CN106966902A - A kind of preparation method of alpha linolenic acid ethyl ester - Google Patents
A kind of preparation method of alpha linolenic acid ethyl ester Download PDFInfo
- Publication number
- CN106966902A CN106966902A CN201710200721.0A CN201710200721A CN106966902A CN 106966902 A CN106966902 A CN 106966902A CN 201710200721 A CN201710200721 A CN 201710200721A CN 106966902 A CN106966902 A CN 106966902A
- Authority
- CN
- China
- Prior art keywords
- alpha
- level
- ethyl linolenate
- preparation
- ethyl
- 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.)
- Pending
Links
Classifications
-
- 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
-
- 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
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/52—Esters of acyclic unsaturated carboxylic acids having the esterified carboxyl group bound to an acyclic carbon atom
- C07C69/587—Monocarboxylic acid esters having at least two carbon-to-carbon double bonds
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
- C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
- C11C3/04—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by esterification of fats or fatty oils
- C11C3/10—Ester interchange
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Crystallography & Structural Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of preparation method of alpha linolenic acid ethyl ester, comprise the following steps：Mixing-in fat acetoacetic ester is obtained after vegetable oil and ethanol are carried out into ester exchange reaction；Mixing-in fat acetoacetic ester with urea, ethanol obtain after urea complexation reaction to the alpha linolenic acid ethyl ester of high-purity after three-level molecular distillation.The preparation method of the alpha linolenic acid ethyl ester of the present invention make use of method associated with three-level molecular distillation urea complexation chromatogram purification, avoid using a large amount of acid, alkali organic solvent, it is few using organic solvent amount, and can be carried out using existing equipment, it is low for equipment requirements.And the obtained few high income of alpha linolenic acid ethyl ester loss, product purity can reach more than 95%, it is adaptable to industrialized production.Meanwhile, the present invention reduces the requirement to raw material content containing alpha linolenic acid, enriches raw material sources, so that production cost is effectively reduced, with very strong practicality using vegetable oil as raw material.
Description
Technical field
The present invention relates to the separation preparation field of industrial chemicals, more particularly to a kind of preparation method of Alpha-ethyl linolenate.
Background technology
Alpha-linolenic acid (α-LinoleicAcid, ALA) is the octatecatrienoic acid (18 of all-cis formula:3n-3), its molecule
Formula is C18H30O2, molecular weight is 278.4296, belongs to Omega-3 polybasic unsaturated fatty acids (PUFAs), can not be closed in human body
Into being essential fatty acid.EPA (docosahexaenoic acid) and DHA (eicosapentaenoic acid) (category Omega- in animal body
It can not 3PUFAs) be directly transformed, but can be transformed by the ALA of homologous series by Omega-6 classes PUFAs, be i.e. ALA can recognize
To be EPA and DHA precursor.ALA extends through dehydrogenation and carbochain, a series of metabolites is generated, wherein important product is EPA
And DHA, and ALA double bond is fewer than EPA and DHA, stability goes with DHA compared with EPA, therefore, and supplement ALA is also to improve people couple
EPA and DHA take the photograph the important means of people's amount.In recent years, numerous domestic and international personnel by numerous studies show alpha-linolenic acid and its
Long-chain metabolin, plays an important role in many physiological activities：It can effectively prevent cardiovascular and cerebrovascular disease, enhancing people
Body immunity, reduce blood pressure with blood glucose, regulation blood fat, suppress cancer generation and transfer, while be improved memory, protection regard
Effect of power and anti-aging.
Since 1980s, people rely primarily on deep sea fish oil to EPA and DHA demand, but fish oil is in recent years
Marine pollution is serious, as all kinds of undesirable substances such as the easy enriching heavy metal of the fish oil on food chain upper strata, agricultural chemicals, bioxin, this
Cholesterol level is also high compared with vegetable oil in the outer grease as animal origin, fish oil.In view of the stability of alpha-linolenic acid compared with EPA and
More preferably, the delicate fragrance of vegetable oil can also make up the fishy smell of fish oil to DHA, the alpha-linolenic acid of vegetable oil source will be deep sea fish oil more
New regeneration product.
In order to synthesize the alpha-linolenic acid of high-purity, prior art is typically using first synthesizing alpha-linolenic acid ester, then hydrolyzes and obtain
Alpha-linolenic acid.At present, the domestic method that Alpha-ethyl linolenate is prepared from vegetable oil has saponification-acidolysis-resterification method, overcritical
Extract, urea chromatography, urea and heavy metal complexometry, the method such as molecularly distilled, preparation chromatogram.Saponification-acidolysis-resterification
Method is, it is necessary to largely bronsted lowry acids and bases bronsted lowry, but also can produce acid waste water and alkaline waste water.Supercritical extracting equipment input is big, produces bar
Part requirement is strict, and cost is high, and batch yield is small, is difficult to carry out industrialization production.Urea column chromatography elution step is more, and solvent disappears
Consumption is big, and treating capacity is small, is also not suitable for technology amplification production.Complexing of metal ion method, complexing agent is difficult to be reclaimed again sharp
With, and heavy metal ion is readily incorporated, serious harm can be caused to human body, the requirement of medicine and health food is not met.
Urea complexation is simple due to its technique, and easy to operate, useless urea can turn into as fertilizer utilization, the features such as environmental pollution is small
The preferred fatty acid mixed purifying process of enterprise.But single urea complexation is endless there is also urea clathration
Entirely, yield is low, and obtained product purity is relatively low, it is necessary to the shortcomings of being complexed repeatedly.
Such as Chinese patent application (publication date：March 12, publication number in 2008：CN101139289A one kind) is disclosed
Purity is more than the production technology of 90% Alpha-ethyl linolenate, and using purple perilla seed as raw material, using saponification ,-acidifying-washing-urinates twice
A series of cumbersome steps such as plain complexing-cold analysis-extraction-resterification, finally obtain purity ＞ 90% Alpha-ethyl linolenate.Should
Technological operation step is more, and 19 steps are, it is necessary to use a large amount of strong acid and highly basic, and produce a large amount of acidic and alkaline waste waters altogether；In addition in
Between need 2 urea complexations, low separation efficiency, yield is low, and 90% Alpha-ethyl linolenate yield is only 2%.
Chinese patent (the day for announcing：September in 2005 21 days, notification number：CN1219744C a kind of production is disclosed in) high-purity
The method of ethyl linolenate is spent, is to be obtained by extraction by carbon dioxide under the conditions of postcritical, it is molten that extractor flows out
The supercritical carbon dioxide that solution has various fatty-acid ethyl ester components is adsorbed into silver nitrate adsorption column, by super containing entrainer
Critical carbon dioxide is desorbed to silver nitrate adsorption column.The invention is big using supercritical carbon dioxide extraction method equipment investment,
Production cost is high, and using the absorption of silver nitrate adsorption column, silver ion is easy to run off, and has a strong impact on product quality, practicality is not high.
Chinese patent (the day for announcing：June 17, notification number in 2009：CN100500632C a kind of urea column is disclosed in)
The method of chromatography production leukotrienes and linolenic acid lower member ester.In column chromatography method stationary phase be pure urea, mobile phase be petroleum ether,
The organic solvents such as n-hexane, chloroform, ethyl acetate, methyl acetate, but solvent consumption is big, product purity is low.
To sum up it can be seen that, the use that has of method of alpha-linolenic acid ester is produced in the prior art to a large amount of organic solvents, is had
It is too high to equipment requirement, the then yield having is relatively low, or the content of product is low, and industrialized production can not be realized very well.
The content of the invention
Present invention aim to provide a kind of preparation method of Alpha-ethyl linolenate, this method is using vegetable oil as original
Material, using organic solvent amount is few, low for equipment requirements, high income, product content are high, it is adaptable to industrialized production.
To achieve the above object, the technical solution adopted by the present invention is：
A kind of preparation method of Alpha-ethyl linolenate, the preparation method of the CLA Arrcostab includes following step
Suddenly：
1) mixing-in fat acetoacetic ester is obtained after vegetable oil and ethanol being carried out into ester exchange reaction；
2) by step 1) in mixing-in fat acetoacetic ester remove first order Light ends by first order molecular distillation, obtain the
One-level heavy component, wherein, first order Light ends include lower boiling water and low carbon chain fatty-acid ethyl ester, and first order heavy component includes
C12~C24 fatty-acid ethyl ester；
3) by step 2) in first order heavy component by second level molecular distillation remove second level Light ends, obtain second
Level heavy component, wherein, second level Light ends include C12~C18 fatty-acid ethyl ester, and second level heavy component includes C16~C22's
Fatty-acid ethyl ester；
4) by step 3) in second level heavy component by third level molecular distillation remove third level heavy component, obtain the 3rd
Level Light ends, wherein, third level heavy component includes residual pigment, polymer, and third level Light ends include Alpha-ethyl linolenate；
5) by step 4) in third level Light ends and urea, ethanol obtained after urea complexation reaction the α of high-purity-
Ethyl linolenate.
It is preferred that, content of the vegetable oil containing alpha-linolenic acid is not less than 30%.
It is furthermore preferred that the vegetable oil is in linseed oil, perilla herb oil, eucommia ulmoides seed oil, Fructus Zanthoxyli oil and peony seed oil
It is a kind of.
The Alpha-ethyl linolenate purity of the high-purity obtained with the inventive method is not less than 80%, and Alpha-ethyl linolenate
Loss is small, and yield is high.As well known to a person skilled in the art the Alpha-ethyl linolenate purity progress to high-purity is further pure
Change can further improve purity, but be likely to result in the loss of a part of Alpha-ethyl linolenate.It is currently preferred, it will walk
The Alpha-ethyl linolenate of the rapid high-purity 5) obtained carries out chromatogram purification, obtains the Alpha-ethyl linolenate that purity is not less than 95%.
It is furthermore preferred that the chromatogram purification is：By step 5) the obtained Alpha-ethyl linolenate of high-purity is with the first flowing
Sample solution is obtained after phased soln and filtering, reverse-phase chromatography filler is loaded in the chromatography column, under the conditions of 20~40 DEG C, on described
Sample liquid is added in the chromatographic column, is then parsed, is existed by UV-detector using the second mobile phase and the first mobile phase successively
Line is detected and collects Alpha-ethyl linolenate cut, and merging is recovered under reduced pressure after solvent, obtains the alpha-linolenic acid that purity is not less than 95%
Ethyl ester.Those skilled in the art can select the species of the first mobile phase and the second mobile phase according to common knowledge, and the present invention is adopted
First mobile phase is preferably methanol or ethanol, and the second mobile phase is preferably methanol aqueous solution or ethanol water, wherein, first
The volume fraction of alcohol solution reclaimed water is between 1~5%, and the volume fraction of ethanol water reclaimed water is between 1~15%.It is described
Chromatograph packing material is generally silica gel, and the chromatograph packing material that the present invention is used is C18Spherical silica gel, 20~50 μm of particle diameter, 120 angstroms of aperture can
To reach lower Alpha-ethyl linolenate loss amount.
It is preferred that, the step 1) in ester exchange reaction be by vegetable oil and ethanol according to mol ratio be 1:(6~12)
Mixing, and the base catalyst that weight is plant weight of oil 0.1~1% is added dropwise, reacted 1~2 hour at 70~80 DEG C, reaction
After end, through recovery unreacted absolute ethyl alcohol, separation glycerine, wash, dehydrate the step of obtain fatty acid mixed second
Ester.
It is furthermore preferred that the base catalyst is one kind in caustic alcohol, sodium hydroxide or potassium hydroxide.
It is preferred that, the step 2) in first order molecular distillation be in vacuum be 100~1000Pa, heating-up temperature is
The flash distillation carried out under the conditions of 120~140 DEG C；The step 3) in second level molecular distillation vacuum be 10~100Pa, heating
Temperature is 140~160 DEG C；The step 4) in third level molecular distillation vacuum be 1~20Pa, heating-up temperature be 140~
160℃.Under this condition, it can be reached by molecular distillation and separate the light, effect of heavy component.It is furthermore preferred that first order molecule
The vacuum of distillation is 200~500Pa, and the vacuum of second level molecular distillation is 10~50Pa, third level molecular distillation it is true
Reciprocal of duty cycle is 1~10Pa.The vacuum of three-level molecular distillation, which is sequentially reduced, can be more beneficial for the light, separation of heavy constituent, preferred at this
Under the conditions of, the separation of three-level molecular distillation is more complete.
It is preferred that, the step 5) in urea complexation reaction be 75~80 by third level Light ends and urea, ethanol
1~2h is complexed under conditions of DEG C backflow, then slow cooling is to 0~10 DEG C, depressurizes overanxious point of isolated urea, filtrate decompression
Ethanol is reclaimed, the Alpha-ethyl linolenate for obtaining high-purity is dried and distilled in washing.
It is furthermore preferred that the step 5) in, the mass ratio of third level Light ends and urea is 1:(1~3), and urea and second
The mass ratio of alcohol is 1:(2~5).The ethanol is preferably the ethanol that volumetric concentration is 90~99%, most preferably 95% second
Alcohol.
In the present invention method compared with the existing technology, with advantages below：
1) present invention uses wide material sources and the lower vegetable oil of alpha-linolenic acid content requirement is raw material, covering scope
Extensively, originate sufficient, technique compatibility is strong, and applicability is wide.
2) triglycerides is switched to fatty-acid ethyl ester by the present invention by ester exchange reaction first, is conducive to follow-up separation,
Then the boiling point difference between each component is utilized by three-level molecular distillation, is partially separated the fatty-acid ethyl ester of each carbochain, afterwards
Urea complexation is recycled according to double bond differential enrichment Alpha-ethyl linolenate, it is finally pure according to polarity difference separation using chromatogram is prepared
Change the Alpha-ethyl linolenate for obtaining high-purity；Each isolation technics is with strong complementarity, and separative efficiency is greatly improved, and high income is beneficial to
Follow-up industrial amplification production.
3) the Alpha-ethyl linolenate purity that the inventive method is prepared is high, compared to single molecular distillation method and urine
Plain complexometry, can obtain the Alpha-ethyl linolenate of more than 90% purity.The present invention is compared to recycling urea complexation simultaneously
Method, more efficient, yield is also higher.And avoid using poisonous and hazardous heavy metal complexometric extraction, not only reduce into
This, and the risk of heavy-metal residual is reduced, expand its application in food and medicine.
Therefore, the preparation method of Alpha-ethyl linolenate of the invention make use of three-level molecular distillation-urea complexation-chromatographically pure
Method associated with change, it is to avoid few using organic solvent amount using a large amount of acid, alkali organic solvents, and set using existing
It is standby to carry out, it is low for equipment requirements.And the obtained few high income of Alpha-ethyl linolenate loss, product purity can reach
More than 95%, it is adaptable to industrialized production.Meanwhile, the present invention reduces and raw material is contained containing alpha-linolenic acid using vegetable oil as raw material
The requirement of amount, enriches raw material sources, so that production cost is effectively reduced, with very strong practicality.
Embodiment
With reference to embodiment, the present invention is described in further detail, is easy to more clearly understand the present invention, but it
Not to the present invention constitute limit.
Embodiment 1
1) by 1000g linseed oil (alpha-linolenic acid content 55.6%) and 400ml absolute ethyl alcohol and 40ml caustic alcohols
Ester exchange reaction is carried out after (ethanol solution of 20% caustic alcohol) mixing, 1 hour is reacted at a temperature of 80 DEG C, after having reacted
Ethanol is reclaimed, stands to divide and removes glycerine, alkali and a small amount of ethanol, be then washed to neutrality, vacuum dehydration obtains alpha-linolenic acid
Ethyl ester content is 55.3% mixing-in fat acetoacetic ester.
2) by step 1) in mixing-in fat acetoacetic ester remove first order Light ends by first order molecular distillation, obtain the
One-level heavy component；
3) by step 2) in first order heavy component by second level molecular distillation remove second level Light ends, obtain second
Level heavy component；
4) by step 3) in second level heavy component by third level molecular distillation remove third level heavy component, obtain α-Asia
The content of numb acetoacetic ester is 59.7% third level Light ends 830g；
5) 200g urea is added in 2000L conical flasks, then adds the ethanol of 700ml 95%, be warming up to 80 DEG C to second
Alcohol reflux, waits after urea is completely dissolved, adds step 4) in third level Light ends 100g, stirring to solvent clarification, and
Keep 1h.Then it is slowly stirred and is cooled in 20~25 DEG C, the refrigerator for being subsequently placed in 4 DEG C and stand still for crystals 4h, vacuum is taken out afterwards
Filtrate and Crystallization Separation, decompression filtrate recycling ethanol, then washing are obtained the Alpha-ethyl linolenate of 43.5g high-purities by filter, its
Middle Alpha-ethyl linolenate relative amount 82.5%.
6) by step 5) the obtained Alpha-ethyl linolenate of high-purity and absolute methanol in mass ratio 1：1 ratio dissolves, mistake
Sample solution is obtained after filter, reverse-phase chromatography filler is loaded in the chromatography column, reverse-phase chromatography filler is C18Spherical silica gel, 50 μm of particle diameter,
120 angstroms of aperture.Under the conditions of 20 DEG C, by sample solution add chromatographic column in, sample solution is fully adsorbed on filler, then again according to
It is secondary to be parsed using a certain amount of 95% methanol aqueous solution and absolute methanol, by UV-detector on-line checking, collect α-flax
Acetoacetic ester content highest cut, merging is recovered under reduced pressure after solvent, obtains the Alpha-ethyl linolenate of purity 95.9%, alpha-linolenic acid
The yield of ethyl ester is 24.2%.
Condition and the component composition of above-mentioned three-level molecular distillation are as shown in table 1：
Condition and the component composition of the three-level molecular distillation of the embodiment 1 of table 1
Embodiment 2
1) 1000g perilla herb oils (alpha-linolenic acid content 59.9%) are mixed laggard with 500ml absolute ethyl alcohol and 8g NaOH
Row ester exchange reaction, reacts 2 hours at a temperature of 80 DEG C, and ethanol is reclaimed after react, stands and point removes glycerine, alkali and on a small quantity
Ethanol, be then washed to neutrality, vacuum dehydration obtains the fatty acid mixed second that Alpha-ethyl linolenate content is 59.3%
Ester.
2) by step 1) in mixing-in fat acetoacetic ester remove first order Light ends by first order molecular distillation, obtain the
One-level heavy component；
3) by step 2) in first order heavy component by second level molecular distillation remove second level Light ends, obtain second
Level heavy component；
4) by step 3) in second level heavy component by third level molecular distillation remove third level heavy component, obtain α-Asia
The content of numb acetoacetic ester is 64.5% third level Light ends 814g；
5) 200g urea is added in 2000L conical flasks, then adds the ethanol of 900ml 95%, be warming up to 80 DEG C to second
Alcohol reflux, waits after urea is completely dissolved, adds step 4) in third level Light ends 75g, stirring protects to solvent clarification
Hold 1h.Then it is slowly stirred and is cooled in 20~25 DEG C, the refrigerator for being subsequently placed in 4 DEG C and stand still for crystals 4h, is filtered by vacuum afterwards
By filtrate and Crystallization Separation, decompression filtrate recycling ethanol, then washing obtains the Alpha-ethyl linolenate of 27.5g high-purities, wherein
Alpha-ethyl linolenate relative amount 86.5%.
6) by step 5) the obtained Alpha-ethyl linolenate of high-purity and absolute ethyl alcohol in mass ratio 1：1 ratio dissolves, mistake
Sample solution is obtained after filter, reverse-phase chromatography filler is loaded in the chromatography column, reverse-phase chromatography filler is C18Spherical silica gel, 30 μm of particle diameter,
120 angstroms of aperture.Under the conditions of 30 DEG C, by sample solution add chromatographic column in, sample solution is fully adsorbed on filler, then again according to
It is secondary to be parsed using a certain amount of 95% ethanol water and absolute ethyl alcohol, by UV-detector on-line checking, collect α-flax
Acetoacetic ester content highest cut, merging is recovered under reduced pressure after solvent, obtains the Alpha-ethyl linolenate of purity 98.7%, alpha-linolenic acid
Ethyl ester'sYield is 18.9%.
Condition and the component composition of above-mentioned three-level molecular distillation are as shown in table 2：
Condition and the component composition of the three-level molecular distillation of the embodiment 2 of table 2
Embodiment 3
1) after 1000g eucommia ulmoides seed oils (alpha-linolenic acid content 60.3%) are mixed with 600ml absolute ethyl alcohol and 6g KOH
Ester exchange reaction is carried out, 2 hours are reacted at a temperature of 80 DEG C, ethanol is reclaimed after react, stands and point removes glycerine, alkali and less
The ethanol of amount, is then washed to neutrality, and vacuum dehydration obtains the fatty acid mixed that Alpha-ethyl linolenate content is 59.4%
Ethyl ester.
2) by step 1) in mixing-in fat acetoacetic ester remove first order Light ends by first order molecular distillation, obtain the
One-level heavy component；
3) by step 2) in first order heavy component by second level molecular distillation remove second level Light ends, obtain second
Level heavy component；
4) by step 3) in second level heavy component by third level molecular distillation remove third level heavy component, obtain α-Asia
The content of numb acetoacetic ester is 63.5% third level Light ends 860g；
5) 200g urea is added in 2000L conical flasks, then adds the ethanol of 1000ml 95%, be warming up to 80 DEG C extremely
Alcohol reflux, waits after urea is completely dissolved, adds step 4) in third level Light ends 75g, stirring to solvent clarification, and
Keep 1h.Then it is slowly stirred and is cooled in 20~25 DEG C, the refrigerator for being subsequently placed in 4 DEG C and stand still for crystals 4h, vacuum is taken out afterwards
Filtrate and Crystallization Separation, decompression filtrate recycling ethanol, then washing are obtained the Alpha-ethyl linolenate of 25.8g high-purities by filter, its
Middle Alpha-ethyl linolenate relative amount 84.5%.
6) by step 5) the obtained Alpha-ethyl linolenate of high-purity and absolute ethyl alcohol in mass ratio 1：1 ratio dissolves, mistake
Sample solution is obtained after filter, reverse-phase chromatography filler is loaded in the chromatography column, reverse-phase chromatography filler is C18Spherical silica gel, 40 μm of particle diameter,
120 angstroms of aperture.Under the conditions of 40 DEG C, by sample solution add chromatographic column in, sample solution is fully adsorbed on filler, then again according to
It is secondary to be parsed using a certain amount of 90% ethanol water and absolute ethyl alcohol, by UV-detector on-line checking, collect α-flax
Acetoacetic ester content highest cut, merging is recovered under reduced pressure after solvent, obtains the Alpha-ethyl linolenate of purity 97.6%, alpha-linolenic acid
The yield 25.7% of ethyl ester.
Condition and the component composition of above-mentioned three-level molecular distillation are as shown in table 3：
Condition and the component composition of the three-level molecular distillation of the embodiment 3 of table 3
Embodiment 4
1) after 1000g Fructus Zanthoxyli oils (alpha-linolenic acid content 35.2%) are mixed with 400ml absolute ethyl alcohol and 8g KOH
Ester exchange reaction is carried out, 2 hours are reacted at a temperature of 80 DEG C, ethanol is reclaimed after react, stands and point removes glycerine, alkali and less
The ethanol of amount, is then washed to neutrality, and vacuum dehydration obtains the fatty acid mixed that Alpha-ethyl linolenate content is 34.7%
Ethyl ester.
2) by step 1) in mixing-in fat acetoacetic ester remove first order Light ends by first order molecular distillation, obtain the
One-level heavy component；
3) by step 2) in first order heavy component by second level molecular distillation remove second level Light ends, obtain second
Level heavy component；
4) by step 3) in second level heavy component by third level molecular distillation remove third level heavy component, obtain α-Asia
The content of numb acetoacetic ester is 43.5% third level Light ends 718g；
5) 200g urea is added in 2000L conical flasks, then adds the ethanol of 1200ml 95%, be warming up to 80 DEG C extremely
Alcohol reflux, waits after urea is completely dissolved, adds step 4) in third level Light ends 50g, stirring to solvent clarification, and
Keep 1h.Then it is slowly stirred and is cooled in 20~25 DEG C, the refrigerator for being subsequently placed in 4 DEG C and stand still for crystals 4h, vacuum is taken out afterwards
Filtrate and Crystallization Separation, decompression filtrate recycling ethanol, then washing are obtained the Alpha-ethyl linolenate of 12.8g high-purities by filter, its
Middle Alpha-ethyl linolenate relative amount 79.5%.
6) by step 5) the obtained Alpha-ethyl linolenate of high-purity and absolute methanol in mass ratio 1：1 ratio dissolves, mistake
Sample solution is obtained after filter, reverse-phase chromatography filler is loaded in the chromatography column, reverse-phase chromatography filler is C18Spherical silica gel, 20 μm of particle diameter,
120 angstroms of aperture.Under the conditions of 30 DEG C, by sample solution add chromatographic column in, sample solution is fully adsorbed on filler, then again according to
It is secondary to be parsed using a certain amount of 90% methanol aqueous solution and absolute methanol, by UV-detector on-line checking, collect α-flax
Acetoacetic ester content highest cut, merging is recovered under reduced pressure after solvent, obtains the Alpha-ethyl linolenate of purity 95.8%, alpha-linolenic acid
The yield of ethyl ester is about 30.2%.
Condition and the component composition of above-mentioned three-level molecular distillation are as shown in table 4：
Condition and the component composition of the three-level molecular distillation of the embodiment 4 of table 4
Embodiment 5
1) after 1000g peony seed oils (alpha-linolenic acid content 33.2%) are mixed with 500ml absolute ethyl alcohol and 8g KOH
Ester exchange reaction is carried out, 2 hours are reacted at a temperature of 80 DEG C, ethanol is reclaimed after react, stands and point removes glycerine, alkali and less
The ethanol of amount, is then washed to neutrality, and vacuum dehydration obtains the fatty acid mixed that Alpha-ethyl linolenate content is 32.7%
Ethyl ester.
2) by step 1) in mixing-in fat acetoacetic ester remove first order Light ends by first order molecular distillation, obtain the
One-level heavy component；
3) by step 2) in first order heavy component by second level molecular distillation remove second level Light ends, obtain second
Level heavy component；
4) by step 3) in second level heavy component by third level molecular distillation remove third level heavy component, obtain α-Asia
The content of numb acetoacetic ester is 42.8% third level Light ends 690g；
5) 200g urea is added in 2000L conical flasks, then adds the ethanol of 600ml 95%, be warming up to 80 DEG C to second
Alcohol reflux, waits after urea is completely dissolved, adds step 4) in third level Light ends 50g, stirring protects to solvent clarification
Hold 1h.Then it is slowly stirred and is cooled in 20~25 DEG C, the refrigerator for being subsequently placed in 4 DEG C and stand still for crystals 4h, is filtered by vacuum afterwards
By filtrate and Crystallization Separation, decompression filtrate recycling ethanol, then washing obtains the Alpha-ethyl linolenate of 13.8g high-purities, wherein
Alpha-ethyl linolenate relative amount 78.5%.
6) by step 5) the obtained Alpha-ethyl linolenate of high-purity and absolute ethyl alcohol in mass ratio 1：1 ratio dissolves, mistake
Sample solution is obtained after filter, reverse-phase chromatography filler is loaded in the chromatography column, reverse-phase chromatography filler is C18Spherical silica gel, 20 μm of particle diameter,
120 angstroms of aperture.Under the conditions of 40 DEG C, by sample solution add chromatographic column in, sample solution is fully adsorbed on filler, then again according to
It is secondary to be parsed using a certain amount of 85% ethanol water and absolute ethyl alcohol, by UV-detector on-line checking, collect α-flax
Acetoacetic ester content highest cut, merging is recovered under reduced pressure after solvent, obtains the Alpha-ethyl linolenate of purity 95.5%, alpha-linolenic acid
The yield of ethyl ester is about 24.5%.
Condition and the component composition of above-mentioned three-level molecular distillation are as shown in table 5：
Condition and the component composition of the three-level molecular distillation of the embodiment 5 of table 5
From above-described embodiment as can be seen that the Alpha-ethyl linolenate prepared with the method for the present invention, raw material is from easy
The vegetable oil obtained, and there is no too high requirement to the alpha-linolenic acid content in vegetable oil.Meanwhile, obtained Alpha-ethyl linolenate
Purity is high, and high income, preparation technology is suitable for industrialized production.
On the premise of claims of the present invention protection domain is not departed from, the numerical value in embodiment is adjusted and also belonged to
In the scope of protection of the invention.
Claims (10)
1. a kind of preparation method of Alpha-ethyl linolenate, it is characterised in that：The preparation method bag of the CLA Arrcostab
Include following steps：
1) mixing-in fat acetoacetic ester is obtained after vegetable oil and ethanol being carried out into ester exchange reaction；
2) by step 1) in mixing-in fat acetoacetic ester by first order molecular distillation remove first order Light ends, obtain the first order
Heavy component, wherein, first order Light ends include lower boiling water and low carbon chain fatty-acid ethyl ester, and first order heavy component includes C12
~C24 fatty-acid ethyl ester；
3) by step 2) in first order heavy component by second level molecular distillation remove second level Light ends, obtain the second level weight
Component, wherein, second level Light ends include C12~C18 fatty-acid ethyl ester, and second level heavy component includes C16~C22 fat
Acetoacetic ester；
4) by step 3) in second level heavy component by third level molecular distillation remove third level heavy component, obtain the third level light
Component, wherein, third level heavy component includes residual pigment, polymer, and third level Light ends include Alpha-ethyl linolenate；
5) by step 4) in third level Light ends and urea, ethanol obtained after urea complexation reaction α-flax of high-purity
Acetoacetic ester.
2. the preparation method of Alpha-ethyl linolenate according to claim 1, it is characterised in that：The vegetable oil contains alpha-linolenic acid
Content be not less than 30%.
3. the preparation method of Alpha-ethyl linolenate according to claim 2, it is characterised in that：The vegetable oil is linseed
One kind in oil, perilla herb oil, eucommia ulmoides seed oil, Fructus Zanthoxyli oil and peony seed oil.
4. the preparation method of Alpha-ethyl linolenate according to claim 1, it is characterised in that：By step 5) obtained high-purity
Alpha-ethyl linolenate carry out chromatogram purification, obtain the Alpha-ethyl linolenate that purity is not less than 95%.
5. the preparation method of Alpha-ethyl linolenate according to claim 4, it is characterised in that：The chromatogram purification is：Will step
The Alpha-ethyl linolenate of the rapid high-purity 5) obtained obtains sample solution with the first flowing phased soln and after filtering, and fills in the chromatography column
Reverse-phase chromatography filler is filled out, under the conditions of 20~40 DEG C, the sample solution is added in the chromatographic column, second is then used successively
Mobile phase and the parsing of the first mobile phase, by UV-detector on-line checking and collect Alpha-ethyl linolenate cut, merge decompression
After recycling design, the Alpha-ethyl linolenate that purity is not less than 95% is obtained.
6. the preparation method of Alpha-ethyl linolenate according to claim 1, it is characterised in that：The step 1) in ester exchange
It by vegetable oil and ethanol according to mol ratio is 1 that reaction, which is,:(6~12) mix, and weight is added dropwise for plant weight of oil 0.1~1%
Base catalyst, reacted 1~2 hour at 70~80 DEG C, after reaction terminates, through recovery unreacted absolute ethyl alcohol, point
From glycerine, wash, dehydrate the step of obtain mixing-in fat acetoacetic ester.
7. the preparation method of Alpha-ethyl linolenate according to claim 6, it is characterised in that：The base catalyst is ethanol
One kind in sodium, sodium hydroxide or potassium hydroxide.
8. the preparation method of Alpha-ethyl linolenate according to claim 1, it is characterised in that：The step 2) in the first fraction
It in vacuum is 100~1000Pa that son distillation, which is, and heating-up temperature is the flash distillation that carries out under the conditions of 120~140 DEG C；The step 3)
The vacuum of middle second level molecular distillation is 10~100Pa, and heating-up temperature is 140~160 DEG C；The step 4) in the third level point
The vacuum of son distillation is 1~20Pa, and heating-up temperature is 140~160 DEG C.
9. the preparation method of Alpha-ethyl linolenate according to claim 1, it is characterised in that：The step 5) in urea network
It is to be complexed 1~2h under conditions of third level Light ends and urea, ethanol flow back at 75~80 DEG C to close reaction, then slow cooling
To 0~10 DEG C, overanxious point of isolated urea is depressurized, decompression filtrate recycling ethanol, washing, dry and distillation obtains high-purity
Alpha-ethyl linolenate.
10. the preparation method of Alpha-ethyl linolenate according to claim 9, it is characterised in that：The step 5) in, the third level
The mass ratio of Light ends and urea is 1:(1~3), and the mass ratio of urea and ethanol is 1:(2~5).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710200721.0A CN106966902A (en) | 2017-03-30 | 2017-03-30 | A kind of preparation method of alpha linolenic acid ethyl ester |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710200721.0A CN106966902A (en) | 2017-03-30 | 2017-03-30 | A kind of preparation method of alpha linolenic acid ethyl ester |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106966902A true CN106966902A (en) | 2017-07-21 |
Family
ID=59337360
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710200721.0A Pending CN106966902A (en) | 2017-03-30 | 2017-03-30 | A kind of preparation method of alpha linolenic acid ethyl ester |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106966902A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109007064A (en) * | 2018-08-28 | 2018-12-18 | 江苏国色天香油用牡丹科技发展有限公司 | A kind of peony seed oil and its processing technology |
| CN110204421A (en) * | 2019-07-17 | 2019-09-06 | 河南利诺生化有限责任公司 | Alpha-linolenic acid washes ethanol recovery process and gradient recyclable device in waste liquid |
| CN111302940A (en) * | 2020-04-08 | 2020-06-19 | 燕园泽龙(涿鹿)生物科技有限公司 | Production method of high-purity α -ethyl linolenate |
| CN112479885A (en) * | 2021-01-01 | 2021-03-12 | 河南利诺生化有限责任公司 | Low-cost environment-friendly production process of ethyl linolenate |
| US11872201B2 (en) | 2018-06-21 | 2024-01-16 | Nuseed Nutritional Us Inc. | DHA enriched polyunsaturated fatty acid compositions |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102993011A (en) * | 2011-09-13 | 2013-03-27 | 丰宁京北第一草原原生态食品科技开发有限公司 | Method for preparing alpha-ethyl linolenate through using Fructus Perillae oil |
-
2017
- 2017-03-30 CN CN201710200721.0A patent/CN106966902A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102993011A (en) * | 2011-09-13 | 2013-03-27 | 丰宁京北第一草原原生态食品科技开发有限公司 | Method for preparing alpha-ethyl linolenate through using Fructus Perillae oil |
Non-Patent Citations (1)
| Title |
|---|
| 张康健 等: "《中国特有植物脂肪 杜仲籽油》", 30 June 2016, 西北农林科技大学出版社 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11872201B2 (en) | 2018-06-21 | 2024-01-16 | Nuseed Nutritional Us Inc. | DHA enriched polyunsaturated fatty acid compositions |
| CN109007064A (en) * | 2018-08-28 | 2018-12-18 | 江苏国色天香油用牡丹科技发展有限公司 | A kind of peony seed oil and its processing technology |
| CN110204421A (en) * | 2019-07-17 | 2019-09-06 | 河南利诺生化有限责任公司 | Alpha-linolenic acid washes ethanol recovery process and gradient recyclable device in waste liquid |
| CN110204421B (en) * | 2019-07-17 | 2024-03-01 | 河南利诺生化有限责任公司 | Method and gradient recovery device for recovering ethanol from alpha-linolenic acid washing waste liquid |
| CN111302940A (en) * | 2020-04-08 | 2020-06-19 | 燕园泽龙(涿鹿)生物科技有限公司 | Production method of high-purity α -ethyl linolenate |
| CN112479885A (en) * | 2021-01-01 | 2021-03-12 | 河南利诺生化有限责任公司 | Low-cost environment-friendly production process of ethyl linolenate |
| CN112479885B (en) * | 2021-01-01 | 2023-04-14 | 河南利诺生化有限责任公司 | Low-cost environment-friendly production process of ethyl linolenate |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106966902A (en) | A kind of preparation method of alpha linolenic acid ethyl ester | |
| Vali et al. | A process for the preparation of food-grade rice bran wax and the determination of its composition | |
| CN106860492A (en) | A kind of preparation method of cannabinol compounds | |
| CN105016956B (en) | A kind of method for extracting squalene | |
| CN104649895B (en) | The preparation method of the alpha-linolenic acid of 98% purity | |
| CN102001947A (en) | Method for preparing honeysuckle chlorogenic acid | |
| CN101870637B (en) | Technology for extracting and preparing policosanol | |
| TWI578985B (en) | Extraction and purification of conjugated triene linoleic acid (CLN) | |
| CN109369397B (en) | Ag+Method for separating methyl linolenate by coupling extraction of-short-chain polyol | |
| CN101654398B (en) | Method for extracting high purity polyprenol from plant needle leaf raw material | |
| CN112430500A (en) | Method for reducing anisidine value in polyunsaturated fatty acid oil | |
| CN1982279A (en) | Preparation of shikimic acid | |
| CN106590939A (en) | Method for purification preparation of high content linoleic acid by using vegetable oil as raw material | |
| CN104418726A (en) | Extraction method of [alpha]-linolenic acid | |
| CN104262076B (en) | A kind of method utilizing Silver Nitrate silica gel chromatography purification plant origin squalene | |
| CN100363378C (en) | Method for producing mixture of phytosterol and vitamin E | |
| CN108084016A (en) | A kind of high-purity linoleic preparation method | |
| CN109528784B (en) | Method for extracting and preparing 4,4' -dimethyl sterol from shea butter | |
| CN101486951A (en) | Method for separating oleate, linolic acid, oleate and linoleate | |
| CN107619716A (en) | A kind of method of bitter substance in removal linseed oil | |
| CN107739296A (en) | A kind of method that oleic acid is collected from tea oil | |
| CN114181778A (en) | Preparation method of ruminant trans-fatty acid | |
| CN108033938B (en) | Method for extracting tocopherol from tea oil deodorized distillate by combining acidic ionic liquid catalytic esterification and column chromatography | |
| CN106588580A (en) | Method for preparing high-purity magnolol from Mangnolia officinalis | |
| CN106748780B (en) | A kind of removal methods of injection Synthetic Oil metal residual |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20170721 |