CN103965155B - A kind of preparation process of natural VE - Google Patents
A kind of preparation process of natural VE Download PDFInfo
- Publication number
- CN103965155B CN103965155B CN201410147994.XA CN201410147994A CN103965155B CN 103965155 B CN103965155 B CN 103965155B CN 201410147994 A CN201410147994 A CN 201410147994A CN 103965155 B CN103965155 B CN 103965155B
- Authority
- CN
- China
- Prior art keywords
- natural
- preparation process
- alcohol
- temperature
- esterification
- 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
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
- C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D311/04—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring
- C07D311/58—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring other than with oxygen or sulphur atoms in position 2 or 4
- C07D311/70—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring other than with oxygen or sulphur atoms in position 2 or 4 with two hydrocarbon radicals attached in position 2 and elements other than carbon and hydrogen in position 6
- C07D311/72—3,4-Dihydro derivatives having in position 2 at least one methyl radical and in position 6 one oxygen atom, e.g. tocopherols
Abstract
The invention discloses a kind of preparation process of natural VE, including esterification, washing, cold crystallization, separation of solid and liquid, molecular distillation, column chromatography technique, the techniques such as quadratic component distillation.Molecular distillation technique and column chromatography technique are combined by the present invention, obtain the natural VE of higher degree, it is that filler carries out column chromatography purification natural VE that resin is adsorbed in the present invention, and the total content of obtained natural vitamin E product is 90% or more, and total recovery is 80% or more.By molecular distillation technique twice, by-product can be removed to greatest extent, obtain better quality, the high quality natural VE that color is more transparent, optical activity is qualified.The process route has the characteristics that few step, high income, operating condition are mild.Technological process can be greatly reduced, obtain the natural VE of high-purity, and yield higher, it is cost-effective.
Description
Technical field
The present invention relates to a kind of preparation processes of natural VE, especially obtain the preparation of high purity natural vitamin E
Purifying technique.
Background technology
Natural VE, also referred to as natural tocopherol are a kind of antioxidant and nutritional agents of function admirable, have simultaneously
The characteristics of bioactivity height, edible safety, it is widely used in the fields such as medicine, health products, food, cosmetics, becomes in recent years
The hot spot product being concerned.
Natural VE is mainly the by-product from vegetable oil and fat refining process --- it is extracted in deodorization distillate, state
There is the content of vitamin E in mixing vitamin E series of products 50%, 70%, 90% outside.The country has " natural VE concentration
Oil " product, content is about 50%.Not only content is low, but also the product transparency is poor, and specific rotatory power is low, does not meet international market and wants
It asks.Concentrated natural vitamin E is extracted from soybean oily distillate, can not only improve the comprehensive of the large grain and oil crop in China such as soybean
Utility value is closed, but also the environmental problem caused by the discharge of distillate can be reduced.State based on natural tocopherol
The advantageous natural conditions in inside and outside consumption market and China, purification natural tocopherol has extremely important from deodorization distillate
Economic value and social reality meaning.
CN 103012351 disclose it is a kind of use alcohols, hydrocarbon solvent for extractant, with crude product natural VE press one
Certainty ratio, in 40-60o C Lower mixed dissolution extraction is adjusted, 0-10 is cooled tooC is filtered after standing precipitation solid, by filtrate decompression
Solvent is distilled off, obtains natural VE.It can will be greatly shortened the standing cold analysis time, and will naturally tieed up by this technique
The content of raw element E improves 30-40 percentage points, but organic solvent used is more, generates a large amount of contaminated wastewaters.Patent
It is disclosed in CN1253951A a kind of using supercritical CO2The method of extraction and concentrated natural vitamin E, including extraction and rectifying
Tower multistage continuous separation technology, finally obtained content of vitamin E is 40-70%, but the yield of this law hands over low, only 48%-
65%, and supercritical CO2Extraction equipment requirement and costly.
Invention content
More purpose of the present invention is to be directed to current natural VE purification step, yield is low, and organic solvent is asked using more
Topic, provides a kind of purifying technique of natural VE.Molecular distillation technique and column chromatography technique are combined, obtained more high-purity
The natural VE of degree.
The present invention uses column chromatography to purify natural VE, obtained natural VE as filler to adsorb resin
The total content of product is 90% or more, and tocopherol yield is 90% or more.The process route has few step, high income, operation item
The mild feature of part.
The present invention adopts the following technical scheme that：
A kind of preparation process of natural VE, it is characterised in that the method includes the following steps：
（1）By soya fatty acid carry out under the conditions of the concentrated sulfuric acid with alcohol carry out esterification, washing 2 times with remove acid and
Water-soluble substances, in 5-20oCrystalline material be separated by solid-liquid separation using the method for press filtration, obtains solid by C cold crystallizations
For sterol crude product, liquid will be obtained in vapo(u)rizing temperature 120-130oC, operating pressure 1-10Pa, under the conditions of carry out molecular distillation, obtain
It is natural VE crude product to obtain residual solution.
（2）Natural VE crude product is 2.5-5ml/min, temperature 25-30 in flow velocityoColumn chromatography is carried out under the conditions of C
Then absorption uses desorbed solution to carry out in 5-10ml/min, temperature 25-30oIt is parsed under the conditions of C, efflux is day
Right vitamin E concentrate,
（3）By natural VE concentrate in vapo(u)rizing temperature 180-220oC, operating pressure 1-10Pa carry out molecular distillation
Purification obtains high-purity vitamin E.
Alcohol can select a kind of alcohol as esterification in methanol, ethyl alcohol, isopropanol in the esterification.
The molar ratio of alcohol and aliphatic acid is 4 in the esterification:1-6:1.
Use the ratio of water and reaction solution for 1 in the washing process：5-1:10.
Temperature is preferably 5-10 when the cold crystallizationoC。
Filler is macroporous absorbent resin in the Adsorption technique.
The macroporous absorbent resin is using the copolymer of styrene and divinylbenzene as the non-polar resin of skeleton.
Natural VE purifying technique using the present invention has the beneficial effect that：
Using column chromatography technology, especially resin column chromatography technique, technological process can be greatly reduced, obtain high-purity
Natural VE, and yield higher is cost-effective.
By molecular distillation technique twice, by-product can be removed to greatest extent, and acquisition better quality, color are more saturating
The high quality natural VE bright, optical activity is qualified.
Description of the drawings
Fig. 1 is the preparation technology flow chart of natural VE.
Specific implementation mode
It is further illustrated the present invention below by embodiment：
Embodiment 1
In soya fatty acid 1Kg input three-necked flasks, 95o C Material is cooled to 65 after water-bath vacuum outgaso C With
Under, the concentrated sulfuric acid is added while stirring（20ml）, methanol is added（340ml）.Water-bath addition is warming up to 65o C , control temperature in the kettle
64-78 degree is stirred at reflux 60min. reflux and finishes, and material is added 90o C The above hot water 150ml, washing, discards water layer, by oil reservoir
It is placed in 5o C Cold analysis under environment, crystallizes out phytosterol.Material is put into press filtration slot and carries out press filtration, obtains oily liquids.Oil
Shape liquid is 120o C , distilled under pressure 1pa.Residual component is natural VE crude product after distillation, and purity is
48%。
Above-mentioned natural VE crude product is subjected to column chromatography using macropore non-polar resin, is 2.5ml/min in flow velocity,
Temperature is 25oResin adsorption is carried out under the conditions of C, then uses eluent in 5ml/min 25oCarry out desorption under C, desorption attached liquid into
Row molecular distillation, vapo(u)rizing temperature 180o C , pressure 1Pa obtains fraction and is high purity natural vitamin E, and purity reaches
97%, yield 50%.
Embodiment 2：
In soya fatty acid 1Kg input three-necked flasks, 95o C Material is cooled to 65 after water-bath vacuum outgaso C With
Under, the concentrated sulfuric acid is added while stirring（20ml）, methanol is added（240ml）.Water-bath addition is warming up to 65o C , control temperature in the kettle
64-78o C It is stirred at reflux 60min. reflux to finish, material is added 90o C The above hot water 220ml, washing, discards water layer, by oil reservoir
It is placed in 10o C Cold analysis under environment, crystallizes out phytosterol.Material is put into press filtration slot and carries out press filtration, obtains oily liquids.Oil
Shape liquid is 130o C , distilled under pressure 5pa.Residual component is natural VE crude product after distillation, and purity is
40%。
Above-mentioned natural VE crude product is subjected to column chromatography using macropore non-polar resin, is 4ml/min, temperature in flow velocity
Degree is 30oResin adsorption is carried out under the conditions of C, then uses eluent in 10ml/min 30oCarry out desorption under C, desorption attached liquid into
Row molecular distillation, molecular distillation, vapo(u)rizing temperature 220o C , pressure 10Pa, obtain fraction and be high purity natural Vitamin
E, purity reach 97%, yield 60%.
Embodiment 3：
In soya fatty acid 1Kg input three-necked flasks, 95o C Material is cooled to 65 after water-bath vacuum outgaso C With
Under, the concentrated sulfuric acid is added while stirring（20ml）, ethyl alcohol is added（440ml）.Water-bath addition is warming up to 65o C controls temperature in the kettle
64-78o C It is stirred at reflux 60min. reflux to finish, material is added 90oCThe above hot water 300ml, washing, discards water layer, by oil reservoir
It is placed in cold analysis under 10 degree of environment, crystallizes out phytosterol.Material is put into press filtration slot and carries out press filtration, obtains oily liquids.Oil
Shape liquid is 120o C , distilled under pressure 10pa.Residual component is natural VE crude product after distillation, and purity is
52%。
Above-mentioned natural VE crude product is subjected to column chromatography using non-polar resin, is 5ml/min in flow velocity, temperature is
25oResin adsorption is carried out under the conditions of C, then uses eluent in 10ml/min 30oDesorption is carried out under C, desorption attached liquid is divided
Son distillation, vapo(u)rizing temperature 200o C, pressure 5Pa, obtain fraction and are high purity natural vitamin E, and purity reaches 98%,
Yield is 40%.
Claims (7)
1. a kind of preparation process of natural VE, it is characterised in that the method includes the following steps：
（1）By soya fatty acid carry out under the conditions of the concentrated sulfuric acid with alcohol carry out esterification, washing 3 times with remove acid and it is water-soluble
Property substance, in 5-20oCrystalline material be separated by solid-liquid separation using the method for press filtration by C cold crystallizations, and it is steroid to obtain solid
Alcohol crude product will obtain liquid in vapo(u)rizing temperature 120-130oMolecular distillation is carried out under the conditions of C, operating pressure 1-10Pa, is obtained residual
Extraction raffinate is natural VE crude product；
（2）Natural VE crude product is 2.5-5ml/min, temperature 25-30 in flow velocityo Column chromatography suction is carried out under the conditions of C
It is attached, then desorbed solution is used to carry out in 5-10ml/min, temperature 25-30oIt is parsed under the conditions of C, efflux is as natural
Vitamin E concentrate；
（3）By natural VE concentrate in vapo(u)rizing temperature 180-220oC, operating pressure 1-10Pa carry out molecular distillation and purify
To high-purity vitamin E.
2. a kind of preparation process of natural VE according to claim 1, it is characterised in that alcohol in the esterification
It can select a kind of alcohol as esterification in methanol, ethyl alcohol, isopropanol.
3. a kind of preparation process of natural VE according to claim 1, it is characterised in that alcohol in the esterification
Molar ratio with aliphatic acid is 4:1-6:1.
4. a kind of preparation process of natural VE according to claim 1, it is characterised in that adopted in the washing process
It is 1 with the ratio of water and reaction solution：5-1:10.
5. a kind of preparation process of natural VE according to claim 1, it is characterised in that the temperature when cold crystallization
Degree is preferably 5-10o C 。
6. a kind of preparation process of natural VE according to claim 1, it is characterised in that the Adsorption work
Filler is macroporous absorbent resin in skill.
7. a kind of preparation process of natural VE according to claim 5, it is characterised in that the macroporous absorbent resin
Using the copolymer of styrene and divinylbenzene as the non-polar resin of skeleton.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410147994.XA CN103965155B (en) | 2014-04-15 | 2014-04-15 | A kind of preparation process of natural VE |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410147994.XA CN103965155B (en) | 2014-04-15 | 2014-04-15 | A kind of preparation process of natural VE |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103965155A CN103965155A (en) | 2014-08-06 |
| CN103965155B true CN103965155B (en) | 2018-10-16 |
Family
ID=51235211
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410147994.XA Active CN103965155B (en) | 2014-04-15 | 2014-04-15 | A kind of preparation process of natural VE |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103965155B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115010572A (en) * | 2022-07-07 | 2022-09-06 | 广州美林生态科技有限公司 | Method for extracting squalene and vitamin E |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1074217A (en) * | 1993-01-14 | 1993-07-14 | 清华大学 | From the vegetable oil refining by product, extract the novel process of vitamin-E and sterol |
| US5487817A (en) * | 1993-02-11 | 1996-01-30 | Hoffmann-La Roche Inc. | Process for tocopherols and sterols from natural sources |
| CN1401644A (en) * | 2002-09-19 | 2003-03-12 | 浙江大学 | Process for extracting high content mixed tocopherol |
| CN1775771A (en) * | 2005-06-28 | 2006-05-24 | 中谷天科(天津)生物工程有限公司 | Method for extracting natural vitamin E from vegetable oil and fat refining and deodorizing distillate |
| CN101323607A (en) * | 2007-06-13 | 2008-12-17 | 浙江医药股份有限公司新昌制药厂 | Preparation of high content mixed tocopherols |
-
2014
- 2014-04-15 CN CN201410147994.XA patent/CN103965155B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1074217A (en) * | 1993-01-14 | 1993-07-14 | 清华大学 | From the vegetable oil refining by product, extract the novel process of vitamin-E and sterol |
| US5487817A (en) * | 1993-02-11 | 1996-01-30 | Hoffmann-La Roche Inc. | Process for tocopherols and sterols from natural sources |
| CN1401644A (en) * | 2002-09-19 | 2003-03-12 | 浙江大学 | Process for extracting high content mixed tocopherol |
| CN1775771A (en) * | 2005-06-28 | 2006-05-24 | 中谷天科(天津)生物工程有限公司 | Method for extracting natural vitamin E from vegetable oil and fat refining and deodorizing distillate |
| CN101323607A (en) * | 2007-06-13 | 2008-12-17 | 浙江医药股份有限公司新昌制药厂 | Preparation of high content mixed tocopherols |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103965155A (en) | 2014-08-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101817859B (en) | Method for separating and extracting cholesterol in lanolin alcohol | |
| CN105016956B (en) | A kind of method for extracting squalene | |
| WO2021036386A1 (en) | Simulated moving bed continuous chromatography system and application thereof, and method for purifying coenzyme q10 | |
| CN103951718A (en) | Method used for preparing high-purity gardenoside and crocin from gardenia jasminoides ellis | |
| CN105367370B (en) | A kind of method that squalene is extracted in heel after the natural VE from extraction | |
| CN107779258B (en) | Preparation method of krill oil with low arsenic content | |
| CN107778277B (en) | Process for the recovery of squalene, vitamin E and/or sterols | |
| CN101824018B (en) | Method for purifying dihydromyricetin | |
| CN104311620A (en) | Method for purifying chenodeoxycholic acid | |
| CN110283034B (en) | Method for obtaining high-purity squalene from vegetable oil deodorized distillate | |
| CN102382095A (en) | Method for separating and mixing d-alpha-tocopherol in tocopherol by utilizing resin adsorption method | |
| CN109400658B (en) | Method for synchronously separating and purifying oleuropein and hydroxytyrosol from olive leaves | |
| CN103203122A (en) | Method for separating and purifying high-purity natural substances from animals and plants by using liquid chromatography column | |
| CN102993134B (en) | A kind of method of purification of Lipstatin | |
| CN102432584B (en) | Method for preparing high-purity natural vitamin E monomers by separating mixed tocopherol | |
| US11180445B2 (en) | Method for recycling urea in urea adduct process | |
| CN103965155B (en) | A kind of preparation process of natural VE | |
| CN102229593A (en) | Method for preparing natural vitamin E from crude oil of Maoyeshan tung tree seed | |
| CN104356105B (en) | A kind of preparation method of EGCG | |
| CN112159300A (en) | Method for extracting squalene from plant deodorized distillate | |
| CN104987952B (en) | Method for extracting volatile oil and salidroside from rhodiola rosea whole plant | |
| CN102070685A (en) | Method for enriching and purifying arctiin from burdock | |
| TWI404797B (en) | Method for preparing sesamin and sesamolin | |
| CN101353294A (en) | Separation and purification method of high-content resveratrol | |
| CN106187980A (en) | Natural low content vitamin E is that raw material extracts natural Vitamin E and the method and apparatus of Squalene |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |