Method for preparing fatty acid and fatty alcohol

Abstract

The invention discloses a method for preparing fatty acid and fatty alcohol, which comprises the following steps: (1) reacting a mixture I containing fatty aldehyde and a catalyst I to obtain fatty acid ester; and (2) reacting a mixture II containing fatty acid ester, a catalyst II and water to obtain the fatty acid and the fatty alcohol, the fatty aldehyde is selected from at least one of C4-C10 fatty aldehydes; the catalyst I is an iminodiacetic acid resin loaded aluminum catalyst; and the catalyst II 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, and belongs to the technical field of organic chemical industry. Background Art

[0002] Fatty acids are organic acids composed of three elements: carbon, hydrogen, and oxygen. They are widely used in the manufacture of daily cosmetics, detergents, industrial fatty acid salts, coatings, paints, rubber, soaps and other chemicals. Fatty acids usually exist in the form of esters, and fatty acids in free form are rare in nature. Fatty alcohols are alcohols with hydroxyl groups connected to aliphatic hydrocarbon groups, and are widely used in the manufacture of synthetic detergents, cosmetics, pharmaceuticals and other chemicals. Fatty acids are mainly produced by oxidation of fatty aldehydes, and fatty alcohols are mainly produced by hydrogenation of fatty aldehydes, which require the use of gases such as oxygen and hydrogen, and usually require higher reaction temperatures and pressures, high energy consumption, and high operating safety risks. Summary of the invention

[0003] In order to solve the problems that the current production process of fatty acids and fatty alcohols requires the use of gases such as oxygen and hydrogen, and usually requires high reaction temperature and pressure, high energy consumption, and high operational safety risks, the present application provides a method for preparing fatty acids and fatty alcohols, which has the advantages of mild reaction conditions, good operational safety, the ability to obtain fatty acids and fatty alcohols at the same time, and continuous reaction with high efficiency.

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

[0005] (1) reacting a mixture I containing a fatty aldehyde and a catalyst I to obtain a fatty acid ester;

[0006] (2) reacting a mixture II containing fatty acid ester, catalyst II and water to obtain the fatty acid and fatty alcohol;

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

[0008] The catalyst I is an aluminum catalyst supported by iminodiacetic acid resin;

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

[0010] Optionally, the C4-C10 fatty aldehyde is selected from at least one of butyraldehyde, valeraldehyde, hexanal, heptanal, octanal, nonanal and decanal.

[0011] Optionally, the strongly acidic cation exchange resin is selected from at least one of 732 resin, D001 resin, and Amberlyst-15 resin.

[0012] Optionally, the aluminum catalyst supported by iminodiacetic acid resin is prepared using iminodiacetic acid resin and aluminum salt as raw materials.

[0013] Optionally, the iminodiacetic acid resin is selected from at least one of CH-90 resin, D401 resin, MTS9300 resin, MTS9301 resin, and S930 resin.

[0014] Optionally, the aluminum salt is selected from at least one of hydrochlorides, sulfates and nitrates containing aluminum.

[0015] Optionally, the preparation method of the iminodiacetic acid resin-supported aluminum catalyst comprises:

[0016] The iminodiacetic acid resin is swollen in an organic solvent, and then mixed with an aluminum salt aqueous solution, reacted in step III, and dried to obtain the iminodiacetic acid resin-supported aluminum catalyst.

[0017] According to the present application, the preparation steps of the iminodiacetic acid resin-supported aluminum catalyst are: the iminodiacetic acid resin is swelled in an organic solvent and then filtered, the obtained solid is added to the aluminum salt aqueous solution, stirred, reacted III, filtered, washed with water, and dried to obtain the iminodiacetic acid resin-supported aluminum catalyst.

[0018] Optionally, the mass ratio of the iminodiacetic acid resin to the organic solvent is 1:1 to 1:2.

[0019] Optionally, the mass ratio of the iminodiacetic acid resin to the organic 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 a range between any two of the above values.

[0020] Optionally, the mass ratio of the iminodiacetic acid resin to the aluminum salt aqueous solution is 1:1 to 1:2.

[0021] Optionally, the mass ratio of the iminodiacetic acid resin to the aluminum salt aqueous solution 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 the above.

[0022] Optionally, the mass concentration of the aluminum salt aqueous solution is 10% to 30%.

[0023] Optionally, the mass concentration of the aluminum salt aqueous solution is independently selected from any value of 10%, 15%, 20%, 25%, 30% or a range between any two of the above.

[0024] Optionally, the organic solvent is selected from at least one of dichloromethane, dichloroethane and chloroform.

[0025] Optionally, the swelling time is 2 to 8 hours.

[0026] Optionally, the swelling time is independently selected from any value among 2h, 3h, 4h, 5h, 6h, 7h, 8h or a range between any two of the above.

[0027] Optionally, the temperature of reaction III is 20-40° C., and the time of reaction III is 2-8 h.

[0028] Optionally, the temperature of the reaction III is independently selected from any value of 20°C, 25°C, 30°C, 35°C, 40°C or a range between any two of the above values.

[0029] Optionally, the time of the reaction III is independently selected from any value of 2h, 3h, 4h, 5h, 6h, 7h, 8h or a range between any two of the above.

[0030] Optionally, the drying temperature is 40 to 80° C., and the drying time is 2 to 8 hours.

[0031] Optionally, the drying temperature is independently selected from any value of 40°C, 50°C, 60°C, 70°C, 80°C or a range between any two of the above values.

[0032] Optionally, the drying time is independently selected from any value among 2h, 3h, 4h, 5h, 6h, 7h, 8h or a range between any two of the above.

[0033] According to the present application, the step (1) of preparing fatty acid esters is: loading the catalyst I into a reaction tube, pumping in at least one of the C4-C10 fatty aldehydes, reacting I at a set reaction temperature to obtain the fatty acid esters.

[0034] Optionally, in step (1), the temperature of reaction I is 20-40°C.

[0035] 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 a range between any two of the above values.

[0036] Optionally, the volume space velocity of reaction I is 0.5 to 2 h -1 .

[0037] Optionally, the volume space velocity of the reaction I is independently selected from 0.5h -1 , 1h -1 , 1.5h -1 , 2h -1 Any value in or a range between any two of the above.

[0038] According to the present application, the step (2) of preparing fatty acids and fatty alcohol esters is: loading the catalyst II into a reaction tube, pumping in a mixture of fatty acid esters and water obtained in step (1), and reacting II at a set reaction temperature to obtain the fatty acids and fatty alcohols.

[0039] Optionally, in step (2), the volume ratio of the fatty acid ester to water is 1:1 to 1:2.

[0040] 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, 1:1.6, 1:1.8, 1:2 or a range between any two of the above.

[0041] Optionally, the temperature of reaction II is 60-100°C.

[0042] Optionally, the temperature of the reaction II is independently selected from any value of 60°C, 70°C, 80°C, 90°C, 100°C or a range between any two of the above values.

[0043] Optionally, the volume space velocity of reaction II is 0.2 to 0.5 h -1 .

[0044] Optionally, the volume space velocity of the reaction II is independently selected from 0.2h -1 、0.3h -1 、0.4h -1 、0.5h -1 Any value in or a range between any two of the above.

[0045] According to the present application, the catalyst is extremely important. When there is no catalyst I or the activity of catalyst I is low, the conversion rate of fatty aldehydes is very low. When the activity and selectivity of catalyst I are high, a high conversion rate of fatty aldehydes and a high yield of fatty acid esters can be obtained. When there is no catalyst II or the activity of catalyst II is low, the conversion rate of fatty acid esters is very low. When the activity and selectivity of catalyst II are high, a high conversion rate of fatty acid esters and a high yield of fatty acids and fatty alcohols can be obtained.

[0046] The beneficial effects of this application include:

[0047] In view of the problems that the production process of fatty acids and fatty alcohols in the prior art requires the use of gases such as oxygen and hydrogen, and usually requires high reaction temperature and pressure, high energy consumption, and great operational safety risks, the present application provides a method for directly converting fatty aldehydes to prepare fatty acid esters and then hydrolyzing them to prepare fatty acids and fatty alcohols. 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

[0048] The present application is described in detail below with reference to embodiments, but the present application is not limited to these embodiments.

[0049] Unless otherwise specified, the raw materials in the examples of this application were purchased through commercial channels.

[0050] Unless otherwise specified, conventional methods were used for testing.

[0051] The conversion rate and yield in the examples of this application are calculated as follows:

[0052]

[0053]

[0054]

[0055]

[0056]

[0057] 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.

[0058] Example 1

[0059] 50 g of D401 resin was swelled in 50 g of dichloromethane for 4 h and then filtered. The obtained solid was added to 50 g of 20% aluminum nitrate aqueous solution, stirred at 40° C. for 4 h, filtered, washed with water, and dried at 80° C. for 2 h to obtain 53 g of D401 resin-supported aluminum catalyst.

[0060] Example 2

[0061] 50 g of CH-90 resin was swelled in 100 g of dichloroethane for 2 h and then filtered. The obtained solid was added to 100 g of 10% aluminum sulfate aqueous solution, stirred at 20°C for 8 h, filtered, washed with water, and dried at 40°C for 8 h to obtain 52 g of aluminum catalyst supported on CH-90 resin.

[0062] Example 3

[0063] 50 g of MTS9300 resin was swelled in 75 g of chloroform for 8 h and then filtered. The obtained solid was added to 75 g of 30% aluminum chloride aqueous solution, stirred at 30° C. for 2 h, filtered, washed with water, and dried at 60° C. for 4 h to obtain 53 g of MTS9300 resin-supported aluminum catalyst.

[0064] Embodiment 4-5

[0065] Examples 4 to 5 are similar to Example 1, except that different iminodiacetic acid resins are used. Other reaction conditions are the same as those of Example 1.

[0066] The difference between Example 4 and Example 1 is that Example 4 uses 50 g of MTS9301 resin instead of 50 g of D401 resin, and finally obtains 53 g of aluminum catalyst supported by 53 g of MTS9301 resin.

[0067] The difference between Example 5 and Example 1 is that Example 5 uses 50 g of S930 resin instead of 50 g of D401 resin, and finally obtains 53 g of aluminum catalyst supported by 53 g of S930 resin.

[0068] Example 6

[0069] 20 g of the D401 resin-supported aluminum catalyst prepared in Example 1 was placed in a reaction tube, and n-butyraldehyde was pumped in. 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%.

[0070] Example 7

[0071] 20 g of the CH-90 resin-supported aluminum catalyst prepared in Example 2 was placed in a reaction tube, and n-heptanal was pumped in. 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 heptaldehyde and the yield of heptyl heptate were both above 99%. After the reaction was run continuously for 24 hours, samples were taken again for analysis. The conversion rate of heptaldehyde and the yield of heptyl heptate were both above 99%.

[0072] Example 8

[0073] 20 g of the MTS9300 resin-supported aluminum catalyst prepared in Example 3 was placed in a reaction tube, and n-decanal was pumped in. The reaction was carried out at 40° C. with a reaction volume space velocity of 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 n-decanal was 92% and the yield of decanoate was 91%.

[0074] Example 9

[0075] 20 g of the MTS9301 resin-supported aluminum catalyst prepared in Example 4 was placed in a reaction tube, and n-valeraldehyde was pumped in. The reaction was carried out at 20° C. and the reaction volume space velocity was 1 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-valeraldehyde was 95% and the yield of pentyl valerate was 94%.

[0076] Example 10

[0077] 20 g of the S930 resin-supported aluminum catalyst prepared in Example 5 was placed in a reaction tube, and n-octanal was pumped in. 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 91% and the yield of octyl octanoate was 90%.

[0078] Embodiment 11

[0079] 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 6 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%.

[0080] Example 12

[0081] 20 g of strong acid cation exchange resin D001 was placed in a reaction tube, and the mixture of heptyl heptanoate and water prepared in Example 7 was pumped in, the volume ratio of heptyl heptanoate to water was 1:2, the reaction was carried out at 60° C., and the reaction volume space velocity was 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%.

[0082] Example 13

[0083] 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 8 was pumped in, the volume ratio of decyl decanoate to water was 1:1.5, the reaction temperature was 80°C, and the reaction volume space velocity was 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%.

[0084] Comparative Example 1

[0085] The difference between Comparative Example 1 and Example 1 is that 50 g of 20% aluminum nitrate aqueous solution is replaced by 50 g of water, and other reaction conditions are the same as those of Example 1, and finally 50 g of D401 resin blank supported catalyst is obtained.

[0086] Comparative Example 2

[0087] The difference between Comparative Example 2 and Example 1 is that 50 g of 20% ferric nitrate aqueous solution is used instead of 50 g of 20% aluminum nitrate aqueous solution, and other reaction conditions are the same as those of Example 1, and finally 53 g of D401 resin-supported iron catalyst is obtained.

[0088] Comparative Example 3

[0089] The difference between Comparative Example 3 and Example 6 is that 20 g of D401 resin blank supported catalyst prepared in Comparative Example 1 is used instead of the D401 resin supported aluminum catalyst used in Example 6, and other reaction conditions are the same as those in Example 6. The final conversion rate of n-butyraldehyde is 0%.

[0090] Comparative Example 4

[0091] The difference between Comparative Example 4 and Example 6 is that 20 g of the D401 resin-supported iron catalyst prepared in Comparative Example 2 is used instead of the D401 resin-supported aluminum catalyst used in Example 6, and other reaction conditions are the same as those in Example 6. The final n-butyraldehyde conversion rate is 8%, and the butyl butyrate yield is 8%.

[0092] The results of Comparative Examples 3 and 4 show that when using the blank catalyst supported by D401 resin and the iron catalyst supported by D401 resin, n-butyraldehyde is not converted or the conversion rate is very low, indicating that the aluminum catalyst supported by iminodiacetic acid resin plays a very important role.

[0093] Comparative Example 5

[0094] The difference between Comparative Example 5 and Example 12 is that the reaction tube is not filled with strongly acidic cation exchange resin D001 resin, and other reaction conditions are the same as those in Example 12. 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%.

[0095] The results of Comparative Example 5 show that when there is no catalyst II, the conversion rate of fatty acid ester is very low.

[0096] In summary, the present application provides a method for directly converting fatty aldehydes to prepare fatty acid esters and then hydrolyzing them to prepare fatty acids and fatty alcohols, in response to the problems that the current production process of fatty acids and fatty alcohols requires the use of gases such as oxygen and hydrogen, and usually requires higher reaction temperatures and pressures, high energy consumption, and high operational safety risks. 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.

[0097] 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, It is characterized in that The method comprises the following steps: (1) reacting a mixture I containing a fatty aldehyde and a catalyst I to obtain a fatty acid ester; (2) reacting a mixture II containing fatty acid ester, catalyst II and water to obtain the fatty acid and fatty alcohol; The fatty aldehyde is selected from at least one of C4 to C10 fatty aldehydes; The catalyst I is an aluminum catalyst supported by iminodiacetic acid resin; The catalyst II is a strongly acidic cation exchange resin.

2. 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 732 resin, D001 resin and Amberlyst-15 resin.

3. The method according to claim 1, It is characterized in that The aluminum catalyst supported by iminodiacetic acid resin is prepared using iminodiacetic acid resin and aluminum salt as raw materials; Preferably, the iminodiacetic acid resin is selected from at least one of CH-90 resin, D401 resin, MTS9300 resin, MTS9301 resin, and S930 resin; Preferably, the aluminum salt is selected from at least one of hydrochlorides, sulfates and nitrates containing aluminum.

4. The method according to claim 1, It is characterized in that The preparation method of the iminodiacetic acid resin-supported aluminum catalyst comprises: The iminodiacetic acid resin is swollen in an organic solvent, and then mixed with an aluminum salt aqueous solution, reacted in step III, and dried to obtain the iminodiacetic acid resin-supported aluminum catalyst.

5. The method according to claim 4, It is characterized in that The mass ratio of the iminodiacetic acid resin to the organic solvent is 1:1 to 1:2; Preferably, the mass ratio of the iminodiacetic acid resin to the aluminum salt aqueous solution is 1:1 to 1:2; Preferably, the mass concentration of the aluminum salt aqueous solution is 10% to 30%; Preferably, the organic solvent is selected from at least one of dichloromethane, dichloroethane and chloroform.

6. The method according to claim 4, It is characterized in that The swelling time is 2 to 8 hours; 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.

7. The method according to claim 1, It is characterized in that In the step (1), the temperature of the reaction I is 20 to 40°C; Preferably, the volume space velocity of reaction I is 0.5 to 2 h -1 .

8. The method according to claim 1, It is characterized in that In the step (2), the volume ratio of the fatty acid ester to water is 1:1 to 1:

2.

9. The method according to claim 1, It is characterized in that The temperature of the reaction II is 60-100°C.

10. The method according to claim 1, It is characterized in that The volume space velocity of reaction II is 0.2 to 0.5 h -1 .

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