KR101627328B1

KR101627328B1 - Apparatus for remediation of contaminated soil

Info

Publication number: KR101627328B1
Application number: KR1020150122795A
Authority: KR
Inventors: 강구영; 박갑성; 김희만; 이성종; 최효섭; 금혜인
Original assignee: 한국외국어대학교 연구산학협력단
Priority date: 2015-08-31
Filing date: 2015-08-31
Publication date: 2016-06-07

Abstract

The present invention relates to a soil recovery apparatus capable of effectively recovering soil contaminated with highly degradable organic chemicals such as TPH (Total Petroleum Hydrocarbons) and PAHs (Polycyclic Aromatic Hydrocarbons). The soil recovery apparatus according to the present invention comprises: Screen apparatus for separating contaminated soil from crude oil contaminants; A soil microorganism culturing apparatus which cultivates a soil microorganism and makes it possible to produce a biosurfactant by the soil microorganism; A bioslurry reactor for receiving a cultured mixture of a culture solution, a soil microorganism and a biosurfactant from the soil microorganism culture apparatus and washing the contaminated soil using the culture; A pressurized floating tank for separating the bioslurry discharged from the bioslurry reactor into a contaminated soil, a culture liquid and a floating material by using a pressurization flotation principle; A cyclone apparatus for subjecting contaminated soil separated by a pressurized floating tank to solid-liquid separation; And a catalytic reactor for decomposing the refractory organic chemicals of the contaminated soil through a catalytic reaction by stirring the contaminated soil with a catalyst containing heme and hydrogen peroxide.

Description

[0001] Apparatus for remediation of contaminated soil [

The present invention relates to a soil remover, and more particularly, to a soil remover capable of effectively recovering soil contaminated with highly degradable organic chemicals such as TPH (Total Petroleum Hydrocarbons) and PAHs (Polycyclic Aromatic Hydrocarbons) .

Soil is very complicated, difficult, and costly to clean up as pollution progresses. Therefore, it is most important to prevent pollution, and for contaminated soil, integrated management according to the type of pollution source and application of effective purification technology are required. In addition, since the soil consists of various media such as solid (soil particles), liquid (soil water, non-water liquid) and vapor (soil air), soil contamination must be handled simultaneously.

The types of contaminated soil remediation techniques are very diverse and can be divided into in-situ and ex-situ techniques depending on the location of the contaminated soil, and these techniques can be classified into thermal, biological , And physicochemical techniques.

Thermal technology is a technology for decomposing harmful substances contained in soil through incineration or pyrolysis by exposing soil to high temperature in controlled environment. It has a high purification efficiency, but it has a high energy treatment cost. In the case of heavy metals, It is not treated and is vitrified at a high temperature. Biological treatment technology is an eco-friendly and economical way to promote biodegradation of organic compounds by activating or optimizing soil microorganisms or adding specially developed microorganisms and optimizing survival conditions.

Physicochemical treatment technologies include extraction of pollutants using organic solvents and surfactants, transport from soil and groundwater to other media, decomposition by chemical oxidation / reduction methods, separation and concentration by adsorption / precipitation And the like. When the removal efficiency of soil contaminants such as soil steam extraction, soil washing, soil washing, and chemical extraction determines the removal efficiency, the physical properties of the contaminants, the cation exchange capacity of the soil, the pH, and the total organic carbon content affect the efficiency. An example of a physicochemical treatment technique is disclosed in Korean Patent Registration No. 1358147 entitled " Method and Apparatus for Detaching Contaminated Soil Using Micro Bubbles ".

On the other hand, existing technologies are not effective for soil contaminated with poorly decomposable harmful substances such as PAHs (Polycyclic Aromatic Hydrocarbons). For example, when biological restoration techniques are applied to soil contaminated with human-made synthetic organic chemical xenobiotic, xenobiotic is an organic carbon source, which is a substrate for microbial growth and cell synthesis And the restoration of the soil is limited. In addition, in the case of soil contaminated with TPH (Total Petroleum Hydrocarbons) due to leakage of crude oil or the like, the biological treatment is impossible because no growth condition of microorganisms is provided.

The present applicant has proposed a mechanism for cleansing soil contaminated with refractory organic chemicals using heme and hydrogen peroxide through Korean Patent Nos. 1334928 and 1474308.

Korean Patent No. 1358147 Korean Patent No. 1334928 Korean Patent No. 1474308

Disclosure of the Invention The present invention has been made to solve the above-mentioned problems, and it is an object of the present invention to provide a soil restoration apparatus capable of effectively restoring soil polluted with highly degradable organic chemicals such as TPH (Total Petroleum Hydrocarbons) and PAHs (Polycyclic Aromatic Hydrocarbons) The purpose is to provide.

According to an aspect of the present invention, there is provided a soil remover comprising: a screen device for separating contaminated soil from crude oil contamination; A soil microorganism culturing apparatus which cultivates a soil microorganism and makes it possible to produce a biosurfactant by the soil microorganism; A bioslurry reactor for receiving a cultured mixture of a culture solution, a soil microorganism and a biosurfactant from the soil microorganism culture apparatus and washing the contaminated soil using the culture; A pressurized floating tank for separating the bioslurry discharged from the bioslurry reactor into a contaminated soil, a culture liquid and a floating material by using a pressurization flotation principle; A cyclone apparatus for subjecting contaminated soil separated by a pressurized floating tank to solid-liquid separation; And a catalytic reactor for decomposing the refractory organic chemicals of the contaminated soil through a catalytic reaction by stirring the contaminated soil with a catalyst containing heme and hydrogen peroxide.

The soil microorganism grows using the crude oil as a carbon source, and generates a biosurfactant during its growth. The soil microorganism may be a soil microorganism extracted from contaminated soil, and the soil microorganism may be any one of Flavobacteriales, Burkholderiales, Pseudomonadales , or a mixture thereof.

In the bio slurry reactor, the biosurfactant dissolves the crude oil component of the contaminated soil through an emulsifying action, and the soil microorganism grows using the dissolved crude oil component as the carbon source.

Wherein the pressurized floatation vessel floats the crude oil component and the biosurfactant component in the bioslurry using a bubble as a float and the contaminated soil and the culture liquid separated by the pressurized floatation tank are transferred to the cyclone apparatus, Device. In addition, the pressurized floatation tank floats the crude oil component and the biosurfactant component in the bioslurry as a float using bubbles, and the contaminated soil separated by the pressurized float tank is transferred to the cyclone apparatus, and the culture liquid and the floating soil microorganism And can be recovered into a culture apparatus.

In the cyclone apparatus, the mixture of the contaminated soil and the culture liquid separated by the pressurized floating tank is subjected to solid-liquid separation using a centrifugal force, and the separated biosurfactant component, the crude oil component desorbed from the contaminated soil, and the culture liquid are recovered in the soil microorganism culture apparatus , And the separated contaminated soil is supplied to the catalytic reaction apparatus. In the cyclone apparatus, the contaminated soil separated by the pressurized floating tank is subjected to solid-liquid separation using centrifugal force. The separated components of the biosurfactant and the crude oil desorbed from the contaminated soil are recovered in the soil microorganism culture apparatus, The soil may be supplied to the catalytic reaction apparatus.

The soil microorganism culture apparatus comprises a culture tank and a storage tank. The culture tank cultivates the soil microorganism using the culture liquid. During the culturing of the soil microorganism, the soil microorganism generates a biosurfactant. In the culture tank, A crude oil component, a biosurfactant component and a culture solution recovered from the cyclone device are supplied. In addition, the biological surfactant generated by the soil microorganism in the culture tank is moved to the storage tank together with the soil microorganism and the culture liquid, and the culture of the storage tank is supplied to the bioslurry reactor.

Hemoglobin may be supplied to the soil microorganism culture apparatus and the bioslurry reactor as a carbon source of the soil microorganism.

The catalytic reaction is carried out, the hem (Hb-Fe ⁺³⁾ is reacted with hydrogen peroxide 4 gacheol heme radical (Hb-Fe ⁺⁴ o) a conversion process, a 4 gacheol heme radical (Hb-Fe ⁺⁴ o) to the I (R) by reacting with the decomposable organic chemical material (RH) to convert it to tetravalent heme (Hb-Fe ^{+ 4} ), and converting the refractory organic chemical material (RH) The process may include a process in which tetravalent heme (Hb-Fe ^{+ 4} ) is reduced to heme (Hb-Fe ⁺³ ) and oxidation of the refractory organic chemical radical (R ㅇ) to generate carbon dioxide.

The catalyst comprises hemoglobin and the weight ratio of hydrogen peroxide / hemoglobin is 2 to 10.

The bioreactor may further include a bioreactor for agitating the reaction effluent of the catalytic reactor under exhalation conditions to decompose the biodegradable organic chemical through growth and activation of the soil microorganism.

The soil restoration apparatus according to the present invention has the following effects.

TPH concentration in contaminated soil can be significantly lowered by washing contaminated soil with biosurfactants generated by soil microorganisms. In addition, as the soil microorganisms grow using the crude oil component as a carbon source, additional biosurfactants can be generated in the course of washing the contaminated soil, thereby doubling the cleaning efficiency.

In addition, by applying a catalytic reaction using hemoglobin and hydrogen peroxide to a contaminated soil in which the TPH concentration is lowered by the biosurfactant, it is possible to effectively remove the refractory organic chemicals in the contaminated soil.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a configuration diagram of a soil recovery apparatus according to an embodiment of the present invention; FIG.
2 is a graph showing the amount of carbon dioxide generated when the soil recovery apparatus according to the present invention is applied to the contaminated soil of crude oil in the Kuwait area.
FIG. 3 is a graph showing changes in TPH concentration when the soil remediation apparatus according to the present invention is applied to the contaminated soil of crude oil in the Kuwait area.

The present invention reduces the TPH of contaminated soil by washing the contaminated soil using a bio-surfactant produced by the soil microorganism and catalyzes the reaction using hemoglobin and hydrogen peroxide (H ₂ O ₂ ) This paper presents a technique for effectively recovering soil contaminated with high concentration of TPH and refractory organic chemicals by decomposing refractory organic chemicals in contaminated soil.

Soil microorganisms such as Flavobacteriales, Burkholderiales and Pseudomonadales produce bio-surfactant in the presence of crude oil components and discharge them to the outside of the cell. The biosurfactant produced by the soil microorganism is mixed with soil contaminated with crude oil And has the property of separating crude oil from contaminated soil. Therefore, washing contaminated soil with biosurfactants produced by soil microorganisms can lower the concentration of TPH in contaminated soil, and can effectively apply subsequent processes such as biological treatment to contaminated soil with lower TPH concentration.

On the other hand, the refractory organic chemical substance means any one of PAHs (Polycyclic Aromatic Hydrocarbons), PCP (Pentachlorophenol, pentachlorophenol) or a mixture thereof, and the refractory organic chemical substance is contained in hemoglobin It is decomposed into carbon dioxide by reaction with heme.

The degradation process of refractory organic chemicals is described in detail as follows: (1) heme radicalization by reaction of heme (Hb-Fe ⁺³ ) with hydrogen peroxide; (2) heme radical (Hb-Fe ⁺ (R ㅇ) and Heme (Hb-Fe ⁺³ ) by radical reaction of organic radicals (R ㅇ) and organic radicals Oxidation and carbon dioxide generation.

The present invention provides an optimal apparatus for washing contaminated soil using a biosurfactant, and catalytic reaction using hemoglobin and hydrogen peroxide.

Hereinafter, a soil recovery apparatus according to an embodiment of the present invention will be described in detail with reference to the drawings.

1, a soil recovery apparatus according to an embodiment of the present invention includes a screen device 110, a bio-slurry reactor 130, a soil microbial culture device 120, a pressurized floating tank 140, A cyclone device 150, a catalytic reaction device 160, and a biological reaction device 170.

The screen device 110 is a device for separating contaminated soil from crude oil contaminated with crude sludge, contaminated soil, etc., and can remove the contaminated soil using a mesh network of about 4 to 10 mm.

The bioslurry reactor 130 is a device for washing contaminated soil using a biosurfactant supplied from the soil microbial culture apparatus 120. The soil microorganism culturing apparatus 120 is an apparatus for cultivating soil microorganisms. The soil microorganism produces a biosurfactant during the culturing of the soil microorganism, and the biosurfactant generated by the soil microorganism is combined with the soil microorganism, The soil microorganism cultivation apparatus 120 will be described later in detail.

When the contaminated soil filtered by the screen device 110 is supplied to the bioslurry reactor 130, contaminated soil is washed by the cultured material when the culture is supplied from the soil microbial culture device 120. The culture means a mixture of culture medium, soil microorganism, and biological surfactant discharged from the soil microorganism culture apparatus 120. The crude oil component adsorbed on the contaminated soil is dissolved through the emulsifying action by the biosurfactant component of the culture.

Also, as the soil microorganism is contained in the culture, the soil microorganism grows continuously in the bioslurry reactor by using the crude oil component dissolved by the biological surfactant as a carbon source, and thereby, a biological surfactant is additionally produced . Additional biosurfactants are also used to clean contaminated soil.

Meanwhile, the bioslurry reactor 130 is operated under aerobic conditions for the growth of soil microorganisms, and the aerobic condition in the bioslurry reactor may be set to a dissolved oxygen concentration of 2 to 5 mg / L. In addition, a stirrer may be provided in the bioslurry reactor 130 to enhance contact efficiency between the contaminated soil and the culture. In addition, the culture supplied to the bioslurry reactor 130 is about 2 to 4 L per 1 kg of contaminated soil. For soil microbial activity in the bioslurry reactor 130, 0.01 to 0.05 g of hemoglobin Can be input. The hemoglobin serves as a carbon source of the soil microorganism.

The pressurized floating tank 140 receives a bio-slurry from the bioslurry reactor 130 and separates the bioslurry into contaminated soil, a culture liquid, and a floating body through a pressurization floating principle. The bio slurry is a result of completion of the washing process in the bioslurry reactor 130, which means that the contaminated soil washed, the culture used, the crude oil component separated from the contaminated soil, and the used biosurfactant are mixed.

When bubbles are injected into the bio slurry through the bubble generator in a state where the bioslurry is supplied to the pressurized floating tank 140, The slurry is separated into contaminated soil, culture, and float (crude oil and biosurfactant). Specifically, the crude oil component and the used biosurfactant component suspended in the used culture medium or adsorbed on the contaminated soil are combined with the air bubbles and floated above the pressurized floating tank 140, whereby the pollutant components Biosurfactant) is removed and the residual contaminants in the contaminated soil are minimized. At this time, a part of the soil microorganisms in the culture liquid may combine with the bubbles and float above the pressurized floating tank 140.

The culture liquid and the floating matter (crude oil component and biosurfactant component) separated by the pressurized floating tank 140 are transferred to the soil microorganism culture apparatus 120 and the contaminated soil separated by the pressurized floating tank 140 And transferred to the cyclone device 150. The float separated by the pressurized floating tank 140, that is, the crude oil component and the biosurfactant component are transferred to the soil microorganism culturing apparatus 120 and separated by the pressurized floating tank 140 The culture medium and contaminated soil may be supplied to the cyclone apparatus 150.

The cyclone device 150 is a device for solid-liquid separation of contaminated soil separated by the pressurized floating tank 140 by centrifugal force. The cyclone device 150 separates the biosurfactant component and the physically detachable crude oil component remaining in the contaminated soil from the contaminated soil It separates. The crude oil component and the biosurfactant component separated from the cyclone reactor are transferred to the soil microorganism culture apparatus 120 and the contaminated soil separated from the cyclone reactor is transferred to the catalyst reaction apparatus 160. At this time, in the case where the culture liquid and the contaminated soil are supplied to the cyclone apparatus 150 together, the crude oil component and the biosurfactant component are desorbed from the contaminated soil by the centrifugal force, and the desorbed crude oil component and the biosurfactant component are separated from the culture liquid And then transferred to the soil microorganism cultivation apparatus 120 together.

The contaminated soil separated by the screen device 110 is washed sequentially in the bioslurry reactor 130, flotation separation in the pressurized floating tank 140, and solid-liquid separation in the cyclone reactor. The crude oil component adsorbed on the contaminated soil is reduced, and the crude oil component is supplied to the catalytic reactor 160 in a state where the crude oil component is minimized.

The catalytic reactor 160 is a device for decomposing a refractory organic chemical substance of a contaminated soil through a catalytic reaction using hemoglobin and hydrogen peroxide (H ₂ O ₂ ) The soil microbial culture apparatus 120 will be described.

The soil microorganism culturing apparatus 120 is a device for cultivating soil microorganisms as described above. The soil microorganism culturing apparatus 120 generates biological surfactant by culturing soil microorganisms, and is recovered from the cyclone apparatus 150 and the pressurized floating tank 140 The crude oil component is decomposed and removed as the carbon source of the soil microorganism.

Specifically, the soil microbial culture apparatus 120 includes a culture tank 121 and a storage tank 122. A culture liquid is provided in the culture tank 121, and soil microorganisms are cultured in the culture liquid. The culture tank 121 is supplied with the culture liquid, the crude oil component, and the used biological surfactant recovered from the pressurized floating tank 140 and the cyclone device 150. As the culture solution, a phosphoric acid solution can be used.

As the soil microorganism cultured in the culture tank 121, it is preferable to apply the soil microorganism extracted from the contaminated soil to be treated. Soil microorganisms present in contaminated soil are alive in the soil environment contaminated with crude oil. Since the soil microorganism is grown by using crude oil as a carbon source, soil microorganisms are extracted and cultured from the contaminated soil to be treated, When applied, it is effective in the purification of contaminated soil. Soil microorganisms grown in soils polluted with crude oil have various types according to the area and environment where the contaminated soil exists. In the soil microorganisms growing in soil contaminated with crude oil, Flavobacterials, Burkholderiales, and Pseudomonadales are typical examples of soil microorganisms. Soil microorganisms such as Flavobacteriales, Burkholderiales, and Pseudomonadales are grown by using crude oil as a carbon source in the presence of crude oil and have a characteristic of generating a biological surfactant during the growth and discharging it to the outside of the cell.

As the crude oil component recovered from the pressurized floating tank 140 and the cyclone apparatus 150 is supplied into the culture tank 121 of the soil microorganism culture apparatus 120, the soil microorganisms cultivated in the culture tank 121 are subjected to pressurization The crude oil supplied from the tank 140 and the cyclone device 150 is used as a carbon source. As the soil microorganisms are cultivated, biosurfactants are produced by the soil microorganisms. As the crude oil component recovered from the pressurized floating tank 140 and the cyclone apparatus 150 is used as a carbon source of the soil microorganism, The formation of the biosurfactant is simultaneously carried out. That is, the soil microorganism culturing apparatus 120 cultivates soil microorganisms to produce a biosurfactant and removes crude oil components recovered from the pressurized floating tank 140 and the cyclone apparatus 150. In order to promote the growth of soil microorganisms (in other words, to promote the production of biological surfactants by soil microorganisms) in culturing the soil microorganisms in the culture tank 121, 1 L of the culture liquid 0.3 to 0.7 g of hemoglobin can be added. The hemoglobin is an additional carbon source of the soil microorganism as it is more easily decomposed by the soil microorganism than the crude oil component.

The biological surfactant generated by the soil microorganism in the culture tank 121 is moved to the storage tank 122 together with the soil microorganism and the culture liquid and the culture of the storage tank 122, that is, the culture liquid, the soil microorganism and the biological surfactant The mixture is fed to the bioslurry reactor (130). The biosurfactant supplied to the bioslurry reactor is used for washing contaminated soil. When soil microorganisms are supplied to the bioslurry reactor, it is possible to generate additional biosurfactants by the soil microorganisms in the bioslurry reactor. The resulting biosurfactant is also used to clean contaminated soil. At this time, soil microorganism grows by using crude oil component of contaminated soil dissolved by biosurfactant as carbon source. The soil microorganism grows in the soil microorganism cultivation apparatus 120 by using the crude oil component recovered from the pressurized floating tank 140 and the cyclone apparatus 150 as a carbon source so that the crude oil component is decomposed and removed, In the slurry reactor, part of the crude oil is decomposed and removed in the bioslurry reactor together with the washing of the contaminated soil as the crude oil component in which the soil microorganisms are dissolved is used as a carbon source. Further, since the soil microorganism exists in the bio slurry discharged from the bioslurry reactor 130 and transferred to the pressurized floating tank 140, the effect of decomposition and removal of some crude oil by the soil microorganisms is also prevented in the pressurized floating tank 140 You can expect.

The screen device 110, the soil microbial culture device 120, the bioslurry reactor 130, the pressurized floating tank 140, and the cyclone device 150 have been described above. Next, the catalytic reaction device 160 and the biological reaction device 170 will be described.

The catalytic reactor 160 is a device for decomposing a refractory organic chemical substance in a contaminated soil through a catalytic reaction using hemoglobin and hydrogen peroxide (H ₂ O ₂ ) (162). The mixing tank 161 provides a mixing space between the catalyst and the contaminated soil discharged from the cyclone device 150. The catalyst reaction tank 162 activates the catalyst to induce a reaction between the catalyst and the refractory organic chemical substance do.

The catalyst means hemoglobin or a mixture of hemoglobin and heme, and the catalyst is supplied to the mixing tank 161 in the form of a solution or a powder. In one embodiment, a solution in which a mixture of hemoglobin or hemoglobin and heme is dissolved in a phosphate buffer solution may be supplied to the mixing tank 161 or hemoglobin powder may be supplied to the mixing tank 161 .

In the present specification, the heme may mean a complex formed by incorporating iron atoms at the center of porphyrin, which is a plane molecule having four pyrrole rings. The heme may be a non-protein portion contained in an in vivo enzyme such as hemoglobin or cytochrome, or may be used when it is separated from an in vivo enzyme or obtained by artificial synthesis. In addition, the heme may include heme a (cytochrome c oxidase), heme b (hemoglobin and the like), heme c (C-type cytochrome), heme d (heme a ₂ ), heloheme or chlorocruroloheme, But is not limited thereto. In addition, heme may be mesoheme, diterateheme, or coopheme, but is not limited thereto. More specifically, the heme may include a complex salt for trivalent iron ions at the center of porphyrin, a plane molecule having four pyrrole rings. In addition, in the present specification, the hemoglobin is a molecule containing four hems and can be used without limitation from its origin.

Next, the catalyst reaction tank 162 provides a space for inducing the reaction of the catalyst and the refractory organic chemicals present in the contaminated soil. When hydrogen peroxide (H ₂ O ₂ ) is supplied to the catalytic reaction tank 162 while the mixture of the contaminated soil and the catalyst is supplied to the catalytic reaction tank 162, the refractory organic chemicals in the contaminated soil react with the catalyst and hydrogen peroxide Lt; / RTI >

Specifically, the decomposition mechanism of the decomposable organic chemical substance is as follows. The following diagram illustrates the reaction between heme (Hb-Fe ⁺³ ), hydrogen peroxide (H ₂ O ₂ ) and refractory organic chemicals (RH), which may be the hem component of the hem itself or hemoglobin .

<MODEL>

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

Hb-Fe ^{+ 4} ㅇ: Heme radicals produced by the reaction of heme and hydrogen peroxide

RH: Hazardous organic chemicals

R ㅇ: Non-degradable organic chemicals produced by catalytic oxidation of RH and Hb-Fe ⁺⁴ ㅇ Radical

Organic oxides of refractory organic chemicals produced by catalytic reduction of R _ox : R ㅇ and heme (Hb-Fe ⁺³ )

CO ₂ : the final product obtained after the decomposition of refractory organic chemicals

As shown in the schematic, the hem (Hb-Fe ⁺³⁾ is hydrogen peroxide and the reaction for 4 gacheol heme radical (Hb-Fe ⁺⁴ o) to a conversion, and instability of the heme gacheol 4 radical (Hb-Fe ⁺⁴ o ) Reacts with refractory organic chemicals (RH) in the contaminated soil and is converted to tetravalent heme (Hb-Fe ^{+ 4} ) and stabilized. At the same time, the refractory organic chemical is converted to a radical form (R) and reacted with 4-heptyl heme (Hb-Fe ^{+ 4} ) to be oxidized (R _ox ). As the cycle progresses, only carbon dioxide (CO ₂ ) is ultimately left as a result, and the refractory organic chemicals in the contaminated soil are purified.

In addition, the mechanism represented in the above formula can be expressed by the following formula.

(1) Hb-Fe ⁺³ + H ₂ O _{2 -} > Hb-Fe ^{+ 4}

(2) Hb-Fe ^{+ 4} + RH + Hb-Fe + ⁴ + R

(3) Hb-Fe + ⁴ + R? -> Hb - Fe ⁺³ + R _ox

The supply amount of hydrogen peroxide to be supplied to the catalytic reaction tank 162 should be determined according to the amount of hemoglobin, and the weight ratio of hydrogen peroxide / hemoglobin should be adjusted to 2 to 10. If the weight ratio of hydrogen peroxide / hemoglobin is less than 2, the production of tetravalent hemacal (Hb-Fe ^{+ 4} ) is deteriorated due to the lack of hydrogen peroxide used as an oxidizing agent in the catalytic reaction, However, there is a problem that the reaction is stopped in the 4-heptane heme (Hb-Fe ^{+ 4} ) reaction step, and the continuous catalytic mechanism is stopped. In addition, when the weight ratio of hydrogen peroxide / hemoglobin is more than 10, trivalent iron is eluted at the central portion of the heme structure, so that it does not act as a catalyst, and the microorganisms existing in the soil are killed by the oxidizing power of excess hydrogen peroxide, Decomposition effect and healthy soil can not be expected.

The bioreactor 170 performs a biological exhalation treatment on the reaction effluent discharged from the catalytic reaction tank 162 to remove the refractory organic chemicals remaining in the contaminated soil. The reaction discharge means contaminated soil, residual catalyst solution, residual hydrogen peroxide, reaction by-products, etc. discharged from the catalyst reaction tank 162.

The microorganisms in the contaminated soil in the reaction effluent are grown by using the globin component of hemoglobin as an organic carbon source under aerobic conditions of the bioreactor 170 and the growth and activation of aerobic microorganisms such as cooxidation or co- Metabolism (cometabolism), the degradable organic chemicals remaining in the contaminated soil are degraded. Further, the bioreactor 170 further includes an agitator, and water contained in the reaction effluent is reduced through the mixing process of the reaction effluent by the agitator, the growth and activation of aerobic microorganisms.

The soil recovery apparatus according to an embodiment of the present invention has been described above. Hereinafter, the present invention will be described in more detail with reference to experimental examples.

FIGS. 3 and 4 show the amount of carbon dioxide generated and the result of TPH concentration after application of the soil remover according to the present invention to the contaminated soil of crude oil in the Kuwait area. The amount of carbon dioxide produced is the result of evaluating the degree of complete oxidation of the refractory organic chemicals, and the TPH concentration means the TPH concentration remaining in the soil.

In FIG. 3, 'H1' represents the amount of carbon dioxide produced when hydrogen peroxide is not added during the catalytic reaction to contaminated soil through a bioslurry reactor, a pressurized float tank, and a cyclone apparatus. 'H2' represents the result of addition of hydrogen peroxide to be. The results of both 'H1' and 'H2' indicate that the amount of carbon dioxide generated during 30 days of treatment increases over time, which means that the crude oil component of the contaminated soil has been continuously removed. The results of FIG. 3 are also confirmed through the results of FIG. Referring to FIG. 4, it can be seen that TPH concentration abruptly decreases for the first 7 days, and most of the TPH in the contaminated soil is removed at about 20 days.

110: Screen device 120: Soil microorganism culture device
121: Culture tank 122: Storage tank
130: Bioslurry reactor 140: Pressurized floating tank
150: cyclone device 160: catalytic reaction device
161: mixing tank 162: catalytic reaction tank
170: Bioreactor

Claims

Screen apparatus for separating contaminated soil from crude oil contaminants;
A soil microorganism culturing apparatus which cultivates a soil microorganism and makes it possible to produce a biosurfactant by the soil microorganism;
A bioslurry reactor for receiving a cultured mixture of a culture solution, a soil microorganism and a biosurfactant from the soil microorganism culture apparatus and washing the contaminated soil using the culture;
A pressurized floating tank for separating the bioslurry discharged from the bioslurry reactor into a contaminated soil, a culture liquid and a floating material by using a pressurization flotation principle;
A cyclone apparatus for subjecting contaminated soil separated by a pressurized floating tank to solid-liquid separation; And
And a catalytic reactor for decomposing the pollutant-decomposing organic chemicals of the contaminated soil through a catalytic reaction by stirring the contaminated soil with a catalyst containing heme and hydrogen peroxide,
Wherein the pressurized floatation vessel floats the crude oil component and the biosurfactant component in the bioslurry using a bubble as a float and the contaminated soil and the culture liquid separated by the pressurized floatation tank are transferred to the cyclone apparatus, Device,
In the cyclone apparatus, the mixture of the contaminated soil and the culture liquid separated by the pressurized floating tank is subjected to solid-liquid separation using a centrifugal force, and the separated biosurfactant component, the crude oil component desorbed from the contaminated soil, and the culture liquid are recovered in the soil microorganism culture apparatus , The separated contaminated soil is supplied to the catalytic reactor,
The bioslurry reactor is operated under aerobic conditions for the growth of soil microorganisms, wherein aerobic conditions in the bioslurry reactor are set to a dissolved oxygen concentration of 2 to 5 mg / L,
A stirrer is provided in the bioslurry reactor to increase the contact efficiency between the contaminated soil and the culture,
Wherein 0.01-0.05 g of hemoglobin is added per liter of the culture for soil microbial activity in the bioslurry reactor.

The soil remover according to claim 1, wherein the soil microorganism grows using a crude oil component as a carbon source, and generates a biosurfactant in a growing process.

The soil restoration apparatus according to claim 1, wherein the soil microorganisms are soil microorganisms extracted from contaminated soil.

The soil remover according to claim 1, wherein the soil microorganism is any one of Flavobacterials, Burkholderiales, Pseudomonadales or a mixture thereof.

The biosurfactant according to claim 1, wherein in the bioslurry reactor, the biosurfactant dissolves the crude oil component of the contaminated soil through an emulsification action, and the soil microorganism grows using the dissolved crude oil component as a carbon source. Device.

delete

The soil microorganism culture apparatus according to claim 1, wherein the soil microbial culture apparatus comprises a culture tank and a storage tank,
The culturing tank cultivates soil microorganisms using a culture medium, and a soil microorganism produces a biosurfactant during the culturing of the soil microorganisms,
Wherein the crude oil component, the biosurfactant component, and the culture liquid recovered from the pressurized floating tank and the cyclone apparatus are supplied to the culture tank.

[Claim 10] The method according to claim 10, wherein the biosurfactant produced by the soil microorganism in the culture tank is transferred to the storage tank together with the soil microorganism and the culture liquid, and the culture in the storage tank is supplied to the bioslurry reactor. Device.

delete

The method according to claim 1,
The process of heme (Hb-Fe ⁺³⁾ is reacted with hydrogen peroxide converted to 4 gacheol heme radical (Hb-Fe ⁺⁴ o) and,
(Hb-Fe ⁺⁴ ) reacts with the refractory organic chemical (RH) to convert it to tetravalent heme (Hb-Fe ^{+ 4} ), and the refractory organic chemical (RH) A process of converting into an organic chemical radical (R)
Characterized in that it comprises a process in which tetravalent heme (Hb-Fe ^{+ 4} ) is reduced to heme (Hb-Fe ^{+ 3} ) and oxidation of the refractory organic chemical radical (R) to produce carbon dioxide Soil restoration device.

2. The soil restoration apparatus according to claim 1, wherein the catalyst comprises hemoglobin and the weight ratio of hydrogen peroxide / hemoglobin is 2 to 10.

The bioreactor according to claim 1, further comprising a bioreactor for agitating the reaction effluent of the catalytic reactor under exhalation conditions to decompose the biodegradable organic chemical through growth and activation of the soil microorganism. Device.