KR101695148B1 - Effective manufacturing method of natural yuju fragrance utilizing ionic liquid and core- chell type capsule containing yuju fragrance - Google Patents

Abstract

The present invention relates to an effective manufacturing method of natural citron fragrance utilizing ionic liquid and a core-shell type capsule containing the citron fragrance. The effective manufacturing method removes rancidified substances in the oil with the citron fragrance utilizing the ionic liquid. The ionic liquid of the present invention has features of removing the rancidified substances without a change or a loss of ingredients for the citron fragrance. The yielded essential oils with the citron fragrance have improved stability and have an edge on being distributed as items like aroma oils, spices, flavors and cosmetic materials, thereby having more advantageous assets than others to be used industrially.

Description

[0001] The present invention relates to a method for efficiently producing natural citron flavor using an ionic liquid and a core-shell type capsule containing citron flavor,

The present invention relates to a method for efficiently producing citron aroma from natural citron and a core-shell type capsule containing citron flavor.

Citrus junos Tanaka is a scientific name of citrus junos Tanaka belongs to the genus Uranus and citrus. Country of origin is not cultivated citrus according to climate change, but is a rare variety of citrus fruits that are special only in Korea and Japan around the world.

Yuzu (citron) is the fruit that has been treated very preciously in Korea since ancient times as a flavor and aroma. It has been used as a source of prevention of cold and supply of vitamins, minerals and various organic acids. The price is lowered due to the development of mass cultivation technology, and it is widely supplied to the market. Especially, it is widely used as a tea carved in sugar.

The citrus scent is very individual and strong compared to the citrus scent, and it is popular with people without people who do not like special with lemon or grapefruit. In the 21st century, it can be said that the age 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 aroma is needed worldwide. In the case of foreign countries, there is a unique flavor of each country, but only natural aroma of Korea is not produced properly.

Domestic citron is the best quality in the world, so it is a unique specialty in the world. Therefore, it is very difficult to develop a proper industrial scale manufacturing factory due to lack of manufacturing technology, It is a reality that a component which is a main cause of deterioration or deterioration in the extraction manufacturing process can not be removed.

Background Art [0002] Prior art related to the technology for producing natural citron aroma is, for example, a method of extracting citron extract obtained by centrifugation after washing the maturation or immature part of citron in Korean Patent Publication No. 2000-0037001, I'm starting refining. Korean Patent Laid-Open Publication No. 2001-0035501 discloses a method for producing distilled liquor essential oil by using steam at 110 to 145 ° C on citron skin, but the method of extracting citron essential oil by cold pressure impregnation has a great effect on product quality There is a disadvantage in that it can not remove shrinking impurities affecting it, and the technique of high temperature distillation at 110 DEG C has a disadvantage that the inherent flavor of citron is destroyed by heat, resulting in deterioration of product quality.

In addition, in the Korean Registered Patent Publication No. 10-0452467, citron, citron peel, or citron seeds are added to supercritical and subcritical reactors, and then the extraction solvent is passed through; 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 general, natural fragrance is easily denatured by heat, and is not easily captured when it is extracted by distillation method due to difference in vapor pressure, and is disadvantageous in that it is volatilized and extraction efficiency is extremely low. In addition, it is desired to extract by using petroleum organic solvent In some cases, chemical reactions with the solvent may occur and the fragrance may be lost.

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.

In the present invention, the present invention has been completed by solving the disadvantages and problems of the prior art, developing a cryogenic distillation process utilizing an ionic liquid, and producing capsules containing the natural citron flavor.

The present invention aims to provide a method for efficiently producing citrus fragrance from natural citron and a core-shell type capsule containing the natural citron flavor prepared therefrom, and more specifically, It is an object of the present invention to provide a method for efficiently producing a high-quality natural fermented flour by removing the acid-decomposable substance by a refining process and a core-shell type capsule containing the natural fermented flour produced therefrom.

As a solution for attaining the object of the present invention, a method for efficiently producing natural citron aroma using an ionic liquid comprises the steps of: a) a process of roughening surface of citron surface and spraying distilled water at the same time, A first step of obtaining a citrus peel extract and then separating the natural citrus oil raw material from the citrus peel extract containing natural citrus oil, b) adding to the natural citrus flavor oil raw material separated in the first step 1-butyl (Trifluoromethylsulfonyl) imide or 1-octyl-3-methyllimidazoium bis (trifluoromethanesulfonyl) imide is mixed at a vacuum pressure of 700 to 760 Torr, And a second step of removing the acidic pulverulent substances contained in the raw material of natural ornamental aroma by vacuum distillation at a concentration temperature of 50 to 70 ° C to obtain pure citron essential oil It consists of.

In order to achieve the above object, the present invention provides a method for effectively producing a natural citron aroma using an ionic liquid, comprising the steps of: adding a pure citron essential oil to a core containing pure citron essential oil; - a shell-type capsule.

In the first step according to the present invention, the citron is put into a peeling machine, and the surface of the citron is roughly surface-treated and the distilled water is simultaneously sprayed to remove the shell from the surface of the citron, and the citron peel extract containing water (distilled water) , The citrus peel extract solution is put into a separating funnel, and the mixture is allowed to stand until it is separated into an oil layer and an aqueous solution. Then, the natural citron essence oil raw material as a supernatant portion is separated and obtained from the separating funnel.

The second step includes a citrus flavor oil purification step of removing the acidic substance which is contained in the natural essential oil and obtained in the first step, which causes deterioration of quality, and obtaining pure natural citron essential oil.

The extracts of natural citron peel extracts contain acidic substances such as fatty acids, vitamins with a high oxidizing power, and caproic acid in an amount of 0.5% of the amount of the perilla extract, and the causative component of the natural citron extract It should be separated from the citron-flavored oil, since it causes deterioration of the quality of the oil.

In the present invention, in order to remove the acid-clenching agent, an ionic liquid such as 1-butyl-3-methylimidazolium bis (trifluoromethylsulfonyl) imide or 1-octyl Methylimidazolium bis (trifluoromethanesulfonyl) imide was carried out by vacuum distillation at a vacuum pressure of 700 to 760 Torr and a temperature in the range of 50 to 70 DEG C and a vacuum pressure of 760 Torr and a temperature of 50 DEG C It is preferable to perform the second step by distillation using a vacuum rotary condenser.

In the second step of the present invention, the ionic liquid selected for removing the acidic pulverulent material from the natural ornamental oil raw material means a liquid composed only of ions. In general, the ionic liquid, which is composed of a large cation and a smaller anion, As a molten salt. Due to its structural characteristics, it has a low melting point and a very low vapor pressure, which is a stable liquid in a wide temperature range. It has excellent thermal stability and ionic conductivity and dissolves various organic, inorganic and polymeric substances having hydrophilic and hydrophobic properties It can be used for high purity purification process of heavy metal ions and ionic impurities. It is a more environmentally friendly material than general organic solvents because it has low volatility, low flammability and low explosibility.

Although various ionic liquids are known, the compounds represented by the following general formula can be exemplified.

[General formula]

The anionic compounds forming the ionic liquid of the above general formula are selected from the group consisting of Cl ^- , Br ^- , NO ₃ ^- , BF ₄ ^- , AlCl ₄ ^- , Al ₂ Cl ₇ ^- , AcO ^- , CH ₂ COO ^- , CH _{^{3 SO 3 -, CF 3 SO}} 3 -, (CF 3 SO 2) 3 C -, (CF 3 CF 2 SO 2) 2 N -, C 3 F 7 COO -, (CF 3 SO 2) (CF 3 CO _{^{) N -, C 4 F 10}} N -, C 2 H 9 SO 3 -, C 2 H 9 NO 4 S 2 -, C 3 F 8 NO 3 S -, CH 3 CH (OH) CO 2 - is selected from Any one of the anionic compounds may be used.

The ionic liquid which can be selected in the present invention is preferably an imidazolium-based ionic liquid having a long alkyl substituent, and is preferably a 1-butyl-3-methylrimidazoium bis (tri Fluoromethylsulfonyl) imide or 1-octyl-3-methylrimidazoium bis (trifluoromethanesulfonyl) imide represented by the following formula 2 is particularly preferable.

[Chemical Formula 1]

(2)

The core-shell type capsule containing pure citron-essential essential oil, which is another object of the present invention, is characterized in that, in addition to the second step, the liquid containing the pure citron-essential essential oil obtained in the second step is surrounded by the solid shell And a third step of preparing a core-shell type capsule.

The core-shell type capsule manufacturing method applied to the present invention uses emulsion beads of natural pure citron essential oil as a core by using a well-known general technique for producing a core-shell type capsule. Shell type capsule forming a coating layer (shell) with a cationic polymer material surrounding the core.

The cationic polymer material forming the emulsion component and the shell layer forming the core according to the production of the core-shell type capsules of the present invention may be prepared by mixing well-known materials generally known in the art of manufacturing core-shell type capsules Disodium EDTA, Butylene glycol, Xanthan gum, Sodium alginate, Agar and the like can be exemplified as a cationic polymer material forming a coating layer (Shell). A known double encapsulator (BUCHI, Encapsulator B -300).

The process for efficiently producing citron aroma according to the present invention is characterized in that an acidic substance contained in the citron aroma is efficiently removed by using an ionic liquid without loss of the citron ingredient and the natural pure citron extract Essential oil has no deterioration and shows improved stability.

Furthermore, since the pure citron essential oil produced by the process for efficiently producing citron aroma according to the present invention exhibits long-term stability without deterioration, it is very advantageous for distribution to products such as aroma oil, spice, fragrance, perfume and cosmetic material, It is advantageous to utilize it as an advantage.

Brief Description of the Drawings Fig. 1 is a schematic view showing a process for obtaining a pure citron essential oil according to the present invention using a still equipped with a vacuum rotary condenser. Fig.

Hereinafter, the present invention will be described in more detail with reference to examples and comparative examples, but the following examples do not limit the present invention. Unless otherwise specified, the units of percentages and parts used in the present invention are all expressed by weight.

The specific fragrance components of natural citron essential oils obtained from the raw citron were Remonene, α-Terpinene, Myrene, α-Pinine , Linaloo, 6-methyl-5-hepten-2-ol and Methyl trisulfide. Vitamin C contains 50 to 105 mg of vitamin C per 100 g of citronellal oil and has an acid value of 0.3 to 0.4 mg NaOH / g and a pH of 5 ~ 6. ≪ / RTI >

≪ Example 1 >

a). The first step of separating the natural citron oil raw material from citrus fruit extract

10kg of freshly washed natural yuzu is put into a peeling machine having a device for spraying distilled water at room temperature and pressure, which is made of a rough plastic cylinder, then the peeling machine is rotated and the surface of the yuzu is roughened by spraying distilled water And 5 kg of citron peel extract containing natural citron fragrance oil was obtained in distilled water.

Thereafter, the citrus peel extract was placed in a separating funnel, NaCl was added to the citrus peel extract in an amount of 1% based on the weight of the citrus peel extract, and the mixture was homogeneously mixed. Thereafter, , The supernatant portion as an oil layer was separated from the separatory funnel to obtain 150 g of a crude oleaginous oil crude.

b). A second step of removing the acid-clenching agent to obtain pure citron-essential essential oil

20 g of each of the natural crude oil fractions obtained above was sampled five times, and each sample was mixed with an ionic liquid 1-butyl-3-methyllimidazoium bis (trifluoromethyl 1%, 2.5%, 5%, 7.5%, and 10% were added to a distillation apparatus (see FIG. 1) equipped with a vacuum rotary condenser, of And the mixture was vacuum-concentrated until it was reduced to 90% of the weight of the feed, and the pure citrus essential oil, from which the acid-decomposable substances contained in the crude oil-containing crude oil had been removed, was received as [Sample 1] to [Sample 5] .

In addition, 1-octyl-3-methylrimidazoium bis (trifluoromethanesulfonyl) imide, which is an ionic liquid, was concentrated by vacuum rotation in the same manner as above, The material was removed, and pure citron aroma essential oil was taken as [samples 1a] to [sample 5a].

≪ Example 2 >

The content of 1-butyl-3-methylrimidazoium bis (trifluoromethylsulfonyl) imide obtained in the above Example 1 was adjusted to 5% (Sample 3) was prepared by using a double encapsulator (model name: Encapsulator B-300) manufactured by BUCHI according to the compositional composition and composition ratio as shown in the following [Table 1] and containing a natural pure citrus essential oil-containing core- Type capsule (sample 3-capsule).

For the comparative test, the core-shell type capsule containing crude oil-containing crude oil was prepared in the same manner as above using the crude oil of crude oil with no acid-removed substance obtained in Example 1 above crude-capsules).

Classification Constituent Composition ratio (total 100g basis) Crude Sample 3 Capsule material Purified water to 100 to 100 Disodium EDTA 0.02 0.02 Butylene Glycol 5.00 5.00 Xanthan gum 0.01 0.01 Sodium alginate 0.50 0.50 Agar 0.50 0.50 Magnesium Aluminum Silicate 0.08 0.08 Bees Wax 0.80 0.80 Dimethicone 0.80 0.80 Butylene Glycol Dicaprylate 3.00 3.00 Caprylic Triglyceride 3.00 3.00 1,2-Hexanediol 2.00 2.00 Cetostearyl alcohol 2.00 2.00 Cetearyl Olivate 1.00 1.00 Natural citron
Essential Oils Crude (acid-free material removal) 10 - Ionic liquid 5% (Removal of acid-decomposable substances) - 10

≪ Test Example 1 >

The crude oleoresin oil crude obtained in Example 1 and not containing the acidic cobalt material and the pure citrus oil obtained by adding the ionic liquid under the condition of removing the acidic cobalt material The results of analyzing the acid value, pH, vitamin C, carproic acid, and fragrance components of each of [Sample 1] to [Sample 5] and [Sample a] to [Sample f] are shown in Table 2 below.

Analysis item Crude By ionic liquid addition amount One% 2.5% 5% 7.5% 10% Sample 1 Sample a Sample 2 Sample b Sample 3 Sample c Sample 4 Sample d Sample 5 The sample f Acid value (mg NaOH / g) 0.42 0.1 0.15 0 0 0 0 0 0 0 0 pH 4.8 6.2 6.0 6.8 6.7 6.8 6.7 6.9 6.9 6.8 6.9 Vitamin C (mg / g) 82 15 17 2 2.1 0 0 0 0 0 0 Carproic acid (mg / g) 1.5 0.2 0.18 0 0.2 0 0 0 0 0 0 incense
castle
minute
(%) Remonene 54.6 54.8 54.2 54.6 54.4 54.2 54.1 54.6 54.4 54.4 54.3 Myrene 21.7 21.4 21.3 21.6 21.3 21.6 21.4 21.5 21.4 21.3 21.4 α-Terpinene 6.2 6.6 5.9 6.3 6.2 6.2 6.3 6.1 6.0 6.1 6.2 α-Pinine 5.2 5.3 5.1 5.0 5.0 5.1 5.0 5.1 5.2 5.1 5.2 β-Pinene 3.2 3.7 3.1 3.5 3.2 3.3 3.1 3.3 3.2 3.5 3.3 Linaloo 2.7 2.4 2.2 2.6 2.2 2.7 2.4 2.5 2.6 2.3 2.6 6-methyl-5-
hepten-2-ol 0.23 0.15 0.14 0.21 0.20 0.21 0.22 0.24 0.23 0.23 0.22 Methyl
trisulfide 0.14 0.13 0.11 0.13 0.13 0.15 0.12 0.16 0.14 0.14 0.13

As shown in the above Table 2, natural citroness essential oil not having the acidic pulverulent material removed had an acid value of 0.42 mg NaOH / g, pH of 4.8, 82 mg of vitamin C and 1.5 mg / g of carproic acid . However, in order to remove acid-clotting substances, the pH value was increased and the content of acid-decomposable substances was decreased in the result of the experiment in which the ionic liquid was added in the range of 1% to 10% Can be confirmed. Especially, when the ionic liquid was added more than 5%, the acid value was 0, the pH was 6.7 or higher, the carproic acid content and the vitamin C content were zero.

As a result, it is preferable to add at least 5% of ionic liquid in order to completely remove acidic pulverulent substances in crude natural citron oil. In addition, as shown in Table 2, It can be seen that the natural citron flavor component does not show any unusual change in the process of removing the acidurisable substance by using the process of the present invention. have.

≪ Test Example 2 &

For the comparative test on the stability, the natural crude oil-containing crude oil, the sample 3, the crude-capsules and the sample 3-capsules prepared in the above Example 1 and Example 2 were heated at 60 ° C ± 2 And the stability was evaluated under the same conditions. The results are shown in [Table 3] and [Table 4] below.

Six-month analysis of samples Crude Sample 3 0 months 2 months 4 months 6 months 0 months 2 months 4 months 6 months Acid value
(mg NaOH / g) 0.42 0.35 0.32 0.25 0 0 0 0 pH 4.8 5.2 6.2 6.3 6.8 6.9 6.9 6.8 Vitamin C
(mg / g) 82 61 50 27 0 0 0 0 Carproicacid
(mg / g) 1.5 1.2 0.7 0.3 0 0 0 0 Presence or absence of color change - Discoloration oil Discoloration oil Discoloration oil Color change Color change Color change Color change

Six-month analysis of samples Crude-Capsules Sample 3-capsule 0 months 2 months 4 months 6 months 0 months 2 months 4 months 6 months Acid value
(mg NaOH / g) 0.12 0.06 0.05 0.01 0 0 0 0 pH 5.6 5.9 6.3 6.6 7.1 7.1 7.1 7.1 Vitamin C
(mg / g) 8 3 2 0 0 0 0 0 Carproicacid
(mg / g) 0.21 0.14 0.12 0.09 0 0 0 0 Presence or absence of color change - - Discoloration oil Discoloration oil Color change Color change Color change Color change

As shown in [Table 3] and [Table 4], Crude-Crude and Crude-Capsule samples of citron fragrance oils showed acid value, pH, vitamin C and carproic acid, which cause the saponification of citron essential oil, It is possible to know that the change in color and change of the fragrance component causes the deterioration of the quality of the product. On the other hand, according to the present invention Sample 3 and Sample 3 capsules from which acid-releasing substances were removed showed no change even after 6 months of acid value, pH, vitamin C, and carproic acid, which cause the saphenicity of natural citron essential oil, It can be predicted that the natural citron essential oil and the product produced according to the present invention are free from discoloration and can be stably distributed for a long period of time without deterioration in quality.

Claims (7)

a) In the process of roughening the surface of the citron and spraying the distilled water at the same time, the citron peel extract containing natural citron aroma oil is obtained from citron peel, and then the natural citron aroma oil raw material is separated from the citron scent extract containing natural citron oil The first step and
b) adding an ionic liquid 1-butyl-3-methylimidazolium bis (trifluoromethylsulfonyl) imide or 1-octyl-3-methylimidazole And a second step of removing the acidic pulverulent material contained in the natural volatile oil raw material by vacuum distillation to obtain a pure citron-essential oil. By weight of an ionic liquid. [Claim 2] The method according to claim 1, wherein the ionic liquid is mixed with a natural ornamental oil raw material in an amount of 2 to 10% based on the weight of the raw material of natural ornamental oil. The method of claim 2, wherein the vacuum distillation is performed at a vacuum pressure of 700 to 760 Torr and a temperature of 50 to 70 ° C. 4. The process according to claim 3, wherein the mixture of the ionic liquid and the natural source of essential oil is mixed at a ratio of 5% based on the weight of the raw material of natural sesame oil, and the vacuum distillation is conducted by vacuum rotation concentrating at a vacuum pressure of 760 Torr and a temperature of 50 ° C A process for producing natural essential oils and essential oils using ionic liquids. The method for producing natural essential oil essential oil according to claim 4, wherein the ionic liquid is 1-butyl-3-methylrimidazoium bis (trifluoromethylsulfonyl) imide . 5. The method of claim 4, wherein the ionic liquid is 1-octyl-3-methylrimidazoium bis (trifluoromethanesulfonyl) imide. The method according to any one of claims 1 to 6, further comprising, in addition to the second step of obtaining the pure citron-essential essential oil, the emulsion bead of the pure citron essential oil obtained in the second step as a core, And a third step of preparing a core-shell type capsule which forms a shell with a cationic polymer material. The method of producing a natural essential oil using the ionic liquid.

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