JPS59117593A - Deterpenation for essential oils - 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 The present invention enables easy removal of terpene hydrocarbons, which cause troubles such as deterioration of stability, deterioration of quality, and formation of resonant substances, from natural essential oils containing terpene hydrocarbons. The present invention relates to a method for deterpenizing essential oils, which can be effectively removed by simple operations and without deterioration or volatilization loss of desirable aroma and flavor active components of the natural essential oils.

By deceiving V, natural essential oil containing terpene hydrocarbons is about 4
A hydrous alcohol solution obtained by treating with aqueous ethanol and/or aqueous methanol at a concentration of 0 to about 95 g
The present invention relates to a method for deterpenizing essential oils, which is characterized by adsorbing and removing chilled hydrocarbons by treatment with a porous polymeric resin or chemically bonded silica dal.

In general, natural products such as flowers, leaves, stems, roots, stems, bark, fruits, etc. of plants are extracted, for example, by steam distillation, pressing, extraction, etc.
Natural essential oils that can be obtained by methods such as combinations thereof include, for example, limonene, α-pinene, β-2ene, myrcene, α-terpinene, r-terpinene,
) Contains at least one kind of terpene hydrocarbons such as monoterpene hydrocarbons such as dicinene, and sesquiterpene hydrocarbons such as caryophyllene, selinene, humulene-farnesene, and pisagalene. is normal.

However, such terpene hydrocarbons do not directly contribute to the aroma and flavor of natural essential oils, but rather contribute to the deterioration of the storage stability of natural essential oils. During storage, it may undergo oxidation, causing undesirable deterioration or odor generation, or may polymerize and form an undesirable resinous substance. When used as modulators, they are often the cause of various troubles. It is mainly the terpene-based oxygenated compounds and other aromatic and aliphatic oxygenated compounds contained in natural essential oils that give them their characteristic flavor and aroma. It is a kind.

Therefore, it is common to perform so-called "deterpenization" to remove the above-mentioned terpene hydrocarbons from natural essential oils, but a fully satisfactory means of deterpenization has not been provided.
, [1i:1 shot of such means is desired.

Conventionally, as a means for deterpenization in natural essential oils,
For example, a distillation method in which natural essential oil is distilled under reduced pressure to remove monoterpene hydrocarbons, or the essential oil is extracted with aqueous ethanol and mono- and sesquiterpene hydrocarbons insoluble in the aqueous ethanol are fractionally removed. A polar solvent such as a solvent extraction method or a low boiling point alcohol solution and the polar solution N?
A liquid-liquid extraction method using a two-leopard solvent, in which natural essential oils are extracted simultaneously using a 2H solvent tank of a non-polar solvent such as a low-boiling hydrocarbon solvent. an adsorption separation method in which the oxygen-containing compound is adsorbed onto the adsorbent by treating it with a blue-absorbing agent such as silica gel or silicic acid, and then the compound is desorbed using an appropriate solvent. It has been known. Furthermore, a method for producing natural fragrances has been proposed in which natural aroma components such as fruits and aromatic substances are adsorbed onto porous polymerized fat, and then eluted and recovered using hydrophilic solvents such as ethanol and propylene dalicol, or their hydrous substances. (Special Publication No. 48-34234).

However, the reality is that no satisfactory method has been proposed that allows deterpenization with easy operation and high yield without causing deterioration or volatilization loss of aroma and flavor active ingredients. For example, it is difficult to remove sesquiterpene hydrocarbons by detillation by distillation, and there are limitations on the degree of deterpenization.
Removal of monoterpene hydrocarbons also requires quite a long period of heated distillation time to remove a relatively large amount of monoterpene hydrocarbons, resulting in thermal alteration of aroma and flavor active ingredients and low boiling point aroma. The concomitant distillation of oxygen-containing compounds, which are active flavor ingredients, is accompanied by troubles that are difficult to avoid.

Father, the non-polar hydrocarbon-based organic solvent and the alcohol-based solvent
#: Regarding the terpenization method using liquid-liquid extraction means using gold, it is difficult to completely separate oxygen-containing compounds and terpene hydrocarbons with a simple operation.

Furthermore, in the adsorption separation method, highly active repellents among the oxygen-containing compounds in natural essential oils have IIφ
Since there is a risk of side reactions such as water and isomerization occurring, strict selection of operating conditions is required, which is industrially difficult.

Furthermore, the method proposed in Japanese Patent Publication No. 48-34234 recovers extremely small amounts of aroma components contained in fruits such as apples, strawberries, melons, bananas, apples, and beech fruits, as well as in the juice of fruits. There is no mention of a method for removing terpene hydrocarbons, especially a method for separating and removing terpene hydrocarbons from essential oils containing a large amount of terpene hydrocarbons.

The present inventor was surprised to overcome the shortcomings of the conventional means as described above, and
We have been conducting research to develop a means that can achieve an excellent deterpenization effect on aroma and flavor with simple operations and without alteration. As a result, approximately 4% of natural essential oils containing terpene hydrocarbons were produced.
By treating a hydroalcoholic solution obtained by treating with aqueous ethanol and/or aqueous methanol with a concentration of 0 to about 95% by weight with a porous polymer resin or chemically bonded silica glue, a natural essential oil containing chilled hydrocarbons can be obtained. It was discovered that terpene-based hydrocarbons can be selectively and efficiently adsorbed and removed, and that oxygenated compounds can be obtained with extremely high purity and high yield without deterioration or volatilization loss of aroma and flavor active ingredients. I did it.

Therefore, an object of the present invention is to provide a method for removing terpene hydrocarbons from a natural essential oil containing terpene hydrocarbons with easy operation and simple gas installation.

The above and many other objects and advantages of the present invention will become apparent from the following description.

The terpene-based hydrocarbon-containing natural essential oil used in the present invention is obtained by extracting the oil from plants such as branches and leaves, rhizomes, fruits, pericarp, seeds, etc., by means known per se, such as compression method, steam distillation method, etc. You can get it by doing it. Examples of natural essential oils containing such terpene hydrocarbons include orange oil, lemon oil, lime oil, tanzuerine oil, mandarin oil, grapefruit oil, bergamot oil, butygrain oil, yuzu oil, neroli oil, etc. An example is essential oil.

According to the method of the present invention, a natural essential oil containing terpene hydrocarbons as exemplified above is treated with aqueous ethanol and/or aqueous methanol at a concentration of about 40 to about 95% by weight, and if necessary, a hydroalcoholic phase is removed from the treatment system. Separate and collect. The alcohol concentration of the hydrous alcohol used in this treatment can be adjusted as appropriate depending on the type of natural essential oil and the type of alcohol, but for example, in the case of ethanol, it is about 40 to about 90.
In the case of methanol, it is preferably in the range of about 45 to about 95% by weight, and in the case of a mixture of methanol and ethanol, the mixing ratio can be changed as appropriate, but for example, about 40 to about 95% by weight. A range of about 95% by weight is preferred.

At this time, the mixing ratio of the natural essential oil and hydrous alcohol can be adjusted as appropriate. For example, the mixing ratio of natural essential oil and hydrous alcohol can range from 1:0.5 to about 9 to about 1,000, preferably from 1:1 to about 100.

The formed treatment system is preferably mixed under stirring conditions, if desired, so that the aroma and flavor active ingredients in the natural essential oil are brought into the hydroalcoholic phase at a sufficient t4M. Although there are limited constraints on mixed diopter and time, for example, about -
Examples include temperature conditions of about 20° to about 80° C. and stirring treatment times of about 1 minute to about 5 hours. After the mixing and stirring process, the stirring is stopped, and if necessary, for example, the mixed system is allowed to stand for at least about 5 minutes, and the alcohol-insoluble portion is filtered.
A hydroalcoholic solution can be obtained by removing it by means such as centrifugation.

Furthermore, the porous polymer resins used in the present invention are known per se, such as styrene and sovinylbenzene copolymers,
Combination of ethylvinylbenzene and sovinylbenzene, 2
．． Examples include a polymer of 6-diphenyl-9-710-enylene oxide and a polycondensation irimer of methacrylic acid and SOOL.

Such porous polymeric resin has a specific surface area of, for example, about 50
02711/f or more, preferably about TOOd/ or more,
and porous polymeric resins having a pore distribution of about 10A to about 500A.

Furthermore, the chemically bonded silica gel itself used in the present invention is known, and it can be used to bind alcohols, amines,
It is a type of silica gel in which silanes, etc. are chemically bonded, and for example, C1 such as octadecylsilane, octylsilane, etc.
A chemically bonded silica gel in which various substituents such as the above alkylsilane, aminopropylsilane, cyanopropylsilane and r-glycidoxyprobylsilane are chemically bonded can be expressed as 1y11, and such chemical bond For example, the pore size of the agent silica cell is about 50A~ and the specific surface A-1' is about 5O! /g or more, about 10 g
0.7// or more, and the particle size is about 3μ to about 16rn1
Preferably, a porous silica cell of chemical type 11 with an ItIii radius of about 5 micrometers to about 51 meters is preferred.

Such a porous polymeric phase is a chemically bonded silica.

The amount of terpene hydrocarbons to be used can be selected depending on the content of terpene hydrocarbons present in the hydroalcoholic solution of natural or essential oils. 1 of the fat or silica gel in an amount sufficient to make hydrocarbons undetectable.
It is desirable to use it for historical purposes.

A preferred embodiment of the present invention is to treat a natural essential oil containing terpene hydrocarbons with water-containing ethanol and/or water-containing methanol at a concentration of about 40 to 95% by weight, for example, as described above, and if necessary, the treatment system This can be carried out by a patch method, in which the hydroalcoholic phase is separated from the aqueous alcohol solution, the obtained hydroalcoholic solution is placed in an appropriate container, a porous polymer resin or chemically bonded silica gel is added, and the mixture is allowed to stand or is brought into contact with the solution by stirring in a tank. A column is filled with the resin or the silica gel, and a hydroalcoholic solution of the terpene-based hydrocarbon-containing essential oil is poured into the column from the top of the column, for example, from SVVO21 to
By passing the liquid at about 30℃, the terpene hydrocarbons remaining in the hydrous alcohol are removed! It can be selectively removed by adsorption to a porous polymeric resin or chemically bonded silica gel, and an extremely pure terpene-free hydroalcoholic solution containing essential oil can be obtained in high yield. Deterpenization treatment using such a column can also be carried out by connecting a plurality of columns, if necessary.

131 According to the present invention, when a natural essential oil containing terpene-based lvhydride is previously treated with hydrostatic methanol and/or hydrous ethanol of about 40 to about 95 gb, the water content of the alcohol is selected. By doing so, most of the terpene hydrocarbons can be completely removed, and the terpene hydrocarbons remaining in the resulting hydroalcoholic solution can be suppressed to an extremely low level. Therefore, the porosity 1 is sufficient to adsorb and remove the terpene-based hydrocarbon bed from the hydroalcoholic solution.
1 resin or chemical binder silica gel can achieve its purpose with a small amount, and oxygen-containing aroma components can be obtained with high purity.

As mentioned above, the concentration of hydroalcohol when treating a hydroalcoholic solution of natural essential oil containing terpene hydrocarbons with a porous polymer resin or chemically bonded silica gel is about 4%.
For example, in the case of a water-containing ethanol solution of the essential oil, once the concentration of 14-ethanol falls below about 40 fF'Z, not only terpene hydrocarbons but all aromatic components will be adsorbed. However, if the ethanol concentration exceeds about 95%, terpene hydrocarbons will not be adsorbed either, and the object of the present invention cannot be achieved.

According to the present invention, the deterpenized essential oil-containing hydroalcoholic solution obtained as described above contains aroma and flavor components in a highly pure pj-, and is a flavor with highly excellent aroma and flavor and excellent storage stability. In particular, those treated with ethanol in the morning can be used as they are in a wide range of fields such as food and beverages, pharmaceuticals, and cosmetics. The solvent can also be removed using other means to obtain a deterpenized essential oil.

A more preferable method for obtaining such a deterpenized essential oil is to add a hydrous alcohol solution containing the deterpenized essential oil obtained as described above to the hydrous alcohol phase with a low boiling point that is miscible or immiscible. Using hydrocarbon solvent silane,
Further extraction processing is performed.

Examples of the low-boiling hydrocarbon solvents include intane, 2-methylbutane, 3-methylbutane, 2,2-damethylbutane, hexane, 2-methylpentane, 3-methylpentane, heptane, 2-methyl-hexane, −
Examples include C8-C1 hydrocarbons such as methylhexane. This can be used alone or in combination with several types. More preferably, the treatment is carried out with at least one hydrocarbon-based solvent selected from the group consisting of n-d-butane, impentane, and n-hexane, the main components of which are selected from the group consisting of n-d-butane, impentane, and n-hexane.

At this time, the mixing ratio of the hydrous alcohol phase and the hydrocarbon solvent can be selected appropriately, but for example, the mixing ratio of the hydrous alcohol phase and the hydrocarbon is 1:1:0.1 to about 1:0. 2
0, preferably l: about 0.5 to about 10.

When extracting with a low boiling point hydrocarbon solvent as mentioned above,
For example, it is preferable to carry out the treatment under stirring conditions so that only the aroma and flavor active ingredients contained in the hydroalcoholic phase are sufficiently transferred to the hydrocarbon solvent phase. For this reason, the hydroalcoholic phase is diluted with water in advance, and the aroma and flavor active ingredients are hydrocarbons! Sodium chloride may be added to make it easier to transfer to the medium, or sodium chloride may be added before extraction or during extraction.

There are no special restrictions on the treatment temperature and time, but for example, about 5
Examples of the treatment include temperature conditions of about 70° C. and treatment time conditions of about 1 minute to 3rd time column.

After this extraction process, for example, the mixed system may be allowed to stand for at least about 5 minutes to separate into an upper hydrocarbon solvent phase and a lower hydrous ethanol phase, and the hydrocarbon solvent phase can be collected.

17- From the mixed system after the contact treatment, the hydrocarbon solvent phase that can be separated, for example, as described above, is dehydrated using a sieve, if necessary, and then distilled to remove the low boiling point hydrocarbon solvent. To leave. Distillation can be carried out under either atmospheric pressure conditions or reduced pressure conditions, but it is more preferable to carry out the distillation under reduced pressure conditions at low temperatures, for example about 5 to about 150 mmH.
D can be carried out under reduced pressure at a temperature of about 40°C or lower.

Furthermore, the above-mentioned distillation treatment can be carried out in the presence of an inert gas such as 9-carbon gas or carbon dioxide gas.

As described above, natural essential oils containing terpene hydrocarbons can be produced using easy operations and simple equipment, without causing any unfavorable deterioration or volatilization loss of the aroma and flavor active ingredients in the natural essential oils.
In addition, it is possible to obtain a de-chilled 18-penated essential oil with a high yield and excellent storage stability, which contains the active ingredients of aroma and flavor in the natural essential oil in a concentrated manner. When the deterpenized essential oil is used, for example, in foods and drinks, problems such as deterioration of the aroma of the food and drinks do not occur, and food and drinks with excellent aroma and high stability can be obtained for a long period of time.

Hereinafter, the present invention will be explained in more detail with reference to examples.

Example 1 Orange essential oil (contains about 1.6% oxygenated compounds) 100
Add 70 centigrade chetanol aqueous solution 8002 to 2 and make 40
Stir for 30 minutes at ~45°C. The mixture was then cooled to 20° C. and allowed to stand still. The lower layer of water-containing ethanol was separated and filtered through P paper to obtain a water-containing alcoholic solution of orange essential oil 8309.

Next, a porous styrene/sobinylbenzene copolymer resin (Diaion HP-2) was soaked in 70% by weight ethanol.
Glass column (diameter 3
A water-containing ethanol solution of the above-mentioned orange essential oil was passed from the upper part of the tube (6n1 height 30 cnr) at 5V=4 to adsorb and remove terpene-based hydrocarbons to obtain a treated solution 8301 which had been deterpened.

Table 1 shows the essential oil content and the ratio of chilled hydrocarbons and oxygenated compounds in the essential oil before and after the resin treatment of the aqueous ethanol solution of orange essential oil. In addition, by the resin treatment of the present invention, 199.2% of the chilled hydrocarbon F was removed. Oxygen-containing compounds were recovered at a high treatment rate of 97.6%.

The obtained hydroalcoholic solution containing the deterpenized essential oil had a fresh orange flavor and had excellent storage stability.

Example 2 To lemon essential oil (containing 3.2% oxygen-containing compounds) 5021-1 was added 200 tk of 80 wt% water-containing ethanol, and the mixture was stirred at 20 to 25°C for 2 hours. Then, the mixture was cooled to 20'C, left to stand, and the aqueous ethanol solution of the -F layer was separated to obtain 2101Fi. The water-containing ethanol solution is prepared in advance by 8
Chemically bonded radicals with octadecyl groups (YMCGELODE 30/60, immersed in 0% ethanol)
Shimaku Awa product) 40f was packed, but the last column (diameter 3cr
The terpene hydrocarbons were adsorbed and removed from the upper part of the tube at 5V=25 to obtain a treated liquid of 210 fk. Table 2 shows the essential oil content and the ratio of terpene hydrocarbons and oxygen-containing compounds in the essential oil before and after the chemically bonded silica glue treatment of a water-containing ethanol solution of lemon essential oil. As is clear from the results in Table 2, by the chemically bonded silica glue treatment of the present invention, 1119
8.9% of oxygenated compounds were removed by adsorption, while 97.5% of oxygenated compounds were removed.
% was recovered in high yield.

-22- The obtained aqueous ethanol solution containing deterpenized lemon essential oil had a fresh and excellent flavor unique to lemon, and had extremely excellent storage stability.

Table 2 Example 3 Orange essential oil (contains 1.6% oxygenated compounds) 2002
Add 400 f'i of a 60 wt% methanol aqueous solution containing 2 wt% sodium chloride to the mixture and heat at 40 to 45°C for 30
Stir for a minute. Next, the water-containing methanol layer was cooled to 20"C, left to stand, and the separated lower layer containing water was dispersed. The remaining orange essential oil further contained 60% by weight of 1.4% sodium chloride.
Methanol aqueous solution 100f'! r- plus 40-45℃
The mixture was stirred for 30 minutes, cooled to 20° C., and allowed to stand, and then the water-containing methanol layer was separated. The separated water-containing methanol layer was mixed and porous ethylvinylbenzene/sovinylbenzene co-Mj resin (trade name: Por
apak Q, Waters) 10 mtku
A resin treatment solution of 510 f'r was obtained by passing the solution through the top of the column (diameter: 1.5 cm, height: 30 cm) at 5V=3. η-Hereαng500F was added to this, stirred at room temperature for 30 minutes, and then cooled down to form a 4′ ML molecule of η-Hereαngzana layer.
The solvent was distilled off under reduced pressure at 35-40°C/10 tuxHQ to obtain deterpenized orenzo essential oil Z5t (containing about 92% oxygen-containing compounds).

This product was a deterpenized essential oil that contained all the active ingredients of orange aroma and flavor in a concentrated manner, had an excellent aroma, and had excellent storage stability.

Patent applicant Hasegawa Perfume Co., Ltd. -25- Procedural amendment May 18, 1981 Patent length '1 Right Sugi No. 1 Husband 1, Incident indication 'r,, I'Li1+LIt: +57-226233
No. 2, Name of the invention Kozue 71iII + 4 bowl terpene conversion method 3, Relationship with the case of the person making the amendment Patent applicant address Kibetsu Ikuchuten-ku Nihon Uzumoto 11.11 4-9, d
↑The 4th generation of the land 107 people (1 person) 7° Supplementary IE') Contents, 11. Tooshi.

('I) The statement in column 1 of claim 1 of the specification is corrected as follows.

1. Approximately 40% natural IN oil containing chillin hydrocarbons.
By treating a hydrous alcohol solution obtained by treating with aqueous ethanol and/or aqueous methanol with a concentration of ~95% by market weight with porous I4F resin or chemically bonded silica dull, terpene hydrocarbons are removed from the resin. Alternatively, a method for deterpenizing essential oils, which comprises adsorbing and removing essential oils on the silica group. "CII) The statement in column 1 of the detailed description of the invention in the specification is corrected as follows.

+l) On page 13 of the specification, line 1, it says "95 car knowledge/chi".

"About 95% by weight" I am corrected.

718-

Claims (1)

[Claims] 1. Natural essential oil containing terpene hydrocarbons from about 40 to about 9
By treating a hydroalcoholic solution obtained by treatment with aqueous ethanol and/or aqueous methanol at a 50% concentration with a porous polymer resin or chemically bonded silica gel, terpene-based hydrogen oxides can be removed from the resin or the 1. A method for detilinating essential oils, which comprises adsorbing and removing essential oils.