JP2005211352A - Detoxication method for dioxins - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To efficiently decompose and detoxicate dioxins, or highly toxic chemicals, at a relatively low temperature at a low cost. <P>SOLUTION: Liquid yeast extract containing water and glutathione is added to a specimen containing the dioxins and stored at 80-100 °C for a week. It is supposed that sulfur atoms possessed by the glutathione are entered in angular positions of a benzene ring of the dioxins, substituted and hydrophilized to decompose the dioxins. Consequently, 99% or more of the dioxins, different according to the isomers, are removed and detoxicated. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a method for detoxification of dioxins.

Conventional techniques for decomposing dioxins (dioxins, dioxin mutants, co-PCB, etc.) include decomposing an object by heating it at about 400 degrees for several hours. However, according to this method, chemical substances such as decomposed chlorine are volatilized and the volatilized chemical substances may adversely affect the surrounding environment. Further, according to this method, volatilized chlorine had to be adsorbed with metallic sodium, and the decomposition of dioxin cost from 150,000 to 200,000 yen per ton. Japanese Patent Application Laid-Open No. 2003-190917 heats waste from 600 degrees to 1000 degrees to 500 degrees to 1000 degrees, but creating and maintaining such a high temperature state requires energy. Japanese Patent Application Laid-Open No. 2003-94001 adds an organic sulfur compound containing a sulfur atom such as a dithiocarbamic acid group or a thiocarbamic acid group to the incinerated fly ash for the treatment of the incinerated fly ash. However, the decrease in the amount of dioxins is a problem in that it is only reduced by about half in some cases and may be only about 30% or about 10%. Further, according to this method, the organic sulfur compound is expensive and expensive.
JP 2003-190917 A JP 2003-94001 A Published by Sadayori Hoshina “Survey Report on Direct Pollution System of Dioxins Contaminated Water Quality and Soil by Fiscal 2002” Published by Japan Society for Promotion of Engineering 2003

  This is a method for efficiently detoxifying dioxins at a temperature of about 80 to 100 degrees and at a low cost.

  Add water and glutathione to dioxins and store at a temperature of 80 to 100 degrees for 1 week.

  Glutathione is also abundant in yeast extract and brewer's yeast. Yeast extract and brewer's yeast are inexpensive and easy to obtain, and can achieve detoxification of dioxins at low cost. Further, according to the present invention, the amount of many dioxins can be reduced by 99% or more. Furthermore, since the temperature at which the sample is stored is 100 ° C. and the temperature is relatively low, detoxification can be realized at a relatively low temperature without preparing an expensive furnace, and dioxins in the sample that are sensitive to high heat can be detoxified.

  The best mode for carrying out the invention will be described below, but the present invention is not limited thereto. Mixing a sample solution containing dioxins and a Tryptic Soy Broth solution made by BBL to 1/4 dilution with a yeast extract (BBL) added to a concentration of 0.1%, The mixed sample is set at 80 to 100 degrees and stored for one week.

The reaction liquid which added yeast extract (made by BBL) to the liquid which diluted the sample in which dioxins exist in Table 1 and the Tryptic Soy Broth liquid made from BBL to 1/4 is added to 0.1%. The experimental results of mixing and setting the mixed sample at 100 degrees and storing for 3 days and the experimental results stored for 1 week are shown. Gas chromatography / mass spectrometry was used to measure dioxins.

  According to the above experimental results, 2, 3,4,8-TCDD (Tetra Chloro Dibenzo Dioxin) is 0.25% (the third decimal place is rounded off, the same applies hereinafter), 1, 2, 3, 7, 8- For PeCCD, 0.43%, 1, 2, 3, 4, 7, 8-HxCDD 0.82%, 2, 3, 7, 8-TCDF (Tetra Chloro Divenzo Fran) decreases to 0.32%, etc. The effect is remarkable as it appears as a significant decrease in other target substances.

Table 2 shows a reaction solution in which a yeast extract (manufactured by BBL) is added to a solution obtained by diluting a sample in which dioxins are present and a Tryptic Soy Broth solution manufactured by BBL to a quarter to 0.1%. The experimental results of mixing and setting the mixed sample at 80 degrees and storing for 3 days and the experimental results stored for 1 week are shown. Gas chromatography / mass spectrometry was used to measure dioxins.

  According to the experimental results, 100% for 2, 3, 7, 8-TCDD, 100% for 1, 2, 3, 7, 8-PeCCD, 98 for 1, 2, 3, 4, 7, 8-HxCDD. %, 2, 3, 7, 8-TCDF is reduced to 99%, and the effect is remarkable as shown as a significant reduction result in other target substances.

化２に１酸素架橋開裂を有する物質の化学式（以下、「Ｂ物質２」という。）を示す。

化３にエーテル結合開裂後の物質の化学式（以下、「Ｃ物質３」という。名称エスクレチン）を示す。

Ａ物質１は蛍光性質を有していない。Ｂ物質２は蛍光性質を有しており所定の波長で発光する。Ｃ物質３も蛍光性質を有しており所定の波長で発光する。化４に２、３、７、８−ＴＣＤＤの化学式を示す。

Ａ物質１は２、３、７、８−ＴＣＤＤと比較して７、８の部位にメチル基等を有するベンゼン環が結合している点を除いて同じ化学構造をしている。参考文献１２９ページ以下ではＡ物質１を擬似的に２、３、７、８−ＴＣＤＤに見立ててBacillus midousujiを使用して化学反応を起こさせ、１酸素架橋開裂やエーテル結合が開裂して各々Ｂ物質２やＣ物質３が生じた場合、その蛍光を観測して擬似的２、３、７、８−ＴＣＤＤが分解し無毒化されるかを実験している。 The principle of the present invention was estimated as follows. Chemical formula 1 of the substance having a fluorescent substrate (hereinafter referred to as “A substance 1”) is shown in Chemical formula 1.

Chemical formula 2 shows the chemical formula (hereinafter referred to as “B substance 2”) of a substance having 1 oxygen cross-link cleavage.

Chemical formula of the substance after the ether bond cleavage (hereinafter referred to as “C substance 3”, name esculetin) is shown in Chemical formula 3.

Substance A 1 does not have fluorescent properties. The substance B 2 has a fluorescent property and emits light at a predetermined wavelength. The substance C 3 also has fluorescent properties and emits light at a predetermined wavelength. Chemical formulas of 2, 3, 7, and 8-TCDD are shown in Chemical formula 4.

Substance A 1 has the same chemical structure except that a benzene ring having a methyl group or the like is bonded to sites 7 and 8 as compared to 2, 3, 7, and 8-TCDD. In Reference Document 129 and below, substance A 1 is simulated as 2, 3, 7, 8-TCDD, and a chemical reaction is caused using Bacillus midousuji, and 1 oxygen bridge cleavage or ether bond is cleaved to form B. When the substance 2 and the substance C 3 are generated, the fluorescence is observed to experiment whether the pseudo 2, 3, 7, 8-TCDD is decomposed and detoxified.

Bacillus midousujiを使用した結果Ｂ物質２、Ｃ物質３が生じてＡ物質１が分解され無毒化されるが、この現象の原理はＡ物質１の酸素原子に隣接するアンギュラー位に硫黄原子Ｓが入り、親水化することによって１酸素架橋開裂が生じエーテル結合が開裂していくと推測されている。グルタチオンは硫黄原子Ｓを有する化学構造を持つが、かかる硫黄原子Ｓがダイオキシン類のベンゼン環のアンギュラー位に入り親水化することで無毒化する。その後１酸素架橋開裂が生じエーテル結合が開裂すると推測される。そして、試料の温度を上げることによって化学反応が円滑に進行し擬似的な２、３、７、８−ＴＣＤＤであるＡ物質１が分解され無毒化されるものと推測される。また、ダイオキシン類における分子の塩素原子に硫黄原子が置換することによって無毒化される場合があると推測される。グルタチオンを含む酵母抽出液のほかグルタチオンを含むビール酵母を溶かした混合物、システイン、メチオニン、硫化鉄を使用しても硫黄元素Ｓがエーテル結合を担う酸素原子を排除し置換することで１酸素架橋開裂が生じエーテル結合が開裂すると推測される。 FIG. 1 shows a diagram inferring the metabolism of substance A 1 by glutathione (page 44 of Reference 1).
Chemical formula of glutathione is shown in Chemical formula 5.

As a result of using Bacillus midousuji, B substance 2 and C substance 3 are produced and A substance 1 is decomposed and detoxified. The principle of this phenomenon is that sulfur atom S enters the angular position adjacent to the oxygen atom of A substance 1. It is presumed that by hydrophilization, monooxygen bridge cleavage occurs and the ether bond is cleaved. Glutathione has a chemical structure having a sulfur atom S, but the sulfur atom S enters the angular position of the benzene ring of dioxins and is rendered hydrophilic by dehydration. Thereafter, it is presumed that one oxygen bridge cleavage occurs and the ether bond is cleaved. Then, it is presumed that the chemical reaction proceeds smoothly by raising the temperature of the sample, and the pseudo A substance 1 which is 2, 3, 7, 8-TCDD is decomposed and detoxified. Moreover, it is estimated that a sulfur atom may substitute for the chlorine atom of the molecule | numerator in dioxins, and it may detoxify. In addition to yeast extract containing glutathione, a mixture of brewer's yeast containing glutathione, cysteine, methionine, and iron sulfide, sulfur element S eliminates oxygen atoms responsible for ether bonds and replaces them, thereby cross-linking one oxygen. And the ether bond is presumed to be cleaved.

  Dioxins can be decomposed and detoxified at a temperature of about 80 to 100 degrees efficiently and at a low cost, and there is a great effect in terms of removal and disposal of contaminants.

Figure inferring metabolism of substance A 1 by glutathione

Explanation of symbols

1 A substance 2 B substance 3 C substance

Claims (6)

  A method for decomposing dioxins by storing a mixture of dioxins with water and glutathione at 80 to 100 degrees for 1 week.   A method of decomposing dioxins by storing a mixture of dioxins with water and yeast extract at 80 to 100 degrees for 1 week.   A method for decomposing dioxins by storing a mixture of dioxins with water and brewer's yeast at 80 to 100 degrees for 1 week.   A method for decomposing dioxins by storing a mixture of dioxins with water and iron sulfide at 80 to 100 degrees for one week.   A method for decomposing dioxins by storing a mixture of dioxins with water and cysteine at 80 to 100 degrees for 1 week.   A method of decomposing dioxins by storing a mixture of dioxins with water and methionine at 80 to 100 degrees for 1 week.

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