CN110790626B - Method for extracting squalene from rapeseed oil - Google Patents
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- CN110790626B CN110790626B CN201910989915.2A CN201910989915A CN110790626B CN 110790626 B CN110790626 B CN 110790626B CN 201910989915 A CN201910989915 A CN 201910989915A CN 110790626 B CN110790626 B CN 110790626B
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/005—Processes comprising at least two steps in series
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/04—Purification; Separation; Use of additives by distillation
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/148—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound
- C07C7/152—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound by forming adducts or complexes
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/20—Use of additives, e.g. for stabilisation
Abstract
The invention relates to the technical field of squalene extraction, and particularly relates to a method for extracting squalene from rapeseed oil, which comprises the following steps: (1) adding a water solution containing a complex enzyme into the rapeseed oil, and then placing the rapeseed oil in a pulse direct current electric field for treatment; (2) adding a microcrystalline fiber solution into the product obtained in the step (1), mixing, adding a crystal modifier, mixing at 50-55 ℃, preserving heat, filtering, and removing filtrate; (3) adding ethanol and levovitamin C into the product obtained in the step (2), placing the mixture in a constant-temperature water bath at the temperature of 60-65 ℃ for reflux, cooling, washing with water until the washing liquid is neutral, and distilling under vacuum; the method has the advantages of high squalene extraction rate, less reagent residue, improvement of squalene purity and reduction of extraction cost.
Description
Technical Field
The invention relates to the technical field of squalene extraction, and particularly relates to a method for extracting squalene from rapeseed oil.
Background
Rapeseed oil, also known as rapeseed oil or coriander oil, is also known as clear oil in the southern Hunan region. The edible oil is widely used in daily life of people due to golden color and faint scent, and is one of the main edible oil at home and abroad. The rapeseed oil has the unsaturated fatty acid content of more than 85 percent, contains rich oleic acid, linoleic acid, linolenic acid and phospholipid, has the digestibility of 99 percent to human bodies, and is rich in bioactive components such as vitamin E, polyphenol, squalene, sterol and the like.
Squalene is a highly unsaturated hydrocarbon compound, a lipid unsaponifiable substance, has a chemical name of 2,6,10,15,19, 23-hexamethyl-2, 6,10,14,18, 22-tetracosahexaene, is an open-chain triterpenoid compound, has various physiological functions of improving the activity of superoxide dismutase (SOD) in vivo, enhancing the immunity of organisms, improving sexual functions, resisting aging, fatigue, tumors and the like, and is widely applied to the fields of medicines, foods, cosmetics, chemical engineering and the like.
For example, patent document CN201510956808.1 discloses a method for extracting a plant-derived squalene composition, a method for preparing a squalene-containing medicine, a squalene-containing medicine prepared by the method, and applications thereof. The method for extracting the plant source squalene composition comprises the following steps: sequentially carrying out pretreatment and enrichment separation on the raw material rich in squalene, wherein the enrichment separation conditions are controlled so that the obtained plant source squalene composition contains 35-80 wt% of squalene, and the raw material rich in squalene contains 5-30 wt% of squalene and 10-40 wt% of sterol.
For another example, patent document CN201110027119.4 discloses a method for extracting squalene from camellia seeds, which comprises the following steps: preparing materials, crushing, leaching, concentrating, carrying out methyl esterification reaction, carrying out complexing agent-borax reaction, carrying out macroporous resin chromatographic separation and purification, concentrating, extracting, washing and concentrating to obtain crude squalene oil, and extracting with supercritical carbon dioxide to obtain squalene essential oil with squalene content being more than or equal to 80%; the tea oil squalene soft capsule is prepared from the following raw materials in percentage by weight: 87-90 parts of squalene essential oil with the squalene content being more than or equal to 80%, 3-5 parts of polyethylene glycol 4003, 2-3 parts of beeswax and 2-5 parts of phospholipid.
In the literature, "influence of refining on the quality of rapeseed oil" (published in 2018 by equantry et al), it is also mentioned that "the acid value, peroxide value, color and phosphorus content of refined rapeseed oil are all reduced, and the contents of VE, sterol, polyphenol and squalene are obviously reduced; the contents of trans fatty acid and 3-chloropropanol are not changed greatly, so the application extracts squalene in order to prevent the reduction of squalene content and the reduction of squalene utilization value.
Disclosure of Invention
The invention provides a method for extracting squalene from rapeseed oil to solve the technical problems.
The method is realized by the following technical scheme:
a method for extracting squalene from rapeseed oil comprises the following steps:
(1) adding a water solution containing complex enzyme into the rapeseed oil until the water-oil ratio is 1: (0.2-0.5), and then treating for 10-20min under a pulse direct current electric field;
(2) adding the microcrystalline fiber solution into the product obtained in the step (1), mixing for 10-15min, adding a crystal modifier, mixing for 3-5min at 50-55 ℃, performing heat preservation treatment for 5-10min, filtering, and removing the filtrate;
(3) adding ethanol into the product obtained in the step (2) until the molar ratio of ethanol to oil is (5-7):1, simultaneously adding levovitamin C to 2-6ppm of the total mass fraction of the system, placing in a constant-temperature water bath at 60-65 ℃ for refluxing for 20-30min, cooling, washing with water until the washing liquid is neutral, and distilling under the vacuum condition of 70-90 Pa.
The working conditions of the pulse direct current electric field are as follows: the peak voltage is 30-35V, the pulse frequency is 1-2kHz, and the duty ratio is 0.1-0.5.
The compound enzyme content in the compound enzyme-containing aqueous solution is 30-50 ppm.
The compound enzyme is prepared from phospholipase, protease and cellulase according to the proportion of 1: (0.5-1): (0.2-0.4) in the ratio of the inoculum size.
The temperature of the distillation is 220-230 ℃.
The mass concentration of the microcrystalline fiber solution is 20-25%.
The addition amount of the microcrystalline fiber solution is 4-10% of the mass of the rapeseed oil.
The crystal transformation agent is a citric acid solution containing catechin, and the mass fraction of the crystal transformation agent is as follows: catechin 0.01-0.05%, citric acid 10-15%, and water in balance.
The addition amount of the crystal transformation agent is 15-25ppm of the mass of the filtrate.
Has the advantages that:
the method has the advantages of high squalene extraction rate and less reagent residue, improves the squalene purity, reduces the extraction cost, and specifically comprises the following steps:
firstly, the invention uses the water solution containing complex enzyme and the pulse direct current electric field to promote the rapeseed oil to break emulsion and provide conditions for fully releasing effective substances.
Secondly, the invention utilizes the action of the cellulose in the microcrystalline fibers and the complex enzyme to damage the crystal structure of the microcrystalline fibers, coats the fatty acid and the impurity elements in the mixing process, and utilizes the crystal transformation agent to improve the crystal structure, so that the effective separation of the squalene, the fatty acid and the impurity elements is realized.
Then, the rapeseed oil is esterified, and the levorotatory vitamin C is added during the esterification to prevent oxidation, so that the yield of squalene is improved.
Finally, the invention utilizes vacuum distillation to effectively cathode squalene, simultaneously reduces the residual quantity of reagents and improves the purity and yield of squalene.
Detailed Description
The following is a detailed description of the embodiments of the present invention, but the present invention is not limited to these embodiments, and any modifications or substitutions in the basic spirit of the embodiments are included in the scope of the present invention as claimed in the claims.
Example 1
A method for extracting squalene from rapeseed oil comprises the following steps:
(1) adding a water solution containing complex enzyme into the rapeseed oil until the water-oil ratio is 1: 0.5, then placing the mixture in a pulse direct current electric field for treatment for 20 min;
(2) adding the microcrystalline fiber solution into the product obtained in the step (1), mixing for 15min, adding a crystal modifier, mixing for 5min at 55 ℃, performing heat preservation treatment for 10min, filtering, and removing filtrate;
(3) adding ethanol into the product obtained in the step (2) until the molar ratio of ethanol to oil is 7:1, simultaneously adding levovitamin C to 6ppm of the total mass fraction of the system, placing in a constant-temperature water bath at 65 ℃ for refluxing for 30min, cooling, washing with water until the washing liquid is neutral, distilling under the vacuum condition of 90Pa for 1h, and collecting the distillate;
the working conditions of the pulse direct current electric field are as follows: the peak voltage is 35V, the pulse frequency is 2kHz, and the duty ratio is 0.5;
the content of the complex enzyme in the aqueous solution containing the complex enzyme is 50 ppm;
the compound enzyme is prepared from phospholipase, protease and cellulase according to the proportion of 1: 1: 0.4 of inoculum size ratio;
the temperature of the distillation is 230 ℃;
the mass concentration of the microcrystalline fiber solution is 25%;
the addition amount of the microcrystalline fiber solution is 10% of the mass of the rapeseed oil;
the crystal transformation agent is a citric acid solution containing catechin, and the mass fraction of the crystal transformation agent is as follows: 0.05% of catechin, 15% of citric acid and the balance of water;
the addition amount of the crystal transformation agent is 25ppm of the mass of the filtrate.
Example 2
A method for extracting squalene from rapeseed oil comprises the following steps:
(1) adding a water solution containing complex enzyme into the rapeseed oil until the water-oil ratio is 1: 0.2, then placing the mixture in a pulse direct current electric field for treatment for 10 min;
(2) adding the microcrystalline fiber solution into the product obtained in the step (1), mixing for 10min, adding a crystal modifier, mixing for 3min at 50 ℃, performing heat preservation for 5min, filtering, and removing the filtrate;
(3) adding ethanol into the product obtained in the step (2) until the molar ratio of ethanol to oil is 5:1, simultaneously adding levovitamin C to 2ppm of the total mass fraction of the system, placing in a constant-temperature water bath at 60 ℃ for refluxing for 20min, cooling, washing with water until the washing liquid is neutral, distilling under 70Pa vacuum for 1h, and collecting the distillate;
the working conditions of the pulse direct current electric field are as follows: the peak voltage is 30V, the pulse frequency is 1kHz, and the duty ratio is 0.1;
the content of the complex enzyme in the aqueous solution containing the complex enzyme is 30 ppm;
the compound enzyme is prepared from phospholipase, protease and cellulase according to the proportion of 1: 0.5: 0.2 of inoculum size ratio;
the temperature of the distillation is 220 ℃;
the mass concentration of the microcrystalline fiber solution is 20%;
the addition amount of the microcrystalline fiber solution is 4% of the mass of the rapeseed oil;
the crystal transformation agent is a citric acid solution containing catechin, and the mass fraction of the crystal transformation agent is as follows: 0.01% of catechin, 10% of citric acid and the balance of water;
the addition amount of the crystal transformation agent is 15ppm of the mass of the filtrate.
Example 3
A method for extracting squalene from rapeseed oil comprises the following steps:
(1) adding a water solution containing complex enzyme into the rapeseed oil until the water-oil ratio is 1: 0.3, then placing the mixture in a pulse direct current electric field for treatment for 15 min;
(2) adding a microcrystalline fiber solution into the product obtained in the step (1), mixing for 12min, adding a crystal modifier, mixing for 4min at 53 ℃, carrying out heat preservation treatment for 8min, filtering, and removing filtrate;
(3) adding ethanol into the product obtained in the step (2) until the molar ratio of ethanol to oil is 6:1, simultaneously adding levovitamin C to 4ppm of the total mass fraction of the system, placing in a constant-temperature water bath at 63 ℃ for refluxing for 25min, cooling, washing with water until the washing liquid is neutral, distilling under 80Pa vacuum for 1h, and collecting distillate;
the working conditions of the pulse direct current electric field are as follows: peak voltage 32V, pulse frequency 1.5kHz, duty cycle 0.3;
the content of the complex enzyme in the aqueous solution containing the complex enzyme is 40 ppm;
the compound enzyme is prepared from phospholipase, protease and cellulase according to the proportion of 1: 0.8: 0.3 of inoculum size ratio;
the temperature of the distillation is 225 ℃;
the mass concentration of the microcrystalline fiber solution is 22%;
the addition amount of the microcrystalline fiber solution is 7 percent of the mass of the rapeseed oil;
the crystal transformation agent is a citric acid solution containing catechin, and the mass fraction of the crystal transformation agent is as follows: 0.03% of catechin, 12% of citric acid and the balance of water;
the addition amount of the crystal transformation agent is 20ppm of the mass of the filtrate.
Comparative example 1
The difference from example 4 is that: the pulsed dc electric field treatment is replaced by mixing.
Comparative example 2
The difference from example 4 is that: the complex enzyme is not added with cellulase.
Comparative example 3
The difference from example 4 is that: no crystal transformation agent was added.
Comparative example 4
The difference from example 4 is that: no L-vitamin C was added.
Comparative example 5
The difference from example 4 is that: step (2) was not taken.
In the present example and the comparative example, the same rapeseed oil was used, the content of squalene in rapeseed oil before extraction was measured according to the method of measuring the content of squalene in deodorized distillate by gas chromatography (luxiangqing is published in 2017), the result was 12.5%, the method of the examples and the comparative example was used for squalene extraction, the method of measuring the content of squalene in deodorized distillate by gas chromatography (luxiangqing is published in 2017) was also used for squalene content measurement, and the yield results are shown in table 1:
TABLE 1
Meanwhile, the inventor respectively weighs 0.075g of each distillate in the examples and the comparative examples, further separates and purifies squalene by using 200-mesh silica gel, samples are loaded by a dry method, an eluant is n-hexane and ethyl acetate which are 100: 1, elution is carried out, each 10mL tube is used for collection, gas phase detection is carried out, and the squalene content of each tube is calculated according to standard curves;
the preparation method of the standard yeast comprises the following steps: accurately weighing 20mg of squalene standard substance, and using normal hexane to fix the volume to 10mL to obtain 2mg/mL squalene standard stock solution; 0.05 mL, 0.25 mL, 0.50 mL, 1.00 mL, and 7.50mL of stock solutions were taken, and the volume was adjusted to 10mL with n-hexane to obtain each concentration. The peak area was plotted as the ordinate (y) and each mass concentration was plotted as the abscissa (x) to prepare a standard curve.
The squalene purity results are shown in table 2:
TABLE 2
| Item | Example 1 | Example 2 | Example 3 | Comparative example 1 |
| Purity/%) | 95.2 | 94.6 | 97.8 | 72.3 |
| Item | Comparative example 2 | Comparative example 3 | Comparative example 4 | Comparative example 5 |
| Purity/%) | 81.9 | 77.5 | 73.7 | 85.9 |
Claims (7)
1. The method for extracting squalene from rapeseed oil is characterized by comprising the following steps of:
(1) adding a water solution containing complex enzyme into the rapeseed oil until the water-oil ratio is 1: (0.2-0.5), and then treating for 10-20min under a pulse direct current electric field;
(2) adding the microcrystalline fiber solution into the product obtained in the step (1), mixing for 10-15min, adding a crystal modifier, mixing for 3-5min at 50-55 ℃, performing heat preservation treatment for 5-10min, filtering, and removing the filtrate;
(3) adding ethanol into the product obtained in the step (2) until the molar ratio of ethanol to oil is (5-7):1, simultaneously adding levovitamin C to 2-6ppm of the total mass fraction of the system, placing in a constant-temperature water bath at 60-65 ℃ for refluxing for 20-30min, cooling, washing with water until the washing liquid is neutral, and distilling under the vacuum condition of 70-90 Pa;
the compound enzyme is prepared from phospholipase, protease and cellulase according to the proportion of 1: (0.5-1): (0.2-0.4) the inoculum size ratio;
the crystal transformation agent is a citric acid solution containing catechin, and the mass fraction of the crystal transformation agent is as follows: catechin 0.01-0.05%, citric acid 10-15%, and water in balance.
2. The method for extracting squalene from rapeseed oil according to claim 1, wherein the working conditions of the pulse direct current electric field are as follows: the peak voltage is 30-35V, the pulse frequency is 1-2kHz, and the duty ratio is 0.1-0.5.
3. The method for extracting squalene from rapeseed oil according to claim 1, wherein the complex enzyme content in the complex enzyme-containing aqueous solution is 30-50 ppm.
4. The method for extracting squalene from rapeseed oil according to claim 1, wherein the mass concentration of the microcrystalline fiber solution is 20-25%.
5. The method for extracting squalene from rapeseed oil according to claim 1, wherein the addition amount of said microcrystalline fiber solution is 4-10% of the mass of rapeseed oil.
6. The method for extracting squalene from rapeseed oil according to claim 1, wherein the addition amount of the crystal modifier is 15-25ppm of the mass of the filtrate.
7. The method for extracting squalene from rapeseed oil according to claim 1, wherein the distillation temperature is 220-230 ℃.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040158083A1 (en) * | 2002-11-27 | 2004-08-12 | Choo Yuen May | Method of extracting and isolating minor components from vegetable oil |
| CN103483305A (en) * | 2013-09-25 | 2014-01-01 | 潘见 | Method for gathering/recovering VE (Vitamins E), squalene and polyunsaturated fatty acids from deodorized distillate of plant oil |
| MY160567A (en) * | 2007-01-19 | 2017-03-15 | Univ Putra Malaysia | Method of recovering squalene from vegetable oil based fatty acid distillate |
| CN106748615A (en) * | 2016-12-09 | 2017-05-31 | 广州白云山汉方现代药业有限公司 | A kind of method that squalene is extracted from grease |
| CN107474093A (en) * | 2017-08-23 | 2017-12-15 | 福建省格兰尼生物工程股份有限公司 | A kind of deodorization distillate continuous production VE, sterol, methyl esters, glycerine, the method for squalene and high-boiling components |
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- 2019-10-17 CN CN201910989915.2A patent/CN110790626B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040158083A1 (en) * | 2002-11-27 | 2004-08-12 | Choo Yuen May | Method of extracting and isolating minor components from vegetable oil |
| MY160567A (en) * | 2007-01-19 | 2017-03-15 | Univ Putra Malaysia | Method of recovering squalene from vegetable oil based fatty acid distillate |
| CN103483305A (en) * | 2013-09-25 | 2014-01-01 | 潘见 | Method for gathering/recovering VE (Vitamins E), squalene and polyunsaturated fatty acids from deodorized distillate of plant oil |
| CN106748615A (en) * | 2016-12-09 | 2017-05-31 | 广州白云山汉方现代药业有限公司 | A kind of method that squalene is extracted from grease |
| CN107474093A (en) * | 2017-08-23 | 2017-12-15 | 福建省格兰尼生物工程股份有限公司 | A kind of deodorization distillate continuous production VE, sterol, methyl esters, glycerine, the method for squalene and high-boiling components |
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