JP3700971B2 - Orange oil production method - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for producing orange oil containing valencene, which is useful as a fragrance material or a fragrance material such as Nootkaton.
[0002]
[Prior art]
Valensen is contained in an orange essence oil obtained by squeezing orange located in the citrus genus Citrus, in an amount of 0.2 to 0.6% by weight. Of these, 90% by weight or more are terpenes having a low boiling point (200 ° C or lower) centered on limonene, which has a low contribution to fragrance, and it is difficult to concentrate valencene to about 100 times by distilling them off. is not. Generally, this is concentrated by distillation and a valencene concentration of 70 to 90% by weight is distributed in the market (Perfumer & Flavorist vol. 21, May / June p9 1996). Valensen is also contained in the oil obtained by distilling the essential oil orange cold press peel oil of the skin part and pulp after squeezing the fruit, etc., but it is also a terpene mainly composed of limonene. Therefore, concentration up to about 100 times can be easily performed. However, since the valencene content in the oil is very small (0.02% by weight) compared to the essence oil, the valencene concentration can be improved only by 2 to 3% by weight even if it is concentrated 100 times. In addition, the oil having a valencene concentration of 2 to 3% by weight contains a large amount of components having a slightly lower boiling point than that of valencene, and it is not easy to further concentrate it. A method for producing an oil containing a high concentration of valencene from benzene has not been known so far.
[0003]
Orange oil containing 70-90% by weight of currently available valencene is produced by concentrating orange essence oil obtained by squeezing fruit, so the production volume is limited and expensive. It was the cause that the amount and use were limited. Therefore, an inexpensive orange oil having a high valencene concentration has been strongly desired.
[0004]
[Problems to be solved by the invention]
Then, the concentration of valencene from the oil obtained from the pericarp and / or the pulp part, which has not been conventionally used as a raw material for orange oil containing valencene, has been intensively studied. As a result, the peel and / or pulp part has a low content of valencene and a high boiling point of valencene (about 240 ° C. at normal pressure), and there are only a few components with a slightly higher boiling point than valencene. In order to completely recover valencene from the skin and / or pulp part by distillation, the temperature in the tank or the tower needs to be increased to 220 ° C. or higher, and the pyrolysis of high-boiling components under such high temperature conditions. It has been found that low-boiling components such as water are generated by side reactions such as water, so that the pressure cannot be maintained and it is difficult to completely recover valencene. Furthermore, it has been found that orange oil obtained from a strong boiling odor by distillation at a high temperature and a low boiling fraction produced by thermal decomposition cannot be used as a fragrance material as it is.
Accordingly, an object of the present invention is to provide a method capable of producing an orange oil containing valencene at a high concentration at a low cost and efficiently.
[0005]
[Means for Solving the Problems]
Therefore, the present inventors prevent side reactions such as thermal decomposition by mixing and distilling the raw oil and a high boiling point solvent exceeding the boiling point of valencene when distilling valencene in the raw oil. It has been found for the first time that valencene can be concentrated by greatly reducing the residual valencene in the distillation residue under a temperature condition of around 200 ° C. As a result, a high-quality orange oil free from distilled odor and low-boiling fraction odor was obtained.
[0006]
That is, the gist of the present invention relates to a method for producing orange oil, characterized by mixing and distilling a raw material oil containing valencene and a high-boiling solvent having a boiling point exceeding 240 ° C. under normal pressure.
[0007]
DETAILED DESCRIPTION OF THE INVENTION
As described above, the present invention is a method for producing orange oil, characterized by mixing and distilling a raw material oil containing valencene and a high-boiling solvent having a boiling point of 240 ° C. at normal pressure.
[0008]
The raw material oil used in the present invention refers to an oil that is a raw material for orange oil, and may contain valencene. Among these, from the viewpoint of the valencene content, those obtained from citrus fruits are preferred. Examples of citrus fruits include sweet orange, mandarin, and sour orange.
[0009]
As the raw material oil, essence oil obtained by squeezing the fruits, raw oil such as cold press peel oil of the skin part or oil obtained from the pulp after squeezing the fruit, and these raw material oils are distilled or Examples include oil that has been subjected to precision distillation. These feedstocks may be used alone or in admixture of two or more.
[0010]
As the high boiling point solvent having a normal pressure boiling point higher than 240 ° C. (hereinafter also referred to as a high boiling point solvent) used in the present invention, a high boiling point solvent having a boiling point exceeding 240 ° C. and not higher than 300 ° C. is preferable. A high boiling point solvent at 0 ° C. is more preferred. Among them, a saturated or unsaturated alcohol having 11 to 20 carbon atoms, particularly 12 to 15 carbon atoms, and a hydrocarbon having 14 to 20 carbon atoms, particularly 15 to 17 carbon atoms are preferable. Examples of the saturated or unsaturated alcohol include n-dodecanol, n-tetradecanol, n-tridecanol and the like. Examples of the hydrocarbon include tetradecane, pentadecane, and hexadecane. These high-boiling solvents can be used alone or in admixture of two or more. These high-boiling solvents may be used by mixing with ether, ester, liquid paraffin or the like.
[0011]
In the production method of the present invention, the raw material oil and the high boiling point solvent are first mixed. The amount of the high boiling point solvent used is preferably 1 to 200 parts by weight, particularly preferably 10 to 100 parts by weight, based on 100 parts by weight of the raw material oil.
[0012]
Next, the mixture of the raw material oil and the high boiling point solvent is distilled. Distillation is preferably performed by rectification from the viewpoint of concentration of valencene, and more preferably rectification under reduced pressure. For example, the number of rectifying columns used for rectification is preferably about 5 to 80. The tower top pressure is preferably from 0.1 to 2.7 kPa, particularly preferably from 0.5 to 0.7 kPa, and the temperature in the tower is preferably from 40 to 150 ° C., particularly preferably from 60 to 120 ° C. At this time, in order to suppress thermal decomposition, it is preferable that the temperature in the tank and the tower be 220 ° C. or lower. Other conditions are not particularly limited.
[0013]
The orange oil thus obtained has a concentration sufficient to be used as a fragrance material or a fragrance material such as nootkaton having a valencene concentration of 20 to 60% by weight.
[0014]
Moreover, the orange oil obtained can be further concentrated by a known method, whereby an orange oil having a higher valencene concentration can be obtained.
[0015]
From the above, by using the method of the present invention, it becomes possible to produce orange oil containing valencene in high concentration at low cost and efficiently. In particular, by using the method of the present invention for orange essence oil that has been conventionally used as a valencene source, it is possible to concentrate valencene more efficiently.
[0016]
【Example】
EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.
[0017]
Example 1
3900 g of raw material oil (concentrated by distillation of oil obtained from the peel and pulp part of sweet orange, valencene concentration of 3% by weight) is mixed with 770 g of n-tetradecanol (boiling point 287 ° C.), and 50-stage filling type Using a distillation column, precision distillation was performed at a tower top pressure of 0.8 kPa and a tower top temperature of 96 to 120 ° C. (final tank temperature 200 ° C.). As a result, 220 g of a fraction having a valencene concentration of 43% by weight was obtained. The obtained fraction was a good-quality fraction free from the distillation odor seen during distillation at a high temperature and the low-boiling fraction odor. The distillation residue did not contain any valencene.
[0018]
Example 2
280 g of n-dodecanol (boiling point 260 ° C.) is added to 1350 g of the raw material oil described in Example 1, and precision distillation is performed at a tower top pressure of 0.7 kPa and a tower top temperature of 97 to 117 ° C. using a packed 50-stage rectification column. (Final temperature in the final bath was 200 ° C.). As a result, 86 g of a fraction having a valencene concentration of 43% by weight was obtained. The obtained fraction was a good-quality fraction free from the distillation odor seen during distillation at a high temperature and the low-boiling fraction odor. The distillation residue did not contain any valencene.
[0019]
Comparative Example 1
The raw material oil described in Example 1 was distilled using a packed 50-stage rectification column with a tower top pressure of 0.7 kPa and a tank temperature of 200 ° C., but no valencene was distilled off. Therefore, an attempt was made to distill at a higher temperature. As a result, although white smoke was generated at around 215 ° C. and the pressure could not be maintained, valencene could be distilled by heating to 250 ° C. However, a large amount of valencene remained in the residue. Further, the obtained valencene had a strong distillation-like odor and a large amount of low-boiling fractions due to thermal decomposition, so that it could not be used as a fragrance material. Distillation did not occur even at 215 ° C., and white smoke came out from the inside of the tower, making it impossible to maintain the reduced pressure.
[0020]
From the above results, it can be seen that the orange oils obtained in Examples 1 and 2 were obtained by efficiently recovering valencene contained in the orange oil as compared with Comparative Example 1.
[0021]
【The invention's effect】
According to the present invention, valencene can be efficiently concentrated not only from fruit-derived orange oil but also from orange peels and pulp parts that are not currently used, and the resulting orange oil containing valencene has a distilled odor and a low-boiling fraction. There is no off-flavor, and it can be suitably used not only as a fragrance intermediate but also as a fragrance material.

Claims (6)

A method for producing orange oil, characterized by mixing and distilling a raw material oil containing valencene and a high-boiling solvent having a boiling point of 240 ° C. at normal pressure. The process according to claim 1, wherein the raw material oil is obtained from a fruit of the citrus citrus genus. The manufacturing method of Claim 1 or 2 with which raw material oil is obtained from the peel or pulp after squeezing. The method according to any one of claims 1 to 3, wherein the high-boiling solvent is a saturated or unsaturated alcohol having 11 to 20 carbon atoms, a hydrocarbon having 14 to 20 carbon atoms, or a mixture thereof. The production method according to any one of claims 1 to 4, wherein the amount of the high-boiling solvent used is 1 to 200 parts by weight per 100 parts by weight of the raw material oil. The production method according to any one of claims 1 to 5, wherein the distillation is rectification under reduced pressure.