CN106187980A - Natural low content vitamin E is that raw material extracts natural Vitamin E and the method and apparatus of Squalene - Google Patents
Natural low content vitamin E is that raw material extracts natural Vitamin E and the method and apparatus of Squalene Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/04—Purification; Separation; Use of additives by distillation
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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
- C07C7/12—Purification; Separation; Use of additives by adsorption, i.e. purification or separation of hydrocarbons with the aid of solids, e.g. with ion-exchangers
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/14—Purification; Separation; Use of additives by crystallisation; Purification or separation of the crystals
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- 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 a kind of natural low content vitamin E is that raw material extracts natural Vitamin E and the method for Squalene, and its step includes: 1) through first order rectification, natural low content vitamin E raw material is separated into the light component of the first order and first order heavy constituent；2) by step 1) in first order heavy constituent be separated into the light component in the second level and second level heavy constituent through second level rectification；3) by step 2) in the second level light component use non-polar organic solvent freezing and crystallizing and be filtrated to get filter cake and filtrate, wherein, filtrate obtains high-load Squalene through chromatographic isolation；By step 2) in second level heavy constituent be separated into the light component of the third level and third level heavy constituent through molecular distillation, wherein, the light component of the third level includes that natural Vitamin E, third level heavy constituent include high boiling point plant asphalt.The preparation method step of the present invention is simple, low cost, prepares yield high, it is adaptable to industrialized production, has the strongest practicality.
Description
Technical field
The present invention relates to the separation preparation field of industrial chemicals, be raw material particularly to a kind of natural low content vitamin E
Extract natural Vitamin E and the method and apparatus of Squalene.
Background technology
Squalene is the most undersaturated hydrocarbon compound of one, and Squalene chemical name is 2,6,10,15,19,23-six
Methyl-2,6,10,14,18,22-tetracosa carbon six alkene, molecular formula is C30H50, belong to terpenoid.Squalene is widely distributed
In animal and plant body, in view of the chemical constitution that it is special, Squalene has antioxidation, promotes that skin health, promotion cardiovascular are good for
Many effects such as health, assisting in preventing and treating tumor, raising human body hypoxia-bearing capability, are widely used in medicine, cosmetic field, in recent years
Application in field of health care products the most progressively extends.
Squalene on market is mainly extraction from the liver oil of deepwater shark, and current deepwater shark quantity progressively subtracts
Few, Some Species is endangered, causes this source the deficientest, so finding new Squalene resource and to develop it corresponding
Extracting method just seems extremely important.About the excavation of Squalene resource, there is a lot of report in the last few years, especially took off with vegetable oil
Extracting the most extensive in smelly distillation, deodorization distillate is the process byproducts during grease deodorization, is plant squalene
Good source.The key component of deodorization distillate is: free fatty, glyceride, tocopherol, sterol, sterol ester, Squalene,
The plant hydrocarbon of non-Squalene and a small amount of pigment, polymer etc., Squalene content has fluctuated with the kind difference of vegetable oil, its
In the highest with content in olive oil deodorization distillate, from its deodorization distillate extract Squalene in Europe industry metaplasia
Produce.But olive oil price is higher, being not main large oil plant, limits throughput, so the Squalene in olive oil source is not
Be enough to the Squalene substituted completely to shark source, it is therefore necessary to exploitation is carried by the deodorization distillate of other vegetable oil material
The method taking Squalene.But it is the most again irrational for individually extracting Squalene from plant oil deodorizing distillate, this
Be because deodorization distillate Squalene content relatively low and be mainly used to extract the i.e. vitamin E of the higher tocopherol of added value (VE),
The nutrients such as plant sterol.
In order to solve this problem, prior art takes such a way:
U.S. Patent application (publication date: January 30, publication number: US5487817 in 1996) points out that sunflower, soybean oil take off
Equal a certain amount of Squalene of content in smelly distillation, but not using Squalene as purpose extract, but mainly extract life
Educate phenol and plant sterol.
Chinese patent application (publication date: June 8, publication number: CN102089263A in 2011) discloses a kind of with plant
Oil deodorization distillate or condensates of physical refining are raw material, through the technique such as the most transesterification, multi-step pressure reduction distillation, cold crystallization
The method extracting Squalene, process is relatively complicated, and its main purpose is also to extract tocopherol and plant sterol, Squalene content and
Yield is not reported.
Chinese patent (publication date: JIUYUE in 2010 15 days, publication number: CN101830770B) discloses a kind of from vegetable oil
Deodorization distillate extracts the Squalene method that simultaneously reclaims vitamin E and plant sterol, the method will through saponification, extract, point
The son step such as distillation, cold analysis, multiple-stage solvent extraction, the technique such as wherein saponification, extraction, multiple-stage solvent extraction is loaded down with trivial details, organic solvent
Consumption is big, the Squalene response rate is low, and large-scale production feasibility is the highest.
Chinese patent application (publication date: May 21, publication number: CN103804337A in 2014) discloses a kind of multistage
Countercurrently liquid-liquid extraction method extracts vitamin E and the method for Squalene, the method by esterification, glycerol rhizolomy, molecular distillation and multistage
Countercurrently step separating natural VE and the Squalene, equally its complex steps such as liquid-liquid extraction, solvent consumption is big, and efficiency is low, cost
Height, large-scale production feasibility is the highest.
Chinese patent application (publication date: March 2, publication number: CN105367370A in 2016) discloses a kind of from natural
VE heel extracts the method for Squalene, to extract the heel after natural VE as raw material, utilizes saponification, rectification and silica gel column chromatography phase
In conjunction with technique, prepare the Squalene of high-load.This patent points out that, during extracting natural VE, a Squalene part is enriched with
In the fatty acid methyl ester being distilled out, another part remains in the natural VE of extraction, especially the natural VE of low content
(30～50%), the natural VE (70%) of high-load the most without Squalene, is all distilled out and is enriched in fatty acid methyl
In ester.Patent process route is relatively reasonable, and initiation material is chosen proper, and separation costs is low, and is prone to industrialization amplification, but patent
In raw material sources more special, need to utilize the heel of natural VE, but also needing be the heel after extraction transition that methylates, and enters
One step limits its versatility, and range of application is narrow.
Chinese patent application (publication date: November 4, publication number: CN105016956A in 2015) discloses a kind of from richness
The method extracting Squalene in raw material containing Squalene, the method includes the described raw material rich in Squalene is carried out Crystallization Separation
To obtain solid phase and liquid phase, described liquid phase is evaporated successively, molecular distillation and chromatographic isolation, wherein, described richness
Raw material containing Squalene contains the Squalene of 5～30 weight %, the sterol of 10～40 weight %.This patent is mentioned rich in angle
The raw material sources of zamene are the most special, need from plant oil deodorizing distillate by esterification, transesterification, solvent crystallization, molecule
Distillation and chromatographic isolation obtain the natural VE of high-load and rich in the raw material of Squalene.Similarly, since high to ingredient requirement, application
Narrow range.
It will be seen that at present plant squalene extract use first raw material is such as esterified, ester exchange, saponification
After pretreatment, then use the separation means such as molecular distillation, rectification, solvent extraction, chromatograph.Therefore generally there is process in these methods
Loaded down with trivial details, the Squalene response rate is low, the problem that separation costs is high.In addition, portion of techniques combines self distinctive raw material data,
Such as utilize the characteristic rich in Squalene in the heel after extracting natural VE, or the Squalene raw material that content is higher, utilize essence
Evaporate or the means angle of departure zamene such as molecular distillation-chromatograph, although efficiency can be solved, but these methods do not have general
Property, narrow application range.
Summary of the invention
Present invention aim to provide a kind of natural low content vitamin E is that raw material extracts natural Vitamin E and angle
The method and apparatus of zamene, the method step is simple, low cost, and it is high to prepare yield, it is adaptable to industrialized production.
For achieving the above object, the technical solution used in the present invention is:
A kind of natural low content vitamin E is that raw material extracts natural Vitamin E and the method for Squalene, and described extraction is natural
The method of vitamin E and Squalene comprises the steps:
1) natural low content vitamin E raw material is separated into the light component of the first order and first order restructuring through first order rectification
Point, the vacuum of first order rectification is 20～40Pa, heating-up temperature is 200～240 DEG C, tower top temperature is 160～180 DEG C；Its
In, the light component of the first order includes low boiling fatty acid ester, low boiling plant hydrocarbon and low carbon chain alcohol, low carbon chain aldehyde and low carbon chain ketone,
First order heavy constituent includes Squalene, natural Vitamin E, high boiling point fatty acid ester, sterol and high boiling point plant hydrocarbon；
2) by step 1) in first order heavy constituent through second level rectification be separated into the light component in the second level and the second level weight
Component, the vacuum of second level rectification is 10～20Pa, heating-up temperature is 240～280 DEG C, tower top temperature is 220～240 DEG C；
Wherein, the light component in the second level includes Squalene, high boiling point plant hydrocarbon and high boiling point fatty acid ester, and second level heavy constituent includes natural
Vitamin E and sterol；
3) by step 2) in the second level light component use non-polar organic solvent freezing and crystallizing and be filtrated to get filter cake and
Filtrate, wherein, filtrate is reconcentration after chromatographic isolation, obtains the Squalene that content is 80～95wt%；By step 2) in
Second level heavy constituent is separated into the light component of the third level and third level heavy constituent through molecular distillation, and the vacuum of molecular distillation is 1
～20Pa vacuum, heating-up temperature are 180～200 DEG C；Wherein, the light component of the third level include content be 50～80wt% natural
Vitamin E, third level heavy constituent includes high boiling point plant asphalt.
Wherein: containing percetage by weight in low content natural Vitamin E raw material is 5～the natural Vitamin E of 50%, weight
The sterol that percent is 5～the Squalene of 30%, percetage by weight are 1～20%, surplus is other inevitable impurity.
Preferably, described step 3) in, described non-polar organic solvent is in normal hexane, normal heptane or petroleum ether
Plant, and the weight ratio of described non-polar organic solvent and the light component in the second level is 0.5～5:1；Freezing and crystallizing is with 1～5 DEG C/h
Rate of temperature fall be cooled to-5～30 DEG C, then growing the grain 1～24h.
It is furthermore preferred that described step 3) in, described non-polar organic solvent is in normal hexane, normal heptane or petroleum ether
Plant, and the weight ratio of described non-polar organic solvent and the light component in the second level is 1～3:1；Freezing and crystallizing is with 3～4 DEG C/h
Rate of temperature fall is cooled to-5～10 DEG C, then growing the grain 5～15h.
Preferably, described step 3) in, described chromatographic isolation is that adsorption chromatography separates, and fixing is 100～200 mesh nonbondings mutually
Closing at least one in silica gel or aluminium oxide, described fixing and the light component in the described second level weight ratio is 1:10～1:2；Stream
Moving and be followed successively by the first eluant, the second eluant and the 3rd eluant mutually, described first eluant is normal hexane, normal heptane, stone
One in oil ether, described 3rd eluant is the one in ethyl acetate, propyl acetate, butyl acetate, described second eluting
Agent is the first eluant and the 3rd eluant mixtures of eluents, and wherein, the volume of the 3rd eluant accounts for mixtures of eluents cumulative volume
1～20%.
It is furthermore preferred that described step 3) in, use in described first eluant and refrigeration crystallization process is nonpolar organic
Solvent phase is same.
A kind of said method extracts the equipment of Squalene, including rectification tower system, crystallization kettle and is connected with crystallization kettle discharging opening
Filter, rectification tower system upper outlet is connected with the charging aperture of crystallization kettle, and rectification tower system lower part outlet enters with molecular still
Material mouth is connected, and described rectification tower system is the two stage rectification tower arranged continuously, wherein, the lower part outlet of first order rectifying column and second
The charging aperture of level rectifying column is connected, and the filtrate (liquid of described filter is connected with chromatography column.
The discovery that applicant is creative, first carries out natural VE (vitamin E) and the enrichment of Squalene during extracting, can
With the carrying out of beneficially crystallisation by cooling, it is directly over crystallisation by cooling removing major part impurity, and can solve directly to carry out color
It is big that spectrum separates the solvent consumption caused, and the shortcoming that energy consumption is high is cost-effective；Meanwhile, the raw material of the present invention is a large amount of on market
The natural low content VE existed, is directly separated by the technique of two-stage rectification, molecular distillation, crystallisation by cooling and chromatographic isolation
Obtain natural VE and the Squalene of high-load (80～95wt%) of high-load (50～80wt%), rectification process amount can be played
Greatly, feature that separation costs is low, the advantage of efficient selective when can play again chromatographic isolation, thus improve greatly and separate effect
Rate, reduces cost, can be used for large-scale industrial production, have the strongest practicality.
Accompanying drawing explanation
Fig. 1 is the process flow diagram of the present invention；
Fig. 2 is the equipment connection diagram of the present invention；
Wherein, 1-raw material, the light component of the 2-first order, 3-first order heavy constituent, the light component in the 4-second level, the restructuring of the 5-second level
Point, the light component of the 6-third level, 7-third level heavy constituent, 8-filter cake, 9-filtrate, 10-Squalene, T1-first order rectifying column, T2-
Second level rectifying column, T3-molecular still, T4-crystallization kettle, T5-filter, T6-chromatography column, T7-concentrator.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described in further detail, it is simple to more clearly understands the present invention, but it
The present invention is not constituted restriction.
The raw material that the present invention uses is commercial goods, and the most natural low content raw material is, Fujian Glan Buddhist nun's biological engineering
The T25/T50 of limited company's sale or the natural Vitamin E of other content；
As depicted in figs. 1 and 2, first low content natural VE raw material is carried out first order rectification in first order rectifying column T1,
Removing the light component of the first order, wherein the light component of the first order includes that boiling point is less than the low boiling fatty acid ester of 200～240 DEG C, low boiling
Point plant hydrocarbon and low carbon chain alcohol, low carbon chain aldehyde and low carbon chain ketone, first order heavy constituent includes Squalene, natural Vitamin E, high boiling
Point fatty acid ester, sterol and high boiling point plant hydrocarbon.Then first order heavy constituent 3 is carried out the second level in the rectifying column T2 of the second level
Rectification, is separated into the light component in the second level and second level heavy constituent, and wherein, the light component in the second level includes that Squalene, boiling point are higher than 200
～the high boiling point plant hydrocarbon of 240 DEG C and high boiling point fatty acid ester, second level heavy constituent includes natural Vitamin E and sterol.By
Two grades of heavy constituents 5 carry out molecular distillation in molecular still T3, obtain the light component of the third level 6 and third level heavy constituent 7, and the 3rd
The light component of level includes the natural Vitamin E that content is 60～70wt%, and third level heavy constituent includes high boiling point plant asphalt.And
The light component in the second level 4 uses non-polar organic solvent freezing and crystallizing filtration in filter T5 in crystallization kettle T4, is filtered
Cake 8 and filtrate 9, wherein, filtrate 9 first passes through after chromatography column T6 eluting separates, then eluent is concentrated to give content is 80
～the Squalene of 95wt%.
Embodiment 1
1) first order rectification
Low content natural VE raw material (VE content 25.5%, Squalene 16.0%) is delivered continuously to the speed of 300mL/h
In first order rectifying column T1, the heating-up temperature of period reboiler maintains 240 DEG C, and holding tower top pressure is between 40Pa simultaneously,
Tower top temperature 180 DEG C, regulates suitable reflux ratio.After the raw material feed liquid carrying about 2kg to feed points, collect about 860g's
The light component of the first order 2, obtains the first order heavy constituent 3 that 1135g contains Squalene and natural VE simultaneously.
2) second level rectification
First order heavy constituent 3 is delivered continuously in the rectifying column T2 of the second level with the speed of about 150mL/h, period reboiler
Heating-up temperature maintain 280 DEG C, tower top temperature 240 DEG C, regulate suitable reflux ratio, keep tower top pressure to exist simultaneously
20Pa.After the raw material feed liquid carrying about 500g to feed points, collect the light component in the second level 4 of about 220g, wherein Squalene
Content 54.7%；Obtain the 275g second level heavy constituent 5 containing natural VE simultaneously.
3) molecular distillation
Second level heavy constituent 5 is delivered continuously in molecular still T3 with the speed of 50mL/h, keeps molecular still
Vacuum under the temperature conditions of 5Pa and 200 DEG C.The condensed light component of the third level 6 and 10g the 3rd of 90g is collected after 2h
Level heavy constituent 7, wherein in the light component of the third level 6, the content of natural VE is about 65.2%.
4) freezing and crystallizing
After light for 200g second level component 4 being dissolved in 100g normal hexane, crystallization kettle T4 is first preheated to 55～60 DEG C
Make dissolving complete, be then cooled to-5 DEG C with the rate of temperature fall of 4 DEG C/h, then after growing the grain 5h, filter in filter T5, filtered
Cake 8 and filtrate 9, be wherein mainly the component such as plant hydrocarbon and wax in filter cake 8.Filtrate 9 is passed through in chromatography column T6.Take 100～
200 mesh nonbonding silica gel 250g add in chromatography column T6, add a small amount of normal hexane, are filled into chromatographic column, with 3 times of chromatographies
The normal hexane of column volume is compacted and balances silicagel column, takes 200ml filtrate 9 loading in chromatography column T6, uses successively after loading
First, second and third elution, wherein the first eluent be normal hexane, the second eluent be the butyl acetate-normal hexane of 10%
Mixed solution (v/v), the 3rd eluent is butyl acetate, the eluent of collection angle zamene fraction, is concentrated by concentrator T7
After obtain the Squalene that content is 94.2%, the response rate is 88.2%.
Embodiment 2
Identical with the method for embodiment 1, difference is: in step 1) in, low content natural VE raw material (VE content
10.5%, Squalene 12.3%), the heating-up temperature of first order rectification maintains 200 DEG C, keep simultaneously tower top pressure 20Pa it
Between, tower top temperature 160 DEG C.In step 2) in the heating-up temperature of second level rectification maintain 240 DEG C, tower top temperature 220 DEG C, tower top
Pressure is 10Pa, and the light component in the second level 4 obtained, wherein Squalene content is 48.2%.In step 3) in, keep molecular distillation
The vacuum of device, under the temperature conditions of 20Pa and 180 DEG C, collects the light component of the third level 6, wherein in the light component of the third level 6 after 2h
The content of natural VE is about 57.4%.In step 4) in, after light for 200g second level component 4 is dissolved in 200g normal heptane,
First being preheated to 55～60 DEG C in crystallization kettle T4 makes dissolving complete, is then cooled to 30 DEG C, then growing the grain with the rate of temperature fall of 3 DEG C/h
After 15h, filter in filter T5, obtain filter cake 8 and filtrate 9.Filtrate 9 is passed through in chromatography column T6.Take 100～200 mesh
Nonbonding silica gel 250g adds in chromatography column T6, adds a small amount of normal heptane, is filled into chromatographic column, with 3 times of chromatography cylinders
Long-pending normal hexane is compacted and balances silicagel column, takes 200ml filtrate 9 loading in chromatography column T6, after loading successively with first,
Two, three elution, wherein the first eluent be normal heptane, the second eluent be the mixing of the ethyl acetate-normal heptane of 8%
Solution (v/v), the 3rd eluent is ethyl acetate, the eluent of collection angle zamene fraction, obtains after being concentrated by concentrator T7
Content is the Squalene of 86.2%, and the response rate is 91.2%.
Embodiment 3
Identical with the method for embodiment 1, difference is: in step 1) in, low content natural VE raw material (VE content 50%,
Squalene 5%), the heating-up temperature of first order rectification maintains 230 DEG C, keeps tower top pressure in 30Pa, tower top temperature 170 simultaneously
℃.In step 2) in, the heating-up temperature of second level rectification maintains 250 DEG C, tower top temperature 230 DEG C, and tower top pressure, at 15Pa, obtains
The light component in the second level 4 arrived, wherein Squalene content is 40.2%.In step 3) in, keep the vacuum of molecular still at 1Pa
Under temperature conditions with 190 DEG C, collecting the light component of the third level 6 after 2h, wherein in the light component of the third level 6, the content of natural VE is about
It is 78.7%.In step 4) in, after light for 200g second level component 4 is dissolved in 600g petroleum ether, the most pre-in crystallization kettle T4
Heat makes dissolving complete, after being then cooled to 0 DEG C, then growing the grain 1h with the rate of temperature fall of 1 DEG C/h, in filter T5 to 55～60 DEG C
Filtering, obtain filter cake 8 and filtrate 9, filtrate 9 is passed through in chromatography column T6.Take 100～200 mesh nonbonding silica gel 250g to add
In chromatography column T6, add a small amount of petroleum ether, be filled into chromatographic column, be compacted with the petroleum ether of 3 times of chromatographic column volumes and put down
Weighing apparatus silicagel column, takes 200ml filtrate 9 loading in chromatography column T6, uses first, second and third elution after loading successively, its
In the first eluent be petroleum ether, the second eluent be the mixed solution (v/v) of the propyl acetate-petroleum ether of 15%, the 3rd washes
De-liquid is propyl acetate, the eluent of collection angle zamene fraction, obtains, after being concentrated by concentrator T7, the angle that content is 80.2%
Zamene, the response rate is 90.3%.
From above-described embodiment it can be seen that the Squalene prepared by the method for the present invention, raw material is easy to get from commercially available
Low content natural VE raw material, natural VE in raw material and Squalene content are not had too high requirement, the suitability is strong.Further, exist
In the case of using less organic solvent, while obtaining high-load Squalene, moreover it is possible to obtain high-load natural VE, save into
This.After freezing and crystallizing completes, directly filtrate can be concentrated to give the response rate higher, the Squalene that content is lower slightly, it is also possible to
Filtrate is obtained the higher Squalene of content after chromatography column separates.
On the premise of without departing from claims of the present invention protection domain, it is adjusted also belonging to the numerical value in embodiment
In the scope of protection of the invention.
Claims (6)
1. a natural low content vitamin E is that raw material extracts natural Vitamin E and the method for Squalene, it is characterised in that: institute
The method stating extraction natural Vitamin E and Squalene comprises the steps:
1) natural low content vitamin E raw material is separated into the light component of the first order and first order heavy constituent through first order rectification,
The vacuum of first order rectification is 20～40Pa, heating-up temperature is 200～240 DEG C, tower top temperature is 160～180 DEG C；Wherein,
The light component of the first order includes low boiling fatty acid ester, low boiling plant hydrocarbon and low carbon chain alcohol, low carbon chain aldehyde and low carbon chain ketone, first
Level heavy constituent includes Squalene, natural Vitamin E, high boiling point fatty acid ester, sterol and high boiling point plant hydrocarbon；
2) by step 1) in first order heavy constituent be separated into the light component in the second level and second level heavy constituent through second level rectification,
The vacuum of second level rectification is 10～20Pa, heating-up temperature is 240～280 DEG C, tower top temperature is 220～240 DEG C；Wherein,
The light component in the second level includes Squalene, high boiling point plant hydrocarbon and high boiling point fatty acid ester, and second level heavy constituent includes that natural dimension is raw
Element E and sterol；
3) by step 2) in the second level light component use non-polar organic solvent freezing and crystallizing and be filtrated to get filter cake and filtrate,
Wherein, filtrate is reconcentration after chromatographic isolation, obtains the Squalene that content is 80～95wt%；By step 2) in the second level
Heavy constituent is separated into the light component of the third level and third level heavy constituent through molecular distillation, and the vacuum of molecular distillation is 1～20Pa
Vacuum, heating-up temperature are 180～200 DEG C；Wherein, the light component of the third level includes the natural complex that content is 50～80wt%
E, third level heavy constituent includes high boiling point plant asphalt.
Wherein: containing percetage by weight in natural low content vitamin E raw material is 5～the natural Vitamin E of 50%, weight percent
The sterol that number is 5～the Squalene of 30%, percetage by weight are 1～20%, surplus is other inevitable impurity.
2. being that raw material extracts natural Vitamin E and the method for Squalene according to the natural low content vitamin E of claim 1, it is special
Levy and be: described step 3) in, described non-polar organic solvent is the one in normal hexane, normal heptane or petroleum ether, and described
Non-polar organic solvent is 0.5～5:1 with the weight ratio of the light component in the second level；Freezing and crystallizing is with the rate of temperature fall of 1～5 DEG C/h
It is cooled to-5～30 DEG C, then growing the grain 1～24h.
3. it is that raw material extracts natural Vitamin E and the method for Squalene according to the natural low content vitamin E of claim 1 or 2, its
It is characterised by: described step 3) in, described non-polar organic solvent is the one in normal hexane, normal heptane or petroleum ether, and institute
The weight ratio stating non-polar organic solvent and the light component in the second level is 1～3:1；Freezing and crystallizing is with the rate of temperature fall of 3～4 DEG C/h
It is cooled to-5～10 DEG C, then growing the grain 5～15h.
4. it is that raw material extracts natural Vitamin E and the method for Squalene according to the natural low content vitamin E of claim 1 or 2, its
It is characterised by: described step 3) in, described chromatographic isolation is that adsorption chromatography separates, and fixing is 100～200 mesh nonbonding silica gel mutually
Or at least one in aluminium oxide, described fixing and the light component in the described second level weight ratio is 1:10～1:2；Flow interdependent
Secondary is the first eluant, the second eluant and the 3rd eluant, and described first eluant is in normal hexane, normal heptane, petroleum ether
One, described 3rd eluant is the one in ethyl acetate, propyl acetate, butyl acetate, and described second eluant is
One eluant and the 3rd eluant mixtures of eluents, wherein, the volume of the 3rd eluant account for mixtures of eluents cumulative volume 1～
20%.
5. being that raw material extracts natural Vitamin E and the method for Squalene according to the natural low content vitamin E of claim 4, it is special
Levy and be: described step 3) in, described first eluant is identical with the non-polar organic solvent used in refrigeration crystallization process.
6. as according to any one of Claims 1 to 5, method extracts natural Vitamin E and an equipment for Squalene, including essence
Evaporate tower system, crystallization kettle and the filter being connected with crystallization kettle discharging opening, the charging aperture phase of rectification tower system upper outlet and crystallization kettle
Even, rectification tower system lower part outlet is connected with molecular still charging aperture, it is characterised in that: described rectification tower system is to arrange continuously
Two stage rectification tower, wherein, the lower part outlet of first order rectifying column is connected with the charging aperture of second level rectifying column, and described filter
Filtrate (liquid be connected with chromatography column.
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| CN115650943A (en) * | 2022-09-13 | 2023-01-31 | 宜春大海龟生命科学有限公司 | Method for enriching polyunsaturated fatty acid ester, squalene, natural vitamin E and phytosterol from plant deodorized distillate |
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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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| CN115650943A (en) * | 2022-09-13 | 2023-01-31 | 宜春大海龟生命科学有限公司 | Method for enriching polyunsaturated fatty acid ester, squalene, natural vitamin E and phytosterol from plant deodorized distillate |
| CN115650943B (en) * | 2022-09-13 | 2024-02-27 | 宜春大海龟生命科学股份有限公司 | Method for enriching polyunsaturated fatty acid ester, squalene, natural vitamin E and phytosterol from plant deodorization distillate |
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