functional group comprises:

[0012] mixing a mixture III of the poly(styrene resin containing amino acid functional group) and an aqueous solution of aluminum salt, reacting III, drying to obtain the poly(styrene resin containing amino acid functional group) supported aluminum catalyst.

[0013] Optionally, the preparation of the poly(styrene resin containing amino acid functional group) supported aluminum catalyst comprises mixing the poly(styrene resin containing amino acid functional group) and the aqueous solution of aluminum salt, reacting III, suction filtering, washing with water, drying to obtain the poly(styrene resin containing amino acid functional group) supported aluminum catalyst.

[0014] Optionally, the mass ratio of the poly(styrene resin containing amino acid functional group) to the aqueous solution of aluminum salt is 1:1-1:2.

[0015] Optionally, the mass ratio of the poly(styrene resin containing amino acid functional group) to the aqueous solution of aluminum salt is independently selected from any value or a range value between any two values selected from 1:1, 1:1.2, 1:1.4, 1:1.5, 1:1.6, 1:1.8, 1:2.

[0016] Optionally, the aluminum salt in the aqueous solution of aluminum salt is at least one selected from aluminum sulfate, aluminum nitrate, aluminum chloride.

[0017] Optionally, the poly(styrene resin containing amino acid functional group) is prepared from a polystyrene resin compound and an amino acid.

[0018] Optionally, the mass concentration of the aqueous solution of aluminum salt is 10%-30%.

[0019] Optionally, the mass concentration of the aqueous solution of aluminum salt is independently selected from any value or a range value between any two values selected from 10%, 12%, 15%, 18%, 20%, 22%, 25%, 28%, 30%.

[0020] Optionally, the temperature of the reacting III is 20-40℃, and the time of the reacting III is 2-8h.

[0021] Optionally, the temperature of the reacting III is independently selected from any value or a range value between any two values selected from 20℃, 25℃, 28℃, 30℃, 35℃, 38℃, 40℃.

[0022] Optionally, the time of the reacting III is independently selected from any value or a range value between any two values selected from 2h, 3h, 4h, 5h, 6h, 7h, 8h.

[0023] Optionally, the temperature of the drying is 40-80℃, and the time of the drying is 2-8h.

[0024] Optionally, the temperature of the drying is independently selected from any value or a range between any two values of 40℃, 45℃, 50℃, 55℃, 60℃, 65℃, 70℃, 75℃, 80℃.

[0025] Optionally, the time of the drying is independently selected from any value or a range between any two values of 2h, 3h, 4h, 5h, 6h, 7h, 8h.

[0026] Optionally, the method for preparing the polystyrene resin containing amino acid functional group comprises:

[0027] The raw materials containing polystyrene resin compounds, amino acids, and water are reacted to obtain the polystyrene resin containing amino acid functional group.

[0028] Optionally, the polystyrene resin containing amino acid functional group is prepared from at least one of chloromethylated polystyrene resin and chloroacetylated polystyrene resin and amino acid.

[0029] Optionally, the preparation step of the polystyrene resin containing amino acid functional group is mixing at least one of the chloromethylated polystyrene resin and the chloroacetylated polystyrene resin, the amino acid, and water, reacting IV, and then filtering to obtain the polystyrene resin containing amino acid functional group.

[0030] Optionally, the amino acid is at least one of L-glycine, L-alanine, L-phenylalanine, L-histidine, and L-proline.

[0031] Optionally, the polystyrene resin compound is selected from chloromethylated polystyrene resin and / or chloroacetylated polystyrene resin.

[0032] Optionally, the chloromethylated polystyrene resin is prepared from polystyrene resin and chloromethyl ether.

[0033] Optionally, the chloroacetylated polystyrene resin is prepared from polystyrene resin and chloroacetyl chloride.

[0034] Optionally, the mass ratio of the polystyrene resin compound to the amino acid is 5:1 to 2:1.

[0035] Optionally, the mass ratio of the polystyrene resin compound to the amino acid is independently selected from any value or a range between any two values of 5:1, 4:1, 3:1, and 2:1.

[0036] Optionally, the mass ratio of the polystyrene resin compound to the water is 1:1 to 1:2.

[0037] Optionally, the mass ratio of the polystyrene resin compound to the water is independently selected from any value or a range value between any two values of 1:1, 1:1.2, 1:1.4, 1:1.6, 1:1.8, 1:2.

[0038] Optionally, the temperature of the reaction IV is 60-100°C, and the time of the reaction IV is 4-12h.

[0039] Optionally, the temperature of the reaction IV is independently selected from any value or a range value between any two values of 60°C, 65°C, 70°C, 75°C, 80°C, 85°C, 90°C, 95°C, 100°C.

[0040] Optionally, the time of the reaction IV is independently selected from any value or a range value between any two values of 4h, 5h, 6h, 7h, 8h, 9h, 10h, 11h, 12h.

[0041] Optionally, the method for preparing the polystyrene resin compound comprises:

[0042] After the polystyrene resin is swelled in a solvent, the polystyrene resin is mixed with a chlorine-containing organic compound to obtain the polystyrene resin compound.

[0043] Optionally, the chlorine-containing organic compound is selected from chloromethyl ether and / or chloroacetyl chloride.

[0044] Optionally, the solvent is selected from at least one of dichloromethane, dichloroethane, and trichloromethane.

[0045] Optionally, the mass ratio of the polystyrene resin to the solvent is 1:1-1:2.

[0046] Preferably, the mass ratio of the polystyrene resin to the solvent is independently selected from any value or a range value between any two values of 1:1, 1:1.2, 1:1.4, 1:1.6, 1:1.8, 1:2.

[0047] Optionally, the time of the swelling is 2-8h.

[0048] Optionally, the time of the swelling is independently selected from any value or a range value between any two values of 2h, 3h, 4h, 5h, 6h, 7h, 8h.

[0049] Optionally, the mass ratio of the polystyrene resin to the chlorine-containing organic compound is 1:1-1:2.

[0050] Optionally, the mass ratio of the polystyrene resin to the chlorine-containing organic compound is independently selected from any value or a range value between any two values of 1:1, 1:1.2, 1:1.4, 1:1.6, 1:1.8, 1:2.

[0051] Optionally, the temperature of the reaction V is 20-60℃, and the time of the reaction V is 4-12h.

[0052] Optionally, the temperature of the reaction V is independently selected from any value or a range value between any two values selected from 20℃, 25℃, 30℃, 35℃, 40℃, 45℃, 50℃, 55℃, 60℃.

[0053] Optionally, the time of the reaction V is independently selected from any value or a range value between any two values selected from 4h, 5h, 6h, 7h, 8h, 9h, 10h, 11h, 12h.

[0054] Optionally, the C4-C10 aliphatic aldehyde is at least one selected from butyl aldehyde, pentyl aldehyde, hexyl aldehyde, heptyl aldehyde, octyl aldehyde, nonyl aldehyde, decyl aldehyde.

[0055] Optionally, the strong acid cation exchange resin is at least one selected from D001 resin, Amberlyst-15 resin, 732 resin.

[0056] Optionally, the preparation step of S1 is: loading the first catalyst into a reaction tube, pumping at least one of the C4-C10 aliphatic aldehyde, and reacting I at a set reaction temperature to obtain the fatty acid ester.

[0057] Optionally, in S1, the temperature of the reaction I is 20-40℃, and the volume space velocity of the reaction I is 0.5-2h -1 .

[0058] Optionally, the temperature of the reaction I is independently selected from any value or a range value between any two values selected from 20℃, 25℃, 30℃, 35℃, 40℃.

[0059] Optionally, the volume space velocity of the reaction I is independently selected from any value or a range value between any two values selected from 0.5h -1 , 0.7h -1 , 1h -1 , 1.2h -1 , 1.5h -1 , 1.8h -1 , 2h -1 .

[0060] Optionally, the preparation step of S2 is: loading the second catalyst into a reaction tube, pumping the mixture of the fatty acid ester and water prepared in step S1, and reacting II at a set reaction temperature to obtain the fatty acid and the fatty alcohol.

[0061] Optionally, in S2, the mixture II further comprises water.

[0062] Optionally, the volume ratio of the fatty acid ester and water is 1:1 to 1:2.

[0063] Optionally, the volume ratio of the fatty acid ester and water is independently selected from any value or a range value between any two values of 1:1, 1:1.2, 1:1.4, 1:1.5, 1:1.6, 1:1.8, 1:2.

[0064] Optionally, in S2, the temperature of the reaction II is 60 to 100℃, and the volume space velocity of the reaction II is 0.2 to 0.5h -1 .

[0065] Optionally, the temperature of the reaction II is independently selected from any value or a range value between any two values of 60℃, 65℃, 70℃, 75℃, 80℃, 85℃, 90℃, 95℃, 100℃.

[0066] Optionally, the volume space velocity of the reaction II is independently selected from any value or a range value between any two values of 0.2h -1 , 0.25h -1 , 0.3h -1 , 0.35h -1 , 0.4h -1 , 0.45h -1 , 0.5h -1 .

[0067] According to the present application, the catalyst is extremely important. When there is no first catalyst or the activity of the first catalyst is low, the conversion rate of the fatty aldehyde is very low. When the activity and selectivity of the first catalyst are high, high conversion rate of the fatty aldehyde and high yield of the fatty acid ester can be achieved. When there is no second catalyst or the activity of the second catalyst is low, the conversion rate of the fatty acid ester is very low. When the activity and selectivity of the second catalyst are high, high conversion rate of the fatty acid ester and high yield of the fatty acid and the fatty alcohol can be achieved.

[0068] The beneficial effects that can be produced by the present application include:

[0069] In view of the problems in the prior art that O2, H2 and other gases are needed in the production process of fatty acids and fatty alcohols, and high reaction temperature and pressure are needed, the energy consumption is high, and the operation safety risk is large, the present application provides a method for preparing fatty acids and fatty alcohols by directly converting fatty aldehydes and then hydrolyzing fatty acid esters, which uses a polystyrene resin loaded with an aluminum catalyst containing an amino acid functional group and a strong acid cation exchange resin for catalysis, has the advantages of mild reaction conditions, good operation safety, simultaneous obtaining of fatty acids and fatty alcohols, continuous reaction efficiency, etc. DETAILED DESCRIPTION

[0070] The application will be described in detail below with reference to examples, but the application is not limited to these examples.

[0071] The raw materials in the examples of the application are all purchased through commercial channels unless otherwise specified.

[0072] The test methods are all conventional methods unless otherwise specified.

[0073] The conversion rate and yield in the examples of the application are calculated as follows:

[0074]

[0075]

[0076]

[0077]

[0078]

[0079] The Agilent Technologies 7890A-5975C gas chromatography-mass spectrometry analysis is used to determine the conversion rate of fatty aldehyde, the yield of fatty acid ester, the conversion rate of fatty acid ester, the yield of fatty acid, and the yield of fatty alcohol.

[0080] Example 1

[0081] After 60 g of polystyrene resin is swelled in 60 g of dichloromethane for 8 h, it is filtered, the obtained solid is mixed with 60 g of chloromethyl ether, and the mixture is reacted at 20°C for 12 h, filtered, to obtain 66 g of chloromethylated polystyrene resin.

[0082] Example 2

[0083] After 60 g of polystyrene resin is swelled in 120 g of dichloroethane for 2 h, it is filtered, the obtained solid is mixed with 120 g of chloroacetyl chloride, and the mixture is reacted at 60°C for 4 h, filtered, to obtain 68 g of chloroacetylated polystyrene resin.

[0084] Example 3

[0085] 20 g of chloromethylated polystyrene resin prepared in Example 1 is mixed with 4 g of L-glycine and 20 g of water, and the mixture is reacted at 60°C for 12 h, filtered, to obtain 23 g of polystyrene resin containing L-glycine functional groups.

[0086] Example 4

[0087] 20 g of chloromethylated polystyrene resin prepared in Example 1 is mixed with 10 g of L-alanine and 40 g of water, and the mixture is reacted at 100°C for 4 h, filtered, to obtain 23 g of polystyrene resin containing L-alanine functional groups.

[0088] Example 5

[0089] 20 g of chloromethylated polystyrene resin prepared in Example 1 and 5 g of L-phenylalanine, 30 g of water were mixed and reacted at 80 °C for 8 h, suction filtered to obtain 24 g of polystyrene resin containing L-phenylalanine functional group.

[0090] Example 6

[0091] 20 g of chloroacetylated polystyrene resin prepared in Example 2 and 4 g of L-histidine, 20 g of water were mixed and reacted at 60 °C for 12 h, suction filtered to obtain 23 g of polystyrene resin containing L-histidine functional group.

[0092] Example 7

[0093] 20 g of chloroacetylated polystyrene resin prepared in Example 2 and 10 g of L-proline, 40 g of water were mixed and reacted at 100 °C for 4 h, suction filtered to obtain 23 g of polystyrene resin containing L-proline functional group.

[0094] Example 8

[0095] 23 g of polystyrene resin containing L-glycine functional group prepared in Example 3 and 23 g of 20% aqueous aluminum nitrate solution were mixed and reacted at 40 °C for 4 h, suction filtered, washed with water and dried at 80 °C for 2 h to obtain 24 g of polystyrene resin containing L-glycine functional group supported aluminum catalyst.

[0096] Example 9

[0097] 23 g of polystyrene resin containing L-alanine functional group prepared in Example 4 and 46 g of 10% aqueous aluminum sulfate solution were mixed and reacted at 20 °C for 8 h, suction filtered, washed with water and dried at 40 °C for 8 h to obtain 24 g of polystyrene resin containing L-alanine functional group supported aluminum catalyst.

[0098] Example 10

[0099] 24 g of polystyrene resin containing L-phenylalanine functional group prepared in Example 5 and 35 g of 30% aqueous aluminum chloride solution were mixed and reacted at 30 °C for 2 h, suction filtered, washed with water and dried at 60 °C for 4 h to obtain 25 g of polystyrene resin containing L-phenylalanine functional group supported aluminum catalyst.

[0100] Example 11

[0101] 23 g of polystyrene resin containing L-histidine functional group prepared in Example 6 and 23 g of 20% aqueous aluminum nitrate solution were mixed and reacted at 40 °C for 4 h, suction filtered, washed with water and dried at 80 °C for 2 h to obtain 24 g of polystyrene resin containing L-histidine functional group supported aluminum catalyst.

[0102] Example 12

[0103] 23g of the L-proline functionalized polystyrene resin prepared in Example 7 was mixed with 46g of 10% aqueous solution of aluminum chloride, and reacted at 20°C for 8h, filtered, washed with water, and dried at 40°C for 8h to obtain 24g of the L-proline functionalized polystyrene resin supported aluminum catalyst.

[0104] Example 13

[0105] 20g of the L-glycine functionalized polystyrene resin supported aluminum catalyst prepared in Example 8 was charged into a reactor, and n-butyraldehyde was pumped in and reacted at 20°C, with a reaction volume space velocity of 1h -1 After the reaction was continuously operated for 4h, a sample was taken and analyzed by gas chromatography-mass spectrometry, and the conversion of n-butyraldehyde and the yield of butyl butyrate were both over 99%. After the reaction was continuously operated for 24h, a sample was again taken and analyzed, and the conversion of n-butyraldehyde and the yield of butyl butyrate were both over 99%.

[0106] Example 14

[0107] 20g of the L-alanine functionalized polystyrene resin supported aluminum catalyst prepared in Example 9 was charged into a reactor, and n-heptyl aldehyde was pumped in and reacted at 30°C, with a reaction volume space velocity of 0.5h -1 After the reaction was continuously operated for 4h, a sample was taken and analyzed by gas chromatography-mass spectrometry, and the conversion of n-heptyl aldehyde and the yield of heptyl heptylate were both over 99%. After the reaction was continuously operated for 24h, a sample was again taken and analyzed, and the conversion of n-heptyl aldehyde and the yield of heptyl heptylate were both over 99%.

[0108] Example 15

[0109] 20g of the L-phenylalanine functionalized polystyrene resin supported aluminum catalyst prepared in Example 10 was charged into a reactor, and n-decyl aldehyde was pumped in and reacted at 40°C, with a reaction volume space velocity of 2h -1 After the reaction was continuously operated for 24h, a sample was taken and analyzed by gas chromatography-mass spectrometry, and the conversion of n-decyl aldehyde was 93% and the yield of decyl decanoate was 92%.

[0110] Example 16

[0111] 20g of the L-histidine functionalized polystyrene resin supported aluminum catalyst prepared in Example 11 was charged into a reactor, and n-pentyl aldehyde was pumped in and reacted at 20°C, with a reaction volume space velocity of 1h -1 After the reaction was continuously operated for 24h, a sample was taken and analyzed by gas chromatography-mass spectrometry, and the conversion of n-pentyl aldehyde was 94% and the yield of pentyl pentanoate was 93%.

[0112] Example 17

[0113] A 20 g of L-proline functionalized polystyrene resin supported aluminum catalyst prepared in Example 12 was charged into a reactor tube, n-octyl aldehyde was pumped in, and the reaction was carried out at 30°C with a reaction volume space velocity of 1 h -1 After the reaction was continuously carried out for 24 h, a sample was taken and analyzed by gas chromatography-mass spectrometry. The conversion of n-octyl aldehyde was 92% and the yield of octanoic acid octyl ester was 91%.

[0114] Example 18

[0115] A 20 g of strongly acidic cation exchange resin 732 resin was charged into a reactor tube, a mixture of butyl butyrate and water prepared in Example 13 was pumped in, the volume ratio of butyl butyrate to water was 1:1, and the reaction was carried out at 100°C with a reaction volume space velocity of 0.5 h -1 After the reaction was continuously carried out for 4 h, a sample was taken and analyzed by gas chromatography-mass spectrometry. The conversion of butyl butyrate was 88%, the yield of n-butyric acid was 88%, and the yield of n-butanol was 88%. After the reaction was continuously carried out for 24 h, a sample was taken again and analyzed by gas chromatography-mass spectrometry. The conversion of butyl butyrate was 88%, the yield of n-butyric acid was 88%, and the yield of n-butanol was 88%.

[0116] Example 19

[0117] A 20 g of strongly acidic cation exchange resin D001 resin was charged into a reactor tube, a mixture of heptyl heptanoate and water prepared in Example 14 was pumped in, the volume ratio of heptyl heptanoate to water was 1:2, and the reaction was carried out at 60°C with a reaction volume space velocity of 0.2 h -1 After the reaction was continuously carried out for 24 h, a sample was taken and analyzed by gas chromatography-mass spectrometry. The conversion of heptyl heptanoate was 82%, the yield of n-heptyl acid was 82%, and the yield of n-heptanol was 82%.

[0118] Example 20

[0119] A 20 g of strongly acidic cation exchange resin Amberlyst-15 resin was charged into a reactor tube, a mixture of decyl decanoate and water prepared in Example 15 was pumped in, the volume ratio of decyl decanoate to water was 1:1.5, and the reaction was carried out at 80°C with a reaction volume space velocity of 0.3 h -1 After the reaction was continuously carried out for 24 h, a sample was taken and analyzed by gas chromatography-mass spectrometry. The conversion of decyl decanoate was 79%, the yield of n-decanoic acid was 79%, and the yield of n-decanol was 79%.

[0120] Comparative Example 1

[0121] Comparative Example 1 differs from Example 8 in that 23 g of chloroacetylated polystyrene resin prepared in Example 2 was used instead of the L-glycine functionalized polystyrene resin used in Example 8, and other reaction conditions were the same as those in Example 8. Finally, 23 g of chloroacetylated polystyrene resin supported aluminum catalyst without amino acid functional groups was obtained.

[0122] Comparative Example 2

[0123] Comparative Example 2 differs from Example 13 in that the aluminum catalyst supported on the chloroacetylated polystyrene resin without amino acid functional group prepared from 20 g of Comparative Example 1 is used instead of the aluminum catalyst supported on the polystyrene resin with L-glycine functional group used in Example 13, and other reaction conditions are the same as those in Example 13. The conversion of n-butyraldehyde is 0%.

[0124] The results of Comparative Example 2 show that n-butyraldehyde is not converted when the aluminum catalyst supported on the chloroacetylated polystyrene resin without amino acid functional group is used, indicating that the amino acid functional group plays a very important role.

[0125] Comparative Example 3

[0126] Comparative Example 3 differs from Example 19 in that no strong acidic cation exchange resin D001 resin is loaded in the reaction tube, and other reaction conditions are the same as those in Example 19. The results show that the conversion of heptyl heptanoate is 1%, the yield of n-heptanoic acid is 1%, and the yield of n-heptanol is 1%.

[0127] The results of Comparative Example 3 show that the conversion of fatty acid ester is very low when there is no second catalyst.

[0128] In summary, the present application provides a method for directly converting fatty aldehyde to fatty acid ester and then hydrolyzing the fatty acid ester to fatty acid and fatty alcohol, which addresses the problems in the current production process of fatty acid and fatty alcohol, such as the need for O2, H2, and other gases, the need for high reaction temperature and pressure, high energy consumption, and high safety risk in operation. The method has the advantages of mild reaction conditions, good operation safety, simultaneous production of fatty acid and fatty alcohol, continuous reaction, and high efficiency.

[0129] The above is only a few embodiments of the present application, and does not limit the present application in any form. Although the above is disclosed as a preferred embodiment, it does not limit the present application. Any person skilled in the art can make some changes or modifications to the above disclosed technical content without departing from the scope of the technical solution of the present application, and such changes or modifications are equivalent to equivalent embodiments, and are within the scope of the technical solution.

Claims

1. A method for preparing a fatty acid and a fatty alcohol from a fatty aldehyde, characterized by, The method comprises the following steps: S1: reacting mixture I containing a first catalyst and a fatty aldehyde to obtain a fatty acid ester; S2: reacting mixture II containing the fatty acid ester obtained in S1 and a second catalyst to obtain a fatty acid and a fatty alcohol; The fatty aldehyde is at least one of C4-C10 fatty aldehydes; The first catalyst is an amino acid functional group-containing polystyrene resin supported aluminum catalyst; The second catalyst is a strong acid cation exchange resin; The preparation method of the amino acid functional group-containing polystyrene resin supported aluminum catalyst comprises: Mixing mixture III containing an amino acid functional group-containing polystyrene resin and an aqueous aluminum salt solution, reacting III, drying to obtain the amino acid functional group-containing polystyrene resin supported aluminum catalyst; The aluminum salt in the aqueous aluminum salt solution is at least one of aluminum-containing sulfate, nitrate, and hydrochloride; The preparation method of the amino acid functional group-containing polystyrene resin comprises: Using raw materials containing a polystyrene resin compound, an amino acid, and water to obtain the amino acid functional group-containing polystyrene resin by reaction IV; The amino acid is at least one of L-glycine, L-alanine, L-phenylalanine, L-histidine, and L-proline; The polystyrene resin compound is selected from chloromethylated polystyrene resin and / or chloroacetylated polystyrene resin.

2. The method of claim 1, wherein, The mass ratio of the amino acid functional group-containing polystyrene resin to the aqueous aluminum salt solution is 1:1 to 1:2; The amino acid functional group-containing polystyrene resin is prepared using a polystyrene resin compound and an amino acid as raw materials; The mass concentration of the aqueous aluminum salt solution is 10% to 30%; The temperature of the reaction III is 20 to 40°C, and the reaction III time is 2 to 8 hours; The drying temperature is 40 to 80°C, and the drying time is 2 to 8 hours.

3. The method of claim 1, wherein, The mass ratio of the polystyrene resin compound to the amino acid is 5:1 to 2:1; The mass ratio of the polystyrene resin compound to the water is 1:1 to 1:2; The temperature of the reaction IV is 60 to 100°C, and the reaction IV time is 4 to 12 hours.

4. The method of claim 1, wherein, The preparation method of the polystyrene resin compound comprises: After the polystyrene resin is swelled in a solvent, it is mixed with a chlorine-containing organic compound to obtain the polystyrene resin compound by reaction V.

5. The method of claim 4, wherein, The chlorine-containing organic compound is selected from chloromethyl ether and / or chloroacetyl chloride; The solvent is at least one of dichloromethane, dichloroethane, and trichloromethane.

6. The method of claim 4, wherein, The mass ratio of the polystyrene resin to the solvent is 1:1 to 1:2; The swelling time is 2 to 8 hours; The mass ratio of the polystyrene resin to the chlorine-containing organic compound is 1:1 to 1:2; The temperature of the reaction V is 20 to 60°C, and the reaction V time is 4 to 12 hours.

7. The method of claim 1, wherein, The C4-C10 fatty aldehyde is at least one of butyl aldehyde, pentyl aldehyde, hexyl aldehyde, heptyl aldehyde, octyl aldehyde, nonyl aldehyde, and decyl aldehyde; The strong acid cation exchange resin is at least one of D001 resin, Amberlyst-15 resin, and 732 resin.

8. The method of claim 1, wherein, In the S1, the temperature of the reaction I is 20-40℃, the volume space velocity of the reaction I is 0.5-2h -1 .

9. The method of claim 1, wherein, In S2, the mixture II further comprises water; The volume ratio of the fatty acid ester and water is 1:1-1:

2.

10. The method of claim 1, wherein, In the S2, the temperature of the reaction II is 60-100°C, the volume space velocity of the reaction II is 0.2-0.5h -1 .

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