Synthesis process of triglyceride type fish oil and triglyceride type fish oil

Abstract

The invention provides a synthesis process of triglyceride type fish oil and the triglyceride type fish oil, and particularly relates to the technical field of fish oil preparation. The synthesis process of the triglyceride type fish oil comprises the following steps: A, adding ethyl ester type fish oil, glycerol and a catalyst into a reaction container for reaction; b, cooling after the reaction is completed, adding a reaction stopping solution, standing and separating to obtain oil liquid; and C, carrying out molecular distillation and refining on the oil liquid to obtain the triglyceride type fish oil. According to the synthesis process provided by the invention, efficient transesterification reaction is realized, fatty acid ethyl ester and glycerol form fatty acid triglyceride in the transesterification process, the occurrence of excessive reaction and side reaction is prevented, and the purity and bioavailability of the final product are ensured. The whole synthesis process not only simplifies the operation and reduces the production cost, but also improves the safety and environmental friendliness of the product, and ensures the nutritional value and health benefits of the triglyceride type fish oil, so that the triglyceride type fish oil becomes a high-value healthy food raw material.

Description

Technical Field

[0001] The invention relates to the technical field of fish oil preparation, in particular to a synthesis process of triglyceride type fish oil and triglyceride type fish oil. Background Art

[0002] Fish oil is rich in DHA and EPA, and has a good effect on improving diseases such as the brain, vision, cardiovascular, joints, and inflammation. The fish oil capsule products on the market are divided into two completely different structures from a chemical point of view, namely triglyceride fish oil (TG) and ethyl ester fish oil (EE). TG is more suitable for human absorption than EE.

[0003] Ethyl ester fish oil has low bioavailability, poor stability and low safety. For example, after being absorbed, ethyl ester fish oil decomposes into ethanol in the gastrointestinal tract, which can easily cause adverse reactions such as allergies in people with poor tolerance to ethyl ester, especially children. In addition, long-term use can easily cause the lack or deficiency of glycerol in the human body, which can easily cause an imbalance in sugar metabolism in the human body and produce side effects.

[0004] First of all, the absorption rate of glyceride fish oil is about three times that of ethyl ester fish oil. The reason is that the main lipase in the human pancreas and liver is specific for hydrolyzing triglycerides, and cannot effectively hydrolyze ethyl esters to release free fatty acids for absorption by the human body. After the triglyceride fish oil is hydrolyzed, the monoglyceride produced helps the recombination of triglycerides. However, since the hydrolysis product of ethyl ester fish oil does not contain monoglycerides, it is necessary to obtain monoglyceride substrates from other sources, which delays the reaction of free fish oil to recombine triglycerides. Free fish oil and other unsaturated fatty acids will gradually enrich and be oxidized, causing oxidative stress to the human body, which is not good for health. In addition, compared with ethyl ester fish oil, triglyceride fish oil has the advantages of strong stability and high safety. At present, most of the fish oil on the market is ethyl ester type, and glyceride type fish oil is imported more and more expensive.

[0005] In the prior art, the methods for synthesizing concentrated triglycerides include lipase method and chemical synthesis method. The lipase method is a relatively environmentally friendly biocatalytic method, but the reaction time is long and the required lipase cost is high. Although the chemical synthesis method can be carried out quickly, the reaction yield is low and there are many by-products, which affects the product quality. With the increasing awareness of the health benefits of ω-3 polyunsaturated fatty acids, the market demand for high-purity fish oil continues to grow.

[0006] In view of this, the present invention is proposed. Summary of the invention

[0007] One of the purposes of the present invention is to provide a synthesis process of triglyceride fish oil, aiming to solve at least one of the above-mentioned technical problems in the prior art.

[0008] A second object of the present invention is to provide a triglyceride fish oil.

[0009] In order to solve the above technical problems, the present invention particularly adopts the following technical solutions:

[0010] The first aspect of the present invention provides a synthesis process of triglyceride fish oil comprising the following steps:

[0011] A. Add ethyl ester fish oil, glycerol and a catalyst into a reaction vessel to react;

[0012] B. After the reaction is completed, the temperature is lowered, a reaction stopping solution is added, and the mixture is allowed to stand and separate to obtain an oil liquid;

[0013] C. The oil is molecularly distilled and refined to obtain triglyceride fish oil.

[0014] Furthermore, in step A, the reaction is carried out under vacuum conditions, the reaction temperature is 100-140° C., and the reaction time is 4-10 h.

[0015] Preferably, the weight ratio of the ethyl ester fish oil to the glycerol is 70-90:5-10.

[0016] Preferably, the catalyst is added in an amount of 0.01 to 2.0% by weight of the ethyl ester fish oil.

[0017] Furthermore, in the ethyl ester fish oil, the total content of DHA and EPA is ≥30%.

[0018] Preferably, the catalyst comprises at least one of sodium methoxide, sodium bicarbonate, sodium carbonate, potassium bicarbonate and potassium carbonate.

[0019] Furthermore, in step B, the temperature after cooling is 55-85°C.

[0020] Preferably, in step B, the reaction stopping solution is a phosphoric acid solution, a citric acid solution, a sulfate solution or an ethanol aqueous solution.

[0021] Preferably, the concentration of the reaction stopping solution is 5 to 60 wt.%.

[0022] Furthermore, in step C, the temperature of the molecular distillation is 160-200°C.

[0023] Furthermore, the refining includes at least one of winterization, decolorization and deodorization.

[0024] Furthermore, the refining includes winterization, primary decolorization, secondary decolorization and deodorization in chronological order.

[0025] Furthermore, an adsorbent is used for the primary decolorization or the secondary decolorization.

[0026] Preferably, the adsorbent comprises activated carbon or activated clay.

[0027] Preferably, the amount of activated carbon added is 0.3-6% of the mass of the oil.

[0028] Preferably, the amount of activated clay added is 2-6% of the mass of the oil.

[0029] Preferably, the temperature for decolorization using the activated carbon is 25-80°C.

[0030] Preferably, the temperature for decolorization using the activated clay is 60-100°C.

[0031] Furthermore, the final winterization temperature is -5 to 0°C and the time is 20 to 28 hours.

[0032] Preferably, the deodorization method is high temperature deodorization.

[0033] Preferably, the temperature of the high-temperature deodorization is 160-190°C.

[0034] The second aspect of the present invention provides a triglyceride fish oil, which is synthesized using the synthesis process described in the first aspect.

[0035] Furthermore, the triglyceride content is greater than 70%.

[0036] Compared with the prior art, the present invention has at least the following beneficial effects:

[0037] The synthesis process provided by the present invention firstly realizes an efficient transesterification reaction by mixing ethyl ester fish oil, glycerol and a catalyst in a reaction vessel, during which fatty acid ethyl ester and glycerol react to form fatty acid triglyceride. Subsequently, the reaction is effectively terminated by cooling and adding a reaction stop solution to prevent overreaction and side reactions; and a pure oil is obtained by standing and separating. Finally, through molecular distillation and refining steps, impurities and non-target components in the oil are further removed to ensure the purity and bioavailability of the final product. The entire synthesis process not only simplifies the operation and reduces the production cost, but also improves the safety and environmental friendliness of the product, while ensuring the nutritional value and health benefits of triglyceride fish oil, making it a high-value health food raw material.

[0038] The triglyceride fish oil provided by the present invention has a triglyceride content of more than 70%. The high-purity triglyceride fish oil has better performance in terms of stability and antioxidant properties, prolongs the shelf life of the product, and reduces losses during storage and transportation. The provision of this high-content triglyceride fish oil has a positive driving effect on downstream industries, such as the health food, medicine and nutritional supplement industries. It provides these industries with a high-value raw material that can be used to develop new products or improve the quality of existing products, enhance the market competitiveness of products, meet consumers' growing demand for health and nutrition, and thus promote technological progress and market expansion in the entire industry. DETAILED DESCRIPTION

[0039] In order to make the purpose, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below in combination with the embodiments of the present invention. Obviously, the described embodiments are part of the embodiments of the present invention, not all of the embodiments. The components of the embodiments of the present invention described and shown herein can be arranged and designed in various different configurations.

[0040] The first aspect of the present invention provides a synthesis process of triglyceride fish oil comprising the following steps:

[0041] A. Add ethyl ester fish oil, glycerol and a catalyst into a reaction vessel to react;

[0042] B. After the reaction is completed, the temperature is lowered, a reaction stopping solution is added, and the mixture is allowed to stand and separate to obtain an oil liquid;

[0043] C. The oil is molecularly distilled and refined to obtain triglyceride fish oil.

[0044] The synthesis process provided by the present invention firstly realizes an efficient transesterification reaction by mixing ethyl ester fish oil, glycerol and a catalyst in a reaction vessel, and during the transesterification process, the ethyl ester group and glycerol react to form triglyceride fish oil. Subsequently, the reaction is effectively terminated by cooling and adding a reaction stop solution to prevent overreaction and side reactions; and a pure oil is obtained by standing and separating. Finally, through molecular distillation and refining steps, impurities and non-target components in the oil are further removed to ensure the purity and bioavailability of the final product. The entire synthesis process not only simplifies the operation and reduces the production cost, but also improves the safety and environmental friendliness of the product, while ensuring the nutritional value and health benefits of triglyceride fish oil, making it a high-value health food raw material.

[0045] Ethyl ester fish oil refers to the ω-3 polyunsaturated fatty acids in fish oil that exist in the form of ethyl esters. For example, DHA (docosahexaenoic acid), EPA (eicosapentaenoic acid), ALA (octadecatrienoic acid, also known as α-linolenic acid), and DPA (docosapentaenoic acid) all exist in the form of ethyl ester of docosahexaenoic acid, ethyl ester of eicosapentaenoic acid, ethyl ester of α-linolenic acid, and ethyl ester of docosapentaenoic acid.

[0046] In the present invention, ethyl ester fish oil is converted into triglyceride fish oil by transesterification reaction under the action of a catalyst, and this process not only improves the bioavailability of ω-3 fatty acids, but also enhances the nutritional value and stability of the product. The generated triglyceride fish oil includes docosahexaenoic acid triglyceride, eicosapentaenoic acid triglyceride, α-linolenic acid triglyceride and docosapentaenoic acid triglyceride, which are all important nutrients required by the human body and play an important role in cardiovascular health, brain development and maintaining normal physiological functions.

[0047] Although diglyceride fish oil or monoglyceride fish oil may be generated during the transesterification process, they are not the target products of the present invention. The presence of these non-target products may affect the purity and quality of the final product. Therefore, in the synthesis process, it is necessary to minimize the generation of these non-target products by accurately controlling the reaction conditions and adopting efficient separation technology, and ensure the high purity and high content of triglyceride fish oil.

[0048] Furthermore, in step A, the reaction is carried out under vacuum conditions, the reaction temperature is 100-140° C., and the reaction time is 4-10 h.

[0049] Typically but not limiting, the reaction temperature may be, for example, 100°C, 105°C, 110°C, 115°C, 120°C, 125°C, 130°C, 135°C or 140°C, or any value within the range of 100°C to 140°C; the reaction time may be, for example, 4h, 5h, 6h, 7h, 8h, 9h or 10h, or any value within the range of 4h to 10h.

[0050] Preferably, the weight ratio of the ethyl ester fish oil to the glycerol is 70-90:5-10.

[0051] Within the above weight ratio range, the yield and selectivity of triglyceride fish oil can be ensured, the complete reaction can be promoted, the generation of by-products can be reduced, and the quality of the final product can be improved. Different ratios of ethyl ester to glycerol can obtain different triglyceride contents to meet different quality requirements. Generally speaking, the higher the ethyl ester feed amount, the higher the triglyceride content. When the weight ratio of ethyl ester fish oil to glycerol is 90:7, the yield of triglyceride fish oil is greater than 70%. When the weight ratio of ethyl ester fish oil to glycerol is about 108:7, the yield of triglyceride fish oil is greater than 90%. The specific mass ratio can be adjusted according to the final product specification requirements.

[0052] Typically but not limiting, the weight ratio of the ethyl ester fish oil to glycerol can be, for example, 70:5, 71:6, 72:7, 73:8, 74:9, 75:10, 76:9, 77:8, 78:7, 79:6 or 80:5, or any ratio within the range of 70-90:5-10.

[0053] Preferably, the catalyst is added in an amount of 0.01 to 2.0% by weight of the ethyl ester fish oil.

[0054] Typically but not limiting, the catalyst may be added in an amount of, for example, 0.01%, 0.1%, 0.5%, 1.0%, 1.5% or 2.0% by weight of the ethyl ester fish oil, or any value within the range of 0.01% to 2.0%.

[0055] Furthermore, in the ethyl ester fish oil, the total content of DHA and EPA is ≥30%.

[0056] Preferably, the catalyst comprises at least one of sodium methoxide, sodium bicarbonate, sodium carbonate, potassium bicarbonate and potassium carbonate.

[0057] Furthermore, in step B, the temperature after cooling is 55-85°C.

[0058] The effect of cooling after the reaction is completed is to reduce the occurrence of hydrolysis side reactions at high temperatures. At the same time, heat will be released after the reaction is quenched, which is conducive to the quenching process. Typically but not limiting, the temperature after cooling can be, for example, 55°C, 60°C, 65°C, 70°C, 75°C, 80°C or 85°C, or any value within the range of 55°C to 85°C.

[0059] Preferably, in step B, the reaction stopping solution is a phosphoric acid solution, a citric acid solution, a sulfate solution or an ethanol aqueous solution.

[0060] The main function of the above-mentioned reaction stop solution is to react with the catalyst in the reaction system, remove the catalyst in the system, and terminate the reaction process. Adding the reaction stop solution helps prevent overreaction, ensure product quality, and facilitate subsequent separation and purification steps.

[0061] Preferably, the concentration of the reaction stopping solution is 5 to 60 wt.%.

[0062] Typically but not limiting, the concentration of the reaction stopping solution can be, for example, 5wt.%, 10wt.%, 15wt.%, 20wt.%, 25wt.%, 30wt.%, 40wt.%, 50wt.% or 60wt.%, or any value within the range of 5wt.% to 60wt.%.

[0063] Furthermore, in step C, the temperature of the molecular distillation is 160-200°C.

[0064] The purpose of molecular distillation of oil is to use the difference in boiling points of different components to achieve separation, thereby removing impurities and non-target components, such as 3-MCPD (full name: 3-chloro-1,2-propanediol), glycidol or fatty acid ethyl esters, and recovering heavy components to improve the purity and stability of the oil.

[0065] Typically but not limiting, the temperature of the molecular distillation can be, for example, 160°C, 165°C, 170°C, 175°C, 180°C, 185°C, 190°C, 195°C, 200°C, or any value within the range of 160°C to 200°C.

[0066] Furthermore, the refining includes at least one of winterization, decolorization and deodorization.

[0067] The main purpose of decolorizing oil is to improve its appearance and enhance its sensory quality. During the extraction and processing of triglyceride fish oil, pigments may be produced due to oxidation, heat treatment or contact with catalysts, causing the color to darken. The bleaching process can remove these pigments and other impurities that cause color, making triglyceride fish oil present a clearer and more consistent appearance, enhancing consumers' visual acceptance of the product.

[0068] In addition, the bleaching process helps to remove compounds that may affect the flavor and stability of triglyceride fish oil, such as oxidation products and volatile substances, thereby improving the taste of triglyceride fish oil and extending its shelf life.

[0069] Preferably, the refining includes winterization, primary bleaching, secondary bleaching and deodorization in this order.

[0070] Furthermore, an adsorbent is used for the primary decolorization or the secondary decolorization.

[0071] Preferably, the adsorbent comprises activated carbon or activated clay.

[0072] Preferably, the amount of activated carbon added is 0.3-6% of the mass of the oil.

[0073] Typically but not limiting, the amount of activated carbon added may be, for example, 0.3%, 0.6%, 1.2%, 1.8%, 2.4%, 3.0%, 4.5% or 6% of the mass of the oil, or any value within the range of 0.3% to 6%.

[0074] Preferably, the amount of activated clay added is 2-6% of the mass of the oil.

[0075] Typically but not limiting, the amount of activated clay added may be, for example, 2%, 3%, 4%, 5% or 6% of the mass of the oil, or any value within the range of 2% to 6%.

[0076] Preferably, the temperature for decolorization using the activated carbon is 25-80°C.

[0077] Preferably, the temperature for decolorization using the activated clay is 60-100°C.

[0078] Furthermore, the minimum temperature of the winterization is -5 to 0°C, and the time is 20 to 28 hours.

[0079] The main purpose of winterizing triglyceride fish oil is to separate and remove some saturated fatty acids and non-target components in the oil by controlling the crystallization process under low temperature conditions. Winterization is a gradient cooling process, with a total winterization time of 20 to 28 hours, a minimum winterization temperature of -5 to 0°C, and a minimum insulation at this minimum temperature of 9 hours. At low temperatures, some saturated fatty acids will crystallize out, while unsaturated fatty acids in triglyceride fish oil remain in liquid form. Through this process, the proportion of unsaturated fatty acids in oils and fats, especially Omega-3 fatty acids, can be increased, thereby enhancing the nutritional value and health benefits of oils and fats. At the same time, winterization also helps to improve the physical properties of oils and fats, such as reducing their viscosity, making them easier to process and use. In addition, the winterization process also helps to improve the stability of oils and fats, extend their shelf life, and ensure that oil products maintain their quality and efficacy during storage and use.

[0080] Typically but not restrictively, the minimum temperature for winterization may be, for example, -5°C, -4°C, -3°C, -2°C, -1°C or 0°C, or any value within the range of -5°C to 0°C, and the shortest insulation time at the minimum temperature is 9 hours; the total winterization time may be, for example, 20 hours, 22 hours, 24 hours, 26 hours or 28 hours, or any value within the range of 20 hours to 28 hours.

[0081] Preferably, the deodorization method is high temperature deodorization.

[0082] The main reason for deodorizing triglyceride fish oil is to remove unpleasant odors and volatile impurities in the oil, which may come from the raw materials, processing or oxidation of the oil. The deodorization process is achieved through high temperature treatment, which can reduce or eliminate oxidation products, free fatty acids, peroxides and other odorous compounds in the oil, thereby improving the flavor and taste of the oil. In addition, deodorization also helps to improve the stability of the oil, extend its shelf life, and ensure that the oil product maintains its sensory quality and nutritional value during storage and use. Through deodorization, triglyceride fish oil can provide a purer and higher quality eating experience.

[0083] Preferably, the temperature of the high-temperature deodorization is 160-190°C.

[0084] Typically but not limiting, the high temperature deodorization temperature may be, for example, 160°C, 165°C, 170°C, 175°C, 180°C, 185°C or 190°C, or any value within the range of 160°C to 190°C.

[0085] The second aspect of the present invention provides a triglyceride fish oil, which is synthesized using the synthesis process described in the first aspect.

[0086] Furthermore, the triglyceride content is greater than 70%.

[0087] The triglyceride fish oil provided by the present invention has a triglyceride content of more than 70%. The high-purity triglyceride fish oil has better performance in terms of stability and antioxidant properties, prolongs the shelf life of the product, and reduces losses during storage and transportation. The provision of this high-content triglyceride fish oil has a positive driving effect on downstream industries, such as the health food, medicine and nutritional supplement industries. It provides these industries with a high-value raw material that can be used to develop new products or improve the quality of existing products, enhance the market competitiveness of products, meet consumers' growing demand for health and nutrition, and thus promote technological progress and market expansion in the entire industry.

[0088] In the following, some embodiments of the present invention are described in detail in conjunction with the embodiments. In the absence of conflict, the following embodiments and the features in the embodiments can be combined with each other. The raw materials used in the present invention can be obtained by commercial purchase unless otherwise specified.

[0089] The concentrated ethyl ester fish oil used in the following examples and comparative examples has a specification of 36 / 24EE and is produced by Sinocare.

[0090] Example 1

[0091] This embodiment provides a triglyceride fish oil, and the specific synthesis process is carried out according to the following steps:

[0092] 1. Add concentrated ethyl ester fish oil and glycerol in a mass ratio of 70:10 to a reactor, heat to 100°C, then add 0.5% sodium carbonate by mass of concentrated ethyl ester fish oil, heat under vacuum, maintain the temperature at 100°C, and react for 8 hours.

[0093] 2. After the reaction is completed, the temperature is lowered to 55-65° C., and a sodium sulfate aqueous solution (the mass concentration of sodium sulfate is 15%) with a weight ratio of 20% of the triglyceride fish oil is added. After stirring evenly, the mixture is allowed to stand for stratification, and the oil layer is separated to obtain an oil liquid.

[0094] 3. The oil is molecularly distilled at 190°C to obtain a heavy component, which is winterized at -2°C for 24 hours and filtered. Then, 4% by weight of activated carbon is added to the filtrate, and the mixture is stirred at 25-80°C under reduced pressure for 1 hour and filtered to obtain a decolorized oil.

[0095] 4. The oil after the primary decolorization is added with 3% of its weight of activated white clay for secondary decolorization, and finally deodorized at 190°C to obtain triglyceride fish oil.

[0096] Example 2

[0097] This embodiment provides a triglyceride fish oil, and the specific synthesis process is carried out according to the following steps:

[0098] 1. Add concentrated ethyl ester fish oil and glycerol in a mass ratio of 80:5 into a reactor, heat to 90°C, then add 1.0% sodium bicarbonate by mass of concentrated ethyl ester fish oil, heat in vacuum, raise the temperature to 120°C, and react for 6 hours.

[0099] 2. After the reaction is completed, the temperature is lowered to 65-75° C., and a phosphoric acid aqueous solution (mass concentration of phosphoric acid is 20%) with a weight percentage of 10% of the triglyceride fish oil is added. After stirring evenly, the mixture is allowed to stand for stratification, and the oil layer is separated to obtain an oil liquid.

[0100] 3. The oil is molecularly distilled at 190°C to obtain a heavy component, which is winterized at -2°C for 24 hours and filtered. Then, 0.8% by weight of activated carbon is added to the filtrate, and the mixture is stirred at 25-80°C under reduced pressure for 1 hour and filtered to obtain a decolorized oil.

[0101] 4. The oil after the primary decolorization is added with 3% of its weight of activated white clay for secondary decolorization, and finally deodorized at 185°C to obtain triglyceride fish oil.

[0102] Example 3

[0103] This embodiment provides a triglyceride fish oil, and the specific synthesis process is carried out according to the following steps:

[0104] 1. Add concentrated ethyl ester fish oil and glycerol in a mass ratio of 90:4 into a reactor, heat to 80°C, then add 1.5% sodium methoxide by mass of concentrated ethyl ester fish oil, heat in vacuum, raise the temperature to 140°C, and react for 4 hours.

[0105] 2. After the reaction is completed, the temperature is lowered to 75-85° C., and an ethanol aqueous solution (the mass concentration of ethanol is 20%) with a weight ratio of 30% of triglyceride fish oil is added. After stirring evenly, the mixture is allowed to stand for stratification, and the oil layer is separated to obtain an oil liquid.

[0106] 3. The oil is molecularly distilled at 190°C to obtain a heavy component, which is winterized at -2°C for 24 hours and filtered. Then, 1% by weight of activated carbon is added to the filtrate, and the mixture is stirred at 25-80°C under reduced pressure for 1 hour and filtered to obtain a decolorized oil.

[0107] 4. The oil after the primary decolorization is added with 3% of its weight of activated white clay for secondary decolorization, and finally deodorized at 165°C to obtain triglyceride fish oil.

[0108] Example 4

[0109] This embodiment provides a triglyceride fish oil. The specific synthesis process is different from that of Example 1 in that in step 4, a deodorization step is performed directly after the primary decolorization without secondary decolorization. The remaining steps are the same as those of Example 1 and will not be described again.

[0110] Example 5

[0111] This embodiment provides a triglyceride fish oil. The specific synthesis process is different from that of Example 1 in that there is no winterization step in step 4, and the remaining steps are the same as those of Example 1, which will not be repeated here.

[0112] Example 6

[0113] This embodiment provides a triglyceride fish oil. The specific synthesis process is different from that of Example 1 in that there is no deodorization step in step 4. The remaining steps are the same as those of Example 1 and will not be described again.

[0114] Example 7

[0115] This embodiment provides a triglyceride fish oil. The difference from Embodiment 1 is that the weight ratio of concentrated ethyl ester fish oil to glycerol is 70:20. The remaining steps are the same as those in Embodiment 1 and will not be described again.

[0116] Example 8

[0117] This embodiment provides a triglyceride fish oil. The difference from Embodiment 1 is that the weight ratio of concentrated ethyl ester fish oil to glycerol is 70:3. The remaining steps are the same as those in Embodiment 1 and will not be described again.

[0118] Comparative Example 1

[0119] This comparative example provides a triglyceride fish oil. The specific synthesis process is different from that of Example 1 in that there is no molecular distillation step in step 3, and the oil obtained in step 2 is directly decolorized once. The remaining steps are the same as those of Example 1 and will not be repeated here.

[0120] Comparative Example 2

[0121] This comparative example provides a triglyceride fish oil. The specific synthesis process is different from that of Example 1 in that the heavy component obtained after the molecular distillation in step 3 is used as the final product, and no decolorization and step 4 are performed. The remaining steps are the same as those in Example 1 and will not be repeated here.

[0122] Test Example 1

[0123] The triglyceride fish oil obtained in the examples and comparative examples was tested, and the test items included chromaticity, peroxide value, anisidine value and triglyceride content. The obtained data are shown in Table 1 below.

[0124] Table 1

[0125]

[0126]

[0127] Test Example 2

[0128] The triglyceride fish oil obtained in the examples and comparative examples was subjected to winterization experiments, and the results obtained are shown in Table 2 below.

[0129] Table 2

[0130] Winterization experiment Example 1 pass Example 2 pass Example 3 pass Example 4 pass Example 5 Not passed Example 6 pass Example 7 pass Example 8 pass Comparative Example 1 pass Comparative Example 2 Not passed

[0131] As can be seen from Table 1 and Table 2, by comparing Example 1 with Example 4, it can be seen that the secondary decolorization can reduce the chromaticity, peroxide value and anisidine; Example 5 does not have a winterization step, and the winterization experiment fails; Example 6 does not perform deodorization, which affects the sensory, chromatic and anisidine value of the product; Example 7 excessive glycerol will cause a large amount of diglyceride to be generated, affecting the yield of the target product triglyceride; In Example 8, there is too little glycerol, and a product with a triglyceride content of more than 90% can be obtained, but the utilization rate of fatty acid ethyl ester fish oil raw materials is extremely low, which increases the recovery cost.

[0132] Comparative Example 1 does not undergo molecular distillation, which will affect the yield of triglycerides and leave a large amount of fatty acid ethyl esters, making the product unqualified. It can be seen that molecular distillation is a step that cannot be omitted. The heavy component of Comparative Example 2 has a large amount of impurities, and a qualified fish oil product cannot be obtained.

[0133] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit it. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned embodiments, or replace some or all of the technical features therein with equivalents. However, these modifications or replacements do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. A synthesis process for triglyceride fish oil, characterized in that: The following steps are involved: A. Add ethyl ester fish oil, glycerol and a catalyst into a reaction vessel to react; B. After the reaction is completed, the temperature is lowered, a reaction stopping solution is added, and the mixture is allowed to stand and separate to obtain an oil liquid; C. The oil is molecularly distilled and refined to obtain triglyceride fish oil.

2. The synthesis process according to claim 1, characterized in that In step A, the reaction is carried out under vacuum conditions, the reaction temperature is 100-140° C., and the reaction time is 4-10 h; The weight ratio of the ethyl ester fish oil to the glycerol is 70-90:5-10; The added amount of the catalyst is 0.01-2.0% of the weight of the ethyl ester fish oil.

3. The synthesis process according to claim 1, characterized in that: The total content of DHA and EPA in the ethyl ester fish oil is ≥30%; The catalyst includes at least one of sodium methoxide, sodium bicarbonate, sodium carbonate, potassium bicarbonate and potassium carbonate.

4. The synthesis process according to claim 1, characterized in that In step B, the temperature after cooling is 55-85°C; In step B, the reaction stopping solution is a phosphoric acid solution, a citric acid solution, a sulfate solution or an ethanol aqueous solution; The concentration of the reaction stopping solution is 5-60 wt.%.

5. The synthesis process according to claim 1, characterized in that: In step C, the temperature of the molecular distillation is 160-200°C.

6. The synthesis process according to any one of claims 1 to 5, characterized in that: The refining includes at least one of winterization, bleaching and deodorization.

7. The synthesis process according to claim 6, characterized in that: The refining includes winterization, primary decolorization, secondary decolorization and deodorization in order; Using an adsorbent to carry out the primary decolorization or the secondary decolorization; The adsorbent includes activated carbon or activated clay; The amount of activated carbon added is 0.3-6% of the mass of the oil; The amount of activated clay added is 2-6% of the mass of the oil; The temperature for decolorization using the activated carbon is 25 to 80°C; The temperature for decolorization using the activated clay is 60-100°C.

8. The synthesis process according to claim 6, characterized in that: The final winterization temperature is -5 to 0°C and the time is 20 to 28 hours; The deodorization method is high temperature deodorization; The temperature of the high temperature deodorization is 160-190°C.

9. A triglyceride fish oil, characterized in that: The compound is synthesized by the synthesis process described in any one of claims 1 to 8.

10. The triglyceride fish oil according to claim 9, characterized in that The triglyceride content is greater than 70%.

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