JPH039985A - Method for deodorizing herb spice or product of treatment thereof - Google Patents

Abstract

PURPOSE:To prepare an odorless herb spice which is nearly completely freed of an odorous component by extracting a herb spice or a product of treatment thereof containing an odorous component with fluid CO2 in a supercritical state. CONSTITUTION:A herb spice, e.g. rosemary or sage, or a product of treatment thereof containing an odorous component, e.g. a residue of hot water extraction of a herb spice, an oleoresin extracted with petroleum ether or toluene, or a residue thereof, is extracted with fluid CO2 in a supercritical state. Especially when extraction is conducted under a pressure of 90-200kg/cm<2> at 40-80 deg.C, the odorous component can be nearly completely removed. The herb spice or the product of treatment thereof is deodorized by transferring the odorous component therefrom to the fluid CO2.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to herbal spices or treatments thereof that are preferably used in producing odorless natural antioxidants from herbal spices such as rosemary and sage. Concerning methods for deodorizing things.

[Conventional technology]

Traditionally, herbal spices contain antioxidant ingredients.

It is known that it has the effect of preventing the oxidation of oil- and fat-containing foods, and various studies on this point have been conducted (Japanese Patent Application Laid-open Nos. 54-130485 and 55-1).
No. 8435, No. 55-102508, No. 56-741
No. 77, No. 56-144078, No. 58-67794
(No. 1, U.S. Pat. No. 3,950,266, etc.), spices, and herbal spices each have their own strong flavor, so if these spices are added directly to foods, cosmetics, pharmaceuticals, etc. as antioxidants, It causes various inconveniences, such as changing its flavor, affecting the balance of fragrances in cosmetics, and restricting its use in pharmaceuticals due to its unique odor.

In response, it has been proposed to remove essential oil components from herbal spices, recover odorless antioxidant components, and use these antioxidant components as antioxidants (U.S. Pat. No. 3,950,266, etc.). ). In this case, recovery of antioxidant components from herbal spices is conventionally performed by extraction using an organic solvent. Further, the deodorizing method for removing odorous components is usually carried out by steam distillation.

[Problem to be solved by the invention]

However, conventional deodorizing methods cannot sufficiently remove the odorous components of herbal spices, and for this reason, conventional antioxidants are not completely odorless, which limits their use. That was the reality.

The present invention was made in view of the above circumstances, and is a deodorizing method that can almost completely remove odor components from herbal spices or processed products thereof, and thus can obtain an almost completely odorless antioxidant. The purpose is to provide a method.

[Means to solve the problem]

In order to achieve the above object, the present inventors have conducted intensive research on methods for effectively removing odorous components contained in herbal spices or processed products thereof. When a processed material containing
We have discovered that odor components can be almost completely removed from this herbal spice or its processed product when extracted under conditions of less than 200 kg/aJ and a temperature of 40 to 80°C, and have thus come to form the present invention. .

Therefore, the present invention extracts herbal spices or processed herbal spices containing odorous components with a fluid made of carbon dioxide in a supercritical state, and extracts the odorous components contained in the herbal spices or processed products thereof. Provided is a method for deodorizing herbal spices or processed products thereof, which comprises transferring herbal spices or processed products thereof into the fluid.

Here, the herbal spices include rosemary sage,
Examples include, but are not limited to, thyme, rum, oregano, and basil. Note that when directly subjecting herbal spices to deodorizing treatment, it is preferable to use the spices in powder form.

Processed products containing odorous components of herbal spices include hot water extraction residues of herbal spices, essential oil extraction residues, ethyl ether, dioxane, acetone, ethanol, methanol, and hydrous ethanol.

Oleoresin extracted with a polar solvent such as ethyl acetate, propylene glycol, glycerin or its extraction residue, n
-Hexane, petroleum ether, ligroin, cyclohexane, carbon tetrachloride, chloroform, dichloromethane, 1,
2-dichloroethane.

Examples include oleoresin extracted with a nonpolar solvent such as toluene and benzene, or an extraction residue thereof.

In addition, in the present invention, herbal spices or processed products thereof are deodorized with a fluid made of carbon dioxide in a supercritical state, and the deodorization conditions are such that the pressure of carbon dioxide is 90 k
g/cm2 or more 200kg/(less than d, temperature 40~8
The temperature is preferably 0°C. If the pressure is less than 90 kg/cd, the extraction of odorous components may be insufficient;
If the antioxidant component and the odorous component coexist at 0 kg/cm2 or more, the antioxidant component may be removed together with the odorous component, and the yield of the antioxidant component may decrease.
If the temperature exceeds ℃, the extraction of odorous components may become insufficient. In addition, a more preferable pressure is 120 to 180 kg/cJ
, the temperature is 40-60°C.

Here, an organic solvent can be mixed as an entrainer into the fluid made of carbon dioxide in a supercritical state, thereby improving the efficiency of extraction of odorous components. Examples of the entrainer include aliphatic lower alcohols, aliphatic hydrocarbons, aromatic hydrocarbons,
Ketones etc. can be used. In addition, the amount of entrainer mixed is preferably 2 to 20% by weight based on the weight of carbon dioxide. If it is less than 2% by weight, the extraction efficiency of odorous components may not increase, and if it exceeds 20% by weight, The entrainer distillation process can be time-consuming. On the other hand, when the content is 2 to 20% by weight, the extraction efficiency can be sufficiently increased and the amount of solvent used can be significantly reduced.

In the present invention, it is preferable to transfer the odorous components into a fluid made of carbon dioxide in a supercritical state by the above-described extraction process, and then separate and recover the components. In this case, the separation conditions are: atmospheric pressure to 80 kg/a (,
Preferably, the temperature is 20 to 80°C. pressure is 80
If it exceeds kg/L:i, the separation and recovery of odorous components may become insufficient, and if the temperature exceeds 80"C, which is higher than the deodorizing treatment temperature, separation and recovery of odorous components may become insufficient. In addition, more preferable separation conditions are a pressure of atmospheric pressure to 60 kg/cd and a temperature of 25 to 60°C.

In the present invention, the processed products of herbal spices containing the above-mentioned odorous components to be deodorized include herbal spices, their hot water extraction residues, essential oil collection residues, oleoresins extracted with polar solvents and their extraction residues, and non-alcoholic spices. An extracted fraction obtained by extracting a raw material selected from oleoresin extracted with a polar solvent and its extraction residue with a fluid consisting of carbon dioxide in a supercritical state can be suitably used. In other words, this extracted fraction contains high-purity antioxidant components and odorous components due to the extraction treatment using carbon dioxide in a supercritical state, so the odorous components are removed from this extracted fraction. By doing this, it is possible to obtain an antioxidant that is odorless and has strong antioxidant power.

In this case, the above-mentioned extraction fraction is obtained by extracting herbal spices, etc. with a fluid made of carbon dioxide in a supercritical state, and the extraction conditions are such that the pressure of carbon dioxide is
It is suitable that the weight is 00 to 450 kg/cot and the temperature is 40 to 80°C. If the pressure is less than 200 kg/cm2, the extraction of antioxidant components may be insufficient.
If it exceeds 0 kg/aif, equipment may become unreasonable. If the temperature is less than 40'C, the extraction of antioxidant components may become insufficient, and even if the temperature exceeds 80C, no increase in the extraction efficiency of antioxidant components may be observed. In addition, the more preferable pressure is 250 to 400 kg/J, and the temperature is 40
~ 60 ° C. 6 In addition, an entrainer can be mixed in the fluid used for this extraction process in the same manner as above,
Thereby, the extraction efficiency of antioxidant components can be improved.

Thus, in the first stage, the pressure is preferably 200~
Extraction of antioxidant components and odorous components is carried out using carbon dioxide in a supercritical state at a pressure of 450 kg/cm2 and a temperature of 40 to 80°C, preferably at a pressure of 90 kg/a as the second stage.
+f or more and less than 200 kg/aJ, temperature 40-80℃
By extracting odorous components (deodorizing treatment) using carbon dioxide in a supercritical state, an odorless natural antioxidant with high antioxidant power can be obtained. Soluble odorous components (including essential oil components) are selectively extracted and removed at a certain pressure range (90-200 kg/ai), while antioxidant components are extracted and removed at a relatively higher pressure (200-200 kg/ai). It is based on the principle that extraction and separation can be performed at a rate of 450 kg/cd).

Furthermore, when a residue containing antioxidant components and odor components removed from herbal spices or their processed products is obtained by the method of the present invention, this residue can be extracted by the above-mentioned extraction method using carbon dioxide in a supercritical state. It is preferable to separate and recover the oxidizing components, and this also makes it possible to obtain an odorless natural antioxidant with high antioxidant power.

Odorless antioxidants obtained using the present invention include fish oil, lard, tallow, head oil, chicken oil, soybean oil, linseed oil, cottonseed oil, safflower oil, rice oil, corn oil, coconut oil, palm oil, Animal and vegetable oils such as oil, sesame oil, cacao oil, castor oil, peanut oil, butter, cheese, margarine, shortening, mayonnaise, dressing, ham, sausage, potato chips, fried rice crackers, fried ramen, curry roux, soy sauce , soft drinks, alcohol, fruit wine,
It can be used by being added to ketchup, jam, fish or meat paste products, other foods, cosmetics such as hair cosmetics, skin cosmetics, mouth cosmetics, and pharmaceuticals.

In this case, the amount of antioxidant added is the total o as a dry product,
The antioxidant according to the present invention preferably has an amount of ~1% by weight, in particular 0.001-0.1% by weight.
This may be used as it is, but if necessary, it may be made into a powder or granule form by adding excipients such as starch or gelatin, or it may be made into a powder or granule form by adding excipients such as starch or gelatin. It may be dissolved and dispersed in a mixture to form a liquid form. Furthermore, the antioxidant according to the present invention may contain a synergist component such as citric acid as necessary.

〔Effect of the invention〕

As explained above, according to the present invention, by deodorizing with supercritical carbon dioxide, odor components can be reliably removed from herbal spices or processed products thereof, and therefore, from herbal spices. Odorless antioxidants can be obtained satisfactorily. In this case, 1. Since the antioxidant used in the present invention is extracted from natural herbal spices, it is highly safe for the human body. food, cosmetics,
It can be suitably used for medicines, etc. Furthermore, since the method of the present invention uses carbon dioxide, the treatment process is highly safe.

Next, the present invention will be concretely illustrated by examples, but the present invention is not limited to the following examples.

〔Example〕

FIG. 1 shows an example of an extraction separation apparatus used in carrying out the present invention, in which 1 is an extraction tank, 2 is a separation tank, 3 is a CO□ cylinder, 4 is an extractant compressor, and 5 is an entrainer container. , 6 is a constant supply pump, 7 is a pressure control valve, 8 is a heat exchanger, 9 is a flow rate adjustment valve, 10 is a pressure holding valve, 11 is a gas flow meter, 1
2 is a weighing platform scale, 13 is an air release valve, 14 is a solvent path, and 15 is an extract recovery valve.

When producing an odorless antioxidant using this apparatus, the first step is to extract the antioxidant component and the odorous component, and the second step is to deodorize the extracted fraction. In this case, first, herbal spices such as rosemary powder are put into the extraction tank 1. Subsequently, carbon dioxide is sent out from the carbon dioxide cylinder 3, and the air in the solvent path 14 including the extraction tank 1 and the separation tank 2 is released by the atmosphere release valve 13 and replaced with carbon dioxide.

Next, the pressure control valve 7 on the input side is set to the first stage processing (extraction) pressure, the flow rate adjustment valve 9 on the output side of the extraction tank 1 is fully closed, and the carbon dioxide compressor 4 and metering pump 6 (
(required when using an entrainer), and set the pressure in extraction tank 1 to the specified pressure (200 to 450 kg/cm).
2). At this time, an entrainer such as alcohol is delivered in a fixed amount from the solvent container 5 to the heat exchanger 8.
The mixed solvent is mixed with carbon dioxide to form a mixed solvent, heated to a predetermined temperature (40 to 80°C), and then supplied in a constant quantity to the extraction tank 1, where herbal spices such as rosemary in the extraction tank 1 are extracted. Extract and process.

After that, the flow rate adjustment valve 9 is gradually opened to reduce the pressure, and the mixed solution containing antioxidant components in the extraction tank 1 is introduced into the separation tank 2.
Both components containing antioxidant components are separated and collected at a temperature of room temperature to 80°C.

At this time, during boat fishing, the pressure in the separation tank 2 is maintained at a constant pressure by the pressure holding valve 10, and the flow rate of the mixed solvent is quantitatively controlled by the flow rate adjustment valve 9.

Furthermore, the separated carbon dioxide containing antioxidant components is returned to the compressor 4 and recycled.

Next, as the second stage treatment, the separated and recovered anti-oxidant components are put into the extraction tank 1 under deodorizing conditions (extraction pressure: 90 kg/a If or more, less than 200 kg/j, extraction temperature: 4 o ~80℃, separation pressure crab atmospheric pressure ~80kg/a
! , separation temperature: room temperature to 80°C). In this case, odorous components are separated and recovered in separation tank 2, and a fraction containing odorless antioxidant components remains in extraction tank 1.

In this apparatus, the order of the two-step process described above can also be reversed. That is, in the first stage, a deodorizing treatment is carried out, and in the extraction tank 1, an extraction tank residue is obtained from which odor components have been removed.Then, in the second stage, the residue is extracted, and in a separation tank 2, antioxidant components are removed. Obtain a separation tank recovery material containing

An experimental example using the apparatus shown in FIG. 1 will be shown below. Note that Experiments A to C are examples in which one-stage processing was performed, and Experiment 2 is an example in which two-stage processing was performed.

[Experiment example]

In order to find the optimal conditions to more efficiently obtain odorless antioxidant ingredients, we conducted experiments by changing the processing and separation conditions for various raw materials. An AOM test was conducted on each substance obtained (extraction tank residue, separation tank residue) to determine the antioxidant power, and a comprehensive evaluation was performed based on the antioxidant power, flavor, yield, etc. The results are shown in Tables 1 to 4 below.

In this case, the antioxidant power in the table below represents the time to reach POV = 30 when an AOM test is performed with 0.01% solid content added as a fraction containing antioxidant components. . Here, the AOM test was conducted in accordance with "Standard Oil and Fat Analysis Test Methods, edited by Japan Oil Chemists'Association." The oil and fat used was lard (antioxidant-free, manufactured by Fuji Essential Oil Co., Ltd.), and the oil bath temperature was 97.8°C. In addition, for the flavors in the table, the undeodorized amount is 1
, represents the average score (9 panelists) when evaluated using a 5-point method with the odorless amount being 5. Therefore, the higher the value of antioxidant power, the stronger the antioxidant power of the residue in the extraction tank or the recovered material in the separation tank, and the higher the value of flavor, the better the removal of odorous components from the residue or collected material. Show that there is.

A1: Nα1-15 Using raw rosemary powder as a raw material, the treatment was performed by changing the pressure without using an entrainer.

Here, the extraction pressure was 80 to 450 kg/ffl, and the separation pressure was 1 to 90 kg/a+f.

Results: For deodorization, the processing pressure is 90-200 kg
/aJ was suitable. In addition, in the case of extraction, a processing pressure of 200 to 450 kg/(!If) was suitable.

B2: Nα16-21 As a raw material, a hot water treatment residue other than raw rosemary powder and oleoresin were treated without using an entrainer and at different treatment temperatures. Here, the processing temperature is set to 3
The temperature was 2 to 90°C.

Result 2: If the processing temperature during extraction is less than 40°C, the extraction of antioxidant components is insufficient, and if it is above 80°C, no increase in the extraction efficiency of antioxidant components is observed, so the extraction processing temperature was set to 4.
0-80°C was suitable.

It was also possible to process materials other than rosemary powder.

C3: Nci22-30 Using rosemary bulk powder, the treatment was carried out by changing the type and addition concentration of the entrainer. Here, ethanol, propane, n-hexane, acetone, and toluene were used as entrainers, and the concentration thereof was 1 to 25%.

Results: Antioxidant components were efficiently obtained using either entrainer. Further, if the addition concentration is less than 2%, the extraction efficiency is poor, and a range of 2 to 20% is suitable.

D4: 31-37 Based on the conditions obtained from Experiments A to C, a two-stage treatment was performed to more efficiently obtain both components containing odorless antioxidant components. Ingredients are sage other than rosemary,
I also did this with thyme and marjoram.

Raw material: Rosemary (Nα31-33: hot water extraction residue.

Nα34: original powder) Nα31: Extraction → deodorization, with entrainer.

Nα32: Extraction → deodorization, no entrainer.

N1133: Deodorization → extraction, with entrainer 6Nα3
4: Deodorization → extraction, no entrainer.

Ingredients: Herbal spices other than rosemary (raw powder) N
α35: Sage, extraction → deodorization, with entrainer.

Isao 36: Time, extraction → deodorization, with entrainer.

Nα37: Marjoram, extraction → deodorization, with entrainer.

Results: It was possible to efficiently obtain odorless components containing antioxidant components either in the order of extraction → deodorization or deodorization → extraction. In addition, by performing the two-step treatment on raw materials other than rosemary, it was possible to efficiently obtain both components containing odorless antioxidant components.

Furthermore, it was found that these antioxidants were much stronger than those of natural vitamin E (Emix 80 manufactured by Eisai) and BHA, which are generally used as antioxidants (see Table 5).

Table 5: Extended time: The extended time required to reach POV=30, minus 21 hours without additives.

From the results shown in Tables 1 to 5 above, it is confirmed that antioxidant components and odorous components can be successfully extracted by extracting herbal spices or their processed products with supercritical carbon dioxide. Ta. In this case, the extraction pressure for the extraction and separation of antioxidant components is 200 to 450 kg/a!
, extraction temperature 40-80℃, separation pressure atmospheric pressure ~ 80k
g/cm2, the separation temperature is 20 to 80℃, and the extraction and separation treatment of odorous components is performed at an extraction pressure of 90kg/cJ or more, 200℃.
It was found that it is appropriate to set the extraction temperature to 40 to 80°C, the separation pressure to atmospheric pressure to 80 kg/cJ, and the separation temperature to 20 to 80°C.

Finally, a formulation example is shown.

[Formulation example]

Based on the above findings, an emulsified dressing with the following formulation was formulated and its antioxidant power was evaluated.

Emulsion stabilizer 50g Sucrose 400g Seasoning 10g Various spices 40g Water 1640g Acetic acid solution 500g Egg yolk 200g Salt 150g Sodium citrate 5g Vegetable salad oil 2000g In this case, in the above dressing, 3g of the antioxidant obtained in the above experiment Nα31, 1.5g, 0.15g+BHA0.
6 g and 3 g of tocopherol were added, and immediately after the production of each dressing, as well as 3 g of these dressings.
After storage at 40°C for 2 days, the pov value (peroxide value) was measured and its stability (antioxidant property) was investigated. The results are shown in Table 6. The pov value is measured using an improved Lea method [Oil Chemistry.

19 (15), 340 (1970)).

As is clear from the results in Table 6, Nα31 was found to exhibit much stronger antioxidant power than BHA, which was said to have a strong antioxidant power even in conventional amounts.

Also, the dressing that added N1131.

Due to its addition, no change in aroma or taste was observed.

It maintained good quality.

Table 6 POV value when added to dressing

[Brief explanation of drawings]

FIG. 1 is a schematic diagram showing an example of an extraction/separation apparatus used for carrying out the present invention. 1... Extraction tank, 2... Separation tank, 3... CO2 cylinder, 4... Extraction compressor. 5... Entrainer container, 6... Constant supply pump, 7... Pressure control valve, 8...
...Heat exchanger, 9...Flow rate adjustment valve, 10...
Pressure holding valve, 11... Gas flow meter, 12... Weighing platform scale, 13... Atmosphere release valve, 14... Solvent path, 15... Extract collection valve.

Claims (1)

[Scope of Claims] 1. Herbal spices or processed herbal spices containing odorous components are extracted with a fluid made of carbon dioxide in a supercritical state, and the herbal spices or the processed products containing the herbal spices are extracted with a fluid made of carbon dioxide in a supercritical state. A method for deodorizing herbal spices or processed products thereof, characterized by transferring odor components into the fluid. 2.The fluid has a pressure of 90kg/cm^2 or more and 200kg
2. The deodorizing method according to claim 1, comprising carbon dioxide in a supercritical state with a temperature of less than /cm^2 and a temperature of 40 to 80C. 3. The deodorizing method according to claim 1 or 2, wherein an organic solvent is mixed into the fluid as an entrainer. 4. Processed products of herbal spices containing odorous components include herbal spices, their hot water extraction residues, essential oil extraction residues, oleoresins extracted with polar solvents and their extraction residues, and oleoresins extracted with nonpolar solvents. The deodorizing method according to claim 1, 2 or 3, wherein the extracted fraction is obtained by extracting a raw material selected from the extraction residue with a fluid consisting of carbon dioxide in a supercritical state.