Fish oil-based amino acid surfactant and its preparation method

Abstract

The present invention provides a fish oil-based amino acid surfactant and a preparation method thereof. Sodium amino acid, sodium hydroxide, and an ethanol-soft water mixture are added into an autoclave and fully dissolved; fish oil fatty acid ethyl ester is added for amidation reaction; after the segmented heat preservation reaction is completed, it is cooled; the acylation reaction mixture is vacuum filtered, the filter cake is carefully rinsed with cold ethanol, and vacuum dried to obtain a fish oil acyl glycine sodium bio-based surfactant. The present invention uses the fish oil fatty acid ethyl ester remaining after enriching eicosapentaenoic acid (EPA) and docosahexaenoic acid (DHA) in polyunsaturated fatty acids ethyl ester as the raw material of the bio-based surfactant after special stabilization and deodorization treatment. The separation is simple and the process flow is relatively short; the synthesized fish oil-based amino acid biosurfactant has good detergency, foaming, emulsifying, and dispersing abilities.

Description

Technical Field

[0001] The present invention belongs to the technical field of fine chemical engineering, and in particular relates to a fish oil-based amino acid surfactant and a preparation method thereof. Technical Background

[0002] Surfactants are a large class of fine chemicals with high added value and have important applications in various industrial fields such as daily chemicals (such as detergents, lotions, toothpastes, etc.), cosmetics, food and feed processing, paints and coatings, metal processing, oil and gas extraction, spinning and weaving, aerospace, electronic information and computers, ecological resources and environmental protection, etc., and are known as the "industrial flavor enhancer".

[0003] The industrial production of surfactants is mainly obtained through a series of chemical reactions using fatty alcohols, aromatic hydrocarbons (including alkylbenzenes, alkylphenols), ethylene oxide, propylene oxide, fatty amines, sulfuric acid (including fuming sulfuric acid), phosphoric acid (including phosphorus pentoxide, etc.), caustic soda, etc. processed from resources such as petroleum and natural gas. The fully synthetic surfactants are widely used and play a crucial role in the development of all walks of life and various industrial fields. At the same time, there are also deficiencies such as limited raw material resources, difficult biodegradation, toxicity, and strong skin irritation. Therefore, the development and production of safe, environmentally friendly, non-toxic, non-irritating, and biodegradable bio-based surfactants have always been the focus and direction in the field of surfactant industry.

[0004] Starting from renewable resources of animals and plants, using green biological resources such as animal and plant fatty acids (referred to as biological fatty acids), fatty alcohols (bio-based fatty alcohols), plant polysaccharides (bio-based polysaccharides), plant fibers (bio-based fibers), animal and plant proteins and their derivative amino acids to synthesize bio-based surfactants also has thirty years of industrial practice. For example, people use coconut oil (or coconut oil methyl ester), palm oil (or palm oil methyl ester), cottonseed oil (or cottonseed oil methyl ester), rapeseed oil (or rapeseed oil) and petrochemical ethanolamine, diethanol to react to obtain a series of fatty acid alkanolamide non-ionic surfactants for thickening, foaming and foam stabilization, and detergency enhancement of liquid detergents, etc.; hydrolyze animal and plant oils to obtain fatty acids and saponify them to obtain fatty acid salt anionic surfactants; use fatty acid methyl esters of animal and plant oils, hydrogenate them to synthesize bio-fatty alcohols, and then carry out etherification reactions with petrochemical ethylene oxide to synthesize non-ionic fatty alcohol polyoxyethylene ether surfactants. These belong to typical industrial practices of bio-surfactants (or semi-bio-surfactants).

[0005] However, in the comprehensive utilization of rich renewable fish oil biological resources, it is currently mainly concentrated on food, or separating and enriching polyunsaturated fatty acids EPA and DHA from fish oil for the production of health care products and cosmetics, using the remaining ethyl fish oil fatty acids for feed processing, or as fuel, and no one has used it in the production of bio-based surfactants; not only the economic value of fish oil biological resources has not been fully utilized, but also resources have been wasted. Summary of the Invention

[0006] The present invention uses the raw material of ethyl fish oil fatty acids with low unsaturation remaining after separating polyunsaturated fatty acid ethyl esters. After special treatment, the fishy smell of fish oil is completely removed and stabilized, and then amidation reaction is carried out with sodium amino acid salt under the action of a catalyst to obtain a fish oil amino acid anionic bio-based surfactant with good color, no odor and good performance.

[0007] The specific technical solution is as follows:

[0008] The fish oil-based amino acid surfactant is obtained by the following preparation method:

[0009] (1) Sodium amino acid, sodium hydroxide, and ethanol-soft water mixture are added into an autoclave. Under nitrogen protection, the pressure is increased to 0.02 MPa; stirred and heated to 80 °C, the pressure of the reaction kettle is 0.12 MPa, and fully stirred for 30 minutes at this temperature and pressure to fully dissolve sodium glycinate.

[0010] (2) Heat the materials in the autoclave to 120 °C, the system pressure rises to 0.18 MPa, and continue stirring; at the same time, take the pre-heated fish oil fatty acid ethyl ester after deodorization and stabilization treatment, and use a micro high-pressure injection pump to continuously add it to the autoclave at a flow rate of 5 mL / min for amidation reaction.

[0011] (3) After adding the fish oil fatty acid ethyl ester, react at 120-130 °C, 145-155 °C, and 165-175 °C for 2.5 hours respectively, and the pressure of the reaction kettle is the self-generated pressure of the materials.

[0012] (4) After the segmented heat preservation reaction is completed, cool down to room temperature, the system returns to a pressure of 0.12 MPa, open the nitrogen inlet valve of the autoclave, slowly open the gas outlet pipe valve of the autoclave, and release the pressure of the system to atmospheric pressure; then open the lid of the autoclave, take out the materials of the amidation reaction, which are milky white to light yellow paste.

[0013] (5) Vacuum filter the acylation reaction mixture, and recover ethanol from the filtrate; carefully wash the filter cake with cold ethanol, and vacuum dry to obtain a white powdery fish oil acyl glycine sodium bio-based surfactant.

[0014] The sodium amino acid is mainly sodium glycinate or sodium aspartate.

[0015] The dosage ratios of the above substances are as follows:

[0016] 0.5 to 1.03 moles of sodium amino acid, 0.1 to 0.2 moles of sodium hydroxide, an ethanol-soft water mixed solution with a volume ratio of 50:50, and 1.0 mole of ethyl fish oil fatty acid.

[0017] The reaction principle of the present invention is:

[0018]

[0019] The specific technical effects of the present invention are:

[0020] (1) Using ethyl fish oil fatty acid as a raw material to synthesize a fish oil-based amino acid surfactant. Due to its own characteristics, ethyl fish oil fatty acid has a pungent fishy smell and is difficult to comprehensively utilize. The present invention uses the ethyl fish oil fatty acid remaining after enriching polyunsaturated fatty acid ethyl esters EPA and DHA, and after special stabilization and deodorization treatment, it is used as the raw material of the bio-based surfactant.

[0021] (2) Using a special amidation catalyst, directly performing an amidation reaction between ethyl fish oil fatty acid and sodium amino acid in a lower carbon alcohol, especially 95% ethanol medium, to produce a sodium fish oil amino acid surfactant; the product is suspended in the reaction medium, and the separation is simple and the process flow is relatively short.

[0022] (3) The sodium amino acid used in the fish oil-based amino acid surfactant is mainly sodium glycine and sodium aspartate.

[0023] (4) The fish oil-based amino acid biosurfactant synthesized by the present invention has good detergency, foaming, emulsifying, and dispersing abilities. Description of the Drawings

[0024] Figure 1 is the flow chart of the present invention. Detailed Embodiments

[0025] The specific technical solutions of the present invention will be described in conjunction with the drawings and embodiments.

[0026] The preparation methods of the following embodiments are as Figure 1 shown in the flow chart.

[0027] Example 1

[0028] In a 2000 - milliliter 316L stainless - steel autoclave equipped with a magnetic stirrer, a thermometer, a pressure gauge, and a nitrogen inlet, 100 grams of sodium glycinate (1.03 moles), 4 grams of sodium hydroxide (0.1 mole), and 1000 milliliters of a 50:50 (by volume) ethanol - soft - water mixture were placed. The autoclave lid was closed. After fully displacing the air with nitrogen, the autoclave was closed and pressurized with nitrogen to 0.02 MPa (gauge pressure). Then, the stirrer of the autoclave was started, and the materials were heated until the temperature of the materials reached 80 °C. At this time, the pressure in the reaction kettle was 0.12 MPa, and stirring was carried out fully for 30 minutes at this temperature and pressure to ensure the complete dissolution of sodium glycinate.

[0029] Then, the materials in the autoclave were heated to 120 °C, and the system pressure rose to 0.18 MPa, and stirring continued. Meanwhile, 300 grams (1.0 mole) of ethyl fish - oil fatty acid ester (acid value 0.89 mg KOH / g, saponification value 186.1 mg KOH / g, iodine value 93.93 mg I2 / g, average molecular weight 301), which had been pre - heated to remove fishy smell and stabilized, were placed in a 500 - milliliter beaker. Using a micro - high - pressure injection pump, it was continuously added to the autoclave at a flow rate of 5 milliliters / min for amidation reaction. After the addition of ethyl fish - oil fatty acid ester was completed, 100 milliliters of 95% ethanol were added to the beaker, and it was continuously added to the autoclave using the injection pump to ensure the complete addition of ethyl fish - oil.

[0030] After adding ethyl fish - oil fatty acid ester, the reaction was maintained at 120 - 130 °C, 145 - 155 °C, and 165 - 175 °C for 2.5 hours respectively, and the pressure in the reaction kettle was the self - generated pressure of the materials.

[0031] After the staged heat - preservation reaction was completed, it was cooled to room temperature, and the system pressure returned to 0.12 MPa. The nitrogen inlet valve of the autoclave was opened, and the gas outlet pipe valve of the autoclave was slowly opened to relieve the pressure of the system to atmospheric pressure. Then, the autoclave lid was opened, and the materials of the amidation reaction were taken out, which were milky - white to light - yellow pastes.

[0032] The acylation reaction mixture was vacuum - filtered. The filtrate was a red - yellow homogeneous liquid and was sent for ethanol recovery; the filter cake was light - yellow, and the filter cake was carefully rinsed with cold ethanol, vacuum - dried, and 285 grams of white - powder - like sodium fish - oil acyl glycinate bio - based surfactant were obtained, with a yield of 81%.

[0033] IR analysis of the product showed that: 3320 cm -1 and 1560 cm -1 absorption peaks were the stretching vibration and deformation vibration absorption peaks of the amide group N - H bond in the molecular structure; 1650 cm -1 was the stretching vibration absorption peak of the carbonyl C = O of the amide group; 1260 cm -1It is the absorption peak of the C-N stretching vibration of the typical amide group. IR analysis confirmed that the synthesized product is sodium fish oil acyl glycinate.

[0034] The melting point test of the product showed that: the melting range of the product was 90-125 °C, and the melting range was relatively wide. The main reason was that the carbon chain of fish oil fatty acid was C 14 -C 20 mixed carbon chains, and the obtained sodium fish oil amide glycinate was sodium mixed fatty acid acyl glycinate.

[0035] Product foaming and foam stability test: Dissolve sodium fish oil acyl glycinate in distilled water. The pH of the 1% aqueous solution was 8.5, and the surface tension was 33.4 dyn / cm; the Ross foam height was used to test the initial foam height of 280 ml at 25 °C, and the foam was white, delicate; after 4 hours, the foam height was 180 ml, and the foam retention rate was 64%, showing good stability.

[0036] Example 2

[0037] In a 2000 ml 316L stainless steel autoclave equipped with a magnetic stirrer, thermometer, pressure gauge, and nitrogen inlet, 88.5 g of sodium aspartate (0.5 mol), 4 g of sodium hydroxide (0.1 mol), and 1000 ml of a 50:50 (volume ratio) ethanol-soft water mixture were added, and the autoclave lid was closed; after fully displacing the air with nitrogen, the autoclave was closed and pressurized with nitrogen to 0.02 MPa (gauge pressure). Then, the stirrer of the autoclave was started, and the material was heated to a material temperature of 80 °C. At this time, the pressure in the reaction kettle was 0.12 MPa, and it was fully stirred for 30 minutes at this temperature and pressure to ensure the complete dissolution of sodium glycinate.

[0038] Then, the material in the autoclave was heated to 120 °C, and the system pressure rose to 0.18 MPa, and stirring continued. At the same time, 150 g (0.5 mol) of fish oil fatty acid ethyl ester (acid value 0.89 mg KOH / g, saponification value 186.1 mg KOH / g, iodine value 93.93 mg I2 / g, average molecular weight 301) that had been preheated to remove fishy smell and stabilized was placed in a 500 ml beaker, and using a micro high-pressure injection pump, it was continuously added to the autoclave at a flow rate of 5 ml / min for amidation reaction; after the addition of fish oil fatty acid ethyl ester was completed, 100 ml of 95% ethanol was added to the beaker, and it was continuously added to the autoclave using the injection pump to ensure the complete addition of fish oil ethyl ester.

[0039] After adding the fish oil fatty acid ethyl ester, reactions were carried out at 120-130 °C, 145-155 °C, and 165-175 °C for 2.5 hours respectively, and the pressure in the reaction kettle was the self-generated pressure of the material.

[0040] After the segmented heat preservation reaction is completed, cool down to room temperature, restore the system to a pressure of 0.12 MPa, open the nitrogen inlet valve of the autoclave, and slowly open the gas outlet pipe valve of the autoclave to relieve the pressure of the system to atmospheric pressure. Then open the lid of the autoclave and take out the material of the amidation reaction, which is a milky white to light yellow paste.

[0041] Vacuum filter the acylation reaction mixture. The filtrate is a uniform red-yellow liquid, which is sent for ethanol recovery; the filter cake is light yellow. Carefully wash the filter cake with cold ethanol, vacuum dry it, and obtain 175 grams of the fish oil acyl glycine sodium bio-based surfactant in the form of a white powder, with a yield of 90.91%.

[0042] Example 3

[0043] In a 2000 ml 316L stainless steel autoclave equipped with a magnetic stirrer, thermometer, pressure gauge, and nitrogen inlet, add 100 grams of sodium glycinate (1.03 moles), 8 grams of sodium hydroxide (0.2 moles), and 1000 ml of a 50:50 (volume ratio) ethanol-soft water mixture. Close the lid of the autoclave; after fully displacing the air with nitrogen, close the autoclave and pressurize it with nitrogen to 0.02 MPa (gauge pressure). Then turn on the stirrer of the autoclave and heat the material, raising the temperature to 80 °C. At this time, the pressure in the reaction kettle is 0.12 MPa. Maintain this temperature and pressure and stir well for 30 minutes to ensure the complete dissolution of sodium glycinate.

[0044] Then heat up the material in the autoclave to 120 °C, and the system pressure rises to 0.18 MPa. Continue stirring. At the same time, take 300 grams (1.0 mole) of fish oil fatty acid ethyl ester (acid value 0.89 mg KOH / g, saponification value 186.1 mg KOH / g, iodine value 93.93 mg I2 / g, average molecular weight 301) that has been preheated for deodorization and stabilization treatment, put it into a 500 ml beaker, and use a micro high-pressure injection pump to continuously add it to the autoclave at a flow rate of 5 ml / min for the amidation reaction; after the addition of the fish oil fatty acid ethyl ester is completed, add 100 ml of 95% ethanol to the beaker and continue to add it to the autoclave using the injection pump to ensure the complete addition of the fish oil ethyl ester.

[0045] After adding the fish oil fatty acid ethyl ester, maintain the reaction at 120 - 130 °C, 145 - 155 °C, and 165 - 175 °C for 3.0 hours respectively. The pressure in the reaction kettle is the self-generated pressure of the material.

[0046] After the segmented heat preservation reaction is completed, cool down to room temperature, restore the system to a pressure of 0.12 MPa, open the nitrogen inlet valve of the autoclave, and slowly open the gas outlet pipe valve of the autoclave to relieve the pressure of the system to atmospheric pressure. Then open the lid of the autoclave and take out the material of the amidation reaction, which is a milky white to light yellow paste.

[0047] The acylation reaction mixture was vacuum filtered. The filtrate was a uniform red-yellow liquid and was sent for ethanol recovery. The filter cake was light yellow. The filter cake was carefully rinsed with cold ethanol, dried under vacuum, and 315 g of a white powdery fish oil acyl glycine sodium bio-based surfactant was obtained, with a yield of 89.7%.

[0048] Example 4

[0049] In a 2000 mL 316L stainless steel autoclave equipped with a magnetic stirrer, thermometer, pressure gauge, and nitrogen inlet, 181 g of sodium aspartate (1.02 mol), 8 g of sodium hydroxide (0.2 mol), and 1000 mL of a 50:50 (by volume) ethanol-soft water mixture were added. The autoclave lid was closed. After thoroughly displacing the air with nitrogen, the autoclave was closed and pressurized with nitrogen to 0.02 MPa (gauge pressure). Then the stirrer of the autoclave was started, and the material was heated. The temperature was raised to 80 °C, and at this time the pressure in the reaction kettle was 0.12 MPa. Stirring was carried out fully for 30 minutes at this temperature and pressure to ensure the complete dissolution of sodium aspartate.

[0050] Then the material in the autoclave was heated to 120 °C, and the system pressure rose to 0.18 MPa, and stirring continued. At the same time, 300 g (1.0 mol) of fish oil fatty acid ethyl ester (acid value 0.89 mg KOH / g, saponification value 186.1 mg KOH / g, iodine value 93.93 mg I2 / g, average molecular weight 301) that had been preheated to remove fishy smell and stabilized was placed in a 500 mL beaker. Using a micro high-pressure injection pump, it was continuously added to the autoclave at a flow rate of 5 mL / min for amidation reaction. After the addition of fish oil fatty acid ethyl ester was completed, 100 mL of 95% ethanol was added to the beaker and continued to be added to the autoclave using the injection pump to ensure the complete addition of fish oil ethyl ester.

[0051] After the addition of fish oil fatty acid ethyl ester, reactions were carried out at 120 - 130 °C, 145 - 155 °C, and 165 - 175 °C for 3.0 hours respectively, and the pressure in the reaction kettle was the self-generated pressure of the material.

[0052] After the staged heat preservation reaction was completed, the temperature was cooled to room temperature, the system pressure returned to 0.12 MPa. The nitrogen inlet valve of the autoclave was opened, and the gas outlet pipe valve of the autoclave was slowly opened to relieve the pressure of the system to atmospheric pressure. Then the autoclave lid was opened, and the material of the amidation reaction was taken out, which was a milky white to light yellow paste.

[0053] The acylation reaction mixture was vacuum filtered. The filtrate was a uniform red-yellow liquid and was sent for ethanol recovery. The filter cake was light yellow. The filter cake was carefully rinsed with cold ethanol, dried under vacuum, and 382 g of a white powdery fish oil acyl aspartate sodium bio-based surfactant was obtained, with a yield of 87.8%.

[0054] IR analysis of the product shows that the absorption peaks at 3318 cm -1 and 1556 cm -1 are the stretching vibration and deformation vibration absorption peaks of the amide N-H bond in the molecular structure; the absorption peak at 1645 cm -1 is the stretching vibration absorption peak of the carbonyl C=O of the amide group; the absorption peak at 1262 cm -1 is the typical C-N stretching vibration absorption peak of the amide group. IR analysis confirms that the synthesized product is sodium fish oil acyl aspartate.

[0055] Melting point test of the product shows that the melting range of the product is 100 - 128 °C, and the melting range is relatively wide. The main reason is that the carbon chain of fish oil fatty acid is a mixed carbon chain of C 14 -C 20 , and the obtained sodium fish oil amide aspartate is sodium mixed fatty acid acyl aspartate.

[0056] Foaming and foam stability test of the product: Dissolve sodium fish oil acyl glycinate in distilled water. The pH of the 1% aqueous solution is 8.5, and the surface tension is 32.4 dyn / cm; the initial foam height measured by Ross-Miles foam height at 25 °C is 240 ml, and the foam is white, delicate; after 4 hours, the foam height is 190 ml, and the foam retention rate is 79%, showing good stability.

Claims

1. Preparation method of fish oil-based amino acid surfactant, characterized in that, It includes the following steps: (1) Sodium amino acid, sodium hydroxide, and ethanol-soft water mixture are added into an autoclave. Under nitrogen protection, the pressure is increased. Stir and heat to 80 °C. The pressure in the reaction kettle continues to rise. Maintain full stirring at this temperature and pressure to fully dissolve sodium glycinate. (2) Heat up and increase the pressure of the materials in the autoclave, and continue stirring. At the same time, take fish oil fatty acid ethyl ester that has been pre-heated to remove fishy smell and stabilized, and continuously add it into the autoclave using a micro high-pressure injection pump for amidation reaction. (3) After adding fish oil fatty acid ethyl ester, carry out staged heat preservation reaction. (4) After the staged heat preservation reaction ends, cool down to room temperature. The system returns to the pressure before the reaction. Open the nitrogen inlet valve of the autoclave, and slowly open the gas outlet pipe valve of the autoclave to relieve the pressure of the system to atmospheric pressure. Then open the lid of the autoclave and take out the materials of the amidation reaction. (5) Vacuum filter the acylation reaction mixture, and recycle the filtrate. Carefully wash the filter cake with cold ethanol, and vacuum dry it to obtain the bio-based surfactant sodium fish oil acyl glycinate.

2. The preparation method of fish oil-based amino acid surfactant according to claim 1, characterized in that, The sodium amino acid described above is sodium glycinate or sodium aspartate.

3. The preparation method of fish oil-based amino acid surfactant according to claim 1, characterized in that, The dosage ratio of substances is: 0.5 - 1.03 moles of sodium amino acid, 0.1 - 0.2 moles of sodium hydroxide, ethanol-soft water mixture with a volume ratio of 50:50, and 1.0 mole of fish oil fatty acid ethyl ester.

4. The preparation method of fish oil-based amino acid surfactant according to claim 1, characterized in that, In step (1), under nitrogen protection, first increase the pressure by 0.02 MPa. Stir and heat to 80 °C. The pressure in the reaction kettle is 0.12 MPa. Maintain full stirring at this temperature and pressure for 30 minutes to fully dissolve sodium glycinate.

5. The preparation method of fish oil-based amino acid surfactant according to claim 1, characterized in that, In step (2), heat up the materials in the autoclave to 120 °C, and the system pressure rises to 0.18 MPa.

6. The preparation method of fish oil-based amino acid surfactant according to claim 1, characterized in that, In step (2), add fish oil fatty acid ethyl ester into the autoclave continuously at a flow rate of 5 mL / min.

7. The preparation method of fish oil-based amino acid surfactant according to claim 1, characterized in that, The temperature of the staged heat preservation reaction in step (3) is: 120 - 130 °C, 145 - 155 °C, 165 - 175 °C, and react for 2.5 hours respectively. The pressure in the reaction kettle is the self-generated pressure of the materials.

8. Fish oil-based amino acid surfactant obtained by the preparation method according to any one of claims 1 to 7.

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