KR101334928B1 - Kit for purification of contaminated soils - Google Patents

Abstract

The purpose of the present invention is to provide a processing kit and a processing method for efficiently processing non-biodegradable harmful contaminants. The kit includes at least one selected from a group composed of heme and hemoglobin and hydrogen peroxide. One selected from the group composed of heme and hemoglobin and hydrogen peroxide separately exist. The soil is contaminated by at least one material selected from a group composed of Naphthalene, Acenaphthalene,Acenaphthene, Fluorene, Pheneanthrene, Anthracene, Fluranthene, Pyrene, Benzo[a]anthracene, Chrysene, Benzo[b]fluoranthene, Benzo[k]fluoranthene, Benzo[a]pyrene, Dibenzo[a,h]anthracene, Benzo[g,h,i]perylene, Ideno[1,2,3 cd]pyrene, and Pentachlorophenol.

Description

KIT FOR PURIFICATION OF CONTAMINATED SOILS}

The present invention relates to a purification treatment kit and a purification treatment method for contaminated soil.

Conventionally, techniques for restoring soil contaminated with hazardous chemicals have been continuously developed. Representatively, there is known a method of growing soil microorganisms to decompose contaminants, and a method of washing and treating harmful substances in contaminated soil using water and organic solvents and thermal desorption reactions at high temperatures.

However, the treatment method for washing and thermally desorption of harmful substances in contaminated soil requires an essential treatment cost after the washing water is required, and the subsequent treatment process is performed because the dioxin substance that is harmful to the human body is doubled during the heat deposition process. Required.

In addition, the decomposition technology using microorganisms, it is also impossible to treat the non-degradable harmful substances that are toxic to the microorganisms in a short time, and Xenobiotic harmful substances, which are man-made synthetic organic chemicals, are the growth of microorganisms and cell synthesis There is a limitation in that it cannot be used as an organic carbon source, which is a necessary substrate.

Republic of Korea Patent Publication No. 10-2002-0000444

It is an object of the present invention to provide a treatment kit and a treatment method for efficiently treating hardly degradable harmful contaminants contained in soil.

In order to achieve the above object, the present invention is a kit for purification of contaminated soil,

The kit comprises at least one hydrogen peroxide and at least one selected from the group consisting of heme and hemoglobin, at least one selected from the group consisting of heme and hemoglobin and hydrogen peroxide are present separately, and the soil is naphthalene (Naphthalene), Acenaphthalene, Acenaphthene, Fluorene, Pheneanthrene, Anthracene, Fluranthene, Pyrene, Benzo [a] anthracene Benzo [a] anthracene, Chrysene, Benzo [b] fluoranthene, Benzo [k] fluoranthene, Benzo [a] pyrene (Benzo [a] pyrene), dibenzo [a, h] anthracene (Dibenzo [a, h] anthracene), benzo [g, h, i] perylene (Benzo [g, h, i] perylene), Ide One or more substances selected from the group consisting of no [1,2,3 cd] pyrene and pentachlorophenol. Characterized in that the, there is provided a kit for purifying soil.

The present invention also includes the steps of: (a) treating the soil with at least one selected from the group consisting of heme and hemoglobin; And (b) treating hydrogen peroxide, wherein the soil is treated with naphthalene, acenaphthalene, acenaphthene, fluorene, pheninsrene, and the like. Pheneanthrene, Anthracene, Fluranthene, Pyrene, Benzo [a] Benzo [a] anthracene, Chrysene, Benzo [b] Fluoranthene [b] fluoranthene), benzo [k] fluoranthene, Benzo [a] pyrene, dibenzo [a, h] anthracene (Dibenzo [a, h] anthracene), benzo [g, h, i] perylene (Benzo [g, h, i] perylene), ideno [1, 2, 3 cd] pyrene (Ideno [1,2,3 cd] pyrene) and penta It provides a method for the purification of contaminated soil, characterized in that the contaminated with one or more substances selected from the group consisting of chlorophenol (Pentachlorophenol).

According to the treatment kit or the treatment method of the present invention, it is possible to quickly and easily purify the soil-degradable pollutants, specifically PAHs and PCP, and when the hard-decomposable pollutants are decomposed, only harmless CO ₂ is finally produced to be environmentally friendly. to be. In addition, the treatment kit or the treatment method of the present invention can regenerate heme (heme) as a catalyst in the process of purifying contaminated soil, and it is possible to continuously purify by continuously adding only hydrogen peroxide, which is another reactant. Heme, which is only supplied to the animal, has the advantage of being easily obtained from animal blood.

Figure 1 shows that after treating heme and hydrogen peroxide in contaminated soil, the content of total petroleum carbon (TPH) over time.

In one aspect, the present invention provides a kit for purifying contaminated soil, wherein the kit comprises hydrogen peroxide and at least one selected from the group consisting of heme and hemoglobin, and in the group consisting of heme and hemoglobin One or more selected and hydrogen peroxide are present separately and the soil is naphthalene, acenaphthalene, acenaphthene, fluorene, pheneneanthrene, anthracene, flu Fluranthene, Pyrene, Benzo [a] anthracene, Chrysene, Benzo [b] fluoranthene, Benzo [k] Fluoranthene (Benzo [k] fluoranthene), benzo [a] pyrene, dibenzo [a, h] anthracene (Dibenzo [a, h] anthracene), benzo [g, h, i Benzo [g, h, i] perylene, Ideno [1,2,3 cd] pyrene and Pentachlorophenol It relates to a soil purification kit, characterized in that contaminated with one or more substances selected from the group consisting of rophenol).

In the present specification, the "heme" may refer to a complex formed by iron atoms entering the center of porphyrin, a planar molecule having four pyrrole rings. In the present specification, the heme may be a non-protein part contained in an enzyme in vivo, such as hemoglobin and cytochrome, and may also be used when it is obtained from an enzyme synthesized in vivo or artificially synthesized. In addition, in the present specification, the heme is specifically, heme a (cytochrome oxidase), heme b (hemoglobin, etc.), heme c (cytochrome C type), heme d (hema ₂ ), silohem or chlorogluolohem It may include, but is not limited thereto. In addition, in the present specification, the heme may be mesohem, deuterohem or coprohem, but is not limited thereto. More specifically, the heme of the present invention may include complex salts in which trivalent iron ions are coordinated in the center of porphyrin, a planar molecule having four pyrrole rings.

In the present specification, the "hemoglobin" is a molecule containing four heme and can be used without limitation.

In a treatment kit of one aspect of the invention, the heme and hydrogen peroxide are present separately in the formulation, which may be mixed with the soil after treatment.

As used herein, the term “soil” includes soil contaminated with one or more substances selected from the group consisting of Polycyclic Aromatic Hydrocarbons (PAHs) and Pentachlorophenol. The PAHs are known to be carcinogenic among the hardly decomposable substances produced by humans, and PCP is one of the substances used as an insecticide or a wood protective agent. In particular, the PCP and PAHs are detected in large quantities not only in the soil around the railroad sleepers but also in the sleeper storage areas of the waste railways, and thus, the present invention can easily clean the contaminated soil.

The mechanism by which the soil is purified by the treatment kit according to one aspect of the present invention is specifically as follows. In the following mechanism, RH includes at least one substance selected from the group consisting of Polycyclic Aromatic Hydrocarbons (PAHs) and Pentachlorophenol.

(1) Hb-Fe ⁺³ : heme in hemoglobin containing trivalent iron

(2) Hb-Fe ^{+ 4 ·} : intermediate radical product produced by the reaction of Heme with hydrogen peroxide

(3) RH: Hardly degradable organic pollutant

(4) R · : Radical organic material in which RH is oxidized in the catalytic oxidation of heme

(5) R _ox : Intermediate organic oxides oxidized in the catalytic reduction mechanism of R · and heme.

(6) CO ₂ : final product obtained after purification

As shown above, heme reacts with hydrogen peroxide to convert to tetravalent iron radical heme, and the unstable radical tetravalent iron heme reacts with harmful substances in contaminated soil to form tetravalent iron heme. Is stabilized. At the same time, the harmful substances are converted into the radical form and are oxidized by reaction with tetravalent iron heme. As the cycle progresses, only carbon dioxide is eventually left as a result, so that harmful substances in the contaminated soil can be purified. According to the above mechanism, since only pollutants are decomposed to generate harmless carbon dioxide, and heme is repeatedly and continuously used as a catalyst, it is an eco-friendly purification method and has the advantage of reducing the purification cost. In particular, if heme is added only once, it is regenerated through redox reaction and only hydrogen peroxide is required to proceed with the second cycle.

More specifically, the mechanism is expressed as follows.

At sites where contaminated soil is present, purifying contaminated soil using a treatment kit and treatment method, which is an aspect of the present invention, can quickly and easily convert contaminants into harmless CO ₂ , resulting in harmless soil at low cost in a short time. Can be restored.

In another aspect, the present invention, (a) treating the heme (heme) in the soil; And (b) treating hydrogen peroxide, wherein the soil is treated with naphthalene, acenaphthalene, acenaphthene, fluorene, pheninsrene, and the like. Pheneanthrene, Anthracene, Fluranthene, Pyrene, Benzo [a] Benzo [a] anthracene, Chrysene, Benzo [b] Fluoranthene [b] fluoranthene), benzo [k] fluoranthene, Benzo [a] pyrene, dibenzo [a, h] anthracene (Dibenzo [a, h] anthracene), benzo [g, h, i] perylene (Benzo [g, h, i] perylene), ideno [1, 2, 3 cd] pyrene (Ideno [1,2,3 cd] pyrene) and penta A method for the purification of contaminated soil contaminated with one or more substances selected from the group consisting of pentachlorophenol.

The treatment method, which is an aspect of the present invention, may include treating the steps (a) and (b) and leaving it for at least one day. When heme is mixed with contaminated soil and hydrogen peroxide is added, the catalytic reaction starts immediately, and the catalyst reaction is completed within 24 hours and one day. When only oxidizing agent hydrogen peroxide is added periodically, it reacts with heme remaining in the soil continuously. It can decompose pollutants. Therefore, if the contaminated soil is treated beyond this period, the amount of pollutants including polycyclic aromatic hydrocarbons (PAHs) and pentachlorophenol in the soil can be significantly reduced. In view of the above, the treatment method, the step (a) and (b) is processed and it is at least 2 days, at least 3 days, at least 4 days, at least 5 days, at least 6 days, at least 7 days or 8 days It may be left over, but is not limited thereto, and may vary depending on soil contamination. Alternatively, the treatment method may include treating the steps (a) and (b) and leaving it to 50 days or less. Specifically, the treatment method may process the steps (a) and (b) and leave it for 45 days or less, 40 days or less, 35 days or less, 30 days or less, or 25 days or less, but is not limited thereto. It may vary depending on soil contamination.

In the treatment method of one aspect of the present invention, the method may proceed to step (b) two or more times. The treatment method, which is one aspect of the present invention, has the advantage of being able to regenerate heme as a catalyst in the process of purifying contaminated soil, so that it is possible to continuously purify only by continuously adding hydrogen peroxide which is another reactant. Specifically, the treatment method, which is an aspect of the present invention, may proceed to step (b) three or more times, four or more times, five or more times, six or more times, or seven or more times, but is not limited thereto. Ie, the higher the degree of contamination, the more the number of times of repeating step (b) can be increased.

Hereinafter, the present invention will be described in more detail with reference to the following examples. However, the following examples are provided only for the purpose of illustration in order to help the understanding of the present invention, the scope and scope of the present invention is not limited thereto.

PAHs  Of contaminated soil Cleansing ability  Confirm

To 1 kg of contaminated soil, 10 g of heme is mixed as an aqueous solution, and 54 g of hydrogen peroxide is evenly added to the mixed heme and mixed for 14 and 42 days, respectively. Table 1 was obtained by measuring the amount of (PAHs). Heme was dissolved in 0.1 M NaOH and then dissolved in phosphate buffer (pH 7). The amount of PAHs in soil samples was U.S. Extracted using EPA Method 3540A (US Environmental Protection 3540A pretreatment method). Specifically, after extracting the contaminants with the Soxhle extractor, oil and grease were removed using the US Environmental Protection Agency 3650 acid / salt purification method. At this time, PAHs and TPH (total petroleum hydrocarbon) remained in methylene chloride. Among them, PAHs were diluted in acetonitril and analyzed by HPLC (C18 column).

PAHs Dose

Time Heme reaction
10g heme / kg soil
54g / kg soil 0day 14 day 42 day Naphthalene 49.32 34.64 0.00 Acenaphthalene 16.64 4.88 0.00 Acenaphthene 102.78 79.72 0.00 Fluorene 3.08 1.62 0.00 Pheneanthrene 11.30 0.10 0.00 Anthracene 5.24 0.58 0.00 Fluranthene 111.84 13.70 0.44 Pyrene 73.40 80.68 3.70 Benzo [a] anthracene 24.62 13.32 0.58 Chrysene 28.28 21.84 0.40 Benzo [b] fluoranthene 12.28 3.78 0.32 Benzo [k] fluoranthene 4.66 1.92 3.00 Benzo [a] pyrene 5.38 2.80 0.00 Dibenzo [a, h] anthracene 3.00 0.18 1.28 Benzo [g, h, i] perylene 8.70 1.70 0.08 Ideno [1,2,3 cd] pyrene 3.26 1.22 0.24 Total PAHs 463.78 262.68 10.04

As a result (Table 1), it was confirmed that the amount of PAH rapidly decreased by the heme or hemoglobin treatment. In particular, it was confirmed that 43% of PAH was removed after the reaction for 14 days and 98% or more of PAH was removed after the reaction for 42 days.

PCP Of contaminated soil Cleansing ability  Confirm

The soil to be used was contaminated with PCP of 273mg / kg on average. 10 g of heme and 54 g of hydrogen peroxide were added and reacted with 1 kg of the soil (Experimental Group A). In addition, 17 g of the powdered hemoglobin and the soil were mixed, and then 160 g of hydrogen peroxide was added and reacted (experimental group B). The amount of PCP was measured after 14 and 42 days for each group (Table 2). PCP amount was measured by U.S. Extracted using Soxhle with EPA Method 3540A (U.S. E. 3540A pretreatment method). Diluted in 50 acetone and analyzed by HP 5880A gas chromatography. The gas chromatography was subjected to quantitative analysis using an ECD (Electron Capture Detector), and a PCP separation column was an Rtx-5 column.

catalyst PCP Contaminated Soil Treatment Results (mg PCP / kg Soil) reaction Heme catalysis Hemoglobin catalysis time 10g heme / kg soil 17g hemoglobin / kg soil (Work) 54 g H ₂ O ₂ / kg soil 160 g H ₂ O ₂ / kg soil 0 273 273 14 170 112 42 11 5

As a result (Table 2), it was confirmed that the amount of PCP rapidly decreased by the heme or hemoglobin treatment.

Before and after purification TPH  compare

The amount of TPH (total petroleum hydrocarbon) remaining in the methylene chloride of Example 1 was compared. Specifically, TPH (total petroleum hydrocarbon) was analyzed by a gas chromatograph analyzer (GC-14A with FID detector, Shimadzu, Japan) equipped with FID after diluting methylene chloride with acetone.

As a result (Fig. 1), it was confirmed that the amount of TPH rapidly decreased by the heme or hemoglobin treatment.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the same is by way of illustration and example only and is not to be construed as limiting the scope of the present invention. Accordingly, the actual scope of the present invention will be defined by the appended claims and their equivalents.

Claims (4)

A cleanup kit for contaminated soil
The kit comprises one or more selected from the group consisting of heme and hemoglobin and hydrogen peroxide,
At least one selected from the group consisting of heme and hemoglobin and hydrogen peroxide are present separately;
The soil is naphthalene, acenaphthalene, acenaphthene, fluorene, fluorene, pheneanthrene, anthracene, fluranthene, pyrene, benzo [a] Benzo [a] anthracene, Chrysene, Benzo [b] fluoranthene, Benzo [k] fluoranthene, Benzo [a] Benzo [a] pyrene, dibenzo [a, h] anthracene (Dibenzo [a, h] anthracene), benzo [g, h, i] perylene (Benzo [g, h, i] perylene), ideno [1,2,3 cd] pyrene (Ideno [1,2,3 cd] pyrene) and pentachlorophenol (Pentachlorophenol), characterized in that it is contaminated with one or more substances selected from the group consisting of Soil purification treatment kit. (a) treating the soil with one or more selected from the group consisting of heme and hemoglobin; And
(b) treating the contaminated soil, comprising treating hydrogen peroxide,
The soil is naphthalene, acenaphthalene, acenaphthene, fluorene, fluorene, pheneanthrene, anthracene, fluranthene, pyrene, benzo [a] Benzo [a] anthracene, Chrysene, Benzo [b] fluoranthene, Benzo [k] fluoranthene, Benzo [a] Benzo [a] pyrene, dibenzo [a, h] anthracene (Dibenzo [a, h] anthracene), benzo [g, h, i] perylene (Benzo [g, h, i] perylene), ideno [1,2,3 cd] pyrene and one or more substances selected from the group consisting of pentachlorophenol,
The method includes the step of (b), and then left for more than one day, the method for the purification of contaminated soil. 3. The method of claim 2,
The method is characterized in that the step (b) two or more times, the contaminated soil purification method.
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