KR20180138000A

KR20180138000A - Effective manufacturing method of natural yuju essential oil from yuja skin

Info

Publication number: KR20180138000A
Application number: KR1020170078016A
Authority: KR
Inventors: 김철웅; 김태완; 정순용; 김성일; 박노영; 손태훈
Original assignee: (주)바이오제닉스; 한국화학연구원
Priority date: 2017-06-20
Filing date: 2017-06-20
Publication date: 2018-12-28

Abstract

The present invention relates to a method for efficiently producing natural citron aromatics by selectively adsorbing and separating ethanol as an extraction solvent, and selectively removing ethanol by a hydrophobic adsorbent from an ethanol extract containing citron oil and then adding NaCl thereto, And an aqueous citron oil was obtained from the organic layer.
INDUSTRIAL APPLICABILITY The present invention is industrially utilized because it is highly advantageous in aroma oil, spice, fragrance, perfume, and cosmetic materials because it has high purity because it can stably obtain natural sequester oil without being denatured by heat by adsorbing and removing ethanol as an extraction solvent at room temperature There is a more advantageous advantage.

Description

[0001] The present invention relates to a method for efficiently producing natural citron essential oil using citron peel,

The present invention relates to a method for producing natural citron essential oil, and more particularly, to a method for efficiently producing Citron essential oil by selective separation of an extraction solvent.

Citrus junos Siebold ex Tanaka is the name of citrus junos Siebold ex Tanaka, which belongs to the genus Udon and citrus. The origin of the Yangtze River originated in the Korean peninsula and spread to Japan. However, the country of origin does not grow citrus according to climate change. It is a rare varieties of citrus fruits that are special only in Korea and Japan.

Yuzu (citrus) scent is very individual and strong compared to other citrus scent, and it is popular with people without anyone particularly disliked with lemon or grapefruit. The volatile components of citrus essential oil, including citron, are found in more than hundreds of volatile components. Among them, limonene is the main ingredient commonly contained in Citrus essential oils, which is 70 ~ 75% It contains a trace amount.

The limonene, which is the most fragrant component of citron, has a relatively low contribution to determining citron-specific fragrance. The content of 6-methyl-5-hepten-2-ol and methyltrisulfide, which are the ingredients that determine the unique flavor of Citron, is contained in trace amounts but has a very high fragrance contribution.

In the industrial background of the present application, the 21st century can be said to be the "era of fragrance", and the demand for natural essential oils is increasing. In particular, the natural cosmetics industry is continuing to grow despite the economic downturn thanks to this boom. From this point of view, the production and size of Korean citron oil are expected to increase. While the use of natural citron as a cosmetic material has a value added more than 20 times.

Currently, the development of natural fragrance is needed worldwide. In the case of foreign countries, there is a unique flavor of each country. However, domestic citron is the best unique product in the world, so it is necessary to develop unique natural fragrance. It has not been possible to develop an industrial scale manufacturing plant. Especially, in case of natural citron scent, it is a reality that the ingredient which is the main cause of deterioration or deterioration in the extraction manufacturing process can not be removed.

As a prior art related to the production technology of natural citron aroma, for example, Korean Patent Laid-Open No. 2001-0035501 discloses a process for producing distilled citron essential oil by using steam at 110 to 145 ° C on citron peel , The technique of high temperature distillation at 110 DEG C has a disadvantage in that the inherent flavor of the citron is destroyed by heat, resulting in deterioration of the quality of the product. In the Korean Registered Patent Publication No. 10-0452467, citron, And then passing the extraction solvent through the critical reactor; A mixture of a co-solvent is used to convert at least one functional material selected from beta- carotene, limonene, cyclohexanone, 2-ethyl-2-methylbutanoic acid, benzene, camphan, linoleic acid, oleic acid, palmitic acid, Extract; Removing at least one oxidative substance selected from the group consisting of linalool, myrcene,? -Pinene,? -Pinene,? -Terpinene and? -Terpinene; Wherein the inner temperature of the supercritical and subcritical reactor is maintained at 33 to 37 DEG C and the inner pressure is maintained at 8 to 12 MPa during the extraction of the functional material and the removal of the oxidative substance. However, since the production cost and the processing capacity per hour of the supercritical system itself are too small, it is not suitable as an industrial scale production facility.

In addition, Korean Patent Laid-Open Publication No. 2000-0037001 discloses a citron-extracted essential oil obtained by washing the maturity or immature part of citron, followed by extraction by cold-pressing, and centrifugation, but the citron essential oil extraction method by cold- There is a disadvantage in that it can not remove the shrinking impurities which greatly affect the quality of the product.

In general, natural fragrance is easily denatured by heat, and is not easily captured when it is extracted by a distillation method due to difference in vapor pressure, and is volatilized, resulting in extremely low extraction efficiency. Especially, extractive raw materials of natural citron peel extract contain 0.5% of dried extracts of fatty acids, vitamins and caproic acid, which are the causative factors of shrub, and pH of the peel extract is 3.8-4.2 There is a problem of quality deterioration of natural citron essential oil.

The present invention has solved the disadvantages and problems of the prior art and confirmed that it is possible to efficiently obtain natural citron essential oil having no shrinking impurities by selectively separating the extraction solvent by the hydrophobic adsorbent at room temperature, and thus completed the present invention.

It is an object of the present invention to provide a process for efficiently producing citron essential oil from natural citron and more specifically to a process for producing Citron essential oil from natural citron by using a hydrophobic adsorbate from a solvent extract of natural citron citron without employing a separation step such as vacuum distillation And a method for efficiently producing high quality citron essential oil by selectively separating the extraction solvent.

A method for efficiently producing natural citron essential oil using citron peel as a solving means for achieving the object of the present invention comprises the steps of: a) separating the citron from natural citron; b) adding ethanol to citron citron obtained in the first step; And c) separating the ethanol by selectively adsorbing ethanol from the citrus essential oil-containing ethanol extract solution of the second step using an adsorption column filled with a hydrophobic adsorbent to obtain an ethanol extract containing citrus essential oil; d) separating the extract of citrus essential oil in which ethanol is separated in the third step into an aqueous layer and an organic layer, and then obtaining a citron essential oil from the organic layer.

The first step according to the present invention is a pretreatment step of a raw material for extracting citron essential oil from natural citron.

The second step according to the present invention is an extraction step using an organic solvent such as ethanol generally known in the art to which the present invention belongs. In the present invention, ethanol is selected as an extraction solvent to obtain an ethanol extract containing citrus essential oil And extracting citron essential oil by ethanol from the citron peel obtained in the first step, and the extraction temperature according to the present invention is preferably about 60 ° C.

The third step according to the present invention is a step of separating and removing only ethanol from the ethanol used as an extraction solvent from the extract of ethanol containing citron essential oil obtained in the second step by using a hydrophobic adsorbent, And then passing through the citrus essential oil-containing ethanol extract obtained in the second step to selectively adsorb only ethanol to the hydrophobic adsorbent, and the extract solution containing the essential oil from which the ethanol has been removed flows out through the filtrate.

When the citrus essential oil-containing ethanol extract is passed through the adsorption column in the third step, it is preferable to maintain a constant residence time so that ethanol can be sufficiently adsorbed and have a residence time of about 30 minutes.

In addition, the hydrophobic adsorbent selected in the third step employs hydrophobic 3A zeolite (alkali metal aluminosilicate) selectively adsorbing only ethanol, and hydrophobic 3A zeolite is a well-known substance. Therefore, An example is the 3A Molecular Sieve available from CHEMXIN, which is readily available.

Generally, in the solvent extraction method in which an organic solvent is used to extract citron essential oil, when the organic solvent is removed from the extract by distillation, there is a problem that the essential oil is denatured by heat, and the organic solvent and the essential oil have similar boiling points. It is not easy to remove the organic solvent in the oil and the organic solvent and ethanol can not be efficiently removed from the extract because the ethanol has an azeotropic point with water and thus the quality of the obtained essential oil is low.

The third step according to the present invention is to solve the disadvantage of the azeotropic mixture in the distillation method by selectively adsorbing and removing ethanol as the extraction solvent from the ethanol extract by the hydrophobic adsorbent, and at the same time, It is characterized by being able to obtain an oil with high purity.

The fourth step according to the present invention is a step for obtaining citron essential oil from citron essential oil extract (filtrate) from which ethanol as an extraction solvent has been removed by the third step, and the citron essential oil extract (filtrate) is added to the separator (Aqueous layer / organic layer), and collecting the organic layer of natural citron essential oil, which is the upper layer, to obtain natural citron essential oil. The essential oil extract solution (filtrate) is added to the separator, It is preferable to add NaCl to the upper and lower layers by adding sodium chloride, which is a salt, and it is preferable to add NaCl at a ratio of 1 to 2 parts by weight to 100 parts by weight of the citron essential oil extract (filtrate) Do.

The process for efficiently producing citron essential oil according to the present invention has an effect of obtaining essential oils having no shrinking impurities at high purity and yield by a simple process of selectively separating and removing ethanol as an extraction solvent by a hydrophobic adsorbent at room temperature have.

Especially, The process for efficiently producing citron essential oil according to the present invention is characterized in that since the extraction and removal of the extraction solvent is carried out at room temperature rather than the distillation step for heating, the yuza essential oil is not denatured by heat, Flavor, fragrance, purfume, and in-cosmetic products, which are more advantageous for use as a product.

BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a block diagram schematically showing steps according to the production method of the present invention. Fig.
2 is a chromatogram of a citron essential oil sample according to the present invention.

Hereinafter, the present invention will be described by way of examples, and the units of the parts and percentages used in the present invention are all expressed by weight unless otherwise specified.

In the examples of the present invention, the contents of limonene, α-terpinene, myrcene, α-pinene, β-pinene, linalool, 6-methyl-5-hepten-2-ol and methyl trisulfide, Analysis samples were prepared according to the pre-treatment method of the fragrance component analysis, and analyzed by GC (Gas Chromatography) equipped with an FID (Flame Ionization Detector) according to the GC analysis conditions and the calculation formula of [Table 2] shown below .

Instrument Agillent system Detector FID detector Column DB5 (30m) Column Flow rate 1.0 ml / min (N2 gas) Split ratio 1: 1 H ₂ : Air 1:10 (30 ml / min: 300 ml / min) Detector Temp./Inject Temp. 250 ° C / 250 ° C Temprature rate 100 ° C for 1 minute hold → 3 ° C / min → 250 ° C for 10 minutes hold: 60 ° C (1 minute hold) → 3 ° C /

Content of citron flavor ingredient (ppm) Formula →

: Citron Essential Oil Content (ppm)

: Standard Substance Content (ppm)

: Peak area integral value of standard substance component on GC analysis data

: Yuzu essential oil component equivalent to standard substance Peak area integral value

: Dilution factor of analytical sample

In the embodiment of the present invention, the formula for calculating the yield of citrus essential oil is as follows.

[Formula 1]

&Lt; Example 1 >

a). The first step to separate the peel from the citron

10.17kg of natural yuzu was cleaned and divided into quarts, and 3.99kg of citron peel was obtained, which was used for producing natural citron essential oil. This procedure was repeated ten times, and the average value of the composition ratio of citrus fruit, pulp, and seed was shown in Table 3 below.

Item result Remarks weight Composition ratio Raw material (citron) input 10.17 kg - Percussion weight 3.99 kg 39.23% Seed Weight Before drying 1.04 kg 10.23% after drying 0.45 kg 4.42% Flesh and juice yield 4.42 kg 43.46% Sum 9.45 kg 92.92% Loss 0.72 kg 7.08%

b). Second step to obtain ethanol extract containing citrus essential oil

500 g of the natural citron peel obtained above was placed in each of the extractors and 1 L of a 10% aqueous ethanol solution was added to the extractor and extracted at 40 DEG C for 2 hours to obtain an ethanol extract containing citron essential oil.

The extract was also extracted by the same method except that the extraction temperature was changed to 50 ° C, 60 ° C, 70 ° C and 80 ° C to obtain an ethanol extract containing citron essential oil.

C). The third step of separating ethanol by selectively adsorbing ethanol

Each of the ethanol extracts obtained above was placed in an open column filled with 2 kg of hydrophobic 3A zeolite (CHEMXIN Co., Ltd.) and allowed to stand at room temperature for 30 minutes, and then each filtrate was obtained.

Each of the filtrates obtained above was placed in a separatory funnel, and 1 part by weight of edible NaCl was added to 100 parts by weight of the filtrate. The resulting mixture was homogeneously mixed and then layered with a natural citronized essential oil layer (upper layer) and an aqueous layer . Then, only the supernatant, which is the natural citroness essential oil layer, was collected from the separating funnel, and the resulting extract was obtained from natural citron essential oil. The results are shown in Table 4 below.

Extraction temperature (캜) 40 50 60 70 80 Yield (%) 0.57 0.75 1.08 1.04 1.05

incense
group
castle
minute
(%) α-Pinene 1.52 1.50 1.65 1.70 1.63 β-Pinene 0.73 0.68 0.75 0.76 0.76 Myrcene 1.76 1.74 1.76 1.73 1.70 α-Terpinene 0.23 0.22 0.23 0.23 0.26 Limonene 79.70 80.67 79.68 80.58 78.20 β-Phellandrene 3.27 3.18 3.29 3.01 3.18 γ-Terpinene 9.73 9.16 9.65 9.41 10.30 p-Cymene 0.46 0.33 0.40 0.62 0.89 Terpinolene 0.48 0.45 0.47 0.47 0.51 Dimethyl trisulfide 0.01 0.01 0.01 0.01 0.01 6-Methyl-5-hepten-2-ol 0.00 0.00 0.00 0.00 0.00 Linalool 1.53 1.51 1.48 0.95 1.99 Perillaldehyde 0.47 0.46 0.52 0.45 0.45 Thymol 0.11 0.09 0.11 0.08 0.12 Sum 100.00 100.00 100.00 100.00 100.00

As shown in Table 4, when the yield according to the extraction temperature was taken into consideration, the yield was the highest at 1.08% at 60 ° C. and the similar yield was obtained at the higher temperature. Is most preferable. In addition, there was no significant difference in compositional composition of extraction temperature and aroma composition, and there was no difference in sensory characteristics.

&Lt; Example 2 >

<Example 1> 500 g of the obtained natural citron peel was put into an extractor, and 1 liter of a 2% ethanol aqueous solution was added to the extractor and extracted at 60 ° C for 2 hours to obtain an ethanol extract containing citron essential oil.

The same procedure was repeated except that the concentration of ethanol aqueous solution was changed to 4%, 6%, 8%, 10%, 20% and 30% to obtain an ethanol extract containing citron essential oil.

Each of the obtained ethanol extracts was put into an open column packed with 2 kg of hydrophobic 3A zeolite (CHEMXIN Co.), and after having a residence time at room temperature for 30 minutes, a filtrate was obtained.

Each of the filtrates obtained above was placed in a separatory funnel, and 1 part by weight of edible NaCl was added to 100 parts by weight of the filtrate. The resulting mixture was homogeneously mixed and then layered with a natural citronized essential oil layer (upper layer) and an aqueous layer , And then only the supernatant, which is the natural yuza essential oil layer, was collected from the separating funnel and obtained from the extracts as natural yuza essential oil. The results are shown in Table 5 below.

Ethanol concentration (%) 0 2 4 6 8 10 20 30 Yield (%) 0.61 0.73 0.88 1.09 1.06 1.07 1.06 1.07

incense
group
castle
minute
(%) α-Pinene 1.60 1.60 1.62 1.66 1.66 1.67 1.62 1.65 β-Pinene 0.72 0.72 0.72 0.73 0.74 0.74 0.73 0.73 Myrcene 1.76 1.73 1.74 1.78 1.78 1.79 1.75 1.77 α-Terpinene 0.21 0.18 0.20 0.23 0.23 0.23 0.21 0.19 Limonene 79.53 79.78 79.81 79.64 79.66 79.70 79.77 79.77 β-Phellandrene 3.49 3.39 3.45 3.51 3.51 3.51 3.49 3.46 γ-Terpinene 9.27 8.79 8.93 9.34 9.33 9.30 9.10 8.54 p-Cymene 0.60 1.12 0.91 0.43 0.44 0.45 0.70 1.29 Terpinolene 0.47 0.45 0.45 0.46 0.46 0.46 0.46 0.44 Dimethyl trisulfide 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 6-Methyl-5-hepten-2-ol 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 Linalool 1.64 1.66 1.59 1.57 1.56 1.55 1.57 1.60 Perillaldehyde 0.59 0.45 0.46 0.54 0.52 0.49 0.48 0.44 Thymol 0.11 0.12 0.11 0.10 0.10 0.10 0.11 0.11 Sum 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00

As shown in Table 5, it was confirmed that the yield of citron essential oil increased to 6% according to the concentration of the ethanol aqueous solution, but thereafter, the yield was found to be 1.09% at 6%. There was no significant difference in the compositional composition of citron fragrances according to the concentration of ethanol aqueous solution, and it was confirmed that there was no difference in sensory characteristics.

As can be seen from the above experiment, the concentration of the ethanol aqueous solution when extracting natural citron essential oil is preferably 6% or more,

&Lt; Example 3 >

The extractive conditions of citron essential oil were the same as those of Example 1 except that the optimum condition indicated by the above Example 1 and Example 2, that is, the concentration of the aqueous ethanol solution was 6% and the extraction temperature was 60 ° C Method, and the average value obtained by repeating 5 times in the same manner is shown in Table 6. < tb > < TABLE >

Extraction temperature (캜) 60 Ethanol concentration (%) 6 Average yield (%) 1.08

incense

group

castle

minute
(%) α-Pinene 1.65 β-Pinene 0.73 Myrcene 1.78 α-Terpinene 0.23 Limonene 79.65 β-Phellandrene 3.50 γ-Terpinene 9.38 p-Cymene 0.45 Terpinolene 0.46 Dimethyl trisulfide 0.01 6-Methyl-5-hepten-2-ol 0.00 Linalool 1.55 Perillaldehyde 0.50 Thymol 0.11 Sum 100.00

According to the results shown in Table 6, it can be seen that the average yield is 1.09% under the optimum condition according to the present invention, and the yield is about twice as efficient as that obtained by the conventional ethanol extraction method (about 0.5%) You can see what you can do.

Claims

a). A first step of separating the peel from the natural citron,
b). A second step of adding ethanol to the citrus peel obtained in the first step to obtain an ethanol extract containing citrus essential oil,
c). A third step of separating ethanol by selectively adsorbing ethanol from the citron essential oil-containing ethanol extract solution of the second step using an adsorption column packed with a hydrophobic 3A zeolite as a hydrophobic adsorbent;
d). And a fourth step of separating the extract containing citron essential oil from which the ethanol has been separated in the third step into an aqueous layer and an organic layer and then obtaining citron essential oil from the organic layer. Way.

[2] The method according to claim 1, wherein the second step of obtaining the ethanol extract is a step of adding an aqueous 6% to 10% ethanol solution to the citrus peel.

[Claim 2] The method according to claim 1, wherein the second step of obtaining the ethanol extract is performed at 60 to 70 < [deg.] &Gt; C.

[4] The method according to claim 1, wherein the fourth step of obtaining citron essential oil comprises adding citronized NaCl to separate citron extracts.

The method according to any one of claims 1 to 4, wherein the second step of obtaining the ethanol extract is a method of efficiently producing natural citron essential oil using citron peel, characterized in that 6% ethanol aqueous solution is added and the process is carried out at 60 ° C .

[Claim 5] The method according to claim 5, wherein the fourth step of obtaining citron essential oil is characterized by adding 1 to 2 parts by weight of edible NaCl to 100 parts by weight of the citron essential oil-containing extract to separate the citron essential oil. Efficient manufacturing method.