KR20150109232A - Process for Manufacturing Camellia seed Oil of High Oxidative Stability and Low Color with Supercritical Fluid - Google Patents

Abstract

The present invention relates to a method for manufacturing camellia seed oil having excellent oxidation stability using a supercritical carbon dioxide and camellia seed oil manufactured by the same. Specifically, the method comprises: a step of extracting camellia seed oil by applying a supercritical carbon dioxide to ground camellia seeds at 35 to 90°C and a pressure 100 to 800 bar; and a step of separating a carbon dioxide from a mixture of the extracted oil and the supercritical carbon dioxide and recycling them. The camellia seed oil manufactured by the present invention improves oxidation stability by containing high antioxidant substances and has an excellent colored property because of decreasing color components by extracting the seeds with low temperature.

Description

TECHNICAL FIELD [0001] The present invention relates to a method for producing camellia seed oil having excellent oxidation stability and color composition using supercritical fluid,

The present invention relates to a method for producing camellia seed oil using a supercritical fluid. More specifically, the present invention relates to a production method using supercritical carbon dioxide, in which a high content of antioxidant components can be extracted, and a pigment content can be lowered to a level, and a camellia seed oil produced by the above method.

Camellia japonica ( Camellia japonica ) belongs to the genus Theaceae and is native to southern Korea, China, Taiwan and southern Japan. It was 6 ~ 9m long and flowered from early October to March. Three black seeds were on the fruit. It grows mainly in the mountains, coasts, and villages. The wood is made of charcoal, furniture, sculpture, and finishing materials. According to the herbal gangmok, the flower is called ashidae, and it is said that it acts to reduce the bleeding and the boil. In addition, seeds were used as raw materials for oil, and in private, they were used as lamp oil and head oil. In Japan, camellia oil is used to treat atopy. Representative physiologically active substances of camellia seed are tocopherol, EGCG, bisabolin, 2-methoxy cinnamaldehyde, mangonolol, caffeic acid, alpha-chuey polysin and salicin.

As a physiologically active substance in camellia seed, tocopherol is a typical example. Of these, alpha (α) type having a strong antioxidative activity accounts for 20%, and the rest is mainly composed of gamma (γ) type. Tocopherol not only has vitality as vitamin E but also has antioxidant effect. The biochemical function of tocopherol as vitamin E is known to have an anticancer effect, an immune function enhancing effect, a thrombosis and inflammatory response modulating effect, and an influence on nucleic acid and protein fat metabolism. Above all, the greatest function of tocopherol is antioxidant in the biomembrane, which is an action to protect damaged cells caused by free radicals and peroxides.

However, it is known that the oxidation stability of camellia seed is superior to that of Meadowfoam oil, which is widely used as general cosmetic oil. In addition, the cambium seed oil produced by the conventional pressing method is extracted at a high temperature of 150 ° C or higher for the purpose of increasing the yield. In this process, the sugar component of the camphor seed is changed to brown by the caramelization reaction, Thereby increasing the composition.

Therefore, supercritical carbon dioxide was used to maximize the extraction of antioxidant components and to minimize the sugar change by low temperature extraction, and to develop an excellent camellia seed oil as a cosmetic raw material.

The present invention has been made to prove that the extraction efficiency of the antioxidant component is increased and the pigment content in the oil is reduced as compared with that of the cambicorn oil extracted with the supercritical carbon dioxide-extracted camellia seed oil by the compression method, and the oxidation stability and color composition are excellent. And it provides the camellia seed oil and it is used for food, cosmetics, medicines and the like.

In order to accomplish the above object, the present invention provides a method for producing camellia seed oil using supercritical carbon dioxide, comprising: extracting camellia seed oil by adding supercritical carbon dioxide to the camellia seeds at 35 to 90 ° C and 100 to 800 bar; Separating carbon dioxide into a gaseous phase from a mixture of the extracted oil and supercritical carbon dioxide; And separating and purifying the extracted oil. At this time, the camphor seed is pretreated in order to increase the extraction efficiency.

As disclosed in European Patent No. 925,724, in order to extract lipid using supercritical carbon dioxide, an extraction device composed of an extraction tank, a heat exchanger, a pump, a carbon dioxide storage tank, a chiller (cooling condenser), a decompression separator, use. In the above extracting apparatus, the extraction tank serves to extract and extract the crushed camellia seeds. The pump performs a function of applying pressure to the supercritical carbon dioxide. The heat exchanger serves to heat the supercritical carbon dioxide, The valve serves to depressurize the supercritical carbon dioxide emitted from the extractor. The decompression separator completely decompresses the supercritical carbon dioxide, separating the carbon dioxide on the gas phase, and the chiller converts the decompressed carbon dioxide into supercritical carbon dioxide And the carbon dioxide storage tank serves to store supercritical carbon dioxide.

In order to extract the oil from the camellia seed using the above extracting apparatus, first, the camphor seed is put into the extraction tank, the supercritical carbon dioxide passed through the pump and the heat exchanger is put into the bottom of the extraction tank, and then the oil extracted from the camellia seed and various components And the supercritical carbon dioxide is discharged to the upper end of the extraction tank and the discharged mixture is decompressed through a pressure reducing valve, then the carbon dioxide is separated into gas phase by the decompression separator and collected, and the extracted oil is collected . At this time, the separated carbon dioxide is converted into liquid carbon dioxide through the chiller and stored in the carbon dioxide storage tank.

Camellia seed oil produced by the conventional pressing method has a poor oxidative stability and has weak points such as sugar change and coloration due to high temperature caramelization reaction. In order to overcome this problem, the inventor of the present invention found that supercritical carbon dioxide , The results showed that cambium seed oil extracted with supercritical carbon dioxide had a high content of antioxidant components and the browning change was minimized.

The camellia seed oil according to the present invention does not deteriorate in lipid quality due to rancidity during storage for a long period of time, has a low pigment content and excellent color composition, and can be utilized as a base oil for functional cosmetics as well as for edible purposes.

The present invention provides a method for producing camellia seed oil excellent in antioxidative activity from crushed camellia seeds using supercritical carbon dioxide and camellia seed oil produced by the method. The high antioxidative and low-tinted camellia seed oil according to the present invention can be used not only for edible but also as a basic oil for functional cosmetics, and can contribute to the improvement of the farm household income by producing high quality camellia seed oil.

Figure 1 shows the results of analysis of tocopherol containing camellia seed oil by high performance liquid chromatography (HPLC).
FIG. 2 is a graph showing the weight increase due to forced rancidity of the pressed and supercritical extracted camellia seeds.

Hereinafter, the present invention will be described in more detail with reference to Examples. These embodiments are only for describing the present invention more specifically, and the scope of the present invention is not limited by these embodiments.

The camellia seeds used in the present invention were obtained from Jeju Sanhak Dongbaek seeds, and the fruits were collected and washed three times with distilled water to remove foreign substances such as branches and then dried in an oven at 60 ° C for 24 hours.

Example 1: Changes in the yield of camellia seed oil and extraction efficiency of antioxidant components according to the extraction method

The yield and the content of tocopherol, an antioxidant, were compared by comparing the conventional crushing method with the supercritical extraction method. In addition, the effect of supercritical fluid temperature and pressure on the extraction efficiency of tobacco oil was investigated in supercritical carbon dioxide extraction. Lastly, oxidative stability was evaluated by calculating the weight gain and peroxide value (POV) of Camellia japonica due to rancidity by rancid ranching in a 60 ℃ oven for 28 days.

Example 1-1: Yield and tocopherol content according to the extraction method

When 100 g of each of the pretreated cambosse was extracted by using the compression method and the supercritical extraction method, the yield of the oil was measured according to each extraction method. The pressure of the supercritical fluid was fixed at 350 bar and the temperature was fixed at 60 ° C. The results are shown in Table 1. The content of tocopherol in the extracted camellia seeds was analyzed by high performance liquid chromatography (HPLC). A C18 column (ABBOTA 5 C18, 150 x 4.6 mm) was used as the stationary phase. 100% methanol was used as the mobile phase at a dissolution rate of 0.8 mL / min. The sample was dissolved in methanol, filtered and then injected with 20 μl. The detector was measured at 254 nm using a multi-channel detector (Photodiode array detector). Figure 1 is a HPLC analytical chromatogram of tocopherol.

As can be seen from the results in Table 1, the yield of the extracted camellia seed was low and the content of tocopherol was low in the case of the compression method.

Yield and Tocopherol content of Camellia seed oil according to extraction method Extraction method Compression method Supercritical extraction The extracted camellia seed flow (mL) 25.8 44.8 Camellia seed oil
Tocopherol Content (mg / L) 127 353

Example 1-2: Influence of supercritical fluid temperature

The above- In the extraction process, the temperature of supercritical carbon dioxide was changed to 35, 40, 50, 60, 70, and 80 ℃ in 100 g of the raw camellia seed material pretreated and disintegrated, and the extract of camellia seed oil was extracted and the tocopherol content Respectively. At this time, supercritical fluid pressure was maintained at 350 bar and extraction was performed until the extraction efficiency of camellia seed oil was 95%.

As can be seen from the results in Table 2, in the case of tocopherol, a representative antioxidant of camellia seed, the extraction efficiency was affected by the temperature of supercritical carbon dioxide. The higher the temperature, the higher the extraction efficiency. However, the increase was not significant at 60 ℃ or higher, but rather decreased at 80 ℃ or higher.

Tocopherol content of camellia seeds extracted with supercritical fluid temperature Temperature (℃) 35 40 50 60 70 80 90 Camellia seed oil
Tocopherol Content (mg / L) 278 291 324 353 356 347 320 Extraction efficiency (%) 74 77 86 94 95 92 85

Example 1-3: Influence of supercritical fluid pressure

Similarly, In the extraction process, the pressure of the supercritical carbon dioxide was changed to 75, 100, 200, 300, 400, 500, 600, 700, 800 bar from 100 g of the pretreated camellia seed material and the camellia seed oil was extracted and the tocopherol content Were measured. At this time, supercritical fluid temperature was maintained at 60 ° C and extraction time was limited to 2 hours at any pressure. The content of tocopherol contained in the extracted camellia seed oil is shown in Table 3 together with the amount of camellia seed oil extracted by the above-mentioned method.

As shown in Table 3, the content of tocopherol in the camellia seeds was not significantly affected by the pressure of supercritical carbon dioxide. However, the amount of camellia seed oil extracted is highly dependent on the pressure. Especially, the extraction yield was continuously increased at a pressure of 300 bar or more, but it was difficult to judge the influence of pressure by extracting all the oil from the cambium before 2 hours before the pressure of 500 bar or more. Therefore, it was found that the higher the pressure, the higher the yield of tocopherol extraction.

Changes in Camellia Seed Flow and Tocopherol Content Dependent on Pressure Changes in Supercritical Fluids Pressure (bar) 75 100 200 300 400 500 600 700 800 The extracted camellia seed flow (mL) 24.8 29.8 35.3 44.8 48.9 51.3 51.2 51.2 51.3 Camellia seed oil
Tocopherol Content (mg / L) 287 339 347 353 361 354 351 360 361 Total amount of tocopherol
(mg) 7.12 10.1 12.2 15.8 17.6 18.2 18.0 18.4 18.5

Example 1-4: Oxidation stability of camellia seed oil according to extraction method

Oxidative stability of the extracts of cambial seed oil and supercritical extract of camellia seed oil (10 g) was measured in an oven at 60 ° C. As a result of this rancidity, weight gain, viscosity change, and odor generation occur, which is caused by the peroxide value (POV) can do. This acidosis is a natural phenomenon, and it differs depending on the content of antioxidants in oil, the presence of externally added antioxidants, and the content of unsaturated fatty acids. Oxidative stability, which inhibits such rancidity, do. Table 4 shows the oxidation stability of camphor oil of compression and supercritical extraction.

Oxidative stability and peroxide value of camellia seed oil according to extraction method Time (day) One 2 3 7 10 14 21 28 Compression Camellia Seed Oil Weight (g) 10.0 10.0 10.0 10.2 10.8 11.9 14.4 17.2 Supercritical Camellia Seed Oil Weight (g) 10.0 10.0 10.0 10.1 10.1 10.0 10.2 10.8 Pressed camellia oil
Peroxide value 0.4 0.3 0.4 0.5 0.9 2.8 5.7 12.1 Supercritical camellia seed oil
Peroxide value 0.4 0.4 0.3 0.4 0.4 0.3 0.6 0.9

As shown in Table 4, squeezed camellia seeds began to rancid after 10th day and the weight and peroxide value increased rapidly after 14th day. On the other hand, supercritical camellia seeds have been rancid since 21st. This is because the antioxidant component of camellia seed oil inhibited the rancidity of tocopherol. Thus, supercritical camellia seed oil having high content of tocopherol was proved to be superior in quality to pressed camellia seed oil.

Example 2: Effect of supercritical extraction on the pigment content of camellia seed oil

Comparing the conventional compression method with the supercritical extraction method, the chromaticity was measured and the color composition was compared. As mentioned above, when oil is extracted by the pressing method, the extraction proceeds at a high temperature to increase the yield. Extraction proceeds at a temperature of at least 150 ° C. At such a high temperature, the sugar content contained in the raw material is changed by the caramelization reaction. The change reaction starts at 110 DEG C for proctozyme, at 160 DEG C for calcitoxin, glucose, sucrose, and 180 DEG C for maltose. The coloring matter produced by this browning change is colored in the camellia seed oil and becomes black or dark brown, and the quality of the product is markedly deteriorated.

Example 2-1: Influence of chromaticity according to extraction method

When 100 g of each of the pretreated cambial seeds were extracted by the compression method and the supercritical extraction method, the color of the oil was measured according to each extraction method. The pressure of the supercritical fluid was fixed at 350 bar and the temperature was fixed at 60 ° C. The results are shown in Table 5. The chromaticity of the extracted camellia seeds was analyzed by spectrophotometer (Scrophco, Scionco, KOREA).

 The color of camellia according to the extraction method Extraction method Compression method Supercritical extraction Extracted camellia seed color
(Gardner NO.) 8.85 0.65

As can be seen from the results in Table 5, it was found that the chromaticity of the extracted camphor seed was high in the case of the compression method. This is a problem that occurs because the temperature is heated to at least 150 ° C in order to increase the yield during squeezing by the pressing method. As a result, the sugar component of camellia seeds is changed into a coloring matter substance by the caramelization reaction, The color composition of the oil becomes high. On the contrary, in case of the supercritical extraction method, extraction is carried out at a temperature of from room temperature to 100 ° C or less, so that coloring matter is not generated, resulting in low chromaticity.

Example 2-2: Influence of supercritical fluid temperature

The above- In the extraction process, the temperature of supercritical carbon dioxide was changed to 35, 40, 50, 60, 70, 80 ℃ in 100 g of pretreated camellia seed raw material. Camellia seed oil was extracted and the chromaticity of camellia seed oil was measured. The supercritical fluid pressure was maintained at 350 bar.

As can be seen from the results in Table 6, the chromaticity of Camellia sinensis was not significantly affected by temperature.

The color of Camellia sinensis extracted according to the temperature change of supercritical fluid Temperature (℃) 35 40 50 60 70 80 90 Color (Gardner No.) 0.62 0.63 0.67 0.65 0.67 0.70 0.72

Example 2-3: Influence of supercritical fluid pressure

Similarly, In the extraction process, the pressure of the supercritical carbon dioxide was changed to 75, 100, 200, 300, 400, 500, 600, 700, 800 bar from 100 g of the pretreated camellia seed material and the camellia seed oil was extracted, The chromaticity was measured. At this time, supercritical fluid temperature was maintained at 60 ° C and extraction time was limited to 2 hours at any pressure.

As shown in Table 7, the chromaticity of Camellia sinensis did not show any significant difference.

The chromaticity of Camellia seed extracted according to the pressure change of supercritical fluid Pressure (bar) 75 100 200 300 400 500 600 700 800 Chromaticity
(Gardner No.) 0.63 0.62 0.65 0.65 0.64 0.63 0.67 0.62 0.65

As a result of the above tests, the supercritical extraction of camellia seed oil showed an increase in the content of tocopherol by 2.7 times and increased oxidation stability, and the color composition was excellent due to the low temperature extraction condition. Therefore, To produce this excellent camellia seed oil.

Claims (6)

A method for producing camellia seed oil having excellent oxidation stability and color composition using supercritical carbon dioxide. The method according to claim 1, wherein the supercritical carbon dioxide is extracted with supercritical carbon dioxide at a temperature of 35 to 90 DEG C and a pressure of 100 to 800 bar. A method for producing camellia seed oil, which is produced by the method of claim 1, wherein the yield is increased as compared with the conventional pressing method. A camellia seed oil having a high tocopherol content, prepared by the method of claim 1. A camellia seed oil produced by the method of claim 1 having improved oxidation stability. A camellia seed oil produced by the method of claim 1, wherein the pigment content is reduced and the color composition is improved.

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