JPS6236177A - Extraction and separation of organic component from grape cluster brewing residue - Google Patents

Abstract

PURPOSE:To improve the extraction efficiency, by drying a grape cluster brewing residue by the vacuum freeze-drying method, etc., extracting organic components with an extraction solvent containing liquefied gaseous carbon dioxide under specific conditions and separating the organic components from the gaseous carbon dioxide. CONSTITUTION:A grape cluster brewing residue is put in a vacuum freeze-drying device 1, and dried by evacuating and heating. An inert gas from an inert gas inlet pipe (1b) is introduced to return the interior to ordinary pressure and the dried residue is put in a high-pressure vessel 2. An extraction solvent 3 of ethanol and carbon dioxide is sent thereto under pressure. The temperature and pressure in the vessel 2 are immediately adjusted to supercritical conditions of 50 deg.C and 200kg/cm<2>G, and the residue is allowed to stand for 4hr. The temperature and pressure in the vessel 2 are cooled to 20 deg.C and 60atm to cause phase change. The resultant extract and liquefied gaseous carbon dioxide mixture containing the ethanol are allowed to stand under the conditions for 2hr. The liquefied gaseous carbon dioxide mixture containing the extract is sprayed into a separation vessel 4 to release gasified carbon dioxide from a blow valve (BV).

Description

[Detailed Description of the Invention] Industrial Application Field The present invention relates to the pomace lees produced when fresh grape bunches are squeezed in the wine brewing process, or the lees produced when fresh grape bunches are fermented and then pressed. This invention was developed for the purpose of effectively utilizing lees in industry, and relates to a method for extracting and separating organic components from grape bunch brewing residue, which is treated as so-called industrial waste. Specifically, it is a method in which organic components such as fats and oils, esters, alcohols, organic acids, glycerides, vitamins, sugars, and aromatic substances contained in grape bunch brewing residue are extracted and separated as a mixture.

Conventional technology The conventional method for utilizing grape bunch brewing residue generated in the wine brewing process is to extract the residue from the grape bunches by a combination of organic solvent extraction methods such as acetone and alcohols, and ion exchange methods. It is only partially used to separate the anthocyanin pigments contained in it.

Problems to be Solved by the Invention The above-mentioned brewing residue produced in the wine brewing process contains substances that are easily degraded by heat and substances that are easily oxidized, so the residue is dried in a normal drying process. In particular, there are practical problems, and extraction methods using only a single organic solvent such as acetone or alcohols will extract anthocyanin-based pigments as organic mixed components such as fats and oils and esters. There is a problem in that it is difficult to selectively extract organic mixed components such as fats and oils, esters, alcohols, organic acids, glycerides, vitamins, sugars, and aromatic substances without extracting pigments.

The purpose of the present invention is to carry out a pretreatment step in which the brewing residue is dried without thermally deteriorating it and without contacting it with air, and to dry the mixed solvent of carbon dioxide and an organic solvent in the same extraction container. In addition to efficiently extracting organic components other than anthocyanin pigments from brewing residue in a short time,
The object of the present invention is to provide a method for extracting and separating a wide range of components from volatile components to high boiling point components at a high extraction rate.

Means for Solving the Problems The present inventors focused on the current situation in which grape bunch brewing residues produced in the wine brewing process are disposed of as industrial waste, and, As a result of intensive research into extracting and separating organic components other than pigments in their natural state, we discovered the following facts.

First, in the pre-drying process of the water-containing residue, the residue is frozen or placed under vacuum conditions, and the residue is frozen using the latent heat of evaporation when water in the residue evaporates, and then heated at 40 to 60 C under vacuum. A drying method (vacuum) that removes moisture by using a phenomenon (ice sublimation) in which the residual ice (solid) turns into water vapor (gas) without passing through the water (liquid) state by applying mild heating. (referred to as freeze-drying method), or vacuum heating drying while heating the residue to 40 to 60C in the presence of an inert gas such as carbon dioxide gas or nitrogen gas. It was confirmed that substances that are easily degraded by heat and substances that are easily oxidized exist in their natural state. Performing this pre-drying treatment allows the organic components contained in the residue to exist in their natural state and at the same time has the effect of making it easier to extract the organic components.

Second, a low boiling point solvent such as ethyl alcohol, ethyl ether, n-7'tan, or a mixed solvent thereof, which is an extraction accelerator, is added to liquefied carbon dioxide and heated to convert the liquid state to supercritical gas mixture. The organic components are taken out from the dried grape bunch brewing residue as the object to be extracted using the dissolution energy when the phase changes to the state, and dissolved, and the organic components are liquefied by returning the gas mixture state to the liquid state. By dissolving or mixing carbon dioxide and a solvent or a mixed solvent in the same high-pressure extraction container, the extraction time can be shortened, and organic components other than anthocyanin pigments can be selectively extracted and the extraction rate can be increased. Furthermore, by fixing part or all of the liquefied carbon dioxide mixed solvent containing the extract as a solid carbon dioxide mixture, we can convert volatile aromatic components such as aldehydes and esters to triglycerides, vitamins, It was discovered that a wide range of components including high boiling point components such as sugars can be efficiently separated, and the present invention was completed.

That is, the technical means of the present invention is to freeze-dry grape bunches or dry them under an inert gas atmosphere and then place them in a high-pressure container for extraction. and after adding liquefied carbon dioxide,
The container is heated to maintain the mixed liquid in the container in a supercritical mixed gas state under conditions above the critical temperature and critical pressure of carbon dioxide, and then the container is cooled to return it to below the critical point. After selectively extracting organic components in the residue into a mixed liquefied carbon dioxide phase consisting of an extraction accelerator and carbon dioxide, organic components containing organic components are extracted from the mixed liquefied carbon dioxide phase. This is a method for extracting and separating organic components from grape bunch brewing residue, which is characterized by separating an extraction promoting aid, and further includes a mixed liquefied carbon dioxide phase containing the organic components obtained in the step of the above extraction method. After being sprayed or transferred in liquid form into a sealed separation container, the solid carbon dioxide is fixed as a solid carbon dioxide mixture by heat of vaporization when released as carbon dioxide gas from the container, cold heat from the outside, or a combination thereof. It is characterized as an extraction/separation method that includes a separation step in which carbon dioxide gas is released by sublimation of the mixture to separate an extraction promoting aid containing organic components.

The extraction step and separation step in the present invention will be explained below.

I) Regarding the extraction process: Raw grape bunches are unfermented or fermented in a high-pressure container, and then the juice or squeezed water-containing grape bunches are fermented, and the fermentation residue is freeze-dried in vacuum or dried under an inert gas atmosphere. After adding the extraction accelerator,
A suitable amount of liquefied carbon dioxide is injected, and the container is heated to the critical point of carbon dioxide (critical temperature 31.11Z", critical pressure cuff 5.28
After heating and pressurizing the liquid mixture in the container to a supercritical gas state (kg/cr/l) and maintaining it for an appropriate period of time, the container is brought under conditions below the critical point of carbon dioxide. The purpose is to selectively transfer organic components other than anthocyanin pigments from the grape bunch brewing residue to the mixed liquefied carbon dioxide phase by returning the grape bunch to a mixed liquefied carbon dioxide phase.

The extraction solvent for extracting the above organic components is a mixture of liquefied carbon dioxide and an extraction promoting aid, and is added to the high-pressure extraction container in a liquid state, or is mixed in a liquid state in advance in a high-pressure cylinder or storage tank. or a mixture of liquefied carbon dioxide and an extraction accelerator in a liquid state in a pipe, etc.
Use either.

n) Regarding the separation process The separation process includes the following embodiments as a separation method.

(1) Mixed liquefied carbon dioxide containing organic substances and components is sprayed under reduced pressure into a separation container to form a solid carbon dioxide mixture, and after releasing the vaporized carbon dioxide from this container, hot water or hot air etc. This is a method in which the extraction promoting aid containing the extract (organic component) is separated by heating the solid carbon dioxide mixture using a carbon dioxide mixture, directly sublimating and releasing the solid carbon dioxide mixture without causing a phase change to liquefied carbon dioxide.

(11) Transfer and fill the mixed liquefied carbon dioxide containing organic components into a separation container, and cool and hold this container using a refrigerant such as solid carbon dioxide or low-temperature liquefied gas to the vicinity of the triple point of OC to carbon dioxide. At the same time, vaporized carbon dioxide is released from the container, and the pressure and temperature inside this container are reduced to the triple point of carbon dioxide (
5,28kf/Cd, -56,6r: ) or less,
After fixing a part of the liquefied carbon dioxide contained in the extract and the extraction promotion aid as a solid carbon dioxide mixture, it is heated using hot water or hot air, and directly sublimated from the solid carbon dioxide mixture to form carbon dioxide. This is a method of separating the extraction promoting aid containing the extract by releasing gas.

(iii) Transfer and fill the mixed liquefied carbon dioxide containing organic components into a separation container, and fill this container with a low-temperature liquefied gas (e.g., liquid nitrogen, liquefied natural gas, etc.) of -80C or less.
This method involves direct sublimation from the solid carbon dioxide mixture, releasing carbon dioxide gas, and separating the extraction accelerator containing the extract.

dv) By mixing in a separation container sprayed mixed liquefied carbon dioxide containing organic components with sprayed low-temperature liquefied gas of -5OC or less, the mixture containing extracts and extraction promotion aids is mixed. After fixing gaseous carbon dioxide as solid carbon dioxide, the container is heated using hot water or hot air to directly gasify the solid carbon dioxide mixture and separate the extraction promoter containing the extract. It's a method.

Whether or not to adopt the side separation method described above is determined depending on the characteristics of the organic components to be separated in the dried grape bunch brewing residue.

Function: In the extraction method of the present invention, since the hydrous grape bunch brewing residue contains organic components that are susceptible to thermal deterioration and oxidation, vacuum freeze-drying or mild temperature conditions under an inert gas atmosphere is required. A high-pressure extraction vessel containing liquefied carbon dioxide and an extraction promoter containing liquefied carbon dioxide and an extraction promoter is heated to reach the critical temperature of carbon dioxide. This is due to the energy and extraction action of the extraction solvent when the mixed liquid is brought to a supercritical gas state by applying conditions above the pressure, and then the container is cooled to return it to below the critical point and the phase changes to mixed liquefied carbon dioxide. Due to the synergistic effect, the organic components contained in the grape bunch brewing residue are extracted in a short time, the extraction rate is significantly improved, and the extracted organic components do not contain anthocyanin pigments. It is. The reason for this is an experimental fact that the solvate extraction effect of liquefied carbon dioxide and an organic solvent is present, and the theoretical extraction effect is not clear at this stage.

Further, the mixture containing the organic component and the extraction and promotion aid obtained by the above extraction method needs to be separated from the mixed liquefied carbon dioxide phase. In this case, the separation method described above is used in combination with the extraction method according to the present invention. By adopting this combined separation method, the mixed liquefied carbon dioxide containing organic components and extraction promoting aids is fixed as a solid carbon dioxide mixture, and by releasing the sublimated carbon dioxide gas, the separated components are released as gas. Extract components can be separated at a high separation rate without migration, and a wide range of components from volatile components to high-boiling components can be separated. As described above, the present invention is characterized by a combination of the above-mentioned extraction method and preferably the above-mentioned separation method.

Effects of the Invention According to the present invention, organic components other than anthocyanin pigments can be selectively extracted in a shorter time and with a higher yield than the conventional extraction method from the grape bunch brewing residue dried by the above-mentioned drying method.

Furthermore, since the present invention is carried out by a combination of the above-mentioned drying, extraction, and separation steps, the organic components containing aroma substances contained in the grape bunch brewing residue are fixed in their natural state, and the organic components are fixed as shown in the examples of the present invention. It brings about amazing extraction and separation effects.

Further, if necessary, when storing the dried brewing residue, it is desirable to place it in a gas-permeable package filled with an inert gas and refrigerate it at a temperature of 50 ℃ or less if possible.

In addition, the method of the present invention is safe because it does not use harmful extraction accelerators, and there is no risk of explosion when it is industrialized, and it has great advantages in terms of equipment and safe operation. Ingredients provide useful raw materials for cosmetics, medicines, foods, etc.

EXAMPLES The present invention will be specifically explained below with reference to Examples, but the present invention is not limited in any way. Further, similar parts in each drawing are indicated by the same reference numerals.

Example 1 Water-containing grape bunch brewing residue 1. Insert the Okf and close the lid (1a) of this device.
After that, the pulp (Vl') provided in the inert gas introduction pipe (1b) is closed, and the pulp (V2') provided in the conduit of the vacuum pump (Pl) is opened and the pulp is passed through the dehumidifier (1c). The degree of vacuum inside the device (1) is increased to 5 x using the vacuum pump (Pl).
The water in the residue was frozen by evacuation to about 10'-2 Torr. While maintaining this vacuum state, the moisture in the residue was reduced from 46% to 4.5% by heating the residue to 500% using the heater (1d) installed in the device for 20 hours. After drying, the vacuum pump and warmer are stopped, and the pulp (v1'
) was introduced into the apparatus (1) to bring it to normal pressure. The obtained dry residue is placed in a high-pressure container (2) with 500 ml of the dried residue, avoiding air exposure as much as possible.
8.2k by weighing the cylinder (3) filled with liquefied carbon dioxide containing 3.2 parts of ethanol.
After weighing and pumping the pulp (Vl) into the container using a pump (PO), hot water is immediately poured into the jacket (2a) provided on the outer periphery of the container to adjust the temperature inside the container. After being left in a supercritical state with a pressure of 50C1200kp/7G for 4 hours, water was flowed through the jacket (2a) to cool the temperature and pressure inside the container to 20C160 atm to form a liquefied carbon dioxide mixture containing the extract and ethanol. After allowing the mixture to undergo a phase change for 2 hours, the liquefied carbon dioxide mixture containing the extract was sprayed into the separation container (4) through the pulp (v2) of the extraction tube provided at the bottom of the container. The gasified carbon dioxide was discharged through a blow valve (VB) provided at the top of the container to separate ethanol containing the extract from carbon dioxide. The pressure inside this container (1 to 5 k, 9/d) was observed with a pressure gauge (P).

The ethanol containing the separated extract was drawn out through the pulp (v3) of the outlet tube provided at the bottom of the container. The volume of the resulting ethanol solution was 290 ml, and the residue after removing the ethanol using a conventional distillation method was 31 Da. Analysis of the residue revealed that it was a mixture of organic substances such as fatty acid esters, higher alcohols, triglycerides, oils and fats, vitamins, and aromatic substances, and no anthocyanin pigments were observed therein.

The same mixed organic matter was obtained as a result of extraction and separation in accordance with Example 1, except that ethanol, which was an extraction accelerator, was replaced with ethyl ether and n-butane, respectively.

Example 2 1 ky of hydrous grape bunch brewing residue was put into the vacuum drying device (1) shown in Fig. 1, a lid (la) was attached to the device, and an inert gas introduction pipe (1b) was prepared. Pulp (Vl
') while supplying nitrogen gas through the vacuum pump (P
The pulp (V2') provided in the pipe line connected to 1) is opened, and the vacuum pump is heated to 5To
The moisture in the residue is dried from 43 to 6 by performing the operation of heating to 40C' with a warmer (1d) installed inside the container while vacuuming to about rr for 32 hours. After that, the vacuum pump and the warmer were stopped, the pulp (V1') was fully opened, nitrogen gas was introduced, and the inside of the apparatus was brought to normal pressure. After putting 500f of the dry residue thus obtained and 340 ml of ethanol into a high-pressure container (2),
After measuring s and oky from a cylinder (3) filled with liquefied carbon dioxide using a scale (A) and pumping it into the container using a liquid feeding pump (Po), immediately place a jacket on the outer periphery of the container. 2a) Run K hot water to check the temperature inside the container.
After leaving the pressure in a supercritical state of 48C and 200kg/dG for 4 hours, water was poured into the jacket to form the container (2).
The temperature and pressure inside the container were cooled to 20C and 160 atm to change the phase to a liquefied carbon dioxide mixture containing the extract and ethanol. After leaving it for 2 hours under this condition, the pulp ( The liquefied carbon dioxide mixture containing the extract is sprayed into the sealed separation container (4) through v2), and the gasified carbon dioxide is released as a gas from the blow valve (BV) provided at the top of the container to extract the extract. Ethanol containing carbon dioxide and carbon dioxide were separated. The pressure inside this container (
1 to 5 kg/d) was observed using a pressure gauge (P).

Ethanol containing the separated extract is stored in a separation container (4)
It was extracted through the pulp (VB) of the outflow pipe provided at the bottom of the machine. The resulting ethanol solution was 292rr+/, and after all the ethanol was removed using a conventional distillation method, the remaining amount was 29.
．． 51! Met. When the residue was analyzed, it was found to be mixed organic substances such as fatty acid esters, higher alcohols, triglycerides, oils and fats, and vitamins. No anthocyanin pigment was observed in it.

An embodiment of a separation method other than the separation method implemented in Example 1 above will be described below.

The separation method shown in Fig. 2 is similar to the separation container (4) shown in Fig. 1 in terms of the structure of the separation container (4). The difference is that a withdrawal tube with pulp (V4) is provided on the lower side of the mantle. The carbon dioxide mixture containing the extract obtained in Example 1 and ethanol was transferred and filled into this separation container, and liquid nitrogen was poured into the mantle (4a) provided around the container to cool the container. After fixing the liquefied carbon dioxide mixture as a solid carbon dioxide mixture, the liquid nitrogen is extracted through the pulp (V4) and the container is heated using room temperature water (or hot air). The sublimated carbon dioxide was discharged through the blow valve (BY), and the ethanol solution containing the extract was taken out through the pulp (Va) of the outflow tube. The obtained extract (organic components) was equivalent to that obtained by the extraction/separation method described in accordance with FIG.

Figure 3 shows a liquid nitrogen spray nozzle (
5a) and (5b) were provided above and below, and the liquefied carbon dioxide mixture containing the extract obtained in Example 1 and ethanol was supplied to the pulp by spraying liquid nitrogen into the container from each nozzle in the inlet tube. (■6) and was sprayed into the container from the nozzle (5C). In the liquefied carbon dioxide mixture, the carbon dioxide mixture gasified during spraying comes into contact with atomized liquid nitrogen to form carbon dioxide snow, which is deposited at the bottom of the container. This accumulated snow-like carbon dioxide is transferred to a separator (4') connected to the bottom of the container, and heated water is poured into a jacket (43') provided on the outer periphery of this separator to sublimate the carbon dioxide. The carbon is removed from the separation vessel (4) with a gas discharge pipe (
The ethanol solution containing the separated extract was taken out through the pulp (v3) of the withdrawal tube. The extract thus obtained was comparable to that obtained by the extraction and separation method described in FIG.

[Brief explanation of the drawing]

FIG. 1 is an explanatory view showing an example of an apparatus for implementing the present invention, and FIGS. 2 and 3 are explanatory views showing embodiments of another separation method.

Claims (2)

[Claims] (1) Grape bunch brewing residue was subjected to vacuum freeze-drying treatment or drying treatment under an inert gas atmosphere, and then placed in a high-pressure container for extraction, and then a low-boiling point solvent and liquefied carbon dioxide, which are extraction accelerators, were added. After that, the container is heated to maintain the mixed liquid in the container in a supercritical mixed gas state under conditions above the critical temperature and critical pressure of carbon dioxide, and then the container is cooled to below the critical point. After the organic components in the residue are selectively extracted by the mixed liquefied carbon dioxide phase consisting of an extraction accelerator and carbon dioxide, the organic components are removed from the mixed liquefied carbon dioxide phase. A method for extracting and separating organic components from grape bunch brewing residue, which comprises separating an extraction promoting aid contained therein. (2) After spraying or transferring the mixed liquefied carbon dioxide phase containing organic components into a sealed separation container,
Carbon dioxide gas is released by sublimation of the solid carbon dioxide mixture while fixing it as a solid carbon dioxide mixture by the heat of vaporization when releasing it as carbon dioxide gas from the container, by cold heat from the outside, or by a combination thereof, and by releasing carbon dioxide gas by sublimation of the solid carbon dioxide mixture. A method for extracting and separating organic components from a grape bunch brewing residue according to claim (1), which comprises separating an auxiliary agent for promoting grape extraction.