CN103708992A - Method for extracting squalene in vegetable oil deodorizer distillate through two-stage column chromatography - Google Patents
Method for extracting squalene in vegetable oil deodorizer distillate through two-stage column chromatography Download PDFInfo
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Abstract
The invention provides a method for extracting squalene in vegetable oil deodorizer distillate through two-stage column chromatography, which comprises the following processing steps: performing saponifying pretreatment to separate unsaponifiable matters, performing first-stage column chromatography to separate tocopherol and sterol, and performing second-stage column chromatography to purify squalene. Through the whole process, the squalene having a content of about 50% can be obtained, and meanwhile, the tocopherol having a content of 70% or above and the sterol having a content of 98% or above can be also obtained. Thus, the method provided by the invention overcomes the problem of low pertinence in the traditional squalene extraction process, achieves favorable selectivity of column chromatography and greatly increases the extraction efficiency. The process has the advantages of simple operation procedure, high separation efficiency, high squalene recovery rate, low investment and the like.
Description
Technical field
The present invention relates to squalene purification field, be specifically related to a kind of method that two stage column chromatography is extracted squalene in plant oil deodorizing distillate.
Background technology
Squalene (Squalene), molecular formula is C
30h
50, molecular weight 410.7, chemical name is 2,6,10,15,19,23-hexamethyl-2,6,10,14,18,22-tetracosa carbon, six alkene belong to open chain triterpene.Squalene is a kind of colourless or micro-yellow transparent oily liquids, is soluble in normal hexane, ether, sherwood oil, acetone and tetracol phenixin, and slightly soluble ethanol is water insoluble.Be easy to oxidation, so need add suitable oxidation inhibitor when preserving.
Squalene anti-oxidant, radioprotective effect is remarkable, and can reinforced immunological regulate and strengthen metabolism.Antitumor, the anticancer active drug of Chang Zuowei medically, participates in treatment cardiovascular and cerebrovascular diseases and as anti-infectives.Squalene is good active oxygen delivery vehicles, containing squalene makeup, can prevent pachylosis, strengthens skin immunization power, make skin distribute healthy and beautiful natural gloss.Healthcare products containing squalene can improve people's body immune function, strengthen resistance against diseases.
Squalene, as a kind of lipid unsaponifiables, is mainly derived from animal livers, especially the squalene content the highest (40%-89%) in deepwater shark liver oil.Therefore, squalene extraction process is raw material based on shark liver oil mostly at present.For the protection to wildlife, the existing plant origin that proposes to find squalene.Squalene distributes very extensively in plant in fact, is that general content is high and extract and to have limited its using value without effective ways.
Deodorization distillate, as the industrial by-products in grease deodorization process, is the good source of squalene.Deodorization distillate chief component is: free fatty acids, glyceryl ester, tocopherol, sterol, squalene etc., wherein squalene content is generally 0.5%-2.5%.If squalene wherein can be extracted, and get both a part of tocopherol, sterol, can not only make full use of industrial waste, cost-saving and protection of the environment, can also produce certain economic benefit, develops new product.
The processing method of extracting at present squalene is also few, especially the squalene in plant oil deodorizing distillate.For example patent CN102146014 discloses a kind of method of tea seed as raw material extraction squalene of take, its technical process relates to esterification, the reaction of coordination-borax, macroporous resin chromatographic separation and purification, supercritical carbon dioxide extraction repeatedly, can obtain the squalene essential oil of squalene content >=80%, in raw material, squalene content is not quite clear, and extraction yield is not quite clear.Patent CN102089263 discloses a kind ofly take deodorization distillate and is that raw material extracts the method for squalene, and the method adopts esterification, three grades of molecular distillations, can arrive the squalene cut of 20 ~ 30% left and right.CN101597204 discloses a kind of method of extracting squalene from sweet oil, and material content is 3.6%, and technique relates to saponification, the extraction of unsaponifiables, secondary molecular distillation and column chromatography, and squalene content can improve 30 times, and extraction yield is not quite clear.
From above example, the extraction of plant squalene at present adopts the combination of several different methods more, such as saponification, esterification, molecular distillation, supercritical carbon dioxide extraction etc., and step is comparatively loaded down with trivial details, and molecular distillation, supercritical extraction unit are expensive, and security is low.Therefore, go for the squalene product that content is very high, often need complicated operation, pay a high price, yet the extraction yield of squalene is but generally not high.
The fine selectivity of column chromatography, and there is the features such as easy and simple to handle, environmental friendliness, solvent recoverable, operational condition gentleness, become the classical way of Separation of Natural Products purifying.The complicacy of deodorization distillate composition and uncertainty, be the major reason that squalene extract purity is not high, and the good selectivity of column chromatography, for the separation and purification of squalene provides may.Common column chromatography type has adsorpting column chromatography, partition column chromatography, ion exchange chromatography etc.Adsorpting column chromatography reaches separated object according to the difference of adsorptive power.Partition chromatography is according to the difference of material to be separated partition ratio in two-phase.Ion exchange chromatography is to utilize ion-exchanger to carry out separation.Deodorization distillate, after pre-treatment, utilizes the difference of the character such as the polarity of heterogeneity and acid-basicity, and the selectivity of single-stage, secondary or multistage column chromatography is distributed or absorption, makes component separating of different nature, reaches the object of purifying squalene.
Consider the problem that current plant squalene extraction step is loaded down with trivial details, efficiency is not high, specific aim is not strong, the highly selective of performance column chromatography when Separation of Natural Products, adopts column chromatography to carry out separating plant squalene.But the deodorization distillate complicated component as raw material, most of composition is lipid acid and glycerolipid, and the content of squalene is generally less than 3%, and directly not only separation efficiency is low, inferior separating effect for column chromatography, and too much impurity can stop up bed, technique cannot be carried out.Therefore design before column chromatography, use saponification method pretreating raw material, remove most saponified, collection unsaponifiables carry out fractionation by adsorption.Separately consider and in unsaponifiables, contain a large amount of tocopherols and sterol, be isolated the purity that can not only improve squalene, can also reclaim tocopherol and the sterol of the concrete commercial value of a part, therefore after one-level column chromatography, adopt two stage column chromatography, further improve the purity of squalene.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of saponification pre-treatment and two stage column chromatography and combine and extract the technique of squalene in plant oil deodorizing distillate.Technique of the present invention has that separation efficiency is high, the squalene rate of recovery is high, simple to operate, invest the advantages such as little.
Technical scheme of the present invention is:
Two stage column chromatography is extracted a method for squalene in plant oil deodorizing distillate, it is characterized in that comprising the steps:
1) separated unsaponifiables: plant oil deodorizing distillate, in the situation that having protection, is added to mineral alkali saponification while stirring, and temperature of reaction is 60-80 ℃, reaction times is 45-60min, forms saponification mixture, after saponification finishes, separated saponified, residuum extraction concentrates to obtain unsaponifiables;
2) one-level column chromatography: the unsaponifiables that the step 1) of take obtains is raw material, lower alcohol is moving phase, and after a small amount of moving phase dilution unsaponifiables, adding basic anion exchange resin is in the chromatography column of stopping composition, moving phase is with certain flow velocity wash-out, and collection moving phase obtains squalene and prepares liquid A;
3) tocopherol reclaims: one-level chromatography column continues to resolve with the low-alcohol solution of lower acid, obtains mixed tocopherol and prepares liquid, concentrates to obtain mixed tocopherol;
4) sterol reclaims: concentrated squalene is prepared liquid A, and a small amount of lower alcohol dissolves, and low temperature is separated out white crystal sterol, filters also repeatedly recrystallization and obtains high-purity plant sterol, and filtrate is that squalene is prepared liquid B;
5) two stage column chromatography: it is raw material that concentrated squalene is prepared liquid B, silica gel is stopping composition, low-pole or non-polar solvent wash-out are collected colourless part, concentrate to obtain plant squalene.
Sfgd. described in step 1) is for leading to nitrogen, adding a kind of or combination in antioxidant; The required alcohol medium of described saponification is a kind of in methyl alcohol, ethanol, 1-propyl alcohol, 2-propyl alcohol and n-butyl alcohol, and described mineral alkali is KOH or NaOH, consumption be saponification value calculate aequum 1.0-1.5 doubly.
Wherein, the saponified method of the separation described in step 1) is phase-splitting, turns one or more combinations in soap, precipitation, centrifugal, cold analysis, filtration; Described extraction solvent is a kind of in normal hexane, sherwood oil, ether.
Wherein, step 2) described lower alcohol is a kind of in methyl alcohol, ethanol, 1-propyl alcohol, 2-propyl alcohol and n-butyl alcohol; Described resin is deacidite, and model is a kind of in HY-2002,201 * 7, JK206, HZ202.
Wherein, the concrete steps of described one-level column chromatography step 2) are: unsaponifiables dilutes with 2-5 times of lower alcohol, at 10-30 ℃, with flow velocity 0.5-3.5BV/h by the chromatography column of resin is housed, lower alcohol wash-out bed, until effluent liquid is water white transparency, collects elutriant squalene and prepare liquid A;
Wherein, the lower alcohol described in step 3) is methyl alcohol, ethanol, and lower acid used is a kind of in formic acid, acetic acid, propionic acid; During parsing, according to the variation of color, collect elutriant, the concentrated tocopherol medicinal extract that gets final product to obtain.
Wherein, a small amount of lower alcohol of use described in step 4) dissolves enriched material, and its ratio is V
enriched material: V
lower alcohol=1: 2-10.
Wherein, the concrete steps that sterol described in step 4) reclaims are: squalene is prepared to liquid A vacuum concentration, after precipitation, with lower alcohol, dissolve completely, the refrigerator and cooled that is put in-4 ℃-0 ℃ is analysed 12-24h, vacuum filtration obtains sterol coarse crystal, coarse crystal repeatedly recrystallization obtains high-purity plant sterol, and filtrate is that squalene is prepared liquid B.
Wherein, the stopping composition described in step 5) is 100-200 order, 200-300 order silica gel; Moving phase is one or more mixing in sherwood oil, normal hexane, ether, hexanaphthene, acetoneand ethyl acetate.
Wherein, the concrete steps of the two stage column chromatography described in step 5) are: concentrated squalene is prepared liquid B, enriched material dilutes by 2-5 times of moving phase, at 10-30 ℃, with flow velocity 0.5-3.5BV/h by the chromatography column of silica gel is housed, moving phase wash-out bed, collects colourless part, concentrates to obtain plant squalene.
The present invention during squalene, has following advantage in extracting deodorization distillate:
1. the selectivity of technique is good, and the content that can make squalene is brought up to 50 ~ 70% left and right from 0.5% ~ 1.5%, and content on average improves 50 times, and separation efficiency is high.
2. overcome the not high shortcoming of the general extraction yield of traditional technology, the feature such as this technique has environmental friendliness, operational condition gentleness has added sfgd. when extracting squalene, has both improved the extraction yield (80 ~ 90%) of squalene, has prevented again the loss of tocopherol.
3. technique is when obtaining plant squalene, and can obtain respectively tocopherol (content 70% left and right) and the sterol (content 98% left and right) of some higher degrees.
4. adopting deodorization distillate is raw material, compares with shark liver oil, sweet oil, tea seed wet goods, and cost is lower, and can better develop deodorization distillate, realizes the comprehensive utilization of oil and fat refining by product.
5. technique avoids using the main equipments such as molecular distillation, supercritical extraction unit, invests littlely, can realize short-term return.
Accompanying drawing explanation
Fig. 1: invented technology schema;
Unsaponifiables GC-MS figure in Fig. 2: embodiment mono-.Wherein appearance time 5.79,6.87,7.95,8.74,10.19,10.55,11.59 is followed successively by squalene, Delta-Tocopherol, Gamma-Tocopherol, alpha-tocopherol, campesterol, Stigmasterol, Sitosterol;
In Fig. 3: embodiment mono-, squalene is prepared liquid A GC-MS figure.Wherein appearance time 5.82,10.22,10.57,11.62 is followed successively by squalene, campesterol, Stigmasterol, Sitosterol;
Tocopherol GC-MS figure in Fig. 4: embodiment mono-, wherein appearance time 6.93,7.98,8.77 is followed successively by Delta-Tocopherol, Gamma-Tocopherol, alpha-tocopherol;
Sterol GC-MS figure in Fig. 5: embodiment mono-.Wherein appearance time 10.04,10.41,11.38 is followed successively by campesterol, Stigmasterol, Sitosterol;
Plant squalene medicinal extract GC-MS figure in Fig. 6: embodiment mono-.Wherein appearance time 6.00 is squalene.
Embodiment
embodiment mono-
This example extracts the squalene in soybean oil deodorizer distillate by the method that adopts saponification pre-treatment and two stage column chromatography to combine, and concrete implementation step is:
1. separated unsaponifiables: get soybean oil deodorizer distillate 108g(squalene content 1.96%); add a small amount of TBHQ as protective material; in the situation that stirring; add 1.5mol/L NaOH-methanol solution 320ml; 80 ℃ of backflow saponification 1h; after reaction finishes, add 300ml distilled water, stir and take out cool to room temperature after 2 minutes.Petroleum ether extraction three times, each 500mL, merges petroleum ether layer, and 5% salt washing petroleum ether layer is to neutral.The petroleum ether layer rotary evaporation under rear 60 ℃ of conditions that anhydrates, except desolventizing, obtains unsaponifiables, through GC-MS, detects (accompanying drawing 2), and in unsaponifiables, squalene content is 12.48%.
2. one-level column chromatography: the gained unsaponifiables in step 1 of take is raw material, methyl alcohol is moving phase, a small amount of methyl alcohol dilutes after this unsaponifiables, adding JK206 anionite-exchange resin is in the chromatography column of stopping composition, moving phase is with certain flow velocity wash-out, collect moving phase, when color becomes when colourless, stop collecting, merge the moving phase of collecting and obtain squalene and prepare liquid A.GC-MS detects and sees accompanying drawing 3.
3. tocopherol reclaims: acetic acid methanol solution one-level chromatography column continuation 6%(wt) is resolved, and according to colour-change Fractional Collections, obtains mixed tocopherol and prepares liquid, and 60 ℃ of rotary evaporation solvents, obtain mixed tocopherol, and tocopherol content can reach more than 70% (accompanying drawing 4).
4. sterol reclaims: get one-level column chromatography gained squalene and prepare liquid A, and after steaming desolventizes, dissolve with methanol, its ratio is V
enriched material: V
methyl alcohol=1: 5.Put into-4 ℃ of refrigerator 12h, visible white crystal is separated out, and vacuum filtration can obtain plant sterol.Press repeatedly recrystallization of above step, can obtain high-purity plant sterol, purity more than 98% (accompanying drawing 5).Gained filtrate is that squalene is prepared liquid B.
5. two stage column chromatography: get squalene in step 4 and prepare liquid B, 60 ℃ of vacuum concentration, as two stage column chromatography raw material.Be placed on silicagel column (100-200 order) top, separated with silica gel column chromatography, sherwood oil wash-out, collects colourless part, concentrates to obtain plant squalene, and after testing, squalene content is 72.85%, total extraction yield 85.44%.
embodiment bis-
This example extracts the squalene in Rice pollard oil deodorization distillate by the method that adopts saponification pre-treatment and two stage column chromatography to combine.Concrete implementation step is:
1. separated unsaponifiables: get Rice pollard oil deodorization distillate 100g(squalene content 0.86%); overhead product is put into three mouthfuls of round-bottomed flasks; add while stirring a small amount of BHA as protective material; add afterwards 1.5mol/L KOH-ethanolic soln (1.5 times that add-on is theoretical amount); 80 ℃ of backflow saponification 1.5h; after reaction finishes, add 300ml distilled water, stir and take out cool to room temperature after 2 minutes.N-hexane extraction three times, each 500mL, merges normal hexane layer, and 5% salt washing normal hexane layer is to neutral.Normal hexane layer anhydrates under rear 60 ℃ of conditions rotary evaporation except desolventizing, both unsaponifiables, through GC-MS, detect, in unsaponifiables, squalene content is 5.63%.
2. one-level column chromatography: the gained unsaponifiables in step 1 of take is raw material, ethanol is moving phase, after a small amount of this unsaponifiables of alcohol dilution, adding 717 anionite-exchange resin is in the chromatography column of stopping composition, moving phase is with certain flow velocity wash-out, collect moving phase, when color becomes when colourless, stop collecting, merge the moving phase of collecting and obtain squalene and prepare liquid A.
3. tocopherol reclaims: acetic acid ethanol one-level column chromatography post continuation 3%(wt) is resolved, and according to colour-change Fractional Collections, obtains mixed tocopherol and prepares liquid, and 60 ℃ of rotary evaporation solvents, obtain mixed tocopherol, and tocopherol content can reach more than 70%.
4. sterol reclaims: get one-level column chromatography gained squalene and prepare liquid A, and after steaming desolventizes, dissolve with methanol, its ratio is V
enriched material: V
methyl alcohol=1: 3.Put into-4 ℃ of refrigerator 24h, visible white crystal is separated out, and vacuum filtration can obtain plant sterol.Press repeatedly recrystallization of above step, can obtain high-purity plant sterol, purity is more than 98%.Gained filtrate is that squalene is prepared liquid B.
5. two stage column chromatography: get squalene in step 4 and prepare liquid B, 60 ℃ of vacuum concentration, as two stage column chromatography raw material.Be placed on silicagel column (100-200 order) top, separated with silica gel column chromatography, sherwood oil wash-out, collects colourless part, concentrates to obtain plant squalene, and after testing, squalene content is 52.78%, total extraction yield 87.92%.
comparative example
This example extracts squalene in plant oil deodorizing distillate by the method that traditional saponification adds molecular distillation, and concrete implementation step is:
1. separated unsaponifiables: get soybean oil deodorizer distillate 108g(squalene content 1.96%),, in the situation that stirring, add 1.5mol/L NaOH-methanol solution 300ml, 80 ℃ of backflow saponification 1h, after reaction finishes, add 320ml distilled water, stir and take out cool to room temperature after 2 minutes.Petroleum ether extraction three times, each 500mL, merges petroleum ether layer, and 5% salt washing petroleum ether layer is to neutral.The petroleum ether layer rotary evaporation under rear 60 ℃ of conditions that anhydrates, except desolventizing, obtains unsaponifiables, and in unsaponifiables, squalene content is 12.48%.
2. secondary molecular distillation extracts squalene: the gained unsaponifiables in step 1 of take is raw material, in vaporization temperature, is that 70 ℃, knifing rotating speed are that 250rpm, input speed are carried out molecular distillation for the first time while being 2.8ml/min.What take molecular distillation for the first time heats up in a steamer excess as raw material, in vaporization temperature, be that 200 ℃, knifing rotating speed carry out molecular distillation for the second time while being 250rpm, input speed 4ml/min, obtain the squalene crude product of about 16g, wherein squalene content is 32.68%, contains a certain amount of tocopherol and sterol in squalene crude extract.
Visible by example one, two and example three contrasts, a kind of two stage column chromatography is extracted the method for squalene in plant oil deodorizing distillate and is compared with traditional method, and the purity of squalene product is higher, and separation efficiency is high; Realize the separation of squalene, sterol, tocopherol, improved utility value; Whole technique process is few, and facility investment is little.
Claims (10)
1. two stage column chromatography is extracted a method for squalene in plant oil deodorizing distillate, it is characterized in that comprising the steps:
1) separated unsaponifiables: plant oil deodorizing distillate, in the situation that having protection, is added to mineral alkali saponification while stirring, and temperature of reaction is 60-80 ℃, reaction times is 45-60min, forms saponification mixture, after saponification finishes, separated saponified, residuum extraction concentrates to obtain unsaponifiables;
2) one-level column chromatography: the unsaponifiables that the step 1) of take obtains is raw material, lower alcohol is moving phase, and after a small amount of moving phase dilution unsaponifiables, adding basic anion exchange resin is in the chromatography column of stopping composition, moving phase is with certain flow velocity wash-out, and collection moving phase obtains squalene and prepares liquid A;
3) tocopherol reclaims: one-level chromatography column continues to resolve with the low-alcohol solution of lower acid, obtains mixed tocopherol and prepares liquid, concentrates to obtain mixed tocopherol;
4) sterol reclaims: concentrated squalene is prepared liquid A, and a small amount of lower alcohol dissolves, and low temperature is separated out white crystal sterol, filters also repeatedly recrystallization and obtains high-purity plant sterol, and filtrate is that squalene is prepared liquid B;
5) two stage column chromatography: it is raw material that concentrated squalene is prepared liquid B, silica gel is stopping composition, low-pole or non-polar solvent wash-out are collected colourless part, concentrate to obtain plant squalene.
2. a kind of two stage column chromatography according to claim 1 is extracted the method for squalene in plant oil deodorizing distillate, it is characterized in that: step 1) described sfgd. for logical nitrogen, add a kind of or combination in antioxidant; The required alcohol medium of described saponification is methyl alcohol, ethanol, 1-propyl alcohol, 2-propyl alcohol, a kind of in n-butyl alcohol, described mineral alkali is KOH or NaOH, consumption be saponification value calculate aequum 1.0-1.5 doubly.
3. a kind of two stage column chromatography according to claim 1 is extracted the method for squalene in plant oil deodorizing distillate, it is characterized in that: wherein the saponified method of the separation described in step 1) is phase-splitting, turns one or more combinations in soap, precipitation, centrifugal, cold analysis, filtration; Described extraction solvent is a kind of in normal hexane, sherwood oil, ether.
4. a kind of two stage column chromatography according to claim 1 is extracted the method for squalene in plant oil deodorizing distillate, it is characterized in that: step 2 wherein) described lower alcohol is a kind of in methyl alcohol, ethanol, 1-propyl alcohol, 2-propyl alcohol and n-butyl alcohol; Described resin is deacidite, and model is a kind of in HY-2002,201 * 7, JK206, HZ202.
5. a kind of two stage column chromatography according to claim 1 is extracted the method for squalene in plant oil deodorizing distillate, it is characterized in that: step 2 wherein) the concrete steps of described one-level column chromatography be: unsaponifiables dilutes with 2-5 times of lower alcohol, at 10-30 ℃, with flow velocity 0.5-3.5BV/h by the chromatography column of resin is housed, lower alcohol wash-out bed, until effluent liquid is water white transparency, collects elutriant squalene and prepare liquid A.
6. a kind of two stage column chromatography according to claim 1 is extracted the method for squalene in plant oil deodorizing distillate, it is characterized in that: wherein the lower alcohol described in step 3) is methyl alcohol, ethanol, and lower acid used is a kind of in formic acid, acetic acid and propionic acid; During parsing, according to the variation of color, collect elutriant, the concentrated tocopherol medicinal extract that gets final product to obtain.
7. a kind of two stage column chromatography according to claim 1 is extracted the method for squalene in plant oil deodorizing distillate, it is characterized in that: wherein a small amount of lower alcohol of the use described in step 4) dissolves enriched material, and its ratio is V
enriched material: V
lower alcohol=1: 2-10.
8. a kind of two stage column chromatography according to claim 1 is extracted the method for squalene in plant oil deodorizing distillate, it is characterized in that: the concrete steps that wherein sterol described in step 4) reclaims are: squalene is prepared to liquid A vacuum concentration, after precipitation, with lower alcohol, dissolve completely, the refrigerator and cooled that is put in-4 ℃-0 ℃ is analysed 12-24h, vacuum filtration obtains sterol coarse crystal, coarse crystal repeatedly recrystallization obtains high-purity plant sterol, and filtrate is that squalene is prepared liquid B.
9. a kind of two stage column chromatography according to claim 1 is extracted the method for squalene in plant oil deodorizing distillate, it is characterized in that: wherein the stopping composition described in step 5) is 100-200 order, 200-300 order silica gel; Moving phase is one or more mixing in sherwood oil, normal hexane, ether, hexanaphthene, acetone, ethyl acetate.
10. a kind of two stage column chromatography according to claim 1 is extracted the method for squalene in plant oil deodorizing distillate, it is characterized in that: wherein the concrete steps of the two stage column chromatography described in step 5) are: concentrated squalene is prepared liquid B, enriched material dilutes by 2-5 times of moving phase, at 10-30 ℃, with flow velocity 0.5-3.5BV/h by the chromatography column of silica gel is housed, moving phase wash-out bed, collects colourless part, concentrates to obtain plant squalene.
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| 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 |
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| CN104151282A (en) * | 2014-08-14 | 2014-11-19 | 山东圣地嘉禾生物工程有限公司 | Method for preparing natural vitamin E and phytosterol with resin absorption method |
| CN105367370A (en) * | 2014-08-27 | 2016-03-02 | 浙江医药股份有限公司新昌制药厂 | Method of extracting squalene from bottom sediment with natural vitamin E extracted |
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| 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 |
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| CN110128238A (en) * | 2019-06-05 | 2019-08-16 | 武汉工程大学 | A method of entrainment extracts and overcritical isolates and purifies squalene from Grain Production of Amaranthus seed |
| CN110575680A (en) * | 2019-09-19 | 2019-12-17 | 福建启元堂生物技术有限公司 | Method for double super-extraction of marine nutrients |
| 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 |
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| CN114409719A (en) * | 2022-01-24 | 2022-04-29 | 浙江工业大学 | Method for extracting phytosterol from rice bran oil deodorizer distillate |
| CN114409719B (en) * | 2022-01-24 | 2023-12-12 | 浙江工业大学 | Method for extracting phytosterol from rice bran oil 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 |
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