KR100620968B1 - Purification of pyroligneous liquid - Google Patents

Abstract

A method for purifying a vinegar solution capable of purifying a vinegar solution of high purity is disclosed. In the method for purifying a vinegar solution according to the present invention, the crude vinegar solution is distilled under reduced pressure three times, and the distilled and purified vinegar solution is purified using a column packed with "AB-8 resin ". Here, in the first vacuum distillation, volatile components are removed. In the second vacuum distillation, the polymer substance having low volatility and the pigment component are removed. In the third vacuum distillation, the polymer substance is removed again. In column refining, most odor components are removed and only high quality wood vinegar is extracted. The purified wood vinegar can be used as a raw material for cosmetics and deodorizing products, and can be used as an additive in cosmetics or other products or added to foods to enhance the merchantability of the products.

Description

Purification of pyroligneous liquid [

Fig. 1 is a graph showing odor components of a pomegranate seed solution,

2 is a graph showing odor components of a distilled and purified wood vinegar solution, and

FIG. 3 is a graph showing odor components of column refined vinegar.

The present invention relates to a method for purifying a vinegar solution capable of purifying a high-purity woodpecker.

Generally, wood vinegar which is made by collecting smoke generated when carbonizing trees such as oak trees is a harmless ingredient and has various effects that can be used for growing, livestocking, and deodorizing of crops. Recently, the use of vinegar for drinking water and medicines It is used as an additive material, and the utilization thereof is gradually increasing.

When the wood is carbonized at a predetermined temperature by injecting the wood into a specific container, smoke is generated from the wood. When the smoke is discharged from the ship, the liquid wood vinegar is obtained. In addition, the apparatus for producing such wood vinegar has been developed in various ways as the use of wood vinegar is increased, and numerous apparatuses for higher production efficiency have been devised.

The above-mentioned collected wood vinegar is usually called wood vinegar. Since the wood vinegar contains a lot of impurities, it can not be used directly. It is put into a certain container and aged at room temperature for 6 months to 1 year. .

Such wood vinegar is being made in various fields in Korea and Japan. In the field of agriculture, it is used for the purpose of preventing the insect pests and the growth of plants by spraying charcoal and wood vinegar for the cultivation of fruit trees and vegetables, and also for the purpose of disinfecting the seeds and increasing the germination rate. In the livestock industry, they are mixed with feed to prevent diseases and control metabolism of livestock. In the field of environment, they are used to remove sulfur dioxide generated in steelworks and automobiles.

In addition, wood vinegar has been used in a wide range of fields, and in the food industry, it is currently mostly not used as a smoke liquid. In other words, in the manufacture of ham, bacon and sausage which generally perform fumigation, smoke is added so as to replace the effect of smoke, but even in this case, due to the dark brown color of smoke, It is used only for low-end products because it has defects that are bad.

The wood vinegar has antimicrobial properties, moisturizing properties, properties as a solvent for other functional materials, and is safer than conventional artificial synthetic preservatives. Therefore, it can be used in foods to replace artificial synthetic additives. In addition, the use of natural substances in the solvent of food additives also has a great advantage. It is expected that the effect of increasing the absorbency of the solute, which has already been found, is expected to be widely used in the food industry. However, This is because the specific charring and color do not match the palatability of the food, and it also contains harmful substances such as tar components. To date, there has not been developed a method for extracting an active ingredient while separately separating harmful components, colors and odors in purifying a vinegar solution.

SUMMARY OF THE INVENTION The present invention has been conceived to solve the above-mentioned problems, and an object of the present invention is to provide a process for purifying a harmful component contained in a wood vinegar by purifying a column, It can be widely used for various food. In the food industry, since the active ingredient of this wood vinegar can be used as an inexpensive natural additive, it can be used as a substitute for a conventional low-grade smoke solution, artificial synthetic preservative, And a method for purifying the vinegar.

According to an aspect of the present invention,

There is provided a method for purifying a wood vinegar which is purified by distillation three times at a reduced pressure of a crude vinegar solution and purified by using a column packed with distilled and purified vinegar solution "AB-8 resin ".

At this time, in the distillation purification method,

A first vacuum distillation step of distillation under reduced pressure at a temperature of 60 ± 1 ° C to remove 5 ± 11% of distillate;

A second vacuum distillation step of distilling the concentrated liquid in the first vacuum distillation step at a temperature of 50 ± 1 ° C to remove 2 ± 1% of the concentrated liquid;

And a third vacuum distillation stage in which the distillate in the second vacuum distillation stage is distilled at a temperature of 40 ± 1 ° C to remove 2 ± 1% of the concentrate.

Hereinafter, a method for purifying vinegar according to a preferred embodiment of the present invention will be described.

The present invention largely accomplishes a primary distillation purification method and a secondary column purification method can be carried out to obtain a high quality wood vinegar solution.

First, the primary distillation purification method employs a three-stage distillation column distillation method.

<Experimental Method>

In the first vacuum distillation method, 500 ml of the vinegar solution is put into a 2000 ml concentrated flask and distilled under reduced pressure at a temperature of 60 ± 1 ° C to remove 5 ± 1% of the distillate. Preferably, the removed distillate is about 25-50 ml, about 4.8%. In such a first vacuum distillation, volatile components such as harmful methanol are included in the distillate, so that they can be removed.

Next, in the second vacuum distillation method, the remaining concentrate from which the distillate has been removed in the first vacuum distillation is distilled under reduced pressure at a temperature of 50 ± 1 ° C to remove 2 ± 1% of the concentrate. Preferably the removed concentrate is 10-15 ml, which is about 2.1%. In such a second vacuum distillation, the pigment materials and the low-volatility polymer substances are contained in the concentrate, so they can be removed.

Next, in the third vacuum distillation method, the distillate obtained in the second vacuum distillation can be distilled at a temperature of 40 ± 1 ° C to remove 2 ± 1% of the concentrate to obtain only a high-quality distillate. Preferably, the removed concentrate is about 5-10 ml, about 1.4%. In the third vacuum distillation, the concentrate containing the remaining polymer substances was removed.

The distillation or concentrate of 10 to 16% is removed by the third-stage decompression distillation, and the vinegar of about 84 to 90% (420 to 460 ml) can be purified and recovered.

From this experiment, it was found through experiments that most of the pigment components were removed by vacuum distillation purification three times. That is, as a result of measurement by a "Spectrophotometer" at 540 nm, the crude stock before purification was 0.436, and the distillate obtained in the third vacuum distillation was 0.004. Therefore, 99.1% of pigments were removed from the vinegar after purification.

Next, column purification was carried out by filling the column with "AB-8 Resin (Alkyl Benzene Polymer)" and distilling the purified wood vinegar through the column.

<Experimental Method>

A column of 2.2 x 15 cm is filled with AB-8 Resin, and 100 ml of distilled and purified wood vinegar is continuously flowed at a flow rate of 192 ml / hr until the volume becomes 200 ml of purified water. Then, 120 ml was further added to measure chromaticity and pH. The "AB-8 Resin" used here is a new material not known in Korea. It was developed at the chemistry window of Nanmen University in Tianjin, China.

<Table-1>

division Chromaticity pH PH of stock solution 420 nm 540 nm Vinegar solution 2 times diluted solution 1.030 0.216 3.13 2.97 Concentrated diluted solution 2 times diluted solution 0.003 0.001 2.59 2.30 Column through-liquid (200ml) -0.003 -0.001 2.59 2.34 The column passed solution (120ml) -0.003 -0.001 3.89

As shown in Table 1, the chromaticity of the vinegared stock solution was 1.030, and the fraction purified by the concentration method was 0.003, and about 99.7% of the pigment was removed.

The pH of the two-fold dilution of the vinegar solution was 3.13 (the pH value of the undiluted solution was 2.97). On the other hand, the pH of the two-fold dilution of the fraction purified by the concentration method and the column passing fraction was decreased to 2.59 It can be seen that the basic substance contained in the vinegar solution was largely removed by the concentration method or the column purification method.

On the other hand, in order to determine the odor component of the crude extract before the purification, the odor component of the concentrated vinegar liquid and the odor component after the column refinement, it was examined by GC / MS. In order to investigate the content of the carbon odor contained in the vinegar liquid, the vinegar liquid purified by the vinegar solution, the concentration (distillation) method and the column purification method was taken and analyzed by SPME (Fiber: Caroxen-Polydimethylsiloane Volatile materials were collected and analyzed by GC / MS (6890GC / 5973MSD, Agilent, USA). GC / MS analysis conditions and SPME treatment method are as follows.

I) GC / MS analysis conditions

- Column: lnnowax 60m × 25mm

- Oven temp. : 50 占 폚 (2 minutes) ==> 3 占 폚 / minute ==> 230 占 폚 (20 minutes)

- Injector temp. : 230 ° C

- Interface temp. : 250 ° C

- Ion voltage: 70eV

- Injector type: splitless

Ii) SPEM treatment conditions

- Sample: Take 2g of vinegar sample in 20ml vial

- Extraction for 20 minutes with SPEM at 35 ° C and 2 minutes with GC

The volatile fraction GC pattern of the vinegene stock solution according to the experimental result, the concentrated vinegar solution and the purified vinegar solution concentrated (distilled) were as shown in Table 2, Table 3 and Table 4, respectively, Respectively.

<Table-2>

number Retentiontime (min) ratio(%) ingredient One 6.05 7.742 메틸 acetate 2 6.95 0.618 ethyl acetate 3 7.28 1.891 methyl propionate 4 9.26 1.227 methyl butyrate 5 11.21 1.077 toluene 6 12.98 0.283 메틸 pentanoate 7 18.07 0.408 cyclopentanone 8 21.04 0.067 Furfuryl methyl ether 9 24.92 0.308 acetol 10 28.27 1.268 2-cyclopentene-1-one 11 28.99 1.046 2-methyl-2-cyclopentene-1-one 12 29.40 0.413 1-hydroxy-2-butanone 13 33.82 30.181 acetic acid 14 35.14 15.641 furfural 15 36.75 0.250 2,3,4-trimethyl-2-cyclopentene-1-one 16 37.54 1.834 2-acetyl furan 17 38.20 0.678 3-methyl-2-cyclopentene-1-one 18 39.49 3.764 propanoic acid 19 41.65 2.380 5-methyl furfural 20 41.91 0.671 furancarboxylic acid, methyl ester 21 44.43 0.211 methyl benzoate 22 44.80 1.239 butanoic acid 23 45.07 1.024 butyrolactone 24 46.61 0.083 퓨르 플릴 알cohol 25 50.07 0.088 3-methyl-2- (5H) -furanone &lt; / RTI &gt;

26 51.00 0.200 valeric acid 27 53.13 0.769 methyl salicylate 28 54.67 0.070 2,3-dimethoxy toluene 29 55.82 0.552 cyclotene 30 56.77 0.103 hexanoic acid 31 57.66 5.685 2-methoxy phenol (= guaiacol) 32 58.18 0.210 2-methoxy-3-methylphenol 33 59.23 0.129 3-ethyl-2-hydroxy-2-cyclopentene-1-one 34 60.20 0.106 2,6-dimethylphenol 35 61.84 0.176 2-methoxy-5-methylphenol 36 62.56 1.729 2-methoxy-4-methylphenol 37 64.96 0.797 2-methylphenol 38 65.12 2.162 phenol 39 66.19 0.809 4-ethyl-2-methoxyphenol 40 68.22 0.081 2-ethylphenol 41 68.52 0.150 2,5-dimethylphenol 42 68.79 0.502 4-methylphenol 43 69.17 0.585 3-methylphenol 44 69.95 0.130 2-methoxy-4-propyl-phenol 45 71.88 0.082 2,4-dimethylphenol 46 73.45 0.083 3-ethylphenol 47 75.24 0.099 3,4-dimethylphenol 48 77.16 0.469 2,6-dimethoxyphenol 49 84.96 0.404 benzoic acid system 90.474

<Table 3>

number Retentiontime (min) ratio(%) ingredient One 6.09 0.327 메틸 acetate 2 18.10 0.167 cyclopentenone 3 24.93 0.308 acetol 4 28.29 1.645 2-cyclopenten-1-one 5 29.00 1.032 2-methyl-2-cyclopenten-1-one 6 29.41 0.280 1-hydroxy-2-butanone 7 33.79 47.255 acetic acid 8 35.12 12.774 furfural 9 36.75 0.152 2,3,4-trimethyl-2-cyclopenten-1-one 10 37.54 2.149 2-acetyl furan 11 38.20 0.444 3-methyl-2-cyclopenten-1-one 12 39.50 4.880 propanoic acid 13 41.65 2.491 5-methyl furfural 14 44.44 0.106 methyl benzoate 15 44.80 1.482 butanoic acid 16 51.00 0.205 valeric acid 17 53.13 0.773 methyl salicylate 18 54.67 0.088 2,3-dimethoxy toluene 19 56.77 0.080 hexanoic acid 20 57.65 6.499 2-methoxyphenol 21 58.17 0.176 2-methoxy-3-methylphenol 22 60.20 0.094 2,6-dimethylphenol 23 61.85 0.216 2-methoxy-5-methylphenol 24 62.64 2.163 2-methoxy-4-methylphenol 25 65.06 0.882 2-methylphenol 26 65.22 1.873 phenol 27 66.29 0.873 4-ethyl-2-methoxyphenol

28 68.29 0.091 2-ethylphenol 29 68.60 0.166 2,5-dimethylphenol 30 68.78 0.178 4-methylphenol 31 69.24 0.478 3-methylphenol 32 70.02 0.165 2-methoxy-4-propyl phenol 33 71.94 0.086 2,4-dimethylphenol 34 73.50 0.075 3-ethylphenol 35 77.21 0.256 2,6-dimethoxyphenol 36 84.99 0.333 benzoic acid system 89.654

<Table-4>

number Retentiontime (min) ratio(%) ingredient One 6.06 1.012 메틸 acetate 2 24.91 0.539 acetol 3 28.27 0.684 2-cyclopenten-1-one 4 29.40 0.536 1-hydroxy-2-butanone 5 33.71 82.070 acetic acid 6 39.50 5.645 propanoic acid 7 44.83 0.121 butanoic acid 8 84.96 0.592 benzoic acid system 91.199

As shown in Table 2, Table 3, and Table 4 above, 49 kinds of volatile substances were identified in the pasture solution before distillation purification, and 36 kinds in the pasture solution after distillation purification, and only 8 in the pasture solution after column refining Only species volatiles were identified.

The distillation purification method is to remove ethyl acetate, methyl propionate, methyl butyrate, toluene, methyl pantanoate, furancarboxylic acid methyl ester, butyrolacone, furfuryl alcohol, cyclotene, 3-methyl-2 2-cyclopentene-1-one and 3,4-dimethyl phenol. The amounts of the major components removed by the distillation purification method were 96% for methyl acetate, 18% for furfuraldl, 64.5% for 4-methyl phenol % And acetic acid was increased proportionally and its content was increased by 65%. In addition, in the purification by column method, only eight volatile components were identified, among which acetic acid accounts for about 82% of the remarkable purification effect.

Furfural, which has a considerable content of about 20% of the total amount of the plant extracts, is a coloring and toxic substance which causes physiological changes in the liver and kidneys of mammals, delays growth, It is known as a mutagenic substance for microorganisms. Experiments have shown that these furfural are all removed by distillation and column purification.

<Example of application of wood vinegar>

There is a saying that "a person who burns charcoal does not have athlete's foot." The feet of those who wear shoes that wash their feet poorly and tightly tighten are no better to grow bamboo buds, but contact with charcoal smoke was the secret of having no athlete's foot. There is also a saying that ancient Annakes lived in the fireplace because they did not have gynecological diseases, and they could preserve them for a long time if they smoked food using smoke. In civilian medicine, it is said to be effective against swine, snake or burn, and it is said to be effective for hangover, athlete's foot, atopic dermatitis. When applying such wood vinegar to daily life, it can be used as follows.

1. Use of Agriculture

If you sprinkle the seedlings in a field, you can sterilize the soil and spray it diligently to multiply the microorganisms in the soil, and the crops will grow well. Wood vinegar can be a great help in restoring the intellectual power because it can reduce the pesticide and reduce the chemical fertilizer in farmland where the intellect is completely degraded due to the mass use of pesticide and chemical fertilizer. Wood vinegar is not a fertilizer nor a pesticide, but it also helps the root development of crops by regulating the environment in the soil. It also helps microbial activity and consequently increases fertilizer's efficacy. It is widely available.

2. Use of animal husbandry

When mixed with the feed of livestock, the role of the liver and the organs is smooth and the blood is cleaned. Therefore, the meat taste is good. Also, when the diarrhea is done, there is a therapeutic effect.

3. Use of aquaculture

If you feed charcoal powder and wood vinegar to appropriate amount of feed in aquaculture such as defense, eel, shrimp, etc., the intestinal function will be improved, and it will prevent diseases and exterminate bad odor of secretion.

4. Role to eliminate odor (deodorization)

The smell removal effect is great if the vinegar is sprayed or sprayed on the toilet, the kitchen, the silk stand, the entrance shoe box, the drainage tank, the bathroom, the trash can, the animal house, the garbage collection place, the landfill, The charcoal removes the smell by the physical action of the adsorption power, but the vinegar liquid is the neutralization or the chemical action called the masking (the masking effect) to remove the smell.

5. Use as a repellent for insects or small animals

The wood vinegar obtained from the charcoal-burning smoke has a unique smell, which can be used as a repellent because it dislikes the smell of a sting, a mole, a sine or a snake.

6. Medical use

Liver disease, diabetes, athlete's foot, dermatitis, and many other diseases are effective.

7. Dye

Mix with iron powder and use dyes. It has been used for a long time in the coloring of the abacus (Jusan).

As described above, according to the method for purifying vinegar according to the present invention, it is possible to remove unnecessary components such as carbohydrate, tar phenol and alcohol without destroying the structure of the main functional ingredient from the vinegar. It is expected that it can be used as an additive to cosmetics or other products by providing it as a raw material of deodorant product or by adding it to food, thereby enhancing the merchantability of the product.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit or scope of the invention as defined by the appended claims. .

Claims (2)

Wherein the crude vinegar solution is distilled under reduced pressure three times, and the distillation purified vinegar solution is purified using a column packed with "AB-8 resin ". The method according to claim 1, I) a step (S1) of distillation under reduced pressure at a temperature of 60 ± 1 ° C to remove 5 ± 1% of distillate; Ii) a step S2) of removing the concentrate of 2 + 1% by distillation under reduced pressure at a temperature of 50 + 1 [deg.] C; Iii) distilling the distillate of step (S2) at a temperature of 40 ± 1 ° C to remove 2 ± 1% of the concentrate (S3).

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