KR100853313B1 - A high efficient method for extracting beta-carotene from persimmon skin - Google Patents

Abstract

A method of extracting beta-carotene from persimmon skin at high efficiency by mixing persimmon skin powder and a salt solution and then supercritically extracting with supercritical carbon dioxide and acetone as an auxiliary solvent is provided to obtain beta-carotene having high-potency vitamin A. Persimmon skin is dried at 40 to 50deg.C for 24 to 48hr, ground to 50 to 100meshes and extruded. The extruded persimmon skin powder is mixed with 50 to 100% by weight of a salt solution containing 5 to 10% by weight of sodium chloride, ground and then dried at 40 to 50deg.C for 24 to 48hr. The dried persimmon skin is pretreated with 85 to 90% by weight of supercritical carbon dioxide and 10 to 15% by weight of acetone as an auxiliary solvent and supercritically extracted at 40 to 60deg.C and 150 to 250bar for 50 to 70min.

Description

A high efficient method for extracting beta-carotene from persimmon skin}

The present invention relates to a high-efficiency extraction method of beta-carotene from persimmon skin, and more particularly, dried persimmon skin, powdered and extruded, and then water containing 5-10 wt% NaCl 50 ~ A method of extracting beta-carotene from persimmon peel in high yield by supercritical extraction using 100% of mixed persimmon pulverized, dried, pretreated and supercritical carbon dioxide and acetone as cosolvent. will be.

Persimmon, Diospyros Kaki , L.) Fruits are subtropical and temperate fruits, and Korea, Japan, and China are the most prominent crops in the Mediterranean region. Persimmon is an alkaline food rich in sugars such as glucose and fructose, vitamins A and C, and is known as fruit having pharmacological action to stop diarrhea and blood. At present, domestic persimmon production is about 239,000M / T per year, and its production is increasing every year, and is being consumed in various forms, including Kunxi. Persimmon skin is generated a lot during persimmon processing, and it contains a large amount of carotenoids, which are fat-soluble pigments.

Beta-carotene, which has the highest titer as vitamin A among carotenoid compounds, has been used for a long time as colorants and additives in foods, medicines, and cosmetics. It is reported as a major source of health, and its importance as a health food is greatly recognized.

However, most of the β-carotene that is currently used industrially is a chemical synthetic product, and as the desire for natural products is increasing due to the recent increase in interest in human health, if a natural β-carotene can be obtained as a commodity on the market, It will be very high value.

However, the most essential factor in producing β-carotene from natural products is the development of a new extraction method that can minimize the denaturation of β-carotene during the extraction process. Supercritical fluid extraction process and the extraction of natural products using a microwave extraction device has recently been the subject of much interest.

Solvent extraction, which has been widely used in the related art, has difficulty in selecting an appropriate solvent, remaining of an organic solvent, removing a solvent, and low separation effect.

On the other hand, supercritical fluid extraction can easily remove the solvent from the solute by simply adjusting the pressure and temperature, and it has the advantage that the thermal energy cost is less than that of the solvent extraction method or the microwave method.

The microwave extraction process is a method of extracting natural products from biological materials using a microwave generator as an energy source, which is more selective and faster than conventional solvent extraction methods.

In view of the above, the present inventors dried persimmon peel at 40-50 ° C. for 24 to 48 hours, and then powdered persimmon skin into 50-100 mesh, extruded powdered persimmon peel, and then 5-10 to the extruded persimmon peel powder. 50% by weight of water containing NaCl containing 50% by weight of persimmon skin powder is mixed and pulverized, dried at 40-50 ° C for 24 to 48 hours, and pretreated as described above. 85-90% by weight of supercritical carbon dioxide The present invention was completed by supercritical extraction using 10-15% by weight of acetone as a cosolvent.

Accordingly, it is an object of the present invention to provide a high efficiency extraction method of beta-carotene from persimmon skin.

The object of the present invention is to dry persimmon peel at 40 ~ 50 ℃ 24 ~ 48 hours and then powdered into 50 ~ 100 mesh and extruding the powdered persimmon peel 5 to 10% by weight of NaCl in the extruded persimmon peel powder 50 ~ 100% of the contained water is mixed with the persimmon skin powder, pulverized, dried for 24 ~ 48 hours at 40 ~ 50 ℃ and pretreated. The pretreated persimmon skin is prepared as 85 ~ 90% by weight of supercritical carbon dioxide and cosolvent. Achieved by supercritical extraction using 10-15% by weight of acetone.

EMBODIMENT OF THE INVENTION Hereinafter, the structure of this invention is demonstrated concretely.

The present invention provides a high efficiency extraction method of beta-carotene from persimmon skin.

In order to efficiently extract β-carotene from persimmon skin in the present invention, it is required to perform extraction after performing a pretreatment including the following steps:

Drying persimmon skin at 40-50 ° C. for 24-48 hours;

Powdering dried persimmon skin into 50-100 mesh;

Extruding the powdered persimmon skin;

Mixing 5 to 10% by weight of water containing NaCl in the extruded persimmon skin powder by mixing 50 to 100% by weight of the persimmon skin powder; And

Drying the milled extruded persimmon skin powder at 40 ~ 50 ℃ 24 ~ 48 hours.

A method of efficiently extracting beta-carotene from persimmon skin of the present invention comprises the following steps:

Drying persimmon skin at 40-50 ° C. for 24-48 hours;

Powdering dried persimmon skin into 50-100 mesh;

Extruding the powdered persimmon skin;

Mixing 5 to 10% by weight of water containing NaCl in the extruded persimmon skin powder by mixing 50 to 100% by weight of the persimmon skin powder;

Pretreating the persimmon skin by drying the pulverized extruded persimmon powder at 40 to 50 ° C. for 24 to 48 hours; And

Supercritical extraction of the pretreated persimmon skin using 85 to 90% by weight of supercritical carbon dioxide and 10 to 15% by weight of acetone as a cosolvent.

In the present invention, the supercritical fluid extraction conditions are preferably 40-60 ° C., pressure 150-250 bar, and time 50-70 minutes.

In the present invention, carotenoid pigment extraction is applied by Curl method to remove soluble sugars using 50% MeOH, and the upper layer extracted by each solvent at room temperature is concentrated below 40 ℃ ethyl ether and saturated NaCl The solution was suspended in solution (1: 1, v / v) and shaken. The 10% KOH / ethanol solution was added to the separated supernatant, filled with nitrogen gas, left for 24 hours, and the separated supernatant was taken up with anhydrous sodium sulfate. After dehydration, the mixture was concentrated under reduced pressure with a rotary evaporator and dried with nitrogen gas.

Β-carotene content of the sample in the present invention is dissolved in 1mL chloroform containing 0.01% BHT in the dried material and analyzed by HPLC method. The HPLC system uses a sykam510 model, a C18 column (waters, 4.6mm x 250mm) and a UV-VIS detector. The detection wavelength is 410 nm, the mobile phase is chloroform: methanol (4:96), and the flow rate is 1 mL / min. The calibration curve is performed by purchasing a sigma (C-4646) standard β-carotene, dissolving it in chloroform containing 0.01% BHT, analyzing it by HPLC, and preparing a peak area.

Hereinafter, the specific method of the present invention will be described in detail with reference to Examples, but the scope of the present invention is not limited only to these Examples.

The present invention is dried persimmon peel at 40 ~ 50 ℃ for 24 to 48 hours and then powdered into 50 ~ 100 mesh and extruded powdered persimmon peel and water containing 5 to 10% by weight NaCl in the extruded persimmon skin 50 to 100% of the persimmon skin powder was mixed and pulverized, dried at 40 to 50 ° C for 24 to 48 hours, and pretreated. The pretreated persimmon skin was 85 to 90% by weight of supercritical carbon dioxide and acetone 10 ~ as cosolvent. Supercritical extraction using 15% by weight has a very good effect of providing a method for extracting beta-carotene with the highest titer as vitamin A from persimmon skin in high yield.

Example  One: Persimmon  Pretreatment

The persimmon peel used in the present invention, namely persimmon peel, was used for peeling to make dried persimmon in Sangju, Gyeongsangbuk-do.

Persimmon peel is dried for 36 hours at 45 ℃ hot air dryer, powdered into 75 mesh, extruded, extruder, water mixed with 7% by weight of NaCl 75% by weight of persimmon peel, and wet mill (LS1, NETZSCH, Germany) After crushing, the resultant was dried for 36 hours at 45 ° C. in a hot air dryer and pretreated.

Experimental Example  One: Preprocessed Persimmon  General Ingredient Analysis

General components of the persimmon skin powder pretreated in Example 1 were analyzed by the conventional method (AOAC). The results are shown in Table 1 below. Spanos et al. Reported that in order to increase the extraction yield of β-carotene from sweet potatoes, it is necessary to reduce the moisture content of the sample, reduce the surface hardening by oven drying, and maximize the surface area by grinding. In this experiment, crude fiber was 86.64% and the majority was 51.82%.

General Components of Pretreated Persimmon Skin Powder ingredient Persimmon Skin Powder (%, db) moisture 4.56 Crude protein 3.9 Geography 1.59 View minutes 3.31 Crude fiber 86.64 A shrine 51.82

Experimental Example  2: investigation of extraction yield according to extraction solvent

To extract pigments from persimmon skin, five kinds of solvents (acetone, ethanol, ether, ethyl acetate, hexane) were used under the same conditions of extraction temperature of 25 ℃, extraction time of 60 minutes and extraction solvent ratio of 1:20. It was.

The results of measuring β-carotene content according to the extraction solvent are shown in FIG. 1. Relative ethanol with higher polarity was higher than hexane or ether with high polarity, and ethylacetate was the highest in the experimental group.

According to Subra et al., In the early stage of extraction, the carotenoids present on the particle surface are extracted by a simple washing process, and most of the carotenoids remaining inside the particles are gradually extracted by the diffusion mechanism. It is reported.

Experimental Example  3: Supercritical  Investigation of Extraction Yield by Carbon Dioxide

The supercritical fluid extraction device used in this experiment is a model that can be used with a maximum pressure of 300bar. The extraction temperature is 50 ℃, the pressure is 200bar, the extraction time is 60 minutes, and the extraction solvent is carbon dioxide (2 ml / min) and cosolvent (carbon dioxide amount). Acetone, ethanol and methanol were used for the extraction, and the degree of sampling was measured for temperature, pressure change, and type of cosolvent, and the β-carotene content of each extract was compared.

Extraction temperature was determined below 60 ℃ in consideration of heat destruction of carotenoids. 2 shows the content of β-carotene obtained at various temperatures as a function of extraction pressure for each cosolvent. The extraction yield of β-carotene tended to increase with increasing pressure at constant temperature and with decreasing temperature at constant pressure. This is because the density of supercritical carbon dioxide increases with increasing pressure and decreasing temperature.

Since the solubility of β-carotene in supercritical carbon dioxide is small, the results of extracting β-carotene from persimmon skin powder by adding acetone, ethanol and methanol of different polarities as cosolvents to the supercritical carbon dioxide to increase the solubility are shown in FIG. When acetone was used as a co-solvent, β-carotene extraction yield was higher than that of ethanol and methanol experiments.

Experimental Example  4: Investigation of extraction yield by microwave

Microwave extractors were used at atmospheric pressure type extractors (Microdigest unit, Prolabo, France) of 2,450MHz frequency. The extraction unit provides energy (power, watt, W) and time control and is equipped with a reflux condenser. The extraction energy was 100-200 W, the extraction time was 3 minutes, and the extraction solvent was extracted with acetone, ethanol and hexane in a ratio of 1:20.

The results of extracting β-carotene using a microwave extractor are shown in FIG. 3. Acetone was used as the extraction solvent, and the β-carotene content was higher as the watt value of extraction energy was increased than that of ethanol and hexane. In the experimental group using ethanol as the extraction solvent, the β-carotene content decreased with increasing watt value, and there was no significant difference in hexane. These results indicate that the polarity varies depending on the solvent selected and is due to the difference in diffusion rate of the particles in the particles. The highest yield of β-carotene extraction was obtained by microwave extraction using acetone as a solvent.

Example  2: From persimmon  Optimal Extraction of Beta-Carotene

After the newly discovered pretreatment process to extract natural β-carotene from persimmon skin, the conventional solvent extraction method was compared with the supercritical fluid extraction and microwave extraction method. . In the case of solvent extraction, ethylacetate was used to extract β-carotene from 12.0593mg / 100g than other solvents.In case of supercritical fluid extraction, acetone was used as a co-solvent at about 40 ℃ and 250bar. The extraction yield was the best with 20.4515mg / 100g.

In the extraction using microwave, acetone was more effective than the experimental group using ethanol, methanol, and nucleic acid, and the effect of the extraction solvent was more affected than the extraction energy source (watt). Therefore, the extraction method using supercritical fluid after the pretreatment process was more effective than the microwave extraction method or the solvent extraction method, and it may be industrially applicable to the natural β-carotene extraction process.

Therefore, beta-carotene was optimally extracted from persimmon skin based on the above results.

That is, supercritical extraction was carried out using 90% by weight of supercritical carbon dioxide and 10% by weight of acetone as a co-solvent as per Example 1, extraction temperature was 50 ° C., pressure was 200 bar, and extraction time was 60 minutes. (See Figure 4).

As described above, the high-efficiency extraction method of beta-carotene from the persimmon peel of the present invention, as described through the above embodiment, dried persimmon peel at 40-50 ° C. for 24 to 48 hours, and then powdered into 50-100 mesh and powdered persimmon peel After extruding and pulverized by mixing 50 ~ 100% of water containing 5 ~ 10% by weight of NaCl in the extruded persimmon skin powder compared to the persimmon skin weight, and pre-treated by drying for 24 to 48 hours at 40 ~ 50 ℃ Supercritical extraction of pretreated persimmon skin with 85-90% by weight of supercritical carbon dioxide and 10-15% by weight of acetone as cosolvent can be used to extract beta-carotene with the highest titer as vitamin A from persimmon skin It is a very useful invention in the food industry because it can provide a method.

1 is a graph comparing beta-carotene yields by extractant of pretreated and unpretreated samples.

2 is a graph comparing beta-carotene yields according to supercritical extraction of pretreated and unpretreated samples.

3 is a graph comparing beta-carotene yields according to the microwave extraction process (by extraction solvent) of the pretreated and unpretreated samples.

Figure 4 is a flow chart showing the optimal extraction process of the present invention for extracting beta-carotene from persimmon skin.

Claims (2)

Drying persimmon skin at 40-50 ° C. for 24-48 hours; Powdering dried persimmon skin into 50-100 mesh; Extruding the powdered persimmon skin; Mixing 5 to 10% by weight of water containing NaCl in the extruded persimmon skin powder by mixing 50 to 100% by weight of the persimmon skin powder; Pretreating the persimmon skin by drying the pulverized extruded persimmon powder at 40 to 50 ° C. for 24 to 48 hours; And A method for extracting beta-carotene from persimmon skin comprising the steps of supercritical extraction of the pretreated persimmon skin using 85-90% by weight of supercritical carbon dioxide and 10-15% by weight of acetone as a cosolvent. The method of claim 1, wherein the supercritical extraction conditions are 40-60 ° C., pressure 150-250 bar, time 50-70 minutes.

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