Method for preparing fatty acid and fatty alcohol from fatty aldehyde

Abstract

The invention 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 fatty acid ester; s2, a mixture II containing the fatty acid ester obtained in the S1 and a second catalyst is subjected to a reaction II, and fatty acid and fatty alcohol are obtained; the fatty aldehyde is at least one of fatty aldehydes of C4-C10; the first catalyst is a polystyrene resin loaded aluminum catalyst containing amino acid functional groups; the second catalyst is strongly acidic cation exchange resin. The method has the advantages of mild reaction conditions, good operation safety, capability of simultaneously obtaining fatty acid and fatty alcohol, continuous reaction, high efficiency and the like.

Description

Technical Field

[0001] The present application relates to a method for preparing fatty acids and fatty alcohols from fatty aldehydes, and belongs to the technical field of organic chemical industry. Background Art

[0002] Fatty acids are organic acids composed of three elements: C, H, and O. They are widely used in the production of cosmetics, detergents, fatty acid salts, coatings, paints, rubber, soaps and other chemicals. Fatty acids usually exist in the form of esters in nature, and fatty acids in free form are rare. Fatty alcohols are alcohols with hydroxyl groups connected to aliphatic hydrocarbon groups. They are widely used in the production of detergents, cosmetics, pharmaceuticals and other chemicals. Fatty acids are mainly produced by catalytic oxidation of fatty aldehydes, and fatty alcohols are mainly produced by catalytic hydrogenation of fatty aldehydes, which requires O 2 , H 2 It uses gases such as chlorinated hydrocarbons, and usually requires higher reaction temperatures and pressures, high energy consumption, and high operational safety risks. Summary of the invention

[0003] In order to solve the current production process of fatty acids and fatty alcohols, O 2 , H 2 The present application provides a method for preparing fatty acid esters from fatty aldehydes and then hydrolyzing them to prepare fatty acids and fatty alcohols, which has the advantages of mild reaction conditions, good operational safety, the ability to simultaneously obtain fatty acids and fatty alcohols, and continuous reaction with high efficiency.

[0004] According to one aspect of the present application, a method for preparing fatty acids and fatty alcohols from fatty aldehydes is provided, the method comprising the following steps:

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

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

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

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

[0009] The second catalyst is a strongly acidic cation exchange resin.

[0010] Optionally, the aluminum catalyst supported on the polystyrene resin containing amino acid functional groups is prepared using the polystyrene resin containing amino acid functional groups and aluminum salt as raw materials.

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

[0012] The mixture III of the polystyrene resin containing amino acid functional groups and the aluminum salt aqueous solution is reacted III and dried to obtain the aluminum catalyst supported by the polystyrene resin containing amino acid functional groups.

[0013] Optionally, the preparation steps of the polystyrene resin-containing amino acid functional groups supported aluminum catalyst are: mixing the polystyrene resin-containing amino acid functional groups and the aluminum salt aqueous solution, reacting III, filtering, washing with water, and drying to obtain the polystyrene resin-containing amino acid functional groups supported aluminum catalyst.

[0014] Optionally, the mass ratio of the polystyrene resin containing amino acid functional groups to the aluminum salt aqueous solution is 1:1 to 1:2.

[0015] Optionally, the mass ratio of the polystyrene resin containing amino acid functional groups to the aluminum salt aqueous solution is independently selected from any value of 1:1, 1:1.2, 1:1.4, 1:1.5, 1:1.6, 1:1.8, 1:2 or any range between two of them.

[0016] Optionally, the aluminum salt in the aluminum salt aqueous solution is selected from at least one of aluminum-containing sulfates, nitrates and hydrochlorides.

[0017] Optionally, the polystyrene resin containing amino acid functional groups is prepared using polystyrene resin compounds and amino acids as raw materials.

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

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

[0020] Optionally, the temperature of reaction III is 20-40° C., and the time of reaction III is 2-8 h.

[0021] Optionally, the temperature of the reaction III is independently selected from any value of 20°C, 25°C, 28°C, 30°C, 35°C, 38°C, 40°C, or any range therebetween.

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

[0023] Optionally, the drying temperature is 40 to 80° C., and the drying time is 2 to 8 hours.

[0024] Optionally, the drying temperature is independently selected from any value of 40°C, 45°C, 50°C, 55°C, 60°C, 65°C, 70°C, 75°C, 80°C, or any range therebetween.

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

[0026] Optionally, the preparation method of the polystyrene resin containing amino acid functional groups comprises:

[0027] The raw materials containing polystyrene resin compounds, amino acids and water are subjected to reaction IV to obtain the polystyrene resin containing amino acid functional groups.

[0028] Optionally, the polystyrene resin containing amino acid functional groups is prepared using at least one of chloromethylated polystyrene resin and chloroacetylated polystyrene resin and amino acid as raw materials.

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

[0030] Optionally, the amino acid is selected from 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 using polystyrene resin and chloromethyl ether as raw materials.

[0033] Optionally, the chloroacetylated polystyrene resin is prepared using polystyrene resin and chloroacetyl chloride as raw materials.

[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 of 5:1, 4:1, 3:1, 2:1, or a range between any two of them.

[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 of 1:1, 1:1.2, 1:1.4, 1:1.6, 1:1.8, 1:2, or a range between any two of them.

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

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

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

[0041] Optionally, the preparation method of the polystyrene resin compound comprises:

[0042] The polystyrene resin is swollen in a solvent and then mixed with a chlorine-containing organic matter to perform a reaction V 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 chloroform.

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

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

[0047] Optionally, the swelling time is 2 to 8 hours.

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

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

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

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

[0052] Optionally, the temperature of the reaction V is independently selected from any value of 20°C, 25°C, 30°C, 35°C, 40°C, 45°C, 50°C, 55°C, 60°C, or any range therebetween.

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

[0054] Optionally, the C4-C10 fatty aldehyde is selected from at least one of butyraldehyde, valeraldehyde, hexanal, heptanal, octanal, nonanal and decanal.

[0055] Optionally, the strongly acidic cation exchange resin is selected from at least one of D001 resin, Amberlyst-15 resin, and 732 resin.

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

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

[0058] Optionally, the temperature of the reaction I is independently selected from any value of 20°C, 25°C, 30°C, 35°C, 40°C, or any range therebetween.

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

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

[0061] Optionally, in S2, the mixture II also includes water.

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

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

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

[0065] Optionally, the temperature of the reaction II is independently selected from any value of 60°C, 65°C, 70°C, 75°C, 80°C, 85°C, 90°C, 95°C, 100°C, or any range therebetween.

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

[0067] According to the present application, the catalyst is extremely important. When there is no first catalyst or the first catalyst has low activity, the conversion rate of fatty aldehydes is very low. When the first catalyst has high activity and selectivity, a high conversion rate of fatty aldehydes and a high yield of fatty acid esters can be obtained. When there is no second catalyst or the second catalyst has low activity, the conversion rate of fatty acid esters is very low. When the second catalyst has high activity and selectivity, a high conversion rate of fatty acid esters and a high yield of fatty acids and fatty alcohols can be obtained.

[0068] The beneficial effects of this application include:

[0069] The production process of fatty acids and fatty alcohols in the prior art requires the use of 2 , H 2The present application provides a method for directly converting fatty aldehydes into fatty acid esters and then hydrolyzing them into fatty acids and fatty alcohols, which uses an aluminum catalyst supported by a polystyrene resin containing amino acid functional groups and a strongly acidic cation exchange resin for catalysis. The method has the advantages of mild reaction conditions, good operational safety, the ability to simultaneously obtain fatty acids and fatty alcohols, and continuous reaction with high efficiency. DETAILED DESCRIPTION

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

[0071] Unless otherwise specified, the raw materials in the examples of this application were purchased through commercial channels.

[0072] Unless otherwise specified, conventional methods were used for testing.

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

[0074]

[0075]

[0076]

[0077]

[0078]

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

[0080] Example 1

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

[0082] Example 2

[0083] 60 g of polystyrene resin was swelled in 120 g of ethylene dichloride for 2 h and then filtered. The obtained solid was mixed with 120 g of chloroacetyl chloride, reacted at 60° C. for 4 h, and filtered to obtain 68 g of chloroacetylated polystyrene resin.

[0084] Example 3

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

[0086] Example 4

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

[0088] Example 5

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

[0090] Example 6

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

[0092] Example 7

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

[0094] Example 8

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

[0096] Example 9

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

[0098] Example 10

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

[0100] Embodiment 11

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

[0102] Example 12

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

[0104] Example 13

[0105] 20 g of the aluminum catalyst supported by polystyrene resin containing L-glycine functional group prepared in Example 8 was placed in a reaction tube, and n-butyraldehyde was pumped into the reaction tube. The reaction was carried out at 20° C. and the reaction volume space velocity was 1 h -1 After the reaction was run continuously for 4 hours, samples were taken and analyzed by gas chromatography-mass spectrometry. The conversion rate of n-butyraldehyde and the yield of butyl butyrate were both above 99%. After the reaction was run continuously for 24 hours, samples were taken again and analyzed. The conversion rate of n-butyraldehyde and the yield of butyl butyrate were both above 99%.

[0106] Embodiment 14

[0107] 20 g of the aluminum catalyst supported by polystyrene resin containing L-alanine functional group prepared in Example 9 was placed in a reaction tube, and n-heptanal was pumped into the reaction tube. The reaction was carried out at 30° C. and the reaction volume space velocity was 0.5 h -1 After the reaction was run continuously for 4 hours, samples were taken and analyzed by gas chromatography-mass spectrometry. The conversion rate of n-heptanal and the yield of heptyl heptate were both above 99%. After the reaction was run continuously for 24 hours, samples were taken again and analyzed. The conversion rate of n-heptanal and the yield of heptyl heptate were both above 99%.

[0108] Embodiment 15

[0109] 20 g of the aluminum catalyst loaded with polystyrene resin containing L-phenylalanine functional groups prepared in Example 10 was placed in a reaction tube, and n-decanal was pumped into the reaction tube. The reaction was carried out at 40° C. and the reaction volume space velocity was 2 h -1After the reaction was run continuously for 24 hours, samples were taken and analyzed by gas chromatography-mass spectrometry. The conversion rate of n-decanal was 93% and the yield of decanoate was 92%.

[0110] Example 16

[0111] 20 g of the aluminum catalyst loaded with polystyrene resin containing L-histidine functional group prepared in Example 11 was placed in a reaction tube, and n-valeraldehyde was pumped into the reaction tube. The reaction was carried out at 20° C. and the reaction volume space velocity was 1 h -1 After the reaction was run continuously for 24 hours, samples were taken and analyzed by gas chromatography-mass spectrometry. The conversion rate of n-valeraldehyde was 94% and the yield of pentyl valerate was 93%.

[0112] Embodiment 17

[0113] 20 g of the aluminum catalyst supported by polystyrene resin containing L-proline functional group prepared in Example 12 was placed in a reaction tube, and n-octanal was pumped into the reaction tube. The reaction was carried out at 30° C. and the reaction volume space velocity was 1 h -1 After the reaction was run continuously for 24 hours, samples were taken and analyzed by gas chromatography-mass spectrometry. The conversion rate of n-octanal was 92% and the yield of octyl octanoate was 91%.

[0114] Embodiment 18

[0115] 20 g of strongly acidic cation exchange resin 732 was placed in a reaction tube, and 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 run continuously for 4 hours, samples were taken and analyzed by gas chromatography-mass spectrometry. The conversion rate 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 run continuously for 24 hours, samples were taken again for analysis. The conversion rate of butyl butyrate was 88%, the yield of n-butyric acid was 88%, and the yield of n-butanol was 88%.

[0116] Embodiment 19

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

[0118] Embodiment 20

[0119] 20 g of strongly acidic cation exchange resin Amberlyst-15 was placed in a reaction tube, and a mixture of decyl decanoate and water prepared in Example 15 was pumped in, the volume ratio of decyl decanoate to water being 1:1.5, the reaction temperature being 80° C., and the reaction volume space velocity being 0.3 h -1 After the reaction was run continuously for 24 hours, samples were taken and analyzed by gas chromatography-mass spectrometry. The conversion rate of decyl decanoate, the yield of n-decanoic acid, and the yield of n-decanol were 79%.

[0120] Comparative Example 1

[0121] The difference between Comparative Example 1 and Example 8 is that 23 g of the chloroacetylated polystyrene resin prepared in Example 2 is used instead of the polystyrene resin containing L-glycine functional group used in Example 8, and the other reaction conditions are the same as those in Example 8, and finally 23 g of chloroacetylated polystyrene resin-loaded aluminum catalyst without amino acid functional group is obtained.

[0122] Comparative Example 2

[0123] The difference between Comparative Example 2 and Example 13 is that 20 g of the aluminum catalyst supported by the chloroacetylated polystyrene resin without amino acid functional groups prepared in Comparative Example 1 is used instead of the aluminum catalyst supported by the polystyrene resin containing L-glycine functional groups used in Example 13, and the other reaction conditions are the same as those in Example 13. The final conversion rate of n-butyraldehyde is 0%.

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

[0125] Comparative Example 3

[0126] The difference between Comparative Example 3 and Example 19 is that the reaction tube is not filled with strongly acidic cation exchange resin D001 resin, and the other reaction conditions are the same as those in Example 19. As a result, the conversion rate 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 when there is no second catalyst, the conversion rate of fatty acid ester is very low.

[0128] In summary, this application is aimed at the current production process of fatty acids and fatty alcohols that requires O 2 , H 2 The invention discloses a method for directly converting fatty aldehydes into fatty acid esters and then hydrolyzing them to prepare fatty acids and fatty alcohols, which has the advantages of mild reaction conditions, good operational safety, the ability to simultaneously obtain fatty acids and fatty alcohols, and high continuous reaction efficiency.

[0129] The above are only a few embodiments of the present application and do not constitute any form of limitation to the present application. Although the present application is disclosed as above with preferred embodiments, it is not intended to limit the present application. Any technician familiar with the profession, without departing from the scope of the technical solution of the present application, using the technical content disclosed above to make slight changes or modifications are equivalent to equivalent implementation cases and fall within the scope of the technical solution.

Claims

1. A method for preparing fatty acids and fatty alcohols from fatty aldehydes, It is characterized in that The method comprises the following steps: S1: reacting a mixture I containing a first catalyst and a fatty aldehyde to obtain a fatty acid ester; S2: reacting the mixture II containing the fatty acid ester obtained in S1 and the second catalyst to obtain fatty acids and fatty alcohols; The fatty aldehyde is at least one of C4 to C10 fatty aldehydes; The first catalyst is an aluminum catalyst supported by polystyrene resin containing amino acid functional groups; The second catalyst is a strongly acidic cation exchange resin.

2. The method according to claim 1, It is characterized in that The preparation method of the polystyrene resin-supported aluminum catalyst containing amino acid functional groups comprises: The mixture III of the polystyrene resin containing amino acid functional groups and the aluminum salt aqueous solution is reacted III, dried, and the aluminum catalyst supported by the polystyrene resin containing amino acid functional groups is obtained; Preferably, the mass ratio of the polystyrene resin containing amino acid functional groups to the aluminum salt aqueous solution is 1:1 to 1:2; Preferably, the aluminum salt in the aluminum salt aqueous solution is selected from at least one of aluminum sulfate, nitrate and hydrochloride; Preferably, the polystyrene resin containing amino acid functional groups is prepared by using polystyrene resin compounds and amino acids as raw materials; Preferably, the mass concentration of the aluminum salt aqueous solution is 10% to 30%; Preferably, the temperature of reaction III is 20-40°C, and the time of reaction III is 2-8h; Preferably, the drying temperature is 40-80° C., and the drying time is 2-8 hours.

3. The method according to claim 2, It is characterized in that The preparation method of the polystyrene resin containing amino acid functional groups comprises: The raw materials containing polystyrene resin compounds, amino acids and water are subjected to reaction IV to obtain the polystyrene resin containing amino acid functional groups.

4. The method according to claim 3, It is characterized in that The amino acid is selected from at least one of L-glycine, L-alanine, L-phenylalanine, L-histidine, and L-proline; Preferably, the polystyrene resin compound is selected from chloromethylated polystyrene resin and / or chloroacetylated polystyrene resin; Preferably, the mass ratio of the polystyrene resin compound to the amino acid is 5:1 to 2:1; Preferably, the mass ratio of the polystyrene resin compound to the water is 1:1 to 1:2; Preferably, the temperature of reaction IV is 60-100° C., and the time of reaction IV is 4-12 h.

5. The method according to claim 3, It is characterized in that The preparation method of the polystyrene resin compound comprises: The polystyrene resin is swollen in a solvent and then mixed with a chlorine-containing organic matter to perform a reaction V to obtain the polystyrene resin compound.

6. The method according to claim 5, It is characterized in that The chlorine-containing organic compound is selected from chloromethyl ether and / or chloroacetyl chloride; Preferably, the solvent is selected from at least one of dichloromethane, dichloroethane and chloroform; Preferably, the mass ratio of the polystyrene resin to the solvent is 1:1 to 1:2; Preferably, the swelling time is 2 to 8 hours; Preferably, the mass ratio of the polystyrene resin to the chlorine-containing organic matter is 1:1 to 1:2; Preferably, the temperature of reaction V is 20-60° C., and the time of reaction V is 4-12 h.

7. The method according to claim 1, It is characterized in that The C4-C10 fatty aldehyde is selected from at least one of butyraldehyde, valeraldehyde, hexanal, heptanal, octanal, nonanal, and decanal; Preferably, the strongly acidic cation exchange resin is selected from at least one of D001 resin, Amberlyst-15 resin and 732 resin.

8. The method according to claim 1, It is characterized in that In S1, the temperature of reaction I is 20-40°C, and the volumetric space velocity of reaction I is 0.5-2h -1 .

9. The method according to claim 1, It is characterized in that In said S2, said mixture II further comprises water; Preferably, the volume ratio of the fatty acid ester to water is 1:1 to 1:

2.

10. The method according to claim 1, It is characterized in that In S2, the temperature of reaction II is 60-100°C, and the volume space velocity of reaction II is 0.2-0.5h -1 .

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