JP3401191B2 - Method for purifying contaminants by halogenated organic compounds - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for purifying pollutants by halogenated organic compounds, particularly chlorinated organic compounds, such as soil, sediment, sludge, and water, and more particularly to chemical and biological reactions. The present invention relates to a method for purifying pollutants by decomposing halogenated organic compounds by a combined reductive dehalogenation reaction.

[0002]

2. Description of the Related Art In recent years,
Contamination of soil and groundwater by halogenated organic compounds such as tetrachlorethylene, trichlorethylene, 1,1,1-trichloroethane, and dichloroethylene, which are widely used as degreasing / cleaning agents for metal parts of electronic devices and cleaning agents for dry cleaning. Has been done. Since these halogenated organic compounds are not easily decomposed in nature and are poorly water-soluble, they easily accumulate in soil and penetrate into groundwater in the contaminated area. Further, the halogenated organic compound causes liver damage and has carcinogenicity. Therefore, it is desired to decompose halogenated organic compounds such as chlorinated organic compounds contained in soil and the like.

Recently, a microbial treatment method (bioremediation) has been attracting attention as a method for purifying soil, groundwater and the like contaminated with halogenated organic compounds. The microbial treatment method is cost-effective and highly safe. However, the microbial treatment method is not always sufficiently satisfactory because the treatment takes a long time and the types and concentrations of substances that can be decomposed are limited, as described below.

As an example of the microbial treatment method, many aerobic decomposition treatment methods of trichlorethylene by methane-utilizing bacteria, toluene / phenol-degrading bacteria, ammonia-oxidizing bacteria, and alkene-assimilating bacteria have been reported. But 1)
The decomposition reaction is unstable, 2) the range of the decomposition target substance is extremely narrow, and 3) highly chlorinated substances such as tetrachloroethylene and carbon tetrachloride do not have a decomposition action.

On the other hand, many anaerobic microorganisms can decompose a wide range of highly chlorinated organic compounds such as tetrachloroethylene, trichlorethylene and carbon tetrachloride.
However, there are drawbacks such as 1) very slow growth of microorganisms, 2) generation and accumulation of highly toxic intermediate metabolites during anaerobic decomposition (Yuo Uchiyama, Shu Yagi, Bioscience and Industry, 1 1994, Vol. 52, No. 11, pp. 879-884).

On the other hand, as a technique for decomposing halogenated organic compounds by a chemical reaction, reductive treatment of chlorinated organic compounds with metallic iron has been reported (Tetsuo Maezaki, treatment of groundwater contaminated with organochlorine compounds-activated iron with metallic iron). Processing Technology at Low Temperature by "PPM", 1995, Volume 26,
No. 5, pp. 64-70). Therefore, the present inventor tried a dechlorination test by adding metallic iron to the soil in the absence of the carbon source of the microorganism. However, no dechlorination reaction was observed under the condition where the microorganism was not cultured, particularly under the condition that the reducing atmosphere and the neutral condition were not maintained. Further, even when an iron salt such as FeCl ₂ , FeCl ₃ , or FeSO ₄ was added instead of metallic iron, the dechlorination reaction was not observed.

Further, a method of injecting metallic iron and high-pressure air into a polluted soil to react a halogenated organic compound with iron powder to make it inorganic and detoxify it has been reported (JP-A-8-257570). ). Also in this method, there are problems such as a problem of air injection equipment and a fear of vaporization of halogenated organic compounds. Furthermore, since high pressure air is used, a cost problem arises and it is not practical.

[0008] Further, there has been reported a method of removing an organic chlorine compound contaminating soil or groundwater by combining a natural substance having a dehalogenation catalytic action and a microbial treatment (Nikkei Biotech) (published by Nikkei BP). 1996, 10
Issued March 7th, No. 361, pp. 14-15). But,
No specific natural substances or microorganisms are mentioned.

US Pat. No. 5,411,664 describes a method for decomposing halogenated organic compounds by adding fibrous organic matter and polyvalent metal particles such as iron to the pollutants. However, this US patent does not describe reducing agents such as reduced iron, cast iron, alloys and water-soluble reducing agents. Further, there is no description of maintaining the contaminants in a reducing atmosphere and a predetermined pH after adding the reducing agent.

Further, depending on the composition of the nutrient source to be added,
Since biological reduction reactions such as sulfuric acid reduction and methane fermentation occur in soil, sulfurous malodorous gases such as hydrogen sulfide and mercaptan, and combustible gases such as methane gas may be generated. In addition, the soil may turn black due to the production of iron sulfide and the like. Furthermore, flammable hydrogen gas may be generated due to the reaction between the metal powder and water.

Furthermore, it is easy to uniformly mix the reducing agent, the nutrient source and the contaminant in the laboratory. On the other hand, in order to actually purify pollutants such as soil,
Civil engineering work is required because a large amount of reducing agents and nutrient sources will be mixed. Also, it is not always easy to mix them uniformly. Furthermore, it is assumed that the conditions at the time of kneading affect the decomposition rate of the halogenated organic compound. In particular, in order to purify contaminants having a volume of 1 m ³ or more, particularly 10 m ³ or more, it is necessary to devise a kneading method.

[0012]

The object of the present invention is to provide a method for purifying pollutants by halogenated organic compounds by decomposing halogenated organic compounds by combining chemical reactions and biological reactions. And

The first aspect of the present invention aims to decompose a halogenated organic compound by a reductive dehalogenation reaction.

The second aspect of the present invention aims to decompose a halogenated organic compound by a chemical dehalogenation reaction.

In the third aspect of the present invention, it is possible to prevent generation of a sulfur-based malodorous gas or a flammable gas which is secondarily generated in the reductive dehalogenation reaction, and an excessive discoloration of pollutants such as soil. With the goal.

In a fourth aspect of the present invention, it is an object to effectively mix the nutrient source and the reducing agent with the contaminant in the case of the contaminant having a large volume.

The first aspect of the present invention is characterized in that a nutrient source for water-soluble heterotrophic anaerobic microorganisms and a predetermined reducing agent are added, and a reducing atmosphere by a microbial decomposition reaction is used.
Promotes the reductive dehalogenation reaction through maintaining the gas .

The second aspect of the present invention is characterized in that a predetermined reducing agent is added, which accelerates the chemical dehalogenation reaction.

[0019]

The fourth aspect of the present invention is characterized by the step of mixing the reducing agent and the nutrient source with the pollutant.
1 m ³ or more, especially when purifying contaminants 10 m ³ or more volumes, it is possible to mix these more uniformly.

[0021]

In a first aspect of the present invention, there is provided a method for purifying contaminants by a halogenated organic compound, wherein a standard electrode potential with respect to a standard hydrogen electrode at 25 ° C. is 130 mV to -2400.
a reducing agent which is mV, and a nutrient source of a heterotrophic anaerobic microorganism consisting of a water-soluble organic carbon source , and a step of adding to the contaminant, the reducing agent is reduced iron, cast iron, iron-silicon alloy , A titanium alloy, a zinc alloy, a manganese alloy, an aluminum alloy, a magnesium alloy, a calcium alloy, and a water-soluble compound are provided. Do not use such water-soluble organic carbon source
In the presence of a nutrient source and a reducing agent, reductive dehalogenation by a combination of chemical reactions and microorganisms can be promoted.

In the present invention, the reducing agent has a standard electrode potential of −400 m with respect to a standard hydrogen electrode at 25 ° C.
V to -2400 mV and reduced iron, cast iron, iron-
Silicon alloy, titanium alloy, zinc alloy, manganese alloy,
At least one selected from an aluminum alloy, a magnesium alloy, and a calcium alloy is preferable. Further, it is preferable that the reducing agent contains reduced iron. Alternatively, the reducing agent preferably contains cast iron. Alternatively, the reducing agent is iron-silicon alloy, titanium-silicon alloy, titanium-aluminum alloy, zinc-
It is at least one selected from the group consisting of aluminum alloys, manganese-magnesium alloys, aluminum-zinc-calcium alloys, aluminum-tin alloys, aluminum-silicon alloys, magnesium-manganese alloys, and calcium-silicon alloys. preferable.

The reducing agent is preferably a water-soluble compound. The reducing agent is an organic acid or a derivative thereof,
More preferably, it is hypophosphorous acid or its derivative, or a sulfide salt.

The reducing agent is preferably a powder having a particle size of 500 μm or less. In the present specification, the powder is not limited to powder having a particle size of 500 μm or less. The water content of the contaminants is preferably at least 25% by weight.

After the adding step, it is preferable to further include a step of maintaining the contaminant in a pH range of 4.5 to 9.0 in order to promote reductive dehalogenation of the halogenated organic compound. It is further preferable to further include a step of maintaining the contaminant in a reducing atmosphere in a pH range of 4.5 to 9.0 after the adding step.

[0027] Various organic composts, composted organic matter,
Alternatively, it is preferable to have a step of adding wastewater or waste containing organic matter to the pollutant and then mixing.

In the first aspect of the present invention, the water-soluble reducing agent has 1 to 20 carbon atoms and may be substituted with a hydroxyl group, such as a monocarboxylic acid, a dicarboxylic acid or a tricarboxylic acid, Alternatively, it is preferably tetracarboxylic acid or a salt thereof, polyhydroxyaryl, or hypophosphorous acid or a salt thereof. The water-soluble reducing agent is preferably hypophosphorous acid or a salt thereof. Further, the water-soluble reducing agent may be a salt composed of an organic acid or hypophosphorous acid and iron, titanium, zinc, manganese, aluminum or magnesium.

In order to adjust the pH of the contaminant, it is preferable to have a step of adding at least one of an alkali metal compound and an alkaline earth metal compound to the contaminant. In the holding step, the halogenated organic compound is preferably converted into an organic compound containing no halogen atom. In the holding step, it is preferable that the halogenated organic compound is converted into a hydrocarbon containing no halogen atom.

[0030]

The reducing agent has a standard electrode potential of −400 mV to −2400 mV with respect to a standard hydrogen electrode at 25 ° C., and a reducing agent, cast iron, iron-silicon alloy, titanium alloy, zinc alloy, manganese alloy, aluminum alloy. At least one selected from a magnesium alloy, a magnesium alloy, and a calcium alloy is preferable.

The dry weight of the contaminant is 1 k
It is preferable that 0.1 g to 100 g of an iron compound is contained based on g, and the pollutant contains 1 g to 100 g of an iron compound based on 1 kg of the dry weight of the contaminant. It is further preferred that the compound contains iron hydroxide (Fe (OH) ₃ ) or triiron tetroxide (Fe ₃ O ₄ ).

Furthermore, the reducing agent is an iron-silicon alloy, titanium-silicon alloy, titanium-aluminum alloy, zinc-aluminum alloy, manganese-magnesium alloy, aluminum-zinc-calcium alloy, aluminum-tin alloy, aluminum- It is preferably at least one selected from the group consisting of silicon alloys, magnesium-manganese alloys, and calcium-silicon alloys.

Alternatively, the reducing agent is preferably a water-soluble compound. Further, the reducing agent is preferably an organic acid or a derivative thereof, a hypophosphorous acid or a derivative thereof, or a sulfide salt. The reducing agent is 5
A powder having a particle size of 00 μm or less is preferable. In addition, in the present specification, the powder has a particle size of 500.
The powder is not limited to powder having a size of μm or less.

[0035]

In the present invention, a heterotrophic anaerobic microorganism
Is a water-soluble organic carbon source. Water-soluble organic carbon
Sources include sugars, organic acids or their derivatives, and lower acids.
Rucor, molasses waste liquor, brewing waste liquor or this
It is preferably a mixture of these. Specifically, grapes
Sugar, sucrose, lactic acid, acetic acid, citric acid, pyruvic acid, as
Corbic acid, sodium lactate, sodium acetate, citric acid
Sodium acid salt, sodium thioglycolate, methanol
It is preferable to use alcohol, ethanol or the like.

Further, the reducing agent has a standard electrode potential of −400 mV to −24 with respect to the standard hydrogen electrode at 25 ° C.
It is preferably a metallic substance having a voltage of 00 mV. The reducing agent is preferably at least one selected from the group consisting of reduced iron, cast iron, iron-silicon alloys, titanium alloys, zinc alloys, manganese alloys, aluminum alloys, magnesium alloys, and calcium alloys.

Alternatively, the reducing agent is preferably a water-soluble compound. The reducing agent is preferably a powder having a particle size of 500 μm or less.

[0039]

It is preferable that the organic carbon source is a saccharide, an organic acid or a derivative thereof, a lower alcohol, a molasses waste liquid, a brewing waste liquid, or a mixture thereof.

In the present invention , water-soluble organic charcoal is used to purify contaminants containing halogenated organic compounds and solids.
A step of mixing a nutrient solution containing a nutrient source of a heterotrophic anaerobic microorganism consisting of an elementary source and water, and a reducing agent having a standard electrode potential of 130 mV to -2400 mV with respect to a standard hydrogen electrode at 25 ° C. with the contaminant. When, wherein said mixing step, said contaminants and comprising the step of preparing a range of PH4.5～9.0; said mixture and a step of standing at low air conditions; comprise virtuous
Good

In the present invention, it is possible that the reducing agent is in powder form, the nutrient solution is added to the contaminant and then mixed, and the reducing agent is added to the mixture and then mixed. preferable.

The reducing agent is preferably a powder having a particle size of 500 μm or less. In the present specification, the powder is not limited to powder having a particle size of 500 μm or less.

Further, the reducing agent is reduced iron, cast iron, iron-
Silicon alloy, titanium alloy, zinc alloy, manganese alloy,
At least one selected from the group consisting of aluminum alloys, magnesium alloys, and calcium alloys is preferable.

In the first step, a step of adding 1 to 10 vol% of the nutrient solution to the contaminants based on the contaminants and mixing them, and then an amount larger than the amount added in the first stage It is preferable that the method further comprises the step of adding the nutrient solution to the contaminants and mixing them.

Alternatively, as a first step, a step of adding 1 to 5 vol% of the nutrient solution to the contaminants based on the contaminants and mixing them, and then, as a second step, a first step
In addition to the step, adding the nutrient solution to the pollutant so as to be 5 to 10 vol% based on the pollutant, and mixing, and further, an amount larger than the amount added in the first step or the second step. It is preferable that the method further comprises the step of adding the nutrient solution to the contaminants and mixing them.

The reducing agent is a water-soluble compound,
It is preferable that the reducing agent be dissolved in the nutrient solution. Furthermore, in the standing step, at least the first 3
It is preferable to keep the contaminants at 17 ° C to 60 ° C for a day.

In the present invention, based on the above contaminants, 15
It is preferable to finally add ˜25 vol% of the nutrient solution to the contaminants.

In the stationary step, it is preferable to keep the contaminants at 17 to 60 ° C. for at least the first 5 days. Further, in the standing step, it is preferable to keep the contaminants at 20 ° C to 40 ° C for at least the first 3 days, preferably 5 days.

It is preferable that the stationary step is performed in a state of being separated from the surroundings. In order to maintain low aeration conditions, it is preferred to coat the contaminants with an impermeable material. In order to maintain low aeration conditions, it is preferable to immerse the contaminant in an aqueous liquid. It is preferable to mix the nutrient solution, the reducing agent, and the contaminant in a container.

According to the present invention, halogenated organic compounds
A method of cleaning pollutants according to the standard at 25 ℃
Standard electrode potential for hydrogen electrode is 130 mV to -2400 mV
Heterotrophic anaerobic type consisting of solid reducing agent and water-soluble organic carbon source
A step of mixing a nutritional source of aerobic microorganisms, and said mixture
Adding to said contaminants.
Be done.

In the present invention, it is preferable to mix the solid reducing agent with a nutrient solution containing the nutrient source and water.

Examples of the solid reducing agent include powder and powder-type reducing agents.

It is preferable that the adding step is started within 24 hours after the mixing step, more preferably within 6 hours, and further preferably within 2 hours. Is more preferable.

In the present invention, contaminants caused by halogenated organic compounds are purified. In the present specification, halogen means
Refers to fluorine, chlorine, bromine and iodine. In the present invention, it is possible to purify pollutants due to an organic compound having a halogen atom, particularly to purify a pollutant due to an organic compound having a chlorine atom and a bromine atom, and more particularly, an organic compound having a chlorine atom. It is possible to purify the pollutants caused by. The chlorinated organic compound is not limited to, for example, an aliphatic compound such as tetrachloroethylene, trichloroethylene, 1,1,1-trichloroethane and dichloroethylene, but an aromatic compound such as pentachlorophenol can be decomposed.

The pollutants which can be treated in the present invention include soil, sediment and sludge. It can also treat compost, composted organic matter, and waste. Then, in the present invention, an aqueous liquid such as groundwater or wastewater can be treated. As used herein, aqueous liquid includes aqueous solutions, suspensions, emulsions, and mixtures thereof.

When the pollutant is soil, sediment, sludge, etc., the water content thereof is preferably at least 25% by weight, more preferably 40 to 60% by weight. This is because it is preferable to make it difficult for air to enter soil, sludge, etc., because anaerobic microorganisms grow. This moisture content (%) is defined as follows.

Moisture content = (weight of water / weight of contaminant containing water) × 100 When the contaminant is water such as ground water or waste water, the moisture content is necessarily 25% by weight or more.

In the present invention, a reducing agent having a standard electrode potential of 130 mV to -2400 mV with respect to a standard hydrogen electrode at 25 ° C. and a nutrient source of a heterotrophic anaerobic microorganism consisting of a water-soluble organic carbon source are used as the contaminants. Addition promotes both chemical and biological reactions and decomposes halogenated organic compounds.

In the case of a substance whose standard electrode potential is higher than 130 mV, sufficient reducing power cannot be obtained. On the other hand, substances whose standard electrode potential is lower than -2400 mV, for example, alkali metals such as sodium metal and potassium are too strong in reducing power to explodely react with water to generate hydrogen gas, which is very high. It is dangerous and not desirable. 25 ° C
The standard electrode potential (E °) with respect to the standard hydrogen electrode in is shown in the following table.

[0061]

[Table 1] The standard electrode potential is a measurement of a battery reaction using a hydrogen electrode as a reference electrode when all chemical species involved in the battery reaction are in standard conditions (pure solid phase, standard concentration, standard pressure, etc.). It is a potential measured when it is performed and is equal to the standard potential E ⁰ . This value is expressed using the following equation.

E ⁰ = −ΔG ⁰ / nF Here, ΔG ⁰ is the standard Gibbs free energy change of the battery reaction, n is the number of electrons involved in the reaction, and F is the Faraday constant. Usually, the redox potential is often indicated by the potential measured using a saturated silver chloride electrode as a reference electrode, but the measured value in this case is about 200 mV compared to the standard potential measured using a hydrogen standard electrode as a reference electrode. Be careful as it shows a low value.

In the present invention, the reducing agent is selected from the group consisting of reduced iron, cast iron, iron-silicon alloys, titanium alloys, zinc alloys, manganese alloys, aluminum alloys, magnesium alloys, calcium alloys and water-soluble compounds. At least one kind.

The reducing agent has a standard electrode potential of −400 mV to −2400 m with respect to the standard hydrogen electrode at 25 ° C.
It is preferably a metallic substance which is V.

In one embodiment of the present invention, reduced iron is used as the reducing agent. The surface of iron powder is usually oxidized to form an oxide film. On the other hand, with reduced iron,
It has little oxide film, is easily oxidized, and has high reactivity.

Here, reduced iron refers to a type of metallic iron produced by reduction of oxides, which is in the form of extremely fine powder and is highly susceptible to oxidation (Chemical Dictionary 2, Chemical Dictionary Editorial Committee, Kyoritsu). Publishing Co.). Typically,
It was reduced with hydrogen gas at high temperature. Iron oxide may be reduced, but the oxide is not limited to iron oxide. Some reduced iron has a Fe content of 90% or more. For example, it can be obtained from Wako Pure Chemical Industries, Ltd.

In another embodiment of the present invention, cast iron is also preferably used as the reducing agent. This is because cast iron is safe, easy to handle, and can achieve a high purification rate. Further, shavings of cast products, that is, cast iron scraps are more preferable. This is because the shavings can be reused.

In general, among the irons industrially used by further removing impurities from pig iron produced by reducing iron ore,
Steel with a carbon concentration of about 2% (weight) or less is called steel, and steel containing more carbon is called cast iron ("Physical and Chemical Dictionary, 4th Edition 1").
987, p. 4 11).

Since steel has excellent mechanical properties, it is used for processing in many industrial products. We examined whether the steel shavings released at that time could be used in a method for cleaning substances polluted with halogenated organic compounds. Contains oil. If an attempt is made to purify the pollutants by the compound of organic chlorine of the present invention using this, there is a possibility of causing secondary pollution by oil. On the other hand, since cast iron used for casting does not use oil during cutting, casting product shavings (cast iron shavings) are similar to steel product shavings described above.
There is no risk of secondary pollution.

In another embodiment of the present invention, an alloy is used as the reducing agent. That is, iron-silicon alloy,
Titanium alloys, zinc alloys, manganese alloys, aluminum alloys, magnesium alloys, and calcium alloys are also used. Examples of titanium alloys include titanium-silicon alloys and titanium-aluminum alloys. Examples of zinc alloys include zinc-aluminum alloys. Examples of the manganese alloy include a manganese-magnesium alloy. Examples of the aluminum alloy include aluminum-zinc-calcium alloy, aluminum-tin alloy, aluminum-silicon alloy and the like.

Examples of magnesium alloys include magnesium-manganese alloys. Examples of calcium alloys include calcium-silicon alloys.

The action of the reducing agent will be described by taking the case of reduced iron as an example. Regarding the reaction mechanism of the anaerobic dehalogenation reaction with metallic iron, the report of Masaki who described the reaction of reduced iron (“Treatment of groundwater contaminated with organochlorine compounds-Treatment technology at low temperature with metallic iron-adhered activated carbon”, PPM, 1995
, Vol. 26, No. 5, pp. 64-70), adsorption of halogenated organic compounds occurs on the surface of the reduced iron, and at the same time, due to the difference in the conditions of the metal side and the environment side on the reduced iron surface, Polarization of the cathode occurs which causes a current flow. Along with this, iron is eluted as iron ions at the anode, while electrons flow into the cathode,
It seems that a reduction reaction such as a dehalogenation reaction occurs.

Anode: Fe → Fe²⁺ + 2e^- As mentioned above, cast iron has a carbon concentration of 2% or more.
Generally, 3 to 3.5% by weight and 13 to 14% by volume
It contains a large amount of carbon as graphite. Iwayu
The shavings (cast iron scraps) of casting products called ruzuku are waste.
It is generally milled before being discharged as.
At the time of crushing, some of the graphite escapes and becomes cast iron powder.
Adhere to the surface. Therefore, this cast iron powder is covered with a water film
And graphite act as the cathode, while iron
Acting as a cathode, current flows as described above, and the anode
Iron elutes at the cathode, and reduction reaction such as dehalogenation reaction occurs at the cathode.
It is thought that a response will occur. The above alloy is also made as an anode
It is thought that the alloy will elute when used. Meanwhile, the cathode
It seems that the dehalogenation reaction occurs at.

Further, in the case of an alloy having a stronger reducing power than metallic iron, the reducing atmosphere is more easily maintained, the potential difference with the halogenated organic compound becomes larger, and the dehalogenation reaction is accelerated.

Furthermore, when an alloy such as a magnesium-manganese alloy, a zinc-aluminum alloy, an aluminum-zinc-calcium alloy, or an aluminum-tin alloy is used, does an oxide film or a corrosion product adhere to the metal surface? Alternatively, even if it adheres, it does not form a dense film that does not hinder the reaction (not passivated), so that there is no problem of reduction in contact efficiency due to the reduction reaction, and the purification reaction can be performed efficiently.

In one embodiment of the present invention, the reducing agent is
It is preferably a water-soluble compound.

The efficiency of contact with the halogenated organic compound is dramatically increased as compared with the case where a solid such as powder is added, and the dehalogenation reaction is accelerated. Further, since the water-soluble reducing agent penetrates into the soil or the like, it is possible to inject the reducing agent using an injection well or the like, which does not require physical excavation and mixing work. Furthermore, if the reducing state becomes unstable during purification operation, it is possible to easily recover the reducing state by collecting the leachate of contaminants, adding a water-soluble reducing agent, and reinjecting it. Is.

Examples of the water-soluble reducing agent include organic acids or their derivatives, hypophosphorous acid or its derivatives, or sulfide salts. Examples of the organic acid include carboxylic acid, sulfonic acid, phenol and its derivatives. Examples of the carboxylic acid include a monocarboxylic acid, a dicarboxylic acid, a tricarboxylic acid, or a tetracarboxylic acid which has 1 to 20 carbon atoms and may be substituted with a hydroxyl group. Specifically, acetic acid, citric acid, terephthalic acid and the like are preferable, and particularly, citric acid and the like 2
Aliphatic dicarboxylic acids having 10 to 10 carbon atoms are preferred.

As the phenol derivative, polyhydroxyaryl is preferable. What is polyhydroxyaryl?
It means aryl substituted with two or more hydroxyl groups, and examples of aryl include benzene, naphthalene, anthracene and the like. In addition, a condensed ring such as naphthalene or indene may be formed. Examples of polyhydroxyaryl include 1,2,3-trihydroxybenzene,
1,4-dihydroxybenzene is preferred. here,
1,2,3-Trihydroxybenzene is also called pyrogallic acid or pyrogallol. The alkaline solution reacts with oxygen to form an oxide.

As the organic acid derivative, salts, esters,
Examples thereof include amides and acid anhydrides, and salts are preferable. The counter ion is not particularly limited, and includes alkali metal ions such as sodium ions; alkaline earth metal ions such as calcium ions; inorganic ions such as transition metal ions such as iron ions and titanium ions; or tetraalkylammonium ions. It may be an organic ion.

Examples of the hypophosphorous acid derivative include salts and esters, and salts are preferred. As the opposite ion,
There is no particular limitation, and alkali metal ions such as sodium ions; alkaline earth metal ions such as calcium ions;
It may be an inorganic ion such as a transition metal ion such as an iron ion or a titanium ion, or an organic ion such as a tetraalkylammonium ion.

Further, the reducing agent may be a salt composed of an organic acid or hypophosphorous acid and iron, titanium, zinc, manganese, aluminum or magnesium.

When these reducing agents were added, no production / accumulation of intermediate metabolites such as vinyl chloride, which is often reported in the anaerobic dehalogenation reaction, was observed, and all reaction products were completely removed. It was found that it was converted into a dehalogenated substance and released into the gas phase. Further, when a reducing agent having a standard electrode potential equal to or lower than that of metallic iron is used, the potential difference from the halogenated organic compound becomes larger and the dehalogenation reaction is promoted, which is preferable.

The amount of reducing agent used is such that when the pollutant is soil,
The amount is preferably 0.01 to 20 g, and more preferably 0.05 to 10 g per 100 g of soil. When the contaminant is water, 0.1 to 30 g is preferable per 100 ml of water,
More preferably, it is 0.2 to 20 g. In any case, when the contamination concentration of the halogenated organic compound to be dehalogenated exceeds 50 mg / kg (or 50 mg / l), 1 mg of the halogenated organic compound is
It is necessary to increase the addition amount of the reducing agent such as metal powder at a ratio of 0.05 to 0.1 g. However, this is only a value under ideal conditions, and at the actual pollution site, the reducing power of the reducing agent may be wastefully consumed if oxygen consumption by microorganisms is not carried out smoothly. In addition, the reducing power of the reducing agent is easily consumed by the supply of oxygen, etc. from rainwater or outside air.Therefore, a preliminary test should be carried out on-site and the addition concentration should be determined individually according to site conditions. .

In order to enhance the contact efficiency between the reducing agent and contaminants, the reducing agent is preferably in powder or solution form. However, many of the above-mentioned substances react with water and easily change to the oxidation state.In that case, it is desirable to directly mix the contaminant with the reducing agent or to dissolve the reducing agent in water immediately before mixing. In the case of powder, it preferably has a particle size of 500 μm or less. This is because when the particle size is small, the decomposition rate of the halogenated organic compound is improved.

Depending on the use, the reducing agent is preferably a powder having a particle size of 0.001 mm to 5 mm, more preferably 0.01 mm to 1 mm.

The particle size controls the rate of the chemical reduction reaction,
Note that the reduction reaction rate per unit weight decreases in proportion to the increase in particle size. Further, when the particle diameter is 5 mm or more and the surface of the metal particles is covered with a relatively thick oxide film when it is a metal substance, there is a high possibility that the metal in the reduced state in the central portion will not be used. On the other hand, when the particle size is 0.001 mm or less, the oxidation rate is very high, and the risk of being oxidized due to contact with water during transportation and mixing increases. When the reducing agent is a metal substance, even if the surface of the powder is oxidized, it can be used if the inside is in a reduced state and not oxidized.

Examples of heterotrophic anaerobic microorganisms include methanogenic bacteria (eg, Methanosarc).
ina genus, Methanothrix genus, Methan
genus Obacterium, Methanobrevib
Acter spp., sulfate-reducing bacteria (eg Desulf
genus ovrio, Desulfotomaculum
Genus, Desulfobacterium, Desul
genus fobacter, Desulfococcus
Genus), acid-producing bacteria (eg Clostridium
Genus, genus Acetivrio, Bacteroid
s genus, Ruminococcus genus, facultative anaerobic bacteria (eg Bacillus genus, Lactobacillus)
Us genus, Aeromonas genus, Streptococ
genus cus, genus Micrococcus) and the like.

In addition, the genus Bacillus, Pseudo
genus monas, genus Aeromonas, Strepto
The genus Coccus and the genus Micrococcus are preferable because they have an oxidized nitrogen reducing activity.

The nutrient source of the heterotrophic anaerobic microorganism is appropriately selected according to the microbial characteristics of the contaminant. For example,
It is only necessary to select a methanogenic microorganism medium, a sulfate-reducing microorganism medium, a nitrate-reducing microorganism medium, or the like. When selecting, a purification treatability test (purification applicability test) is performed to examine the purification efficiency of halogenated organic compounds. You can decide.

The nutrient source of the methanogenic microorganism may be a nutrient generally known as a growth nutrient source of the methanogenic microorganism represented by lactic acid, methanol, ethanol, acetic acid, citric acid, pyruvic acid, polypeptone and the like. Further, as a growth nutrient source for sulfate-reducing microorganisms, nutrients generally known as growth nutrient sources for sulfate-reducing microorganisms represented by lactic acid, methanol, ethanol, acetic acid, citric acid, pyruvic acid, polypeptone, sugar-containing organic substances and the like. Good.

Furthermore, organic wastewater / waste subjected to methane fermentation treatment is effective as a growth nutrient source for heterotrophic anaerobic microorganisms. For example, beer brewing wastewater, starch wastewater, dairy wastewater. , Sugar-making wastewater, beer lees, okara, sludge and the like.

When a liquid microbial medium is added, if an excessive amount is added, the permeation of halogenated organic compounds into the ground may proceed and the contamination may diffuse. On the contrary, if it is too small, microbial growth may occur. An appropriate water content cannot be secured, and growth is suppressed. For this reason, it is advisable to adjust and add a liquid microbial medium so that the water content in soil (sludge and the like is similar to soil) is 25 to 60%, preferably 35 to 60%. The amount of the medium to be added should be determined after sufficiently considering the soil water content, porosity, particle size composition, and hydraulic conductivity. Therefore, both the concentration of the microbial medium used for addition and the amount of the medium differ depending on the state of the contaminated soil, and should be carefully determined by the purification treatability test.

Further, in order to stably secure the water content in the soil, it is effective to appropriately mix diatomaceous earth, various water-retaining materials, saponified soil and the like.

When the pollutant is a substance having low water permeability such as clay soil or solid silt, it takes a long time because dechlorination treatment using only the reducing agent has low contact efficiency. It is considered that the reduced state becomes unstable depending on the supply conditions of the oxide from the outside. In this case, in addition to the reducing agent, an organic carbon source that serves as a growth substrate for microorganisms is added,
By decomposing and purifying under neutral conditions, the reduced state can be stabilized and complete dehalogenation purification can be achieved.

In the present invention, after adding the reducing agent,
The contaminants are preferably maintained in a reducing atmosphere. Here, the reducing atmosphere means that oxygen gas in the air is blocked by water or the like, for example. This is because heterotrophic anaerobic microorganisms are involved in the decomposition, and the presence of oxygen or the like inhibits the growth of such microorganisms. Further, it is considered that the reducing atmosphere is easily achieved by oxidizing the reducing agent. When the reducing agent is completely consumed, it may be difficult to maintain the reducing atmosphere.

As the reducing atmosphere, the standard electrode potential with respect to the standard hydrogen electrode at 25 ° C. is +200 to −24.
The range of 00 mV is preferable, and +200 to -1000 mV
Is more preferable, and the range of +100 to −600 mV is still more preferable.

In the present invention, it is preferable to maintain a predetermined pH during the progress of the reductive dehalogenation reaction. Specifically, the pH is preferably 5.8 to 8.5, more preferably pH 6 to 8, and still more preferably pH 6.2.
Is about 7.6. As described above, when a predetermined pH and an anaerobic environment are stably secured, the dehalogenation activity of the organic compound on the surface of the reducing agent can be kept high.

Further, a pH adjusting agent can be added to the contaminants in advance. As such a pH adjuster, in the case of acidic soil, it is preferable to use an alkali metal compound or an alkaline earth metal compound, and specifically, one that has been conventionally used as an inorganic soil conditioner is used. You can Examples thereof include limestone, quick lime, slaked lime, calcium sulfate (gypsum), magnesium oxide, bentonite, barlite and zeolite.

Further, when this treatment is carried out, it is preferable to mix various composts, composted organic substances and the like in order to promote the reaction. These mainly act on the effect of addition of microorganisms, supply of microbial nutrient sources, and water retention, and indicate those conventionally known as organic soil conditioners.

These act to secure a source of microbial nutrients and an anaerobic environment, and further, a malodorous gas generated by anaerobic fermentation of soil, particularly a sulfurous malodorous gas such as hydrogen sulfide and methyl mercaptan. I think that it also works for decomposition and removal.

It is well known that various composts contain various microorganisms such as actinomycetes and bacteria, and many microorganisms that efficiently decompose sulfur malodorous substances are present. Therefore, it can be easily inferred from the fact that a large number of useful deodorizing microorganisms are isolated from various composts and that compost is used as a measure for removing malodor in livestock excrement treatment.

According to the above-mentioned conditions, the pH of the soil such as alkali metal compounds and alkaline earth metal compounds is
Anaerobic substances existing in the soil by adding inorganic substances (often referred to as inorganic soil conditioners), organic substances (organic soil conditioners), and microbial media that serve as regulators Since the growth of the sex microorganisms starts immediately and the neutral and anaerobic environment of the soil is rapidly formed, the mixing timing of the reduced iron responsible for the chemical dehalogenation reaction according to the present invention into the soil is material,
Mix at the same time when adding organic substances and microbial medium,
There is no hindrance at all, rather it is better to mix them at the same time to secure an anaerobic environment for a long time.
The cost is also low, and it is advantageous in controlling the pollution purification process.

When the reductive dehalogenation reaction according to the present invention is applied to an actual contaminated site, it is not necessary to construct any large-scale facility, and various soil conditioners and reducing agents are added to the target contaminated soil. After mixing, it is sufficient to add a microbial growth medium and cover the purification area with a vinyl sheet or the like for the purpose of preventing water evaporation and rainwater contamination and keeping heat. Further, it is desirable to spread mulch or compost on the surface layer of the soil in the purification area as necessary in order to prevent the generation of malodorous gas and suppress the evaporation of water.

Although the reaction mechanism of the reductive dehalogenation reaction according to the present invention has not been clarified at present,
The present inventors consider as follows. First, in a contaminant such as soil, the standard electrode potential with respect to the standard hydrogen electrode at pH 4.5 to 9.0 and 25 ° C. is +200 to −24.
In order to secure an anaerobic environment in the range of 00 mV, an inorganic substance and an organic substance and a microbial medium as a microbial activator are added to the soil to create an anaerobic environment utilizing the growth reaction of microorganisms in the soil. Preferably. In this case, since the anaerobic microorganisms in the soil grow quickly, the chemical dehalogenation reaction is hardly suppressed, and the biological dehalogenation reaction and the chemical dehalogenation reaction start almost at the same time.

The mechanism of the biological anaerobic dehalogenation reaction is not clear because it has not been sufficiently pursued microbiologically and enzymatically, but in an anaerobic environment, methanogenic microorganisms and sulfate reduction are not found. When obligate anaerobic microorganisms such as microorganisms and various anaerobic sludge and anaerobic microorganisms in the bottom sludge are growing, it is reported that chlorine is sequentially dechlorinated one by one by a very slow microbial reaction. Therefore, it is considered that the similar gradual reductive dehalogenation reaction is progressing also in the present invention.

In the present invention, the chemical dehalogenation reaction occupies most of the initial reaction up to one month after the start of purification.
After that, the chemical dehalogenation reaction converged as the pollutant concentration of the halogenated organic compound decreased and the reducing activity of the reducing agent decreased, and instead, the biological dehalogenation reaction slowly became dominant, and Dechlorination will proceed over a long period of time. At the time when this biological dehalogenation reaction starts to work, the concentration of the halogenated organic compound contamination is considerably reduced, and does not cause concentration inhibition in the biological dehalogenation reaction. It acts more actively as a dehalogenation reaction with a low concentration of pollutants. Therefore, in the purification of the halogenated organic compound contamination according to the present invention, it becomes possible to purify it to an extremely low concentration by the interaction between the chemical dehalogenation reaction and the biological dehalogenation reaction.

According to the chemical and biological anaerobic dechlorination method of the present invention, halogenated organic compounds are eluted from the contaminated soil by combining the inorganic substances and organic substances of the soil-improving agents having low solubility. Without doing, and
To clean the halogenated organic compound-contaminated soil easily in a short period of time at low cost without penetrating the halogenated organic compound-contaminated underground deeper than the contaminated position by appropriately maintaining the water-holding capacity of the contaminated soil. Is possible.

In the reaction of the present invention, the above-mentioned dechlorination reaction can be allowed to proceed until a completely chlorine-free organic compound is obtained as a main product. This is preferable from the viewpoint of sufficiently purifying contaminants due to. For example, in the purification of pollutants with tetrachloroethylene and trichlorethylene, the main products that are completely chlorine-free organic compounds are ethylene and ethane, and in this reaction most of the intermediate products containing harmful chlorine are contained. Since it does not generate, very favorable results are obtained.

[0110]

Further, in the second aspect of the present invention, the reducing agent has a standard electrode potential of −445 mV to −2400 mV with respect to a standard hydrogen electrode at 25 ° C., and an iron-silicon alloy, a titanium alloy, a zinc alloy, It is preferably at least one selected from a manganese alloy, an aluminum alloy, a magnesium alloy, and a calcium alloy. These reducing agents have a stronger reducing power than iron. Therefore, when a pollutant such as soil contains an iron compound, particularly a divalent or trivalent iron compound, it can be involved in the dehalogenation reaction by reducing these iron compounds to iron. There is a possibility.

From the above viewpoints, it is preferable that the pollutant contains 0.1 g to 100 g of an iron compound based on 1 kg of the dry weight of the pollutant, and the pollutant has a dry weight of the pollutant. Based on 1 kg, 1 to 100 g of iron compound is contained, and the iron compound is iron hydroxide (Fe (O
H) ₃ ) or triiron tetroxide (Fe ₃ O ₄ ) is more preferable. Further, as the iron compound, FeO, F
Iron oxides such as e ₂ O _{3 and} iron chloride may be contained. Further, it is more preferable that the reducing agent has a standard electrode potential of −450 mV to −2400 mV with respect to the standard hydrogen electrode at 25 ° C. Alternatively, the reducing agent may be a water-soluble compound.

[0113]

[0114]

The reducing agent used in the present invention has a standard electrode potential of −400 mV to −2400 m with respect to the standard hydrogen electrode at 25 ° C.
It is preferably a metallic substance which is V. The reducing agent is preferably at least one selected from the group consisting of reduced iron, cast iron, iron-silicon alloys, titanium alloys, zinc alloys, manganese alloys, aluminum alloys, magnesium alloys, and calcium alloys.

Alternatively, the reducing agent is preferably a water-soluble compound. The reducing agent is preferably a powder having a particle size of 500 μm or less.

[0117]

[0118]

[0119]

[0120]

It has been confirmed by a test using soil that the organic carbon source, which is a growth substrate, is mainly utilized by microorganisms having an oxidizing nitrogen reducing activity, and that methane fermentation and sulfate reduction reaction are suppressed. Nitrogen gas is mainly generated from the soil, and hydrogen gas is also generated, but since it is diluted with nitrogen gas, there is no risk of fire explosion. Further, by not using a salt containing a sulfur content or a sulfate group as a substance added as a nutrient salt, it is possible to more reliably suppress the generation of hydrogen sulfide, a mercaptan-based gas or iron sulfide.

[0122]

[0123]

[0124]

[0125]

In the present invention, organic carbon is preferably supplied as a water-soluble organic carbon source. this is,
The present invention is not necessarily limited to the third aspect of the present invention, and may be applied to the first and fourth aspects of the present invention. The water-soluble organic carbon is preferably sugar, organic acid or its derivative, lower alcohol, molasses waste liquid, brewing waste liquid, or a mixture thereof. Organic carbon acts as a growth substrate for growing microorganisms. As organic carbon, use sugars such as glucose and sucrose, organic acids such as acetic acid, citric acid, lactic acid or organic acid salts, molasses waste liquid, brewing waste liquid, beer lees, organic waste liquid such as okara, and waste. can do. The amount of organic carbon added should be determined in consideration of the oxidizing power of the pollutant and the pollutant concentration of the halogenated organic compound, but if the pollutant is ordinary unsaturated soil, it is 1 for 1 kg of soil.
About g of organic carbon is necessary for maintaining the reduced state. Furthermore, when the contamination concentration of the halogenated organic compound to be dehalogenated exceeds 50 mg / kg,
It is necessary to increase the amount of organic carbon added at a ratio of 10 to 20 mg with respect to 1 mg of the halogenated organic compound. However, this is only a guideline, and in actual pollution sites, not only the oxidizing power of pollutants, but also the reducing power of organic carbon and metal powder described below is consumed by the supply of oxygen, etc. from rainwater or air, so Preliminary tests should be carried out in order to individually determine the addition concentration.

In the present invention, the standard hydrogen electrode at 25 ° C is used.
Solid reducing agent with a standard electrode potential of 130 mV to -2400 mV
And a heterotrophic anaerobic microorganism consisting of a water-soluble organic carbon source
And a halogen source for the mixture.
A step of adding to the pollutant by a volatile organic compound,
It

Preferably, the reducing agent is in powder form, the nutrient solution is added to the contaminants, then mixed, and the reducing agent is added to the mixture, then mixed. This can prevent the reducing agent from being oxidized by the nutrient solution and exert its reducing power in the contaminant.

On the other hand, the reducing agent is a water-soluble compound,
The reducing agent may be dissolved in the nutrient solution. It will be easier to implement on site than solid reducing agents. In addition, it becomes easy to store and move a large amount of nutrient solution. In addition, in order to prevent the reducing agent from being oxidized during storage, it is preferable to store the nutrient solution containing the reducing agent in a closed container.

Alternatively, in this mixing step, the nutrient solution may be added to the contaminant in two or more times. When a large amount of nutrient liquid is mixed with, for example, soil, it is difficult for shearing force to act on the soil mass in the liquid, and the soil mass may move in the liquid without breaking. On the other hand, when a small amount of nutrient solution is added, the shearing force facilitates the collapse of soil lumps, and more uniform mixing is possible. Then, next, more nutrient solution may be further added. In one embodiment, as a first step, a step of adding 1 to 10 vol% of the nutrient solution to the contaminants based on the contaminants and mixing them, and then, adding more than the amount added in the first step It is preferable that the method further comprises the step of adding an amount of the nutrient solution to the contaminant and mixing them. In another embodiment, the first step is 1-5v based on the contaminants.
ol% of the nutrient solution is added to and mixed with the contaminant, and then, as a second step, the nutrient solution is added so as to be 5 to 10 vol% based on the contaminant in combination with the first step. Adding to the contaminants and mixing, further comprising:
It is preferable to further include a step of adding the nutrient solution in an amount larger than the amount added in the step or the second step to the contaminants and mixing them. In any of the embodiments, since a small amount of nutrient solution is added in the first stage, shearing force acts on the mixture, which facilitates more uniform mixing. In any of the embodiments, it is preferable to finally add 15 to 25 vol% of the nutrient solution to the contaminants based on the contaminants. The final means the total of these nutrient solutions when the nutrient solution is added in several times.

The mixture is then allowed to stand under low aeration conditions. In this stationary step, contaminants are removed by reductive dehalogenation. For example, it is allowed to stand for 2 weeks or more, preferably 1 month or more.

It is preferable that the stationary step is performed in a state of being separated from the surroundings. This can prevent the halogenated organic compound in the mixture from diffusing and penetrating into the surroundings.

Further, in order to maintain the low ventilation condition, it is preferable to coat the contaminant with an impermeable material. For example,
Cover the soil with a vinyl sheet. This is to promote the culture of anaerobic microorganisms. In order to maintain low aeration conditions, it is preferable to immerse the contaminant in an aqueous liquid.

Furthermore, in the stationary step, it is preferable to keep the contaminants at 17 ° C. to 60 ° C. for at least the first 3 days. This particularly promotes the cultivation of the microorganisms in the mixture and increases the concentration. In addition, in the stationary step, it is preferable to keep the contaminants at 17 ° C to 60 ° C for at least the first 5 days. Further, in the standing step, it is preferable to keep the contaminants at 20 ° C to 40 ° C for at least the first 3 days, preferably 5 days.

[0135]

EXAMPLES The present invention will be specifically described below with reference to examples. However, the present invention is not limited to these examples.

In the tetrachloroethylene purification experiment carried out in the examples of the present invention, the methanogenic microorganism medium shown in Table 2 or the sulfate-reducing microorganism medium shown in Table 3 was used as the microorganism medium. In addition, in any purification test,
It carried out at room temperature (12-23 degreeC).

The pH was measured by adjusting the soil: pure water = 1: 1 (weight ratio) and using a pH meter HM-5B manufactured by Toa Denpa Kogyo.
It was measured with a mold. In addition, in the measurement of redox potential with respect to a saturated silver chloride electrode, soil: oxygen-free water = 1: 1 (weight ratio)
Was adjusted to 0, and the ORP composite electrode PS-8160 type was dipped in ORP Meiyu ODIC-3 type manufactured by Toa Denpa Kogyo Co., Ltd. and left for 30 minutes for measurement.

The analysis of ethylene chloride in soil was carried out by the method developed by Yokohama National University (Kenichi Miyamoto et al., “Method for measuring low boiling organic pollutant content in soil”, Journal of Japan Society on Water Environment, 199.
5th year, Vol. 18, No. 6, pp. 477-488), after immersing the sample soil in ethanol and extracting ethylene with ethanol, re-extracting ethylene with decane,
Hitachi Gas Chromatograph G- with decane solution of ethylene
It was put into a 5000-type column and analyzed by an FID detector.

On the other hand, in measuring the ethylene chloride gas generated in the gas phase, the generated ethylene chloride gas was measured using a Hitachi Gas Chromatograph G-5000 20% TCP Chromosorb WAW DM.
It was analyzed by injecting it into a CS 60-80 mesh column and detecting with a FID detector. When measuring ethylene and ethane gas generated in the gas phase, Pora is used as the column.
Hitachi Gas Chromatograph G-5000 using pack Q column
It was analyzed by detecting with a mold and FID detector. In addition, for the measurement of hydrogen, carbon dioxide, and methane generated in the gas phase, GL Science Gas Chromatograph-320, TC
Activated carbon 30/60 or Molecular sieve 1 with D detector
It was analyzed at 3X.

As reduced iron, Wako Pure Chemical Industries, Ltd.,
Wako first grade reduced iron, product code 096-00785 was used. In addition, reduced iron refers to powder unless otherwise specified.

Examples 1 to 5 and 7 to 10 mainly relate to the first aspect of the present invention.

Example 1 In Example 1, reduced iron powder was used as the reducing agent.

The contaminated soil collected from the surface layer of the contaminated soil of Factory A was used. The pollutant in the contaminated soil is mainly tetrachloroethylene, and the amount of tetrachlorethylene contained in 1 kg of dry contaminated soil is 25 mg. About 14 samples obtained by collecting 30 g of this contaminated soil in a 125 ml capacity vial bottle, the time-dependent changes of pH of contaminated soil, redox potential with respect to a saturated silver chloride electrode, and tetrachloroethylene reduction amount were measured under the following 14 kinds of experimental conditions. Examined. The water content in each experimental system was set in the range of 48 to 53%. At the time of sample preparation and after sample collection, the gas phase part of the vial was replaced with nitrogen gas.

The contaminated soil under test is from the loam layer, and its physical properties are as follows: water content 47%, hydraulic conductivity 10 ^-4 〜.
It was 10 ⁻⁵ cm / sec, pH 6.6, and had a redox potential of 380 mV with respect to a saturated silver chloride electrode.

Experimental conditions A. Control of reaction system contaminated soil using methanogenic microorganism medium (Table 2) Contaminated soil + methanogenic medium 9.0 ml Contaminated soil + methanogenic medium 9.0 ml + reduced iron 1.0
g Contaminated soil + methanogenic medium 9.0 ml + reduced iron 1.0
g + mixed calcareous fertilizer A (main component limestone) 1.0 g + cow dung compost 1.0 g + mulch soil 0.5 g Contaminated soil + methanogenic medium 9.0 ml + reduced iron 1.0
g + mixed calcareous fertilizer B (main component limestone and azmin) 1.
0 g Ten sewage sludge compost 1.0 g + mulch soil 0.5 g Contaminated soil + methanogenic medium 9.0 ml + reduced iron 1.0
g + mixed shell fossil fertilizer (main component shell fossil) 1.0 g + sewage sludge compost 1.0 g + leaf soil 0.5 g Contaminated soil + methanogenic medium 9.0 ml + reduced iron 1.0
g + mixed calcareous fertilizer A 1.0 g + humus soil 1.0 g In addition, "Azumin" is humic acid magnesia fertilizer, and its component composition is humic acid (50-60%), magnesia (15%),
Total nitrogen (3%), silicic acid (3%).

Table 2 shows a medium for methanogenic microorganisms.

[0147]

[Table 2] * 1 mineral liquid means 6g of K in 1 liter of distilled water
₂ A liquid containing HPO ₄ .

* Mineral 2 liquid means 6 g of KH ₂ PO ₄ , 6 g of (NH ₄ ) ₂ SO ₄ , 1 in 1 liter of distilled water.
A solution containing ₂ g of NaCl, 2.6 g of MgSO ₄ .7H ₂ O, and 0.16 g of CaCl ₂ .2H ₂ O.

* A trace amount of mineral liquid means 1.5 g of nitrilotriacetic acid and 3.0 g of MgS in 1 liter of distilled water.
_{O 4 · 7H 2 O, MnSO} 4 · 2H 2 O of 0.5 g, 1.0
g NaCl, 0.1 g FeSO ₄ .7H ₂ O, 0.1
g CoSO ₄ or CoCl ₂ , 0.1 g CaCl ₂ ·
2H ₂ O, 0.1 g ZnSO ₄ , 0.01 g CuSO
₄ · 5H ₂ O, 0.01g of AlK (SO _{4) 2,} 0.01
g of H ₃ BO ₃ and 0.01 g of Na ₂ MoO ₄ .2H
A liquid containing ₂ O. First, nitrilotriacetic acid is dissolved with KOH while adjusting the pH to 6.5, and then other minerals are added. Finally, the pH was adjusted to 7.0 with KOH.

* A trace amount of vitamin liquid means 2 mg of biotin and 2 mg of folic acid (f
olic acid, 10 mg of pyridoxine, hydrochloric acid, 5 mg of thiamine, hydrochloric acid, 5 mg of riboflavin (r
iboflavin), 5 mg of nicotinic acid, 5
mg DL-calcium pantothate
enate), 0.1 mg of vitamin B ₁₂ , 5 mg of p-aminobenzoic acid, and 5 mg of lipoic acid.

Under the above experimental conditions, the meanings of the equations representing the reaction system are as follows, for example, when the experimental conditions are explained.

30 g of contaminated soil was sampled and put into a vial of 125 ml capacity, which contained 1.0 g of reduced iron and mixed calcareous fertilizer A.
After mixing 1.0 g, 9.0 ml of the methanogenic microbial medium shown in Table 2 was added to this mixture, and then 1.0 g of cow dung compost and 0.5 g of mulch soil were added, followed by a butyl stopper and an aluminum seal. It was sealed. The series of operations for preparing the experimental sample was carried out promptly without any time interval.

As shown in FIG. 1, the above 7 kinds of specimens thus prepared were examined for the content of tetrachloroethylene after 3 days, the pH value after 7 days, and the redox reaction with respect to the saturated silver chloride electrode. Measure the potential.

The following measurement intervals are as shown in FIG.

B. Control of Reaction System Contaminated Soil Using Sulfate-Reducing Microorganism Medium (Table 3) Contaminated soil + Sulfuric acid reduction medium 9.0 ml Contaminated soil + Sulfuric acid reduction medium 9.0 ml + Reduced iron 1.0 g Contaminated soil + Sulfuric acid reduction medium 9.0 ml + Reduced iron 1.0 g
+ Mixed calcareous fertilizer A (main component limestone) 1.0 g + cow dung compost 1.0 g + humus soil 0.5 g Contaminated soil + Sulfuric acid reducing medium 9.0 ml + reduced iron 1.0 g
+ Mixed calcareous fertilizer B (main components limestone and azmin) 1.0
g + sewage sludge compost 1.0 g + mulch soil 0.5 g Contaminated soil + sulfate reducing medium 9.0 ml + reduced iron 1.0 g
+ Mixed shell fossil fertilizer (main component shell fossil) 1.0 g + Sewage sludge compost 1.0 g + mulch soil 0.5 g Contaminated soil + Sulfuric acid reducing medium 9.0 ml + Reduced iron 1.0 g
+ 1.0 g of mixed calcareous fertilizer A (main component lime right) + 1.0 g of mulch Table 3 shows a medium for sulfate-reducing microorganisms.

[0156]

[Table 3] * The trace vitamin liquid is the same as the trace vitamin liquid in Table 2.

The test results of Example 1 are shown in FIGS. 1 and 2. In Experiment A- and Experiment B-, tetrachloroethylene was reduced in almost the same manner as Experiment A-1 or Experiment B-, and therefore, the illustration thereof is omitted.

From this, by mixing reduced iron, inorganic fertilizer and various composts in the contaminated soil and mixing the medium for methane-producing microorganisms or the medium for sulfate-reducing microorganisms, neutral and anaerobic environments near soil pH 7 were obtained. Is stably secured, and it is clear that tetrachlorethylene in soil is rapidly decomposed. It is also shown in FIGS. 1 and 2 that tetrachloroethylene decomposition is hardly observed only by mixing the contaminated soil with the medium for methanogenic microorganisms or the medium for sulfate-reducing microorganisms. Further, instead of the mixed calcareous fertilizer A, the same effect was obtained by using slaked lime.

Example 2 In Example 2, reduced iron powder was used as the reducing agent. In addition, iron (II) chloride or iron (II) sulfate was used as a control.

High-concentration pollution prepared by adding tetrachloroethylene to tetrachloroethylene-contaminated soil collected from the same factory A as in Example 1 and adjusting the final pollution concentration to about 75 mg of tetrachloroethylene in dry soil per kg. Experiments were conducted on soil. As in Example 1, 30 g of contaminated soil was collected in a 125 ml vial, and pH, redox potential with respect to a saturated silver chloride electrode, tetrachloroethylene reduction amount, ethylene / ethane production amount, hydrogen were collected for the following eight experimental conditions. -The amount of carbon dioxide and methane produced was examined. The water content in each experimental system was 4
The range was 8 to 53%. In Experiment A- and Experiment B-, contaminated soil, sewage sludge compost and leaf soil were sterilized by steam pressure for 60 minutes in an autoclave to sterilize the microorganisms originating from them and to remove the microorganisms in the tetrachloroethylene decomposition reaction system. The effect was examined.

At the time of sample preparation, the gas phase portion of the vial was replaced with nitrogen.

Experimental conditions A. Reaction system contaminated soil using methanogenic microorganism medium (Table 2) + methanogenic medium 9.0 ml + reduced iron 1.0
g + mixed calcareous fertilizer B (main component lime right and azmin) 1.
0g + sewage sludge combo 1.0g + mulch 0.5g Contaminated soil + methanogenic medium 9.0ml + FeCl
₂ 1.0 g + mixed calcareous fertilizer B (main component limestone and azmin) 1.0 g + sewage sludge compost 1.0 g + mulch soil 0.5 g Contaminated soil + methanogenic medium 9.0 ml + FeSO
₄ 1.0 g + mixed calcareous fertilizer B (main component limestone and azmin) 1.0 g + sewage sludge compost 1.0 g + mulch soil 0.5 g Sterilized contaminated soil + methanogenic medium 9.0 ml + reduced iron 1.0 g + mixed calcareous fertilizer B (main Ingredients limestone and azmin) 1.0 g + sterilized sewage sludge compost 1.0 g +
Sterilized leaf soil 0.5 g B.I. Reaction system contaminated soil using a sulfate reducing microorganism medium (Table 3) + sulfate reducing medium 9.0 ml + reduced iron 1.0 g
+ Mixed calcareous fertilizer B (main component limestone and atsmine) 1.0
g + sewage sludge compost 1.0 g + mulch soil 0.5 g Contaminated soil + sulfate reducing medium 9.0 ml + FeCl ₂ 1.
0g + mixed calcareous fertilizer B (main components limestone and atsmine)
1.0g + sewage sludge compost 1.0g + mulch 0.5
g Contaminated soil + Sulfuric acid reducing medium 9.0 ml + FeSO ₄ l.
0g + mixed calcareous fertilizer B (main component limestone and azmin)
1.0g + sewage sludge compost 1.0g + mulch 0.5
g Sterilized contaminated soil + Sulfuric acid reducing medium 9.0 ml + Reduced iron 1.0 g + Mixed calcareous fertilizer B (main component lime right and azmin) 1.0 g + Sterilized sewage sludge compost 1.0 g +
0.5 g of sterilized leaf soil The results of Example 2 are shown in Tables 4 and 5.

From Tables 4 and 5, it is understood that tetrachloroethylene is decomposed in reduced iron. That is, by mixing reduced iron, inorganic fertilizer (pH adjuster) and various composts into the contaminated soil, and mixing the methanogenic microorganism medium or the sulfate reducing microorganism medium, the soil is
It is clear that a neutral environment and an anaerobic environment around pH 7 are stably secured, and that tetrachloroethylene in soil is rapidly decomposed. On the other hand, instead of reduced iron, F
It is clear that tetrachloroethylene decomposition hardly progresses when eCl ₂ or FeSO ₄ is added. That is, it is not decomposed by a ferrous salt such as FeCl ₂ or FeSO ₄ or a ferric salt such as FeCl ₃ .

Even when the microorganisms were sterilized (Experiment A
-, B 1) The amount of tetrachloroethylene decomposed is considerably low, indicating that in the method of the present invention, the reductive dehalogenation reaction proceeds by a synergistic action between a biological reaction and a chemical reaction.

Table 5 shows the analysis results of the gas components generated in the vials in Experiments A- and B-1. In all of these experimental systems, large amounts of hydrogen, carbon dioxide and ethylene-ethane were found to be produced. In addition, in Experiments A- and B-, extremely small amounts of tetrachloroethylene and cis-DCE were detected. Almost no vinyl chloride was detected, and its accumulation did not occur. Calculating the material balance in Experiments A and B-, it is calculated that about 71% and 58% of the decomposition amount of tetrachloroethylene in soil was converted to ethylene and ethane.

Similar results were obtained by using livestock compost instead of sewage sludge compost.

Table 4 shows the results of the dehalogenation reaction test using highly contaminated soil (after 55 days of culture).

[0168]

[Table 4] Table 5 shows the evolved gas (after 55 days of culturing) when the dehalogenation reaction of tetrachloroethylene was performed under anaerobic conditions.

[0169]

[Table 5] Even if tetrachloroethylene is decomposed, ethylene,
Can be decomposed into ethane.

Example 3 In Example 3, reduced iron was used as the reducing agent.

Tetrachloroethylene was added to the lake bottom mud (X) adjacent to the industrial area and the surface bottom mud (Y) of the wetland to add tetrachloroethylene 35 mg / dry mud 1 k.
Adjusted to a final concentration of g. A 25-liter cylindrical stainless can (diameter 300 mm x height 370 mm) was provided with 4 series of experimental systems (X system control and purification section, Y system control and purification section) in which 15 kg of contaminated bottom mud was collected. . The conditions of each experimental system are as follows. Note that these experimental containers were covered with a cover for the purpose of preventing evaporation of water and mixing of water and keeping the temperature warm. Laying compost and mulch on the surface layer of the bottom mud is not an essential condition, so it was not performed in this experiment. These three series of experiments were installed outdoors, and pH, redox potential with respect to a saturated silver chloride electrode, and tetrachloroethylene reduction amount were examined with time. During the experiment, the outdoor temperature range was 7-18 ° C, and the water content of the bottom mud was about 4
1 to 50%.

(Experimental conditions) X system control: Contaminated bottom mud + pure water 3000 ml X system purification area: Contaminated bottom mud beer saccharified lees wastewater 3200 ml
+ Reduced iron 500g + Mixed calcareous fertilizer B (main component limestone and azmin) 500g + Sewage sludge compost 500g + humus 250g Y-based control: Contaminated bottom mud + pure water 3300ml Y-based purification area: Contaminated bottom mud beer saccharified lees wastewater 3500ml
＋ Reduced iron 500g ＋ Mixed calcareous fertilizer B (main component limestone and azmin) 500g ＋ Sewage sludge compost 500g ＋ Loaf soil 250g The main component of beer saccharified lees wastewater is reducing sugar 9600
mg / l, acetic acid 180mg / l, lactic acid 31
00 mg / l, suspended matter 8100 mg / l, BOD (biochemical oxygen demand) 12700 mg /
Liter and total organic carbon concentration 5100 mg / liter.

Table 6 shows the results of changes in the tetrachloroethylene concentration. Regarding the pH and the redox potential with respect to the saturated silver chloride electrode, both the X-based control and the Y-based control had pH of 4.6 to 5.3 and ORP of 180 to 30.
It is about 0 mV, and both the X-based purification section and the Y-based purification section have p
It was H7-7.4 and ORP-400-570 mV. As a result, in either the X-based purification area or the Y-based purification area,
It can be seen that tetrachlorethylene can be effectively decomposed by the purification method according to the present invention.

Table 6 shows the change in tetrachloroethylene concentration in the bottom mud (unit: mg / kg dry mud).

[0175]

[Table 6] In the present invention, by combining a chemical reaction and a biological anaerobic reaction, contaminants of halogenated organic compounds such as soil and groundwater can be quickly and easily purified. Moreover, according to the method of the present invention, the halogenated organic compound can be purified from the contaminants without being eluted. For example, in the case of contaminated soil or the like, it is possible to purify the contaminated halogenated organic compound without penetrating underground deeper than the contaminated position by appropriately maintaining the water retention property of the contaminated soil or the like.

In the present invention, the halogenated organic compound can also be converted to a chlorine-free organic compound such as ethylene or ethane, and the reaction does not remain with the harmful intermediate product, and the harmful intermediate product There is no problem of accumulation of.

Example 4 In Example 4, reduced iron or cast iron scrap was used as the reducing agent.

In the tetrachloroethylene soil remediation experiment in Example 4, the media for methanogenic microorganisms shown in Table 7 were used. The redox potential shown in Example 4 is
The potential measured using a platinum electrode as a metal electrode and a saturated silver chloride electrode as a reference electrode is shown.

Table 7 shows a medium for methanogenic microorganisms.

[0180]

[Table 7] Mineral 1 liquid, mineral 2 liquid, trace mineral liquid, and
The trace vitamin solution is the same as that used in Table 2.

A purification experiment was carried out on tetrachloroethylene-contaminated soil (contamination concentration was 25 mg of tetrachlorethylene contained in the soil corresponding to 1 kg of dry soil) collected from Factory A.

In the experiment, 30 g of contaminated soil was collected in a vial of 125 ml capacity, and a methanogenic microbial medium, reduced iron or cast iron scraps, and sewage sludge compost were mixed under the following conditions, and the decomposition of tetrachloroethylene was examined. The amount of reduced iron, cast iron scrap, and sewage sludge compost added to the soil was 5% (by weight). Cast iron scrap is separated by sieving, particle size is 5
Cast iron scraps A of 500 μm or less were cast iron scraps B of 500 to 800 μm, and cast iron scraps C of 800 μm or more. In addition,
At the time of sample preparation, the gas phase portion of the vial was replaced with nitrogen.

Soil water content during soil remediation is 48.4-
It was 48.9%. The water content (%) here means
(Water weight / wet soil weight) × 100.

In the experiment, the cells were cultured for 60 days. And
PH in soil, redox potential for saturated silver chloride electrode,
The amount of tetrachloroethylene decreased, the amount of ethylene / ethane produced in the gas phase, and the amount of hydrogen / carbon dioxide / methane produced were investigated.

The reduced iron used here is as described above.
It is commercially available as a first grade reduced iron powder from Wako Pure Chemical Industries.

Experimental Conditions 30 g of contaminated soil (control, comparative example) 30 g of contaminated soil + 9.0 ml of methanogenic medium + 1.5 g of reduced iron + 1.5 g of sewage sludge compost 1.5 g of contaminated soil + 9.0 ml of methanogenic medium + 1.5 g of cast iron scrap A + 1.5 g of sewage sludge Compost 1.5 g Contaminated soil 30 g + Methanogenic medium 9.0 ml + Cast iron scrap B 1.5 g + Sewage sludge compost 1.5 g Contaminated soil 30 g + Methanogenic medium 9.0 ml + Cast iron scrap C 1.5 g + Sewage sludge compost 1.5 g Test in Example 4 The results are shown in Tables 8 and 9.

Table 8 shows the concentration of tetrachlorethylene in the soil when it is purified with cast iron scraps and the like.

Table 9 shows the gas generated when the tetrachlorethylene in the soil was purified by cast iron scrap or the like.

Table 8 shows the results of purification of tetrachloroethylene in soil with cast iron scraps and the like (after 60 days of culture).

[0190]

[Table 8] Table 9 shows the amount of gas generated (after 60 days of culturing) during purification of tetrachlorethylene in soil by cast iron scraps and the like.

[0191]

[Table 9] In addition, in Table 8 "soil tetrachlorethylene (PC
"E), pH, ORP" represent values after 60 days of culture.
The "ethylene / ethane conversion rate of tetrachloroethylene (PCE)" in Table 9 represents the rate of tetrachloroethylene converted to ethylene / ethane during 60 days of culture. "H
₂ , CH ₄ , CO ₂ ”represents the amount of gas generated during that period per 1 kg of dry soil.

In the system using reduced iron and the system using cast iron scrap A, tetrachlorethylene in the soil was purified to a level not detected.

As with reduced iron, it is understood that tetrachloroethylene can be dechlorinated and converted into ethylene and ethane by using cast iron scrap. In particular, it is found that tetrachloroethylene dechlorinates very efficiently by using cast iron scrap A, that is, cast iron scrap having a small particle size.

When tetrachloroethylene-contaminated soil was purified with cast iron waste, the soil pH was neutral at 7.2 to 7.3, and the redox potential with respect to the saturated silver chloride electrode was -225 to 225.
A reducing environment of -375 mV was maintained. Therefore,
Comparing the soil purification method using reduced iron and the soil purification method using cast iron scrap, it can be said that there is no difference in the soil environment between the two.

Further, in both the system and the system to which the methanogenic microbial medium was added, carbon dioxide was generated in the gas phase of the vial, so it can be said that microbial growth has occurred. That is, it can be said that cast iron scrap is a substance that does not hinder the growth of soil microorganisms.

Example 5 Samples of contaminated soil having different tetrachloroethylene contents were prepared by further adding tetrachloroethylene to the same tetrachlorethylene contaminated soil as in Example 4. As a result, 1 kg of soil is converted to dry soil,
Contaminated soil containing 50 mg of tetrachlorethylene, 75 m
g of contaminated soil and 140 mg of contaminated soil were obtained.
And the purification test was done about each contaminated soil.

In the experiment, as in Example 4, 30 g of various contaminated soils were collected in a 125 ml capacity vial, and 9.0 ml of methanogenic microbial medium shown in Table 7 and cast iron scrap A1. 5 g and 1.5 g of sewage sludge compost were mixed, and the decomposition of tetrachloroethylene was examined. In addition,
At the time of sample preparation, the gas phase portion of the vial was replaced with nitrogen.

In the experiment, cultivation was continued at room temperature, and after 63 days, pH in soil, redox potential with respect to a saturated silver chloride electrode,
The amount of tetrachloroethylene reduced and the amount of ethylene / ethane produced in the gas phase were examined.

Experimental Conditions Contaminated soil (50 mg-tetrachloroethylene / kg
-Dry soil) 30 g (control) Contaminated soil (50 mg-tetrachloroethylene / kg
-Dry soil) 30 g + methanogenic medium 9.0 ml + cast iron scrap A 1.5 g + sewage sludge compost 1.5 g Contaminated soil (75 mg-tetrachloroethylene / k
g-dry soil) 30 g (control) contaminated soil (75 mg-tetrachloroethylene / k
g-dry soil) 30 g + methanogenic medium 9.0 ml + cast iron scrap A 1.5 g + sewage sludge compost 1.5 g Contaminated soil (140 mg-tetrachloroethylene /
30 g (control) Contaminated soil (140 mg-tetrachloroethylene / k)
g-dry soil) 30 g + methanogenic medium 9.0 ml + cast iron scrap A 1.5 g + sewage sludge combo strike 1.5 g The test results of Example 5 are shown in Table 10. From this, by using cast iron scrap A having a particle size of 500 μm or less in highly concentrated contaminated soil containing 50 mg, 75 mg, and 140 mg of tetrachloroethylene in 1 kg of soil in terms of dry soil, It was found that dehalogenation to ethylene / ethane is possible and the effectiveness of this soil purification method is shown. In this soil remediation experiment, slight amounts of trichlorethylene and cis-DCE were detected in the gas phase and in the soil as tetrachloroethylene decomposition products, but vinyl chloride was hardly detected.

[0200] In the purification of high-concentration tetrachlorethylene-contaminated soil using cast iron scrap A, the soil pH was 7.2.
.About.7.3, the redox potential with respect to neutral and saturated silver chloride electrodes was -350 to -380 mV, and the reducing environment was stably maintained.

“Tetrachloroethylene in soil, pH, ORP” in Table 10 represents the value after 63 days of culture. Table 10
The "ethylene / ethane conversion rate of tetrachloroethylene" in the table means the ratio of tetrachloroethylene converted to ethylene / ethane during 63 days of culture.

Table 10 shows the purification results (after 63 days of culture) of high-concentration tetrachlorethylene-contaminated soil with cast iron scrap.

[0203]

[Table 10] In the present invention, it has been found that by using cast iron powder or reduced iron powder as the metal powder, a high purification rate can be achieved for a wide range of contaminant concentrations from low concentrations of halogenated organic compounds to high concentrations. By using cast iron, for example, cast iron scrap, contaminants due to halogenated organic compounds can be produced at a low cost, safely and with a simple treatment system.
It can be purified and the industrial waste can be effectively used.

Furthermore, by combining a soil improving agent having a low solubility, it is possible to prevent the halogenated organic compound from being eluted from the contaminated soil. Moreover, if the water-holding capacity of the contaminated soil is appropriately maintained, the purification can be achieved from the contamination position of the organochlorine compound contamination that has already occurred underground to a deeper depth without spreading and permeating the contamination.

Example 6 Example 6 corresponds to the second aspect of the present invention. Example 6
Shows that halogenated organic compounds can be decomposed even when a nutrient source for heterotrophic anaerobic microorganisms is not added.

As a reducing agent, (1) metallic iron (comparative example),
(2) manganese, (3) aluminum-silicon alloy,
(4) Comparison was made using four types of sodium hypophosphite.

Table 11 shows the standard electrode potential of each reducing agent.

Table 11 shows the standard electrode potential of the reducing agent.

[0209]

[Table 11] (1) 20 g of metallic iron, (2) 10 g of manganese as a reducing agent for 6500 g of loamy soil (water content 60%) containing 150 mg / kg of tetrachloroethylene,
(3) Add 10 g of aluminum-silicon alloy or (4) 20 g of sodium hypophosphite, and add 2
The temperature was maintained at 0 ° C. and the subsequent conditions were measured.

In (2) and (3), the oxidation-reduction potential decreased to -500 mV or less within 1 hour, and then -50 for 10 days.
It was maintained below 0 mV. Tetrachloroethylene is 10
By the day, ethylene and ethane were completely dehalogenated. In (4), the redox potential was -450 within 1 hour.
It fell below mV and was maintained below -450 mV for 10 days thereafter. By 10 days, tetrachloroethylene was completely dehalogenated to ethylene and ethane. On the other hand, in (1), it took 5 days for the redox potential to drop to −400 mV, and then the temperature was kept at −400 mV or lower for 5 days. Tetrachlorethylene 2 within 10 days
Only ethylene and ethane were dehalogenated.

Example 7 (1) A system containing only a reducing agent and no organic carbon source was compared with a system containing (2) a reducing agent and an organic carbon source. Calcium-silicon alloy (standard electrode potential-1900 mV) was used as the reducing agent, and sodium acetate was used as the organic carbon source.

In (1) and (2), 100 g of calcium-silicon alloy was added to 65 kg of clay soil (water content 55%) in which trichlorethylene was adsorbed at 200 mg / kg. In (2), in addition to this, 70 g of sodium acetate and 7 g of nutrient salts were added. In each case, the temperature was maintained at 20 ° C. and the subsequent state was measured.

In both (1) and (2), the oxidation-reduction potential dropped to -500 mV or less within 1 hour. In (1), the redox potential was maintained at −500 mV or lower for 10 days, then gradually shifted to the oxidized state, and the redox potential increased to 0 mV by 40 days later. 80% of trichlorethylene was reduced to ethylene and ethane, but 20% remained in the soil. In contrast, (2) has an oxidation-reduction potential of −500 mV for 40 days.
Maintained below, trichloroethylene was reduced to 99% ethylene and ethane.

Since the reducing agent of the present invention is hard to be coated with a stable oxide film on the surface and is easily dissolved in water, it becomes easy to contact with contaminants and the decomposition rate is improved. Even if the pollutant is a substance having low water permeability such as clayey soil or solid silt, it is possible to carry out the dehalogenation reaction by combining it with an organic carbon source that serves as a growth substrate for microorganisms.

Example 8 As a reducing agent, (1) metallic iron powder (control),
Comparisons were made using (2) sodium hypophosphite powder or (3) titanium citrate aqueous solution.

(Test conditions) A loamy soil containing 120 mg / kg of tetrachloroethylene in terms of dry soil was used. The initial redox potential is +350 mV,
The amount of soil was 100 m ³ .

(Test Results) In (2) and (3), the oxidation-reduction potential decreased to -450 mV or less within 1 hour, and was maintained at -450 mV or less for 5 days thereafter. By 5 days, tetrachloroethylene was completely dehalogenated to ethylene and ethane.

On the other hand, in (1), it took 10 days to completely knead the soil and the metal with one backhoe, and then it took 5 days until the redox potential dropped to −400 mV, and then 5 It was maintained below −400 mV for a day. By 20 days, 20% of tetrachloroethylene was dehalogenated to ethylene and ethane.

Example 9 Ascorbic acid was used as a reducing agent in all the systems. In system (1), no organic carbon source was added. On the other hand, in system (2), sodium acetate was also used as an organic carbon source.

A clay containing 100 mg / kg of tetrachloroethylene in terms of dry soil was used. The initial redox potential was +320 mV and the initial pH was 6.5.

(Test Results) In both systems (1) and (2), the redox potential dropped to +130 mV or less within 1 hour after injection of the reducing solution. In (1), the redox potential was maintained at +130 mV or less for 10 days, then gradually changed to the oxidative state and +3 by 40 days.
The redox potential increased to 00 mV. pH is 6.3 on day 0
Gradually decreased to 5.5 after 40 days. About 50% of trichlorethylene was reduced to ethylene and ethane, but
Fragment remained in the soil.

On the other hand, in (2), the oxidation-reduction potential gradually decreased after that, and after 20 days, became -150 mV or less,
It remained below -150 mV until 40 days later. The pH gradually decreased from 7.5 on day 0 to 6.8 after 40 days. Trichloroethylene was reduced to 99.9% to ethylene and ethane.

In this embodiment, since the water-soluble reducing agent is used, it is possible to bring the contaminants from the halogenated organic compound into good contact with the reducing agent, and to promote the reductive dehalogenation reaction.

Since the standard electrode potential of the reducing agent used in this embodiment is equal to or lower than that of metallic iron, the potential difference between the reducing agent and the halogenated organic compound is larger, and dehalogenation is accelerated. is there. Even if the pollutant is a substance having low water permeability such as clayey soil or solid silt, it is possible to carry out the dehalogenation reaction by combining it with an organic carbon source that serves as a growth substrate for microorganisms. Also, these reducing agents, like metallic iron,
No passivation.

Example 10 The present invention shows that a halogenated aromatic compound can be decomposed.

20 g of metallic iron was added to 6 kg of loam soil having a concentration of 10 mg / kg of pentachlorophenol (hereinafter abbreviated as PCP). In system 10-1, 1 liter of the medium for nitrate-reducing microorganisms shown in Table 12 was further added. On the other hand, in system 10-2, 1 liter of water was added as a control.

Table 12 shows the medium for nitrate-reducing microorganisms.

[0228]

[Table 12] Then, after kneading, the temperature was maintained at 28 ° C., and changes in PCP concentration and product concentration were examined.

The results are shown in Tables 13 and 14.

Table 13 shows the results for system 10-1.

[0231]

[Table 13] Table 14 shows the results for system 10-2.

[0232]

[Table 14] In Tables 13 and 14, TeCP and CP are 2, 3 and 4, respectively.
Shows 5,6-tetrachlorophenol and 3-chlorophenol. Further, Eh is a value converted into the standard electrode potential with respect to the standard hydrogen electrode.

In the system 10-1, compared with the system 10-2,
It can be seen that pentachlorophenol was rapidly decomposed. In system 10-1, pentachlorophenol is
2,3,5,6-tetrachlorophenol and / or 3
-Suspected to have been decomposed into phenol via chlorophenol. Also, 2,3,5,6-tetrachlorophenol and 3-chlorophenol were finally dehalogenated and did not accumulate. It is considered that phenol was further decomposed into other compounds.

Example 11 Example 11 mainly corresponds to the third aspect of the present invention.

In Example 11, the tetrachlorethylene-contaminated soil was purified using the oxidative nitrogen-reducing microbial medium of Table 15 and the methanogenic microbial medium of Table 16 (control). The oxidized nitrogen in the medium composition in Table 15 corresponds to 23% by weight of organic carbon. Purification test at room temperature (12 ~
It was carried out at 23 ° C.) for 30 days, and changes in various soil properties were measured and summarized in Table 17.

The pH was measured by soil: pure water = 1: 1 (Wt).
And was measured with a pH meter HM-5B manufactured by Toa Denpa Kogyo. In addition, in the measurement of redox potential (ORP) with respect to a saturated silver chloride electrode, soil: oxygen-free water = 1: 1 (W
t), Central Science ORP meter UK-2
The electrode was dipped at 030 and left for 30 minutes for measurement. The redox potential with respect to the saturated silver chloride electrode shown in this example is a potential measured using a platinum electrode as a metal electrode and a saturated silver chloride electrode as a comparison electrode. Analysis of soil ethylene chlorides was carried out by Yokohama National University (Kenichi Miyamoto et al., “Method of measuring low boiling point halogenated organic compound content of soil”, Journal of Japan Society on Water Environment, 1995, Vol. 18, No. 6).
No. 477-488), and then converted into decane after extraction with ethanol, and Hitachi Gas Chromatograph G-5000.
Type, FID detector with 20% TCP Chromoso
It was analyzed by a rb WAW DMCS60-80 mesh column. Furthermore, for the measurement of hydrogen, carbon gas, methane, and nitrogen generated in the gas phase, Ac was measured with a GL Science Gas Chromatograph GC-320 type and a TCD detector.
live carbon 30/60 or Molec
An ulular sieve 13X was used. The nitrate nitrogen and nitrite nitrogen ion concentrations in the soil were measured using a Hitachi anion chromatograph 2010i for the extracted water adjusted to soil: pure water = 1: 1 (Wt).

Table 15 shows microbial medium for reducing oxidized nitrogen.

[0238]

[Table 15] Table 16 shows the medium for methanogenic microorganisms.

[0239]

[Table 16] A purification experiment was conducted on tetrachlorethylene-contaminated soil (pollution concentration of about 25 mg / kg-dry soil) collected from a chemical factory. In the experiment, 30 g of the contaminated soil was collected in a 50 ml vial bottle, and the medium and the metal powder were mixed under the conditions shown below, and after 30 days, the state of changes in various soil properties including decomposition of tetrachloroethylene (Table 17) was measured. Examined. As the metal powder, a first grade reduced iron powder manufactured by Wako Pure Chemical Industries, Ltd. was used. In addition, at the time of sample preparation, the gas phase portion of the vial was replaced with helium gas.

Experimental conditions 30 g of contaminated soil 30 g of contaminated soil + 9.0 ml of water + 0.07 g of reduced iron 30 g of contaminated soil + 9.0 microbial medium for reducing oxidized nitrogen
ml + reduced iron 0.07 g contaminated soil 30 g + methanogenic microorganism medium 9.0 ml
+ Reduced iron 0.07 g Table 17 shows the test results. It was confirmed that when the oxidized nitrogen-reducing medium was used, not only dechlorination of tetrachloroethylene with ethylene and ethane, but also blackening of soil, generation of methane gas, and generation of mercaptan odor could be suppressed. It was also found that the hydrogen gas generated by the nitrogen gas was diluted. In addition, no oxide nitrogen or nitrous oxide residue was found in the soil.

On the other hand, in the system in which only metal and water are added, the pH is
Was significantly decreased, and the redox potential with respect to the saturated silver chloride electrode was also increased to +2 mV after 30 days, so that sufficient reductive dechlorination decomposition could not be performed. As a result, some tetrachloroethylene remained in the soil, and the conversion rate to ethylene was only 26%. From these, it is difficult to maintain an appropriate reduced state for a long period in a system to which only metal powder is added, and stable decomposition can be achieved only by coexisting with biological reaction due to addition of nutrients. Was shown. Furthermore, in a system to which only metal powder was added, hydrogen gas with a concentration of almost 100% was generated, and there was a risk of explosion. On the other hand, it was shown that nitrogen was diminished in the system to which the oxidative nitrogen-reducing microbial medium was added, and carbon dioxide was generated in the system to which the methanogenic microbial medium was added to dilute hydrogen gas. However, generation of odor and discoloration of soil were observed in the system to which the methanogenic microbial medium was added.

Table 17 shows the results of purification of tetrachloroethylene (PCE) in soil (after 30 days of culture).

[0243]

[Table 17] In the third aspect of the present invention, by using a nutrient source containing 20% to 50% by weight of organic carbon of oxidized nitrogen,
When decomposing the halogenated organic compound, it is possible to suppress blackening of the soil and generation of odorous gases such as methane gas and mercaptan.

Example 12 In Example 12, organic carbon was supplied as a water-soluble organic carbon source.

6 g of (1) glucose, (2) molasses waste liquor, and (3) compost were added as organic carbon sources to 5 kg of soil (moisture 60%) containing 10 mg / kg of organic chlorine compounds, In addition, 200 mg of nutrient salts was added and the temperature was maintained at 28 ° C.

The subsequent states were measured.

In (1) and (2), the number of anaerobic bacteria grew to 10 ⁷ viable bacteria / g soil in a few days, and the redox potential (ORP) with respect to the saturated silver chloride electrode was maintained at -600 mV or less for 30 days. The tetrachlorethylene was dehalogenated to ethylene and ethane.

On the other hand, in (3), 10
^It took 20 days to grow to ⁷ viable bacteria / g soil, ORP increased after 13 days, and became -23 mV after 30 days.
Tetrachlorethylene was not completely dehalogenated, with 50% remaining in the form of cDCE (cis-dichloroethylene).

Example 13 To 200 kg of soil (water content: 65%) containing 30 mg / kg of a halogenated organic compound, 240 g of glucose as an organic carbon source was added, and 8 g of nutrient salts was added to the solution to purify in winter. As the work, the treatment was carried out under the conditions of (1) enclosure in a greenhouse and heating with warm water (average temperature 22 ° C.), and (2) outdoor field stacking.

In (1), the number of anaerobic bacteria was 10 ^{7 within} a few days.
Proliferate to viable bacteria / g soil, ORP for 30 days-600mV
Maintained below, tetrachloroethylene was dehalogenated to ethylene, ethane.

On the other hand, in (2), 10
^It takes 30 days to grow to ⁷ viable bacteria / g soil, ORP
Increased after 10 days and reached +52 mV after 30 days. Tetrachlorethylene was not completely dehalogenated, with 20% remaining undegraded, 40% remaining in the form of cDCE (cis-dichloroethylene).

Example 14 Example 14 mainly corresponds to the fourth aspect of the present invention.

[0253] A contaminated soil remediation work was carried out to purify contaminants due to halogenated organic compounds in-situ.

Excavation was carried out from the site of a chemical factory, and purification was carried out on tetrachloroethylene-contaminated soil (average pollution concentration: about 11 mg / kg-soil) stored in a concrete pit.

The purification work was carried out by the following three methods.

[Method 1] 5 m ³ of contaminated soil in the concrete pit was put into a non-leakable container made of steel plate having a volume of 10 m ³ using a backhoe. Next, Table 15
A nutrient solution obtained by mixing the oxidative nitrogen-reducing microbial medium described above with the methanogenic microbial medium shown in Table 16 (hereinafter referred to as nutrient A)
0.2 m ³ (4 vol.% Of soil) was added to a steel plate bucket, and the soil and the nutrient A were kneaded using a backhoe. Furthermore, the nutritional supplement A 0.2 m ³ (4 vol.
%) Was added to a steel plate bucket, and the soil and the nutrient A were kneaded using a backhoe. And further, nutritional supplement A
0.7 m ³ (14 vol.% Of soil) was added to a steel plate bucket to mix the soil and the nutrient A. After the soil and the nutrient A were sufficiently mixed, reduced iron was sprayed on the soil in the steel plate bucket, and the kneading was performed again. The kneaded soil was returned to the concrete pit.

[Method 2] 5 m ³ of contaminated soil in the concrete pit was put into the steel plate bucket using a backhoe. Next, the nutrient A1.1 m ³ (2 of soil)
2 vol. %) Was added to a steel plate bucket, and the soil and the nutrient A were kneaded using a backhoe. Soil and nutrient A
Was mixed sufficiently, the reduced iron was sprayed on the contaminated soil in the steel plate bucket, and the kneading was performed again. The kneaded soil was returned to the concrete pit.

[Method 3] 5 m ³ of contaminated soil in the concrete pit was put into the steel plate bucket using a backhoe. Then, 15 to 20 hours before the addition, a suspension of reduced iron in the oxidative nitrogen-reducing microbial medium shown in Table 15 and the methanogenic microbial medium shown in Table 16 (hereinafter referred to as nutrient B). 2 m ³ (4 vol.% Of soil) was added to a steel plate bucket, and the soil and nutrient B were kneaded using a backhoe. In addition, 0.2m ^{3 of} nutrient B (4vo of soil
l. %) Was added to a steel plate bucket, and the soil and the nutrient B were kneaded using a backhoe. Further, the nutrient B0.7m ³ (14 vol.% Of soil) was added to a steel plate bucket, and these were sufficiently kneaded. The kneaded soil was returned to the concrete pit.

A part of the soil kneaded by the methods 1 to 3 was taken out, passed through a 10 mm mesh sieve, and the amount of soil lump contained in the soil after the kneading was visually confirmed. The soil mass was 1 to 10% of the soil mass, whereas the soil made by Method 2 was 15 to 30%.
It was shown that the degree of kneading differs depending on the method of adding the nutrient and the method of kneading.

In any of the methods 1 to 3, after kneading, in order to suppress the inflow and outflow of oxygen with the outside, the entire upper surface of the soil in the concrete pit was covered with a vinyl sheet and fixed with an iron plate. In addition to the method of covering with a vinyl sheet, water is flooded from the top surface of the soil to about 5 to 15 cm so that oxygen in and out of the soil can be suppressed and the moisture in the soil can be sufficiently maintained. May be.

In any of the methods 1 to 3, the soil is returned to the concrete pit in order to prevent the outflow of tetrachlorethylene or the like. In practice, the contaminated soil in the ground may be put into a bucket, the contaminated soil and the nutrient solution may be kneaded in the bucket, and then the kneaded product may be returned to the hole from which the contaminated soil has been removed. Alternatively, instead of kneading with a bucket, kneading may be performed in the ground at the site.

Two months after the surface covered with the vinyl sheet, the concentration of tetrachlorethylene in the soil was measured.
The results are shown in Table 18. That is, Table 18 shows the result of the purification work for the tetrachlorethylene-contaminated soil.

[0263]

[Table 18] In the soil kneaded by the method 1, 99.8% of the soil was decomposed, the method 2 decomposed 89%, and the method 3 decomposed 62%.
From this, it is understood that when the nutritional supplement is added in several times and kneading is performed each time as in Method 1, the decomposition rate is improved. Further, as in Method 2, when the reducing agent in powder form is added after kneading the nutrient solution and the soil, the decomposition rate is improved.

[0264]

[0265]

[0266]

[0267]

[0268]

[0269]

[0270]

[0271]

[0272]

[0273]

[0274]

[0275]

[0276]

[0277]

[0278]

[0279]

A method for purifying pollutants containing halogenated organic compounds and solids, comprising a water-soluble organic carbon source.
Nutrient solution containing a nutrient source and water heterotrophic anaerobic microorganisms that, and the steps of the standard electrode potential against a standard hydrogen electrode at 25 ° C. The reducing agent is 130mV~-2400mV, mixed with the contaminants, Here, the mixing step includes a step of adjusting the contaminant to a pH range of 4.5 to 9.0; and a step of allowing the mixture to stand under a low aeration condition.

A method wherein the reducing agent is in powder form, the nutrient solution is added to the contaminant, then mixed, and the reducing agent is added to the mixture, and then mixed.

A method in which the reducing agent is a powder having a particle size of 500 μm or less.

A method in which the reducing agent is at least one selected from the group consisting of reduced iron, cast iron, iron-silicon alloys, titanium alloys, zinc alloys, manganese alloys, aluminum alloys, magnesium alloys, and calcium alloys. .

As a first step, 1
Further, a step of adding 10 vol% of the nutrient solution to the contaminants and mixing, and a step of adding the nutrient solution in an amount larger than the amount added in the first step to the contaminants and mixing How to have.

As a first step, 1
Adding 5 to 5 vol% of the nutrient solution to the contaminants and mixing, and then, as a second step, together with the first step, the nutrient solution to be 5 to 10 vol% based on the contaminants. Is added to the contaminant and mixed, and the method further comprises the step of adding to the contaminant a larger amount of the nutrient solution than the amount added in the first or second step, and mixing.

A method in which the reducing agent is a water-soluble compound and the reducing agent is dissolved in the nutrient solution.

A method of keeping the contaminants at 17 ° C. to 60 ° C. for at least the first 3 days in the stationary step.

[Brief description of drawings]

FIG. 1 uses a methanogenic medium according to the invention,
The graph showing the test result which performed the reductive dehalogenation reaction on the tetrachlorethylene contaminated soil on anaerobic conditions is shown.

FIG. 2 is a graph showing test results obtained by performing a dehalogenation reaction test on tetrachloroethylene-contaminated soil under anaerobic conditions using a sulfuric acid reducing medium according to the present invention.

Front page continuation (51) Int.Cl. ⁷ identification code FI C02F 3/00 B09B 3/00 304K 11/02 (31) Priority claim number Japanese Patent Application No. 9-310599 (32) Priority date November 1997 12th (November 12, 1997) (33) Country of priority claim Japan (JP) (31) No. of priority claim Japanese Patent Application No. 9-346511 (32) Priority date December 16, 1997 (December 1997) 16) (33) Priority claim country Japan (JP) (31) Priority claim number Japanese Patent Application No. 9-357607 (32) Priority date December 25, 1997 (December 25, 1997) (33) Priority right Claiming country Japan (JP) (72) Inventor Koji Niimura 2-33-1, Hiyoshihoncho, Kohoku-ku, Yokohama-shi, Kanagawa Ebara Corporation Hiyoshi Dormitory 351 (56) Reference JP-A-7-136632 (JP, A) 8-510138 (JP, A) US Patent 5480579 (US, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) B09C 1/00-1/10 A62D 3/00 C02F 1/70 C02F 3 / 28-3/34 C02F 11/02-11/04

Claims (12)

(57) [Claims] 1. A method for purifying pollutants by a halogenated organic compound, wherein a standard electrode potential with respect to a standard hydrogen electrode at 25 ° C. is 130 m.
V--2400 mV reducing agent and water-soluble organic carbon source
That nutrients heterotrophic anaerobic microorganism, comprising the step of adding to the contaminant, the reducing agent is reduced iron, cast iron, iron - silicon alloy, titanium alloy, zinc alloy, manganese alloy, aluminum alloy,
A method which is at least one selected from the group consisting of magnesium alloys, calcium alloys and water-soluble compounds. 2. The reducing agent has a standard electrode potential of −400 mV to −2400 mV with respect to a standard hydrogen electrode at 25 ° C., and a reducing agent, cast iron, iron-silicon alloy, titanium alloy, zinc alloy, manganese alloy, The method according to claim 1, wherein the method is at least one selected from aluminum alloys, magnesium alloys, and calcium alloys. 3. The method of claim 1, wherein the reducing agent comprises reduced iron. 4. The method of claim 1, wherein the reducing agent comprises cast iron. 5. The reducing agent is an iron-silicon alloy, titanium-silicon alloy, titanium-aluminum alloy, zinc-aluminum alloy, manganese-magnesium alloy, aluminum-zinc-calcium alloy, aluminum-tin alloy, aluminum-silicon. The method according to claim 1, wherein the method is at least one selected from the group consisting of alloys, magnesium-manganese alloys, and calcium-silicon alloys. 6. The method according to claim 1, wherein the reducing agent is a water-soluble compound. 7. The method according to claim 6, wherein the reducing agent is an organic acid or a derivative thereof, a hypophosphorous acid or a derivative thereof, or a sulfide salt. 8. The method according to claim 1, wherein the reducing agent is a powder having a particle size of 500 μm or less. 9. The method of claim 1, wherein the contaminant has a water content of at least 25% by weight. 10. The method according to claim 1, further comprising, after the adding step, a step of maintaining the contaminant in a pH range of 4.5 to 9.0 in order to promote reductive dehalogenation of the halogenated organic compound. The method described. 11. A contaminant due to a halogenated organic compound
It is a purification method, and the standard electrode potential for standard hydrogen electrode at 25 ℃ is 130m.
From a solid reducing agent that is V to -2400 mV and a water-soluble organic carbon source
Of heterotrophic anaerobic microorganisms
And a step of adding the mixture to the contaminants.
Law. 12. The said mixing step, the method according to claim 11 is mixed with the solid reducing agent, and nutrient solution containing nutrients and water comprising the water-soluble organic carbon source.