CN105016956B - A kind of method for extracting squalene - Google Patents
A kind of method for extracting squalene Download PDFInfo
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- CN105016956B CN105016956B CN201410165539.2A CN201410165539A CN105016956B CN 105016956 B CN105016956 B CN 105016956B CN 201410165539 A CN201410165539 A CN 201410165539A CN 105016956 B CN105016956 B CN 105016956B
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Abstract
The present invention relates to a kind of method for extracting squalene, this method includes carrying out Crystallization Separation to obtain solid phase and liquid phase by the raw material rich in squalene, the liquid phase is evaporated successively, molecular distillation and chromatographic isolation, wherein, the raw material rich in squalene contains 5 30 weight % squalene, 10 40 weight % sterol.Method disclosed by the invention can obtain the higher squalene of purity, while obtaining purity higher vitamin E and phytosterol, take full advantage of raw material, material consumption energy consumption is reduced to a greater extent.
Description
Technical field
The present invention relates to a kind of method for extracting squalene.
Background technology
Squalene is a kind of highly undersaturated hydrocarbon compound, and its systematic naming method is 2,6,10,15,19,23- pregnancy
Base -2,6, the alkene of 10,14,18,22- tetracosa carbon six, molecular formula is C30H50, belongs to terpenoid.Squalene is widely distributed
In animal and plant body, in view of its special chemical constitution, squalene has anti-oxidant, promotion skin health, promotes cardiovascular be good for
Many effects such as health, assisting in preventing and treating tumour, raising human body hypoxia-bearing capability, are widely used in medicine, cosmetic field, in recent years
Also progressively to be extended in the application of field of health care products.
The squalene of in the market is mainly extracted from the liver oil of deepwater shark, and current deepwater shark quantity progressively subtracts
Few, Some Species are endangered, cause this source increasingly deficient, so finding new squalene resource and to develop its corresponding
Extracting method just seems extremely important.
On the excavation of squalene resource, there are many reports in the last few years, following four classes method can be divided into：
First kind method is to transform microorganism by the means of genetic engineering, can produce or be enriched with squalene.Such as
CN102787074A disclose it is a kind of can produce the microalgae bacterial strain of squalene, its squalene content reach 1g/100g dry weights give birth to
Material；In patent application CN103266137A, by the way that squalene synthetase gene is cloned and is total in Escherichia coli
Expression, constructing a kind of can synthesize the recombinant bacterial strain of squalene.However, the squalene of Institute of Micro-biology's production of genetic engineering transformation is such as
Fruit uses in food or health products, and its security is also to be assessed.
Equations of The Second Kind method is extracted from Special Category plant, such as from tobacco leaf (CN102161611A), tealeaves
(CN101417916A), extracted in tail Eucalyptus (CN1810744A).Squalene content difference is larger in different types of plant, difficult
To find general extracting method, and plant material of the consumption with higher application value is frequently necessary to, cost is high, material consumption energy
Consumption is high.CN102161611A, which is disclosed, uses organic solvent extraction, the method for chromatographed on silica gel to be made by raw material of tobacco
More than the weight % of content 95 squalene.But due to direct chromatographic isolation, cause solvent consumption big, material consumption high energy consumption.
3rd class method is that squalene is extracted from oil crops, grease, such as from tea oil (CN102146014A), olive oil
(CN101597204A), extracted in palm oil (CN1782052A).CN102146014A is disclosed to be extracted by raw material of tea seed
The disclosed method that high-purity squalene is extracted by raw material of olive oil of the method and CN101597204A of squalene was all present
Journey is cumbersome, material consumption high energy consumption the problem of.Squalene content is substantially all in below 1 weight % in oil crops, grease, from these originals
Squalene cost is extracted in material higher, uneconomical.
4th class method is that separation squalene is extracted from oil crops, the accessory substance of grease, is such as evaporated from vegetable oil deodorized
Go out in thing (CN101830770A), condensates of physical refining (CN102089263A) and mixed tocopherol (CN103288571A)
Extract squalene.Plant oil deodorizing distillate be it is vegetable oil deodorized during the byproduct that produces, squalene content is in 0.5-2 weights
Measure between % (olive oil deodorization distillate squalene content reach at 10-30 weight %), also containing phytosterol, phytosterin ester,
The functional components such as vitamin E.2013, domestic more than 6,000 ten thousand tons of refined edible vegetable oil, vegetable oil per ton produced about thousand points
Five deodorization distillate, the deodorization distillate that about 300,000 tons or so of total generation, this squalene raw material sources are stable.Institute
So that one technique of design is using plant oil deodorizing distillate as raw material, while separating plant sterol, vitamin E, phytosterin ester etc.
Functional component is a kind of economically viable processing mode.CN101830770A discloses one kind and carried from plant oil deodorizing distillate
Squalene is taken while reclaiming the method for vitamin E and phytosterol, this method will be through saponification, extraction, molecular distillation, cold analysis, many
The technique such as the steps such as level solvent extraction, wherein saponification, extraction, multiple-stage solvent extraction is cumbersome, organic solvent consumption is big, squalene is returned
Yield is low (more than 60 weight %), and large-scale production feasibility is not high.CN102089263A discloses one kind with vegetable oil deodorized
Distillate or condensates of physical refining are raw material, and angle is extracted by techniques such as multiple transesterification, multi-step pressure reduction distillation, cold crystallizations
The method of MF59, process is relatively complicated.The universal process of these methods is cumbersome, and the squalene rate of recovery is low.
From squalene raw material extract squalene more be related to saponification, esterification, molecular distillation, vacuum distillation, solvent extraction,
The techniques such as supercritical fluid extraction, chromatography.Wherein supercritical fluid extraction is the most environmentally friendly, but its purification is limited in one's ability, and
Using less in oil prodution industry.Obtain high-purity squalene and all employ chromatography technique substantially, but directly carry out color
Spectrum chromatography is there is also a problem, and solvent consumption is big, material consumption high energy consumption.
The content of the invention
Material consumption high energy consumption, the squalene rate of recovery in method it is an object of the invention to overcome existing extraction squalene
There is provided a kind of method for extracting squalene for the problem of low, scale production feasibility is not high.
It was found by the inventors of the present invention that in extraction process be enriched with first the squalene in raw material, then carry out chromatography,
It is big thus, it is possible to solve directly to carry out solvent consumption caused by chromatography, the problem of material consumption high energy consumption, so as to ensure ratio
Make extraction process more economically effective on the premise of higher squalene DNA purity, improve the scale of squalene extractive technique
The feasibility of production.
The invention provides a kind of method for extracting squalene, this method includes carrying out the raw material rich in squalene
Second Crystallization Separation to obtain the second solid phase and second liquid phase, by the second liquid mutually be evaporated successively, second point
Son distillation and the second chromatographic isolation, wherein, the raw material rich in squalene contains the squalene and 10-40 weights of 5-30% weight
Measure % sterol.
The Heterosis of the method for the extraction squalene that the present invention is provided exists：
1) the squalene purity obtained by the present invention is up to more than 90 weight %, and the rate of recovery can reach more than 80%；
2) present invention is by optimizing the process combinations such as used esterification, crystallization, molecular distillation, chromatographic isolation so that institute
Organic solvent amount is few, environmental protection, available for large-scale industrial production；
3) present invention obtains high-purity vitamin E, high-purity vegetable sterol while squalene raw material is obtained, fully
The functional component in plant oil deodorizing distillate is make use of, can also be former by foregoing obtained squalene by further method
The squalene of high-purity is extracted in material, while also having reclaimed the sterol in raw material, raw material is taken full advantage of.
Other features and advantages of the present invention will be described in detail in subsequent embodiment part.
Embodiment
The invention provides a kind of method for extracting squalene, this method includes carrying out the raw material rich in squalene
Second Crystallization Separation to obtain the second solid phase and second liquid phase, by the second liquid mutually be evaporated successively, second point
Son distillation and the second chromatographic isolation, wherein, the raw material rich in squalene contains 5-30 weight % squalene and 10-40 weights
Measure % sterol.
Under preferable case, squalene and 10-40 containing 10-30 weight % in the raw material of the present invention rich in squalene
Weight % sterol.
A small amount of other hydro carbons, alcohols and esters thing can also be contained in the raw material of the present invention rich in squalene
Matter etc..
In the present invention, the raw material rich in squalene can be the various conventional raw materials for meeting above-mentioned composition.
In a kind of preferred embodiment, the raw material rich in squalene can be obtained by the technique comprised the following steps：
(1) plant oil deodorizing distillate is subjected to esterification and transesterification successively, and by obtained reaction product
The first Crystallization Separation is carried out, the first solid phase and the first liquid phase is obtained；
(2) liquid phase of gained first is subjected to the first molecular distillation, obtains the cut rich in vitamin E and squalene；With
And
(3) the resulting cut rich in vitamin E and squalene is subjected to the first chromatographic isolation and evaporation successively, obtained
The vitamin E of high-purity and the raw material rich in squalene.
In the present invention, it is preferred to which the plant oil deodorizing distillate is the by-product that vegetable oil is produced during refining and deodorizing
Thing.
In the present invention, it is preferred to aliphatic acid, 10-30 weights containing 10-80 weight % in the plant oil deodorizing distillate
Amount % glyceride, 0.5-20 weight % vitamin E, 0.5-20 weight % phytosterol, 0.5-20 weight % plant
The squalene of sterol ester and 0.5-30 weight %.
In the present invention, the esterification and transesterification can use Publication No. CN101774997A patent
Method used in application.In one embodiment of the invention, the esterification reaction process includes：In acidic catalyst
In the presence of, plant oil deodorizing distillate is contacted with lower alcohol and reacted.The condition of the esterification includes：Temperature is
60-90 DEG C, the time is 1-5 hours.The acidic catalyst can be the conventional acidic catalyst for esterification, preferably
In the case of, the acidic catalyst of the invention in the concentrated sulfuric acid, toluene sulfonic acide and strong acidic ion resin one
Plant or a variety of.The lower alcohol can be methanol and/or ethanol.
In the present invention, the weight of the acidic catalyst is the 1-5%, preferably 3- of plant oil deodorizing distillate weight
4%.
In the present invention, it is preferred to which the process of the transesterification includes：In the presence of base catalyst, ester will be passed through
Reactant mixture obtained by change reaction is contacted with lower alcohol to be reacted.The condition of transesterification of the present invention includes：
Temperature is 60-90 DEG C, and the time is 1-5 hours.Base catalyst can be the conventional base catalyst for transesterification,
Under preferable case, one or more of the base catalyst in sodium methoxide, sodium hydroxide, caustic alcohol.
In the present invention, the consumption of the base catalyst for the weight of plant oil deodorizing distillate 1-5 weight %, it is excellent
Elect 3-4 weight % as.
In the present invention, it is preferred to which the process of first Crystallization Separation includes：It will pass through obtained by the transesterification
Product carry out the first cooling, growing the grain and separation of solid and liquid successively, the liquid for then again obtaining separation of solid and liquid carries out second successively
Cooling, growing the grain and separation of solid and liquid.
In the present invention, it is preferred to which the process of second Crystallization Separation includes：The raw material rich in squalene is dissolved in
First organic solvent, then carries out the first cooling, growing the grain and separation of solid and liquid successively, the liquid for then again obtaining separation of solid and liquid according to
It is secondary to carry out the second cooling, growing the grain and separation of solid and liquid.
In the present invention, it is preferred to, the product obtained by the separation of solid and liquid is thick phytosterol solid；The solid-liquid point
From method can for filtering.
With the method for the invention it is preferred to which methods described is also included first solid phase and/or second solid
Mutually rinsed, recrystallized with the second organic solvent, obtaining the phytosterol of high-purity.Used in the present invention preferably step
Second organic solvent is the one or more in ethanol, n-hexane, dichloromethane, chloroform, acetone.
In the present invention, it is preferred to, during first Crystallization Separation and the second Crystallization Separation, first drop
Warm process causes the temperature of solution to be reduced to 15-40 DEG C, is preferably decreased to 15-30 DEG C.
In the present invention, it is preferred to, during first Crystallization Separation and the second Crystallization Separation, second drop
Warm process causes the temperature of solution to be reduced to 5-20 DEG C, is preferably decreased to 5-15 DEG C.
In the present invention, it is preferred to, during first Crystallization Separation and the second Crystallization Separation, first drop
Rate of temperature fall during temperature is 1-10 DEG C/h, more preferably 3-5 DEG C/h；Rearing crystal time is 1-24 hours, further excellent
Elect as 5-15 hours.
In the present invention, it is preferred to, during first Crystallization Separation and the second Crystallization Separation, second drop
Cooling rate during temperature is 1-5 DEG C/h, more preferably 3-4 DEG C/h；Rearing crystal time is 1-24 hours, preferably 5-15
Hour.
In the present invention, it is preferred to, in second Crystallizing process, first organic solvent be pentane,
One or more in hexamethylene, normal octane, normal heptane, chloroform, ethanol, n-hexane, petroleum ether and acetone；It is further excellent
Elect the one or more in ethanol, n-hexane and acetone as；One or more more preferably in n-hexane and acetone.
In the present invention, it is preferred to, it is during second Crystallization Separation, the raw material rich in squalene is molten
The weight ratio of raw material and first organic solvent described in when the first organic solvent rich in squalene is 1：0.3-10, enters
One step is preferably 1：0.5-2.
In the present invention, the process of further preferably second Crystallization Separation includes：The raw material that will be enriched in squalene is pre-
The first organic solvent is dissolved in after heat, and solution will be obtained and carries out the first cooling, growing the grain and separation of solid and liquid successively, then will be isolated
Liquid carry out the second cooling, growing the grain and separation of solid and liquid successively again.Using above-mentioned preferred Crystallizing process, it can make to be rich in
Need ingredients to be separated largely to be separated in the raw material of squalene, and the steroid of purity more than 90% can be obtained
Alcohol.
In the present invention, it is preferred to which the preheating temperature during second Crystallization Separation is 40-70 DEG C, further preferably
For 50-60 DEG C.
In the present invention, it is preferred to which first molecular distillation is three-level molecular distillation, then obtain being rich in vitamin E and angle
The cut of MF59.
In the present invention, it is preferred to which the condition of first molecular distillation is：
The pressure of first order molecular distillation is 0-20Pa；Temperature is 80-120 DEG C；Knifing rotating speed is 100-350rpm；
The pressure of second level molecular distillation is 0-20Pa；Temperature is 120-160 DEG C；Knifing rotating speed is 100-350rpm；
The pressure of third level molecular distillation is 0-20Pa；Temperature is 140-200 DEG C, and knifing rotating speed is 100-350rpm.
In the present invention, it is preferred to, second molecular distillation is distilled including at least secondary molecules, and for example secondary molecules steam
Evaporate, three-level molecular distillation and quaternary molecule distillation etc., and collect experience second level molecular distillation obtained by light phase.
Further preferred second molecular distillation includes three-level molecular distillation, and by obtained by third level molecular distillation
Light phase undergo second level molecular distillation again.
In the present invention, described " light phase " refers to resulting distillate after distillation.
In the present invention, it is preferred to which the condition of second molecular distillation is：
The pressure of first order molecular distillation is 0-50Pa, and temperature is 70-130 DEG C, and knifing rotating speed is 100-350rpm；
The pressure of second level molecular distillation is 0-50Pa, and temperature is 100-160 DEG C, and knifing rotating speed is 100-350rpm；
The pressure of third level molecular distillation is 0-50Pa, and temperature is 130-180 DEG C, and knifing rotating speed is 100-350rpm.
In the case of further preferably, in the present invention, the condition of second molecular distillation is：
The pressure of first order molecular distillation is 0-20Pa, and temperature is 80-110 DEG C, and knifing rotating speed is 200-300rpm；
The pressure of second level molecular distillation is 0-20Pa, and temperature is 120-140 DEG C, and knifing rotating speed is 200-300rpm；
The pressure of third level molecular distillation is 0-20Pa, and temperature is 130-160 DEG C, and knifing rotating speed is 200-300rpm.
In the present invention, first chromatographic isolation can be using institute in Publication No. CN101475557A patent application
The method used.According to one embodiment of the present invention, first chromatographic separation process includes：Take the first molecular distillation institute
Loading in absolute ethyl alcohol must be dissolved in rich in the cut of vitamin E and squalene, chromatograph packing material can be anion exchange resin, stream
Dynamic phase can use absolute ethyl alcohol.It is rinsed after loading with mobile phase, collects unadsorbed material, you can obtains being rich in angle
The raw material of MF59.Again toward sour gas is poured in chromatographic column, desorbed such as carbon dioxide, then rushed with mobile phase
Wash, collect the liquid phase that must be desorbed mutually as rich in the raw table E of dimension, the liquid phase for obtaining being enriched with vitamin E is concentrated, then enters
Row is refined, you can obtain high-purity vitamin E.
In the present invention, it is preferred to, in the second chromatographic separation process, the filler for second chromatographic isolation is silicon
At least one of glue, macroreticular resin and aluminum oxide, more preferably silica gel or aluminum oxide.
In the present invention, it is preferred to, it is in the second chromatographic separation process, the product obtained by undergoing after molecular distillation is molten
In mobile phase in chromatographic isolation, then by resulting solution loading, that is, inject in chromatographic column, then carried out with mobile phase
Rinse, collect squalene outflow section and the squalene of high-purity is obtained after being concentrated.
In the present invention, it is preferred to, in the second chromatographic separation process, solvent for use is selected from pentane, n-hexane, positive heptan
Alkane, isooctane, petroleum ether, n-butyl ether, chloroform, dichloromethane, isopropanol, tetrahydrofuran, ethyl acetate, ethanol, methanol and third
One or more in ketone.
In the present invention, the pressure of chromatographic system is 0.1-0.2MPa in second chromatographic separation process.
It should be noted that above-mentioned embodiment illustrates and nots limit the present invention, and without departing from appended right
It is required that scope under, those skilled in the art can design many optional embodiments.In addition, in above-mentioned embodiment
It can also be combined between each described particular technique feature, as long as it is without prejudice to the thought of the present invention, its is same
Sample should be considered as content disclosed in this invention.In order to avoid unnecessary repetition, the present invention is to various possible combinations
No longer separately illustrate.
In case of no particular description, various reagents used in the present invention are all from commercially available.
The pure material that the rate of recovery (%) in the present invention is accounted in raw material according to the weight of finally obtained pure material is total
The percentage composition of weight is calculated.
Preparation example
1000g rapeseed oil deodorized distillates (as shown in table 1, remaining is impurity for composition and relevant parameter) are taken, 35g is added
The concentrated sulfuric acid and 300g methanol carry out esterification at 70 DEG C, and esterification reaction product is washed and dehydration by evaporation to moisture contains
Measure below 0.4 weight %, then add 40g sodium methoxides and 300g methanol carries out transesterification at a temperature of 70 DEG C, then will
Transesterification product carries out the first Crystallization Separation.Cooled in the first Crystallization Separation step with 8 DEG C/h rate of temperature fall
To 15 DEG C, this temperature growing the grain is maintained 10 hours, then carry out first time separation of solid and liquid；The liquid that first time separation of solid and liquid is obtained
Body carries out second and cooled, and rate of temperature fall is 4 DEG C/h, is cooled to 5 DEG C, maintains this temperature growing the grain 10 hours, carries out solid for the second time
Liquid is separated.Solid (i.e. thick phytosterol solid) obtained by separation of solid and liquid is cleaned through ethanol, recrystallized, obtaining purity after drying twice
For 94.8 weight % phytosterol 118.14g, the rate of recovery 71.79%.
Filtrate carries out the first molecular distillation obtained by second of separation of solid and liquid, and the pressure of wherein first order molecular distillation is
15Pa, temperature is 120 DEG C, and knifing rotating speed is 280rpm；The pressure of second level molecular distillation is 20Pa, and vapo(u)rizing temperature is 160 DEG C,
Knifing rotating speed is 280rpm；The pressure of third level molecular distillation is 15Pa, and vapo(u)rizing temperature is 200 DEG C, and knifing rotating speed is 280rpm；
First order molecular distillation and second level molecular distillation light phase cut are collected, fatty acid ester about 750g is obtained；
Collect light phase cut obtained by third level molecular distillation and carry out the first chromatographic isolation, filler uses anion exchange tree
Fat, mobile phase is used after absolute ethyl alcohol, loading and is rinsed with mobile phase, collects unadsorbed material, that is, obtains being rich in spiny dogfish
The raw material of alkene.
The composition and content of the resulting raw material rich in squalene are respectively the weight % of squalene 15, the weight of sterol 28
Measure %.
Desorbed toward pouring carbon dioxide in chromatographic column, rinsed with mobile phase again, collect that must to desorb be mutually richness
The liquid phase of the raw table E containing dimension, the liquid phase for obtaining being enriched with vitamin E is concentrated, then is refined, and it is 90.3 to obtain purity
Weight % vitamin E product 43.19g, the rate of recovery 90.70%.
Table 1
| Component | Content (weight %) |
| Aliphatic acid and glyceride | 77.01 |
| Content of phytosterol | 15.60 |
| Content of vitamin E | 4.30 |
| Squalene content | 2.01 |
Embodiment 1
Raw material preheatings of the 58g rich in squalene obtained by taking in preparation example 1 is then dissolved in anhydrous the third of 70ml to 55 DEG C
In 55 DEG C of the mixture (the first organic solvent) of ketone and 45ml n-hexane composition.Then obtained by being made with 4 DEG C/h speed
Solution be cooled to 25 DEG C for the first time, maintain this temperature first time growing the grain 10 hours, and carry out first time filtering (solid-liquid point
From), gained filtrate, to 5 DEG C, maintains second of growing the grain of this temperature 10 hours with 4 DEG C/h speed regulation reducing temperature twice, Ran Houjin
Row second is filtered, twice filtering gained solid through washes of absolute alcohol, recrystallization, dry after collect, and obtained after refined
To phytosterol.
Second liquid obtained by after second is filtered carries out the second molecular distillation after thin film evaporation, wherein,
The pressure of first order molecular distillation is 10Pa, and temperature is 100 DEG C, and knifing rotating speed is 250rpm；
The pressure of second level molecular distillation is 10Pa, and temperature is 130 DEG C, and knifing rotating speed is 250rpm；
The pressure of third level molecular distillation is 10Pa, and temperature is 150 DEG C, and knifing rotating speed is 250rpm.
Light phase obtained by resulting second level molecular distillation is dissolved in mobile phase, then is transferred to the chromatographic column that filler is silica gel
The second chromatographic isolation of middle progress, mobile phase is used as using petroleum ether.Obtain the squalene that purity is 92.5%.
The rate of recovery and purity of products obtained therefrom are listed in the table below in 2 in said process.
Table 2
| Product title | The rate of recovery (%) | Purity (weight %) |
| Phytosterol | 80.05 | 94.1 |
| Squalene | 89.66 | 92.5 |
It can be seen from the results in table 2 the purity for the squalene that the method provided using the present invention is obtained is high, and reclaim
Rate is high.
Embodiment 2
Using method similar to Example 1, except that：
Resulting solution is cooled to 30 DEG C for the first time with 3 DEG C/h speed, maintain this temperature first time growing the grain 5 small
When, and carry out first time filtering (separation of solid and liquid).
The condition of second molecular distillation is：
The pressure of first order molecular distillation is 20Pa, and temperature is 110 DEG C, and knifing rotating speed is 200rpm；
The pressure of second level molecular distillation is 5Pa, and temperature is 120 DEG C, and knifing rotating speed is 300rpm；
The pressure of third level molecular distillation is 20Pa, and temperature is 160 DEG C, and knifing rotating speed is 300rpm.
Remaining operation and parameter are same as Example 1.
The rate of recovery and purity of products obtained therefrom are listed in the table below in 3 in said process.
Table 3
| Product title | The rate of recovery (%) | Purity (weight %) |
| Phytosterol | 78.20 | 93.2 |
| Squalene | 86.21 | 92.1 |
The purity that the squalene that the method provided using the present invention is obtained is can be seen that from the result in table 3 is high, and reclaims
Rate is high.
Embodiment 3
Using method similar to Example 1, except that：
The condition of second molecular distillation is：
The pressure of first order molecular distillation is 15Pa, and temperature is 80 DEG C, and knifing rotating speed is 300rpm；
The pressure of second level molecular distillation is 5Pa, and temperature is 140 DEG C, and knifing rotating speed is 200rpm；
The pressure of third level molecular distillation is 15Pa, and temperature is 130 DEG C, and knifing rotating speed is 200rpm.
Remaining operation and parameter are same as Example 1.
The rate of recovery and purity of products obtained therefrom are listed in the table below in 4 in said process.
Table 4
| Product title | The rate of recovery (%) | Purity (weight %) |
| Phytosterol | 86.97 | 93.8 |
| Squalene | 85.36 | 92.5 |
The purity that the squalene that the method provided using the present invention is obtained is can be seen that from the result in table 4 is high, and reclaims
Rate is higher.
Embodiment 4
Using method similar to Example 1, except that：
The speed cooled for the first time in the present embodiment is 8 DEG C/h.
Remaining operation and parameter are same as Example 1.
The rate of recovery and purity of products obtained therefrom are listed in the table below in 5 in said process.
Table 5
| Product title | The rate of recovery (%) | Purity (weight %) |
| Phytosterol | 63.42 | 91.2 |
| Squalene | 80.46 | 90.3 |
The purity that the squalene that the method provided using the present invention is obtained is can be seen that from the result in table 5 is high, and reclaims
Rate is higher.
Embodiment 5
Using method similar to Example 2, except that：
The condition of the second molecular distillation is in the present embodiment：
The pressure of first order molecular distillation is 38Pa, and temperature is 120 DEG C, and knifing rotating speed is 350rpm；
The pressure of second level molecular distillation is 0.1Pa, and temperature is 100 DEG C, and knifing rotating speed is 100rpm；
The pressure of third level molecular distillation is 45Pa, and temperature is 180 DEG C, and knifing rotating speed is 300rpm.
Remaining operation and parameter are same as Example 2.
The rate of recovery and purity of products obtained therefrom are listed in the table below in 6 in said process.
Table 6
| Product title | The rate of recovery (%) | Purity (weight %) |
| Phytosterol | 75.15 | 92.3 |
| Squalene | 60.36 | 88.6 |
The purity that the squalene that the method provided using the present invention is obtained is can be seen that from the result in table 6 is high, and reclaims
Rate is higher.
Embodiment 6
Using method similar to Example 3, except that：
After the second molecular distillation is carried out, light phase obtained by resulting second level molecular distillation is transferred to filler for macropore
The second chromatographic isolation is carried out in the chromatographic column of resin, mobile phase is used as using ethanol.
Remaining operation and parameter are same as Example 3.
The rate of recovery and purity of products obtained therefrom are listed in the table below in 7 in said process.
Table 7
| Product title | The rate of recovery (%) | Purity (weight %) |
| Phytosterol | 75.23 | 90.2 |
| Squalene | 71.02 | 86.5 |
The purity that the squalene that the method provided using the present invention is obtained is can be seen that from the result in table 7 is higher, and returns
Yield is higher.
Embodiment 7
Using method similar to Example 3, except that：
After the second molecular distillation is carried out, it is oxidation that light phase obtained by resulting second level molecular distillation is transferred into filler
The second chromatographic isolation is carried out in the chromatographic column of aluminium, the mobile phase used is hexamethylene and the mixed liquor of ethyl acetate.
Remaining operation and parameter are same as Example 3.
The rate of recovery and purity of products obtained therefrom are listed in the table below in 8 in said process.
Table 8
| Product title | The rate of recovery (%) | Purity (weight %) |
| Phytosterol | 75.94 | 93.2 |
| Squalene | 81.73 | 88.5 |
The purity that the squalene that the method provided using the present invention is obtained is can be seen that from the result in table 8 is higher, and returns
Yield is higher.
Embodiment 8
Using method similar to Example 1, except that：
Raw material rich in squalene does not use gradient cooling, and it is directly cooled to 5 DEG C from 55 DEG C, and maintains this temperature
Growing the grain 20 hours are spent, are then filtered, gained solid is collected after being dried through washes of absolute alcohol after filtering, and by refined.
Remaining operation and parameter are same as Example 1.
The rate of recovery and purity of products obtained therefrom are listed in the table below in 9 in said process.
Table 9
| Product title | The rate of recovery (%) | Purity (weight %) |
| Phytosterol | 58.13 | 87.2 |
| Squalene | 80.23 | 92.5 |
The purity that the squalene that the method provided using the present invention is obtained is can be seen that from the result in table 9 is high, and reclaims
Rate is higher.
Embodiment 9
Using method similar to Example 1, except that：
First organic solvent is 106ml 55 DEG C of anhydrous propanones, and remaining operation and parameter are same as Example 1.
The rate of recovery and purity of products obtained therefrom are listed in the table below in 10 in said process.
Table 10
| Product title | The rate of recovery (%) | Purity (weight %) |
| Phytosterol | 72.13 | 87.2 |
| Squalene | 78.15 | 89.5 |
The purity that the squalene that the method provided using the present invention is obtained is can be seen that from the result in table 10 is higher, and
The rate of recovery is higher.
Embodiment 10
Using method similar to Example 1, except that：
The mixture that first organic solvent constitutes for 300ml 55 DEG C of anhydrous propanones and 200ml 55 DEG C of n-hexanes,
Remaining operation and parameter are same as Example 1.
The rate of recovery and purity of products obtained therefrom are listed in the table below in 11 in said process.
Table 11
| Product title | The rate of recovery (%) | Purity (weight %) |
| Phytosterol | 80.16 | 91.2 |
| Squalene | 84.05 | 90.5 |
The purity that the squalene that the method provided using the present invention is obtained is can be seen that from the result in table 11 is higher, and
The rate of recovery is higher.
Comparative example 1
The method provided during patent publication No. is used for CN101830770A is from rapeseed oil deodorized distillate (squalene content
For 2.05 weight %, content of vitamin E is 4.84 weight %, and phytosterol is 16.23 weight %, aliphatic acid and glyceride content
For 75.2 weight %, remaining is impurity) middle extraction squalene, the purity and the rate of recovery of product are obtained respectively such as institute in table 12
Show.
Table 12
| Product title | The rate of recovery (%) | Purity (weight %) |
| Phytosterol | 35.26 | 80.1 |
| Squalene | 45.21 | 68.9 |
Contrast can be seen that this hair using embodiments of the invention 1-10 and using the result of the comparative example 1 of prior art
Process combination shown in bright disclosed method can obtain purity and the higher squalene of the rate of recovery, while obtaining purity more
High vitamin E and phytosterol, takes full advantage of raw material, material consumption and energy consumption is reduced to a greater extent.
The preferred embodiment of the present invention described in detail above, still, the present invention are not limited in above-mentioned embodiment
Detail, in the range of the technology design of the present invention, a variety of simple variants can be carried out to technical scheme, this
A little simple variants belong to protection scope of the present invention.
Claims (14)
1. it is a kind of extract squalene method, this method include by it is described rich in squalene raw material progress the second Crystallization Separation with
The second solid phase and second liquid phase are obtained, the second liquid is mutually evaporated successively, the second molecular distillation and the second color
Spectrum separation, wherein, the raw material rich in squalene contains 5-30 weight % squalene and 10-40 weight % sterol；With
And
The raw material rich in squalene is obtained by the technique comprised the following steps：
(1) plant oil deodorizing distillate is subjected to esterification and transesterification successively, and obtained reaction product is carried out
First Crystallization Separation, obtains the first solid phase and the first liquid phase；
(2) liquid phase of gained first is subjected to the first molecular distillation, obtains the cut rich in vitamin E and squalene；And
(3) the resulting cut rich in vitamin E and squalene is subjected to the first chromatographic isolation and evaporation successively, respectively obtained
The vitamin E of high-purity and the raw material rich in squalene.
2. according to the method described in claim 1, wherein, the process of second Crystallization Separation includes：Described it will be rich in spiny dogfish
The raw material of alkene is dissolved in the first organic solvent, the first cooling, growing the grain and separation of solid and liquid is then carried out successively, then again by separation of solid and liquid
Obtained liquid carries out the second cooling, growing the grain and separation of solid and liquid successively.
3. method according to claim 2, wherein, first organic solvent is pentane, hexamethylene, normal octane, just
One or more in heptane, chloroform, ethanol, n-hexane, petroleum ether and acetone.
4. method according to claim 2, wherein, when the raw material rich in squalene is dissolved in into the first organic solvent
The weight ratio of the raw material rich in squalene and first organic solvent is 1：0.3-10.
5. method according to claim 2, wherein, when the raw material rich in squalene is dissolved in into the first organic solvent
The weight ratio of the raw material rich in squalene and first organic solvent is 1：0.5-2.
6. method according to claim 2, wherein, first temperature-fall period causes the temperature of solution to be reduced to 15-40
DEG C, second temperature-fall period causes the temperature of solution to be reduced to 5-20 DEG C.
7. method according to claim 2, wherein, during second Crystallization Separation, described first cooled
Rate of temperature fall in journey is 1-10 DEG C/h, and rearing crystal time is 1-24 hours；Cooling rate in second temperature-fall period is 1-5
DEG C/h, rearing crystal time is 1-24 hours.
8. method according to claim 2, wherein, during second Crystallization Separation, described first cooled
Rate of temperature fall in journey is 3-5 DEG C/h, and rearing crystal time is 5-15 hours；Cooling rate in second temperature-fall period is 3-4
DEG C/h, rearing crystal time is 5-15 hours.
9. the method according to any one in claim 1-8, wherein, second molecular distillation includes at least two fractions
Son distillation, and collect the light phase obtained by experience second level molecular distillation.
10. the method according to any one in claim 1-8, wherein, second molecular distillation includes three-level molecule
Distillation, and the light phase obtained by third level molecular distillation is undergone into second level molecular distillation again.
11. method according to claim 10, wherein,
The condition of first order molecular distillation is：Pressure is 0-50Pa, and temperature is 70-130 DEG C, and knifing rotating speed is 100-350rpm；
The condition of second level molecular distillation is：Pressure is 0-50Pa, and temperature is 100-160 DEG C, and knifing rotating speed is 100-350rpm；
The condition of third level molecular distillation is：Pressure is 0-50Pa, and temperature is 130-180 DEG C, and knifing rotating speed is 100-350rpm.
12. the method according to any one in claim 1-8, wherein, in the second chromatographic separation process, for described
The filler of second chromatographic isolation is at least one of silica gel, macroreticular resin and aluminum oxide.
13. the method according to any one in claim 1-8, wherein, in the second chromatographic separation process, for described
The filler of second chromatographic isolation is silica gel or aluminum oxide.
14. the method according to any one in claim 1-8, wherein, in the second chromatographic separation process, solvent for use
Selected from pentane, n-hexane, normal heptane, isooctane, petroleum ether, n-butyl ether, chloroform, dichloromethane, isopropanol, tetrahydrofuran,
One or more in ethyl acetate, ethanol, methanol and acetone.
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| CN106892791A (en) * | 2015-12-18 | 2017-06-27 | 中粮集团有限公司 | Extract method and the medicine containing squalene of plant source spiny dogfish ene compositions and its preparation method and application |
| CN106890199A (en) * | 2015-12-18 | 2017-06-27 | 中粮集团有限公司 | Extract method and the medicine containing squalene of plant source spiny dogfish ene compositions and its preparation method and application |
| CN106890200A (en) * | 2015-12-18 | 2017-06-27 | 中粮集团有限公司 | Extract method and the medicine containing squalene of plant source spiny dogfish ene compositions and its preparation method and application |
| CN105949025A (en) * | 2016-05-31 | 2016-09-21 | 中山大学惠州研究院 | Method for adsorbing and separating squalene from vegetable oil deodorized distillate |
| CN106187980A (en) * | 2016-07-15 | 2016-12-07 | 武汉藤欣生物工程有限公司 | Natural low content vitamin E is that raw material extracts natural Vitamin E and the method and apparatus of Squalene |
| CN107778277B (en) * | 2016-08-24 | 2022-09-16 | 丰益(上海)生物技术研发中心有限公司 | Process for the recovery of squalene, vitamin E and/or sterols |
| CN108635251B (en) * | 2018-05-07 | 2021-07-23 | 宜春大海龟生命科学有限公司 | Plant squalene composition, preparation method and application thereof, and product using plant squalene composition |
| CN110283034B (en) * | 2019-07-12 | 2022-04-12 | 陕西海斯夫生物工程有限公司 | Method for obtaining high-purity squalene from vegetable oil deodorized distillate |
| CN112159300A (en) * | 2020-10-27 | 2021-01-01 | 中国科学院青岛生物能源与过程研究所 | Method for extracting squalene from plant deodorized distillate |
| CN114525172B (en) * | 2022-03-07 | 2022-08-12 | 陕西海斯夫生物工程有限公司 | A method for separating high-value lipid product from olive pomace |
| CN116947589B (en) * | 2023-09-21 | 2024-04-12 | 北京华诺泰生物医药科技有限公司 | Extraction and purification method for biosynthesis squalene |
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| CN101774997A (en) * | 2010-02-02 | 2010-07-14 | 中粮天科生物工程(天津)有限公司 | Method for completely and continuously extracting natural vitamin E and phytosterol |
| CN102089263A (en) * | 2008-07-07 | 2011-06-08 | 索菲姆公司 | Process for the extraction of squalene, sterols and vitamin e contained in condensates of physical refining and/or in distillates of deodorization of plant oils |
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| FR2803598B1 (en) * | 2000-01-12 | 2002-04-26 | Pharmascience Lab | PROCESS FOR EXTRACTING INSAPONIFIABLE FROM VEGETABLE OILS USING CHLORO-1-BUTANE, COMPOSITION COMPRISING SUCH UNSAPONIFIABLE |
| JP2005255563A (en) * | 2004-03-10 | 2005-09-22 | Chikuno Shokuhin Kogyo Kk | Functional concentrate of non-saponifiable material of rice bran oil |
| CN101830770B (en) * | 2010-06-02 | 2013-06-05 | 天津大学 | Method for extracting squalene from vegetable oil deodorized distillate |
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| CN102089263A (en) * | 2008-07-07 | 2011-06-08 | 索菲姆公司 | Process for the extraction of squalene, sterols and vitamin e contained in condensates of physical refining and/or in distillates of deodorization of plant oils |
| CN101774997A (en) * | 2010-02-02 | 2010-07-14 | 中粮天科生物工程(天津)有限公司 | Method for completely and continuously extracting natural vitamin E and phytosterol |
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