JPS61221299A - Extraction and separation of organic component from animal and vegetable materials - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to a method for extracting and separating organic components from animal and plant materials. For more details, see the fats and oils contained in animal and plant materials,
This is a method of extracting and separating organic components such as aroma substances, vitamins, and sugars as single substances or mixtures thereof.

BACKGROUND OF THE INVENTION Conventionally, extraction methods, absorption methods, adsorption methods, ion exchange methods, etc. have been used alone or in combination as means for extracting and separating organic components from various animal and plant materials.

Among conventional extraction and separation techniques, extraction methods include a compression extraction method, a centrifugal extraction method, a solvent extraction method, and the like.

For example, to extract oil from oil fruits and oil seeds, press extraction method,
Solvent extraction methods are common, and sometimes combination methods are used. By the way, the disadvantage of the compression extraction method is that it has poor extraction efficiency, and the solvent extraction method uses harmful solvents such as n-hexane, so a large amount of energy is required to remove and recover the solvent from the extract. , complex separation technology and quality control are required to eliminate the risk of residual solvent, and the equipment must be explosion-proof because large amounts of flammable solvent are used.
．． The disadvantage of this method is that it is expensive in terms of equipment.

In addition, as a method for extracting aroma substances from vanilla husk,
Solvent extraction methods (e.g., water or ethanol) are generally used, and the extracts include vanillin, which is useful for food flavoring.
It is used as vanilla 2 sense, which is a mixture of vanillic acid and other aromatic ingredients. As a method for extracting aroma substances from vanilla shells using ethyl alcohol as a solvent, the Soxhlet extraction and concentration method, which involves circulating the solvent, is used. In this extraction method, the temperature is heated to or near the boiling point of ethyl alcohol, which evaporates the aromatic volatile components contained in vanilla shells, and may cause polymerization of aldehydes due to thermochemical reactions. However, these causes may contribute to quality deterioration, and furthermore, it is difficult to completely extract and separate the natural components contained in vanilla husk.

Furthermore, when decaffeinating green coffee beans, extraction and separation are generally performed using a halogenated organic solvent method or a steam distillation method. Among these methods, the former method is disadvantageous in that harmful organic solvents remain, and the latter method has problems such as thermal deterioration of components in the coffee beans.

In addition, as a method for extracting and separating the liver oil component from the liver of deep-sea sharks, a pre-preparation method is generally used in which the liver oil is eluted by placing the liver in an iron pot and heating it over an open flame. Furthermore, methods for extracting oil components containing vitamins from the liver of cod species include steaming and squeezing, or adding IJum and heating to dissolve the liver tissue. The oil component and water are separated using a separation method. Since these methods are carried out using high-pressure steam or direct heating, substances in the fats and oils that are easily degraded by heat or easily decomposed by oxidation may cause unpleasant spoilage odors.

In order to improve the shortcomings of the above-mentioned series of extraction and separation methods, a supercritical gas extraction technique has recently been developed which is performed at a temperature above the critical temperature and critical pressure of carbon dioxide. In this method, the conditions in which the critical temperature and pressure are exceeded in a high-pressure container are called "supercritical gas state," and as the pressure increases at a constant temperature, the gas density increases. Increases solubility.

Next, we will discuss some proposed extraction and separation methods using supercritical gas extraction technology.
No. 02 discloses a method for separating oil from plants and animals, JP-A-58-74797 discloses a method for extracting aroma substances from vanilla shells, and JP-A-46-1820 discloses a method for extracting aroma substances from green coffee beans. Several methods have been proposed.

Furthermore, Japanese Patent Application Laid-Open No. 48-68754 describes a method for producing extracts of plant and animal substances under the condition of liquefied carbon dioxide gas, and Japanese Patent Application Laid-Open No. 48-68755 discloses a method for producing extracts of plant and animal substances. A method of extracting animal and plant substances under a mixed state of carbon dioxide gas and an organic solvent has been proposed.

Problems to be Solved by the Invention However, in any of the above methods, there are practical dissatisfaction such as the extraction time of organic components is long, a satisfactory extraction effect cannot be obtained, and the expected separation effect cannot be obtained. The purpose of the present invention is to extract organic components from animal and plant materials in a short time in the same extraction vessel, and to extract a wide range of components from volatile to high boiling point components at a high extraction rate.・Means for solving zero problems in the separation method The present inventors have continued intensive research on the extraction and separation of organic components contained in animal and plant materials using liquefied carbon dioxide. By adding a solvent such as water, ethyl alcohol, alcohol, methyl ether, n-butane, or a mixed solvent thereof and heating it, the dissolution energy of the phase change from a liquid state to a supercritical gas mixture state is used. The same high-pressure extraction process involves extracting organic components from animal and plant materials as extractants, dissolving them, returning them from a gas mixture state to a liquid state, and dissolving or mixing the organic components in liquefied carbon dioxide and a solvent or mixed solvent. By conducting the extraction in a container, the extraction time can be shortened and the extraction rate of organic components can be increased.Furthermore, the liquefied carbon dioxide mixed solvent contained in the extract can be partially or completely fixed as a solid carbon dioxide mixture. Finally, they discovered that a wide range of components, from volatile components to high-boiling components, can be separated with high efficiency, leading to the completion of the present invention. That is, in the extraction method of the present invention, animal and plant materials are placed in a high-pressure container, an extraction accelerator is added, and then an appropriate amount of liquefied carbon dioxide is injected, or an appropriate amount of liquefied carbon dioxide containing the extraction accelerator is injected, and the The container is heated to bring all or a portion of the mixed liquid in the container into a supercritical gas state under conditions exceeding the critical temperature and critical pressure of carbon dioxide, and then maintained for an appropriate period of time, and then cooled. This method is characterized in that the organic components are extracted into the mixed liquefied carbon dioxide phase by returning the temperature to below the critical point and changing the phase to mixed liquefied carbon dioxide.

In addition, in an extraction/separation method that combines a method of separating an extraction promoter containing extracted organic components from a mixed liquefied carbon dioxide phase containing extracted organic components and an extraction promoter obtained by the above extraction method, , the mixed liquefied carbon dioxide phase containing the organic components obtained in the step of the above extraction method is sprayed or transferred in liquid form into a sealed separation container, and then the heat of vaporization or the outside when released from the container as carbon dioxide gas. Addition of a separation step in which the solid carbon dioxide mixture is fixed as a solid carbon dioxide mixture by cold heat or a combination thereof, and carbon dioxide gas is released by sublimation of the solid carbon dioxide mixture to separate the extraction promoting aid containing the extracted organic components. It is characterized as a method of extraction and separation.

The present invention will be explained in detail below.

■) About the extraction process Dry or natural animal and plant materials are crushed, crushed, pulverized, cut, or in their original state into a high-pressure container, and after adding an extraction accelerator, an appropriate amount of liquefied carbon dioxide is injected, and the container is turned into a carbon dioxide gas. Critical point of carbon (critical temperature 31.1 t:',
After heating and pressurizing the liquid mixture in the container to a supercritical gas state or a partially supercritical gas state by heating and pressurizing the mixture to a critical pressure cuff of 5.28ヰ/m) or higher, and holding it for an appropriate period of time,
The purpose is to return this container to conditions below the critical point of carbon dioxide and change the phase of mixed liquefied carbon dioxide, thereby transferring the organic components contained in the animal and plant materials to the mixed liquefied carbon dioxide phase.

The extraction solvent for extracting the above organic components is a mixture of liquefied carbon dioxide and an extraction accelerator, which is added in an appropriate amount to the 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 method in which liquefied carbon dioxide and an extraction accelerator are mixed in a liquid state in a pipe, and the phase of the mixed extraction solvent is changed from liquid state to completely gas state or partially gas state to liquid state. It is.

1) About the separation process 1) Spray mixed liquefied carbon dioxide containing extracted organic components and extraction promotion aid into a separation container under reduced pressure to generate a solid carbon dioxide mixture.0 Vaporized carbon dioxide is released from this container. After that, the mixture is heated using hot water or hot air, and the solid carbon dioxide mixture is directly sublimated and released without causing a phase change to liquefied carbon dioxide, thereby separating the extraction promoting aid contained in the extract.

11) Transfer and fill the mixed liquefied carbon dioxide containing the extract and the extraction promotion aid into a separation container, and use a refrigerant such as solid carbon dioxide or low-temperature liquefied gas to transfer the container to the vicinity of the triple point of Oc~carbon dioxide. The vaporized carbon dioxide is released from the container while being cooled and maintained until the temperature reaches the triple point of carbon dioxide (5.28 kg/cr/l, -56,6C) or less to fix a part of the liquefied carbon dioxide containing the extract and the extraction promoting agent as a solid carbon dioxide mixture,
This is a method of separating the extraction promoter contained in the extract by heating with hot water or hot air, and directly sublimating the solid carbon dioxide mixture to release carbon dioxide gas.

111) Transfer and fill the mixed liquefied carbon dioxide containing the extract and the extraction promotion aid into a separation container,
Direct sublimation from a solid carbon dioxide mixture by cooling using a low-temperature liquefied gas (liquid nitrogen, liquefied natural gas, etc.) below C,
This is a method in which the extraction promoting agent contained in the extract is separated by releasing carbon dioxide gas.

iv) The extract and the extraction promoting aid are mixed in a separation container by spraying mixed liquefied carbon dioxide containing the extract and the extraction promoting aid and spraying a low temperature liquefied gas of -80C or less. After fixing the gaseous carbon dioxide contained in the agent as solid carbon dioxide, the container is heated using hot water or hot air to directly gasify the solid carbon dioxide mixture and extract the extraction promoter containing the extract. Which of the above separation methods to use for separating the agent is determined depending on the characteristics of the organic components contained in the animal and plant materials.

Function In the present invention, an extraction container containing animal and plant materials is heated in the presence of an extraction solvent of liquefied carbon dioxide and an extraction promoting agent to bring the material to a temperature and pressure higher than the critical temperature and pressure of carbon dioxide. Contained in animal and plant materials by the energy and extraction action of the extraction solvent when converting all or part of the mixed liquid into a supercritical gas state and then cooling the container to return it below the critical point to change the phase to mixed liquefied carbon dioxide. Organic components are extracted in a short time and the extraction rate is significantly improved. The reason for this is not clear at this stage.

Japanese Patent Publication No. 51-36341 describes the removal of caffeine from green coffee beans by bringing them into contact with carbon dioxide at a temperature above the critical temperature and critical pressure. It has been stated that supercritical gaseous carbon dioxide at a pressure higher than the pressure is relatively easily absorbed, whereas dry caffeine is not. The present invention is characterized in that the extraction rate is not affected in any way even by dry raw materials.

Depending on the characteristics of the organic components contained in the animal and plant materials, it is necessary to separate the mixture containing the extract and the extraction promoter from the mixed liquefied carbon dioxide phase. In this case, the separation method described above is used in combination with the extraction method of 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 when the sublimated carbon dioxide gas is released, the separated components are separated. Extraction components can be separated at a high separation rate without being transferred into emitted gas, and a wide range of components from volatile components to high boiling point components can be separated. As described above, the method of fixing the solid carbon dioxide mixture and then separating the extraction promoting aid containing extracted organic components is a feature of the present invention. Organic components can be extracted from animal and plant materials in a short time and at a high rate.

Furthermore, the extraction promoting aid containing the extracted extract can be separated at a high rate, and separation commensurate with the extracted components is possible, resulting in surprising extraction and separation effects as shown in the examples of the present invention. In addition, it is safe because no harmful auxiliaries are used, and when it is industrialized, there is no risk of explosion-proofing, and it has great advantages in terms of equipment and safe operation.

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

Example 1 As shown in Fig. 1, a blow valve (BV) and a pressure gauge (P)
1,000 liters of coffee beans are placed in a high-pressure extraction container (1) equipped with a top plate, and a pump (PO) is used to pump the water layer through a flow meter (L) installed in a flow path connected to a water tank (2). 11!
is pumped through the pulp (Vl), then 6kt is weighed with a scale (B) from a high-pressure cylinder (3) filled with liquefied carbon dioxide, and then pumped (Po) from a channel equipped with pulp (v2). After pressure-feeding, hot water was poured into a jacket (la) provided on the outer periphery of the container, and while the mixture was left in a supercritical gas state of 600.180 atm for 4 hours, the water-containing supercritical carbon dioxide mixture was The gas extracted and dissolved the caffeine in the green coffee beans. Then, the jacket of the container (1a
) by flowing cold water into the container to lower the gas temperature and pressure in the container to 20
When cooled to C160 atm, water containing caffeine and liquefied carbon dioxide are separated, since water as an extraction aid is hardly dissolved in liquefied carbon dioxide at 2°C.
The water dissolved into the standing water at the bottom (1b) of the container, and the liquefied carbon dioxide was separated into the upper aqueous layer. The liquid in the aqueous layer in the container was taken out into a collection container (4) through a sampling pipe equipped with pulp (V3). If it is not yet completely decaffeinated, add water II! to the container (1). was fed under pressure, hot water was flowed through the jacket, and the mixture was left in a supercritical gas state of 6oC and 2oO atm for 4 hours. The subsequent operations were carried out in the same manner as the above method, and then the liquefied carbon dioxide in the container was extracted through the pulp (V4) provided in the pipe branched into the extraction pipe. The amount of caffeine remaining in green coffee beans has decreased from the original 1.3 tsun to 0.6 tsun.
'Z, and in two operations it decreased from 0.64 to 0.1.

Example 2 1 to 1 crushed soybean was placed in the extraction container (1) shown in Figure 2, and 7 kg was weighed using a scale (B) from a high-pressure cylinder (3) filled with liquefied carbon dioxide in which 2 parts of ethanol had been dissolved. After weighing and pumping it into the container (1) through the nozzle (■2) using the pump (Po), it was left to stand for one hour.Then, hot water was poured into the jacket (la) provided on the outer periphery of the container. The gas temperature and pressure inside the container were increased to 80tll:,20
After being left in a supercritical state at 0 atm for 5 hours,
la) Flow K water to reduce the temperature and pressure inside the container to 20C160.
After cooling to atmospheric pressure to change the phase to a liquefied carbon dioxide mixture containing the extract and ethanol, and leaving it for 2 hours under this condition, remove the noklup ('v) of the extraction tube installed at the bottom of the container.
Through 3), the liquefied carbon dioxide mixture containing the extract is sprayed into the sealed separation container (5), and the gasified carbon dioxide is released as a gas from the blow valve (BV) installed at the top of the container (1). Ethanol containing the extract and carbon dioxide were separated. The pressure inside this container was monitored with a pressure gauge (P). The separated ethanol containing the extract was extracted through the pulp (■5) of the outflow pipe provided at the bottom of the separation container (5), and when the ethanol was removed using a conventional distillation method, it turned yellow. Soybean oil 0.16 ml was obtained.
The oil content in the raw soybean was 17.84, and the residual oil content in the soybean obtained by the method of the present invention was 1.8. Furthermore, since ethanol was used as an extraction accelerator, the oil in the soybeans hardly adhered to pipes, pulp, etc.

Example 3 0.54 g of crushed vanilla husk was placed in the extraction container (1) shown in Fig. 2, and 7 kg of liquefied carbon dioxide mixture was added from a high-pressure cylinder (3) filled with a liquefied carbon dioxide mixture containing 3 parts of ethanol. After pressure-feeding the water into the container using the pump (Po), hot water is immediately poured into the jacket (1a) of the container to maintain the temperature and pressure inside the container in a supercritical state of 740,250 atm.
After standing for a while, water was poured through the jacket of the container to cool the gas temperature and pressure inside the container to 20 tons, 60 atmospheres, and the phase changed to a liquefied carbon dioxide mixture containing the extract and ethanol. After being left for 2 hours, the liquefied carbon dioxide mixture is transferred and filled into the separation container (5) through the pulp' (V3) of the extraction tube provided at the bottom of this container.
) to (5a) with solid carbon dioxide
Pour the cooled brine solution into C, and while cooling, pour the cooled brine solution into the container (
5) is released as carbon dioxide through a blow valve (BV) installed at the top of the container, and when the inside of this container becomes below the triple point of carbon dioxide, the liquefied carbon dioxide mixture becomes a solid carbon dioxide mixture. Next, stop cooling and remove the container (5)
Warm water was poured into a), and sublimated carbon dioxide was released from a blow valve (BV) provided at the top of the container (5), thereby obtaining an ethanol solution 190F containing vanilla essence.

The combination of resin and essential oil (oleoresin) contained in it is 94f, and the oleoresin concentration in ethanol is 4
It was 9.51. The yield was 97.84 with respect to vanillin at a raw vanilla shell ratio of 18.84.

For evaluation of the extract, an extract obtained by a conventional alcohol extraction method was adjusted to have the same concentration as that obtained in the present invention, and the following sensory test was conducted.

Ice cream mixture 10001 contains 1 me of a vanilla extract alcohol solution (containing 20 parts of oleoresin) obtained by a conventional alcohol extraction method and 1 m of a vanilla extract alcohol solution (containing 20 parts of oleoresin) obtained by the method of the present invention.
l! A panel test of 10 people was conducted to examine the additives. As a result, the ice cream mixture to which vanilla extract obtained by the method of the present invention was added was unanimously judged to be good. Furthermore, according to the results of a sensory test, the vanilla extract obtained by the method of the present invention has a volatile sweet scent.
It was determined that the content was higher than that obtained using a conventional method.

Example 4 Put 100 f of the liver of a merganser shark in the extraction container (1) shown in Fig. 2, and add 6 kg of the mixture to a high-pressure cylinder (3) filled with a carbon dioxide mixture containing 1 liter of ethanol using a scale (B).
After weighing g and pressurizing it into the container using a pump (PO),
Warm water is poured into the jacket (la) of the container to maintain the temperature and pressure inside the container at 800.200 atm in a supercritical gas state.
After leaving for a while, water was poured through the jacket of the container to cool the gas temperature and pressure inside the container to 20 tll' and 60 atm to form a liquefied carbon dioxide mixture containing the extract and ethanol, and leave it in that state for 2 hours. , the liquefied carbon dioxide mixture is separated from the pulp (■3) in the extraction tube of the container (5).
) and the gasified carbon dioxide was released from the blow valve (BV) of this container to obtain an ethanol mixture containing the extract. Ethanol was removed using conventional distillation methods and the oily residue was 64jF. Liver oil content 8
No oxidation or odor was observed even though the oil was heated under carbon dioxide and ethanol atmosphere for several hours.

Embodiments other than the separation methods implemented in Examples 2 to 4 above are shown below.

The separation container (5) shown in FIG. 3 is the same in structure as the separation container (5) shown in FIG. The difference is that a withdrawal tube with pulp (V6) is provided on the lower side of the mantle. The carbon dioxide mixture containing the extract obtained in Example 3 and ethanol was transferred and charged into this separation container, and liquefied nitrogen was put into the mantle around this container to cool the container. After being fixed as a solid carbon dioxide mixture, the liquefied nitrogen is extracted through the pulp (V6) and the container is heated using room temperature water (or hot air). The sublimated carbon dioxide was released through the blow valve (BV) and removed as an ethanolic solution containing the extract through the pulp (Vs) of the outflow tube. The obtained ethanol solution containing vanilla two senses contained more volatile and sweet components than that obtained in the separation step of Example 3.

Figure 4 shows the liquid nitrogen spray nozzle (6) in the separation container (5).
a) and (6b) were placed above and below, and while spraying liquid nitrogen from the nozzle in the container (5), the liquefied carbon dioxide mixture containing the extract obtained in Example 3 and ethanol was introduced into the container through the nozzle (6c). ). In the liquefied carbon dioxide mixture, the carbon dioxide mixture that is gasified during spraying comes into contact with atomized liquid nitrogen to form carbon dioxide snow, which is deposited at the bottom of the container. The accumulated snow-like carbon dioxide is transferred to the separator (5') connected to the bottom of the container (5), and the carbon dioxide sublimated by flowing hot water through the separator (58'') is transferred to the gas release pipe. The ethanol released through (BP) and containing the separated extract is taken out through the pulp of the withdrawal tube (V5).The extract obtained was comparable to that obtained with the separation method of FIG.

[Brief explanation of drawings]

FIGS. 1 and 2 are explanatory views showing an example of an apparatus for carrying out the present invention, and FIGS. 3 and 4 are explanatory views showing another embodiment of the separation method. (1)... Extraction container, (2)... Water tank, (3)...
...High pressure cylinder, (4)...Collection container, (5)...
Separation container for extraction. lI 3 Figure Ajakera Figure q

Claims (6)

[Claims] (1) Place animal and plant materials in a high-pressure container, add a solvent such as water, ethyl alcohol, ethyl ether, n-butane, or a mixture thereof as an extraction accelerator, and then press in an appropriate amount of liquefied carbon dioxide or use the above extraction accelerator. After pressurizing an appropriate amount of liquefied carbon dioxide containing liquefied carbon dioxide, the container is heated to a condition above the critical temperature and critical pressure of carbon dioxide, and all or part of the mixed liquid in the container is brought into a supercritical gas state. After holding the container for an appropriate period of time, the container is cooled to a temperature below the critical point to undergo a phase change to mixed liquefied carbon dioxide, and the organic components are extracted into the mixed liquefied carbon dioxide phase. How to extract. (2) Place animal and plant materials in a high-pressure container, add a solvent such as water, ethyl alcohol, ethyl ether, n-butane, or a mixture thereof as an extraction accelerator, and then press-inject an appropriate amount of liquefied carbon dioxide or After pressurizing an appropriate amount of liquefied carbon dioxide containing the agent, the container is heated to a condition higher than the critical temperature and critical pressure of carbon dioxide, and all or part of the mixed liquid in the container is brought into a supercritical gas state. After holding the container for an appropriate period of time, the container is cooled to below the critical point to change the phase to mixed liquefied carbon dioxide, and the organic components are transferred to the mixed liquefied carbon dioxide phase. After the carbon phase is sprayed or transferred in liquid form into a sealed separation container, the carbon phase is fixed as a solid carbon dioxide mixture using the heat of vaporization when releasing it as carbon dioxide gas from the container, the cooling heat from the outside, or a combination thereof. A method for extracting and separating organic components from animal and plant materials, comprising a separation step of releasing carbon dioxide gas through sublimation of a solid carbon dioxide mixture to separate an extraction promoting aid containing extracted organic components. (3) The separation container in which the mixed liquefied carbon dioxide containing the extracted organic components and the extraction promotion aid was formed into a solid carbon dioxide mixture is heated with hot water or hot air, and the solid carbon dioxide mixture is phased into the liquefied carbon dioxide. A method for extracting and separating organic components from animal and plant materials according to claim 2, which releases sublimated carbon dioxide without changing it and separates an extraction promoting aid containing extracted organic components from a solid carbon dioxide mixture. . (4) Cool the separation container filled with mixed liquefied carbon dioxide containing extracted organic components and extraction promoting aids to near the triple point of carbon dioxide using solid carbon dioxide or low-temperature liquefied gas refrigerant directly or indirectly. 3. The method for extracting and separating organic components from animal and plant materials according to claim 2, wherein the liquefied carbon dioxide mixture is fixed as a solid carbon dioxide mixture by releasing the carbon dioxide gas from the container while holding the carbon dioxide. (5) The separation container filled with the mixed liquefied carbon dioxide containing extracted organic components and extraction promotion aids is cooled with low-temperature liquefied gas at -80°C or lower, and the mixed liquefied carbon dioxide is completely fixed as a solid carbon dioxide mixture. Claim 2
A method for extracting and separating organic components from animal and plant materials as described in Section 1. (6) Mix the sprayed mixed liquefied carbon dioxide containing extracted organic components and extraction promotion aid with the sprayed low-temperature liquefied gas below -80°C, and directly convert the gaseous mixed carbon dioxide into solid dioxide. A method for extracting and separating organic components from animal and plant materials according to claim 2, wherein the organic components are fixed as a carbon mixture.