JPS5924795A - Manufacture of deterpenated essential oil - 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 aims to remove terpene-based hydrocarbons, which cause troubles such as deterioration of stability, deterioration of quality, and formation of resinous substances in cough essential oils, from natural cinnamon oil containing terpene-based hydrocarbons. It is easy to operate, and it is advantageous for all aspects of deterioration and volatilization loss of the preferred aroma and flavor active ingredients of the natural essential oil! A method for producing deterpenized essential oil that can be produced: A hydrous alcohol consisting of aqueous ethanol and/or aqueous methanol, preferably with an alcohol concentration of about 30% to about 90% (li%) consisting of aqueous ethanol and/or aqueous methanol. The hydroalcoholic phase separated and collected from the treated system is further extracted with a low-boiling hydrocarbon solvent that is poorly miscible or immiscible with the hydroalcoholic phase to obtain the low-boiling hydrocarbon solvent phase. The method of collecting and removing the solvent gold from the obtained solvent phase: k% relates to a method for producing a deterpenized essential oil.

In general, natural products such as flowers, leaves, roots, stems, skins, fruits, etc. of plants are extracted using intermediate methods such as steam distillation, pressing, and combinations of Natural oils, such as limonene, α
- Carbonization of monoterpene hydrocarbons such as bi't, pine, β-pinene, myrcene, α-terpinene, r-terpinene, terbinolene, etc., and sesquiterpene hydrocarbons such as caryophyllene, selinene, humulene, pizzaborene, etc. It usually contains at least one type of terpene hydrocarbon such as hydrogen.

However, such terpene hydrocarbons do not directly affect the richness and flavor of natural nitrate oil, as they do not require much IF.
4? Rather, it is involved in deteriorating the storage stability of natural treetop oil, and -! In addition, it may undergo oxidation during storage, causing undesirable deterioration and odor generation, or may cause the formation of unsuitable resonant Vio (7) due to oxidation, for example. Adding or changing flavor to foods and drinks, etc.
When used as a J agent, it is often the cause of divine trouble1, and the characteristic flavor and aroma of natural treetop oil is mainly imparted to the Fit oil by natural essential oils. Contains n-myo n6 terpene type, +4
They are 12-element compounds, and their cousins are aromatic and aliphatic 3-oxygen compounds.

Therefore, the so-called deterpenization 1, which removes the above-mentioned terpene hydrocarbons from natural nitrate oil, is carried out in one tube.
However, it is difficult to find a means for deterpenization that requires sufficient 114 steps, and the development of such a means is desired.

. Conventionally, eJl,
For example, natural essential oils are distilled under reduced pressure to remove monotyl terpene hydrocarbons, or the essential oil is extracted with water and ethanol to remove mono- and sesquiterpene hydrocarbons that are insoluble in the aqueous ethanol. Solvent extraction method to remove the solvent gold using the ethanol phase of the distilled water, or a low-boiling alcohol system ffJf! Natural In oil is extracted using two solvents simultaneously: a polar solvent such as 1^ and a non-polar solvent such as a low boiling point hydrocarbon solvent that is immiscible with the polar solvent, and the rotten bath phase is separated. 21 to remove the solvent gold from the solvent phase.
Extraction method using tunic bath u1^/IIj, 9μ is treated with natural 1#4 oil on silica/ft, and treated with Ull absorbing agent such as silicic acid [:! 31. L, compound compound'1 After applying a vacuum to the abrasive powder, the compound' is added using an appropriate solvent.
Adsorption separation methods such as #1 and #1 desorption are known.

However, no satisfactory method has been proposed that can provide stable and excellent deterpenization of sheath oil with easy operation and high yield without deterioration or volatilization loss of the active ingredients. 11 For example, it is difficult to remove sesquiterpene hydrocarbons by distillation. However, since there is a limit to the degree of deterpenization, the removal of monoterpene hydrocarbons requires a considerable length of 11:r to remove a relatively large number of monoterpene hydrocarbons. Heating distillation time
As a result, troubles such as blackening of the aromatic and flavoring active ingredients and concomitant distillation of the aromatic and flavoring active ingredients, which are low-boiling point aromatic and flavoring active ingredients, are difficult to avoid.

Although it is necessary to completely remove the deterpene solvent by liquid-liquid extraction using the non-polar hydrocarbon organic solvent and alcohol solvent, for example, the solvent can be completely removed by steaming. In this case, the low boiling point alcoholic solvent has a strong affinity with the oxygen-precipitating compounds in natural essential oils, so IC takes a long time to completely remove the solvent. !
! At this time, it is important to note that there is a volatilization loss of the aroma and flavor active ingredients with a relatively low boiling point, and that there is also a change in quality such as oxidation of the aroma and flavor active ingredients due to the presence of oats and moisture. There's a problem. Furthermore, when adding Okawa water to an alcoholic solvent to separate the terpene-free oil and fractionating the essential oil, it is difficult to form an emulsion and collect only the essential oil in a high yield.

In the 1m stubble separation method, very active compounds in natural essential oils are likely to cause isomerization when absorbed into the adsorbent, so strict methods (1 It is necessary to select the cropping row P4'', which is industrially difficult.

The present inventors have developed a means to overcome the troubles of conventional means as described above and to obtain high yields of essential oils that can achieve excellent terpenization effects with aroma and flavor without deterioration through simple operations. We have conducted research to extract the aroma and flavor from the hydrocarbon phase extracted into the hydroalcoholic phase using a secret two-stage extraction method. Ingredients are further extracted with a low-boiling hydrocarbon solvent, and since the solvent can be distilled off from the hydrocarbon solvent phase at a low temperature and in a short time, there is no possibility of deterioration or fear of the Nλ flavor active ingredient. Loss loss?
It is possible to obtain terpenized natural 48 pores of C with excellent aroma and flavor, 7C and storage stability, and FC theory in high yield with easy operation and compact equipment.
I discovered that.

It is an object of the present invention to provide an improved method for preparing deterpenized essential oils with superior stability.

In addition to the above objects and history, many other objects and advantages of the present invention will become more apparent from the following description.

It can be obtained by oil extraction using an essential oil extraction method such as the terpene-based hydrocarbon-containing natural nitrate A' distillation method used in the present invention. Examples of natural essential oils containing terpene hydrocarbons include: 1. [For example, essential oils such as orange oil, lemon oil, lime oil, tannoerin oil, mandarin oil, grapefruit oil, bergamot oil, ftiglen oil, yuzu oil, and neroli oil may be mentioned.]

According to the method of the present invention, a 1v hydroalcoholic phase is separated and collected from the terpene treatment system as exemplified above.

However, for example, the use of 7° alcohol can be used to reduce the concentration of IW from about 10% to about 95%. It is preferable to treat it with a water-containing alcohol containing preferably about 30 to about 90% molten water.

At this time, the mixing ratio of the natural essential oil and hydrous alcohol can be selected as appropriate.
Approximately 20, good 1 < 11 approximately l: range such as approximately 0.5 to approximately lO? It can show rl series.

The processing system formed fl, 7j may be provided with a V stirring bar f'I' as desired.
It is preferable that the aromatic and flavor active ingredients in the natural treetop oil be thoroughly dissolved in the hydroalcoholic phase. The mixing temperature and time are ll+1. , although there are no other restrictions, for example, i of about -20' to about so'c
Crystallinity article 14: and about 1 minute to about 5 hours
[11] When carrying out operations such as [11], for example, sodium chloride can be added at any stage to facilitate the separation of the terpene hydrocarbon phase and the hydroalcoholic phase. It can be appropriately selected depending on the level of addition of sodium chloride (eJ1) and the 4% hydroalcohol used. .

According to the method of the present invention, for example, the hydroalcoholic phase that can be separated and collected from the mixed system as described above? ,
Using a low black hydrocarbon solvent that is difficult to miscible or immiscible with the water-containing alcohol phase, further development 11! r Bamboo Tsu.

Examples of low-boiling hydrocarbon solvents include pentane, 2-methylbutane, 3-methylbutane, 2.
2-methylbutane, hexane, 2-methylpentano,
Hydrocarbon solvents such as 3-methylpentane, heptane, 2-methyl-xane, 3-methylbutane, etc. can be used. More preferably, the group consisting of ?L-pentane, isopentane and ?1-hexane is selected. - It is best to treat with a solvent.

At this time, the mixing ratio of the hydrous alcohol phase and the hydrocarbon solvent can be selected as appropriate, but for example, the mixing ratio r of the hydrous alcohol phase and the hydrocarbon, the weight ratio - ('l: about 08
Examples include a range of 1 to about 20, preferably 124 to 0.5 to about 10. .

When using a low boiling point hydrocarbon solvent as described above, for example, it is carried out under stirring, agitation FF, and only the aroma and flavor active ingredients that are present in the water anocol phase are transferred to the hydrocarbon solvent phase. It is better to move 1↓1j-J so that there is sufficient transition. For that purpose, dilute it with Miyamizu alcoholic water in advance [7
2. The aromatic and flavor active ingredients may be added to the hydrocarbon solvent before or after the extraction.1. Treatment temperature and time] In the river
Yo! 1) There are no other restrictions, but if the temperature is about 5 to about 70 degrees Celsius, one piece of υ1 should be heated for about 1 minute to 3 hours.
The processing can be exemplified in 1. After this extraction process, even +;l
: il, i, f middle thread for at least 5 minutes 1↓4
The mixture is allowed to stand still and separated into an upper hydrocarbon solvent phase and a lower hydrous ethanol phase, and the hydrocarbon solvent phase can be collected. .

According to the method of the present invention, from the mixed system after the catalytic treatment, for example, the hydrocarbon-based medium phase, which can be separated by the above-mentioned method, is dehydrated using mirabilite or the like. , to remove the low boiling point hydrocarbon 1/- solvent. Distillation can be carried out under either atmospheric pressure conditions or reduced pressure conditions, but it is particularly preferable to perform the distillation under reduced pressure at a low temperature under reduced pressure. Height 9 can be achieved at temperatures below 40°C.

In history, inert gases such as -4 gas and carbon dioxide gas,
1. Button Distillery 1! II ke can be done.

According to Akira Kitake, in the above-mentioned manner, it is possible to extract natural nitric oil containing terpene-based hydrocarbons using a simple process, easy operation, and simple equipment to extract I in the natural essential oil. ! If
ζtH! le:Ti' active ingredient ingredient f:r: Without deterioration or volatilization (ha loss), and with high yield,
62(~!Lk; iT effect related fraction'+Cμ
One of the most storage stable F&F i L fcn in the world! You can obtain de-chilled essential oils. For example, if the deterpenized nitric oil is used in food and beverage products, it will not cause any problems such as deterioration of the aroma of food and beverages, and will maintain an excellent aroma for a long period of time. A high fIK quality product can be achieved.

This will be explained in detail by way of implementation 4).

Real hilj 1tlJ 1 Orange 6 flavor (contains about 2% oxygenated compounds) 2110y '11 Natriuno h '6', 2 It East h1%
60 tons of white ethanol water I'f 841'J'
Add 400y of H solution and stir directly at 40-45'C for 300 minutes.
The aqueous ethanol layer was separated. orange 6
The flavor is 60% M% ethanol water containing sodium chloride.

II was added, stirred for 30 minutes at 40-45''C, cooled in a 20°C trench, separated into a Shizumoe stage, and separated into a Miyamizu ethanol layer.

The separated aqueous ethanol layer is mixed with Jl, n-1)
Add exane 500111 and stir for 30 minutes at 'aM. Orange 4W oil ta2.9
(approximately 24% oxygen-containing compounds fj-14') and cl
707) (% methanol aqueous solution 400
．． In addition to 9, 11 was stirred at 20-25°C for 2 hours at 4+N.
Next, after oIK, the lower J- was separated from the official methanol solution, and 320 Jl', r of isopentane was added thereto, stirred at 15°C for 1 hour, left to stand, inpentane Jt4'v dispersed, dehydrated with sodium sulfate, and dried with L. The solvent was distilled off at 30 to 35°C under normal pressure to remove terpenes, resulting in mononitrified oil 1a5,9 (about 2
(Contains 9%)) [100g of 100g of orange essential oil (contains about 2% of oxygen-containing compounds)
Add 400% ethanol aqueous solution and separate the layer. The remaining orange nitrate oil was further removed by 60 m.
Add 100.9% ethanol water bath solution゛[40-45''
(:, stirred for 30 minutes, cooled at 20' to '1', and separated the water-containing ethanol layer. The separated water-containing ethanol layer was mixed and then distilled at 35-40°C to remove the bath medium. Deterpenized orange essential oil 111, 6.1% (containing 22% oxygen-containing compounds) was obtained.

Actual addition jt tally 3 In Example 1 and Comparative Example? (Each of the deterpenized orenzo essential oils was added and dissolved in 100 oils of 0.1 III-00, and 10 people evaluated the aroma and flavor. 11 cases 1 profit 1 piece/1 (
The aged product obtained in the comparative example has significantly less rancid odor and has a strong fresh orange flavor6? ＋[Acknowledged meeting with C. fcn l] Shoes "Applicant Hasegawa Perfume Co., Ltd. (and 1 other))"

Claims (1)

[Scope of Claims] 1. Natural essential oil containing terpene hydrocarbons treated with a hydrous alcohol consisting of fully aqueous ethanol and/or aqueous methanol E2: A hydrous alcohol phase separated and collected from the treatment system, which is hardly miscible with the hydrous alcohol phase. Low sex or immiscibility? J
A method for producing a deterpenized essential oil, which comprises further extraction treatment with a point 1 hydrocarbon solvent to collect the low boiling point hydrocarbon solvent phase, and then completely removing the solvent from the solvent phase. 2. Is the natural nitric oil a citrus essential oil? L-/l”
J [sign 71! J, -1' The manufacturing method according to claim 1. 3. The low-boiling hydrocarbon solvent is n-pentane, in-
The group consisting of pentane and 9-hexano:
Special F! which is at least one glaze of the solvent used or a solvent whose main component is the glaze! The manufacturing method described in item 1 of the scope of 'I'M'. 4. The manufacturing method according to any one of items 1 to 3, when the alcohol concentration of the hydrous alcohol is about 30 to about 90 iff 37%, the range of ft'F iff is determined.