KR20030061119A - Extraction of functional materials and removal of oxidation compounds from citrus junos using subcritical and supercritical carbon dioxide - Google Patents

Abstract

PURPOSE: Provided is a method to extract a functional material and eliminate an oxidative material from citron using supercritical and subcritical fluid which extracts pigment, flavor component, oil component or so on at high yield from citron so that it is possibly utilized for various industrial use. CONSTITUTION: The method to extract the functional material and eliminate the oxidative material from citron using supercritical and subcritical fluid comprises the steps of: (i) putting the citron, processed material of the citron and processed byproduct of the citron to a supercritical and a subcritical reactor; (ii) adding the supercritical and the subcritical fluid to the reactor as extraction solvent; and (iii) using an auxiliary solvent to extract the functional material such as the pigment, the flavor component and the oil component.

Description

EXTRACTION OF FUNCTIONAL MATERIALS AND REMOVAL OF OXIDATION COMPOUNDS FROM CITRUS JUNOS USING SUBCRITICAL AND SUPERCRITICAL CARBON DIOXIDE}

The present invention relates to a method for extracting a functional substance from an citron and removing an oxidizing substance using a supercritical or subcritical fluid.

In the present specification, citron is defined as a meaning including all citrons, citrus fruits, and citron waste (by-products).

When a substance is at a temperature and pressure above its critical point, that is, above its critical point, the state of the substance is called a supercritical fluid, and supercritical fluid extraction is a technique for separating a substance using a supercritical fluid as a solvent. It is called technology.

Extraction and separation technology using supercritical fluid selectively extracts specific substances from mixed components due to the physical properties of the supercritical fluid in the region above the critical point, that is, density changes greatly due to pressure or temperature change, so that extraction efficiency of the solute is increased. And because of the different components, because it is possible to selectively separate substances such as a simple process of small and medium-sized plants (plant) and a small amount of processing, it is widely used in the fields of chemistry, medicine, biochemistry, etc. as a new separation process.

The skin of the citron is rich in unique natural fragrances and essential oils, the flesh is rich in amino acids, free sugars and organic acids, and the seeds contain vegetable oils. Do. Nevertheless, citron is not active for use as another food material or other industrial material. The reason for this is that there is a decrease in awareness of the available ingredients of citron, limited use range, limited production time, and rapid oxidation rate. In addition, the rapid oxidation rate of citron has become a factor that hinders the commercialization of citrus fruits such as citron juice.

Although it is possible to consider using the conventional organic solvent extraction method, hot water extraction method, neutral salt extraction method for the extraction of useful substances as described above in the citron, when the useful components are extracted using the organic solvent extraction method, there are many impurities and harmful substances. As it is impossible to recover the solvent as a substance, there is a problem about the quality of the product, and the process is complicated by several steps, and useful components may be lost, and there may be mixing of foreign substances by chemicals, and the purity of the extract There are disadvantages such as low. In addition, the hot water extraction method and the neutral salt extraction method also has the disadvantages as described above.

Accordingly, the present invention can effectively extract functional substances (pigment, fragrance components and essential oil components) from the citron or its processed by-products in consideration of all the problems of the existing extraction method as described above, by effectively removing the oxidizing substances from the It is a technical problem to improve the stability of dairy products.

In order to solve the above problems, the present inventors use a supercritical or subcritical fluid and a cosolvent, not only do not go through several steps from the citron or its processed by-products, but also effectively maintain the state of the raw materials, pigments, fragrance components, Functional materials such as essential oil components can be extracted, and processed products such as citron juice can effectively remove oxidative substances, thereby improving the stability of the dairy products, thereby completing the present invention. .

1 is a standard calibration curve of the extract,

2 is a graph showing the result of extracting fatty acids from citron seed using supercritical carbon dioxide,

3 is a graph showing the extraction amount of the odor component according to the change in pressure at a certain temperature,

Figure 4 is a graph showing the amount of extraction of the odor component according to the temperature change in the reactor at a constant pressure.

Therefore, according to the present invention, after adding the liquid or powdery citron, its processed product or processed by-products to the supercritical and subcritical reactors, the pigment, the fragrance component, There is provided a method for extracting functional substances and removing oxidative substances of citron, which extracts functional substances such as essential oil components and extracts and removes oxidizing substances.

In addition, according to the present invention there is provided a functional material extracted by the above method.

According to the present invention, there is provided an organic product from which an oxidative substance is extracted by the above-described method.

Hereinafter, the present invention will be described in more detail.

The present invention is mainly to extract the functional material of the citron using supercritical or subcritical carbon dioxide and cosolvent and to remove the oxidizing substance.

According to the present invention, pigments such as beta-carotene and the like from functional substances, i.e., beta-carotene; Scents of limonene, cyclohexanone, 2-ethyl-2-methyl-butanoic acid, benzene groups, camphan ingredient; Limonene, linoleic acid, oleic acid, palmitic acid, myristic acid, etc. can be extracted, and oxidizing substances that inhibit the stability of dairy products can be extracted and removed. In addition, the extract obtained because no harmful ingredients are mixed during such extraction can be usefully used in various industrial fields such as food, pharmaceuticals and cosmetics.

In the present invention, as the supercritical or subcritical fluid, carbon dioxide, ethylene, ethane, propane, acetylene, ammonia, and the like are preferable, and carbon dioxide is particularly preferable. Do.

As the cosolvent, one or a mixture of two or more selected from the group consisting of ethanol, iso-propanol, methanol, normal hexane and water can be used. Particularly preferred among the above cosolvents is the use of ethanol only.

Since carbon dioxide is volatilized immediately after the end of extraction, it is a great advantage as a solvent that does not remain in the product. Ethanol has an advantage of high extraction efficiency and easy removal in a general manner.

The method can increase the extraction efficiency by appropriately adjusting the flow rate of the auxiliary solvent, the temperature and pressure of the reactor during extraction by supercritical or subcritical fluid.

Preferably, the flow rate of the auxiliary solvent is suitably 1 to 50% (v / v) of the total solvent flow rate.

In addition, the temperature of the reactor at the time of extraction by supercritical or subcritical fluid is suitable 10 to 80 ℃, the pressure is suitable 6 to 20MPa. Especially preferable temperature conditions are 30-40 degreeC, and pressure conditions are 8-18 MPa.

Hereinafter, the present invention will be described in detail with reference to the following examples, but the present invention is not limited by the following examples.

EXAMPLE

The content of citron peel (shell) and seeds from the citron farm in Namhae was dried below 10%, respectively, and 30 g of each was put in a supercritical extractor (domestic production) reactor to extract oxidizing substances and functional substances by the following method. .

The conditions for extraction and removal of the oxidizing material were 25-45 ° C. in the reactor and 7-17.2 MPa pressure. At this time, the co-solvent was not used, but the co-solvent was used when extracting the pigment, the flavor component and the essential oil component.

The extraction result was evaluated by the following method.

The extract was analyzed by gas chromatography, and then the content was determined by substituting the peak area of each material in the standard calibration curve of FIG. 1. 1 is a reference to the contents of the essential oil and flavor components of citron peel, seven standard materials, namely limonene, linalool (linalool), myrsen (myrcene), alpha-pinene (α-pinene), beta-pinene (β-pinene), alpha-terpinene (α-terpinene), gamma-terpinene (γ-terpinene) is a standard calibration curve prepared by analyzing with gas chromatography.

Gas chromatography operating conditions for volatile essential oils extracted from citron peel are shown in Table 1, and gas chromatography operating conditions for fatty acids extracted from citron seeds are shown in Table 2 below.

Gas Chromatography Operation Conditions for Volatile Essential Oils Extracted from Citron Peel Item Operation Condition device Hewlett Packard 5890 Ⅱ column DB-5 Bounded & crosslinked (5% -phenyl) -methylpolysiloxane capillary column, 30 m × 0.25 mm I.D., film thickness 0.25 μm, J & W Carrier gas N ₂ 1ml / min Split ratio 1: 1 Temperature Detector (FID): 250 ℃ Injector: 250 ℃ Oven temperature condition 60 ° C., 1 min residence; Temperature increase to 100 ° C at a temperature increase rate of 3 ° C / min, stay for 1 minute, temperature increase to 200 ° C at temperature increase rate of 3 ° C / min, and hold for 10 minutes

Gas Chromatography Operation Conditions for Fatty Acids Extracted from Citron Seed Item Operation Condition device Hewlett Packard 5890 Ⅱ column HP-Innowax (melted crosslinked polyethyleneglycol capillary column, 30m × 0.32mm I.D., film thickness 0.25μm, Hewlett Packard) Carrier gas N ₂ 1ml / min Split ratio 64: 1 Temperature Detector (FID): 300 ℃ Injector: 250 ℃ Oven temperature condition 150 ° C., 10 min residence; Temperature increase to 201 ° C at a temperature increase rate of 3 ° C / min, stay for 12 minutes, temperature increase to 210 ° C at temperature increase rate of 3 ° C / min, and hold for 15 minutes

In addition, the conditions for analysis by UV-spectrophotometer when oxidizing material is extracted using supercritical carbon dioxide are shown in Table 3.

UV spectrophotometer analysis conditions Item Condition device UVICON wavelength 292 nm Sample 1 ml

The extraction results are shown in Table 4 below, and the extraction results obtained by other extraction methods were compared with the effects of this extraction method.

extract Extraction Method Solvent extraction Supercritical Fluid Extraction SDE ethanol ether Limonene 2127.11 2254.61 1894.94 3441.08 Linarul 559.90 271.70 212.06 289.1 Myrsen 66.35 55.89 37.76 76.03 α-pinene 96.15 95.05 77.77 185.64 β-pinene 101.22 108.59 87.95 172.91 α-terpinene 26.70 17.48 11.94 22.74 β-terpinene 735.57 849.20 440.01 1229.16 Sum 3710.98 3652.52 2762.43 5416.64

As can be seen from the results of Table 4, according to the present invention, the functional material can be extracted more than 1.5 times as much as the solvent extraction method.

Figure 2 shows the result of fatty acid extraction from citron seed using supercritical carbon dioxide, it was found that the content of linoleic acid is the highest in the citron seed.

In this embodiment, the extraction efficiency according to the temperature and pressure of the extraction reactor was tested. The results are shown in FIGS. 3 and 4.

Figure 3 shows the measurement of the amount of extraction of the odor component according to the change in pressure at a certain temperature. From the graph of FIG. 3, it can be seen that the maximum extraction occurs at a pressure of about 10 to 11 MPa at the temperature of 30 ° C., 40 ° C. and 45 ° C. in the reactor, and the maximum extraction occurs at a pressure of 13.8 MPa at 35 ° C.

Figure 4 shows the measurement of the removal rate of the oxidizing material according to the temperature change in the reactor at a constant pressure. From the graph of FIG. 4, it can be seen that the maximum removal was performed at 33 to 35 ° C. at pressures of 8.3, 10.3, 12.4, and 17.2 MPa in the reactor, and the maximum removal was performed at about 45 ° C. at 13.8 MPa in the reactor.

When the results of FIG. 3 are synthesized, it can be seen that the maximum extraction occurs at a pressure of 12 to 14 MPa at a temperature of 33 to 37 ° C. When the results of FIG. 4 are combined, the optimum temperature condition is about 33 to 37 ° C. It can be seen that the pressure conditions are about 8 to 12 MPa.

As described above, according to the present invention, functional substances such as pigments, fragrance components, and essential oil components can be extracted in high yield from citron and processed by-products, and thus it is expected that they can be actively utilized in various industrial fields such as food, medicine, and cosmetics. In addition, in the case of the workpiece, by effectively extracting and removing the oxidizing material, it is possible to achieve the effect of greatly improving the stability of the product.

Claims (7)

After adding citron, its processed products or processed by-products to the supercritical and subcritical reactors, and extracting functional substances such as pigments, fragrance components and essential oils by using a co-solvent while passing supercritical or subcritical fluids as extraction solvents, A method for extracting functional substances and removing oxidative substances of citron, characterized by extracting and removing oxidizing substances. The method of claim 1, wherein the functional material is extracted in the presence of the cosolvent after extracting and removing the oxidizing material in the absence of the cosolvent. The method of claim 1, wherein the extractant is carbon dioxide, and the cosolvent is one or a mixture of two or more selected from the group consisting of methanol, ethanol, isopropanol, normal hexane and water. The method of claim 1 wherein the flow rate of the auxiliary solvent is 1-50% (v / v) of the total solvent flow rate. The method of claim 1 wherein the temperature of the reactor is 10-80 ° C. and the pressure is 8-20 MPa. Extract extracted by the method of claim 1. An organic raw material in which an oxidizing substance is extracted and removed by the method of claim 1.