KR100718235B1 - A Method for Refining Wood Vinegar and Refined Wood Vinegar Thereby - Google Patents

Abstract

The present invention relates to a method for purifying crude wood vinegar using a catalyst and thus purified high-purity wood vinegar. The crude wood liquor and hydrogen peroxide were oxidized in the presence of catalyst phosphoric acid at about 30 ~ 70 ℃ for about 8 ~ 12 hours, then left for about 36 ~ 40 hours, and after removing the aggregates formed at about 3.5 ℃ at about 90 ~ 120 ℃ A method of purifying wood vinegar distilled for ˜4.5 hours and thus purified wood vinegar is provided. According to the method of the present invention, the carbonized suspension and the coal in the crude wood vinegar are removed in a short time and with high efficiency. The wood vinegar purified by the method of the present invention is excellent in bactericidal activity, does not contain harmful substances, odors are removed, and can be applied in various methods and fields.

Crude wood liquor, wood vinegar, phosphoric acid, hydrogen peroxide, acetic acid, peracetic acid, methanol, formic acid

Description

A Method for Refining Wood Vinegar and Refined Wood Vinegar Thereby}

1 shows a synthetic route diagram of the crude wood vinegar purification method of the present invention,

Figure 2a is a photograph showing the antimicrobial effect of wood vinegar purified by the method according to the present invention,

Figure 2b is a photograph showing the antimicrobial effect of ethanol as a comparative example.

The present invention relates to a method for purifying crude wood vinegar and thus a purified wood vinegar, and more particularly, to a method for purifying crude wood vinegar using a phosphate catalyst and thus purified high-purity wood vinegar.

Crude vinegar is a liquid obtained by aging and refining a liquid obtained by cooling smoke generated during carbonization of wood for a long time. The main component is acetic acid, and various organic acids such as furfuryl acid; It is a mixed composition containing alcohols, such as methanol and ethanol.

In other words, when wood is heated to 300-400 ℃ in a place where there is little air, such as charcoal kiln, carbonization occurs and white smoke is generated. The liquid obtained by cooling the smoke generated at this time is crude wood vinegar, and the crude wood vinegar contains harmful substances such as tar, methanol, phenol and benzopyrene.

Wood vinegar has excellent ability to remove free radicals in cells, and it is known to be effective for various diseases such as atopic skin, allergy and acne, diabetes, constipation, indigestion, athlete's foot, otitis media, cancer, etc. Or drinking together.

However, as described above, crude wood vinegar contains harmful ingredients such as tar, phenol, methanol, cresol, benzopyrene and the like, and its application is limited due to the intrinsic charcoal. Therefore, there is a need for purification and deodorization of crude wood vinegar to make it suitable for application directly to the skin or for use as an additive in food, beverages and cosmetics.

For example, Korean Patent No. 212472 discloses a method of distilling at 95-105 ° C. and removing methanol and phenol from crude wood liquor using activated carbon.

Korean Patent Application No. 2001-61278 discloses a method for producing a drinking wood vinegar by aging and distilling using non-leaflets, but it is inefficient to require long-term aging of 6 months or more.

Korean Patent Application No. 2001-9198 discloses a reduced pressure distillation purification method of wood vinegar comprising distilling at a very low pressure of -40 to -7 atm, but it requires a considerable cost to maintain the low pressure as described above. There is a problem.

Accordingly, an object of the present invention is to provide a method for efficiently purifying crude wood vinegar in a short time.

Another object of the present invention is to provide a method for purifying crude wood vinegar using a catalyst.

Still another object of the present invention is to provide a purified wood vinegar solution from which harmful components and coals are removed by using the purification method of the present invention.

According to one aspect of the invention,

Oxidation of crude wood vinegar and hydrogen peroxide solution in the presence of phosphoric acid at 30-70 ° C. for about 8-12 hours;

After the oxidation reaction, leaving for about 36-40 hours to remove the aggregates formed when left; And

Distilling at about 90-120 ° C. for about 3.5-4.5 hours;

There is provided a method for purifying wood vinegar, characterized in that it comprises a.

According to another aspect of the present invention, wood vinegar purified by the purification method of the present invention is provided.

According to still another aspect of the present invention, a food and drink containing the wood vinegar solution of the present invention are provided.

According to still another aspect of the present invention, a cosmetic containing the wood vinegar solution of the present invention is provided.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.

Crude wood vinegar obtained by cooling the smoke generated during the carbonization of wood contains carbon and harmful substances from carbonization. Therefore, in the method of the present invention, purified organic vinegar having excellent bactericidal activity and removing harmful substances and coals is obtained by allowing an effective organic acid to be formed from acid and alcohol components contained in a large amount in vinegar using a catalyst.

The crude wood vinegar is mostly composed of various acids including acetic acid, perpriic acid and the like, and alcohols such as methanol and ethanol. In the present invention, crude wood vinegar containing various acids and alcohols is used as a starting material.

According to the method of the present invention, among the various components in crude wood vinegar, in particular acetic acid and methanol are converted into effective organic acids, which are peracetic acid and formic acid, respectively, and the crude wood vinegar is purified by the adsorption power of formic acid. 1 shows a synthetic route diagram of the crude wood vinegar purification method of the present invention.

The crude wood acetate is reacted with hydrogen peroxide so that acetic acid and methanol in the crude wood component are oxidized to an effective organic acid such as peracetic acid and formic acid, and is reacted at 30 to 70 ° C, preferably 50 to 70 ° C, in the presence of phosphoric acid. Hydrogen peroxide solution is used as oxidant and phosphoric acid as catalyst.

When the crude wood vinegar is reacted with hydrogen peroxide solution in the presence of phosphoric acid at 30-70 ° C., acetic acid is oxidized to peracetic acid and methanol is formic acid, as shown in the following formula (1). In the oxidation reaction, a small amount of furfuric acid contained in crude wood vinegar is converted to furfural acetic acid, phenol to carbolic acetic acid and ethanol to acetic acid, respectively. Furyl acetic acid and carboacetic acid are present in traces, removed in a subsequent distillation step and acetic acid is oxidized to peracetic acid.

As shown in Scheme 1, acetic acid is oxidized to peracetic acid and methanol is formic acid as shown in Scheme 2 below. In the oxidation reaction, a small amount of furfuric acid contained in crude wood vinegar is converted to furfural acetic acid, phenol to carbolic acetic acid and ethanol to acetic acid, respectively. Furyl acetic acid and carboacetic acid are present in traces, removed in a subsequent distillation step and acetic acid is oxidized to peracetic acid.

Scheme 1

CH ₃ COOH + H ₂ O _2- > CH ₃ COOOH + H ₂ O

Scheme 2

CH ₃ OH + H ₂ O _2- > HCOOH + 2H ₂ O

The addition of hydrogen peroxide (H ₂ O ₂ ) to the resulting carboxylic acid provides the effect of supplying active hydrogen (H ₂ ) with a strong reducing effect and oxygen (O ₂ ) with a high electronegativity, Forming a stable dimer such as (dimer) exhibits a high bactericidal power of medicinal activity and reduces the active oxygen by the active hydrogen, side effects are reduced.

[Formula 1]

Acetic Dimer Structure

[Formula 2]

Formic Acid Dimer Structure

[Formula 3]

Propionate Dimer Structure

Peracetic acid has excellent removal ability and inhibitory activity against fungi and molds, and formic acid has excellent insecticidal properties. Therefore, according to the purification method of the present invention, the wood vinegar solution obtained by oxidizing acetic acid to peracetic acid and methanol to formic acid has excellent sterilization, insecticide and Antifungal effect shows antibacterial effect.

In addition, formic acid (HCOOH) is an acid that acts to aggregate rubbery substances and organic proteins, such as tar, phenol, cresol, benzopyrene, etc. contained in crude wood vinegar by formic acid formed by the reaction of Scheme 2. Impurities and the like containing harmful components are aggregated into a carbonized suspension, and the aggregated carbonized suspension is easily removed by filtration. As the carbonized suspension is coagulated by the formic acid, the coal is also simultaneously removed.

The oxidation reaction using hydrogen peroxide solution of acetic acid and methanol is performed at about 30-70 degreeC, Preferably it is 50-70 degreeC. When the reaction temperature is less than 30 ℃ takes a long time to the reaction, if it exceeds about 70 ℃ low boiling alcohols are volatilized is not preferred.

In addition, the oxidation reaction is performed for about 8-12 hours. When the reaction time is less than 8 hours, acetic acid and methanol are not sufficiently oxidized with peracetic acid and formic acid, and when the reaction is carried out for about 12 hours, the oxidation reaction according to Chemical Formulas 1 and 2 proceeds sufficiently and the reaction does not proceed any further. Reacting over time is uneconomical.

After the oxidation reaction, the mixture is left for about 36 to 40 hours, and the carbonized suspension contained in the crude wood vinegar is agglomerated by formic acid during the time of standing. If the standing time is less than 36 hours, the carbonized suspension is not sufficiently agglomerated, and if it exceeds 40 hours, the carbonized suspension is sufficiently agglomerated by being left for about 36 to 40 hours.

Hydrogen peroxide used as oxidant in the process of the present invention can be used in stoichiometric amounts to measure the content of acetic acid and methanol in the wood vinegar and they can be sufficiently converted to peracetic acid and formic acid according to Schemes 1 and 2. However, in the actual reaction, the reaction may be added in a somewhat excessive amount, for example, about 5-10% by weight, so that the reaction proceeds sufficiently, but is not limited thereto. For example, 2.5 to 4.0 g of hydrogen peroxide per 100 g of crude wood vinegar. Water can be added.

Phosphoric acid as a catalyst may be used in a small amount, but is not limited thereto. For example, 0.1 to 2.5 g of phosphoric acid may be used per 100 g of crude wood vinegar. If less than 0.1g of phosphoric acid is used, the reaction efficiency is lowered, and if it is used more than 2.5g, the efficiency of reaction is not economically improved.

The aggregate of the carbonized suspension formed by aggregation by formic acid is filtered off as a solid. That is, tar, phenol, cresol, benzopyrene, etc., which are harmful components in wood vinegar, are not only removed in the form of aggregates, but also in the coal.

The highly purified high-purity wood vinegar from which impurities are removed is obtained by distilling the wood vinegar solution from which the carbonized suspension is removed at about 90-120 ° C. for about 3.5-4.5 hours. Distillation is carried out for about 3.5-4.5 hours at about 90 ~ 120 ℃ considering the boiling point of peracetic acid and formic acid. Preferably the distillation is carried out until the yield reaches about 60%. By distillation, peracetic acid, formic acid, and the like are volatilized, and it is cooled and taken to obtain purified wood vinegar. Furfural acetic acid and carboacetic acid produced during the oxidation reaction have a higher boiling point than distillation temperature and are thus removed without distillation.

On the other hand, after removal of the carbonized suspension formed by leaving the oxidation reaction, by adding an adsorbent to further remove the remaining impurities and / or unknown toxic substances such as heavy metals in the treated wood vinegar to remove the impurities by additional adsorption. Can be. As the adsorbent, any material capable of adsorbing and removing impurities and / or heavy metals may be used. However, without limitation, charcoal and / or activated carbon powder may be used in an amount of 3 to 5% by volume based on the volume of wood vinegar. . If the content is less than 3% by volume, it is insufficient for sufficient adsorption, and if it exceeds 5% by volume, impurities and / or heavy metals are not only sufficiently adsorbed, but also undesirable in view of the subsequent filtration and removal of the adsorbent.

The adsorbent is added and left for about 20-30 hours to allow the adsorbent to sufficiently adsorb impurities and / or heavy metals, and then the adsorbent is removed by filtration under reduced pressure. If the leaving time is less than 20 hours, impurities are not sufficiently adsorbed and removed by the adsorbent, and even if it exceeds 30 hours, the adsorption is not increased any more and it is uneconomical.

Furthermore, the method of purifying crude wood vinegar of the present invention adds the dried mugwort powder to the distillate after the distillation step in an amount of about 1-3% by weight, preferably about 2% by weight and 3.5 to 70-90 ° C. After flavoring for 4.5 hours, further distillation may be further included. At this time, the mugwort powder added acts as a flavoring agent and significantly reduces the ethanol of wood vinegar. If the added amount of mugwort powder is less than 1% by weight, the flavoring effect is insignificant, and if it exceeds 3% by weight, it is not preferable because a too thick mugwort may cause rejection. If the flavoring condition is out of the above range, no suitable mugwort flavor can be provided. In addition, the conditions for performing such further distillation are not limited thereto, but it is preferably performed at about 90-120 ° C. for about 3.5-4.5 hours. Preferably the further distillation is carried out until the yield reaches about 80%.

In addition, the method of purifying crude wood vinegar of the present invention may further comprise the step of adjusting the pH of the further distilled distillate to 3-3.5. If the pH of the further distilled distillate is less than 3, sodium acetate is added, and if the pH exceeds 3.5, it is preferable to adjust the pH to 3-3.5 by adding zinc sulfate. As such, by adjusting the pH of the purified wood vinegar to 3-3.5, acetic acid, formic acid and propionic acid can be maintained without being denatured, respectively.

By purifying crude wood vinegar as in the method of the present invention, wood vinegar can be purified within a short time of about 60 hours, and purified wood vinegar is obtained in high yield of 70-80%. Purified wood vinegar contains a large amount of peracetic acid and formic acid, which have excellent antibacterial properties such as insecticidal and sterilization, and carbonaceous suspensions containing harmful substances such as tar, phenol, cresol, and benzopyrene are removed, and at the same time, the carbon content is significantly reduced.

The wood vinegar obtained according to the present invention includes 2 to 4% by weight of acetic acid, 0.05 to 0.15% by weight of formic acid, 0.05 to 0.15% by weight of propionic acid, 1-3% by weight of wormwood components, 0.01-1% by weight of sodium acetate and purified water remaining amount. Or may comprise 2 to 4% by weight of acetic acid, 0.05 to 0.15% by weight of formic acid, 0.05 to 0.15% by weight of propionic acid, 1-3% by weight of wormwood components, 0.01-1% by weight of zinc sulfate and the remaining amount of purified water. have.

Toxic substances purified by the method of the present invention and ethanol removed from the ethanol can be diluted and drinkable, can be directly applied to the skin, etc., can be used as additives in food, beverages and other cosmetics. Therefore, it is expected to be used in various fields. For example, woody liquor purified by the method according to the invention in food, beverages and cosmetics can be added in an amount of up to 5% by weight. Purified wood vinegar of the present invention may be added in a suitable amount in consideration of the action, effect, etc. required for food, beverages and cosmetics. However, since the food additive is currently regulated by the maximum amount of 5% by weight, purified wood vinegar can be added to food, beverages and cosmetics, such as 5% by weight or less, preferably 1-5% by weight. Wood vinegar can also be used as a main ingredient in the synthesis of pharmaceuticals.

Hereinafter, the present invention will be described in detail through examples. However, the following examples are illustrative of the present invention, which does not limit the present invention.

Example  One

To the round flask was added 600 g of crude wood vinegar and 2 g of 80% phosphoric acid. Thereafter, a cooling condenser device was installed in the flask, and 24 g of 30% hydrogen peroxide solution was slowly added to the crude wood vinegar and heated to 70 ° C. while stirring at 110 rpm to react for 8 hours. Thereafter, the resulting aggregates were left to stand at room temperature for 40 hours, filtered, and then heated and distilled at 90-120 ° C. for 4 hours in a distiller to obtain 410 g of purified wood vinegar (about 68% yield).

The physical properties of the purified wood vinegar and the presence of toxic substances were evaluated.

(1) physical properties

Purified wood vinegar was tested by the method according to the standard and quality Article 9 quality standards and quality test standards of the National Forest Research Institute Notice 2004-04 (2004.6.22), the results are shown in Table 1 below.

TABLE 1

Bome weight (g / ml) Acid amount (%)  pH Melt Tar (%) Refractive Index (% Brix) color 0.8 3.7 2.5 0.01 2.6 Transparent pale yellow

(2) Contains toxic substance

The content of toxic substances in the wood vinegar purified by GC-ECD method was measured (Korea Testing and Research Institute). As a result, α-BHC, β-BHC, γ-BHC, δ-BHC, op-DDT, pp-DDT, op-DDD, pp-DDD, op-DDE, pp-DDE, aldrin, Dieldrin and Endrin were not detected.

Example  2

600 g of crude wood vinegar was added to the round flask and 1 g of 83% phosphoric acid was added thereto. Thereafter, a cooling condenser was installed in the flask, and 20 g of 30% hydrogen peroxide solution was slowly added to the crude wood vinegar, and the mixture was heated at 60 ° C. with stirring at 100 rpm to react for 6 hours. Thereafter, the heating was stopped and left for 40 hours to allow the carbonized suspension to aggregate, and then the aggregated carbonized suspension was filtered off.

Charcoal powder 2g was added to the wood vinegar from which the carbonized suspension was removed, and the mixture was left at room temperature for 24 hours, followed by filtration under reduced pressure at 9.0 mbar to remove charcoal powder. After filtration, the mixture was heated and distilled at 90-120 ° C. for about 4 hours to obtain 390 g (yield 63%) of purified wood vinegar.

Antimicrobial properties, physical properties and the presence of harmful substances of the obtained wood vinegar was measured by the following method.

(1) antibacterial

Antimicrobial activity was determined by the Halo Test according to KS K 0692.

That is, in the antimicrobial test, spore suspension was prepared from Trichophyton rubrum bacteria stored in Sabouraud Dextrose Agar, and then rod culture of 200 µl of spore suspension was carried out, and a sterile disc was placed in the center of the medium. 50 μl of purified wooden vinegar and 50 μl of 70% ethanol as a control sample were dropped, and then cultured at 24-26 ° C. for 7 days, and then the diameter of the inhibition zone was measured. Evaluated. The photograph showing the restraint band when using the purified wood vinegar in the present Example is shown in FIG. 1A, and the photograph showing the restraint band formed when ethanol is used is shown in FIG. As can be seen in Figure 1a, in the case of purified wood vinegar in the present embodiment, a wide antibacterial inhibitory band is formed from the center, while the alcohol is used in Figure 1b almost no antimicrobial inhibitors are formed, from which the excellent antimicrobial activity Able to know.

(2) Physical properties and content of harmful substances

The acidity and solid content of wood vinegar were tested in accordance with the National Forest Research Institute Notice 2004-04 Specification and Quality Article 9 Quality Standards and Quality Test Criteria. Other harmful substances content was determined in accordance with the Korean Food Additives Code. The test was conducted by the Environmental Testing Institute, and the results are shown in Table 2 below.

TABLE 2

Test Items Test result Acidity (%) 2.9 Solid content (%) 0.03 Lead (mg / kg) Not detected Cadmium (mg / kg) Not detected Iron (mg / kg) Not detected Tar color Not detected Methyl alcohol (mg / kg) 743 Phenolic (%) Not detected Salicylic Acid (mg / kg) Not detected

Example  3

500 g of crude wood vinegar was added to the round flask and 2 g of 83% phosphoric acid was added thereto.

Thereafter, a cooling condenser was installed in the flask, and 15 g of 30% hydrogen peroxide solution was slowly added to the crude wood vinegar and heated to 30 ° C. while stirring at 100 rpm to react for 10 hours. Thereafter, the heating was stopped and left for 35 hours to allow the carbonized suspension to aggregate, and then the aggregated carbonized suspension was filtered off.

5 g of activated carbon powder was added to the wood vinegar from which the carbonized suspension was removed, and the activated carbon powder was removed by filtration under reduced pressure at 9.0 mbar for 25 hours. After filtration, heat distillation was performed at 90-120 ° C. for about 3 hours to obtain 300 g of purified wood vinegar (60% yield).

After the first distillation, the dried mugwort powder was added to the distillate in an amount of 2% by weight, and the second distillation was performed at 80 ° C. for 4 hours. The pH of the second distilled distillate was adjusted to 3 to 3.5 using sodium acetate or zinc sulfate to obtain 240 g of purified wood vinegar (80% yield).

1) Toxicity test of single oral administration in rats

Toxicological tests of single oral administration were performed on rats using the wood vinegar obtained in Example 3. The test was conducted by the Institute for Safety Evaluation, affiliated with the Korea Research Institute of Chemical Technology, and the test method was conducted in accordance with Korean Food and Drug Administration Notification No. 1999-61, 'Toxicity Test Standards for Drugs.'

In order to investigate the toxicity of acute oral administration of test substance, mortality, general symptoms, weight change and autopsy findings were observed for 15 days after single oral administration of 5 male and female doses of 0 and 20 ml / kg to SD male rats. . The test results are as follows.

A) No dead animals were observed in males, but only one in 20ml / kg female group.

B) In general symptoms, ptosis was observed in 20ml / kg group of male animals, spontaneous exercise deterioration, ptosis and flow in female 20ml / kg group.

C) In the case of body weight change, no change due to the test substance was observed in all the male and female test groups.

Autopsy Results Gross necropsy findings due to the test substance were not observed in all test groups.

2) Toxicity test of single transdermal administration using rats

Toxicological tests of single transdermal administration were performed on rats using the wood vinegar obtained in Example 3. The test was conducted by the Institute for Safety Evaluation, affiliated with the Korea Research Institute of Chemical Technology, and the test method was conducted in accordance with Korean Food and Drug Administration Notification No. 1999-61, 'Toxicity Test Standards for Drugs.'

In order to investigate the acute dermal toxicity of the test substance, 15 days of mortality, general symptoms, weight change and necropsy were observed after single transdermal administration with 5 male and female doses of 0 and 2,000 mg / kg in 5 male and female rats. The test results are as follows.

A) Death animals were not observed in all male and female test groups.

B) In the general symptom, flow was observed in the male and female 2,000 mg / kg group.

C) In the case of body weight change, no change due to the test substance was observed in all the male and female test groups.

Autopsy Results Gross necropsy findings due to the test substance were not observed in all test groups.

3) Skin irritation test using rabbit

Skin irritation test was performed on rabbits using the wood vinegar obtained in Example 3. The test was conducted by the Institute for Safety Evaluation, affiliated with the Korea Research Institute of Chemical Technology, and the test method was conducted in accordance with Korean Food and Drug Administration Notification No. 1999-61, 'Toxicity Test Standards for Drugs.'

To investigate the skin irritation of the test substance in New Zealand White male rabbits, the test substance was applied to the abrasion and non-abrasion areas for 24 hours, and then mortality, general symptoms, weight change and local irritation up to 72 hours were evaluated. It was. The results of the test are summarized as follows.

A) No dead animals due to test substance application were observed during the test period.

B) As a result of general symptoms, abnormal findings due to the application of the test substance were not observed.

C) As a result of weight measurement, no weight change due to application of the test substance was observed.

D) As a result of observing the local irritation of the abrasion and non-abrasive areas after finishing the application of the test substance, no abnormal findings were observed by applying the test substance. Therefore, the primary irritation index of this test substance was '0' and was evaluated as non-irritant.

From the above results, it was determined that the skin application of the wood vinegar obtained in Example 3 in New Zealand White rabbits did not cause any irritation to the abrasion and non-abrasive areas. Therefore, the wood vinegar obtained in Example 3 is considered to be a non-irritating substance.

4) Eye irritation test using rabbit

The ocular mucosa stimulation test was performed on rabbits using the wood vinegar obtained in Example 3. The test was conducted by the Institute for Safety Evaluation, affiliated with the Korea Research Institute of Chemical Technology, and the test method was conducted in accordance with Korean Food and Drug Administration Notification No. 1999-61, 'Toxicity Test Standards for Drugs.'

In order to investigate ocular irritation of the test substance in New Zealand White male rabbits, the mortality, general symptoms, weight change and local irritation were evaluated for 7 days after treatment with 0.1 ml of test substance. The test results are summarized as follows.

A) No dead animals due to test substance application were observed during the test period.

B) As a result of general symptoms, abnormal findings due to the application of the test substance were not observed.

C) As a result of weight measurement, no weight change due to application of the test substance was observed.

D) As a result of local irritation, conjunctival abnormalities were observed up to 4 days after application, but no abnormalities were observed in cornea and iris. Therefore, the acute ocular irritation index of the test substance was evaluated as '4.0' in the non-eye group and '6.0' in the eye group.

In conclusion, ophthalmic mucosa application of the wood vinegar obtained in Example 3 in New Zealand White male rabbits causes mild abnormalities in the conjunctiva but does not show any abnormalities in corneas and irises. The wood vinegar obtained in Example 3 is determined to be a mild-irritant.

5) Skin sensitization test using guinea pig

Skin sensitization tests were performed on guinea pigs using the wood vinegar obtained in Example 3. The test was conducted by the Institute for Safety Evaluation, affiliated with the Korea Research Institute of Chemical Technology, and the test method was conducted in accordance with Korean Food and Drug Administration Notification No. 1999-61, 'Toxicity Test Standards for Drugs.'

In order to investigate skin sensitization, T1 group (test substance sensitization group, 10 animals), V1 group (5 sensitizers for excipients for test substance, 5), T2 group (positive control) using 30 Hartley male guinea pigs Guinea pig maximization tests were performed, consisting of four groups: substance sensitization group (10) and V2 group (sensitization of excipients for positive control, 5). Two sensitizations (first sensitization: intradermal administration, second sensitization: closed patch) were performed on the back of the animal at 1 week intervals, and the test substance was caused on the flanks of the flanks 2 weeks after the second sensitization. The skin reaction was observed.

Throughout the observation period, no general symptoms or body weight changes presumed to be due to administration of the test substance were observed. At 48 hours, erythema and edema of the test substance applied were 0.0% and the sensitization rate was 0%, which was significantly lower than that of the positive control skin and 1.6 and 100% sensitization rate, and the excipient control group (mean skin response: 0.0, A very weak skin sensitization was observed, with the same percentage of sensitization. Similarly, the 72-hour observation showed that the average skin response was 0.3 and the sensitization rate was 30%.

As a result, it is judged that the skin sensitization of wood vinegar obtained in Example 3 in Hartley guinea pig is very weak (grade 1).

In the crude wood liquor purification method of the present invention using a phosphate catalyst, the carbonized suspension and the coal in the crude wood vinegar are effectively removed in a short time, so that high purity, for example, high purity wood vinegar of 99% or more is obtained. In addition, the wood vinegar purified by the method of the present invention is excellent in bactericidal activity and does not contain harmful substances, there is no toxicity, and odor is removed, it is expected to be utilized in various methods and fields.

Claims (16)

Oxidizing the crude wood vinegar and hydrogen peroxide solution in the presence of phosphoric acid at 30-70 ° C. for 8-12 hours; After the oxidation reaction, leaving for 36 to 40 hours to remove the aggregates formed when left; And Distilling at 90-120 ° C. for 3.5-4.5 hours; Purifying crude wood vinegar characterized in that it comprises a. After the distillation step, the dried mugwort powder is added to the distillate in an amount of 1 to 3% by weight and flavored at 70 to 90 ° C. for 3.5 to 4.5 hours, and then at 90 to 120 ° C. for 3.5 to 4.5 hours. During the purification method of crude wood vinegar further comprising the step of distilling further. The method according to claim 1 or 2, wherein after removing the aggregates, the method of purifying crude wood vinegar comprises adding an adsorbent to further remove and remove impurities and then filtering and removing the adsorbent. The method of claim 3, wherein the adsorbent is selected from at least one of charcoal and activated carbon. The method of claim 3, wherein the adsorbent is added and left for 20-30 hours. The method of claim 1, wherein the distillation is performed at 90-120 ° C. for 3.5-4.5 hours until the yield reaches 60%. The process according to claim 2, wherein further distillation is carried out until the yield reaches 80%. The method of claim 2, further comprising adjusting the pH of the distilled distillate to 3 ~ 3.5. The method of claim 8, wherein the pH of the distilled further distillate is less than 3, the method of producing wood vinegar, characterized in that the pH is adjusted by the addition of sodium acetate. The method according to claim 8, wherein the pH of the distilled distillate further exceeds 3.5 to adjust the pH by adding zinc sulfate. Wood vinegar purified by the purification method of claim 1. A tablet characterized in that it comprises 2 to 4% by weight of acetic acid, 0.05 to 0.15% by weight of formic acid, 0.05 to 0.15% by weight of propionic acid, 1-3% by weight of mugwort components, 0.01-1% by weight of sodium acetate and the remaining amount of purified water Wood vinegar. A tablet characterized in that it comprises 2 to 4% by weight of acetic acid, 0.05 to 0.15% by weight of formic acid, 0.05 to 0.15% by weight of propionic acid, 1-3% by weight of wormwood components, 0.01-1% by weight of zinc sulfate and the remaining amount of purified water Wood vinegar. Food containing 1-5% by weight of the wood vinegar according to any one of claims 11 to 13. Cosmetics containing 1-5% by weight of the wood vinegar according to any one of claims 11 to 13. A beverage containing 1-5% by weight of the wood vinegar according to any one of claims 11 to 13.

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