Method for extracting squalene from tea oil cake
Through supercritical carbon dioxide extraction and transesterification reaction, combined with molecular distillation and supercritical carbon dioxide distillation, squalene and vitamin E are successfully extracted from tea oil cakes efficiently, solving the problem of waste of residual oil and low extraction efficiency in tea oil cakes, realizing the Efficient and environmentally friendly product separation.
Patent Information
- Application Number
- CN202210792419.X
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- Filing Date
- 2022-07-07
- Publication Date
- 2024-12-10
- Estimated Expiration
- 2042-07-07
AI Technical Summary
There are few reports of extracting and isolating squalene from camellia oil in the prior art, and the low oil yield of cold pressing method leads to waste of residual oil in the tea oil cake, and lacks efficient utilization methods.
Camellia oil was extracted from the tea oil cake by supercritical carbon dioxide extraction method, and the vitamin E-rich camellia fatty acid ethyl ester was obtained through transesterification reaction and molecular distillation, and then the enriched squalene was obtained through continuous countercurrent distillation of supercritical carbon dioxide.
It has achieved efficient extraction of residual oil in tea oil cakes, reduced oil content, and obtained products rich in squalene and vitamin E, which have great economic benefits and environmental advantages.
Smart Images
Figure HDA0003734345680000011
Abstract
Description
Technical Field
[0001] The invention relates to the technical field of extraction, in particular to a method for extracting squalene from tea oil cake. 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 squalene, which has great economic benefits. Summary of the invention
[0006] Based on this, it is necessary to provide a method for extracting squalene from tea oil cake to address the above problems, which can fully extract the camellia oil in the tea oil cake and obtain a squalene-enriched product and a camellia oil fatty acid ethyl ester product rich in vitamin E.
[0007] A method for extracting squalene from tea oil cake comprises the following steps:
[0008] Extraction: Take the cold-pressed tea oil cake and perform supercritical carbon dioxide extraction to obtain camellia oil;
[0009] Transesterification: Mix camellia oil, ethanol solution and alkaline catalyst, heat and carry out transesterification reaction;
[0010] Purification: molecular distillation is performed on the camellia oil fatty acid ethyl ester product after the ester exchange reaction to remove residual ethanol and water, and camellia oil fatty acid ethyl ester containing vitamin E, glycerol and crude squalene are obtained in sequence;
[0011] Enrichment: The crude squalene is subjected to continuous countercurrent distillation with supercritical carbon dioxide to obtain a squalene-enriched product.
[0012] In the above method, tea oil cake is used as a raw material, and the residual oil therein is fully extracted and purified, so that the oil content of the tea oil cake can be reduced to below 1wt%, and a product rich in squalene and a product of camellia oil fatty acid ethyl ester rich in vitamin E are obtained; camellia oil fatty acid ethyl ester is rich in linoleic acid ethyl ester, has the effect of cholesterol and blood lipids, and can be used as a drug raw material for preventing and treating arteriosclerosis.
[0013] The method of the invention can not only efficiently extract the residual oil in the tea oil cake, but also obtain a product rich in squalene and a product rich in camellia oil fatty acid ethyl ester of vitamin E through purification.
[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 40-60° C., the pressure is 10-30 MPa, and the extraction time is 1-2 h.
[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] In one embodiment, in the esterification step, the alkaline catalyst is sodium hydroxide and / or potassium hydroxide.
[0018] In one embodiment, in the esterification step, the ethanol solution is a 90-95% ethanol solution.
[0019] In one embodiment, in the transesterification step, the weight ratio of the camellia oil, ethanol and alkaline catalyst is (850-1000): (140-420): (1-5).
[0020] In one of the embodiments, in the esterification step, the heating temperature is 60-80° C., the esterification reaction pressure is 0-0.1 MPa, the reaction time is 30-60 min, and stirring is performed during the esterification reaction at a stirring speed of 10-60 rpm.
[0021] In one embodiment, in the purification step, the molecular distillation includes first-stage thin film evaporation, second-stage molecular distillation and third-stage molecular distillation in sequence, wherein the first-stage thin film evaporation removes ethanol and water, the second-stage molecular distillation evaporates camellia oil fatty acid ethyl ester containing vitamin E, and the third-stage molecular distillation separates glycerol to obtain crude squalene.
[0022] The molecular distillation separation temperature is low, which avoids the destruction of heat-sensitive components and retains the unsaturated fatty acids in camellia oil. The produced camellia oil has high content of active substances such as polyphenols, phospholipids, cutinol and phytol, and can obtain camellia oil fatty acid ethyl ester and glycerol rich in vitamin E, as well as products enriched with squalene.
[0023] In one embodiment, in the first-stage thin film evaporation step, the temperature is 55-75° C., the pressure is 1-2000 Pa, and the speed of the scraper is 60-360 rpm.
[0024] In one embodiment, in the second stage molecular distillation step, the temperature is 100-120° C., the pressure is 1-50 Pa, and the speed of the scraper is 60-360 rpm.
[0025] In one embodiment, in the third stage molecular distillation step, the temperature is 140-160° C., the pressure is 1-5 Pa, and the speed of the scraper is 60-360 rpm.
[0026] In one of the embodiments, in the enrichment step, a supercritical carbon dioxide distillation tower is used to perform continuous countercurrent extraction on the crude squalene, the tower height of the distillation tower is 1 to 3 m, the reflux ratio is (1 to 6): 1, and the filler in the distillation tower is a plurality of glass balls with a diameter of 5 to 20 mm; the pressure in the distillation tower is 10 to 30 MPa, and the temperature is 40 to 60°C.
[0027] The supercritical carbon dioxide fluid continuous countercurrent extraction distillation tower has a high pressure resistance, high separation accuracy, and large material processing capacity, and can achieve the separation and purification of multi-component materials. The distillation tower uses glass beads as filler, which has a large porosity, large specific surface area, and no chemical reaction, and is easy to clean and replace. Continuous countercurrent distillation is adopted, the separation temperature is low, the product purity is high, there is no solvent residue, no three wastes are discharged, and there is no pollution to the environment.
[0028] Compared with the prior art, the present invention has the following beneficial effects:
[0029] The method of the invention can not only efficiently extract the residual oil in the tea oil cake, but also obtain a product rich in squalene and a product rich in camellia oil fatty acid ethyl ester of vitamin E through purification, and has good economic benefits. BRIEF DESCRIPTION OF THE DRAWINGS
[0030] Figure 1 Schematic diagram of the structure of the supercritical carbon dioxide distillation tower in the embodiment.
[0031] 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
[0032] 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.
[0033] 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.
[0034] 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.
[0035] Example 1
[0036] A method for extracting squalene from tea oil cake comprises the following steps:
[0037] (1) Extraction: Take the tea oil cake (oil content of about 6 wt%) after cold pressing as raw material, extract the tea oil cake with supercritical carbon dioxide, the supercritical carbon dioxide extraction temperature is 50°C, the pressure is 20 MPa, and the extraction time is 1.5 hours to obtain camellia oil. Through this extraction step, the oil content in the tea oil cake is reduced to less than 1 wt%.
[0038] (2) Transesterification: By weight, 280 parts of 95 wt% ethanol and 1 part of potassium hydroxide were added to 1000 parts of camellia oil; after being evenly mixed, the mixture was heated to 70°C, the pressure in the reactor was controlled to 0.05 MPa, the stirring speed was 40 rpm, and the esterification reaction was carried out for 45 minutes. In the reaction, squalene and vitamin E did not participate in the transesterification, and the conversion rate of camellia oil fatty acid ethyl ester was ≥95%.
[0039] (3) Purification: The camellia oil fatty acid ethyl ester product after the transesterification reaction is purified by 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 ethanol and water; the second-stage molecular distillation uses a molecular distiller at a temperature of 110°C, a pressure of 20Pa, and a film scraper speed of 200rpm to evaporate the byproduct of camellia oil fatty acid ethyl ester rich in 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 separate glycerol and obtain crude squalene. According to GC-MS analysis, the squalene content in the product of this step is greater than 5wt%.
[0040] (4) Enrichment: The crude squalene is passed through Figure 1 Continuous countercurrent extraction is carried out in the supercritical carbon dioxide distillation tower shown; the distillation tower has a height of 2 m, is filled with fillers, has a reflux ratio of 4:1, has a pressure of 20 MPa, and a temperature of 50°C.
[0041] Figure 1 It is a structural schematic diagram of a supercritical carbon dioxide distillation tower, 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 purified product. 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 the target product is obtained after carbon dioxide escapes. 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.
[0042] Continuous countercurrent extraction is carried out in a supercritical carbon dioxide distillation tower, and the top of the tower is the enriched squalene finished product. According to the standard NY / T3673-2020 gas chromatography (GC) method "Determination of squalene content in animals and plants", the squalene content in the finished product is greater than 30wt%.
[0043] 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.
[0044] 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 from tea oil cake, 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 temperature of supercritical carbon dioxide extraction is 40-60°C, the pressure is 10-30MPa, and the extraction time is 1-2h; Transesterification: Mix camellia oil, ethanol solution and alkaline catalyst, heat and carry out transesterification reaction; In the transesterification step, the alkaline catalyst is sodium hydroxide and / or potassium hydroxide, the ethanol solution is a 90-95 wt % ethanol solution; the weight ratio of the camellia oil, ethanol and alkaline catalyst is (850-1000): (140-420): (1-5); The heating temperature is 60-80°C, the pressure is 0-0.1MPa, the reaction time is 30-60min, and stirring is performed during the esterification reaction at a stirring speed of 10-60rpm; Purification: molecular distillation is performed on the camellia oil fatty acid ethyl ester product after the ester exchange reaction to remove residual ethanol and water, and camellia oil fatty acid ethyl ester containing vitamin E, glycerol and crude squalene are obtained in sequence; In the purification step, the molecular distillation includes first-stage thin film evaporation, second-stage molecular distillation and third-stage molecular distillation in sequence, wherein the first-stage thin film evaporation removes ethanol and water, the second-stage molecular distillation evaporates camellia oil fatty acid ethyl ester containing vitamin E, and the third-stage molecular distillation separates glycerol to obtain crude squalene; In the first-stage thin film evaporation step, the temperature is 55-75°C, the pressure is 1-2000 Pa, and the speed of the film scraper is 60-360 rpm; In the second molecular distillation step, the temperature is 100-120°C, the pressure is 1-50Pa, and the speed of the scraper is 60-360rpm; In the third molecular distillation step, the temperature is 140-160°C, the pressure is 1-5 Pa, and the speed of the scraper is 60-360 rpm; Enrichment: subjecting the crude squalene to continuous countercurrent distillation with supercritical carbon dioxide to obtain a squalene-enriched product; In the enrichment step, a supercritical carbon dioxide distillation tower is used to continuously countercurrent extract the crude squalene. The tower height of the distillation tower is 1 to 3 meters, the reflux ratio is (1 to 6): 1, and the filler in the distillation tower is a plurality of glass balls with a diameter of 5 to 20 mm. The pressure in the distillation tower is 10 to 30 MPa, and the temperature is 40 to 60° C.