JP5725487B1 - Bioremediation agent - Google Patents

Abstract

The present invention provides a technology for efficiently purifying soil contaminated with petroleum hydrocarbons by a bioremediation method. SOLUTION: Bioremediation agent containing awamori distiller as an active ingredient, bioremediation composition containing awamori distiller and phosphorus compound as active ingredients, and awamori distiller and phosphorus compound contaminated with petroleum hydrocarbons A method for purifying petroleum hydrocarbons in soil, characterized by being sprayed on the soil. [Selection] Figure 5

Description

  The present invention relates to a bioremediation agent. More specifically, the present invention relates to a bioremediation agent for decomposing petroleum hydrocarbons and a bioreagent that can effectively decompose petroleum hydrocarbons in soil by activating microorganisms in the soil. The present invention relates to a composition for mediation.

  In establishments that handle petroleum products such as petroleum-based hydrocarbons, such as sites for oil supply facilities, factories, military bases, etc., petroleum products often leak and contaminate the soil. When diverting these sites to other uses or businesses, the soil contaminated with petroleum hydrocarbons (hereinafter abbreviated as “petroleum”) is removed or the petroleum in the soil is decomposed. Or is collected and removed.

  Conventional methods for purifying soil contaminated with petroleum include, for example, methods for removing soil contaminated with petroleum by excavation, chemical decomposition using lime and oxidative decomposition, and adsorption using an adsorbent. Methods and bioremediation methods using microorganisms are known.

  The bioremediation method described above is a biological environment remediation (purification) technique, which is roughly divided into the following two methods. In other words, biostimulation that enhances and strengthens the self-cleaning action against pollution by supplying nutrients and oxygen to indigenous microorganisms that originally inhabit in contaminated soil, and activating them, and degrading pollutants This is bioaugmentation in which exogenous microorganisms having the ability are cultured in advance in another place and introduced into the contaminated soil (Patent Document 1).

  This purification method using bioremediation has the advantage of low environmental impact and treatment costs, but it has sufficient microorganisms that have the ability to decompose petroleum in the soil, and it has sufficient capacity for petroleum. Since it is necessary to decompose the oil, it is not always available, and there is a problem that it is necessary to determine the type of petroleum that is the cause of pollution and the degree of contamination.

JP 2002-307051 JP2002-224658

  This invention is made | formed in view of the said situation, and makes it the subject to provide the technique which purifies the soil contaminated with petroleum efficiently by the bioremediation method.

  The present inventor has recognized that, in soil contaminated with petroleum, microorganisms that are resistant to petroleum and have the ability to decompose them should grow. Based on this, the idea was that if such microorganisms could be further activated, it would be easy to decompose petroleum in the soil. In addition, when eagerly searching for substances that improve resistance to petroleum and the activity of microorganisms having degradability, it was found that Awamori distillery is useful for activating microorganisms that decompose petroleum. .

  And if this is sprayed on the soil contaminated with petroleum and bioremediation is performed, the petroleum in the contaminated soil can be decomposed efficiently, and if the phosphorus compound is further added to this, the petroleum in the contaminated soil is more efficient. The present invention was completed.

That is, the present invention provides a bioremediation agent for petroleum hydrocarbon cracking containing awamori distillery as an active ingredient.

The present invention also provides a bioremediation composition for petroleum hydrocarbon cracking containing awamori distillate and a phosphorus compound as active ingredients.

  Furthermore, the present invention is a method for purifying petroleum in soil, characterized in that awamori distillery and a phosphorus compound are sprayed on soil contaminated with petroleum.

It is drawing which shows the fall of the oil content in the soil over time about the test group 1 of Example 1. FIG. It is drawing which shows the fall of the oil content in the soil over time about the test group 2 of Example 1. FIG. It is drawing which shows the fall of the oil content in the soil over time about the test group 3 of Example 1. FIG. It is drawing which shows the fall of the oil content in the soil over time about the test group 4 of Example 1. FIG. It is drawing which showed the TPH residual rate with time in the heavy oil addition soil of Example 4. FIG.

  In the present invention, the bioremediation agent and the composition for bioremediation are applied to soil contaminated with petroleum to increase the activity of microorganisms in the soil, and decompose the petroleum in the soil by the action of these microorganisms. Refers to formulations and compositions. Petroleum means petroleum-based hydrocarbons, and includes naphtha (gasoline), kerosene, light oil, heavy oil, and the like.

  In the present invention, a awamori distiller used as an active ingredient of a bioremediation agent or a composition for bioremediation is obtained by distilling mash in the process of producing awamori. More specifically, the portion remaining after separating the alcohol component from the alcohol fermentation mash by distillation can be used as a awamori distillery.

  Awamori is distilled liquor produced in Okinawa Prefecture. So-called shochu is (1) using indica rice as raw rice, (2) using black koji mold as koji mold, and (3) all raw materials. It is different in the point that it is the primary preparation with rice bran. Therefore, the awamori distiller by-produced by this awamori production is also different from the shochu distiller in terms of, for example, the type and amount of organic acid contained.

  Next, the analysis value of the composition of a general awamori distiller and the results reported on the components of awamori distiller already reported are shown below. Among these, Table 1 is the value which analyzed the component of the awamori distillery used in the Example of this invention, and Table 2 and Table 3 are quoted from the paper which reported the various components and organic acid composition of the awamori distillery. It is a thing.

  The above awamori distiller can be used as an active ingredient of the bioremediation agent of the present invention, but this may be used as it is as the awamori distiller solution, and the liquid and solids are separated by an appropriate means, The liquid may be used as it is or in the form of a concentrated concentrate, a dried product obtained by drying the concentrate, or a dilute solution obtained by diluting a awamori distillate solution with an appropriate solvent. Further, the solid content may be used as it is or after being dried by an appropriate means and further powdered.

  The amount of awamori distillery used as a bioremediation agent is preferably determined experimentally according to the amount of petroleum contained in the soil and its quality (whether heavy oil or heavy oil). For example, for 1 kg of soil containing about 10 g / kg of light oil, awamori distillers may be sprayed in an amount of about 5 to 100 g in terms of dry solids. In addition, the solid content in the awamori distillery (solution) in the state obtained normally is about 0.5 to 10%.

  Under such conditions, awamori distillate is sprayed on the soil and left for about 14 to 28 days, so that petroleum in the soil is decomposed to 0.6 g / kg or less.

  Patent Document 2 discloses a method for decomposing organochlorine compounds in soil and groundwater using a distillation tank. However, this method decomposes an organic chlorine-based compound, and the distiller specifically used is a shochu obtained by a production method different from Awamori, so it is not related to the present invention. Is.

  In the composition for bioremediation of the present invention, a phosphorus compound can be blended in order to further enhance the effect. Examples of the phosphorus compound to be blended include potassium phosphate, dipotassium hydrogen phosphate, potassium dihydrogen phosphate, calcium phosphate, lime superphosphate, lime heavy superphosphate, magnesium phosphate, ammonium phosphate, and phosphoric acid. Chicken feces etc. that are known to contain can be used.

  This phosphorus compound is used in combination with the above awamori distiller and used in a composition for bioremediation, but its form is not particularly limited. However, when the awamori distiller is in a liquid state, it is preferable to dissolve the phosphorus compound in a suitable solvent to form a liquid and mix it.

  In the preparation of the composition for bioremediation of the present invention, when a phosphorus compound is blended, it is 0.01 in terms of normal phosphoric acid with respect to soil contaminated with petroleum (hereinafter referred to as “oil-contaminated soil”). To about 0.5 mass%, preferably 0.05 mass% to 0.2 mass%.

  The composition for bioremediation in which the phosphorus compound and awamori distiller are combined may be used in substantially the same manner as the bioremediation agent described above, but this composition has the ability to decompose petroleum in the soil. Since it is high, it is suitable for soil to be treated that is highly contaminated with petroleum, and soil to be treated with more heavy oil among petroleum.

  In addition, in the composition for bioremediation of this invention, a nitrogen-containing compound can also be further mix | blended if necessary. Examples of such nitrogen-containing compounds include ammonium salts such as ammonium sulfate, ammonium chloride, ammonium phosphate, and ammonium nitrate, amino acids, proteins, and the like. The amount of the nitrogen-containing compound is not particularly limited, but the amount added can be determined experimentally for the oil-contaminated soil to be treated. In addition, it replaces with these nitrogen-containing compounds, and the microorganisms which have the capability to fix | immobilize nitrogen in air can also be utilized.

  Next, a method for purifying oil-contaminated soil using the bioremediation agent and the composition for bioremediation of the present invention (hereinafter referred to as “remediation agent etc.”) will be described.

  In order to purify oil-contaminated soil using the remediation agent or the like of the present invention, a necessary amount of the remediation agent or the like may be sprayed on the oil-contaminated soil. Here, the required amount of remediation agent, etc., may be sprayed in general usage, but a representative part of oil-contaminated soil to be treated in advance is collected and the amount required for the decomposition of petroleum in this It is preferable to spray after exploring experimentally.

  Further, in the remediation method of the present invention, oils in the soil are decomposed mainly by the action of aerobic microorganisms. Therefore, after spraying the remediation agent or the like, it is preferable to perform a treatment suitable for this. . That is, it is preferable to perform stirring and / or aeration so as to come into contact with air in the atmosphere.

  In the above remediation method, it usually takes about 21 to 180 days, preferably about 90 days, until petroleum in the soil is decomposed and purified, but the end point is a simple method. Then, by the disappearance of petroleum odor, it can be judged accurately by analyzing petroleum in the soil.

In the soil subjected to the remediation treatment as described above, microorganisms having resistance to petroleum and microorganisms having the ability to decompose petroleum show a dominant bacterial flora as compared to general soil. Specifically, the genus Achromobacter , Agromyces , Arthrobacter , Bacillus , Bordetella , Cupriavidus , Endosymbiont , Ensifer , Enterobacter , Gordonia , Lysobacter , Microbacterium , Micrococcus , Ochrobactrum , Pandoraea , Pseudomonas, genus Sinorhizobium spp, Stenotrophomonas spp., of the genus Streptomyces such as microbes (bacteria) to assimilate alkane is a component of mineral oil, storage and published strains isolated [Okinawa microbial libraries in Okinawa (http: // Omljp.jimdo.com/functionality evaluation / alkane utilization /) ] It is thought that petroleum is decomposed by the action of microorganisms and the like known as ) .

  EXAMPLES Next, although an Example is given and this invention is demonstrated in more detail, this invention is not restrict | limited at all by these Examples.

Example 1
Light oil purification experiment (1):
Using Ogimi (Kunigami merge) as a test soil, a decomposition experiment of light oil in the soil was conducted. First, the test soil was air-dried and then sieved through a 2 mm sieve, and the moisture in the soil was adjusted to about 20 to 21%. 1 kg of this was placed in a plastic container, and awamori distillers (converted to solid content) and dipotassium hydrogen phosphate (converted to normal phosphoric acid) were added thereto so that the composition of each test group described below was obtained.

  The Awamori distillery used in this test was the above-described distillery B (obtained from Tadataka Shuzo), and the nutrients in Kunigami merge, which is the test soil, were as shown in Table 4 below.

  Next, light oil (manufactured by Eneos Co., Ltd.) weathered for 2 days to 1 week was added to this so as to be 1% by mass, and left in a greenhouse at 30 ° C. While stirring this every week, the content of light oil was measured by gas chromatography. At the same time, the amount of water was also measured.

  The results of measuring the light oil content every week, the results for test group 1 in FIG. 1, the results for test group 2 in FIG. 2, the results for test group 3 in FIG. 3, and the results for test group 4 The results are shown in FIG.

Test group 1-a: Distilled water 0% (control)
Test group 1-b: Distilled water 0.5%
Test group 1-c: Distilled water 1%
Test group 1-d: Distilled water 5%
Test group 1-e: Distilled water 10%

Test group 2-a: Distilled water 0% (control)
Test group 2-b: Distilled water 0%, phosphorus 0.01%
Test group 2-c: Distilled water 0.5%, phosphorus 0.01%
Test group 2-d: Distilled water 1%, phosphorus 0.01%
Test group 2-e: 5% distilled water, 0.01% phosphorus
Test group 2-f: 10% distilled water, 0.01% phosphorus

Test group 3-a: Distilled water 0% (control)
Test group 3-b: Distilled water 0%, phosphorus 0.05%
Test group 3-c: Distilled water 0.5%, phosphorus 0.05%
Test group 3-d: Distilled water 1%, phosphorus 0.05%
Test group 3-e: Distilled water 5%, phosphorus 0.05%

Test group 4-a: Distilled water 0% (control)
Test group 4-b: Distilled water 0%, phosphorus 0.1%
Test group 4-c: Distilled water 0.5%, phosphorus 0.1%
Test group 4-d: Distilled water 1%, Phosphorus 0.1%
Test group 4-e: 5% distilled water, 0.1% phosphorus
Test group 4-f: 10% distilled water, 0.1% phosphorus

  From the results shown in FIG. 1 to FIG. 4, the decomposition of light oil is accelerated by the addition of distilled lees, but the effect reaches a peak at 5% or more (FIG. 1), and the light oil is further increased by adding a phosphorus compound. It became clear that decomposition | disassembly of becomes quick (FIGS. 2-4). Further, gas oil was confirmed to be decomposed and disappeared by gas chromatography.

Example 2
Light oil purification experiment (2):
Using Ogimi (Kunigami merge) as a test soil, a decomposition experiment of light oil in the soil was conducted. First, the test soil was air-dried and then sieved through a 2 mm sieve, and the moisture in the soil was adjusted to about 20 to 21%. To 55 kg of this soil, add 550 g of the same light oil (produced by Eneos Co., Ltd.) as in Example 1, and further add the following amounts of distilled straw (obtained from Tadataka Shuzo) and phosphorus compound or chicken manure, and mix and stir well. Group 5 and 6 soils. This test soil is put in a plastic box (width 54 to 54.5 cm × depth 36 to 37 cm × height 30 cm) provided with an air supply device and three air diffusers at the bottom, and air is blown into the soil with a compressor. I sent it. The air supply amount was adjusted to 1.25 L / min.

Test Group 5: Dipotassium hydrogen phosphate 30.9g
Distilled rice cake (dry solid content 10%) 1,100g
Test group 6: Chicken manure (N 3%, P 6%, K 3.5%, C / N = 6)
91.6 g (0.01% in terms of P)
Distilled rice cake (dry solid content 10%) 1,100g

  This was left as it was in a greenhouse at 30 ° C. and stirred every week, and the total petroleum hydrocarbon (TPH) concentration was measured by gas chromatography. At the same time, the amount of water was also measured. In addition, as a control group, soil after moisture adjustment to which only light oil was added was used.

  Table 5 shows the residual ratio of TPH in the soil calculated from the measurement of TPH by gas chromatography.

  As is clear from this result, in the control where nothing was added, about 80% of the light oil remained even after 5 weeks, distillers and phosphorus compounds (dipotassium hydrogen phosphate or chicken manure) were added. In some cases, the residual amount of light oil was reduced to about 10 to 20%.

Example 3
Light oil purification experiment (3):
Test soil was prepared in the same manner as in Example 2. Next, 550 g of the same light oil as used in Example 1, 550 g of distilled water (obtained from Tadataka Shuzo) and superphosphate lime were added to 55 kg of this soil in the following amounts, and mixed well and stirred. Soil. This test soil is put in a plastic box (width 54 to 54.5 cm × depth 36 to 37 cm × height 30 cm) provided with an air supply device and three air diffusers at the bottom, and air is blown into the soil with a compressor. I sent it. The air supply amount was adjusted to 1.25 L / min.

Test group 7: Calcium superphosphate (14.5% as water-soluble phosphoric acid) 38 g
Distilled rice cake (dry solid content 10%) 550g
Test group 8: Calcium superphosphate (14.5% as water-soluble phosphoric acid) 38 g
Distilled rice cake (dry solid content 10%) 1,100g

  This was left in a greenhouse at 30 ° C. and stirred every week, and the total petroleum hydrocarbon (TPH) concentration was measured by gas chromatography. At the same time, the amount of water was also measured. In addition, as a control group, soil after moisture adjustment to which only light oil was added was used.

  Table 6 shows the residual ratio of TPH in the soil calculated from the measurement of TPH by gas chromatography.

  As is clear from this result, in the control group to which nothing is added, about 65% of the added light oil remains even after 10 weeks, whereas when distillers and lime superphosphate are added, The remaining amount was reduced to 10% or less.

Example 4
Heavy oil purification experiment:
Test soil was prepared in the same manner as in Example 2. Next, 550 g of A heavy oil, 1,100 g of distilled lees (obtained from Tadataka Shuzo) and 61.8 g of dipotassium hydrogen phosphate were added to 55 kg of this soil, and this was used as the soil of Test Group 9. This test soil is put in a plastic box (width 54 to 54.5 cm × depth 36 to 37 cm × height 30 cm) provided with an air supply device and three air diffusers at the bottom, and air is blown into the soil with a compressor. I sent it. The air supply amount was adjusted to 1.25 L / min.

  This was left in a greenhouse at 30 ° C. and stirred every week, and the total petroleum hydrocarbon (TPH) concentration was measured by gas chromatography. At the same time, the amount of water was also measured. Moreover, as a control group, the soil after moisture adjustment to which only A heavy oil was added was used.

  The residual ratio of TPH in the soil calculated from the measurement of TPH by gas chromatography is shown in FIG.

As is clear from this result, in the control group to which nothing was added, almost 100% of the A heavy oil remained even after about 5 weeks, whereas in the test group 9 in which distilled spirit and dipotassium hydrogen phosphate were added, Then, the residual amount of A heavy oil was reduced to about 30%.

Claims (8)

Bioremediation agent for petroleum hydrocarbon cracking containing awamori distillery as an active ingredient. The bioremediation agent for cracking petroleum hydrocarbons according to claim 1, which is applied to soil contaminated with petroleum hydrocarbons . The bioremediation agent for petroleum hydrocarbon decomposition according to claim 1 or 2 , wherein the awamori distiller is obtained as a residue during alcohol distillation from awamori moromi. A composition for bioremediation for petroleum hydrocarbon cracking, comprising awamori distillery and a phosphorus compound as active ingredients. Petroleum hydrocarbon cracking bioremediation composition according to claim 4, wherein in which spraying the soil contaminated with petroleum hydrocarbons. The phosphorus compound is selected from the group consisting of potassium phosphate, dipotassium hydrogen phosphate, potassium dihydrogen phosphate, calcium phosphate, lime superphosphate, lime heavy superphosphate, magnesium phosphate and ammonium phosphate. The composition for bioremediation according to claim 4 or 5 .   A method for purifying petroleum hydrocarbons in soil, characterized in that awamori distillery and phosphorus compounds are sprayed on soil contaminated with petroleum hydrocarbons.   Per 1 kg of soil contaminated with petroleum hydrocarbons, it was contaminated with 5 to 100 g of awamori distillate in terms of dry solids and petroleum hydrocarbons spraying 0.1 to 5 g of phosphorus compounds in terms of normal phosphoric acid. Soil purification method.

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