CN103396310B - Method for separating and purifying eicosapentaenoic acid ester and docosahexenoic acid ester from micro-algal oil or fish oil - Google Patents

Method for separating and purifying eicosapentaenoic acid ester and docosahexenoic acid ester from micro-algal oil or fish oil Download PDF

Info

Publication number
CN103396310B
CN103396310B CN201310319421.6A CN201310319421A CN103396310B CN 103396310 B CN103396310 B CN 103396310B CN 201310319421 A CN201310319421 A CN 201310319421A CN 103396310 B CN103396310 B CN 103396310B
Authority
CN
China
Prior art keywords
ester
extraction
liquid
acid ester
micro
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201310319421.6A
Other languages
Chinese (zh)
Other versions
CN103396310A (en
Inventor
任其龙
邢华斌
张肖
杨启炜
苏宝根
张治国
鲍宗必
杨亦文
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Zhejiang University ZJU
Original Assignee
Zhejiang University ZJU
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Zhejiang University ZJU filed Critical Zhejiang University ZJU
Priority to CN201310319421.6A priority Critical patent/CN103396310B/en
Publication of CN103396310A publication Critical patent/CN103396310A/en
Application granted granted Critical
Publication of CN103396310B publication Critical patent/CN103396310B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids

Landscapes

  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Fats And Perfumes (AREA)

Abstract

The invention discloses a method for separating and purifying eicosapentaenoic acid ester and docosahexaenoic acid ester from micro-algal oil or fish oil. The method comprises the steps of: by taking a non-polar solvent as a raw solvent and a polar solvent, ionic liquid and ionic liquid-polar organic solvent binary mixed solvent as an extractant, separating and preparing high-purity eicosapentaenoic acid ester (EPA ester) and docosahexaenoic acid ester (DHA ester) from the micro-algal oil or fish oil containing aliphatic esters with different saturability. The method is simple to operate, high in separation efficiency, less in solvent consumption, high in product purity, high in yield, easy to industrially produce and the like.

Description

A kind of method of separation and purification eicosa-pentaenoic acid esters and docosahexenoic acid ester from micro-algae oil or fish oil
Technical field
The present invention relates to technical field of chemical separation, the method for specific design a kind of separation and purification eicosa-pentaenoic acid esters (EPA ester) and docosahexenoic acid ester (DHA ester) from micro-algae oil or fish oil.
Background technology
Timnodonic acid (EPA) and docosahexenoic acid (DHA) all belong to ω-3 race unsaturated fatty acids, are the lipid acid of needed by human.Micro-algae, belongs to containing the chlorophyllous marine microorganism that swims, " can eat " carbonic acid gas, produce grease by photosynthesis, containing abundant polyenoic acid lipid acid in its grease.In addition, bathypelagic fish contains the high unsaturated fatty acid of a large amount of high values, especially EPA and DHA.Micro-algae oil and fish oil are all main raw materials of the high-purity EPA ester of preparation and DHA ester.
EPA and DHA plays vital effect to the healthy of people, has multiple physiological function.The laudatory title that EPA has " blood vessel street cleaner ", it mainly acts on cardiovascular systems, has reducing blood-fat, blood pressure and cholesterol, and prevention of arterial hardens; Reduce thrombosis, prevention cardiovascular and cerebrovascular diseases; Prevention senile dementia; Anticancer, Tumor suppression; The effect such as prevent and treat diabetes, anti-inflammatory, delay senility.And DHA, be commonly called as " DHA (docosahexaenoic acid) ", hemato encephalic barrier can be passed through; enter brain; act on neural system, DHA is except all physiological functions with EPA, and DHA also has to protect retina, improves eyesight, promotes infant intelligent development, improves the effects such as memory.
In the micro-algae oil of methyl esters type after just extracting or ethyl ester type fish oil, EPA ester and DHA ester and other low-unsaturation-degrees and polyunsaturated fatty acid ester exist jointly, go for highly purified EPA ester and DHA ester, need to take suitable separation method, EPA ester and DHA ester are separated with other fatty acid esters.Because the structure of fatty acid ester is all comparatively similar with physico-chemical property, be separated from the micro-algae oil of ester type or fish oil with DHA ester by EPA ester, the difficulty obtaining high purity EPA ester and DHA ester is larger.The separation method of patent and bibliographical information mainly contains the crystallizing process under low temperature, molecular distillation method, urea adduct method, supercritical fluid extraction, AgNO 3complexometry, absorption method etc.
CN200910159368.1 discloses a kind of method extracting DHA from dino flagellate fermentation liquor, and fermentation liquor process obtains thick algae oil, and then thick algae oil is through 5 grades of continuous molecular distillations, and obtain the product that DHA content is 40%-50%, product purity is relatively low.
Patent CN1263145 discloses and adopts urea adduct method enrichment from crude fish oil to produce to be rich in the refined fish oil of polyenoid acid esters, and this technique can obtain the product that EPA ester and DHA ester total content are more than or equal to 75%.CN200810052840.7 and CN201210247842.8 discloses a kind of urea adduct method that adopts and be separated the method preparing clupanodonic acid and docosahexenoic acid mixed fatty acid from micro-algae oil, the cost of this technique is lower, be applicable to industrial applications, but this method (urea adduct method) consumes a large amount of organic solvents and urea, and product purity is relatively low.
Patent CN1478875A discloses a kind of employing AgNO 3aqua-solution method, to the technology of the separation of fish oil esterified prod, can be prepared EPA ester+DHA ester total content and be greater than 95% and the DHA ester content product that is greater than 95%.But heavy metal Ag can bring in product by this method, and AgNO 3expensive, be not suitable for suitability for industrialized production.
CN200810052839.4 discloses a kind of silver ions column chromatography that adopts and is separated the high-purity clupanodonic acid methyl esters of preparation and Methyl docosahexaenoate, although this method can obtain clupanodonic acid methyl esters and the Methyl docosahexaenoate of higher degree, but employ expensive silver, and treatment capacity is less, solvent-oil ratio is comparatively large, easily causes the loss of silver and the heavy metal contamination of product.
CN1634852A discloses a kind of method utilizing supercritical fluid chromatography technology separation to prepare high-purity EPA ester and DHA ester, and obtain EPA ester and DHA ester product that purity is greater than 90%, but its treatment capacity is quite little, equipment cost is higher.JP09263787 adopts the method for liquid-liquid extraction to be separated to prepare highly unsaturated fatty acids ester, and this method uses acetonitrile-water mixture to be extraction agent, but due to the high hydrophobicity of fatty acid ester, causes its loading capacity and yield all very low.
In order to obtain the higher EPA ester of purity and DHA ester, the conbined usage of 2 kinds or separation method of more than two kinds is also the method often used.CN102285880A discloses a kind of half preparation/preparative high performance liquid chromatography-mass spectrometric hyphenated technique and is separated preparation EPA ester and DHA ester, obtains EPA ester and DHA ester that first reading is greater than 99%.Although the separation selectivity that this method can obtain high purity EPA ester and DHA ester is better, treatment capacity is less, and cost is higher, and the solvent that the toxicity such as more use tetrahydrofuran (THF) or acetonitrile is larger.CN1986515A discloses the omega-3 unsaturated fatty acid in the direct enrichment Turtle Oil of a kind of technology adopting supercritical extraction to combine with the crystallizing process under low temperature, and in the Turtle Oil extract obtained, the total content of EPA and DHA is 25%-30%.JP09157684A reports and adopts supercritical extraction to be separated with the coupling technique of chromatography and to prepare highly purified high unsaturated fatty acid ester, although this coupling technique can obtain highly purified single product, but chromatographic treatment capacity is less, and consume a large amount of organic solvents.
Summary of the invention
The invention provides a kind of method of separation and purification eicosa-pentaenoic acid esters and docosahexenoic acid ester from micro-algae oil or fish oil.Preparation technology is simple, product yield and purity high, cost is low.
A method for separation and purification eicosa-pentaenoic acid esters and docosahexenoic acid ester from micro-algae oil or fish oil, comprises the following steps:
(1) micro-for ester type algae oil or ester type fish oil are dissolved in non-polar solvent preparation raw material liquid, with the binary mixed solvent of polar solvent or ionic liquid or ionic liquid-polar solvent composition for extraction agent, with the solvent identical with material solution for washing composition, carry out fractionation extraction, collect extraction liquid;
(2) described extraction liquid is stripped through described non-polar solvent, strip liquor is obtained after vacuum concentration, washing also drying the mixture of eicosa-pentaenoic acid esters and docosahexenoic acid ester.Described fractionation extraction is divided into extraction section and washing section, extraction agent enters fractionation extraction system from the extraction section first step, stock liquid enters fractionation extraction system from extraction section last step, washing composition enters fractionation extraction system from the washing section first step, mix with stock liquid at the last step of extraction section, enter extraction section together, extraction phase carries out multi-stage countercurrent mutually with washing and contacts.Flow out the extraction liquid being rich in eicosa-pentaenoic acid esters (EPA ester) and docosahexenoic acid ester (DHA ester) from the washing section first step, collect extraction liquid; Flow out the raffinate being rich in low unsaturated and polyunsaturated fatty acid ester from the extraction section first step, collect raffinate.
For fractionation extraction, its core of innovation and technological difficulties are that the design of extraction agent is with preferred.Extraction agent must can identify the small structural differences of EPA ester and DHA ester and other fatty acid esters, realizes optionally extracting and separating, and extraction agent also needs to have higher loading capacity to fatty acid ester simultaneously.But because fatty acid ester is a quasi-grease compound, structure lacks polar group, the solubleness thus in polarity extracting agent is lower, thus cause the loading capacity of extraction agent lower, be unfavorable for large-scale application.
The room temperature that ionic liquid is made up of zwitterion or close to being liquid material under room temperature is the novel separating medium of a class green.The zwitterion structure of ionic liquid is adjustable, can for the fine difference on the structures and characteristics of target compound and impurity, by designing the zwitterion structure of ionic liquid to regulate interaction mode and the intensity of ionic liquid and solute, reach specific separating effect.The ion liquid abstraction agent of the present invention's design has higher loading capacity and selectivity is high.
Major part viscosity of il is lower, can be directly used in extraction.The viscosity of some ionic liquid is comparatively large, is difficult to be directly used in extraction.Research finds in ionic liquid, add dimethyl sulfoxide (DMSO), dimethyl formamide, acetonitrile, methyl alcohol polar solvent, and composition ionic liquid-polar solvent composite extractant, has higher separation selectivity and loading capacity equally, and viscosity is lower simultaneously.
Described ionic liquid is by positively charged ion M +and anion N -two portions are formed:
Described positively charged ion M +for the one that there is single or multiple substituent choline cation, there is single or multiple substituting group glyoxaline cation, there is single or multiple substituent pyridine type positively charged ion, there is single or multiple substituting group quaternary ammonium cation and have in single or multiple substituting group benzimidazolium; Described substituting group to be carbonatoms be 1 ~ 8 alkyl, when substituting group has multiple, each substituting group can identical also can not be identical.
Anion N -for the one that carbonatoms is in the fatty acid radical of 1-18, thiocyanate ion, dicyanamide root, three cyanogen methane roots, four cyanogen borates, halide-ions, tetrafluoroborate and phenol.
Described anion N -for fatty acid radical, thiocyanate ion, dicyanamide root, three cyanogen methane roots, four cyanogen borates, halide-ions, one in tetrafluoroborate and phenol that carbonatoms is 1 ~ 18.
Preferred carbonatoms is the negatively charged ion of fatty acid radical as ionic liquid of 1-18, and this type of ionic liquid, owing to having long non-polar carbon chains, has very high loading capacity to EPA ester and DHA ester.
Described non-polar solvent is the one in normal hexane, normal heptane, octane and sherwood oil.
Described intensive polar solvent to be carbon atom number be 1 ~ 4 monohydroxy-alcohol, carbon atom number be 1 ~ 4 polyvalent alcohol, furfural, acetonitrile, dimethyl formamide (DMF), dimethyl sulfoxide (DMSO) (DMSO), N-Methyl pyrrolidone (NMP), one in tetramethylene sulfone.
The massfraction of described binary mixed solvent intermediate ion liquid is 5 ~ 70%.When using binary mixed solvent for extraction agent and forming two-phase extraction system with non-polar organic solvent, the separation selectivity of extraction system to EPA ester and DHA ester can be significantly improved, especially, when the viscosity of il used is larger, the resistance to mass transfer of effective reduction two-phase system, improve extraction efficiency, be conducive to large-scale commercial production.
The micro-algae oil of described ester type is methyl esters type, and in the micro-algae oil of ester type, the total mass mark of eicosa-pentaenoic acid esters and docosahexenoic acid ester is 5% ~ 50%; Described ester type fish oil is ethyl ester type, and in ester type fish oil, the total mass mark of eicosa-pentaenoic acid esters and docosahexenoic acid ester is 5% ~ 80%.
In described stock liquid, the total concn of fatty acid ester is preferably 10 ~ 200g/L, more preferably 20 ~ 150g/L.
If the total concn of fatty acid ester is too high in stock liquid, the viscosity of stock liquid is too large, is unfavorable for extracting mass transfer process, and can reduces separation selectivity; If the concentration of fatty acid ester is too low in stock liquid, then there is the shortcomings such as feed throughput is little, solvent consumption large, process economy reduction.
The temperature of described fractionation extraction is 20 ~ 40 DEG C.If temperature is too low, two-phase rate of mass transfer reduces, and reaches extraction equilibrium required time longer, is unfavorable for production operation; If temperature is too high, solvent evaporates is serious, and esters of polyunsaturated fatty acids is heat-sensitive substance, is at high temperature very easily oxidized, and reduces partition ratio and the selectivity of extraction.
Described stock liquid, extraction agent, washing composition stream ratio are 0.2 ~ 0.8:0.3 ~ 0.8:0.8 ~ 3.
The vacuum concentration of strip liquor, washing, drying step are routine operation.
The extraction plant that the extraction plant used in described fractionation extraction process is packing tower, sieve-tray tower, rotating disc contactor, mixer-settler, centrifugal extractor etc. are common.
In flash liberation process, stock liquid solvent, washing composition and back extraction time extraction agent be same solvent.
The present invention adopts gas-chromatography (GC) to analyze, concrete GC analysis condition is: CP7489(100m x2.5mm ID, thickness 0.2 μm), fid detector, sampler temperature 250 DEG C, detector temperature 280 DEG C, column temperature adopts temperature programming: initial temperature is 80 DEG C, keep 4min, rise to 220 DEG C with the temperature rise rate of 10 DEG C/min, keep 30min.Carrier gas is N 2, flow velocity 1ml/min, splitting ratio is 50.
In the present invention, the method for calculation of yield and purity are as follows:
In yield=product EPA ester and DHA ester quality/raw material in quality × 100% of EPA ester and DHA ester;
Total mass × 100% of the EPA ester in absolute purity=product and the quality/product of DHA ester;
Compared with prior art, tool of the present invention has the following advantages:
1. the present invention adopts the binary mixed solvent-nonpolar solvent extraction system of polar solvent-non-polar solvent, ionic liquid-non-polar solvent, ionic liquid and polar solvent, to the various fatty acid esters of structural similitude, there is higher selective separation ability, and loading capacity is large.
2. the present invention adopts fractionation extraction technology, have easy and simple to handle, flow process is simple, yield is high, product purity is high, also has the advantage that treatment capacity is large, be easy to industrial applications in addition.
3. the inventive method adopts the condition optimized, and the purity of EPA ester+DHA ester can reach 90-99%, and the rate of recovery of EPA ester+DHA ester can reach more than 90%.
4. the ion liquid abstraction agent that the inventive method uses has high, the nonflammable feature such as non-explosive of stability, improves the security of separating and extracting process; Ionic liquid is a kind of eco-friendly solvent simultaneously, as extraction agent, can reduce the pollution to environment, have broad application prospects; The recovery of ionic liquid is easier to, and is convenient to the recycling of extraction agent.
Embodiment
In below implementing, vapor-phase chromatography (GC) is adopted to carry out quantitative analysis to EPA ester and DHA ester.Raw material used all adopts commercial goods.
The process of fractionation extraction is:
Extraction agent enters fractionation extraction system from the extraction section first step, stock liquid enters fractionation extraction system from extraction section last step, washing composition enters fractionation extraction system from the washing section first step, mix with stock liquid at the last step of extraction section, enter extraction section together, extraction phase carries out multi-stage countercurrent mutually with washing and contacts.Flow out the extraction liquid being rich in eicosa-pentaenoic acid esters (EPA ester) and docosahexenoic acid ester (DHA ester) from the washing section first step, collect extraction liquid; Flow out the raffinate being rich in low unsaturated and polyunsaturated fatty acid ester from the extraction section first step, collect raffinate.
Embodiment 1
By the mixture (ester type fish oil) of fatty-acid ethyl ester, be dissolved in normal hexane, be made into the stock liquid that fatty-acid ethyl ester total concn is 40g/L, wherein, the massfraction about 5% of EPA-EE+DHA-EE.Be extraction agent with DMF, take normal hexane as washing composition, the stream of stock liquid, extraction agent, washing composition three carries out fractionation extraction than for 0.4:0.5:1.2 at 30 DEG C, collects extraction liquid and raffinate.By extraction liquid through normal hexane back extraction, vacuum concentration, obtain the mixture of EPA-EE+DHA-EE.Wherein, the purity of EPA-EE+DHA-EE is 91.1%, and yield is 94.6%.
Embodiment 2
Be dissolved in octane by the mixture (the micro-algae oil of ester type) of fatty acid methyl ester, preparation fatty acid methyl ester total concn is the stock liquid of 60g/L, the wherein content about 6% of EPA methyl esters+DHA methyl esters.Being extraction agent with dimethyl sulfoxide (DMSO), take octane as washing composition, and the stream of stock liquid, extraction agent, washing composition three, than being 0.2:0.4:2, carries out fractionation extraction at 35 DEG C, collects extraction liquid and raffinate.By extraction liquid through octane back extraction, vacuum concentration, obtain the mixture of EPA methyl esters+DHA methyl esters.Wherein, the purity of EPA methyl esters+DHA methyl esters is 94.1%, and yield is 86.5%.
Embodiment 3
The mixture (the micro-algae oil of ester type) of fatty acid ester is dissolved in sherwood oil, is mixed with the stock liquid that fatty acid methyl ester total concn is 80g/L, wherein, the content about 25% of EPA methyl esters+DHA methyl esters.With 1-butyl-3-Methylimidazole thiocyanate ion liquid for extraction agent, take sherwood oil as washing composition, the stream of stock liquid, extraction agent, washing composition three carries out fractionation extraction than for 0.4:0.6:2.5 at 25 DEG C, collects extraction liquid and raffinate.By extraction liquid through sherwood oil back extraction, vacuum concentration, obtain the mixture of EPA methyl esters+DHA methyl esters.Wherein, the purity of EPA methyl esters+DHA methyl esters is 96.8%, and yield is 83.2%.
Embodiment 4
The mixture (ester type fish oil) of fatty-acid ethyl ester is dissolved in normal hexane, is mixed with the stock liquid that fatty-acid ethyl ester total concn is 40g/L, wherein, the content about 30% of EPA-EE+DHA-EE.With 1-butyl-3-Methylimidazole dintrile amine salt ionic liquid for extraction agent, take normal hexane as washing composition, the stream of stock liquid, extraction agent, washing composition three, than being 0.2:0.4:1.8, carrying out fractionation extraction and collects extraction liquid and raffinate at 30 DEG C.By extraction liquid through normal hexane back extraction, vacuum concentration, obtain the mixture of EPA-EE+DHA-EE.Wherein, the purity of EPA-EE+DHA-EE is 94.8%, and yield is 87.4%.
Embodiment 5
The mixture (the micro-algae oil of ester type) of fatty acid ester is dissolved in normal hexane, is mixed with the stock liquid that fatty acid methyl ester total concn is 20g/L, wherein, the content about 50% of EPA methyl esters+DHA methyl esters.With N-butyl-pyridinium acetate ionic liquid for extraction agent, take normal hexane as washing composition, the stream of stock liquid, extraction agent, washing composition three, than being 0.5:0.5:3, carrying out fractionation extraction, collects extraction liquid and raffinate at 20 DEG C.By extraction liquid through normal hexane back extraction, vacuum concentration, obtain the mixture of EPA methyl esters+DHA methyl esters.Wherein, the purity of EPA methyl esters+DHA methyl esters is 93.5%, and yield is 89.1%.
Embodiment 6
The mixture (ester type fish oil) of fatty-acid ethyl ester is dissolved in normal hexane, is mixed with the stock liquid that fatty-acid ethyl ester total concn is 40g/L, wherein, the content about 80% of EPA-EE+DHA-EE.With 1-ethyl-3-methylimidazole three nitrile carbon ionic liquid for extraction agent, take normal hexane as washing composition, the stream of stock liquid, extraction agent, washing composition three, than being 0.8:0.6:2, carrying out fractionation extraction, collects extraction liquid and raffinate at 40 DEG C.By extraction liquid through normal hexane back extraction, vacuum concentration, obtain the mixture of EPA-EE+DHA-EE.Wherein, the purity of EPA-EE+DHA-EE is 96.2%, and yield is 89.2%.
Embodiment 7
The mixture (the micro-algae oil of ester type) of fatty acid methyl ester is dissolved in normal hexane, is mixed with the stock liquid that fatty acid methyl ester total concn is 150g/L, wherein, the content about 35% of EPA methyl esters+DHA methyl esters.With 1-butyl-3-methyl imidazolium tetrafluoroborate ionic liquid-N, dinethylformamide binary mixed solvent (in mixed solvent, the massfraction of 1-methyl-3-octylimidazole tetrafluoroborate ion liquid is 20%) is extraction agent, take normal hexane as washing composition, the stream of stock liquid, extraction agent, washing composition three is than being 0.5:0.4:1.9, at 30 DEG C, carry out fractionation extraction, collect extraction liquid and raffinate.By extraction liquid through normal hexane back extraction, vacuum concentration, obtain the mixture of EPA methyl esters+DHA methyl esters.Wherein, the purity of EPA methyl esters+DHA methyl esters is 96.0%, and yield is 91.8%.
Embodiment 8
The mixture (ester type fish oil) of fatty-acid ethyl ester is dissolved in normal heptane, is mixed with the stock liquid that fatty-acid ethyl ester total concn is 180g/L, wherein, the content about 50% of EPA-EE+DHA-EE.With tetraethyl-amine-dicyanamide ionic liquid-dimethyl sulfoxide (DMSO) binary mixed solvent (in mixed solvent, the massfraction of tetraethyl-amine-dicyanamide ionic liquid is for 50%) for extraction agent with normal heptane for washing composition, the stream of stock liquid, extraction agent, washing composition three is than being 0.4:0.4:1.3, at 30 DEG C, carry out fractionation extraction, collect extraction liquid and raffinate.By extraction liquid through normal heptane back extraction, vacuum concentration, obtain the mixture of EPA-EE+DHA-EE.Wherein, the purity of EPA-EE+DHA-EE is 91.9%, and yield is 83.1%.
Embodiment 9
The mixture (the micro-algae oil of ester type) of fatty acid methyl ester is dissolved in normal hexane, is mixed with the stock liquid that fatty acid methyl ester total concn is 100g/L, wherein, the content about 15% of EPA methyl esters+DHA methyl esters.With choline lauroleate ionic liquid-N, dinethylformamide binary mixed solvent (in mixed solvent, the massfraction of choline lauroleate ionic liquid is 70%) is extraction agent, take normal hexane as washing composition, the stream of stock liquid, extraction agent, washing composition three is than being 0.4:0.6:1, at 30 DEG C, carry out fractionation extraction, collect extraction liquid and raffinate.By extraction liquid through normal hexane back extraction, vacuum concentration, obtain the mixture of EPA methyl esters+DHA methyl esters.Wherein, the purity of EPA methyl esters+DHA methyl esters is 98.5%, and yield is 84.3%.

Claims (7)

1. the method for separation and purification eicosa-pentaenoic acid esters and docosahexenoic acid ester from ester type micro-algae oil or fish oil, is characterized in that, comprise the following steps:
(1) micro-for ester type algae oil or ester type fish oil are dissolved in non-polar solvent preparation raw material liquid, the binary mixed solvent formed with ionic liquid or ionic liquid-polar solvent is for extraction agent, with the solvent identical with material solution for washing composition, carry out fractionation extraction, collect extraction liquid;
Described ionic liquid is by positively charged ion M +and anion N -two portions are formed:
Described positively charged ion M +for the one that there is single or multiple substituent choline cation, there is single or multiple substituting group glyoxaline cation, there is single or multiple substituent pyridine type positively charged ion, there is single or multiple substituting group quaternary ammonium cation and have in single or multiple substituting group benzimidazolium;
Anion N -for the one that carbonatoms is in the fatty acid radical of 1-18, thiocyanate ion, dicyanamide root, three cyanogen methane roots, four cyanogen borates, halide-ions, tetrafluoroborate and phenol;
Described polar solvent to be carbon atom number be 1 ~ 4 monohydroxy-alcohol, carbon atom number be one in the polyvalent alcohol of 1 ~ 4;
The massfraction of described binary mixed solvent intermediate ion liquid is 5 ~ 70%;
(2) described extraction liquid is stripped through described non-polar solvent, strip liquor is obtained after vacuum concentration, washing also drying the mixture of eicosa-pentaenoic acid esters and docosahexenoic acid ester.
2. method according to claim 1, is characterized in that, described substituting group to be carbonatoms be 1 ~ 8 alkyl.
3. method according to claim 1, it is characterized in that, described non-polar solvent is the one in normal hexane, normal heptane, octane and sherwood oil.
4. method according to claim 1, it is characterized in that, the micro-algae oil of described ester type is methyl esters type, and in the micro-algae oil of ester type, the total mass mark of eicosa-pentaenoic acid esters and docosahexenoic acid ester is 5% ~ 50%; Described ester type fish oil is ethyl ester type, and in ester type fish oil, the total mass mark of eicosa-pentaenoic acid esters and docosahexenoic acid ester is 5% ~ 80%.
5. method according to claim 1, it is characterized in that, in described stock liquid, the total concn of fatty acid ester is 10 ~ 200g/L.
6. method according to claim 1, it is characterized in that, the temperature of described fractionation extraction is 20 ~ 40 DEG C.
7. method according to claim 1, is characterized in that, described stock liquid, heating up in a steamer than being 0.2 ~ 0.8:0.3 ~ 0.8:0.8 ~ 3 between extraction agent and washing composition three.
CN201310319421.6A 2013-07-25 2013-07-25 Method for separating and purifying eicosapentaenoic acid ester and docosahexenoic acid ester from micro-algal oil or fish oil Active CN103396310B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201310319421.6A CN103396310B (en) 2013-07-25 2013-07-25 Method for separating and purifying eicosapentaenoic acid ester and docosahexenoic acid ester from micro-algal oil or fish oil

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201310319421.6A CN103396310B (en) 2013-07-25 2013-07-25 Method for separating and purifying eicosapentaenoic acid ester and docosahexenoic acid ester from micro-algal oil or fish oil

Publications (2)

Publication Number Publication Date
CN103396310A CN103396310A (en) 2013-11-20
CN103396310B true CN103396310B (en) 2015-02-25

Family

ID=49560095

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201310319421.6A Active CN103396310B (en) 2013-07-25 2013-07-25 Method for separating and purifying eicosapentaenoic acid ester and docosahexenoic acid ester from micro-algal oil or fish oil

Country Status (1)

Country Link
CN (1) CN103396310B (en)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104001540B (en) * 2014-02-12 2016-04-06 南昌航空大学 A kind of ionic-liquid catalyst and preparation method thereof
CN105384635B (en) * 2014-09-09 2018-03-09 浙江医药股份有限公司新昌制药厂 A kind of method that the fatty-acid ethyl esters of Omega 3 are isolated and purified from fish oil
CN105132189B (en) * 2015-08-06 2018-07-24 天津大学 A kind of fine separation method of C18 series and C20~C22 series fatty acid methyl esters
CN105062694B (en) * 2015-08-06 2018-07-24 天津大学 A kind of method that C18 series fatty acids and C20~C22 series fatty acids finely detach
CN107459455B (en) * 2016-06-02 2020-08-11 中国石化扬子石油化工有限公司 Method for extracting methyl stearate from benzoyl methane stearate residual liquid
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
CN115466180A (en) * 2022-09-13 2022-12-13 江苏海莱康生物科技有限公司 Method for purifying eicosapentaenoic acid ethyl ester

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1055079C (en) * 1996-08-23 2000-08-02 中国科学院化学研究所 Extraction method of unsaturated fatty acid from fish oil
CN1084380C (en) * 1999-08-30 2002-05-08 朱惠祥 Process for producing refined fish oil with high polyenoic acid ethyl ester content from crude fish oil

Also Published As

Publication number Publication date
CN103396310A (en) 2013-11-20

Similar Documents

Publication Publication Date Title
CN103396310B (en) Method for separating and purifying eicosapentaenoic acid ester and docosahexenoic acid ester from micro-algal oil or fish oil
CN103396303B (en) Method for separating and purifying eicosapentaenoic acid and docosahexaenoic acid from micro-algal oil or fish oil
CN104529772B (en) A kind of simulated moving bed chromatography prepares high-purity EPA ester and the method for DHA ester monomer
CN102001947A (en) Method for preparing honeysuckle chlorogenic acid
CN112592268B (en) Method for separating EPA (eicosapentaenoic acid) in fish oil by using continuous chromatographic system
JP2013542927A5 (en)
CN105272844B (en) Method for purifying high-purity fish oil EPA(eicosapentaenoic acid) ethyl ester and DHA(docosahexaenoic acid) ethyl ester
JP2020090680A (en) Chromatographic process for the production of highly purified polyunsaturated fatty acids
CN101278743A (en) Silkworm pupa oil and extracting method and applications
CN107216252A (en) A kind of preparation method of high content Omega-3 fatty-acid ethyl esters
US8802880B1 (en) Chromatographic process for the production of highly purified polyunsaturated fatty acids
CN103254225A (en) Method for extracting and separating and purifying phosphatidylcholine by use of ionic liquid
KR20160096110A (en) Method for chromatographic purification of a fatty acid
CN106590939A (en) Method for purification preparation of high content linoleic acid by using vegetable oil as raw material
CN102070647B (en) Method for separating ginkgolide B from ginkgolide mixture
CN103288870B (en) A kind of preparation method of injection stage lecithin in high purity
CN104311613A (en) Method for extracting oleuropein from olive leaves
CN108164415B (en) Method for completely separating EPA and DHA from fish oil
CN103865642B (en) A kind of preparation method of non-solvent high purity DHA algal oil
CN102381974A (en) Method for separating and preparing caffeic tannic acid from honeysuckle by utilizing high speed countercurrent chromatography
CN117209376A (en) Method for completely separating oleic acid and linoleic acid
CN107162910B (en) Method for preparing high-purity EPA-EE from fish oil
CN116375784A (en) Method for separating hyodeoxycholic acid and chenodeoxycholic acid
US9428711B2 (en) Chromatographic process for the production of highly purified polyunsaturated fatty acids
CN103086873B (en) High speed adverse current chromatogram is separated preparation high purity DHA method

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant