CN106083518B - A kind of separation method of squalene and vitamin E - Google Patents
A kind of separation method of squalene and vitamin E Download PDFInfo
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- CN106083518B CN106083518B CN201610440848.5A CN201610440848A CN106083518B CN 106083518 B CN106083518 B CN 106083518B CN 201610440848 A CN201610440848 A CN 201610440848A CN 106083518 B CN106083518 B CN 106083518B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/005—Processes comprising at least two steps in series
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/10—Purification; Separation; Use of additives by extraction, i.e. purification or separation of liquid hydrocarbons with the aid of liquids
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/148—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound
- C07C7/152—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound by forming adducts or complexes
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- 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
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Abstract
The invention discloses the separation methods of a kind of squalene and vitamin E.This method contains squalene and natural VE mixture using the separation of beta-cyclodextrin inclusion, using the difference of beta-cyclodextrin and squalene, natural VE difference substrate weak interaction force, purifies and separates are achieved the purpose that by the Preferential adsorption of squalene under mild conditions.The squalene and natural VE mixture of a small amount of ethyl alcohol dissolution, are added drop-wise under constant temperature conditions in saturation beta-cyclodextrin aqueous solution, constant temperature stirring, inclusion complex is precipitated in cooling and standings, filtering is dried in vacuo, and the squalene and natural VE in inclusion complex are extracted with dehydrated alcohol.The present invention has the characteristics that separation condition is mild, simple process, energy conservation and environmental protection, carrier of separating is reusable, also avoids substance because having the be easy to happen oxidative phenomena of thermal sensitivity.
Description
Technical field
The invention belongs to isolate and purify field, specifically, being related to the separation method of a kind of squalene and vitamin E.
Background technique
Natural VE also known as tocopherol, are mainly derived from animal and plant fat, for treat infertility, habitual abortion and
Threatened abortion, and belong to antioxidant, prevents the unsaturated bond of peroxidase to be incorporated on cell membrane, to incised wound, burn, old
Year spot pigmentation, has dry skin, prevents ultraviolet injury from having important effect.Squalene also known as squalene, squalene,
Squalene, molecular formula C30H50, molecular weight 410.71 is a kind of height unsaturation hydrocarbon compound, and squalene also has significant anti-
Oxidability.Natural VE and squalene are mainly used in health care product and cosmetic industry at present, with mentioning for quality of life
It rises, it is higher and higher to the quality requirement of natural VE and squalene.
Natural VE and squalene are industrially prepared at present mainly using plant oil deodorizing distillate as raw material, it
There are also free fatty acid, alcohol lipid, glycerolipid and other substances in addition to natural VE, squalene for main component.According to oil
The difference of material, natural VE proportion differ between 1%-20%, wherein soybean oil content highest, and squalene is in olive
Content highest in olive oil.Natural VE and squalene are higher boiling and boiling point close to active material, both easy to oxidize,
Industrial common extracting method is first to be pre-processed raw material to be concentrated and purified again, in conjunction with multiple-grade molecular distillation,
But isolated product purity is low, and in separation process because high temperature is easy to aoxidize.
Recent domestic has delivered the extraction point about squalene in by-product of vegetable oil and natural VE successively
From paper and patent application.Hongtao Wan etc. separates tocopherol and spiny dogfish in soybean oil oil using SCF-CO 2
Alkene, but extraction operation process is complicated, separates somewhat expensive, purity is not high, lower (the Industrial & of the rate of recovery
2753-2758 pages of volume 43 of Engineering Chemistry Research 2004).Qu Delin et al. proposes one
The process route of tocopherol is extracted from the lower deodorization distillate of tocopherol content, including first is extremely changed, washes, distilling, is secondary
First extremely changes, secondary washing, second distillation, methanol extraction, cooling removal of impurities, strong-base anion-exchange resin processing, produces
Tocopherol content is up to 50-60% in product, though this technique treating capacity is big, complex process, the rate of recovery is low, and purity does not reach requirement
(application number CN 1034367).Posada etc. extracts squalene using molecular distillation technique from palm oil, and has investigated distillation
The influence to squalene content in palm oil such as temperature, charging rate, the results showed that squalene can enter light under low temperature
Xiang Zhong, content 3.94% have certain directive significance (Separation and to squalene is extracted using molecular distillation
220-229 pages of the Purification Technology2007 second phase), though treating capacity is big, energy consumption is excessive, and cost is excessively high,
Purity is lower.In addition patent " technique of fractionally extracting natural VE by supercritical CO 2 fluid " (application number
02115535.6) " supercritical fluid extraction and the method (application number 00103260.7) of concentrated natural vitamin E have with patent
There are complex operation, the excessively high disadvantage of cost.Said extracted concentrated natural vitamin E and squalene related work both for
Respective method expansion research, there is significant limitations, especially in the preparation side of high-purity squalene and natural VE
Face is still difficult to reach.
Super molecular compound of the cyclodextrin as a kind of " external hydrophilicity, internal drainage ", can pass through intermolecular force and ruler
Very little, different guest molecule forms different inclusion complexes, so that certain ingredients in mixed system are carried out selectivity
Separation, wherein beta-cyclodextrin production cost is low, and stability is good, and molecular structure and physical property are more advantageous to and certain organic matters point
Son formed inclusion complex, have the characteristics that it is easy to operate, environmentally protective, to be widely used in isolation technics.
Summary of the invention
The purpose of the present invention is to overcome the deficiency in the prior art, provides the separation side of a kind of squalene and natural VE
Method.
To achieve the goals above, the present invention adopts the following technical scheme:
A kind of separation method of squalene and vitamin E, it is characterised in that using beta-cyclodextrin inclusion separation squalene and
Natural VE realizes the separation of squalene and natural VE.
Above-mentioned separation method specifically includes the following steps: (1) inclusion complex preparation: in the round-bottomed flask of 100 mL, will
Beta-cyclodextrin is added in deionized water, and stirring prepares saturated solution in water-bath, and squalene and vitamin E/ethanol are mixed
Solution is added in the aqueous solution of beta-cyclodextrin, is reacted under constant temperature；Reactant is refrigerated into 24 h in 4 DEG C of conditions, vacuum filtration adds
Enter anhydrous ether washing inclusion complex three times, to remove remaining squalene and vitamin E, resulting white filter cake cryogenic vacuum
It is dry；
(2) separation of inclusion complex: inclusion complex addition solvent is extracted, filtrate is collected by filtration, high-efficient liquid phase analysis is surveyed
The content of fixed wherein squalene and natural VE.
Preferably, the temperature of water-bath is 35 DEG C in above-mentioned separation method, duration of oscillation is 4 h.
Preferably, in above-mentioned separation method, in the squalene and vitamin E/ethanol mixed solution, spiny dogfish
Alkene and vitamin E are equimolar.
Preferably, in above-mentioned separation method, the squalene and vitamin E/ethanol mixed solution and beta-cyclodextrin
Molar ratio be 1:4-1:1.
Preferably, the extractant is ethyl alcohol in above-mentioned separation method.
It, can be by being evaporated under reduced pressure, depressurizing in obtained filtrate after inclusion complex extraction is filtered in above-mentioned separation method
The separation of the methods of rotary evaporation is concentrated to get natural VE and squalene mixture, then mixture is rejoined saturation
The preparation that inclusion complex is carried out in cyclodextrin solution, repeats above-mentioned process several times, high concentration squalene can be obtained.The extractant of recycling
It can be applied to inclusion complex of the extraction containing natural VE and squalene again；Meanwhile using same method to cleaning solution
In natural VE be concentrated under reduced pressure, the natural VE of high-purity can be obtained in the separation of multiple inclusion.
The technology is right using the molecular recognition mechanism of supramolecular chemistry based under the weak interaction power drive of cyclodextrin
The difference of the molecular structure of natural VE and squalene, equimolar is more subconditional than guest molecule to vie each other down, host molecule
Beta-cyclodextrin, which is easier to be inclined to, forms stable inclusion complex with guest molecule squalene, under cooling, with crystal form
It is precipitated, and most of natural VE then stays in the solution, to realize efficiently separating for natural VE and squalene.
Compared with prior art, the method have the advantages that:
1, separation process conditions of the invention are mild, easy to operate, avoid Conventional espresso and cause high energy consumption, easily to material
Generate the problems such as cost caused by high-temperature oxydation and supercritical extract is excessively high, complicated for operation.
2, the recyclable recycling of the beta-cyclodextrin that the present invention uses, and repeat performance is stablized, cost recovery price
It is cheap.
3, separating technology of the invention is environmentally protective, and using beta-cyclodextrin as inclusion main body, extractant is nontoxic nothing
Harmful ethyl alcohol.
4, products obtained therefrom purity is high of the present invention.The present invention is by the molar ratio of research material, heating temperature and repeats inclusion
Influence of the factors such as number to inclusion separating resulting, thus obtain Optimum separation condition, repeat inclusion separating technology 2 times or more,
The natural VE and squalene of high-purity can be obtained.
Specific embodiment
The present invention will be further explained with reference to the examples below, but scope of protection of the present invention is not limited thereto.
Embodiment 1:
1.135g β-CD (1mmol) is added to deionized water to be made in saturated solution, is placed in 35 DEG C of stirred in water bath,
After β-CD all dissolution, the mixture solution of 0.0822g squalene and 0.0860g vitamin E is added dropwise to β-CD
Aqueous solution in.Revolving speed reacts 6h under conditions of being 180 rpm, reactant is then freezed 24 h in 4 DEG C of conditions, vacuum is taken out
Filter, and filter cake, low-temperature vacuum drying are washed with deionized water and n-hexane.Inclusion complex is extracted using solvent extraction,
At room temperature, inclusion complex is added in 25ml dehydrated alcohol and is extracted, stir 2 h, extracted by filtration under magnetic agitation effect
Liquid, then the method by being evaporated under reduced pressure obtain the higher squalene of purity and natural VE, can obtain purity by HPLC analysis
Respectively 87% and 83%, separation factor 4.001.
Embodiment 2:
1.135g β-CD (1mmol) is added to deionized water to be made in saturated solution, is placed in 45 DEG C of stirred in water bath,
After β-CD all dissolution, the mixture solution of 0.0822g squalene and 0.0860g vitamin E is added dropwise to β-CD
Aqueous solution in.Revolving speed reacts 6h under conditions of being 180 rpm, reactant is then freezed 24 h in 4 DEG C of conditions, vacuum is taken out
Filter, and filter cake, low-temperature vacuum drying are washed with deionized water and n-hexane.Inclusion complex is extracted using solvent extraction,
At room temperature, inclusion complex is added in 25ml dehydrated alcohol and is extracted, stir 2 h, extracted by filtration under magnetic agitation effect
Liquid, then the method by being evaporated under reduced pressure obtain the higher squalene of purity and natural VE, can obtain purity by HPLC analysis
For 84% and 79%, separation factor 3.495.
Embodiment 3:
1.135g β-CD (1mmol) is added to deionized water to be made in saturated solution, is placed in 45 DEG C of stirred in water bath,
After β-CD all dissolution, the mixture solution of 0.1233g squalene and 0.1290g vitamin E is added dropwise to β-CD
Aqueous solution in.Revolving speed reacts 6h under conditions of being 180 rpm, reactant is then freezed 24 h in 4 DEG C of conditions, vacuum is taken out
Filter, and filter cake, low-temperature vacuum drying are washed with deionized water and n-hexane.Inclusion complex is extracted using solvent extraction,
At room temperature, inclusion complex is added in 25ml dehydrated alcohol and is extracted, stir 2 h, extracted by filtration under magnetic agitation effect
Liquid, then the method by being evaporated under reduced pressure obtain the higher squalene of purity and natural VE, can obtain purity by HPLC analysis
For 81% and 77%, separation factor 3.415.
Embodiment 4:
1.135g β-CD (1mmol) is added to deionized water to be made in saturated solution, is placed in 35 DEG C of stirred in water bath,
After β-CD all dissolution, the mixture solution of 0.0822g squalene and 0.0860g vitamin E is added dropwise to β-CD
Aqueous solution in.Revolving speed reacts 6h under conditions of being 180 rpm, reactant is then freezed 24 h in 4 DEG C of conditions, vacuum is taken out
Filter, and filter cake, low-temperature vacuum drying are washed with deionized water and n-hexane.Inclusion complex is extracted using solvent extraction,
At room temperature, inclusion complex is added in 25ml dehydrated alcohol and is extracted, stir 2 h, extracted by filtration under magnetic agitation effect
Liquid, then the method by being evaporated under reduced pressure obtain the higher squalene of purity and natural VE, and inclusion is isolated again
Saturation β-CD is added in squalene and natural VE, repeats above inclusion technique 2 times, finally high-purity spiny dogfish can be obtained in concentration
Alkene and natural VE, can obtain purity by HPLC analysis is 93% and 91%.
Claims (1)
1. the separation method of a kind of squalene and vitamin E, it is characterised in that using beta-cyclodextrin inclusion separation squalene and dimension
Raw element E, realizes the separation of squalene and natural VE；
The following steps are included: the preparation of (1) inclusion complex: in the round-bottomed flask of 100 mL, beta-cyclodextrin being added to deionization
In water, stirring prepares saturated solution in water-bath, and squalene and vitamin E/ethanol mixed solution are added to beta-cyclodextrin
In aqueous solution, reacted under constant temperature；Reactant is refrigerated into 24 h in 4 DEG C of conditions, vacuum filtration is added anhydrous ether and washs inclusion complex
Three times, to remove remaining squalene and vitamin E, resulting white filter cake low-temperature vacuum drying；
(2) separation of inclusion complex: inclusion complex addition solvent is extracted, filtrate is collected by filtration, high-efficient liquid phase analysis measures it
The content of middle squalene and natural VE；
The temperature of water-bath is 35 DEG C, and duration of oscillation is 4 h；
In the squalene and vitamin E/ethanol mixed solution, squalene and vitamin E are equimolar；
The extractant is ethyl alcohol.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101830770A (en) * | 2010-06-02 | 2010-09-15 | 天津大学 | Method for extracting squalene from vegetable oil deodorized distillate |
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| KR100832796B1 (en) * | 2006-08-23 | 2008-05-27 | 주식회사 마크로케어 | Method for extraction of squalene or squalane using cyclodextrin and cosmetic composition containing squalene or squalane-cyclodextrin inclusion complex prepared thereby |
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| CN101830770A (en) * | 2010-06-02 | 2010-09-15 | 天津大学 | Method for extracting squalene from vegetable oil deodorized distillate |
Non-Patent Citations (1)
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| 维生素E 、β-环糊精包合物的制备工艺研究;范晶等;《亚太传统医药》;20090331;第5卷(第3期);第27-29页 |
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