A method for preparing a triglyceride type fish oil

Abstract

The application belongs to the technical field of fish oil refining, and particularly relates to a preparation method of triglyceride fish oil. The application provides a preparation method of triglyceride fish oil, which comprises the following steps: mixing, stirring and reacting an ethyl ester fish oil, glycerol and a composite catalyst to perform esterification, then washing, stirring and standing the product, removing a water layer, then performing decolorization treatment, and finally performing filtration to obtain a filtrate, which is the triglyceride fish oil; the composite catalyst is a mixture of an organic amine and polypropylene. The mixture of the organic amine and the polypropylene is used as the catalyst, so that the yield of esterification of the ethyl ester fish oil and the glycerol into the triglyceride fish oil can be improved.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of fish oil refining, and particularly relates to a preparation method of triglyceride fish oil. BACKGROUND

[0002] Polyunsaturated fatty acids (PUFA) in deep sea fish oil are familiar functional fatty acids, mainly including eicosapentaenoic acid (EPA) and docosahexaenoic acid (DHA), which have important physiological functions in human and organisms. EPA and DHA are mainly derived from marine fish oil, but the PUFA content in natural fish oil is relatively low and a large amount of saturated fatty acids exist, so the medical and health care effects are not ideal. The key to development and utilization of marine fish oil resources is how to effectively concentrate and purify PUFA in fish oil and improve the economic utilization value of fish oil. The traditional chemical synthesis of glyceride products rich in PUFA has the disadvantages of high reaction temperature and poor product quality.

[0003] In the prior art, an alkali catalyst is used to convert ethyl ester fish oil and glycerol into triglyceride fish oil. For example, the prior art discloses a preparation method of triglyceride fish oil, which comprises the following steps: taking raw materials of ethyl ester fish oil, glycerol and an alkali catalyst, and the weight ratio of the above raw materials is 100-150:10-15:1-1.5; and using the alkali catalyst to convert the ethyl ester fish oil and the glycerol into triglyceride fish oil. In addition, organic alkali catalysts such as amines are also being developed at home and abroad.

[0004] However, when the organic amine is used as the catalyst, a relatively high conversion rate can be achieved after 6-10 hours of reaction at normal pressure and low temperature, but the content of monoglyceride and diglyceride in the product is very high, and the amount of triglyceride is very low, which is difficult to be applied in industry; when the reaction pressure and temperature are increased, amide is likely to be generated in the reaction process, thereby reducing the product quality. SUMMARY

[0005] The application provides a preparation method of triglyceride fish oil, which aims to solve the problems in the prior art that when the organic amine is used as the catalyst, a relatively high conversion rate can be achieved after 6-10 hours of reaction at normal pressure and low temperature, but the content of monoglyceride and diglyceride in the product is very high, and the amount of triglyceride is very low, which is difficult to be applied in industry; when the reaction pressure and temperature are increased, amide is likely to be generated in the reaction process, thereby reducing the product quality.

[0006] In view of the above technical defects, one of the purposes of the application is to provide a preparation method of triglyceride fish oil.

[0007] In a first aspect, the application provides a preparation method of triglyceride fish oil, which comprises the following steps:

[0008] The esterified fish oil is obtained by mixing, stirring, esterification, washing, stirring, standing, removing water layer, decolorizing and filtering the ethyl ester fish oil, glycerol and composite catalyst.

[0009] The composite catalyst is a mixture of organic amine and polypropylene.

[0010] In the preparation method, as a preferred embodiment, the organic amine includes one of trimethylamine, triethylamine, aniline, pyrimidine and imidazole.

[0011] The mass ratio of the organic amine and polypropylene is (10-15):(10-15).

[0012] In the preparation method, as a preferred embodiment, the mass ratio of the ethyl ester fish oil, glycerol and composite catalyst is (100-150):(20-25):(3-8).

[0013] In the preparation method, as a preferred embodiment, the esterification time is 2-10h.

[0014] And / or, the esterification temperature is 25-40℃.

[0015] And / or, the esterification pressure is 1-10MPa.

[0016] In the preparation method, as a preferred embodiment, the washing is performed by using deionized water.

[0017] And / or, the added mass of the deionized water is 1.5-2 times of the ethyl ester fish oil.

[0018] In the preparation method, as a preferred embodiment, the standing time is until the oil layer and water layer are obviously separated.

[0019] In the preparation method, as a preferred embodiment, the decolorization is performed by using one or more of activated clay and attapulgite.

[0020] And / or, the decolorization temperature is 75-80℃.

[0021] In the preparation method, as a preferred embodiment, the added mass of the activated clay or attapulgite is 0.01-0.05 times of the ethyl ester fish oil during the decolorization.

[0022] In the preparation method, as a preferred embodiment, the ethyl ester fish oil is a pharmaceutical grade.

[0023] And / or, the glycerol is a pharmaceutical grade.

[0024] In the above preparation method, as a preferred embodiment, the yield of the triglyceride fish oil is 85-95%.

[0025] Compared with the prior art, the present application has the following beneficial effects:

[0026] The present application provides a preparation method of triglyceride fish oil, comprising the following steps:

[0027] 1. The present application provides a preparation method of triglyceride fish oil, comprising the following steps: mixing and stirring ethyl ester fish oil, glycerol and a composite catalyst, performing esterification reaction, then washing, stirring and standing the product, removing the water layer, then performing decolorization treatment, and finally performing filtration to obtain the filtrate, which is the triglyceride fish oil; the composite catalyst is a mixture of organic amine and polypropylene. The present application uses a mixture of organic amine and polypropylene as a catalyst, which can improve the yield of esterification of ethyl ester fish oil and glycerol into triglyceride fish oil.

[0028] 2. The present application further improves the yield of triglyceride fish oil under specific esterification temperature, esterification time and esterification pressure. DETAILED DESCRIPTION

[0029] In the present application, unless otherwise specified and / or described, all numerical values related to the amount of components are "parts by weight". The process parameters not specified in the following examples are generally in accordance with conventional conditions.

[0030] The preparation method of triglyceride fish oil of the present application is further described in detail through the following examples, and the examples are given only to illustrate the present application, but not to limit the scope of the present application. The examples provided below can serve as a basis for further improvement or application by those skilled in the art, and do not constitute a specific limitation on the present application in any way.

[0031] Example 1

[0032] The present embodiment provides a preparation method of triglyceride fish oil, comprising the following steps:

[0033] 100 g of ethyl ester type fish oil, 20 g of glycerol, and 5 g of a composite catalyst (a mixture of 2.5 g of triethylamine and 2.5 g of polypropylene) were added to a reaction vessel (the pressure in the reaction vessel was 5 MPa) and stirred and mixed, and while stirring and mixing, the reaction was heated to 40°C, and then esterification was performed for 5 h. After the esterification reaction, 200 g of deionized water was added to the reaction vessel, stirring and standing until the oil layer and the water layer were clearly separated, and then the water layer was removed, 5 g of activated clay was added, and then the reaction vessel was heated to 80°C to perform decolorization. The product in the reaction vessel was filtered using a plate and frame filter, the filter cake was activated clay, which was recovered, and the filtrate was a triglyceride type fish oil.

[0034] The triglyceride type fish oil obtained using the preparation method of Example 1 had a yield of 92.6%.

[0035] Example 2

[0036] The present example provides a method for preparing a triglyceride type fish oil, including the following steps:

[0037] 100 g of ethyl ester type fish oil, 20 g of glycerol, and 5 g of a composite catalyst (a mixture of 2.5 g of triethylamine and 2.5 g of polypropylene) were added to a reaction vessel (the pressure in the reaction vessel was 1 MPa) and stirred and mixed, and while stirring and mixing, the reaction was heated to 40°C, and then esterification was performed for 5 h. After the esterification reaction, 200 g of deionized water was added to the reaction vessel, stirring and standing until the oil layer and the water layer were clearly separated, and then the water layer was removed, 5 g of activated clay was added, and then the reaction vessel was heated to 80°C to perform decolorization. The product in the reaction vessel was filtered using a plate and frame filter, the filter cake was activated clay, which was recovered, and the filtrate was a triglyceride type fish oil.

[0038] The triglyceride type fish oil obtained using the preparation method of Example 2 had a yield of 89.2%.

[0039] Example 3

[0040] The present example provides a method for preparing a triglyceride type fish oil, including the following steps:

[0041] 100 g of ethyl ester type fish oil, 20 g of glycerol, and 5 g of a composite catalyst (a mixture of 2.5 g of triethylamine and 2.5 g of polypropylene) were added to a reaction vessel (the pressure in the reaction vessel was 10 MPa) and stirred and mixed, and while stirring and mixing, the reaction was heated to 40°C, and then esterification was performed for 5 h. After the esterification reaction, 200 g of deionized water was added to the reaction vessel, stirring and standing until the oil layer and the water layer were clearly separated, and then the water layer was removed, 5 g of activated clay was added, and then the reaction vessel was heated to 80°C to perform decolorization. The product in the reaction vessel was filtered using a plate and frame filter, the filter cake was activated clay, which was recovered, and the filtrate was a triglyceride type fish oil.

[0042] The triglyceride fish oil obtained by the method of Example 3 has a yield of 91.3%.

[0043] Example 4

[0044] The present example provides a method for preparing a triglyceride fish oil, comprising the following steps:

[0045] 100 g of ethyl ester fish oil, 20 g of glycerol, and 5 g of a composite catalyst (a mixture of 3 g of triethylamine and 2 g of polypropylene) were added to a reaction kettle (the pressure in the reaction kettle was 5 MPa) and stirred and mixed, while the reaction was heated to 40°C, and then esterification was performed for 5 h. After the esterification reaction, 200 g of deionized water was added to the reaction kettle, and stirring and standing were performed until the oil layer and the water layer were clearly separated, then the water layer was removed, 5 g of activated clay was added, and then the reaction kettle was heated to 80°C for decolorization. The product in the reaction kettle was filtered with a plate and frame filter, the filter cake was activated clay, which was recovered, and the filtrate was the triglyceride fish oil.

[0046] The triglyceride fish oil obtained by the method of Example 4 has a yield of 92.4%.

[0047] Example 5

[0048] The present example provides a method for preparing a triglyceride fish oil, comprising the following steps:

[0049] 100 g of ethyl ester fish oil, 20 g of glycerol, and 5 g of a composite catalyst (a mixture of 3 g of triethylamine and 2 g of polypropylene) were added to a reaction kettle (the pressure in the reaction kettle was 5 MPa) and stirred and mixed, while the reaction was heated to 40°C, and then esterification was performed for 5 h. After the esterification reaction, 200 g of deionized water was added to the reaction kettle, and stirring and standing were performed until the oil layer and the water layer were clearly separated, then the water layer was removed, 5 g of activated clay was added, and then the reaction kettle was heated to 80°C for decolorization. The product in the reaction kettle was filtered with a plate and frame filter, the filter cake was activated clay, which was recovered, and the filtrate was the triglyceride fish oil.

[0050] The triglyceride fish oil obtained by the method of Example 5 has a yield of 93.1%.

[0051] Example 6

[0052] The present example provides a method for preparing a triglyceride fish oil, comprising the following steps:

[0053] 100 g of ethyl ester type fish oil, 25 g of glycerol, and 5 g of a composite catalyst (a mixture of 2.5 g of triethylamine and 2.5 g of polypropylene) were added to a reaction vessel (the pressure in the reaction vessel was 5 MPa) and stirred and mixed, and while stirring and mixing, the reaction was heated to 40°C, and then esterification was performed for 5 h. After the esterification reaction, 200 g of deionized water was added to the reaction vessel, stirring and standing until the oil layer and the water layer were clearly separated, and then the water layer was removed, 5 g of activated clay was added, and then the reaction vessel was heated to 80°C to perform decolorization. The product in the reaction vessel was filtered using a plate and frame filter, the filter cake was activated clay, which was recovered, and the filtrate was a triglyceride type fish oil.

[0054] The triglyceride type fish oil obtained using the preparation method of Example 6 had a yield of 92.5%.

[0055] Example 7

[0056] The present example provides a method for preparing a triglyceride type fish oil, including the following steps:

[0057] 100 g of ethyl ester type fish oil, 20 g of glycerol, and 5 g of a composite catalyst (a mixture of 2.5 g of triethylamine and 2.5 g of polypropylene) were added to a reaction vessel (the pressure in the reaction vessel was 5 MPa) and stirred and mixed, and while stirring and mixing, the reaction was heated to 25°C, and then esterification was performed for 5 h. After the esterification reaction, 200 g of deionized water was added to the reaction vessel, stirring and standing until the oil layer and the water layer were clearly separated, and then the water layer was removed, 5 g of activated clay was added, and then the reaction vessel was heated to 80°C to perform decolorization. The product in the reaction vessel was filtered using a plate and frame filter, the filter cake was activated clay, which was recovered, and the filtrate was a triglyceride type fish oil.

[0058] The triglyceride type fish oil obtained using the preparation method of Example 7 had a yield of 91.4%.

[0059] Example 8

[0060] The present example provides a method for preparing a triglyceride type fish oil, including the following steps:

[0061] 100 g of ethyl ester type fish oil, 20 g of glycerol, and 5 g of a composite catalyst (a mixture of 2.5 g of triethylamine and 2.5 g of polypropylene) were added to a reaction vessel (the pressure in the reaction vessel was 5 MPa) and stirred and mixed, and while stirring and mixing, the reaction was heated to 40°C, and then esterification was performed for 2 h. After the esterification reaction, 200 g of deionized water was added to the reaction vessel, stirring and standing until the oil layer and the water layer were clearly separated, and then the water layer was removed, 5 g of activated clay was added, and then the reaction vessel was heated to 80°C to perform decolorization. The product in the reaction vessel was filtered using a plate and frame filter, the filter cake was activated clay, which was recovered, and the filtrate was a triglyceride type fish oil.

[0062] The triglyceride fish oil obtained by the method of Example 8 had a yield of 87.2%.

[0063] Comparative Example 1

[0064] The comparative example provides a method for preparing a triglyceride fish oil, comprising the following steps:

[0065] 100 g of ethyl ester fish oil, 20 g of glycerol, and 5 g of triethylamine were added to a reaction kettle (the pressure in the reaction kettle was 5 MPa) and stirred and mixed, while the reaction was heated to 40°C, and then esterification was performed for 5 h. After the esterification reaction, 200 g of deionized water was added to the reaction kettle, and stirring and standing were performed until the oil layer and the water layer were clearly separated, then the water layer was removed, 5 g of activated clay was added, and then the reaction kettle was heated to 80°C for decolorization. The product in the reaction kettle was filtered with a plate and frame filter, and the filter cake was activated clay, which was recovered, and the filtrate was the triglyceride fish oil.

[0066] The triglyceride fish oil obtained by the method of Comparative Example 1 had a yield of 65.6%.

[0067] Comparative Example 2

[0068] The comparative example provides a method for preparing a triglyceride fish oil, comprising the following steps:

[0069] 100 g of ethyl ester fish oil, 20 g of glycerol, and 5 g of polypropylene were added to a reaction kettle (the pressure in the reaction kettle was 5 MPa) and stirred and mixed, while the reaction was heated to 40°C, and then esterification was performed for 5 h. After the esterification reaction, 200 g of deionized water was added to the reaction kettle, and stirring and standing were performed until the oil layer and the water layer were clearly separated, then the water layer was removed, 5 g of activated clay was added, and then the reaction kettle was heated to 80°C for decolorization. The product in the reaction kettle was filtered with a plate and frame filter, and the filter cake was activated clay, which was recovered, and the filtrate was the triglyceride fish oil.

[0070] The triglyceride fish oil obtained by the method of Comparative Example 2 had a yield of 38.7%.

[0071] Comparative Example 3

[0072] The comparative example provides a method for preparing a triglyceride fish oil, comprising the following steps:

[0073] 100 g of ethyl ester type fish oil, 20 g of glycerol, and 5 g of a composite catalyst (a mixture of 2.5 g of triethylamine and 2.5 g of polypropylene) were added to a reaction vessel (the pressure in the reaction vessel was 5 MPa) and stirred and mixed, and while stirring and mixing, the reaction was heated to 50°C, and then esterification was performed for 5 h. After the esterification reaction, 200 g of deionized water was added to the reaction vessel, stirring and standing until the oil layer and the water layer were clearly separated, and then the water layer was removed, 5 g of activated clay was added, and then the reaction vessel was heated to 80°C to perform decolorization. The product in the reaction vessel was filtered using a plate and frame filter, the filter cake was activated clay, which was recovered, and the filtrate was a triglyceride type fish oil.

[0074] The triglyceride type fish oil obtained using the method of Comparative Example 3 had a yield of 79.7%.

[0075] Comparative Example 4

[0076] This comparative example provides a method for preparing a triglyceride type fish oil, including the following steps:

[0077] 100 g of ethyl ester type fish oil, 20 g of glycerol, and 5 g of a composite catalyst (a mixture of 2.5 g of triethylamine and 2.5 g of polypropylene) were added to a reaction vessel (the pressure in the reaction vessel was 5 MPa) and stirred and mixed, and while stirring and mixing, the reaction was heated to 20°C, and then esterification was performed for 5 h. After the esterification reaction, 200 g of deionized water was added to the reaction vessel, stirring and standing until the oil layer and the water layer were clearly separated, and then the water layer was removed, 5 g of activated clay was added, and then the reaction vessel was heated to 80°C to perform decolorization. The product in the reaction vessel was filtered using a plate and frame filter, the filter cake was activated clay, which was recovered, and the filtrate was a triglyceride type fish oil.

[0078] The triglyceride type fish oil obtained using the method of Comparative Example 4 had a yield of 83.6%.

[0079] Comparative Example 5

[0080] This comparative example provides a method for preparing a triglyceride type fish oil, including the following steps:

[0081] 100 g of ethyl ester type fish oil, 20 g of glycerol, and 5 g of a composite catalyst (a mixture of 2.5 g of triethylamine and 2.5 g of polypropylene) were added to a reaction vessel (the pressure in the reaction vessel was 5 MPa) and stirred and mixed, and while stirring and mixing, the reaction was heated to 50°C, and then esterification was performed for 5 h. After the esterification reaction, 200 g of deionized water was added to the reaction vessel, stirring and standing until the oil layer and the water layer were clearly separated, and then the water layer was removed, 5 g of activated clay was added, and then the reaction vessel was heated to 80°C to perform decolorization. The product in the reaction vessel was filtered using a plate and frame filter, the filter cake was activated clay, which was recovered, and the filtrate was a triglyceride type fish oil.

[0082] The triglyceride fish oil obtained by the preparation method of Comparative Example 5 has a yield of 75.8%.

[0083] Comparative Example 6

[0084] The present comparative example provides a preparation method of triglyceride fish oil, comprising the following steps:

[0085] 100 g of ethyl ester fish oil, 20 g of glycerol, and 5 g of a composite catalyst (a mixture of 2.5 g of triethylamine and 2.5 g of polypropylene) were added to a reaction kettle (the pressure in the reaction kettle was 5 MPa) and stirred and mixed. While stirring and mixing, the reaction was heated to 40°C, and then esterification was performed for 1 h. After the esterification reaction, 200 g of deionized water was added to the reaction kettle, and stirring and standing were performed until the oil and water layers were clearly separated, then the water layer was removed, 5 g of activated clay was added, and then the reaction kettle was heated to 80°C for decolorization. The product in the reaction kettle was filtered with a plate and frame filter, and the filter cake was activated clay which was recovered, and the filtrate was the triglyceride fish oil.

[0086] The triglyceride fish oil obtained by the preparation method of Comparative Example 6 has a yield of 69.1%.

[0087] The above only describes the preferred embodiments of the present application and is not intended to limit the present application. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application is within the scope of protection of the claims of the present application.

Claims

1. A method for preparing a triglyceride-type fish oil, characterized by, The method comprises the following steps: The ethyl ester type fish oil, glycerol and composite catalyst are mixed and stirred to perform esterification reaction, then the product is washed, stirred and settled, the water layer is removed, then decolorization treatment is performed, finally filtration is performed, and the filtrate is the triglyceride type fish oil; The composite catalyst is a mixture of organic amine and polypropylene; The organic amine comprises one of trimethylamine, triethylamine, aniline, pyrimidine and imidazole; the mass ratio of the organic amine to the polypropylene is (10-15):(10-15); The mass ratio of the ethyl ester type fish oil, glycerol and composite catalyst is (100-150):(20-25):(3-8); The esterification reaction time is 2-10h; The esterification reaction temperature is 25-40℃; The esterification reaction pressure is 1-10MPa.

2. The method of claim 1, wherein the triglyceride-type fish oil is prepared by the steps of: The washing is performed by using deionized water; The added mass of the deionized water is 1.5-2 times of the ethyl ester type fish oil.

3. The method of claim 1, wherein the triglyceride-type fish oil is prepared by the steps of: The settling time is until the oil layer and the water layer are obviously separated.

4. The method of claim 1, wherein the triglyceride-type fish oil is prepared by the steps of: The decolorization is performed by using one or both of activated white clay and attapulgite clay; The decolorization temperature is 75-80℃.

5. The method of claim 4, wherein the triglyceride-type fish oil is prepared by the steps of: The added mass of the activated white clay or attapulgite clay is 0.01-0.05 times of the ethyl ester type fish oil during the decolorization treatment.

6. The method of claim 1, wherein the triglyceride-type fish oil is prepared by the steps of: The ethyl ester type fish oil is a drug grade; The glycerol is a drug grade.

7. The method of claim 1-6, wherein the triglyceride-type fish oil is prepared by, The yield of the triglyceride type fish oil is 85-95%.