JPH0829202B2 - Method for separating useful substances from natural raw materials - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a natural raw material for selectively and efficiently extracting and separating a useful substance from a natural raw material such as plant material such as mustard and horseradish, animal material such as shrimp and the like. Relates to a method for separating a useful substance.

[Public technology and its problems]

Mustard seed, a method for extracting and separating useful substances such as oil and fat, allyl isothiocyanate from natural plant materials such as wasabi,
Alternatively, as a method for extracting and separating a useful substance contained therein from an animal natural raw material such as Ise shrimp, a solvent extraction method utilizing an organic solvent having a low boiling point has been conventionally used, but this method is useful in a solvent. There is a drawback that it takes time to recover the useful substance from the solvent after the substance is extracted and separated, and an extraction method using a supercritical gas has been developed in recent years as a method for improving this defect.

Supercritical gas means a fluid in a state in which it exceeds the gas-liquid critical points (critical temperature, critical pressure) of a substance. It exhibits excellent solubility in many substances, and thus extraction efficiency is improved and Since recovery of the critical gas can be achieved only by changing the pressure or temperature, it is easy to recover useful substances from the solvent.
As an extraction technique using such a supercritical gas, for example, the method described in JP-A-55-54003 is known.

However, in the above-mentioned known method, since the raw material to be extracted is extracted as it is without crushing, the recovery efficiency of useful substances is poor, and even if this is crushed, it is useful due to the friction heat generated during crushing. There are drawbacks such as volatilization and deterioration of the substance.

[Object of the Invention]

The object of the present invention is to efficiently and effectively extract and separate useful substances from natural raw materials such as plant materials or animal materials, and a method for separating useful substances from natural raw materials in which the above-mentioned drawbacks in the known art are improved. To provide.

[Main points of the invention]

In order to achieve the above-mentioned object, according to the present invention, a natural raw material made of plant or animal material is freeze-pulverized, and then contacted with a solvent harmless to the human body under a pressure of 30 to 400 atm, to obtain the natural raw material. In a method for separating a useful substance present in a raw material by extraction and separation, a freeze-pulverized product obtained by the freeze-pulverization up to a temperature sufficient to activate the useful substance present therein by an enzymatic reaction. It is characterized in that the useful substance obtained by the enzyme reaction is extracted and separated by contacting with the solvent while heating.

In the above-mentioned present invention, the solvent containing the useful substance is phase-separated into a gas phase and a liquid phase under reduced pressure, and the useful substance is separated and recovered from the solvent.

[Specific Description of the Invention]

 Hereinafter, the present invention will be described in detail.

The drawings are block diagrams for explaining the method of the present invention. The present invention will be described with reference to this drawing.
The natural raw material is put into the cooling tank 1 and frozen at a low temperature below the freezing point, and then is pulverized by the pulverizer 2 while maintaining this frozen state. The natural raw material is a plant material, an animal material, etc., and the plant material includes, for example, mustard seeds, wasabi, horseradish, garlic, ginger, and the like, and the animal material includes the head or shell of Ise shrimp, and others. Various animals of. The coolant in the cooling tank 1 is liquid nitrogen or the like. Also,
The crusher 2 is an ordinary crusher or a grater.

Next, the frozen material pulverized by the pulverizer 2 is filled in the extraction tank 3 to be heated and a solvent is introduced and pressurized. This solvent is a solvent harmless to the human body, and examples thereof include carbon dioxide, ethane, propane, ethylene, etc., but carbon dioxide is most suitable. Further, the temperature and pressure are such that they reach a state of being extracted by the solvent, and are arbitrarily selected depending on the type of solvent or the type of raw material to be extracted. If this range is shown, the temperature is in the range of -195 ° C to 100 ° C and the pressure is in the range of 30 to 400 atm. However, it is preferable that the raw material is heated to a temperature sufficient to activate it, for example, by causing the useful substance present therein to undergo an enzymatic reaction to generate allyl isothiocyanate, etc. Maintained at a higher temperature.

The solvent containing the useful substance thus obtained is introduced into the separation tank 4, decompressed and phase-separated into a gas phase and a liquid phase, and released from the separation tank 4 as a gas to selectively extract only the useful substance. Are separated and collected.

As described above, according to the present invention, since natural raw materials are frozen, there is little disappearance due to volatilization of useful substances, and since they are crushed, extraction and separation are easy, and further, activation of useful substances is achieved during the extraction step. Extraction becomes easier because it is heated to a sufficient temperature, and extraction with supercritical gas under such favorable conditions improves extraction efficiency. Further, in the present invention, since the pulverization is carried out in a frozen state, the useful substance is not deteriorated by heat.

Hereinafter, the present invention will be described in more detail with reference to Examples.

Example 1 300 g of mustard seeds were prepared and divided into three 100 g portions,
Samples a, b, and c were used. The sample a was directly applied to the sample b, the sample b was applied to a pressing machine, the sample c was immersed in liquid nitrogen to be frozen, and then applied to a crusher to be crushed.

Put such samples a, b, c into the extraction tank,
Extraction temperature 40 ° C, extraction pressure 300 atm, solvent CO ₂ used, flow rate 20
/ Min., Extraction time was separated for 3 hours, the solvent was introduced into the separation tank, and gas was released at 40 atm to extract fats and oils as useful substances. This extraction amount is 3g for sample a
(7.9%), sample b 31g (81.5%), sample c 34g (89.
5%), and the method of the present invention was the most efficient.

The amount of allyl isothiocyanate in the residue in the extraction tank was also measured. As a result, sample a was 0.9% and sample b was
Although it was 1.1%, sample c was 1.2%, which was a value that could be sufficiently used as mustard powder.

The quantification of allyl isothiocyanate was performed as follows. First, 0.2 g of a sample was weighed in a small test tube, 2 ml of pure water was added thereto, and the container was sealed and kept in a 37 ° C. constant temperature bath for 10 minutes.
Then, this was steam-distilled for about 8 minutes, and 25 ml of the distillate was placed in a test tube containing 4 cc of an ethanol-ammonia mixed solution in advance and left for 24 hours to obtain 25 ml of a urethanized product. This product was adjusted to a volume of 200 ml with distilled water and then calibrated with a spectrophotometer at UV237 nm to quantify allyl isothiocyanate.

Example 2 200 g of wasabi rhizome was prepared, and 100 g of this was divided into two samples a and b. Sample a was ground at room temperature with grazing glass, and sample b was -50 ° C. In a freezer and frozen in an atmosphere of −20 ° C. and then crushed with grated glasses.

Each of these samples a and b was placed in an extraction tank and CO ₂ extraction was performed. The extraction conditions are: extraction tank pressure 200 atm, temperature 37 ° C,
The separation tank pressure is 30 atm, the extraction time is 2 hours, and the CO ₂ flow rate is 8.0 / min.

As a result, the useful substances extracted were allyl isothiocyanates, and the extracted amount was 250 mg (65.6%) for sample a.
%) Sample b was 350 mg (91.7%), and Sample b according to the present invention had significantly better extraction efficiency.

Example 3 200 g of garlic was prepared, and 100 g of this was divided into two samples a and b. Sample a was ground at room temperature with grazing glass, and sample b was placed in a freezer at -40 ° C. It was put into a frozen state, and then pulverized in a frozen state by a pulverizer cooled to -10 ° C. Each of the samples a and b was immediately put into an extraction tank and CO ₂ extraction was performed. The extraction conditions are an extraction tank pressure of 150 atm, a separation tank pressure of 40 atm, an extraction tank temperature of 35 ° C to 37 ° C, an extraction time of 1 hour, and a CO ₂ flow rate of 9 / min.

As a result, the amount of essential oil extracted as a useful substance was 0.65 g (75%) for sample a and 0.79 g (92.8%) for sample b,
Sample b according to the present invention had better extraction efficiency. Regarding the scent of the extracted essential oil, the fresh scent was weak for sample a, but a fresh scent was felt for sample b.

Example 4 200 g of raw ginger was prepared, and 100 g of this was divided into two samples a and b. Sample a was finely chopped at room temperature, and sample b was cut into 10 mm cubic dice. Pour into liquid nitrogen to freeze, then-
It was ground in a frozen state by a grinder cooled to a temperature of 10 ° C or lower. Each of these samples a and b was immediately put into an extraction tank and CO ₂ extraction was performed.

Extraction conditions are extraction tank pressure 100 atm, separation tank pressure 30 atm,
The extraction tank temperature is 45 ° C, the extraction time is 2 hours, and the CO ₂ flow rate is 25 / min.

As a result, the amount of essential oil extracted as a useful substance was 2.1 g (77.8%) for sample a and 2.8 g for sample b.
(89.3%), and the sample b according to the present invention had a better extraction rate.

Example 5 Prepare heads and shells of Ise shrimp, which have been blanched, and each weigh 100 g.
Separately into samples a and b. Sample a is crushed as it is with a hammer, 98 g of 8 mesh pass part is put into an extraction tank, extracted with CO ₂ , and sample b is put into liquid nitrogen and frozen. And then crushed in a -20 ° C. crusher, 99 g of this crushed product was introduced into an extraction tank, and CO ₂ extraction was performed.

Extraction conditions are extraction tank pressure 150 atm, separation tank pressure 30 atm,
The extraction tank temperature is 60 ° C, the extraction time is 2.5 hours, and the CO ₂ flow rate is 15 / min.

As a result, the extracted ether-soluble substances as useful substances were 1.4 g (57.2%) for sample a and 1.45 g (82.7%) for sample b, indicating that sample b had a higher extraction rate. Regarding the scent, sample a had a weak shrimp scent, while sample b had a strong shrimp scent.

〔The invention's effect〕

As described above, the present invention is useful because the natural raw material is freeze-pulverized prior to performing the supercritical gas extraction, and the freeze-pulverized natural raw material is extracted while heating to a temperature sufficient to activate the useful substance. It is possible to exert an effect that the substance can be selectively and efficiently extracted and separated without further alteration.

[Brief description of drawings]

 The drawings are block diagrams showing the steps of the present invention. 1 ... Cooling tank, 2 ... Crusher, 3 ... Extraction tank, 4 ... Separation tank

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Masayuki Taniguchi 1-9-5 Kita Chikusa, Chikusa-ku, Nagoya-shi, Aichi Prefecture RL-14 (72) Inventor Shin-ichi Imai 76, Meiren-cho, Minami-ku, Nagoya-shi, Aichi- 5 (72) Inventor Noriyuki Kanemoto 4-15-5 Koga, Komaki City, Aichi Prefecture

Claims (2)

[Claims] 1. A natural raw material composed of a plant material or an animal material is freeze-pulverized, and then contacted with a solvent harmless to the human body under a pressure of 30 to 400 atm to extract a useful substance present in the natural raw material. In the method for separating a useful substance from a natural raw material to be separated, the freeze-pulverized product obtained by the freeze-pulverization is contacted with the solvent while heating to a temperature sufficient to activate the useful substance present therein by an enzymatic reaction. A method for separating a useful substance from a natural raw material, comprising extracting and separating the useful substance obtained by the enzyme reaction. 2. The separation method according to claim 1, wherein the solvent containing the useful substance obtained by the enzyme reaction is further decompressed to perform phase separation into a gas phase and a liquid phase. A method of separating and recovering a useful substance obtained by the enzyme reaction from the above.