CN105016956A - Squalene extracting method - Google Patents
Squalene extracting method Download PDFInfo
- Publication number
- CN105016956A CN105016956A CN201410165539.2A CN201410165539A CN105016956A CN 105016956 A CN105016956 A CN 105016956A CN 201410165539 A CN201410165539 A CN 201410165539A CN 105016956 A CN105016956 A CN 105016956A
- Authority
- CN
- China
- Prior art keywords
- squalene
- molecular distillation
- temperature
- raw material
- rich
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a squalene extracting method. The method comprises the steps of carrying out crystal separation on a squalene-enriched raw material to obtain a solid phase and a liquid phase; and sequentially carrying out evaporation, molecular distillation and chromatographic separation on the liquid phase, wherein the squalene-enriched raw material contains 5-30wt% of squalene and 10-40wt% of sterol. By using the method disclosed by the invention, squalene with higher purity can be obtained, meanwhile, vitamin E and plant sterol which have higher purity are obtained, the raw material is sufficiently utilized, and thus the material consumption and the energy consumption are reduced to the greater extent.
Description
Technical field
The present invention relates to a kind of method extracting squalene.
Background technology
Squalene is the highly undersaturated hydrocarbon compound of one, and its systematic naming method is 2,6,10,15,19,23-hexamethyl-2,6,10,14,18,22-tetracosa carbon six alkene, and molecular formula is C30H50, belongs to terpenoid.Squalene is extensively distributed in animal and plant body, in view of the chemical structure that it is special, squalene have anti-oxidant, promote skin health, promote cardiovascular health, assisting in preventing and treating tumour, improve many effects such as human body hypoxia-bearing capability, be widely used in medicine, cosmetic field, also progressively expanded in the application of field of health care products in the last few years.
Squalene on market mainly extracts from the liver oil of deepwater shark, current deepwater shark quantity gradually reduces, Some Species is endangered, causes this source increasingly deficient, just seems extremely important so find new squalene resource and develop its corresponding extracting method.
About the excavation of squalene resource, there is a lot of report in the last few years, following four class methods can be divided into:
First kind method is by engineered means transformation microorganism, can produce or enrichment squalene.As CN102787074A discloses a kind of micro-phycomycete strain can producing squalene, its squalene content reaches 1g/100g dry weight biomass; In patent application CN103266137A, by squalene synthetase gene is carried out cloning and in intestinal bacteria coexpression, construct a kind of can the recombinant bacterial strain of accumulated angle MF59.But if the squalene that genetic engineering modified Institute of Micro-biology produces uses in food or healthcare products, its security need assessment.
Equations of The Second Kind method extracts from particular variety plant, as extracted from tobacco leaf (CN102161611A), tealeaves (CN101417916A), tail Eucalyptus (CN1810744A).In different types of plant, squalene content difference is comparatively large, is difficult to find general extracting method, and often needs to consume the plant material with higher using value, and cost is high, and material consumption energy consumption is high.CN102161611A discloses and adopts organic solvent extraction, the method for chromatographed on silica gel take tobacco as the squalene that raw material has obtained content more than 95 % by weight.But due to direct chromatographic separation, cause solvent consumption large, material consumption energy consumption is high.
3rd class methods extract squalene from oil crops, grease, as extracted from tea oil (CN102146014A), sweet oil (CN101597204A), plam oil (CN1782052A).CN102146014A is disclosed is that the method that raw material extracts high-purity squalene all exists the problem that process is loaded down with trivial details, material consumption energy consumption is high with tea seed with sweet oil for raw material extracts disclosed in the method for squalene and CN101597204A.In oil crops, grease, squalene content is substantially all below 1 % by weight, extracts squalene cost higher, uneconomical from these raw materials.
4th class methods are extraction and isolation squalenes from the by product of oil crops, grease, as extracted squalene from plant oil deodorizing distillate (CN101830770A), condensates of physical refining (CN102089263A) and mixed tocopherol (CN103288571A).Plant oil deodorizing distillate is the byproduct produced in vegetable oil deodorized process, squalene content is (sweet oil deodorization distillate squalene content reaches 10-30 % by weight) between 0.5-2 % by weight, also containing functional ingredient such as plant sterol, plant sterol ester, vitamin-Es.2013, domestic refined edible vegetables oil more than 6,000 ten thousand tons, vegetables oil per ton produced the deodorization distillate of about 5/1000ths, adds up to the deodorization distillate producing about about 300,000 tons, this squalene raw materials enjoy stable sources.So designing a technique take plant oil deodorizing distillate as raw material, simultaneously the functional component such as separating plant sterol, vitamin-E, plant sterol ester is a kind of economically viable processing mode.CN101830770A discloses and a kind ofly from plant oil deodorizing distillate, extracts the method that squalene reclaims vitamin-E and plant sterol simultaneously; the method will through steps such as saponification, extraction, molecular distillation, cold analysis, multiple-stage solvent extractions; the techniques such as wherein saponification, extraction, multiple-stage solvent extraction are loaded down with trivial details, organic solvent consumption large, the squalene rate of recovery low (more than 60 % by weight), and large-scale production feasibility is not high.CN102089263A disclose a kind of with plant oil deodorizing distillate or condensates of physical refining for raw material, through the method for the technique extraction squalenes such as repeatedly transesterification, multi-step pressure reduction distillation, cold crystallization, process is comparatively loaded down with trivial details.The general process of these methods is loaded down with trivial details, and the squalene rate of recovery is low.
From squalene raw material, extract squalene relate to the techniques such as saponification, esterification, molecular distillation, underpressure distillation, solvent extraction, supercritical fluid extraction, chromatography more.Wherein supercritical fluid extraction environmental protection the most, but its purification is limited in one's ability, and apply less in oil prodution industry.Obtain high-purity squalene and substantially all have employed chromatography technique, but directly carry out chromatography and also there is a problem, solvent consumption is large, and material consumption energy consumption is high.
Summary of the invention
The object of the invention is to overcome the problem that in the method for existing extraction squalene, material consumption energy consumption is high, the squalene rate of recovery is low, the feasibility of scale production is not high, a kind of method extracting squalene is provided.
The present inventor finds; the squalene enrichment in raw material is first made in leaching process; carry out chromatography again; can solve that directly to carry out the solvent consumption that chromatography causes large thus; the problem that material consumption energy consumption is high; thus under the prerequisite ensureing higher squalene DNA purity, make extraction process effective more economically, improve the feasibility of the large-scale production of squalene extractive technique.
The invention provides a kind of method extracting squalene, the method comprises carries out the second Crystallization Separation to obtain the second solid-phase and second liquid phase by the described raw material being rich in squalene, described second liquid is carried out mutually successively evaporate, the second molecular distillation and the second chromatographic separation, wherein, the raw material being rich in squalene described in contains the squalene of 5-30% weight and the sterol of 10-40 % by weight.
The Heterosis of the method for extraction squalene provided by the invention exists:
1) the squalene purity that the present invention obtains can reach more than 90 % by weight, and the rate of recovery can reach more than 80%;
2) the present invention is by optimizing the process combination such as esterification, crystallization, molecular distillation, chromatographic separation adopted, and makes organic solvent amount used few, environmental protection, can be used for large-scale industrial production;
3) the present invention obtains high purity vitamin-E, high-purity vegetable sterol while obtaining squalene raw material, take full advantage of the functional component in plant oil deodorizing distillate, highly purified squalene can also be extracted by the aforementioned squalene raw material obtained by further method, also reclaim the sterol in raw material simultaneously, take full advantage of raw material.
Other features and advantages of the present invention are described in detail in embodiment part subsequently.
Embodiment
The invention provides a kind of method extracting squalene, the method comprises carries out the second Crystallization Separation to obtain the second solid-phase and second liquid phase by the described raw material being rich in squalene, described second liquid is carried out mutually successively evaporate, the second molecular distillation and the second chromatographic separation, wherein, the raw material being rich in squalene described in contains the squalene of 5-30 % by weight and the sterol of 10-40 % by weight.
Under preferable case, of the present invention being rich in the raw material of squalene contains the squalene of 10-30 % by weight and the sterol of 10-40 % by weight.
Can also containing a small amount of other hydro carbons, alcohols and Ester etc. in the raw material of squalene of the present invention being rich in.
In the present invention, the raw material being rich in squalene described in can be the raw material meeting above-mentioned composition of various routine.In a preferred embodiment, the raw material being rich in squalene described in can be obtained by the technique comprised the following steps:
(1) plant oil deodorizing distillate is carried out esterification and transesterification successively, and the reaction product obtained is carried out the first Crystallization Separation, obtain the first solid-phase and first liquid phase;
(2) gained first liquid is carried out the first molecular distillation mutually, obtain the cut of rich in vitamin E and squalene; And
(3) cut of obtained rich in vitamin E and squalene is carried out the first chromatographic separation and evaporation successively, obtain highly purified vitamin-E and the raw material being rich in squalene.
In the present invention, preferred described plant oil deodorizing distillate is the by product that vegetables oil produces in refining and deodorizing process.
In the present invention, the squalene of the glyceryl ester containing the lipid acid of 10-80 % by weight, 10-30 % by weight in preferred described plant oil deodorizing distillate, the vitamin-E of 0.5-20 % by weight, the plant sterol of 0.5-20 % by weight, the plant sterol ester of 0.5-20 % by weight and 0.5-30 % by weight.
In the present invention, the method used in the patent application that described esterification and transesterification can adopt publication number to be CN101774997A.In one embodiment of the invention, described esterification reaction process comprises: under the existence of an acidic catalyst, is contacted by plant oil deodorizing distillate react with lower alcohol.The condition of described esterification comprises: temperature is 60-90 DEG C, and the time is 1-5 hour.Described an acidic catalyst can be the conventional an acidic catalyst for esterification, in preferred situation, described an acidic catalyst of the present invention be selected from the vitriol oil, toluene sulfonic acide and strong acidic ion resin one or more.Described lower alcohol can be methyl alcohol and/or ethanol.
In the present invention, the weight of described an acidic catalyst is the 1-5% of plant oil deodorizing distillate weight, is preferably 3-4%.
In the present invention, the process of preferred described transesterification comprises: under the existence of basic catalyst, is contacted by the reaction mixture obtained react through esterification with lower alcohol.The condition of transesterification of the present invention comprises: temperature is 60-90 DEG C, and the time is 1-5 hour.Basic catalyst can be the conventional basic catalyst for transesterification, under preferable case, described basic catalyst be selected from sodium methylate, sodium hydroxide, sodium ethylate one or more.
In the present invention, the consumption of described basic catalyst is the 1-5 % by weight of the weight of plant oil deodorizing distillate, is preferably 3-4 % by weight.
In the present invention, preferably the process of described first Crystallization Separation comprises: the product obtained through described transesterification is carried out the first cooling, growing the grain and solid-liquid separation successively, and then liquid solid-liquid separation obtained carries out the second cooling, growing the grain and solid-liquid separation successively.
In the present invention, preferably the process of described second Crystallization Separation comprises: the described raw material being rich in squalene is dissolved in the first organic solvent, then carry out the first cooling, growing the grain and solid-liquid separation successively, and then liquid solid-liquid separation obtained carries out the second cooling, growing the grain and solid-liquid separation successively.
In the present invention, preferably, the product that described solid-liquid separation obtains is thick plant sterol solid; The method of described solid-liquid separation can for filtering.
According to method of the present invention, preferred described method also comprises carries out rinsing, recrystallization by described first solid-phase and/or described second solid-phase the second organic solvent, obtains highly purified plant sterol.The second organic solvent that the present invention preferably uses in this step is ethanol, one or more in normal hexane, methylene dichloride, chloroform, acetone.
In the present invention, preferably, in the process of described first Crystallization Separation and the second Crystallization Separation, described first temperature-fall period makes the temperature of solution be reduced to 15-40 DEG C, is preferably reduced to 15-30 DEG C.
In the present invention, preferably, in the process of described first Crystallization Separation and the second Crystallization Separation, described second temperature-fall period makes the temperature of solution be reduced to 5-20 DEG C, is preferably reduced to 5-15 DEG C.
In the present invention, preferably, in the process of described first Crystallization Separation and the second Crystallization Separation, the rate of temperature fall in described first temperature-fall period is 1-10 DEG C/h, more preferably 3-5 DEG C/h; Rearing crystal time is 1-24 hour, more preferably 5-15 hour.
In the present invention, preferably, in the process of described first Crystallization Separation and the second Crystallization Separation, the cooling rate in described second temperature-fall period is 1-5 DEG C/h, more preferably 3-4 DEG C/h; Rearing crystal time is 1-24 hour, is preferably 5-15 hour.
In the present invention, preferably, in described second Crystallizing process, described first organic solvent is one or more in Skellysolve A, hexanaphthene, octane, normal heptane, trichloromethane, ethanol, normal hexane, sherwood oil and acetone; One or more more preferably in ethanol, normal hexane and acetone; Be more preferably in normal hexane and acetone one or more.
In the present invention, preferably, in the process of described second Crystallization Separation, be rich in the raw material of squalene described in when the described raw material being rich in squalene being dissolved in the first organic solvent and the weight ratio of described first organic solvent is 1:0.3-10, more preferably 1:0.5-2.
In the present invention, preferably the process of described second Crystallization Separation comprises further: be dissolved in the first organic solvent by after the raw material preheating being rich in squalene, and solution will be obtained carry out the first cooling, growing the grain and solid-liquid separation successively, then isolated liquid is carried out the second cooling, growing the grain and solid-liquid separation more successively.Adopt above-mentioned preferred Crystallizing process, can make to be rich in the raw material of squalene needs separated composition to be separated largely, and can obtain the sterol of purity more than 90%.
In the present invention, the preheating temperature in the process of preferred described second Crystallization Separation is 40-70 DEG C, more preferably 50-60 DEG C.
In the present invention, preferably described first molecular distillation is three grades of molecular distillations, then obtains the cut of rich in vitamin E and squalene.
In the present invention, preferably the condition of described first molecular distillation is:
The pressure of first step molecular distillation is 0-20Pa; Temperature is 80-120 DEG C; Knifing rotating speed is 100-350rpm;
The pressure of second stage molecular distillation is 0-20Pa; Temperature is 120-160 DEG C; Knifing rotating speed is 100-350rpm;
The pressure of third stage molecular distillation is 0-20Pa; Temperature is 140-200 DEG C, and knifing rotating speed is 100-350rpm.
In the present invention, preferably, described second molecular distillation comprises at least secondary molecules distillation, such as secondary molecules distillation, three grades of molecular distillations and quaternary molecule distillation etc., and collects the light phase experiencing second stage molecular distillation and obtain.
Preferably described second molecular distillation comprises three grades of molecular distillations further, and the light phase obtained by third stage molecular distillation experiences second stage molecular distillation again.
In the present invention, described " light phase " refers to the overhead product obtained after distillation.
In the present invention, preferably the condition of described second molecular distillation is:
The pressure of first step molecular distillation is 0-50Pa, and temperature is 70-130 DEG C, and knifing rotating speed is 100-350rpm;
The pressure of second stage molecular distillation is 0-50Pa, and temperature is 100-160 DEG C, and knifing rotating speed is 100-350rpm;
The pressure of third stage molecular distillation is 0-50Pa, and temperature is 130-180 DEG C, and knifing rotating speed is 100-350rpm.
Under further preferable case, in the present invention, the condition of described second molecular distillation is:
The pressure of first step molecular distillation is 0-20Pa, and temperature is 80-110 DEG C, and knifing rotating speed is 200-300rpm;
The pressure of second stage molecular distillation is 0-20Pa, and temperature is 120-140 DEG C, and knifing rotating speed is 200-300rpm;
The pressure of third stage molecular distillation is 0-20Pa, and temperature is 130-160 DEG C, and knifing rotating speed is 200-300rpm.
In the present invention, the method used in the patent application that described first chromatographic separation can adopt publication number to be CN101475557A.According to one embodiment of the present invention, described first chromatographic separation process comprises: the cut getting the first molecular distillation gained rich in vitamin E and squalene is dissolved in loading in dehydrated alcohol, chromatograph packing material can be anionite-exchange resin, and moving phase can adopt dehydrated alcohol.Rinse by moving phase after loading, collect the material do not adsorbed, namely can obtain the raw material being rich in squalene.In chromatographic column, pour sour gas again, such as carbon dioxide etc. carry out desorb, then rinse by moving phase, collect desorb is the liquid phase being rich in the table E that supports one's family mutually, the liquid phase obtaining enrichment vitamin-E is concentrated, then refines, high purity vitamin-E can be obtained.
In the present invention, preferably, in the second chromatographic separation process, the filler for described second chromatographic separation is at least one in silica gel, macroporous resin and aluminum oxide, is more preferably silica gel or aluminum oxide.
In the present invention, preferably, in the second chromatographic separation process, the product obtained after experience molecular distillation is dissolved in the moving phase in chromatographic separation, then by obtained solution loading, namely inject chromatographic column, then rinse by moving phase, collection angle MF59 flow out section and carry out concentrated after obtain highly purified squalene.
In the present invention, preferably, in the second chromatographic separation process, solvent for use be selected from Skellysolve A, normal hexane, normal heptane, octane-iso, sherwood oil, n-butyl ether, chloroform, methylene dichloride, Virahol, tetrahydrofuran (THF), ethyl acetate, ethanol, methyl alcohol and acetone one or more.
In the present invention, in described second chromatographic separation process, the pressure of chromatographic system is 0.1-0.2MPa.
It should be noted that, above-mentioned embodiment illustrates instead of restriction the present invention, and under the scope not departing from claims, those skilled in the art can design many optional embodiments.In addition, between the concrete technical characteristic of each described in above-mentioned embodiment, also can carry out arbitrary combination, as long as it is without prejudice to thought of the present invention, it should be considered as content disclosed in this invention equally.In order to avoid unnecessary repetition, the present invention illustrates no longer separately to various possible array mode.
In case of no particular description, all ingredients used in the present invention is all from being purchased.
The percentage composition that the rate of recovery (%) in the present invention accounts for the pure substance gross weight in raw material according to the weight of final obtained pure substance calculates.
Preparation example
Get 1000g rapeseed oil deodorized distillate (composition and correlation parameter as shown in table 1, all the other are impurity), add the 35g vitriol oil and 300g methyl alcohol carries out esterification at 70 DEG C, esterification reaction product is carried out washing dehydration by evaporation to moisture content less than 0.4 % by weight, then add 40g sodium methylate and 300g methyl alcohol carries out transesterification at 70 DEG C of temperature, then transesterification product is carried out the first Crystallization Separation.In described first Crystallization Separation step, be cooled to 15 DEG C with the rate of temperature fall of 8 DEG C/h, maintain this temperature growing the grain 10 hours, then carry out first time solid-liquid separation; Liquid first time solid-liquid separation obtained carries out the second cooling, 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 second time solid-liquid separation.Twice solid-liquid separation gained solid (i.e. thick plant sterol solid) obtains the plant sterol 118.14g that purity is 94.8 % by weight, the rate of recovery 71.79% after ethanol purge, recrystallization, drying.
Second time solid-liquid separation gained filtrate carries out the first molecular distillation, and wherein the pressure of first step molecular distillation is 15Pa, and temperature is 120 DEG C, and knifing rotating speed is 280rpm; The pressure of second stage molecular distillation is 20Pa, and distillation temperature is 160 DEG C, and knifing rotating speed is 280rpm; The pressure of third stage molecular distillation is 15Pa, and distillation temperature is 200 DEG C, and knifing rotating speed is 280rpm;
Collect first step molecular distillation and the light phase cut of second stage molecular distillation, obtain fatty acid ester and be about 750g;
Collect the third stage light phase cut of molecular distillation gained and carry out the first chromatographic separation, filler adopts anionite-exchange resin, and moving phase adopts dehydrated alcohol, rinses after loading by moving phase, collects the material do not adsorbed, namely obtains the raw material being rich in squalene.
The composition being rich in the raw material of squalene obtained and content are respectively squalene 15 % by weight, sterol 28 % by weight.
In chromatographic column, pour carbon dioxide again carry out desorb, rinse by moving phase, collect desorb is the liquid phase being rich in the table E that supports one's family mutually, the liquid phase obtaining enrichment vitamin-E is concentrated, refine again, obtain the vitamin-E product 43.19g that purity is 90.3 % by weight, the rate of recovery 90.70%.
Table 1
| Component | Content (% by weight) |
| Lipid acid and glyceryl ester | 77.01 |
| Content of phytosterol | 15.60 |
| Content of vitamin E | 4.30 |
| Squalene content | 2.01 |
Embodiment 1
Get the raw material preheating to 55 DEG C that the 58g obtained in preparation example 1 is rich in squalene, be then dissolved in the mixture (the first organic solvent) of 55 DEG C of the anhydrous propanone of 70ml and the normal hexane composition of 45ml.Then obtained solution first time is made to be cooled to 25 DEG C with the speed of 4 DEG C/h, maintain this temperature control growing the grain 10 hours, and carry out first time filtration (solid-liquid separation), gained filtrate is with the speed regulation reducing temperature twice to 5 DEG C of 4 DEG C/h, maintain this temperature control secondary growing the grain 10 hours, then carry out second time to filter, filter gained solid twice and collect after washes of absolute alcohol, recrystallization, drying, and obtain plant sterol after refining.
The second liquid obtained after second time being filtered carries out the second molecular distillation after thin film evaporation, wherein,
The pressure of first step molecular distillation is 10Pa, and temperature is 100 DEG C, and knifing rotating speed is 250rpm;
The pressure of second stage molecular distillation is 10Pa, and temperature is 130 DEG C, and knifing rotating speed is 250rpm;
The pressure of third stage molecular distillation is 10Pa, and temperature is 150 DEG C, and knifing rotating speed is 250rpm.
Obtained second stage molecular distillation gained is gently dissolved in moving phase mutually, then to proceed to filler be carry out the second chromatographic separation in the chromatographic column of silica gel, adopt sherwood oil as moving phase.Obtain the squalene that purity is 92.5%.
In said process, the rate of recovery of products obtained therefrom and purity are listed in the table below in 2.
Table 2
| Product title | The rate of recovery (%) | Purity (% by weight) |
| Plant sterol | 80.05 | 94.1 |
| Squalene | 89.66 | 92.5 |
Result as can be seen from table 2, the purity of the squalene adopting method provided by the invention to obtain is high, and the rate of recovery is high.
Embodiment 2
Adopt the method similar to embodiment 1, difference is:
Make obtained solution first time be cooled to 30 DEG C with the speed of 3 DEG C/h, maintain this temperature control growing the grain 5 hours, and carry out first time filtration (solid-liquid separation).
The condition of the second molecular distillation is:
The pressure of first step molecular distillation is 20Pa, and temperature is 110 DEG C, and knifing rotating speed is 200rpm;
The pressure of second stage molecular distillation is 5Pa, and temperature is 120 DEG C, and knifing rotating speed is 300rpm;
The pressure of third stage molecular distillation is 20Pa, and temperature is 160 DEG C, and knifing rotating speed is 300rpm.
All the other operation and parameter identical with embodiment 1.
In said process, the rate of recovery of products obtained therefrom and purity are listed in the table below in 3.
Table 3
| Product title | The rate of recovery (%) | Purity (% by weight) |
| Plant sterol | 78.20 | 93.2 |
| Squalene | 86.21 | 92.1 |
Result as can be seen from table 3, the purity of the squalene adopting method provided by the invention to obtain is high, and the rate of recovery is high.
Embodiment 3
Adopt the method similar to embodiment 1, difference is:
The condition of the second molecular distillation is:
The pressure of first step molecular distillation is 15Pa, and temperature is 80 DEG C, and knifing rotating speed is 300rpm;
The pressure of second stage molecular distillation is 5Pa, and temperature is 140 DEG C, and knifing rotating speed is 200rpm;
The pressure of third stage molecular distillation is 15Pa, and temperature is 130 DEG C, and knifing rotating speed is 200rpm.
All the other operation and parameter identical with embodiment 1.
In said process, the rate of recovery of products obtained therefrom and purity are listed in the table below in 4.
Table 4
| Product title | The rate of recovery (%) | Purity (% by weight) |
| Plant sterol | 86.97 | 93.8 |
| Squalene | 85.36 | 92.5 |
Result as can be seen from table 4, the purity of the squalene adopting method provided by the invention to obtain is high, and the rate of recovery is higher.
Embodiment 4
Adopt the method similar to embodiment 1, difference is:
In the present embodiment, the speed of first time cooling is 8 DEG C/h.
All the other operation and parameter identical with embodiment 1.
In said process, the rate of recovery of products obtained therefrom and purity are listed in the table below in 5.
Table 5
| Product title | The rate of recovery (%) | Purity (% by weight) |
| Plant sterol | 63.42 | 91.2 |
| Squalene | 80.46 | 90.3 |
Result as can be seen from table 5, the purity of the squalene adopting method provided by the invention to obtain is high, and the rate of recovery is higher.
Embodiment 5
Adopt the method similar to embodiment 2, difference is:
In the present embodiment, the condition of the second molecular distillation is:
The pressure of first step molecular distillation is 38Pa, and temperature is 120 DEG C, and knifing rotating speed is 350rpm;
The pressure of second stage molecular distillation is 0.1Pa, and temperature is 100 DEG C, and knifing rotating speed is 100rpm;
The pressure of third stage molecular distillation is 45Pa, and temperature is 180 DEG C, and knifing rotating speed is 300rpm.
All the other operation and parameter identical with embodiment 2.
In said process, the rate of recovery of products obtained therefrom and purity are listed in the table below in 6.
Table 6
| Product title | The rate of recovery (%) | Purity (% by weight) |
| Plant sterol | 75.15 | 92.3 |
| Squalene | 60.36 | 88.6 |
Result as can be seen from table 6, the purity of the squalene adopting method provided by the invention to obtain is high, and the rate of recovery is higher.
Embodiment 6
Adopt the method similar to embodiment 3, difference is:
After carrying out the second molecular distillation, it is carry out the second chromatographic separation in the chromatographic column of macroporous resin that obtained second stage molecular distillation gained is gently proceeded to filler mutually, adopts ethanol as moving phase.
All the other operation and parameter identical with embodiment 3.
In said process, the rate of recovery of products obtained therefrom and purity are listed in the table below in 7.
Table 7
| Product title | The rate of recovery (%) | Purity (% by weight) |
| Plant sterol | 75.23 | 90.2 |
| Squalene | 71.02 | 86.5 |
Result as can be seen from table 7, the purity of the squalene adopting method provided by the invention to obtain is higher, and the rate of recovery is higher.
Embodiment 7
Adopt the method similar to embodiment 3, difference is:
After carrying out the second molecular distillation, it is carry out the second chromatographic separation in the chromatographic column of aluminum oxide that obtained second stage molecular distillation gained is gently proceeded to filler mutually, and the moving phase of employing is the mixed solution of hexanaphthene and ethyl acetate.
All the other operation and parameter identical with embodiment 3.
In said process, the rate of recovery of products obtained therefrom and purity are listed in the table below in 8.
Table 8
| Product title | The rate of recovery (%) | Purity (% by weight) |
| Plant sterol | 75.94 | 93.2 |
| Squalene | 81.73 | 88.5 |
Result as can be seen from table 8, the purity of the squalene adopting method provided by the invention to obtain is higher, and the rate of recovery is higher.
Embodiment 8
Adopt the method similar to embodiment 1, difference is:
The raw material being rich in squalene does not adopt gradient cooling, and directly it is cooled to 5 DEG C from 55 DEG C, and maintains this temperature growing the grain 20 hours, then filters, and after filtering, gained solid is collected after washes of absolute alcohol drying, and through refining.
All the other operation and parameter identical with embodiment 1.
In said process, the rate of recovery of products obtained therefrom and purity are listed in the table below in 9.
Table 9
| Product title | The rate of recovery (%) | Purity (% by weight) |
| Plant sterol | 58.13 | 87.2 |
| Squalene | 80.23 | 92.5 |
Result as can be seen from table 9, the purity of the squalene adopting method provided by the invention to obtain is high, and the rate of recovery is higher.
Embodiment 9
Adopt the method similar to embodiment 1, difference is:
Described first organic solvent is 55 DEG C of anhydrous propanones of 106ml, all the other operation and parameter identical with embodiment 1.
In said process, the rate of recovery of products obtained therefrom and purity are listed in the table below in 10.
Table 10
| Product title | The rate of recovery (%) | Purity (% by weight) |
| Plant sterol | 72.13 | 87.2 |
| Squalene | 78.15 | 89.5 |
Result as can be seen from table 10, the purity of the squalene adopting method provided by the invention to obtain is higher, and the rate of recovery is higher.
Embodiment 10
Adopt the method similar to embodiment 1, difference is:
Described first organic solvent is the mixture of 55 DEG C of normal hexanes compositions of 55 DEG C of anhydrous propanones of 300ml and 200ml, all the other operations and parameter identical with embodiment 1.
In said process, the rate of recovery of products obtained therefrom and purity are listed in the table below in 11.
Table 11
| Product title | The rate of recovery (%) | Purity (% by weight) |
| Plant sterol | 80.16 | 91.2 |
| Squalene | 84.05 | 90.5 |
Result as can be seen from table 11, the purity of the squalene adopting method provided by the invention to obtain is higher, and the rate of recovery is higher.
Comparative example 1
From rapeseed oil deodorized distillate, (squalene content is 2.05 % by weight for the method that provides in CN101830770A to adopt patent publication No., content of vitamin E is 4.84 % by weight, plant sterol is 16.23 % by weight, lipid acid and glyceride content are 75.2 % by weight, all the other are impurity) in extract squalene, institute obtains the purity of product and the rate of recovery is distinguished as shown in Table 12.
Table 12
| Product title | The rate of recovery (%) | Purity (% by weight) |
| Plant sterol | 35.26 | 80.1 |
| Squalene | 45.21 | 68.9 |
Contrast adopts embodiments of the invention 1-10 and adopts the result of the comparative example 1 of prior art to find out, process combination shown in method disclosed by the invention can obtain purity and the higher squalene of the rate of recovery, and obtain the higher vitamin-E of purity and plant sterol simultaneously, take full advantage of raw material, decrease material consumption and energy consumption to a greater extent.
More than describe the preferred embodiment of the present invention in detail; but the present invention is not limited to the detail in above-mentioned embodiment, within the scope of technical conceive of the present invention; can carry out multiple simple variant to technical scheme of the present invention, these simple variant all belong to protection scope of the present invention.
Claims (10)
1. one kind is extracted the method for squalene, the method comprises carries out the second Crystallization Separation to obtain the second solid-phase and second liquid phase by the described raw material being rich in squalene, described second liquid is carried out mutually successively evaporate, the second molecular distillation and the second chromatographic separation, wherein, the raw material being rich in squalene described in contains the squalene of 5-30 % by weight and the sterol of 10-40 % by weight.
2. method according to claim 1, wherein, described in be rich in squalene raw material obtained by the technique comprised the following steps:
(1) plant oil deodorizing distillate is carried out esterification and transesterification successively, and the reaction product obtained is carried out the first Crystallization Separation, obtain the first solid-phase and first liquid phase;
(2) gained first liquid is carried out the first molecular distillation mutually, obtain the cut of rich in vitamin E and squalene; And
(3) cut of obtained rich in vitamin E and squalene is carried out the first chromatographic separation and evaporation successively, obtain highly purified vitamin-E and the raw material being rich in squalene respectively.
3. according to the method in claim 1-2 described in any one, wherein, the process of described second Crystallization Separation comprises: the described raw material being rich in squalene is dissolved in the first organic solvent, then carry out the first cooling, growing the grain and solid-liquid separation successively, and then liquid solid-liquid separation obtained carries out the second cooling, growing the grain and solid-liquid separation successively.
4. method according to claim 3, wherein, described first organic solvent is one or more in Skellysolve A, hexanaphthene, octane, normal heptane, trichloromethane, ethanol, normal hexane, sherwood oil and acetone.
5. method according to claim 3, wherein, is rich in the raw material of squalene described in when the described raw material being rich in squalene being dissolved in the first organic solvent and the weight ratio of described first organic solvent is 1:0.3-10, is preferably 1:0.5-2.
6. method according to claim 3, wherein, described first temperature-fall period makes the temperature of solution be reduced to 15-40 DEG C, and described second temperature-fall period makes the temperature of solution be reduced to 5-20 DEG C;
Preferably in the process of described second Crystallization Separation, the rate of temperature fall in described first temperature-fall period is 1-10 DEG C/h, more preferably 3-5 DEG C/h, and rearing crystal time is 1-24 hour, more preferably 5-15 hour; Cooling rate in described second temperature-fall period is 1-5 DEG C/h, more preferably 3-4 DEG C/h, and rearing crystal time is 1-24 hour, is preferably 5-15 hour.
7. according to claim 1,2, method in 4-6 described in any one, wherein, described second molecular distillation comprises at least secondary molecules distillation, and collects the light phase that experience second stage molecular distillation obtains; Preferably described second molecular distillation comprises three grades of molecular distillations, and the light phase obtained by third stage molecular distillation experiences second stage molecular distillation again.
8. method according to claim 7, wherein,
The condition of described first step molecular distillation comprises: pressure is 0-50Pa, and temperature is 70-130 DEG C, and knifing rotating speed is 100-350rpm;
The condition of described second stage molecular distillation comprises: pressure is 0-50Pa, and temperature is 100-160 DEG C, and knifing rotating speed is 100-350rpm;
The condition of described third stage molecular distillation comprises: pressure is 0-50Pa, and temperature is 130-180 DEG C, and knifing rotating speed is 100-350rpm.
9. according to claim 1,2, method in 4-6 described in any one, wherein, in the second chromatographic separation process, the filler for described second chromatographic separation is at least one in silica gel, macroporous resin and aluminum oxide, is preferably silica gel or aluminum oxide.
10. according to claim 1,2, method in 4-6 described in any one, wherein, in the second chromatographic separation process, solvent for use be selected from Skellysolve A, normal hexane, normal heptane, octane-iso, sherwood oil, n-butyl ether, chloroform, methylene dichloride, Virahol, tetrahydrofuran (THF), ethyl acetate, ethanol, methyl alcohol and acetone one or more.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410165539.2A CN105016956B (en) | 2014-04-23 | 2014-04-23 | A kind of method for extracting squalene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410165539.2A CN105016956B (en) | 2014-04-23 | 2014-04-23 | A kind of method for extracting squalene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105016956A true CN105016956A (en) | 2015-11-04 |
| CN105016956B CN105016956B (en) | 2017-08-08 |
Family
ID=54407321
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410165539.2A Active CN105016956B (en) | 2014-04-23 | 2014-04-23 | A kind of method for extracting squalene |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105016956B (en) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
| 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 |
| CN107778277A (en) * | 2016-08-24 | 2018-03-09 | 丰益(上海)生物技术研发中心有限公司 | The method for reclaiming squalene, vitamin E and/or sterol |
| CN110283034A (en) * | 2019-07-12 | 2019-09-27 | 陕西海斯夫生物工程有限公司 | A method of obtaining high-purity squalene from plant oil deodorizing distillate |
| WO2019214410A1 (en) * | 2018-05-07 | 2019-11-14 | 宜春大海龟生命科学有限公司 | Plant squalene composition and preparation method therefor and application thereof, and product applying same |
| 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 |
| CN114525172A (en) * | 2022-03-07 | 2022-05-24 | 陕西海斯夫生物工程有限公司 | A method for separating high-value lipid product from olive pomace |
| CN116947589A (en) * | 2023-09-21 | 2023-10-27 | 北京华诺泰生物医药科技有限公司 | Extraction and purification method for biosynthesis squalene |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030130532A1 (en) * | 2000-01-12 | 2003-07-10 | Sandrine Bardet | Method for extracting unsaponifiable matters from vegetable oils using chloro-1-butane, composition containing said unsaponifiable matters |
| JP2005255563A (en) * | 2004-03-10 | 2005-09-22 | Chikuno Shokuhin Kogyo Kk | Functional concentrate of non-saponifiable material of rice bran oil |
| 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 |
| CN101830770A (en) * | 2010-06-02 | 2010-09-15 | 天津大学 | Method for extracting squalene from vegetable oil deodorized distillate |
| 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 |
-
2014
- 2014-04-23 CN CN201410165539.2A patent/CN105016956B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030130532A1 (en) * | 2000-01-12 | 2003-07-10 | Sandrine Bardet | Method for extracting unsaponifiable matters from vegetable oils using chloro-1-butane, composition containing said unsaponifiable matters |
| JP2005255563A (en) * | 2004-03-10 | 2005-09-22 | Chikuno Shokuhin Kogyo Kk | Functional concentrate of non-saponifiable material of rice bran oil |
| 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 |
| CN101830770A (en) * | 2010-06-02 | 2010-09-15 | 天津大学 | Method for extracting squalene from vegetable oil deodorized distillate |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
| 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 |
| CN107778277A (en) * | 2016-08-24 | 2018-03-09 | 丰益(上海)生物技术研发中心有限公司 | The method for reclaiming squalene, vitamin E and/or sterol |
| WO2019214410A1 (en) * | 2018-05-07 | 2019-11-14 | 宜春大海龟生命科学有限公司 | Plant squalene composition and preparation method therefor and application thereof, and product applying same |
| CN110283034A (en) * | 2019-07-12 | 2019-09-27 | 陕西海斯夫生物工程有限公司 | A method of obtaining high-purity squalene from plant oil deodorizing distillate |
| 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 |
| CN114525172A (en) * | 2022-03-07 | 2022-05-24 | 陕西海斯夫生物工程有限公司 | A method for separating high-value lipid product from olive pomace |
| 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 |
| CN116947589A (en) * | 2023-09-21 | 2023-10-27 | 北京华诺泰生物医药科技有限公司 | Extraction and purification method for biosynthesis squalene |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105016956B (en) | 2017-08-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105016956A (en) | Squalene extracting method | |
| CN109232346B (en) | Industrial preparation method of lutein and marigold flavone | |
| JP5036210B2 (en) | Process for producing polyphenol-containing product mainly containing kaempferol-3-O-rhamnoside | |
| CN101597204B (en) | Method for extracting high-purity squalene by taking olive oil as raw material | |
| CN107778277B (en) | Process for the recovery of squalene, vitamin E and/or sterols | |
| CN105367370B (en) | A kind of method that squalene is extracted in heel after the natural VE from extraction | |
| CN108046993B (en) | Method for preparing peppermint oil and menthol with various specifications by azeotropic and vacuum rectification technology | |
| CN104761528B (en) | A method of natural VE is extracted with ion liquid abstraction agent | |
| CN103804337A (en) | Novel technology for extracting vitamin E and squalene by employing multi-stage counter-current liquid-liquid extraction method | |
| CN105848748B (en) | The chromatographic purification method of aliphatic acid | |
| CN103012351B (en) | A kind of purifying technique of natural VE | |
| CN103467432B (en) | A kind of method extracting vitamin E from deodorizer distillate of idesia polycarpa oil | |
| JP2900238B2 (en) | Natural Menaquinone-7 High Lipid Content | |
| CN103012352A (en) | Separation and purification method for mixed tocopherols | |
| CN112159300A (en) | Method for extracting squalene from plant deodorized distillate | |
| CN104987952B (en) | Method for extracting volatile oil and salidroside from rhodiola rosea whole plant | |
| CN105418575A (en) | Method for extracting natural vitamin E through two-step reextraction method | |
| CN105851068A (en) | Method for preparing antibacterial agent and bacterial quorum sensing inhibitor by using fennel | |
| CN104017042A (en) | Separation purification method for 7-dehydrocholesterol | |
| Quek et al. | Commercial extraction of vitamin E from food sources | |
| CN105177073B (en) | A kind of method preparing Phosphatidylserine | |
| CN106187980A (en) | Natural low content vitamin E is that raw material extracts natural Vitamin E and the method and apparatus of Squalene | |
| CN109528784B (en) | Method for extracting and preparing 4,4' -dimethyl sterol from shea butter | |
| CN106890200A (en) | Extract method and the medicine containing squalene of plant source spiny dogfish ene compositions and its preparation method and application | |
| JP2015166326A (en) | Method of producing teasaponin and/or floratheasaponin |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |