KR20030060361A - Purification of pyroligneous liquid - Google Patents

Abstract

PURPOSE: Provided is a purifying method of pyroligneous liquid solution eliminating unnecessary carbonization odor, tar, phenol and alcohol without destroying the major functional components. The purified pyroligneous liquid solution is used as additives in cosmetics and foods for deodorizing purposes. CONSTITUTION: The purification method comprises adding the pyroligneous liquid solution in a supercritical-pressure or subcritical-pressure extractor reactor and flushing with supercritical or subcritical fluid such as carbon dioxide, ethylene, ethane, propane, acetylene, ammonia and methane at 5-100deg.C under 20-500bar.

Description

Purification method of wood vinegar {PURIFICATION OF PYROLIGNEOUS LIQUID}

The present invention relates to a method of purifying wood vinegar, and more specifically, to remove tar and carbonized odor, phenols, alcohols, etc. And to a method for purifying.

When a substance is at a temperature and pressure above its critical point, that is, above its critical point, the state of the substance is called a supercritical fluid, and supercritical fluid extraction is a technique for separating a substance using a supercritical fluid as a solvent. It is called technology.

Extraction and separation technology using supercritical fluid selectively extracts specific substances from mixed components due to the physical properties of the supercritical fluid in the region above the critical point, that is, density changes greatly due to pressure or temperature change, so that extraction efficiency of the solute is increased. And because of the different components, because it is possible to selectively separate substances such as a simple process of small and medium-sized plants (plant) and a small amount of processing, it is widely used in the fields of chemistry, medicine, biochemistry, etc. as a new separation process.

In Korea and Japan, the use of wood vinegar is made in various fields. In the field of agriculture, carbon and wood vinegar are sprayed in the cultivation of fruit trees and vegetables to prevent pests and promote plant growth, and also to disinfect seeds and increase germination rates. In the livestock industry, it is mixed with feed and used for animal disease prevention and metabolism control. In the environmental field, it is used to remove sulfur dioxide from steel mills and automobiles.

In addition, woody liquor is used in a wide range of fields, and most of the food industry is not currently used as a smoking solution. In other words, in the manufacture of ham, bacon, sausage, etc., which smoke generally, the fact that a smoked liquid is added to replace the effect of smoking. In this case, too, the dark brown color of the smoked liquid causes the color of the product to be deteriorated, which is used only for low-end products.

Wood vinegar has the property of antibacterial, moisturizing, and other functional substances as a solvent, and since it is a safer substance than the existing synthetic synthetic preservatives, it can be used in foods to replace artificial synthetic additives, which is expected to have a great effect. In addition, there is a great advantage in using a natural substance in the solvent of food additives, and the effect of increasing the absorbency of the solutes already known is expected to be widely used in the food industry. The reason why it is not used is that the characteristic carbonization and color does not match the palatability of the food, and also contains harmful substances such as tar ingredients. To date, in purifying wood vinegar, a method for extracting an active ingredient while separating harmful components, colors, and odors has not been developed.

Therefore, the present invention develops a special non-thermal treatment method that can solve the above problems and can be widely used in various foods by separating the active ingredient contained in the wood vinegar, such as tar, pigment, odor, etc., in the food industry such wood vinegar Since the active ingredient can be used as a cheap natural additive, it aims to be able to replace the existing low-grade fumes, artificial synthetic preservatives, physical property modifiers and the like.

In the present inventor's research for achieving the above object, when the liquid type wood vinegar is put into a supercritical or subcritical extraction reactor and the pressure, temperature and flow rate of the supercritical or subcritical fluid are adjusted, it is contained in the wood vinegar as a food additive of wood The present invention has been completed by knowing that the components limiting the use of the components, that is, the tar or some pigments and odor components can be separated and removed and the active component can be separated and extracted.

1 is a schematic diagram of a supercritical extraction device.

Therefore, according to the present invention, a method of purifying wood vinegar is characterized in that the wood vinegar is introduced into a supercritical and subcritical extraction reactor and then purified by passing through a supercritical or subcritical fluid as an extraction solvent.

Hereinafter, the present invention will be described in more detail.

When using a supercritical or subcritical fluid according to the present invention, components contained in wood vinegar obtained by pyrolyzing wood such as conifers and hardwoods, in particular, components that may cause problems in the application of wood vinegar (hereinafter referred to as "restricted ingredients"). By extracting), it is possible to apply wood vinegar to various purposes, and it is possible to selectively extract active ingredients in wood vinegar.

For example, unrefined wood vinegar includes tar, carbonized odor, phenols, alcohols, and the like, which restrict the use of food additives. By using the purification method of the present invention, it is possible to extract these ingredients from the wood vinegar. Therefore, the wood vinegar purified by the present invention is to be used as a food additive.

In addition, the above application limiting ingredients extracted from wood vinegar can also obtain the side advantage that can be effectively used for other uses that require it.

In the present invention, carbon dioxide, ethylene, ethane, propane, acetylene, ammonia, methane, and the like can be used as the supercritical or subcritical fluid as the extraction solvent, and among these, carbon dioxide is particularly preferable. Since carbon dioxide is volatilized immediately after the end of extraction, it does not remain in the product, which is a great advantage as an extraction solvent.

According to the present invention, when a supercritical or subcritical fluid is passed through a supercritical or subcritical extraction reactor containing wood vinegar in order to extract the use-limiting component from the wood vinegar, the reactor temperature is 5-100 ° C. and the pressure is 20-500 bar. It is preferable.

Moreover, it is preferable to use the continuous purification method or the semi-batch purification method for the wood vinegar purification method of this invention.

Through the following examples will be described in detail the present invention. The present invention is not limited by the following examples.

EXAMPLE

The wood vinegar from the oak wood vinegar processing company in Pohang was supplied to a continuous supercritical extraction tower as shown in FIG. 1 and passed supercritical carbon dioxide at a temperature of 25-45 ° C. and a pressure of 102.04-170.07 bar in the reactor. The pressurized carbon dioxide and extract material passed through the extraction tower were controlled by a pressure regulator, and after passing through the heat exchanger, the extract material was sent to the separation tank and the pressurized carbon dioxide was fed back to the extraction tower and reused. Recovered.

The amount of carbon odor, tar, and phenol components in the wood vinegar before and after supercritical extraction and the wood vinegar after extraction were analyzed using the headspace method, and the analyzer was analyzed by chromatography (GC-MS: HP 6890 for GC, detector for MS JMS-700, column is HP-5).

ingredient Before refining Wood Vinegar (%) After purification Wood Vinegar (%) 2,3-Butanedione 4.89 - 2,3-Dihydrofuran 0.66 - 2,3-Pentanedione 0.76 - 2-Propen-1-ol 1.65 - Octanal 0.12 - Cyclopentanone 1.80 - Cyclopentanone, 3-methyl 0.11 - dihydro-2-methyl-3 (2H) -Furanone 0.07 - tetrahydro-Pyran-4-one, 0.24 - 2-Propanone, methyl hydrazone 0.20 - tetrahydro-2-methyl-Furan, 0.26 - 3-hydroxy-2-Butanone, (acetoin) 1.40 5.62 1-hydroxy-2-Propanone, (acetol) 3.21 27.20 2-methyl-3-Hexyne 0.82 - methyl-Cycloheptene 0.77 - 3-methyl-2-Cyclopenten--one 1.01 - 3,4-di-methyl-2-Cyclopenten--one 0.37 - (2-cyclopentenone) -2-Cyclopentene-1-one 6.15 8.23 2-methyl-2-Cyclopentene-1-one, 4.29 - 1-Hydroxy-2-butanone 1.60 8.52 dihydro-Pyran-3 (4H) -one 0.84 1.55 2-Cyclohexene-1-one 0.65 - Acetic acid 1.71 6.20 1- (acetyloxy) -2-Propanone, (acetone) - 1.23 Furfural 21.44 - 2-ethyl-1-Hexanol - 3.05 2-Ethylisovaleraldehyde 0.88 - 5-methyl-2-Furanocarboxaldehyde 0.54 - 2,3,4-trimethyl--2-Cyclopentene-1-one 0.55 - 1- (2-furanyl) -Ethanone 4.41 - 2,5-Hexanoedione - 0.43 3--methyl-2-Cyclopenten-1-one - 1.26 Propanoic acid - 0.86

ingredient Before refining Wood Vinegar (%) After purification Wood Vinegar (%) 4-hydroxy-Butanoic acid - 0.57 2,3-dimethyl-2-Cyclopentene-1-one 1.55 - 5-methyl-2-Furanocarboxaldehyde 6.23 - 2-Acetyl-5-methylfuran 0.63 - 3-ethyl-2-Cycylopentene-1-one 0.44 - 2,5-dihydro-3,5-dimethyl-2-Furanone - 1.12 2,5-dihydro-3,5-dimethyl-Acetophenone and 2-Furanone 0.80 - 2-ethyl-Hexanoic acid, - 1.29 Heptadecane 0.48 - Dimethyoxytoluene 0.24 - 2-methoxy-Phenol 10.40 1.90 2-methoxy-3-methylPhenol 0.91 - 2,3-dimethyl-Phenol 0.60 - Hexadecanal - 3.98 2-methoxy-4-methyl-Phenol 4.65 1.02 2-methyl-Phenol 3.48 0.52 Phenol 3.64 6.82 4-ethyl-2-methoxy-Phenol 1.06 1.06 2-ethyl-Phenol 0.47 - 2,4-dimethyl-Phenol 0.85 - 4-methyl-Phenol 0.60 2.37 3-methyl-Phenol 0.83 5.33 3,4-dimethyl-Phenol - 2.47 3-ethyl-Phenol - 1.07 Nonanoic acid 0.71 - Dimethyl phthalate - 5.41 Octadecanal - 1.90

As can be seen from Table 1 and Table 2, Furfural, which has a significant content of about 20% of the total grass stock, is a colored and toxic substance, causing physiological changes in the liver and kidneys of mammals, It is a substance that causes delays, changes in hormones in the brain, and causes mutations for microorganisms. On the other hand, in the case of purified organic acid by supercritical treatment, furfural, which had a content of 20%, did not appear at all. In addition, cyclo-pentenone, similar to the acetoin and peppermint flavors, which had a fresh aroma, also exhibited 8.23% higher than the initial content of 6.15%. In addition, phenol-based para-cresol, ortho-cresol, and meta-cresol, which are a type of fungicide used in food, are purified raw natural acids. It is present in almost the same amount, showing that it can selectively remove only the substances harmful to the human body while having the same antibacterial and antiseptic properties as the raw materials before purification. This shows the availability of safer food additives using natural extracted and purified ingredients in place of conventional synthetic fungicides and food preservatives.

As described above, according to the present invention, components such as carbonized odor, tar, phenol and alcohol, which are unnecessary components, can be removed from the wood vinegar without destroying the structure of the main functional ingredient. The purified wood vinegar is used as a raw material for cosmetic and deodorant products. It is anticipated that the product may be used as an additive in cosmetics or other products or added to foods to increase the commerciality of the product.

Claims (3)

A method for purifying wood vinegar, characterized in that the wood vinegar is put into supercritical and subcritical extraction reactors and purified by passing through a supercritical or subcritical fluid as an extraction solvent. The method of claim 1, wherein the supercritical or subcritical fluid is carbon dioxide, ethylene, ethane, propane, acetylene, ammonia or methane. The method for purifying wood vinegar according to claim 1, wherein the extraction reactor has a temperature of 5-100 ° C and a pressure of 20-500 bar.