A method for extracting squalene and vitamin E

Abstract

The present invention provides a method for extracting squalene and vitamin E, and relates to the technical field of extraction. The method for extracting squalene and vitamin E of the present invention comprises the following steps: extraction: taking a tea oil cake after cold pressing, performing supercritical carbon dioxide extraction to obtain camellia oil; saponification: mixing camellia oil, ethanol solution, water and inorganic base, and performing saponification reaction; salting out: adding a salt solution to the saponified product, separating the upper solution and the lower solution after stratification; separation: performing supercritical carbon dioxide distillation on the lower solution to obtain a crude squalene product; purification: taking the crude squalene product, removing residual ethanol and water by thin film evaporation, separating vitamin E in turn by first-stage molecular distillation, and separating glycerol by second-stage molecular distillation to obtain a product enriched in squalene. The method of the present invention can fully extract camellia oil in tea oil cakes, and obtain camellia oil saponification, vitamin E, glycerol and a product rich in squalene.

Description

Technical Field

[0001] The invention relates to the technical field of extraction, in particular to a method for extracting squalene and vitamin E. Background Art

[0002] Camellia is native to China and plays an important role in the economic development of southern my country. Camellia seed kernels are rich in nutrients. The pressed camellia oil is rich in highly unsaturated fatty acids, camellia glycosides, tea polyphenols, squalene and other physiologically active ingredients, as well as vitamin E and trace elements such as calcium, iron, and zinc. Its nutritional composition is similar to that of olive oil. The unsaturated fatty acid content in camellia oil is as high as 92% (oleic acid content 78%, linoleic acid content 14%). Compared with other edible oils, camellia seed oil has a higher oleic acid content. Therefore, camellia oil enjoys the reputation of "the king of oils" and "Oriental olive oil".

[0003] Squalene has many physiological functions, such as increasing the activity of superoxide dismutase (SOD) in the body, enhancing basal immunity, anti-fatigue, and anti-tumor. Studies have also shown that squalene is highly skin-friendly and can easily penetrate into the skin base; squalene also increases cell oxygen content, enhances cell vitality, and promotes metabolism; squalene can also gather immune cells, repair wound tissue, and play an anti-inflammatory role. Therefore, squalene is in great demand in high-end skin care products and other fields. At present, there are few reports on the extraction and separation of squalene from camellia oil.

[0004] Cold pressing is a method of producing oil at low temperature. Since the processing temperature is usually below 60°C, the effect of high temperature on active ingredients can be avoided, and nutrients can be retained to the greatest extent. In addition, cold pressed oil is clear in color and light in taste. However, the oil yield of cold pressing is low, only about 50% of that of hot pressing, resulting in a higher price for cold pressed products. The residual oil content in the tea oil cake after cold pressing of camellia oil is high, reaching more than 6%. If it cannot be recycled, it will cause great waste.

[0005] Therefore, if the residual oil in the oil cake can be fully utilized to extract squalene, it can not only reduce the waste of oil cake, but also obtain camellia oil saponification, vitamin E, glycerol and squalene and other products, which will produce greater economic benefits. Summary of the invention

[0006] Based on this, it is necessary to provide a method for extracting squalene and vitamin E to address the above problems, which can fully extract the camellia oil in the tea oil cake and obtain camellia oil saponification, vitamin E, glycerol and squalene-rich products.

[0007] A method for extracting squalene and vitamin E, comprising the following steps:

[0008] Extraction: Take the cold-pressed tea oil cake and perform supercritical carbon dioxide extraction to obtain camellia oil;

[0009] Saponification: Mix camellia oil, ethanol solution, water and inorganic base to carry out saponification reaction;

[0010] Salting out: Add salt solution to the saponification product, and after stratification, separate the upper solution from the lower solution. The upper solution is camellia oil saponification product, and the lower solution is a mixture of salt-containing glycerol, crude squalene, and vitamin E.

[0011] Separation: The lower layer solution is subjected to supercritical carbon dioxide distillation to obtain crude squalene;

[0012] Purification: The crude squalene is taken, and residual ethanol and water are removed by first-stage thin film evaporation, vitamin E is separated in sequence by second-stage molecular distillation, and glycerol is separated by third-stage molecular distillation to obtain a product enriched in squalene.

[0013] The method uses tea oil cake as raw material, fully extracts and purifies the residual oil therein, and can reduce the oil content of tea oil cake to below 1wt%. The present invention utilizes the characteristics that squalene and vitamin E do not participate in saponification reaction to separate saponified products, and then uses supercritical carbon dioxide distillation to obtain camellia oil unsaponifiable products (squalene crude products), and then purifies through molecular distillation to obtain vitamin E, glycerol and products enriched with squalene.

[0014] In one embodiment, in the extraction step, the oil content of the tea oil cake is ≥ 6wt%.

[0015] In one of the embodiments, in the extraction step, the temperature of supercritical carbon dioxide extraction is 40-50°C, the pressure is 10-30 MPa, and the extraction time is 1-2 hours.

[0016] Supercritical carbon dioxide extraction takes a short time, does not require decolorization and other refining treatments, is non-toxic, has no chemical reagent residues and pollution, and does not require deacidification. In addition, squalene is a non-polar, highly unsaturated aliphatic hydrocarbon compound. It is a colorless oily liquid at room temperature and is almost insoluble in water, but easily soluble in non-polar solvents such as supercritical carbon dioxide. Using supercritical carbon dioxide extraction can increase the content of squalene.

[0017] Compared with the traditional pressing method, the metal ions (such as Fe 3+ , Ca 2+ Mg 2 + ) content is lower, avoiding the reaction of metal ions with inorganic bases in the subsequent saponification reaction to produce insoluble salts.

[0018] In one embodiment, in the saponification step, the inorganic base is sodium hydroxide or potassium hydroxide.

[0019] In one embodiment, in the saponification step, the ethanol solution is a 90-95 wt % ethanol solution.

[0020] In one embodiment, in the saponification step, the weight ratio of camellia oil, ethanol solution, water and inorganic base is (850-1000): (100-200): (100-500): (120-180).

[0021] In one embodiment, the inorganic base is sodium hydroxide, and the weight ratio of camellia oil, ethanol solution, water and sodium hydroxide is (850-1000): (100-200): (100-500): (120-140).

[0022] In one embodiment, the inorganic base is potassium hydroxide, and the weight ratio of camellia oil, ethanol solution, water and sodium hydroxide is (850-1000): (100-200): (100-500): (168-180).

[0023] In one embodiment, in the saponification step, the saponification reaction is carried out under a nitrogen atmosphere, the reaction temperature is 70-80° C., the stirring speed is 10-60 rpm, and the reaction time is 0.5-4 h.

[0024] In one of the embodiments, in the salting-out step, the salt solution is a 4-6 wt % NaCl aqueous solution, and the weight ratio of the salt solution to the saponification product is (500-1000):(1170-1880).

[0025] In one embodiment, in the separation step, a supercritical carbon dioxide distillation tower is used to circulate and distill the lower layer solution, the pressure in the tower is 10-30 MPa, the temperature is 40-70°C, the circulation distillation time is 1-3 hours, the reflux ratio is (4-8):1, the filler in the tower is a plurality of glass balls with a diameter of 5-20 mm, and the tower height is 1-3 meters. The unsaponifiable matter of camellia oil (crude squalene) is obtained from the top of the tower.

[0026] In one of the embodiments, in the purification step, the temperature of the first-stage thin film evaporation is 55-75° C., the pressure is 1-2000 Pa, and the speed of the scraper is 60-360 rpm.

[0027] In one of the embodiments, in the purification step, the temperature of the second stage molecular distillation is 100-120° C., the pressure is 1-50 Pa, and the speed of the scraper is 60-360 rpm.

[0028] In one of the embodiments, in the purification step, the temperature of the third stage molecular distillation is 140-160° C., the pressure is 1-5 Pa, and the speed of the scraper is 60-360 rpm.

[0029] Compared with the prior art, the present invention has the following beneficial effects:

[0030] The method of the present invention uses tea oil cake as a raw material, fully extracts and purifies the residual oil therein, and can reduce the oil content of the tea oil cake to less than 1wt%. The present invention utilizes the characteristics that squalene and vitamin E do not participate in saponification reaction to separate saponified products, and then uses supercritical carbon dioxide distillation to obtain camellia oil unsaponifiable products (squalene crude products), and then undergoes molecular distillation purification to obtain vitamin E, glycerol and squalene-enriched products. BRIEF DESCRIPTION OF THE DRAWINGS

[0031] Figure 1 A schematic diagram of the structure of a supercritical carbon dioxide distillation tower in an embodiment.

[0032] In the figure, 100 is a compression pump, 200 is a raw material pump, 300 is a tower body, 310 is a filler, 400 is a separation kettle, 500 is a material pump, and 600 is a collection kettle. DETAILED DESCRIPTION

[0033] For the convenience of understanding the present invention, the preferred embodiments will be given below to describe the present invention in more detail. However, the present invention can be implemented in many different forms and is not limited to the embodiments described herein. On the contrary, the purpose of providing these embodiments is to make the understanding of the disclosure of the present invention more thorough and comprehensive.

[0034] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those commonly understood by those skilled in the art of the present invention. The terms used in the specification of the present invention herein are only for the purpose of describing specific embodiments and are not intended to limit the present invention.

[0035] In the following examples and comparative examples, unless otherwise specified, reagents, materials, and equipment are commercially available, and the experimental methods are conventional experimental methods in the art.

[0036] Example 1

[0037] A method for extracting squalene and vitamin E, comprising the following steps:

[0038] (1) Extraction: Using cold pressed tea oil cake (oil content of about 6 wt%) as raw material, supercritical carbon dioxide extraction is performed at an extraction temperature of 50°C, a pressure of 20 MPa, and an extraction time of 1.5 h to obtain camellia oil. Through this extraction step, the oil content in the tea oil cake is reduced to less than 1 wt%.

[0039] (2) Saponification: 850 parts by weight of camellia oil, 100 parts of 95 wt% ethanol solution, and 200 parts of distilled water were mixed, and then 120 parts of sodium hydroxide were added. The saponification reaction was carried out under a pure nitrogen atmosphere at a reaction temperature of 75° C., a stirring speed of 40 rpm, and a saponification reaction time of 2 h.

[0040] (3) Salting out: Add 500 parts of 5 wt% NaCl aqueous solution to the saponification product of step (2), mix well and let stand for 2 hours to separate the layers. The upper layer solution after salting out is the camellia oil saponification product, and the lower layer solution is a mixture of salt-containing glycerol, crude squalene and vitamin E, which is discharged from the bottom of the soap pot.

[0041] (4) Separation: Use Figure 1 The supercritical carbon dioxide distillation tower shown in the figure performs supercritical carbon dioxide circulating distillation on the lower layer solution to obtain unsaponifiable camellia oil (crude squalene). The pressure in the tower is 20MPa, the temperature is 55℃, the circulating distillation time is 2h, the reflux ratio is 6:1, the filler in the tower is a number of glass balls with a diameter of 16mm, and the tower height is 2m.

[0042] Figure 1 The structure diagram of the supercritical carbon dioxide distillation tower is shown in FIG. 3 , which includes a tower body 300, a separation kettle 400 and a collection kettle 600. A supercritical carbon dioxide inlet is provided at the bottom of the tower body 300, and a compression pump 100 is provided on the pipeline connected to the inlet for conveying supercritical carbon dioxide; a raw material inlet is provided in the middle of the tower body 300, and a raw material pump 200 is provided on the pipeline connected to the raw material inlet for conveying the product of step (3). The tower body 300 is filled with a filler 310, and the filler 310 is a plurality of glass balls with a diameter of 16 mm. Supercritical carbon dioxide flows upward, and the purified product flows downward, so that continuous countercurrent extraction is performed. The light component after extraction enters the separation kettle 400, and waits for carbon dioxide to escape. The heavy component after extraction enters the collection kettle 600 for recycling. A material pump 500 is also connected below the collection kettle 600, and the material in the collection kettle 600 can be introduced into the tower body 300 for cyclic extraction.

[0043] (5) Purification: The crude squalene is subjected to first-stage thin film evaporation, second-stage molecular distillation and third-stage molecular distillation in sequence. The first-stage thin film evaporation uses a thin film evaporator at a temperature of 65°C, a pressure of 1000Pa, and a film scraper speed of 200rpm to remove residual ethanol and residual water; the second-stage molecular distillation uses a molecular distiller at a temperature of 120°C, a pressure of 25Pa, and a film scraper speed of 200rpm to separate vitamin E; the third-stage molecular distillation uses a molecular distiller at a temperature of 140°C, a pressure of 1Pa, and a film scraper speed of 200rpm to remove glycerol from the saponification reaction, and the distillation residue is the final product enriched with squalene.

[0044] According to the gas chromatography (GC) method in standard GB 14756-2010, the vitamin E content of the molecular distillation distillate is greater than 80wt%. According to the gas chromatography (GC) method in standard NY / T 3673-2020 "Determination of squalene content in animals and plants", the squalene content in the molecular distillation residue is greater than 35wt%.

[0045] The technical features of the above-described embodiments may be arbitrarily combined. To make the description concise, not all possible combinations of the technical features in the above-described embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0046] The above-mentioned embodiments only express several implementation methods of the present invention, and the descriptions thereof are relatively specific and detailed, but they cannot be understood as limiting the scope of the invention patent. It should be pointed out that, for ordinary technicians in this field, several variations and improvements can be made without departing from the concept of the present invention, and these all belong to the protection scope of the present invention. Therefore, the protection scope of the patent of the present invention shall be subject to the attached claims.

Claims

1. A method for extracting squalene and vitamin E, characterized in that: The following steps are involved: Extraction: Take the cold-pressed tea oil cake and perform supercritical carbon dioxide extraction to obtain camellia oil; In the extraction step, the oil content of the tea oil cake is ≥6wt%; the supercritical carbon dioxide extraction temperature is 40~50°C, the pressure is 10~30 MPa, and the extraction time is 1~2 h; Saponification: Mix camellia oil, ethanol solution, water and inorganic base to carry out saponification reaction; In the saponification step, the inorganic base is potassium hydroxide and / or sodium hydroxide, and the ethanol solution is a 90-95wt% ethanol solution; The weight ratio of camellia oil, ethanol solution, water and inorganic base is (850-1000): (100-200): (100-500): (120-180); The saponification reaction was carried out under nitrogen atmosphere, the reaction temperature was 70-80 °C, the stirring speed was 10-60 rpm, and the reaction time was 0.5-4 h; Salting out: Add salt solution to the saponification product, and after stratification, separate the upper solution from the lower solution. The upper solution is camellia oil saponification product, and the lower solution is a mixture of salt-containing glycerol, crude squalene, and vitamin E. In the salting-out step, the salt solution is a 4-6 wt% NaCl aqueous solution, and the weight ratio of the salt solution to the saponification product is (500-1000): (1170-1880); Separation: The lower layer solution is subjected to supercritical carbon dioxide distillation to obtain crude squalene; In the separation step, a supercritical carbon dioxide distillation tower is used to circulate and distill the lower layer solution, the pressure in the tower is 10-30 MPa, the temperature is 40-70°C, the circulating distillation time is 1-3 h, the reflux ratio is (4-8):1, the filler in the tower is a plurality of glass balls with a diameter of 5-20 mm, and the tower height is 1-3 m; Purification: taking the crude squalene, removing residual ethanol and water by first-stage thin film evaporation, separating vitamin E by second-stage molecular distillation, and separating glycerol by third-stage molecular distillation to obtain a product enriched in squalene; In the purification step, the temperature of the first-stage thin film evaporation is 55-75°C, the pressure is 1-2000 Pa, and the speed of the scraper is 60-360 rpm; The temperature of the second stage molecular distillation is 100~120℃, the pressure is 1~50 Pa, and the speed of the scraper is 60~360 rpm; The temperature of the third stage molecular distillation is 140~160℃, the pressure is 1~5 Pa, and the speed of the scraper is 60~360 rpm.

Images