CN117229313A - Preparation method and application of phospholipid polyunsaturated fatty acid by chemical catalytic method - Google Patents
Preparation method and application of phospholipid polyunsaturated fatty acid by chemical catalytic method Download PDFInfo
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- CN117229313A CN117229313A CN202210640694.XA CN202210640694A CN117229313A CN 117229313 A CN117229313 A CN 117229313A CN 202210640694 A CN202210640694 A CN 202210640694A CN 117229313 A CN117229313 A CN 117229313A
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- 230000003197 catalytic effect Effects 0.000 title claims abstract description 6
- 238000002360 preparation method Methods 0.000 title abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 67
- 239000003513 alkali Substances 0.000 claims abstract description 53
- 238000011282 treatment Methods 0.000 claims abstract description 48
- 238000005809 transesterification reaction Methods 0.000 claims abstract description 37
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- JAZBEHYOTPTENJ-JLNKQSITSA-N all-cis-5,8,11,14,17-icosapentaenoic acid Chemical compound CC\C=C/C\C=C/C\C=C/C\C=C/C\C=C/CCCC(O)=O JAZBEHYOTPTENJ-JLNKQSITSA-N 0.000 claims description 2
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- 229940114079 arachidonic acid Drugs 0.000 claims description 2
- CYQFCXCEBYINGO-IAGOWNOFSA-N delta1-THC Chemical compound C1=C(C)CC[C@H]2C(C)(C)OC3=CC(CCCCC)=CC(O)=C3[C@@H]21 CYQFCXCEBYINGO-IAGOWNOFSA-N 0.000 claims description 2
- HOBAELRKJCKHQD-QNEBEIHSSA-N dihomo-γ-linolenic acid Chemical compound CCCCC\C=C/C\C=C/C\C=C/CCCCCCC(O)=O HOBAELRKJCKHQD-QNEBEIHSSA-N 0.000 claims description 2
- JAZBEHYOTPTENJ-UHFFFAOYSA-N eicosapentaenoic acid Natural products CCC=CCC=CCC=CCC=CCC=CCCCC(O)=O JAZBEHYOTPTENJ-UHFFFAOYSA-N 0.000 claims description 2
- 229960005135 eicosapentaenoic acid Drugs 0.000 claims description 2
- VZCCETWTMQHEPK-UHFFFAOYSA-N gamma-Linolensaeure Natural products CCCCCC=CCC=CCC=CCCCCC(O)=O VZCCETWTMQHEPK-UHFFFAOYSA-N 0.000 claims description 2
- 235000020664 gamma-linolenic acid Nutrition 0.000 claims description 2
- VZCCETWTMQHEPK-QNEBEIHSSA-N gamma-linolenic acid Chemical compound CCCCC\C=C/C\C=C/C\C=C/CCCCC(O)=O VZCCETWTMQHEPK-QNEBEIHSSA-N 0.000 claims description 2
- 229960002733 gamolenic acid Drugs 0.000 claims description 2
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- 229940033080 omega-6 fatty acid Drugs 0.000 claims description 2
- JIWBIWFOSCKQMA-UHFFFAOYSA-N stearidonic acid Natural products CCC=CCC=CCC=CCC=CCCCCC(O)=O JIWBIWFOSCKQMA-UHFFFAOYSA-N 0.000 claims description 2
- 239000002994 raw material Substances 0.000 abstract description 26
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- 239000000047 product Substances 0.000 description 75
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 64
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 34
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 30
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 24
- 238000010438 heat treatment Methods 0.000 description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
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- JBYXPOFIGCOSSB-GOJKSUSPSA-N 9-cis,11-trans-octadecadienoic acid Chemical compound CCCCCC\C=C\C=C/CCCCCCCC(O)=O JBYXPOFIGCOSSB-GOJKSUSPSA-N 0.000 description 5
- 229940108924 conjugated linoleic acid Drugs 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- OYHQOLUKZRVURQ-IXWMQOLASA-N linoleic acid Natural products CCCCC\C=C/C\C=C\CCCCCCCC(O)=O OYHQOLUKZRVURQ-IXWMQOLASA-N 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 4
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- PORPENFLTBBHSG-MGBGTMOVSA-N 1,2-dihexadecanoyl-sn-glycerol-3-phosphate Chemical compound CCCCCCCCCCCCCCCC(=O)OC[C@H](COP(O)(O)=O)OC(=O)CCCCCCCCCCCCCCC PORPENFLTBBHSG-MGBGTMOVSA-N 0.000 description 3
- 102000004190 Enzymes Human genes 0.000 description 3
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- 235000021122 unsaturated fatty acids Nutrition 0.000 description 3
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 3
- 235000010469 Glycine max Nutrition 0.000 description 2
- 244000068988 Glycine max Species 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 125000004494 ethyl ester group Chemical group 0.000 description 2
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- AWUCVROLDVIAJX-UHFFFAOYSA-N alpha-glycerophosphate Natural products OCC(O)COP(O)(O)=O AWUCVROLDVIAJX-UHFFFAOYSA-N 0.000 description 1
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- 125000004185 ester group Chemical group 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
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- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
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- 150000008103 phosphatidic acids Chemical class 0.000 description 1
- RPDAUEIUDPHABB-UHFFFAOYSA-N potassium ethoxide Chemical compound [K+].CC[O-] RPDAUEIUDPHABB-UHFFFAOYSA-N 0.000 description 1
- BDAWXSQJJCIFIK-UHFFFAOYSA-N potassium methoxide Chemical compound [K+].[O-]C BDAWXSQJJCIFIK-UHFFFAOYSA-N 0.000 description 1
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- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical group [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention relates to the technical field of oil industry, in particular to a method for preparing phospholipid polyunsaturated fatty acid by a chemical catalytic method and a preparation method and application thereof. The method provided by the invention comprises the following steps: under the action of an alkaline catalyst, performing chemical transesterification on phospholipid powder and polyunsaturated fatty acid esters and derivatives thereof; wherein prior to the chemical transesterification, the phospholipid is subjected to an alkali treatment. The invention reduces the occurrence of side reaction in the chemical transesterification reaction process by carrying out alkali treatment on the phospholipid raw material, so that the product is easier to separate from the system, the re-dissolution is realized, meanwhile, the access efficiency of polyunsaturated fatty acid is improved, and the problems of high requirement on the content of polyunsaturated fatty acid raw material and harsh reaction conditions in the existing phospholipid polyunsaturated fatty acid synthesis are solved. The phospholipid polyunsaturated fatty acid obtained by the method has the target fatty acid content reaching more than 33 percent, and good redissolution, and meets the industrial production requirement.
Description
Technical Field
The invention relates to the technical field of oil industry, in particular to a method for preparing phospholipid polyunsaturated fatty acid by a chemical catalytic method and a preparation method and application thereof.
Background
Currently, the industrial synthesis method of phospholipid polyunsaturated fatty acid mainly comprises enzymatic transesterification or chemical transesterification.
The enzymatic transesterification is to exchange the ester compound of the target fatty acid with the fatty acid on the phospholipid by using the enzyme as a catalyst, and has a relatively large restriction by the enzyme itself and a relatively low conversion rate.
The chemical transesterification is a strong alkaline catalyst such as sodium methoxide, and the ester compound of the target fatty acid and the fatty acid on the phospholipid are exchanged. Compared with enzyme catalyst, the chemical transesterification has the advantages of high conversion rate, relatively low price, easy separation from the reaction system, etc.
In order to increase the content of the target polyunsaturated fatty acids in the phospholipids, chemical transesterification processes generally require refined starting materials, high temperature reaction conditions and more catalyst to achieve a strong transesterification reaction.
For example, CN201710602340.5 discloses a preparation method of phospholipid type DHA/EPA with higher polyunsaturated fatty acid content, which takes refined fish oil methyl ester/refined fish oil ethyl ester (DHA content is more than 70%) as raw materials, and prepares the phospholipid at a high temperature of 100-150 ℃, wherein the DHA content in the product phospholipid can be 50-90% of the total fatty acid content in the phospholipid.
The preparation process of phospholipid rich in conjugated linoleic acid also discloses a method for improving the content of polyunsaturated fatty acids, which determines the optimal reaction condition through a single factor test and an orthogonal test: the mol ratio of the conjugated linoleic acid ethyl ester to the soybean powder phospholipid is 4:1, the catalyst dosage is 4% of the mass of the soybean powder phospholipid, the reaction temperature is 130 ℃, and the reaction time is 3 hours. Under this condition, the total content of conjugated linoleic acid in the obtained phospholipid reaches 59.23%.
Although the process utilizes a chemical transesterification method to obtain the polyunsaturated fatty acid containing phospholipid, and the content of the target fatty acid in the product can meet certain requirements, the technical personnel of the invention find that the product obtained by the process can not be completely redissolved in n-hexane after simple acetone fractionation technology when further verifying the target product. After insoluble substances are separated and detected, analysis shows that the products obtained by the method have more side reaction products, wherein the side reaction products comprise fatty acid salts such as sodium fatty acid, glycerophosphate and the like, the content of the fatty acid salts is up to more than 20 percent, the fatty acid and the fatty acid salts are repeatedly exchanged in a reaction system, the products are disordered, and the real phospholipid polyunsaturated fatty acid target products are few. It can be seen that the prior art only pursues the access rate or the content of the target fatty acid in the product, but does not pay much attention to whether the obtained product contains phospholipid polyunsaturated fatty acid with higher content and whether the obtained product can completely redissolve n-hexane.
In addition to the above main problems, the existing preparation method has the problems of high raw material cost, harsh process conditions, complex separation technology and the like, for example, as described in CN201710602340.5, the raw material refined fish oil methyl ester/refined fish oil ethyl ester is required to be obtained by using a multi-stage distillation and rectification method; and the preparation process of phospholipid rich in conjugated linoleic acid requires that the polyunsaturated fatty acid content in the raw materials is at least more than 80%, and higher reaction temperature is required.
Therefore, how to prepare a product which has high actual content (high purity) and can be completely redissolved in n-hexane of phospholipid type polyunsaturated fatty acid by using low-cost raw materials, milder reaction conditions and simple separation technology becomes a key problem to be solved in the production and preparation of phospholipid type polyunsaturated fatty acid.
Disclosure of Invention
The invention provides a novel method for synthesizing phospholipid polyunsaturated fatty acid aiming at the technical problems which are not existed in the prior art. The method has the advantages that the content of target polyunsaturated fatty acid in the product is relatively high, the obtained product can be separated by a simple acetone fractionation technology, the re-solubility is good, the industrial production requirement is met, meanwhile, the method has no strict requirement on the unsaturated fatty acid content in the raw material ester compound, the raw material cost is reduced, the reaction can be carried out under the condition of relatively low temperature, the reaction condition is milder, and the industrial production is facilitated.
In a first aspect, the present invention provides a method for preparing a phospholipid polyunsaturated fatty acid by chemical catalysis, comprising: under the action of an alkaline catalyst, performing chemical transesterification between phospholipid and polyunsaturated fatty acid ester and derivatives thereof; and requires an alkaline treatment of the phospholipids; meanwhile, the reaction condition of chemical transesterification is that the reaction temperature is 60-90 ℃ and the reaction time is 1-4h under the vacuum condition.
The invention discovers that the commercially available conventional phospholipids have wide sources and low price, and can be used as the preparation raw materials to reduce the production cost and improve the overall economic benefit; however, the conventional phospholipids on the market have the problem of extensive standard, and the physicochemical indexes of the conventional phospholipids are usually based on acetone insoluble substances, n-hexane insoluble substances, acid values and the like, wherein the acid values are only required to be lower than 38mgKOH/g, and the components of the conventional phospholipids comprise various phospholipids, phosphatidic acid, free fatty acid and the like, are very complex and are easy to react at high temperature, such as various cracking reactions and the like; polyunsaturated fatty acid esters are also easy to oxidize under high temperature (130 ℃) conditions, and the catalysis in the environment causes too many side reactions, so that the actual content of the phospholipid polyunsaturated fatty acid which is a real target product is relatively low, and the side reaction product and the target product cannot be thoroughly separated by a simple acetone fractionation technology, so that the obtained product is difficult to redissolve in n-hexane.
Indeed, the selection of high standard grade phospholipids or polyunsaturated fatty acid esters as starting materials is a solution but is not suitable for industrial operations where low costs are sought. The polyunsaturated fatty acid content in the phospholipid product prepared directly under milder reaction conditions is very low, and the industrial transformation is difficult. Therefore, how to obtain the phospholipid product with higher target polyunsaturated fatty acid content and better redissolution effect under milder reaction conditions becomes one of the technical problems of the process for preparing the phospholipid polyunsaturated fatty acid by the chemical catalytic method.
In an accidental attempt, the technical staff of the invention find that the acid value of the phospholipid is reduced by carrying out alkali treatment on the phospholipid, so that the occurrence of side reaction in chemical transesterification can be obviously reduced, and the generation of side reaction products is further reduced, thereby being beneficial to the separation of target products and realizing the complete re-dissolution of the products in n-hexane; meanwhile, the reduction of side reaction is also beneficial to improving the access efficiency of polyunsaturated fatty acid, so that the excessively high requirements on the unsaturated fatty acid content and the reaction temperature in the raw material ester compound are reduced, the raw material and the production cost are reduced, and finally, the purpose of obtaining the phospholipid product with higher target polyunsaturated fatty acid content and better redissolution effect under milder reaction conditions is realized.
The applicant has emphasized that although "alkali treatment" is a conventional means in the art, it is also used in the production of conventional phospholipid polyunsaturated fatty acids, such as alkali treatment of polyunsaturated fatty acid esters and derivatives thereof, and the alkali treatment works differently depending on the object of treatment.
In particular, in the existing enzymatic preparation, when the polyunsaturated fatty acid ester and the derivative thereof are subjected to alkali treatment, the alkali treatment is used for promoting enzymatic catalysis, and the free fatty acid is converted into a small amount of fatty acid salt, so that the enzymatic catalysis can be better assisted by utilizing the fatty acid salt, but experiments show that the fatty acid salt is one of main factors influencing byproducts.
The invention adopts a chemical transesterification method, and the reaction mechanism is different from enzymatic catalysis. In the invention, the purpose of alkali treatment is to form phosphatidic acid and other substances in phosphatidic acid into phosphatidic acid salt, thereby reducing side reaction in chemical transesterification, not only playing the roles of simplifying separation and realizing product redissolution, but also playing the role of improving the access efficiency of polyunsaturated fatty acid, and solving the problems of high requirements on unsaturated fatty acid content and reaction temperature in raw material ester compounds and high production cost in the existing method.
It is apparent that although both are alkali-treated, the actions are different depending on the treatment object, and the prior art does not give any technical suggestion that the side reaction in the chemical transesterification reaction can be reduced by alkali treatment of the phospholipid, so that the technical means for alkali treatment of the phospholipid proposed by the present invention is not obvious.
In addition, the invention adopts the technical means of treating the phospholipid alkali, and adopts a vacuum heating mode and controls the reaction temperature, thereby not only increasing the contact time of materials and promoting the reaction to be fully carried out and improving the conversion rate, but also removing the water possibly generated, preventing the materials from being oxidized to form soap and improving the product quality.
Further, the present invention reduces the acid value of the phospholipid to 2mgKOH/g or less by alkali treatment. Research shows that the phospholipid acid value is controlled below 2mgKOH/g, which can obviously reduce the occurrence of side reaction in chemical transesterification and obviously improve the access efficiency of polyunsaturated fatty acid.
The alkali treatment according to the invention can be carried out prior to or simultaneously with the chemical transesterification.
In some embodiments, the phospholipid feedstock may be optionally treated with a base to reduce its acid value, and then mixed with a polyunsaturated fatty acid ester for transesterification under the influence of a basic catalyst. Wherein the alkali treatment agent may be selected differently from the basic catalyst.
When the alkali treatment is carried out before chemical transesterification, the specific process comprises the following steps: dissolving phospholipid in a solvent, adding an alkali treatment agent, reacting for a period of time, separating to obtain clear liquid, and removing the solvent; wherein the alkali treatment agent is selected from NaOH, KOH, naOC 2 H 5 、KOC 2 H 5 、NaOCH 3 、KOCH 3 And various commercial solid bases, and the like.
In the above alkali treatment process, the reaction temperature corresponds to the boiling point of the solvent, and the skilled person can determine according to the solvent selected. In some practical cases, if the solvent is selected to be n-hexane, the reaction temperature can be controlled between 40 and 50 ℃ during the alkali treatment.
In other embodiments, the alkali treatment agent is the same type of alkali catalyst as the alkali catalyst used in the chemical transesterification reaction. In this case, the addition amount of the basic catalyst is the sum of the two effects of acid value reduction and catalysis, and the solvent component required for the single alkali treatment can be omitted, that is, the additional raw material desolventizing step is not required, and the method can be directly carried out in the oil system.
The alkaline catalyst is selected from sodium ethoxide, sodium methoxide, potassium ethoxide, potassium methoxide and the like. The addition amount of the alkaline catalyst is 1.8-6% of the mass of the phospholipid; preferably 3-6% of the mass of the phospholipid, and can be specifically adjusted according to the chemical transesterification effect to stably obtain the phospholipid product with the polyunsaturated fatty acid content of more than or equal to 30%.
Preferably, the system temperature at the time of dosing of the basic catalyst is controlled not to exceed 45 ℃ to reduce oxidation of phospholipids/oils and fats.
Preferably, the conditions of the chemical transesterification are: the reaction temperature is 60-80 ℃ under the vacuum condition, and the reaction time can be controlled to be 2-4h. Specifically, the system is vacuumized and slowly warmed up according to the conventional operation of the person skilled in the art.
The reaction conditions including alkali concentration, alkali type, alkali addition amount, reaction time, temperature, etc. and subsequent separation, desolventizing, etc. may be regulated by one skilled in the art. For example, according to the scale of operation, the separation method may be centrifugation, membrane filtration, etc., and the desolventizing method may be rotary evaporation desolventizing, etc.
Further, in the chemical transesterification reaction, the molar ratio of the phospholipid to the polyunsaturated fatty acid ester and the derivative thereof is 1:2-1:6.
Further, the phospholipids are mixed with polyunsaturated fatty acid esters and their derivatives before the chemical transesterification reaction is performed, and then dehydrated. The method can specifically adopt a vacuum heating mode to remove partial components affecting the reaction degree, such as water, low boiling point acidic substances and the like, in the raw materials, thereby being beneficial to improving the conversion efficiency; specifically, the materials are mixed, vacuumized, heated and stirred, and slowly heated to 100 ℃ to remove water.
Further, after the reaction of the invention is finished, adding n-hexane for dissolution and citric acid solution for stopping the reaction; and (3) for the reaction of alkali treatment and chemical transesterification, taking the supernatant through centrifugation after the reaction is finished, and then carrying out treatments such as acetone deoiling and drying to obtain the target phospholipid product. For hardening by synchronous alkali treatment and chemical transesterification, the treatments of acetone deoiling, drying and the like can be directly carried out in an oil system without additional raw material desolventizing steps, so that the target phospholipid product is obtained.
Furthermore, in the polyunsaturated fatty acid ester and the raw materials of the derivative thereof, the content of polyunsaturated fatty acid is not less than 50 percent; wherein the polyunsaturated fatty acid is one or more of omega-3 fatty acid, omega-6 fatty acid, docosahexaenoic acid, eicosapentaenoic acid, docosapentaenoic acid, arachidonic acid, gamma-linolenic acid, dihomo-gamma-linolenic acid or stearidonic acid.
The polyunsaturated fatty acid ester and its derivative are required to have an acid value of less than or equal to 1mgKOH/g. In some embodiments, if the acid value of the polyunsaturated fatty acid ester and its derivative is higher, the acid value can be reduced by alkali treatment, and the alkali treatment agent can be different from the alkali catalyst, or can be the same as the alkali treatment agent for treating phospholipid, and under the same condition, the alkali catalyst and the alkali treatment agent can be added into the reaction system at the same time, and the total addition amount is the sum of the two effects of reducing the acid value and catalyzing.
The ester groups in the polyunsaturated fatty acid esters and derivatives thereof include methyl, ethyl, and glycerides, preferably glycerides.
In a second aspect, the present invention provides a phospholipid polyunsaturated fatty acid prepared by the chemical transesterification process described above.
The phospholipid polyunsaturated fatty acid obtained by the method has the target polyunsaturated fatty acid content of not less than 30 percent and the fatty acid salt content of not more than 5 percent, so that the phospholipid polyunsaturated fatty acid can be completely redissolved in n-hexane and meets the requirements of industrial production and application.
The target polyunsaturated fatty acid refers to the polyunsaturated fatty acid which accords with the preparation purpose, and is usually the polyunsaturated fatty acid accounting for the majority of the content in a reaction system; for example, if it is desired to prepare a phospholipid-type DHA, DHA (docosahexaenoic acid) must be the highest in the reaction system, and DHA (docosahexaenoic acid) is the target polyunsaturated fatty acid, and in some reaction systems, the target fatty acid may be present in two or more kinds, and the total content of these fatty acids must be the highest in the system. The invention adopts DHA with higher acidity of unsaturated fat as implementation mode, and due to high unsaturation degree of DHA, side reactions such as oxidation and the like are easier to occur at high temperature, so the invention is most suitable for embodying the gist of the invention.
In a third aspect, the present invention also provides a composition comprising the above-described phospholipid polyunsaturated fatty acids; the fatty acid salt content of the composition is less than 5%.
Preferably, the composition has a content of target polyunsaturated fatty acids of not less than 30% and a content of fatty acid salts of not more than 3%.
The beneficial effects of the invention are as follows:
1. the invention reduces the occurrence of side reaction in the chemical transesterification reaction process by treating the phospholipid with alkali, so that the product is easier to separate from the system, the re-dissolution is realized, meanwhile, the access efficiency of polyunsaturated fatty acid is improved by treating with alkali, and the problems of high requirement on polyunsaturated fatty acid raw material content, harsh reaction conditions and lower actual target product in the existing phospholipid polyunsaturated fatty acid synthesis are solved.
2. The inventive composition of the present invention is: currently, there is no industrialized and standardized phospholipid polyunsaturated fatty acid product on the market, and conventional chemically catalyzed phospholipid polyunsaturated fatty acids react under high temperature conditions to improve the access rate, while the currently marketed phospholipids do not have raw materials with acid values as low as the range of the present invention, which inevitably results in the formation of a large amount of fatty acid salts in the product; while most of the fatty acid salts are insoluble in n-hexane, so that the product is not re-soluble in a suitable amount of n-hexane. Although the prior art has been able to remove the fatty acid salt component from the final product, at this point some of the target fatty acid has formed salts, which removal necessarily results in a reduced content of target fatty acid in the composition.
The invention controls the generation of fatty acid salt through the treatment of raw materials, and can realize the complete re-dissolution of the phospholipid type polyunsaturated fatty acid composition in normal hexane after the acetone crude extraction of the composition, and meanwhile, the content of phosphate substances in the composition is inevitably greatly improved due to the reduction of fatty acid salt. This is an essential difference from the prior art phospholipid polyunsaturated fatty acid compositions obtained by chemical transesterification, which only focus on the rate of access, and is an improvement for downstream applications.
Drawings
FIG. 1 shows the reconstitution contrast effect of the products of the examples and comparative examples. In the figure, the left is the reconstitution effect of the product of comparative example 2 and the right is the reconstitution effect of the product of example 1.
Detailed Description
The following examples are illustrative of the invention and are not intended to limit the scope of the invention.
The main experimental raw materials involved in the following embodiments:
commercially available conventional powder phospholipids (acetone insoluble matter is more than or equal to 95%, n-hexane insoluble matter is less than or equal to 0.3%, phospholipid content is about 60-77%, acid value is less than or equal to 38 mgKOH/g) are purchased from new hundred-vitamin;
DHA triglyceride with DHA content of 52.3% and acid value less than or equal to 0.5mgKOH/g is commercial DHA oil.
Example 1
The embodiment provides a preparation method of phospholipid polyunsaturated fatty acid, which comprises the following steps:
(1) Alkali treatment of phospholipid raw material:
dissolving powder phospholipid in n-hexane, adding NaOH solution, reacting at 45 ℃, centrifuging to obtain supernatant after the reaction is finished, and removing solvent to obtain phospholipid with acid value of 2.0 mgKOH/g;
(2) Adding 10g of the phospholipid obtained in the step (1) and 50g of DHA triglyceride into a flask, vacuumizing, stirring (300 rpm), and slowly heating to 100 ℃ to remove water;
(3) Cooling the system obtained in the step (2) to below 45 ℃, breaking vacuum, and adding 0.6g of sodium methoxide;
(4) Vacuumizing the system obtained in the step (3), slowly heating to 80 ℃, and stirring for 2h (300 rpm);
(5) After the reaction is completed, adding n-hexane for dissolution and citric acid solution for stopping the reaction; and (3) centrifuging to obtain a supernatant, desolventizing, acetone deoiling, drying and the like to obtain a target phospholipid product.
Through detection, the DHA content of the obtained target phospholipid product is 36.8%, and the product can be completely redissolved in n-hexane, so that the soap content (fatty acid salt) is 2.3%.
Example 2
The embodiment provides a preparation method of phospholipid polyunsaturated fatty acid, which comprises the following steps:
(1) Alkali treatment of phospholipid raw material:
dissolving the powder phospholipid in normal hexane, adding NaOH, reacting at 45 ℃, centrifuging to obtain supernatant after the reaction is finished, and removing the solvent to obtain the phospholipid with the acid value of 1.2mgKOH/g;
(2) Adding 10g of the phospholipid obtained in the step (1) and 40g of DHA triglyceride into a flask, vacuumizing, stirring (300 rpm), and slowly heating to 100 ℃ to remove water;
(3) Cooling the system obtained in the step (2) to below 45 ℃, breaking vacuum, and adding 0.6g of sodium methoxide;
(4) And (3) vacuumizing the system obtained in the step (3), slowly heating to 75 ℃, and stirring for 2.5h (300 rpm).
(5) After the reaction is completed, adding n-hexane for dissolution and citric acid solution for stopping the reaction; and (3) centrifuging to obtain a supernatant, desolventizing, acetone deoiling, drying and the like to obtain a target phospholipid product.
Through detection, the DHA content in the obtained target phospholipid product is 33.5%, and the product can be completely redissolved in normal hexane, so that the soap content (fatty acid salt) is 3.0%.
Example 3
The embodiment provides a preparation method of phospholipid polyunsaturated fatty acid, which comprises the following steps:
(1) Pretreatment of phospholipid:
dissolving powder phospholipid in normal hexane, adding NaOH, reacting at 45 ℃, and removing a solvent after the reaction is finished to obtain phospholipid with acid value of 5 mgKOH/g;
(2) Adding 12g of the phospholipid obtained in the step (1) and 50g of DHA triglyceride into a flask, vacuumizing, stirring (300 rpm), and slowly heating to 100 ℃ to remove water;
(3) Cooling the system obtained in the step (2) to below 45 ℃, breaking vacuum, and adding 0.6g of sodium methoxide;
(4) And (3) vacuumizing the system obtained in the step (3), slowly heating to 80 ℃, and stirring for 2h (300 rpm).
(5) After the reaction is completed, adding n-hexane for dissolution and citric acid solution for stopping the reaction; and (3) centrifuging to obtain a supernatant, desolventizing, acetone deoiling, drying and the like to obtain a target phospholipid product.
Through detection, the DHA content of the obtained target phospholipid product is 25.3%, a small amount of the product can not be completely redissolved in normal hexane, and the soap content (fatty acid salt) is 8.2%.
The result shows that when the acid value is relatively high, the DHA content in the obtained target phospholipid product is reduced, and the redissolution effect of the product is affected.
Example 4
The embodiment provides a preparation method of phospholipid polyunsaturated fatty acid, which comprises the following steps:
(1) The alkali treatment and the catalytic reaction of the phospholipid raw material are realized in a system at the same time;
10g of phospholipid and 50g of DHA triglyceride are added into a flask, vacuumizing and stirring (300 rpm) are carried out, and the temperature is slowly increased to 100 ℃ to remove water;
(2) Cooling the system obtained in the step (2) to below 45 ℃, breaking vacuum, and adding 0.98g of sodium methoxide, wherein the overall acid value of the system is measured to be lower than 1mgKOH/g;
(3) Vacuumizing the system obtained in the step (3), slowly heating to 80 ℃, and stirring for 2h (300 rpm);
(4) After the reaction is completed, adding n-hexane for dissolution and citric acid solution for stopping the reaction; and (3) centrifuging to obtain a supernatant, desolventizing, acetone deoiling, drying and the like to obtain a target phospholipid product.
Through detection, the DHA content in the obtained target phospholipid product is 35.0%, and the product can be completely redissolved in n-hexane, so that the soap content (fatty acid salt) is 2.0%.
Compared with the example 1, the DHA content in the obtained target phospholipid product is not greatly different after adopting the synchronous alkali treatment mode, and the product redissolution effect is good.
Example 5
(1) Alkali treatment of phospholipid raw material:
dissolving powder phospholipid in n-hexane, adding NaOH solution, reacting at 45 ℃, centrifuging to obtain supernatant after the reaction is finished, and removing solvent to obtain phospholipid with acid value of 2.0 mgKOH/g;
(2) Adding 10g of the phospholipid obtained in the step (1) and 50g of DHA triglyceride into a flask, vacuumizing, stirring (300 rpm), and slowly heating to 100 ℃ to remove water;
(3) Cooling the system obtained in the step (2) to below 45 ℃, breaking vacuum, and adding 0.2g of sodium methoxide;
(4) Vacuumizing the system obtained in the step (3), slowly heating to 80 ℃, and stirring for 2h (300 rpm);
(5) After the reaction is completed, adding n-hexane for dissolution and citric acid solution for stopping the reaction; and (3) centrifuging to obtain a supernatant, desolventizing, acetone deoiling, drying and the like to obtain a target phospholipid product.
Through detection, the DHA content of the obtained target phospholipid product is 19.6%, and the product can be completely redissolved in n-hexane.
The result shows that the addition amount of sodium methoxide is relatively small, the DHA content in the target phospholipid product is affected, but the product has good resolubility.
Comparative example 1
This comparative example provides a process for the preparation of a phospholipid polyunsaturated fatty acid, which differs from example 1 in that the starting phospholipid material is not subjected to an alkali treatment, but only to a conventional starting pretreatment, and has an acid value of 31.2mgKOH/g.
The method comprises the following specific steps:
(1) After conventional pretreatment, the acid value of the powder phospholipid is 31.2mgKOH/g;
(2) Adding 10g of the phospholipid obtained in the step (1) and 50g of DHA triglyceride into a flask, vacuumizing, stirring (300 rpm), and slowly heating to 100 ℃ to remove water;
(3) Cooling the system obtained in the step (2) to below 45 ℃, breaking vacuum, and adding 0.6g of sodium methoxide;
(4) And (3) vacuumizing the system obtained in the step (3), slowly heating to 80 ℃, and stirring for 2h (300 rpm).
(5) After the reaction is completed, adding n-hexane for dissolution and citric acid solution for stopping the reaction; and (3) centrifuging to obtain a supernatant, desolventizing, acetone deoiling, drying and the like to obtain a target phospholipid product.
Through detection, the DHA content in the obtained target phospholipid product is too low and is only 0.77%.
The results show that, with phospholipids not subjected to an alkali treatment, the DHA content of the resulting target phospholipid product is too low.
Comparative example 2
This comparative example provides a process for the preparation of phospholipid polyunsaturated fatty acids, which differs from example 1 in that the reaction conditions are the optimum reaction conditions for the literature preparation Process for phospholipids enriched with conjugated linoleic acid.
The method comprises the following specific steps:
(1) After conventional pretreatment, the acid value of the powder phospholipid is 31.2mgKOH/g;
(2) Adding 10g of the phospholipid obtained in the step (1) and 40g of DHA triglyceride into a flask, vacuumizing, stirring (300 rpm), and slowly heating to 100 ℃ to remove water;
(3) Cooling the system obtained in the step (2) to below 45 ℃, breaking vacuum, and adding 0.6g of sodium methoxide;
(4) And (3) vacuumizing the system obtained in the step (3), slowly heating to 130 ℃, and stirring for 2h (300 rpm).
(5) After the reaction is completed, adding n-hexane for dissolution and citric acid solution for stopping the reaction; desolventizing, deoiling with acetone, drying, etc. to obtain the target phospholipid product.
Through detection, the DHA content of the obtained phospholipid product is 37.9%, but the product cannot be redissolved in n-hexane.
However, the water introduced in step (5) forms a turbid emulsion with the oil in the presence of soap, so that the soap component cannot be separated, and the soap content in the product is measured to be 20.5%; after insoluble substances are removed through centrifugation, DHA content detection is carried out on a target phospholipid product, and the DHA content in the product is 24.8%.
This comparative example is sufficient to demonstrate that the phospholipid product obtained at high temperature, although the DHA content may be higher, part of the DHA actually forms soap, so the DHA content in the actual target product will be lower.
Comparative example 3
Based on the soap content of comparative example 2, it is considered whether the addition of the base catalyst is excessive resulting in too much fatty acid salt formation. The comparative example provides a preparation method of phospholipid polyunsaturated fatty acid, which comprises the following steps:
(1) After conventional pretreatment, the acid value of the powder phospholipid is 31.2mgKOH/g;
(2) Adding 10g of the phospholipid obtained in the step (1) and 40g of DHA triglyceride into a flask, vacuumizing, stirring (300 rpm), and slowly heating to 100 ℃ to remove water;
(3) Cooling the system obtained in the step (2) to below 45 ℃, breaking vacuum, and adding 0.2g of sodium methoxide;
(4) And (3) vacuumizing the system obtained in the step (3), slowly heating to 130 ℃, and stirring for 2h (300 rpm).
(5) After the reaction is completed, adding n-hexane for dissolution and citric acid solution for stopping the reaction for desolventizing, removing oil from acetone, drying and the like, thus obtaining the target phospholipid product.
Through detection, the DHA content in the obtained phospholipid product is 8.9%, the product still has a small amount of insoluble n-hexane, and the DHA content is greatly reduced.
Comparative example 4
This example provides a process for the preparation of phospholipid polyunsaturated fatty acids, which differs from example 1 in that the reaction temperature is raised to 130 ℃, as follows:
(1) Alkali treatment of phospholipid raw material:
dissolving powder phospholipid in n-hexane, adding NaOH solution, reacting at 45 ℃, centrifuging to obtain supernatant after the reaction is finished, and removing solvent to obtain phospholipid with acid value of 2.0 mgKOH/g;
(2) Adding 10g of the phospholipid obtained in the step (1) and 50g of DHA triglyceride into a flask, vacuumizing, stirring (300 rpm), and slowly heating to 100 ℃ to remove water;
(3) Cooling the system obtained in the step (2) to below 45 ℃, breaking vacuum, and adding 0.6g of sodium methoxide;
(4) Vacuumizing the system obtained in the step (3), slowly heating to 130 ℃, and stirring for 2h (300 rpm);
(5) After the reaction is completed, adding n-hexane for dissolution and citric acid solution for stopping the reaction for desolventizing, removing oil from acetone, drying and the like, thus obtaining the target phospholipid product.
Through detection, the DHA content in the obtained phospholipid product is 39.5%, and partial substances still remain undissolved in normal hexane, so that the soap content in the product is 12.6%.
The result shows that the phospholipid is easy to crack or oxidize at high temperature, and more byproducts are brought to the product, so that the DHA content of the phospholipid product obtained at high temperature is lower in the actual target product although the DHA content is higher.
While the invention has been described in detail in the foregoing general description and with reference to specific embodiments thereof, it will be apparent to one skilled in the art that modifications and improvements can be made thereto. Accordingly, such modifications or improvements may be made without departing from the spirit of the invention and are intended to be within the scope of the invention as claimed.
Claims (10)
1. A method for preparing phospholipid polyunsaturated fatty acids by a chemical catalytic method, comprising: under the action of an alkaline catalyst, performing chemical transesterification between phospholipid and polyunsaturated fatty acid ester and derivatives thereof; characterized in that the phospholipid is subjected to an alkali treatment;
the conditions of the chemical transesterification are: the reaction temperature is 60-90 ℃ under the vacuum condition, and the time is 1-4h.
2. The method according to claim 1, wherein the acid value of the phospholipid is reduced to 2mgKOH/g or less by alkali treatment.
3. The method according to claim 2, wherein the alkali treatment is performed prior to or simultaneously with chemical transesterification.
4. A process according to claim 3, wherein when the alkaline treatment is carried out before chemical transesterification, the specific procedure comprises: dissolving phospholipid in a solvent, adding an alkali treatment agent, reacting for a period of time, separating to obtain clear liquid, and removing the solvent;
when the alkali treatment and the chemical transesterification are performed simultaneously, the alkali treatment agent is the alkali catalyst.
5. The method according to claim 4, wherein the basic catalyst is added in an amount of 1.8 to 6% by mass of the phospholipid; preferably 3-6%;
the system temperature during the feeding of the alkaline catalyst is controlled to be not more than 45 ℃.
6. The method of claim 5, wherein the conditions of the chemical transesterification are: the reaction temperature is 60-80 ℃ under the vacuum condition, and the time is 2-4h.
7. The method according to claim 6, wherein the polyunsaturated fatty acid ester and its derivatives have a polyunsaturated fatty acid content of not less than 50%; the acid value of the polyunsaturated fatty acid ester and the derivative thereof is less than or equal to 1mgKOH/g;
the polyunsaturated fatty acid is one or more of omega-3 fatty acid, omega-6 fatty acid, docosahexaenoic acid, eicosapentaenoic acid, docosapentaenoic acid, arachidonic acid, gamma-linolenic acid, dihomo-gamma-linolenic acid or stearidonic acid.
8. A polyunsaturated fatty acid of the phospholipid type, characterised in that it has been prepared by a process comprising any one of claims 1 to 7.
9. A composition comprising the phospholipid-type polyunsaturated fatty acid of claim 8; the fatty acid salt content of the composition is less than 5%.
10. The composition of claim 9, wherein the composition has a target polyunsaturated fatty acid content of not less than 30% and a fatty acid salt content of not more than 3%.
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