CN106117050A - Improve the method for the purity of EPA-E in fish oil - Google Patents
Improve the method for the purity of EPA-E in fish oil Download PDFInfo
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- CN106117050A CN106117050A CN201610475726.XA CN201610475726A CN106117050A CN 106117050 A CN106117050 A CN 106117050A CN 201610475726 A CN201610475726 A CN 201610475726A CN 106117050 A CN106117050 A CN 106117050A
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- fish oil
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- acid ethyl
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- 235000021323 fish oil Nutrition 0.000 title claims abstract description 67
- 238000000034 method Methods 0.000 title claims abstract description 48
- SSQPWTVBQMWLSZ-AAQCHOMXSA-N ethyl (5Z,8Z,11Z,14Z,17Z)-icosapentaenoate Chemical compound CCOC(=O)CCC\C=C/C\C=C/C\C=C/C\C=C/C\C=C/CC SSQPWTVBQMWLSZ-AAQCHOMXSA-N 0.000 title claims abstract description 21
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 173
- 239000004202 carbamide Substances 0.000 claims abstract description 88
- 238000000199 molecular distillation Methods 0.000 claims abstract description 64
- 235000014113 dietary fatty acids Nutrition 0.000 claims abstract description 44
- 229930195729 fatty acid Natural products 0.000 claims abstract description 44
- 239000000194 fatty acid Substances 0.000 claims abstract description 44
- 239000000203 mixture Substances 0.000 claims abstract description 39
- 238000005809 transesterification reaction Methods 0.000 claims abstract description 27
- 235000013877 carbamide Nutrition 0.000 claims description 85
- 239000000047 product Substances 0.000 claims description 79
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 66
- 239000007788 liquid Substances 0.000 claims description 43
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 25
- 229960004756 ethanol Drugs 0.000 claims description 20
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 claims description 18
- 235000019198 oils Nutrition 0.000 claims description 14
- 238000004821 distillation Methods 0.000 claims description 13
- 239000002253 acid Substances 0.000 claims description 9
- 230000036760 body temperature Effects 0.000 claims description 8
- 239000012153 distilled water Substances 0.000 claims description 8
- 239000000706 filtrate Substances 0.000 claims description 8
- 238000010992 reflux Methods 0.000 claims description 8
- 238000013517 stratification Methods 0.000 claims description 8
- 239000006228 supernatant Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims 1
- MBMBGCFOFBJSGT-KUBAVDMBSA-N docosahexaenoic acid Natural products CC\C=C/C\C=C/C\C=C/C\C=C/C\C=C/C\C=C/CCC(O)=O MBMBGCFOFBJSGT-KUBAVDMBSA-N 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 7
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 235000020669 docosahexaenoic acid Nutrition 0.000 abstract description 2
- 229940090949 docosahexaenoic acid Drugs 0.000 abstract description 2
- 238000003756 stirring Methods 0.000 description 16
- 238000002425 crystallisation Methods 0.000 description 8
- 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 description 7
- DVSZKTAMJJTWFG-UHFFFAOYSA-N docosa-2,4,6,8,10,12-hexaenoic acid Chemical compound CCCCCCCCCC=CC=CC=CC=CC=CC=CC(O)=O DVSZKTAMJJTWFG-UHFFFAOYSA-N 0.000 description 7
- JAZBEHYOTPTENJ-UHFFFAOYSA-N eicosapentaenoic acid Natural products CCC=CCC=CCC=CCC=CCC=CCCCC(O)=O JAZBEHYOTPTENJ-UHFFFAOYSA-N 0.000 description 7
- 235000020673 eicosapentaenoic acid Nutrition 0.000 description 7
- 229960005135 eicosapentaenoic acid Drugs 0.000 description 7
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 7
- 210000002700 urine Anatomy 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 238000011084 recovery Methods 0.000 description 6
- 241000251468 Actinopterygii Species 0.000 description 5
- 238000009835 boiling Methods 0.000 description 5
- 238000004508 fractional distillation Methods 0.000 description 5
- 239000012071 phase Substances 0.000 description 5
- 238000001953 recrystallisation Methods 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 4
- 230000032050 esterification Effects 0.000 description 4
- 238000005886 esterification reaction Methods 0.000 description 4
- 150000004665 fatty acids Chemical class 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 235000021003 saturated fats Nutrition 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000007171 acid catalysis Methods 0.000 description 3
- 238000005815 base catalysis Methods 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 235000019197 fats Nutrition 0.000 description 3
- -1 fatty acid esters Chemical class 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 102000004190 Enzymes Human genes 0.000 description 2
- 108090000790 Enzymes Proteins 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerol Natural products OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 230000000750 progressive effect Effects 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 201000001320 Atherosclerosis Diseases 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 230000036772 blood pressure Effects 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- RXKJFZQQPQGTFL-UHFFFAOYSA-N dihydroxyacetone Chemical compound OCC(=O)CO RXKJFZQQPQGTFL-UHFFFAOYSA-N 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- ITNKVODZACVXDS-YNUSHXQLSA-N ethyl (4Z,7Z,10Z,13Z,16Z,19Z)-docosahexaenoate Chemical compound CCOC(=O)CC\C=C/C\C=C/C\C=C/C\C=C/C\C=C/C\C=C/CC ITNKVODZACVXDS-YNUSHXQLSA-N 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 238000000589 high-performance liquid chromatography-mass spectrometry Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 208000001491 myopia Diseases 0.000 description 1
- 230000004379 myopia Effects 0.000 description 1
- XRRQZKOZJFDXON-UHFFFAOYSA-N nitric acid;silver Chemical compound [Ag].O[N+]([O-])=O XRRQZKOZJFDXON-UHFFFAOYSA-N 0.000 description 1
- 235000020777 polyunsaturated fatty acids Nutrition 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
- C07C67/52—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
- C07C67/54—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
- C07C67/62—Use of additives, e.g. for stabilisation
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Fats And Perfumes (AREA)
Abstract
The invention discloses and a kind of improve the method for the purity of EPA-E in fish oil, including: fish oil is carried out transesterification, obtains fatty-acid ethyl ester product.Fatty-acid ethyl ester product is carried out urea clathration, obtains urea clathration mixture.Urea clathration mixture is carried out at least 3 grades of molecular distillations, obtains molecular distillation product.Molecular distillation product is carried out rectification.The method technique is simple, it is possible to the content of the EPA-E being effectively improved in fish oil, reduces the content of docosahexaenoic acid ethyl, and good separating effect simultaneously so that it is can preferably carry out industrialized production.
Description
Technical field
The present invention relates to fish oil composition purification technique field, improve eicosapentaenoic in fish oil in particular to one
The method of the purity of acetoacetic ester.
Background technology
Rich in w-3 polyunsaturated fatty acid in crude fish oil, wherein with eicosapentaenoic acid (EPA), docosahexenoic acid
(DHA) content is main, but EPA and DHA has the most different applications: EPA to be mainly used in blood fat reducing, blood pressure lowering, prevent
Atherosclerosis；DHA is mainly used in hypermnesis, pre-myopia prevention, EPA and DHA in fish oil product with EPA-EE and
Presented in DHA-EE, thus the EPA-EE and the DHA-EE that purify and separate in fish oil are the focuses instantly studied.But
Owing to EPA-EE and DHA-EE are dopller signal, carbon atom number is close, boiling point is close, chemical property phase
Closely, general method for purifying and separating has urea adduct method, molecularly distilled, slaine freezing method, method supercritical methanol technology, nitric acid silver layer
Analysis methods etc., either one or more combinations of these methods all cannot be kept completely separate EPA-EE and DHA-EE.Wherein, HPLC method
Can realize being kept completely separate, but the fixing of HPLC involves great expense mutually, it is impossible to unlimited recycling, and need to use substantial amounts of when separating
Mobile phase solvent and limits throughput, cause high cost, it is impossible to carry out industrialized production, thus it is not a kind of preferably production
Technology.Therefore, it is bad generally to there is separating effect in the method for purifying and separating of above-mentioned EPA-EE and DHA-EE, complex process, becomes
This higher problem.
Summary of the invention
A kind of method that it is an object of the invention to provide purity improving fish oil EPA-E, with by letter
Single process improves the content of the EPA-E in fish oil, reduces containing of docosahexaenoic acid ethyl simultaneously
Amount, and good separating effect so that it is can preferably carry out industrialized production.
The present invention solves it and technical problem is that and realize by the following technical solutions.
A kind of improve the method for the purity of EPA-E in fish oil, including: fish oil is carried out transesterification,
Obtain fatty-acid ethyl ester product.Fatty-acid ethyl ester product is carried out urea clathration, obtains urea clathration mixture.By carbamide
Inclusion mixture carries out at least 3 grades of molecular distillations, obtains molecular distillation product.Molecular distillation product is carried out rectification.
Further, in preferred embodiment of the present invention, above-mentioned transesterification is by fish oil, dehydrated alcohol and Sodium ethylate
Mixing, is stirred 3～6h at a temperature of 60～80 DEG C.
Further, in preferred embodiment of the present invention, the mass ratio of above-mentioned fish oil, dehydrated alcohol and Sodium ethylate is 1:2
～3:0.005～0.01.
Further, in preferred embodiment of the present invention, the acid value of above-mentioned fish oil is less than 3.0mgKOH/g.
Further, in preferred embodiment of the present invention, the purity of EPA-E in above-mentioned raising fish oil
Method is additionally included in the mixed liquor stratification of transesterification gained after transesterification, takes supernatant liquid in vacuum
For-0.08MPa～-0.09MPa, temperature reclaims dehydrated alcohol under conditions of being 55～65 DEG C, adds distilled water and wash,
Separate oil reservoir, obtain fatty-acid ethyl ester product.
Further, in preferred embodiment of the present invention, above-mentioned urea clathration is by fatty-acid ethyl ester product and with second
Alcohol be solvent urea liquid mix and blend after crystallize, refilter, gained filtrate is urea clathration mixture.
Further, in preferred embodiment of the present invention, the above-mentioned temperature carrying out mix and blend is 70～80 DEG C.
Further, in preferred embodiment of the present invention, above-mentioned fatty-acid ethyl ester product and the volume ratio of urea liquid
For 1:4.5～5.5, in urea liquid, carbamide is 1:3～4 with the volume ratio of ethanol.
Further, in preferred embodiment of the present invention, above-mentioned at least 3 grades of molecular distillations are 5 grades of molecular distillations, 5 fraction
Son distillation vacuum be 0.01～100Pa, the vapo(u)rizing temperature of 5 grades of molecular distillations be followed successively by 110～115 DEG C, 115～120 DEG C,
120～125 DEG C, 145～150 DEG C, 155～165 DEG C.
Further, in preferred embodiment of the present invention, the above-mentioned vacuum carrying out rectification is 0～100Pa, and rectifying column is managed
The opinion number of plates is more than 20, and reflux ratio 6:1, bottom heating-up temperature is 190～200 DEG C, tower body temperature 180～190 DEG C.
The method of a kind of purity improving fish oil EPA-E of the embodiment of the present invention provides the benefit that: logical
Cross and fish oil is first carried out transesterification, obtain fatty-acid ethyl ester product so that EPA and DHA is with EPA-EE and DHA-EE
Form exist in fish oil, and follow-up carry out isolated and purified operation, then fatty-acid ethyl ester product urinated
Element inclusion, thus effectively remove saturated fat acetoacetic ester, EPA-EE and the content of DHA-EE in progressive raising fish oil.Will urine
The urea clathration mixture formed after element inclusion carries out at least 3 grades of molecular distillations, obtains molecular distillation product, passes through EPA-EE
With DHA-EE and the difference of other fatty acid esters boiling point under a high vacuum, remove part DHA-EE and satisfied fatty acid second
Ester and other lower boiling fatty-acid ethyl esters, eliminate the most simultaneously the pigment in product, partial fat ketone, solid impurity and
Polymer etc., and then improve EPA-EE content in the product, then the molecule that will be formed after at least 3 grades of molecular distillations
Product of distillation carries out rectification, utilizes the difference of each component volatilization degree in molecular distillation product, improves the content of EPA-EE, simultaneously
Reduce the content of DHA-EE, to reach further the content of EPA-EE in fish oil to be increased to greater than 90%.Above-mentioned raising fish
The method of the purity of EPA-EE in oil, technique is simple, and cost is relatively low, the shortest, and has reached good isolated and purified effect
Really, it is suitable for large-scale Commercial cultivation, overcomes the problem that safety is difficult to ensure that.
Detailed description of the invention
For making the purpose of the embodiment of the present invention, technical scheme and advantage clearer, below will be in the embodiment of the present invention
Technical scheme be clearly and completely described.In embodiment, unreceipted actual conditions person, builds according to normal condition or manufacturer
The condition of view is carried out.Agents useful for same or instrument unreceipted production firm person, being can be by the commercially available conventional product bought and obtain
Product.
Below the method for a kind of purity improving fish oil EPA-E of the embodiment of the present invention is carried out specifically
Explanation.
A kind of improve the method for the purity of EPA-E in fish oil, including:
The first step, carries out transesterification by fish oil, obtains fatty-acid ethyl ester product.
Specifically, the step of transesterification is: be equipped with fish oil after dehydrated alcohol and Sodium ethylate mix homogeneously
In reactor or directly by dehydrated alcohol add and fish oil adds Sodium ethylate, at a temperature of 60～80 DEG C, be stirred 3
～6h.Wherein, the mass ratio of fish oil, dehydrated alcohol and Sodium ethylate is 1:2～3:0.005～0.01.
During above-mentioned transesterification, Sodium ethylate participates in reaction as catalyst, and whole process is base catalysis esterification.
The catalysis process of fish oil ethyl ester is a lot, typically has acid catalysis, base catalysis, solid acid catalysis, enzyme catalysis etc..Use acid catalysis work
Skill, reaction temperature is high, and product easily aoxidizes, and produces polymer, and wastewater flow rate is big, and ethanol reclaims difficulty, product colour carbon deep, easy
Change, coking.Using enzyme catalysis technique, the response time is long, and conversion ratio is low, and catalyst price is high, purification process difficulty.The present invention's
Using base catalysis technique in embodiment, its reaction temperature is low, and catalyst price is low, and wastewater flow rate is little, and the response time is short, course of reaction
Middle product does not aoxidizes.Ethanol reclaims simple, is not required to carry out rectification process.
Preferably, the acid value of fish oil is less than 3.0mgKOH/g.The fish oil of the low acid value in this value range carries out above-mentioned transesterification
Change reaction, so that esterification yield is greatly improved, reach more than 98%.Thus the carrying of the follow-up purity to EPA-EE
High.
By the mixed liquor stratification of transesterification gained after transesterification, take supernatant liquid vacuum for-
0.08MPa～-0.09MPa, temperature be 55～65 DEG C under conditions of concentration and recovery dehydrated alcohol, add distilled water and wash
Wash, separate oil reservoir, thus obtain fatty-acid ethyl ester product.
Second step, carries out urea clathration by fatty-acid ethyl ester product, obtains urea clathration mixture.
Specifically, first ethanol is loaded in urine bag tank, then add carbamide, after stirring and dissolving, form urea liquid, then
Fatty-acid ethyl ester product is added in urea liquid, stirring 1～2h, then crystallisation by cooling under the conditions of 70～80 DEG C, then tie
Mixture after crystalline substance filters, and gained filtrate is urea clathration mixture.Carbamide is stirred when dissolving ethanol is put into
Temperature is also 70～80 DEG C.
Wherein, the volume ratio of fatty-acid ethyl ester product and urea liquid is 1:4.5～5.5, in urea liquid carbamide with
The volume ratio of ethanol is 1:3～4.By said process and the setting of component ratio, enabling to fatty-acid ethyl ester product
Reach urea clathration effect well.Carbamide is food stage, and ethanol is food stage, and ethanol mass percentage content is more than 95%.
The principle of urea adduct method be urea molecule in crystallization process with saturated fat acetoacetic ester or single unsaturated fatty acid
Ethyl ester forms more stable crystal inclusion compound and separates out, and dopller signal is more due to double bond, and carbochain bends, and has
Certain steric configuration, is difficult to by urea clathration.Thus during urea clathration, many based on EPA-EE and DHA-EE
Unsaturated fatty acid ethyl ester will not form clathrate with carbamide..By above-mentioned urea clathration so that fatty-acid ethyl ester
Satisfied fatty acid and single unsaturated lipid acetoacetic ester in product carry out inclusion crystallization respectively with carbamide, and by the way of filtration
Remove, so that it may obtain the dopller signal of higher degree, thus improve the content of EPA-EE and DHA-EE, make
EPA-EE in the urea clathration mixture that must obtain and the total content of DHA-EE are between 58～62%.
3rd step, carries out at least 3 grades of molecular distillations by urea clathration mixture, obtains molecular distillation product.
Molecular distillation is a kind of distillating method operated under a high vacuum, the mean free path of steam molecule during distillation procedure
More than the distance between evaporating surface and condensing surface, thus the difference of each component evaporation rate in available feed liquid, to liquid
Mixture separates.
At least 3 grades of molecular distillations are preferably 5 grades of molecular distillations, and the vacuum of 5 grades of molecular distillations is 0.01～100Pa, 5 grades
The vapo(u)rizing temperature of molecular distillation be followed successively by 110～115 DEG C, 115～120 DEG C, 120～125 DEG C, 145～150 DEG C, 155～165
℃。
Urea admixture is passed sequentially through the distillator of 1～5 grade of molecular distillation carries out molecular distillation successively, finally give
Molecular distillation product, the vapo(u)rizing temperature of rear stage is higher than the vapo(u)rizing temperature of previous stage.
Certainly, at least 3 grades of molecular distillations can also be 3 grades, 4 grades or 6 grades of molecular distillations.
The content being substantially increased EPA-EE by the molecular distillation of at least 3 grades reduces DHA-EE and other fatty acids
Ethyl ester and partial glycerol ketone, solid impurity, polymer etc., thus obtain molecular distillation product.
4th step, carries out rectification by molecular distillation product.
Specifically, being passed through in rectifying column by molecular distillation product and carry out rectification, the vacuum of rectifying column is 0～100Pa, essence
Fractional distillation column theoretical cam curve is more than 20, and reflux ratio 6:1, bottom heating-up temperature is 190～200 DEG C, tower body temperature 180～190 DEG C.
Rectification is to utilize the difference of each component volatilization ability in mixture, by the backflow of liquid and gas, makes air-liquid two
Contrary is to MULTI CONTACT, under the constraint of heat-driven and phase equilibrium relationship so that volatile components (light component) is constantly from liquid
Shift in gas phase, and difficult volatile component is migrated by gas phase in liquid phase, makes the process that mixture is constantly separated.
The difference of each component volatilization degree in molecular distillation product can be utilized by above-mentioned distillation process, improve EPA-EE
Content, reduce the content of DHA-EE so that the content of EPA-EE reaches more than 90%, and the content of DHA-EE is little simultaneously
In 1%.
Wherein, the detection of the content of EPA-EE and DHA-EE can be by routine sides such as high performance liquid chromatography mass spectrometries
Method detects.
The method of the purity of EPA-EE in above-mentioned raising fish oil, technique is simple, and cost is relatively low, the shortest, and reaches
Good isolated and purified effect, is suitable for large-scale Commercial cultivation, product no solvent residue, overcomes what safety was difficult to ensure that
Problem.
Below in conjunction with embodiment, inventive feature and performance are described in further detail.
Embodiment 1
First, it is equipped with in the reactor of fish oil after dehydrated alcohol and Sodium ethylate mix homogeneously, the temperature of 68 DEG C
Under be stirred 6h, carry out transesterification.Wherein, the mass ratio of fish oil, dehydrated alcohol and Sodium ethylate is 1:3:0.01；Fish oil
Acid value be 2.9mgKOH/g.
Secondly, the mixed liquor stratification to transesterification gained, taking supernatant liquid in vacuum is-0.09MPa, and temperature is
Concentration and recovery dehydrated alcohol under conditions of 65 DEG C, adds distilled water and washs, and separates oil reservoir, thus obtains fatty-acid ethyl ester
Change product.
Afterwards, first ethanol is loaded in urine bag tank, then add carbamide, after stirring and dissolving, form urea liquid, more past
Urea liquid adds fatty-acid ethyl ester product, under the conditions of 80 DEG C, stirs 2h, then crystallisation by cooling, the mixing after recrystallization
Thing filters, and gained filtrate is the urea clathration mixture that total content is 62% of EPA-EE and DHA-EE.Wherein, fatty acid second
Esterification products is 1:5.5 with the volume ratio of urea liquid, and in urea liquid, carbamide is 1:4 with the volume ratio of ethanol.
Afterwards, urea clathration mixture carrying out 5 grades of molecular distillations, obtaining EPA-EE content is 72.5%, DHA-EE
Content is the molecular distillation product of 8%.Wherein, the vacuum of 5 grades of molecular distillations is 3Pa, and the vapo(u)rizing temperature of 5 grades of molecular distillations depends on
Secondary is 115 DEG C, 120 DEG C, 125 DEG C, 150 DEG C, 165 DEG C.
Then, being passed through in rectifying column by molecular distillation product and carry out rectification, wherein, the vacuum of rectifying column is 100Pa, essence
Fractional distillation column theoretical cam curve is 23, reflux ratio 6:1, and bottom heating-up temperature is 200 DEG C, tower body temperature 190 DEG C.The fish obtained after distillation
In oil product, the content of EPA-EE is 91.7%, and the content of DHA-EE is 0.85%.
Embodiment 2
First, dehydrated alcohol is equipped with in the reactor of fish oil, adds Sodium ethylate, then enter at a temperature of 68 DEG C
Row stirring 3h, carries out transesterification.Wherein, the mass ratio of fish oil, dehydrated alcohol and Sodium ethylate is 1:2:0.005；Fish oil
Acid value is 2.0mgKOH/g.
Secondly, the mixed liquor stratification to transesterification gained, taking supernatant liquid in vacuum is-0.08MPa, and temperature is
Concentration and recovery dehydrated alcohol under conditions of 55 DEG C, adds distilled water and washs, and separates oil reservoir, thus obtains fatty-acid ethyl ester
Change product.
Afterwards, first ethanol is loaded in urine bag tank, then add carbamide, after stirring and dissolving, form urea liquid, more past
Urea liquid adds fatty-acid ethyl ester product, under the conditions of 70 DEG C, stirs 1h, then crystallisation by cooling, the mixing after recrystallization
Thing filters, and gained filtrate is the urea clathration mixture that total content is 58% of EPA-EE and DHA-EE.Wherein, fatty acid second
Esterification products is 1:4.5 with the volume ratio of urea liquid, and in urea liquid, carbamide is 1:3 with the volume ratio of ethanol.
Afterwards, urea clathration mixture carrying out 5 grades of molecular distillations, obtaining EPA-EE content is 71%, and DHA-EE contains
Amount is the molecular distillation product of 9%.Wherein, the vacuum of 5 grades of molecular distillations is 0.01Pa, the vapo(u)rizing temperature of 5 grades of molecular distillations
It is followed successively by 110 DEG C, 115 DEG C, 120 DEG C, 145 DEG C, 155 DEG C.
Then, being passed through in rectifying column by molecular distillation product and carry out rectification, wherein, the vacuum of rectifying column is 0Pa, rectification
Post theoretical cam curve is 21, reflux ratio 6:1, and bottom heating-up temperature is 190 DEG C, tower body temperature 180 DEG C.The fish oil obtained after distillation
In product, the content of EPA-EE is 91.2%, and the content of DHA-EE is 0.9%.
Embodiment 3
First, dehydrated alcohol is equipped with in the reactor of fish oil, adds Sodium ethylate, then enter at a temperature of 68 DEG C
Row stirring 4h, carries out transesterification.Wherein, the mass ratio of fish oil, dehydrated alcohol and Sodium ethylate is 1:2.5:0.008；Fish oil
Acid value be 1.5mgKOH/g.
Secondly, the mixed liquor stratification to transesterification gained, taking supernatant liquid in vacuum is-0.08MPa, and temperature is
Concentration and recovery dehydrated alcohol under conditions of 60 DEG C, adds distilled water and washs, and separates oil reservoir, thus obtains fatty-acid ethyl ester
Change product.
Afterwards, first ethanol is loaded in urine bag tank, then add carbamide, after stirring and dissolving, form urea liquid, more past
Urea liquid adds fatty-acid ethyl ester product, under the conditions of 75 DEG C, stirs 1.5h, then crystallisation by cooling, mixing after recrystallization
Compound filters, and gained filtrate is the urea clathration mixture that total content is 60% of EPA-EE and DHA-EE.Wherein, fatty acid
Ethyl esterified product is 1:5 with the volume ratio of urea liquid, and in urea liquid, carbamide is 1:3.5 with the volume ratio of ethanol.
Afterwards, urea clathration mixture carrying out 5 grades of molecular distillations, obtaining EPA-EE content is 72%, and DHA-EE contains
Amount is the molecular distillation product of 8.5%.Wherein, the vacuum of 5 grades of molecular distillations is 15Pa, the vapo(u)rizing temperature of 5 grades of molecular distillations
It is followed successively by 113 DEG C, 119 DEG C, 123 DEG C, 148 DEG C, 159 DEG C.
Then, being passed through in rectifying column by molecular distillation product and carry out rectification, wherein, the vacuum of rectifying column is 50Pa, essence
Fractional distillation column theoretical cam curve is 25, reflux ratio 6:1, and bottom heating-up temperature is 195 DEG C, tower body temperature 185 DEG C.The fish obtained after distillation
In oil product, the content of EPA-EE is 90.8%, and the content of DHA-EE is 0.87%.
Embodiment 4
First, dehydrated alcohol is equipped with in the reactor of fish oil, adds Sodium ethylate, then enter at a temperature of 72 DEG C
Row stirring 5h, carries out transesterification.Wherein, the mass ratio of fish oil, dehydrated alcohol and Sodium ethylate is 1:2.6:0.006；Fish oil
Acid value be 1.3mgKOH/g.
Secondly, the mixed liquor stratification to transesterification gained, taking supernatant liquid in vacuum is-0.09MPa, and temperature is
Concentration and recovery dehydrated alcohol under conditions of 61 DEG C, adds distilled water and washs, and separates oil reservoir, thus obtains fatty-acid ethyl ester
Change product.
Afterwards, first ethanol is loaded in urine bag tank, then add carbamide, after stirring and dissolving, form urea liquid, more past
Urea liquid adds fatty-acid ethyl ester product, under the conditions of 73 DEG C, stirs 1.3h, then crystallisation by cooling, mixing after recrystallization
Compound filters, and gained filtrate is the urea clathration mixture that total content is 61% of EPA-EE and DHA-EE.Wherein, fatty acid
Ethyl esterified product is 1:4.8 with the volume ratio of urea liquid, and in urea liquid, carbamide is 1:3.3 with the volume ratio of ethanol.
Afterwards, urea clathration mixture carrying out 4 grades of molecular distillations, obtaining EPA-EE content is 70.4%, DHA-EE
Content is the molecular distillation product of 8.3%.Wherein, the vacuum of 4 grades of molecular distillations is 15Pa, the distillation temperature of 5 grades of molecular distillations
Degree is followed successively by 112 DEG C, 118 DEG C, 124 DEG C, 147 DEG C.
Then, being passed through in rectifying column by molecular distillation product and carry out rectification, wherein, the vacuum of rectifying column is 32Pa, essence
Fractional distillation column theoretical cam curve is 24, reflux ratio 6:1, and bottom heating-up temperature is 193 DEG C, tower body temperature 187 DEG C.The fish obtained after distillation
In oil product, the content of EPA-EE is 90.4%, and the content of DHA-EE is 0.91%.
Embodiment 5
First, dehydrated alcohol is equipped with in the reactor of fish oil, adds Sodium ethylate, then enter at a temperature of 80 DEG C
Row stirring 4.5h, carries out transesterification.Wherein, the mass ratio of fish oil, dehydrated alcohol and Sodium ethylate is 1:2.4:0.007；Fish
The acid value of oil is 1.0mgKOH/g.
Secondly, the mixed liquor stratification to transesterification gained, taking supernatant liquid in vacuum is-0.09MPa, and temperature is
Concentration and recovery dehydrated alcohol under conditions of 62 DEG C, adds distilled water and washs, and separates oil reservoir, thus obtains fatty-acid ethyl ester
Change product.
Afterwards, first ethanol is loaded in urine bag tank, then add carbamide, after stirring and dissolving, form urea liquid, more past
Urea liquid adds fatty-acid ethyl ester product, under the conditions of 77 DEG C, stirs 1.2h, then crystallisation by cooling, mixing after recrystallization
Compound filters, and gained filtrate is the urea clathration mixture that total content is 59% of EPA-EE and DHA-EE.Wherein, fatty acid
Ethyl esterified product is 1:4.6 with the volume ratio of urea liquid, and in urea liquid, carbamide is 1:3.6 with the volume ratio of ethanol.
Afterwards, urea clathration mixture carrying out 5 grades of molecular distillations, obtaining EPA-EE content is 72.4%, DHA-EE
Content is the molecular distillation product of 8.1%.Wherein, the vacuum of 5 grades of molecular distillations is 15Pa, the distillation temperature of 5 grades of molecular distillations
Degree is followed successively by 112 DEG C, 118 DEG C, 124 DEG C, 147 DEG C, 158 DEG C.
Then, being passed through in rectifying column by molecular distillation product and carry out rectification, wherein, the vacuum of rectifying column is 72Pa, essence
Fractional distillation column theoretical cam curve is 29, reflux ratio 6:1, and bottom heating-up temperature is 198 DEG C, tower body temperature 184 DEG C.The fish obtained after distillation
In oil product, the content of EPA-EE is 91.4%, and the content of DHA-EE is 0.85%.
In sum, by fish oil first being carried out transesterification, fatty-acid ethyl ester product is obtained so that EPA and DHA
Exist in fish oil with the form of EPA-EE and DHA-EE, and follow-up carry out isolated and purified operation, then by fat
Acetoacetic ester product carries out urea clathration, thus effectively removes saturated fat acetoacetic ester, progressive improve in fish oil EPA-EE and
The content of DHA-EE.The urea clathration mixture formed after urea clathration is carried out at least 3 grades of molecular distillations, obtains molecule and steam
Evaporate product, by EPA-EE and DHA-EE and the difference of other fatty acid esters boiling point under a high vacuum, remove part DHA
Ethyl ester and saturated fat acetoacetic ester and other lower boiling fatty-acid ethyl esters, eliminate the pigment in product, part the most simultaneously
Aliphatic ketone, solid impurity and polymer etc., and then improve EPA-EE content in the product, then will be through at least 3 fraction
The molecular distillation product formed after son distillation carries out rectification, utilizes the difference of each component volatilization degree in molecular distillation product, improves
The content of EPA-EE, reduces the content of DHA-EE simultaneously, to reach to be brought up to greatly by the content of EPA-EE in fish oil further
In 90%.The method of the purity of EPA-EE in above-mentioned raising fish oil, technique is simple, and cost is relatively low, the shortest, and reaches
Good isolated and purified effect, is suitable for large-scale Commercial cultivation, product no solvent residue, overcomes what safety was difficult to ensure that
Problem.
Embodiments described above is a part of embodiment of the present invention rather than whole embodiments.The reality of the present invention
The detailed description executing example is not intended to limit the scope of claimed invention, but is merely representative of the selected enforcement of the present invention
Example.Based on the embodiment in the present invention, those of ordinary skill in the art are obtained under not making creative work premise
Every other embodiment, broadly falls into the scope of protection of the invention.
Claims (10)
1. one kind is improved the method for the purity of EPA-E in fish oil, it is characterised in that including:
Fish oil is carried out transesterification, obtains fatty-acid ethyl ester product；
Described fatty-acid ethyl ester product is carried out urea clathration, obtains urea clathration mixture；
Described urea clathration mixture is carried out at least 3 grades of molecular distillations, obtains molecular distillation product；
Described molecular distillation product is carried out rectification.
The method of the purity of EPA-E in raising fish oil the most according to claim 1, it is characterised in that institute
Stating transesterification is fish oil, dehydrated alcohol and Sodium ethylate to be mixed, and is stirred 3～6h at a temperature of 60～80 DEG C.
The method of the purity of EPA-E in raising fish oil the most according to claim 2, it is characterised in that institute
The mass ratio stating fish oil, described dehydrated alcohol and described Sodium ethylate is 1:2～3:0.005～0.01.
4., according to the method for the purity of EPA-E in the raising fish oil described in Claims 2 or 3, its feature exists
In, the acid value of described fish oil is less than 3.0mgKOH/g.
The method of the purity of EPA-E in raising fish oil the most according to claim 2, it is characterised in that also
It is included in the mixed liquor stratification of described transesterification gained after described transesterification, takes supernatant liquid in vacuum
For-0.08MPa～-0.09MPa, temperature reclaims described dehydrated alcohol under conditions of being 55～65 DEG C, adds distilled water and carries out
Washing, separates oil reservoir, obtains described fatty-acid ethyl ester product.
The method of the purity of EPA-E in raising fish oil the most according to claim 1, it is characterised in that institute
Stating urea clathration is to be crystallized after the urea liquid mix and blend with ethanol as solvent by described fatty-acid ethyl ester product,
Refiltering, gained filtrate is described urea clathration mixture.
The method of the purity of EPA-E in raising fish oil the most according to claim 6, it is characterised in that enter
The temperature of the described mix and blend of row is 70～80 DEG C.
8., according to the method for the purity of EPA-E in the raising fish oil described in claim 6 or 7, its feature exists
In, described fatty-acid ethyl ester product is 1:4.5～5.5 with the volume ratio of described urea liquid, carbamide in described urea liquid
It is 1:3～4 with the volume ratio of described ethanol.
The method of the purity of EPA-E in raising fish oil the most according to claim 1, it is characterised in that institute
Stating at least 3 grades of molecular distillations is 5 grades of molecular distillations, and the vacuum of described 5 grades of molecular distillations is 0.01～100Pa, described 5 fraction
The vapo(u)rizing temperature of son distillation is followed successively by 110～115 DEG C, 115～120 DEG C, 120～125 DEG C, 145～150 DEG C, 155～165 DEG C.
The method of the purity of EPA-E in raising fish oil the most according to claim 1, it is characterised in that
The vacuum carrying out described rectification is 0～100Pa, rectifying column theoretical cam curve be more than 20, reflux ratio 6:1, bottom heating-up temperature
It is 190～200 DEG C, tower body temperature 180～190 DEG C.
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| CN107459456A (en) * | 2016-06-02 | 2017-12-12 | 中国石化扬子石油化工有限公司 | A kind of method that methyl stearate is extracted in the benzoyl methane raffinate from stearic acid |
| CN107586609A (en) * | 2017-10-27 | 2018-01-16 | 宁波雅可生物技术有限公司 | A kind of fish oil and its purification process of the EPA-E containing high concentration |
| CN109280060A (en) * | 2017-07-21 | 2019-01-29 | 浙江医药股份有限公司新昌制药厂 | A kind of phosphatide object of the fatty acid containing Omega-3 and preparation method thereof |
| CN109438227A (en) * | 2018-04-27 | 2019-03-08 | 南京健友生化制药股份有限公司 | A kind of production method of ω -3 polyene fatty acid ethylester |
| CN109762658A (en) * | 2019-01-31 | 2019-05-17 | 安徽省新洲海洋生物制品有限公司 | A kind of method of purification of refined fish oil |
| CN111116353A (en) * | 2020-01-02 | 2020-05-08 | 广西小藻农业科技有限公司 | Method for purifying EPA in microalgae oil |
| CN111995517A (en) * | 2020-08-19 | 2020-11-27 | 中国科学院深圳先进技术研究院 | Preparation method of eicosapentaenoic acid ethyl ester |
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| CN113480431A (en) * | 2021-06-16 | 2021-10-08 | 四川国为制药有限公司 | Method for reducing environmental pollutants and isomer impurities in EPA ethyl ester product |
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| CN106675775A (en) * | 2016-12-29 | 2017-05-17 | 山东禹王制药有限公司 | Method for removing cholesterol in fish oil by subcritical extraction |
| CN109280060A (en) * | 2017-07-21 | 2019-01-29 | 浙江医药股份有限公司新昌制药厂 | A kind of phosphatide object of the fatty acid containing Omega-3 and preparation method thereof |
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| CN111116353A (en) * | 2020-01-02 | 2020-05-08 | 广西小藻农业科技有限公司 | Method for purifying EPA in microalgae oil |
| CN111995517A (en) * | 2020-08-19 | 2020-11-27 | 中国科学院深圳先进技术研究院 | Preparation method of eicosapentaenoic acid ethyl ester |
| CN113201397A (en) * | 2021-04-08 | 2021-08-03 | 四川国为制药有限公司 | Method for reducing plasticizer content in fish oil product |
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| CN113480431A (en) * | 2021-06-16 | 2021-10-08 | 四川国为制药有限公司 | Method for reducing environmental pollutants and isomer impurities in EPA ethyl ester product |
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