KR101333430B1 - Method for manufacturing high quality pyroligneous liquid using ozone gas - Google Patents

Abstract

The present invention is for the effective deodorization and color control of crude wood vinegar, and more specifically comprising the step of reacting by injecting ozone 1,000 ~ 25,000ppm concentration for 5 to 20 hours to crude wood vinegar at a temperature of 10 ~ 40 ℃ It relates to a method for producing a high quality wood vinegar. The present invention can produce a high-quality wood vinegar by effectively removing the smell and color peculiar to crude wood vinegar in a shorter time in a simpler process than the prior art.

Description

Method for manufacturing high quality vinegar solution using ozone gas {Method for manufacturing high quality pyroligneous liquid using ozone gas}

The present invention relates to a method for producing wood vinegar, and more particularly, to a method for producing a high quality wood vinegar that can be deodorized and color control of the crude wood vinegar by treating the crude wood vinegar with ozone under specific conditions.

Wood vinegar is a substance produced by liquefying the gaseous components emitted when dry wood pyrolysis of various trees. The components of wood vinegar differ depending on the dry distillation method, the type of raw material, and the type of pyrolysis device. 80-90% of wood vinegar is water and the remaining 10-20% is organic compound and contains 200 kinds of various components such as organic acids, phenols, carbonyl compounds, alcohols, neutral and basic fractions. Organic acids in wood vinegar are the components that directly affect pH, and phenols are the main cause of the irritating odor of wood vinegar, mainly due to the thermal decomposition of cellulose, a component of wood.

Wood vinegar is used for various purposes such as natural pesticides, food preservatives, environmental pollution treatment and pharmaceutical raw materials, food and beverage, and is known to be effective in athlete's foot and atopic dermatitis. In addition, the wood vinegar contains a large amount of useful ingredients for the skin, such as antioxidants, antibacterial ingredients, promoting blood circulation, which is very likely as a cosmetic and pharmaceutical material. However, in order to utilize these wood vinegar, it is necessary to remove the irritating smell of wood vinegar.

As a conventional patent related to wood vinegar purification, in the case of the vinegar distillation method and apparatus (Korea Patent No. 10-0458503), ozone is added during the distillation of wood vinegar, and the wood vinegar is filtered through a filter of activated carbon and diatomaceous earth. By going through the third step, by removing impurities and harmful components in the purified wood vinegar, there is proposed a method for producing wood vinegar that consumers can safely drink as a medicine or functional health food. However, this is a method for preparing a beverage vinegar solution is a process that is repeated three times, such as filtration, distillation and oxidation treatment has the disadvantage of excessive processing cost and complicated process.

In another related patent, 'The method for preparing purified wood vinegar powder and refined wood vinegar powder (Korea Patent Publication No. 10-2003-0012575)' is used in a powdered activated carbon using 3 to 5% by weight relative to the total wood vinegar weight and 30 to 30 After stirring for 60 minutes, and filtered to add the excipient to the purified wood vinegar to remove the coal and provides a method for producing a wood vinegar powder by spray-drying and the wood vinegar powder prepared accordingly. However, this manufacturing method has a disadvantage in that the process is complicated because the addition of powdered activated carbon requires adsorption and removal of impurities for a certain period of time, followed by a filtration process.

In another patent, the method of purifying crude wood vinegar and thus purified wood vinegar (Korean Patent No. 10-0718235) relates to a method of purifying crude wood vinegar using a catalyst and thus purified high-purity wood vinegar More specifically, the crude wood liquor and hydrogen peroxide are oxidized in the presence of catalyst phosphoric acid at 30 to 70 ° C. for about 8 to 12 hours, then left for about 36 to 40 hours, and after removing the formed aggregates, about 90 to 120 It relates to a method of purifying wood vinegar by distillation at 3.5 ℃ for 4.5 hours and adsorption treatment with activated carbon. However, this method also has a disadvantage that the process is complicated and time-consuming because it includes a filtration process of powdered activated carbon.

Therefore, the inventors of the present invention, while studying a method for producing wood vinegar in a simple process in a short time to establish a unique crude wood vinegar warming conditions and ozone reaction conditions, to remove the smell and color peculiar to the crude wood vinegar to obtain a high quality wood vinegar A method of preparing high quality wood vinegar was completed.

It is therefore an object of the present invention to provide an optimized wood vinegar preparation method using ozone for producing high quality wood vinegar.

In order to achieve the above object, the present invention provides a method for producing a high-quality wood vinegar comprising the step of reacting by injecting ozone at a concentration of 1,000 ~ 25,000ppm for 5-20 hours at a temperature of 10 ~ 40 ℃.

In one embodiment of the present invention, the temperature may be 20 ~ 40 ℃.

In one embodiment of the present invention, the ozone concentration may be 10,000 ~ 25,000ppm.

In one embodiment of the present invention, the ozone injection time may be 6 ~ 12 hours.

In one embodiment of the present invention, it may further comprise the step of measuring the UV absorbance at 390nm for the reaction product wood vinegar.

In addition, the present invention provides a wood vinegar deodorization and color control method comprising the step of reacting by injecting ozone at a concentration of 1,000 ~ 25,000ppm for 5 to 20 hours to crude wood vinegar at a temperature of 10 ~ 40 ℃.

According to the present invention, it is possible to efficiently deodorize and adjust the color of the crude wood salt simply by injecting a certain concentration of ozone into the crude wood salt under the specific conditions. In particular, there is an advantage that the phenols, which are the cause of odor unique to wood vinegar, can be removed by a simple process compared to the prior art. Therefore, the method for preparing wood vinegar according to the present invention has an effect that a high-quality wood vinegar can be produced by removing the smell and color peculiar to crude wood vinegar in a shorter time than a conventional process.

Figure 1 shows the change in absorbance of the sample over time for each reaction temperature.
Figure 2 shows the change in absorbance of the sample over time for each injected ozone concentration.

The present invention relates to a high-quality wood vinegar preparation method comprising the step of reacting by heating the crude wood vinegar at a temperature of 10 ~ 40 ℃, injecting ozone at a concentration of 1,000 ~ 25,000ppm for 5 to 20 hours.

The crude wood vinegar as a starting material of the present invention is a material obtained by cooling the smoke generated during the carbonization process of wood, and includes coal and harmful substances due to carbonization. In particular, phenols contained in crude wood vinegar is the main cause of the odor peculiar to wood vinegar, the production method of the present invention can remove various harmful substances including phenols.

In the production method of the present invention, the temperature can be kept constant by using a device such as a constant temperature water bath. The temperature is 10 to 40 ° C, preferably 20 to 40 ° C. If the temperature is lower than 10 ℃, ozone should be injected for a long time to remove the harmful substances. If the temperature is higher than 40 ℃, the heating efficiency is inferior because the temperature is similar to the case of 10 ~ 40 ℃. In the present invention, the temperature added to crude wood vinegar is preferably 10 to 40 ° C. However, even at 10 ° C, it is only 10 ° C lower than 20 ° C, but the removal rate of harmful substances is significantly lower at 20-40 ° C with similar activity, so warming crude wood solution at 20-40 ° C is most preferred. (See Figure 1).

In the production method of the present invention, ozone can be easily injected into the crude wood vinegar through a device such as an ozone generator. It is appropriate that the ozone concentration is 1,000 to 25,000 ppm, and 10,000 to 25,000 ppm is most preferable. If the ozone concentration is lower than 1,000 ppm, ozone should be continuously injected for a long time to remove some harmful substances. If the concentration is higher than 25,000 ppm, the concentration is similar to that of 1,000 to 25,000 ppm. Since the efficiency of the dose is extremely low, the concentration of ozone in the present invention is suitable for 1,000 ~ 25,000ppm. However, at 1,000 ppm in fact, as shown in Figure 2, it can be seen that the removal of the harmful substance is not significantly superior dosage. When the 10,000ppm or so is excellent in the removal of harmful substances over time, it is most preferable to inject ozone at a concentration of 10,000 ~ 25,000ppm to crude wood vinegar (see Fig. 2).

In addition, in the production method of the present invention, ozone may be injected into the heated crude wood solution to react for a predetermined time. The reaction time may be adjusted according to the temperature, ozone concentration or the degree of removal of harmful substances, the reaction time in the conditions according to the invention is preferably 5 to 20 hours, most preferably reacted for 6 to 12 hours. Only when the reaction time is 5 hours or more can be expected to remove the main harmful substances present in the crude wood vinegar. On the other hand, when reacting for 20 hours or more, there is almost no change in the effect of removing harmful substances for 20 hours and the effect of removing harmful substances, thus causing unnecessary reaction time, and thus it is impossible to provide an efficient and rapid method of preparing wood vinegar solution. Because it becomes.

More specifically, the production method according to the present invention shows a very effective removal of harmful substances from the reaction time of 6 hours or more, in particular, the optimum crude wood solution heating temperature (20 ~ 40 ℃) and ozone injection concentration ( 10,000 ~ 25,000ppm) Since the reaction time is rarely increased when the reaction time exceeds 12 hours, it is most preferable to react for 6-12 hours (see Figs. 1 and 2), within this numerical range It can be said to have a critical significance.

On the other hand, the manufacturing method of the present invention may further comprise the step of measuring the absorbance at 390nm with respect to the reactant (wood vinegar) to confirm the degree of removal of harmful substances. If the absorbance is 0.5 or less, it can be considered that the harmful substances have been sufficiently removed.

Accordingly, the present invention provides a high-quality wood vinegar is removed from the harmful crude wood vinegar and the ethanol is removed, the chromaticity is adjusted.

In addition, the present invention provides a method for removing harmful substances and carbon in the wood vinegar under unique conditions and a method of controlling color using ozone gas.

The high-quality wood vinegar from which the harmful substances and coals removed by the method of the present invention are removed can be diluted and drinkable, and can be directly applied to skin, etc., and can be used as additives in food, drinks 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, the purified wood vinegar may be added to the food, beverage and cosmetics, such as 5% by weight or less, preferably 1 to 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 with reference to examples. However, these examples are intended to illustrate the present invention in more detail, and the scope of the present invention is not limited to these examples.

< Example  1>

Analysis of the effect of removing harmful substances according to the ozone concentration

<1-1> concentration 10,000 ppm  Of ozone-infused wood liquor UV  Absorbance measurement

A 500 mL gas washing bottle with a bifurcation with a filter disc capable of increasing the contact efficiency of the gas-liquid was used as a reactor, and 300 mL of sample wood vinegar was placed and placed in a constant temperature water bath maintained at a temperature of 20 ° C. Oxygen was released from the cylinder bottle, changed into ozone through the ozone generator, introduced into the reactor, and then discharged after the vinegar and gas-liquid reactions proceeded. In the ozone generator, the ozone concentration was adjusted to 10,000 ppm by changing the voltage. At 10 minutes, 1 hour, 6 hours, 12 hours, and 24 hours after the reaction time, 10 mL of the sample solution was aliquoted to measure absorbance.

Here, the maximum absorbance was shown at the wavelength of 390 nm as a result of analysis at various wavelength changes in order to obtain the optimal UV absorbance for the wood vinegar sample. Therefore, the absorbance of each sample was analyzed at 390 nm.

As a result, as shown in FIG. 1 and FIG. 2, when the reaction temperature was 20 ° C, it was found that the absorbance of the sample liquid dropped to 0.5 or less through ozone treatment for about 12 hours. In addition, GC-mass analysis was performed on the sample, and as a result, it was confirmed that the phenol component was removed through ozone treatment for about 12 hours (see Table 1).

<1-2> concentration 1,000 ppm  Of ozone-infused wood liquor UV  Absorbance measurement

The experiment was conducted in the same manner as in Example 1, but the ozone concentration was adjusted to 1,000 ppm by changing the voltage in the ozone generator. At 10 minutes, 1 hour, 6 hours, 12 hours, and 24 hours after the reaction time, 10 mL of the sample solution was aliquoted to measure absorbance.

As a result, as shown in FIG. 2, when the ozone concentration was 1,000 ppm, it was found that the absorbance of the sample liquid dropped to 0.5 or less through ozone treatment for about 20 hours or more.

<1-3> concentration 25,000 ppm  Of ozone-infused wood liquor UV  Absorbance measurement

The experiment was conducted in the same manner as in Example 1, but the ozone concentration was adjusted to 25,000 ppm by changing the voltage in the ozone generator. At 10 minutes, 1 hour, 6 hours, 12 hours, and 24 hours after the reaction time, 10 mL of the sample solution was aliquoted to measure absorbance.

As a result, as shown in FIG. 2, when the ozone concentration was 25,000 ppm, it was found that the absorbance of the sample liquid dropped to 0.5 or less through ozone treatment for about 5 hours.

< Example  2>

Crude  Analysis of the effect of removing harmful substances by reaction temperature

<2-1> of the wood vinegar prepared at a temperature of 30 ℃ UV  Absorbance measurement

The experiment was carried out under the same conditions as in Example 1, but the reactor was placed in a constant temperature bath maintained at a temperature of 30 ° C to react. At 10 minutes, 1 hour, 6 hours, 12 hours, and 24 hours after the reaction time, 10 mL of the sample solution was aliquoted to measure absorbance.

As a result, as shown in FIG. 1, when the reaction temperature is 30 ° C., the absorbance of the sample liquid drops to 0.5 or less through ozone treatment for about 12 hours.

<2-2> of the wood vinegar prepared at a temperature of 40 ℃ UV  Absorbance measurement

The experiment was carried out in the same manner as in Example 1, but the reactor was placed in a constant temperature bath maintained at a temperature of 40 ℃ to react. At 10 minutes, 1 hour, 6 hours, 12 hours, and 24 hours after the reaction time, 10 mL of the sample solution was aliquoted to measure absorbance.

As a result, when the reaction temperature is 40 ℃ as shown in Figure 1, it can be seen that the absorbance of the sample liquid drops to 0.5 or less through ozone treatment for about 10 hours.

<2-3> of the wood vinegar prepared at a temperature of 10 ℃ UV  Absorbance measurement

The experiment was conducted in the same manner as in Example 1, but the reactor was placed and reacted in a constant temperature bath maintained at a temperature of 10 ° C. At 10 minutes, 1 hour, 6 hours, 12 hours, and 24 hours after the reaction time, 10 mL of the sample solution was aliquoted to measure absorbance.

As a result, as shown in FIG. 1, when the reaction temperature was 10 ° C., it was confirmed that the absorbance of the sample liquid dropped to 0.5 or less through ozone treatment for about 20 hours or more.

Therefore, through the above conclusions, the inventors found that the absorbance was greatly reduced to 0.5 or less by about 12 hours of ozone treatment when the reaction temperature was 20 ° C. or higher, and the absorbance was 0.5 through about 12 hours of ozone treatment when the ozone concentration was 10,000 ppm or more. It confirmed that it fell below.

So far I looked at the center of the preferred embodiment for the present invention. It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims. Therefore, the disclosed embodiments should be considered in an illustrative rather than a restrictive sense. The scope of the present invention is defined by the appended claims rather than by the foregoing description, and all differences within the scope of equivalents thereof should be construed as being included in the present invention.

Claims (5)

Method of producing a high quality wood vinegar comprising injecting ozone at a concentration of 10,000 ~ 25,000ppm to crude wood vinegar at a temperature of 20 ~ 40 ℃ and reacting for 6 to 12 hours. delete delete delete delete

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