JP5222234B2 - Device for supplying electron donor to microorganism and method of using the same - Google Patents

Description

  The present invention relates to an electron donor supply device to a microorganism and a method for using the same. More specifically, the present invention relates to an apparatus and method for supplying an electron donor substance to a microorganism only when necessary without wastefully consuming the electron donor substance, and a wastewater treatment method using this apparatus. The present invention relates to an environmental purification method and a gaseous ammonia removal method.

  When performing biological treatment using microorganisms, it is sometimes necessary to supply an organic substance such as alcohol as an electron donor that serves as an energy source for microorganisms. For example, in a sewage treatment process in which nitrogen compounds such as ammonia present in the water to be treated are removed by biological treatment, methanol is used as a microorganism to accelerate the denitrification reaction after the nitrification reaction. As an electron donor serving as an energy source, a required amount is supplied by a pump device controlled by a control device (Patent Document 1).

  In addition, the liquid to be treated is brought into contact with one surface of a sheet-like polymer gel on which microorganisms effective for removing nitrogen compounds such as ammonia existing in the water to be treated and the energy necessary for denitrification treatment on the other surface. Also in a nitrogen removal bioreactor (Patent Documents 2 and 3) in which an electron donor as a source is contacted, alcohol serving as an energy source of microorganisms is supplied as an electron donor. Alcohol is supplied by operating a circulation pump, various valves, and instruments using a circulation path that connects the space inside the polymer gel carrier formed in the bioreactor and the alcohol storage tank with piping. The alcohol supply timing and amount are controlled.

  Here, if the supply of alcohol is excessive, microorganisms may not be consumed and alcohol may remain in the water and deteriorate the water quality. On the other hand, if the supply amount of alcohol is small, the energy source will be insufficient. As a result, the denitrification reaction becomes insufficient and the concentration of nitrous acid increases. Therefore, the supply of alcohol is controlled such that the supply amount and timing are controlled using a pump or the like, and alcohol diluted to a concentration of about 10% by volume is supplied from the alcohol storage tank.

  Such an alcohol supply method requires a series of equipment such as a pump and a control device for maintaining a constant supply amount of an alcohol solution such as methanol or ethanol. Operation is also complicated. Therefore, a liquid made of alcohol or a gaseous substance such as hydrogen or methane is sealed as an electron donor substance in a container formed of a nonporous film such as a polyethylene film or a polypropylene film, and the electron donor is removed from the nonporous film. There has been proposed a method of supplying the microorganisms with permeation (Patent Document 4).

Japanese Patent No. 3260554 Japanese Patent No. 3340356 Japanese Patent No. 2887737 International Publication WO2006 / 135028

  When the above electron donor substance is sealed in a container formed of a non-porous film such as a polyethylene film or a polypropylene film, permeation of the electron donor substance from the non-porous film occurs in both water and air environments. . Therefore, the electron donor substance sealed in the container leaks out in the process of circulating the electron donor supply device in which the electron donor substance is sealed in a container formed of a non-porous film such as a polyethylene film or a polypropylene film. There is a problem that it is consumed in vain. That is, even in a situation where it is not necessary to give the electron donor substance to the microorganism, the electron donor substance gradually leaks from a non-porous film such as a polyethylene film or a polypropylene film and is wasted.

  In addition, biological treatment using microorganisms is generally performed in wastewater or in an environment that contains a large amount of water such as soil. Therefore, an electron donor substance is only added when contacted with water. It would be sufficient if it could be supplied to microorganisms. Therefore, it is desirable to establish a technique that can supply an electron donor substance to a microorganism only when it comes into contact with water.

  The present invention has been made in view of such problems, and an object of the present invention is to provide an electron donor supply device in which an electron donor substance does not leak and is not consumed wastefully in the distribution process.

  The present invention also provides an apparatus capable of supplying an electron donor substance to a microorganism when brought into contact with water, and capable of controlling the supply amount of the electron donor substance without using a pump or a control device. It aims to provide a method.

The electron donor supply device for a microorganism according to claim 1 for solving the above object includes at least a part of an electron donor material serving as an energy source for the microorganism and a hydrophobic non-porous film. A container having a hermetically sealed structure and a hydrophilic non-porous membrane, the container being filled with an electron donor material, and at least a hydrophobic non-porous membrane portion on the outer surface of the container being hydrophilic non-porous It is covered with a conductive film. The electron donor material has a property that does not corrode the hydrophobic non-porous membrane and the hydrophilic non-porous membrane, and can pass through the hydrophobic non-porous membrane, so that it is hydrophilic in contact with water. Selected from alcohols and organic acids having a molecular weight and properties that can permeate a porous non-porous membrane.

In addition, an electron donor supply method for a microorganism according to claim 7 for solving the above-described object is provided with an electron donor that is provided with at least part of a hydrophobic non-porous film and serves as an energy source for the microorganism. A hydrophilic non-porous membrane between a hydrophobic non-porous membrane portion of a sealed container filled with a substance and an electron donor supply region to which an electron donor substance is supplied to a microorganism To prevent the hydrophobic non-porous membrane portion of the container from coming into direct contact with the electron donor supply region, and contacting the hydrophilic non-porous membrane with water to The barrier property is lowered, and the electron donor material is supplied to the electron donor supply region at a speed governed by the molecular permeation performance of the hydrophobic non-porous membrane of the container. The electron donor material has a property that does not corrode the hydrophobic non-porous membrane and the hydrophilic non-porous membrane, and can pass through the hydrophobic non-porous membrane, so that it is hydrophilic in contact with water. Selected from alcohols and organic acids having a molecular weight and properties that can permeate a porous non-porous membrane.

  Thus, at least the hydrophobic non-porous membrane part on the outer surface of the container is covered with the hydrophilic non-porous film, and the hydrophobic non-porous film part of the container and the electrons By interposing a hydrophilic non-porous membrane between the donor material and the electron donor supply region to be supplied to the microorganism, the electron donor material that has permeated the hydrophobic non-porous membrane becomes hydrophilic. Contact with non-porous porous membrane. In the atmosphere, the hydrophilic non-porous film functions as a barrier film, and permeation of the electron donor substance from the hydrophilic non-porous film is suppressed.

  Further, when the hydrophilic non-porous film is brought into contact with water, the function of the hydrophilic non-porous film as a barrier film is lowered. The molecular permeation performance of the hydrophilic nonporous membrane in contact with water is higher than that of the hydrophobic nonporous membrane, and the electron donor substance is hydrophobic. Supplied to microorganisms around the container at a speed governed by the molecular permeation performance of the container.

  In the present specification, the “non-porous membrane having hydrophobicity” includes not only a hydrophobic non-porous membrane but also a non-porous membrane having both hydrophobic and hydrophilic properties. .

Here, it is preferable that a water-permeable carrier capable of supporting microorganisms is disposed around the electron donor supply device according to claim 1 . With this configuration, when the electron donor supply device is brought into contact with water, the water permeates through the carrier and comes into contact with the hydrophilic non-porous membrane, and the microorganisms present in the water are supported by the carrier. It is carried on. Therefore, the electron donor substance is supplied to the microorganism supported on the carrier, and the function of the microorganism is exhibited.

  The electron donor supply apparatus for microorganisms of the present invention can be applied to all facilities, apparatuses and environments for performing biological treatment. For example, it can be used for biological wastewater treatment equipment, gaseous ammonia removal equipment, and environmental purification by microorganisms. Further, by arranging a carrier fixed with microorganisms effective for removing the target component around the electron donor supply device to the microorganism of the present invention, and supplying water to the carrier and the electron donor supply device, The component to be removed can also be removed.

According to the apparatus for supplying an electron donor to a microorganism according to claim 1 and the method for supplying an electron donor to a microorganism according to claim 7 , the electron donor substance is outside the hydrophilic nonporous membrane in the atmosphere. Can be prevented from leaking. Therefore, it is possible to prevent the electron donor substance from leaking out and being wasted in the course of distribution of the electron donor supply device. In addition, long-term storage in the atmosphere is possible.

  Moreover, since it is possible to supply the electron donor substance to the microorganism only when the hydrophilic non-porous membrane is brought into contact with water, the electron donor substance is supplied to the microorganism only when necessary. Can do. Therefore, the electron donor material is not wasted.

  Furthermore, since the electron donor substance is supplied to the microorganism at a speed controlled by the molecular permeation performance of the non-porous membrane having hydrophobicity, the permeation speed of the non-porous membrane having hydrophobicity of the electron donor substance molecules is taken. By adjusting the membrane material with the membrane material, film thickness, membrane density, etc., which are the factors that determine the molecular permeation performance of hydrophobic non-porous membranes, it is possible to constantly and slowly supply electron donor substances to microorganisms. It becomes. Therefore, it is no longer necessary to provide equipment for maintaining a constant supply amount of the electron donor substance, and the equipment cost and running cost are greatly reduced compared to the case where the supply amount is controlled by a pump or a control device as in the past. It is possible to make it. In addition, when the entire apparatus is composed of a hydrophobic non-porous membrane and a hydrophilic non-porous membrane, the electron donor substance is gently supplied over a wide range from the entire surface of the non-porous membrane. Is possible.

  In addition, even if a bactericidal electron donor substance that can kill microorganisms when in direct contact with microorganisms, for example, undiluted alcohol, is used, the permeation amount of alcohol molecules per unit area is sufficiently reduced to reduce the concentration. Since it can be supplied to the microorganisms in a diluted state, the microorganisms are not killed even if an alcohol stock solution is used. In addition, it is possible to save labor by omitting the conventional process of adjusting the concentration so that microorganisms do not die by diluting alcohol with water, and supplying alcohol with the same volume of liquid for a long time. Is possible.

According to the electron donor supply device for a microorganism according to claim 2 , a water-permeable carrier capable of supporting the microorganism is disposed around the electron donor supply device according to claim 1. When the donor supply device is brought into contact with water, the water permeates the carrier and comes into contact with the hydrophilic non-porous membrane, and the microorganisms contained in the water are carried on the carrier. Therefore, the electron donor substance is supplied to the microorganism supported on the carrier, and the function of the microorganism can be exhibited. In addition, by arranging the carrier around the electron donor supply device, this carrier functions as a protective material, and can be protected from external impacts and prevented from being damaged. This carrier also functions as a reinforcing material, and can prevent the container from being torn or torn due to the weight of the electron donor material filled in the container.

According to the waste water treatment method of the third aspect , since the electron donor supply device for microorganisms of the present invention is used, the microorganisms present in the waste water are supplied with the electron donor material to the electron donor material. It is not necessary to provide equipment for maintaining the supply amount at a constant amount, and it is possible to significantly reduce the running cost for wastewater treatment. In addition, since the electron donor material can be supplied to the microorganism only when the waste water comes into contact, the electron donor material is not wasted.

According to the environmental purification method of claim 4 , since the electron donor supply apparatus for microorganisms of the present invention is used, the supply amount of electron donor substances to microorganisms existing in the decontamination target region It is not necessary to provide equipment for maintaining a constant amount of water, and the running cost for environmental purification can be greatly reduced. In addition, since the electron donor material can be supplied to the microorganism only when the water contained in the decontamination target region comes into contact, the electron donor material is not wasted.

According to the method for removing gaseous ammonia according to claim 5 , since the electron donor supply apparatus for microorganisms of the present invention is used, the supply amount of the electron donor substance to denitrifying bacteria is maintained at a constant amount. Therefore, it is not necessary to provide a facility for performing the operation, and the running cost for removing gaseous ammonia can be greatly reduced. In addition, since the electron donor substance can be supplied to the denitrifying bacteria only when water in which gaseous ammonia is dissolved contacts, the electron donor substance is not wasted.

According to the sixth aspect of the present invention, a carrier on which an effective microorganism for removing a target component is disposed around the electron donor supply device for the microorganism of the present invention, and the carrier and the electron donor supply device. Since water is supplied to the microorganism, water and an electron donor substance can be supplied to the microorganisms supported on the carrier to activate the microorganisms, and the target components can be removed. It becomes.

It is a figure which shows an example of the electron donor supply apparatus of this invention, (A) is a perspective view, (B) is a longitudinal cross-sectional view. It is a longitudinal cross-sectional view which shows the example provided with the support | carrier in the electron donor supply apparatus of this invention. It is a figure which shows the example which floats and uses the electron donor supply apparatus of this invention for waste_water | drain. It is a figure which shows the example which equips the electron donor supply apparatus of this invention with a weight, and is immersed in waste_water | drain. It is a figure which shows the example which arrange | positions and uses the electron donor supply apparatus of this invention in a decontamination object area | region. It is a figure which shows the example which uses the electron donor supply apparatus of this invention for a gaseous ammonia removal apparatus. It is a figure which shows the example which arrange | positions and uses the electron donor supply apparatus of this invention around the support | carrier which carry | supported the microorganisms effective in the removal of the target component. It is a longitudinal cross-sectional view which shows the other example of the electron donor supply apparatus of this invention. It is a longitudinal cross-sectional view which shows the example of the replenishment type which is other embodiment of the electron donor supply apparatus of this invention. It is the schematic which shows the whole structure of the electron donor supply apparatus of embodiment of FIG. It is a figure which shows the example which enforces the electron donor supply method of this invention in a wastewater treatment tank. It is a graph which shows the time-dependent change of the weight in the air | atmosphere of the various bags which sealed ethanol. It is a graph which shows the time-dependent change of the TOC density | concentration of water when the various bags which sealed ethanol are immersed in water. It is a longitudinal cross-sectional view which shows the other example of the electron donor supply apparatus of this invention. It is a longitudinal cross-sectional view which shows the example at the time of comprising the electron donor supply apparatus of this invention with the polylactic acid film | membrane.

  Hereinafter, embodiments for carrying out the present invention will be described in detail with reference to the drawings.

  FIG. 1 shows an embodiment of an electron donor supply apparatus for microorganisms according to the present invention. The electron donor supply apparatus 1 for a microorganism includes an electron donor material 3 that serves as an energy source for the microorganism, a sealed container 4 having at least a part of a non-porous membrane 2a having hydrophobicity, and hydrophilicity. Of non-porous membrane 2b. The container 4 is filled with the electron donor substance 3, and at least the hydrophobic non-porous film 2 a portion on the outer surface of the container 4 is covered with a hydrophilic non-porous film 2 b.

  A non-porous membrane 2a having hydrophobicity is filled by filling an electron donor substance 3 serving as an energy source for microorganisms in a container 4 having a sealed structure including at least a part of the non-porous membrane 2a having hydrophobicity. The electron donor material 3 permeates through the non-porous membrane 2a having hydrophobicity at a speed governed by the molecular permeation performance. The hydrophilic non-porous film 2b covering the hydrophobic non-porous film 2a portion on the outer surface of the container 4 functions as a barrier film in the atmosphere, and the electron donated through the hydrophobic non-porous film 2a The body material 3 can be prevented from passing through the hydrophilic non-porous film 2b. On the other hand, when the hydrophilic non-porous film 2b comes into contact with water, the function as a barrier film is lowered, and the electron donor substance 3 that has permeated the hydrophobic non-porous film 2a becomes a hydrophilic non-porous film. 2b is transmitted.

  In the present embodiment, as an example of a form in which at least the hydrophobic non-porous film 2a portion on the outer surface of the container 4 is covered with the hydrophilic non-porous film 2b, the sealing provided with the hydrophilic non-porous film 2b A sealed container 4 (hereinafter referred to as a hydrophobic container 4) having a hydrophobic non-porous membrane 2a is contained in a container 6 (hereinafter referred to as a hydrophilic container 6) and sealed. The form which was done is demonstrated.

  In this embodiment, the hydrophobic container 4 is formed on a bag composed of a non-porous membrane 2a having hydrophobicity as a whole, and the periphery is welded by heat sealing or bonded with an adhesive. Thus, the electron donor material 3 is sealed, but the shape and structure are not particularly limited. For example, the hydrophobic container 4 may be formed in a tube shape or a sheet shape, or the tip of the tube may be sharpened with a hard member and inserted into soil for use. Further, the bag-like hydrophobic container 4 (sometimes simply referred to as a hydrophobic bag) is not particularly limited to the one composed entirely of the non-porous membrane 2a having hydrophobicity, and only one surface thereof is hydrophobic. You may make it comprise with the porous membrane 2a, and may comprise only a part of one surface with the nonporous membrane 2a which has hydrophobicity. When the non-porous membrane 2a having a hydrophobic property is used, a metal or plastic rigid frame, a membrane that does not allow the electron donor material 3 to permeate, or the like may be used for the other portions.

  Moreover, in this embodiment, the hydrophilic container 6 forms the bag shape comprised with the hydrophilic non-porous film | membrane 2b as a whole, and the periphery is welded by a heat seal or it adhere | attaches with an adhesive agent. The hydrophobic container 4 is hermetically sealed, but the shape is not particularly limited, and the shape of the hydrophobic container 4 can cover the outside of the hydrophobic non-porous membrane 2a. That's fine. For example, when using a hydrophobic container 4 composed of only one surface with a non-porous membrane 2a having hydrophobicity or a hydrophobic container 4 composed of only one surface with a hydrophobic non-porous membrane 2a, Although all of the hydrophobic container 4 may be sealed in the hydrophilic container 6, only the portion of the hydrophobic non-porous membrane 2a of the hydrophobic container 4 is covered with the hydrophilic non-porous membrane 2b. It may be. Alternatively, only the portion for covering the non-porous membrane 2a having hydrophobicity is constituted by the hydrophilic non-porous membrane 2b, and the other portion permeates the metal or plastic rigid frame or the electron donor material 3. You may comprise the hydrophilic container 6 using the film | membrane etc. which are not made. Further, a part of the portion for covering the hydrophobic non-porous film 2a is constituted by a hydrophilic non-porous film 2b, and the other part is a rigid frame made of metal or plastic, an electron donor substance 3 or the like. The hydrophilic container 6 may be configured using a film or the like that does not permeate.

  The electron donor material 3 serving as an energy source for the microorganism is a substance that is not toxic to the microorganism and does not corrode the hydrophobic non-porous film 2a and the hydrophilic non-porous film 2b. A material having a property and a molecular weight and property capable of permeating the hydrophobic non-porous membrane 2a and permeating the hydrophilic non-porous membrane 2b in contact with water is appropriately selected. Examples thereof include gaseous substances such as hydrogen, hydrogen sulfide, methane, and ethane, liquids such as alcohols such as methanol and ethanol, and organic acids such as formic acid and acetic acid, but are not limited thereto. Depending on the microorganism, phenol, benzene, toluene, or the like can be used as the electron donor substance 3.

  Here, when alcohol is used as the electron donor substance 3, it can be used as it is. Conventionally, when alcohol such as methanol or ethanol is used as an energy source for microorganisms, it has been necessary to dilute with water to a concentration that does not cause the microorganisms to die. Since it is supplied slowly, the microorganisms will not die even if a stock solution of alcohol is used. Even in the case where impurities are mixed in the alcohol stock solution, only the alcohol molecules permeate the hydrophobic non-porous membrane 2a and bring the hydrophilic non-porous membrane 2b into contact with water. When this occurs, the alcohol molecules permeate the hydrophilic non-porous membrane 2b and are slowly supplied to the microorganisms. Therefore, even if antibacterial molecules that are toxic to microorganisms, such as impurities such as catechin and cyanide, are mixed in alcohol, catechins having a large molecular weight and cyanogen compounds having a large polarity are hydrophobic non-porous membranes. Alcohol that is difficult to permeate 2a and diluted to a concentration that is not harmful to microorganisms can be permeated as a main component to be supplied to the microorganisms, and impurities almost remain in the container 4. Therefore, an alcohol containing impurities such as waste alcohol can be used.

  The non-porous membrane 2a having hydrophobicity has a property of allowing the molecules of the electron donor material 3 to pass through little by little. In other words, it has the property of allowing the molecules of the electron donor material 3 to permeate at a speed governed by the molecular permeation performance of the hydrophobic non-porous membrane 2a. Further, the hydrophilic non-porous membrane 2b functions as a barrier membrane in a state where it is not in contact with water, and has a property of suppressing permeation of molecules of the electron donor substance 3 that has permeated through the hydrophobic non-porous membrane 2a. However, when in contact with water, the function as a barrier film is lowered, and the molecule of the electron donor substance 3 that has permeated through the hydrophobic non-porous film 2a is transmitted.

  Here, the molecular permeation performance of the hydrophilic nonporous membrane 2b in contact with water is higher than that of the nonporous membrane 2a having hydrophobicity. Accordingly, the supply rate of the electron donor to the microorganism in the state of contact with water is limited by the molecular permeation performance of the hydrophobic non-porous membrane 2a. That is, by appropriately controlling the molecular permeation performance of the hydrophobic non-porous membrane 2a, the supply rate of the electron donor substance 3 to the microorganism can be controlled to a desired rate.

  In addition, moisture (water vapor) exists in the atmosphere, and the moisture in the atmosphere increases as the humidity increases. Therefore, the barrier property of the hydrophilic non-porous film 2b decreases as the humidity increases. In such a case, when the electron donor supply apparatus 1 is distributed or stored, a waste or consumption environment of the electron donor substance 3 is substantially reduced by making the distribution or storage environment dry using a desiccant such as silica gel. It can be completely suppressed.

  Examples of the material of the nonporous membrane 2a having hydrophobicity include polyethylene, polypropylene, and other olefinic membranes that are hydrophobic nonporous membranes. Further, ethylene / vinyl alcohol copolymer and ethylene / vinyl acetate copolymer, which are films having both hydrophobic and hydrophilic properties, can be mentioned. Here, the use of polyethylene or polypropylene is particularly preferred. Polyethylene and polypropylene have the advantage that they have moderate material permeability and thermoreversibility, and are flexible and easy to mold. In addition, it is stable against various substances. Moreover, since it is difficult for water to permeate, when the alcohol diluted with water is used as the electron donor substance 3, water does not permeate and the barrier property of the hydrophilic non-porous membrane 2b is reduced in the atmosphere. There is no. Of course, it is not specifically limited to what was mentioned above including polyethylene and a polypropylene.

  The non-porous membrane 2a having hydrophobicity has a rate of supply of the electron donor substance 3 to the microorganisms depending on the membrane material, film thickness, surface area of the membrane, molecular weight and properties of the electron donor substance 3, temperature, external pressure, and the like. It is possible to control. According to the inventors' experiments on polyethylene membranes, it has been confirmed that the molecular permeation rate varies depending on the film thickness in the case of the same membrane material. Therefore, a necessary amount of the electron donor material 3 can be supplied at a necessary speed by appropriately selecting a film thickness or the like according to the supply amount of the electron donor material 3 necessary for the microorganism. When a film having both hydrophobic and hydrophilic properties is used, the supply rate of the electron donor substance 3 can be controlled by the ratio of the hydrophilic molecule and the hydrophobic molecule constituting the film. That is, the higher the ratio of hydrophilic molecules, the closer to the properties of the hydrophilic non-porous film 2b. Therefore, it is preferable to include a hydrophobic molecule so that at least the hydrophilic non-porous membrane 2b has a permeation performance lower than that of the electron donor substance 3 when it is in contact with water.

Here, the non-porous membrane 2a having hydrophobicity also changes the molecular permeation rate depending on the density of the membrane. Taking polyethylene as an example, when using a low density polyethylene (density of 910 kg / m ³ or more and less than 930 kg / m ³ ) classified by JIS K6922-2, the electron donor material 3 is sufficiently transmitted. Although it permeates, when high-density polyethylene (density 942 kg / m ³ or more) is used, the permeation rate of the electron donor material 3 decreases. Therefore, the balance between the film thickness and the film density of the hydrophobic non-porous film 2a may be controlled in accordance with the desired electron donor substance supply rate. In addition, since the molecular arrangement can be controlled by the stretching process, the electron donor substance supply rate can be controlled.

  Permeation of the electron donor material 3 through the hydrophobic non-porous membrane 2a occurs when the electron donor material molecules dissolve in the membrane and the dissolved molecules diffuse inside the membrane and reach the opposite side. Accordingly, catechin, highly polar water, cyanide, and the like, which are large molecules that do not dissolve into the film, do not easily pass through the non-porous film. In addition, since polyethylene, polypropylene, and the like are hydrophobic, low-polarity films that do not have a functional group that is compatible with water, water that is a polar molecule hardly dissolves in the film. Further, since hydrogen bonds between water molecules are strong, water hardly permeates the membrane at room temperature. Therefore, the non-porous membrane 2a having hydrophobicity hardly penetrates impurities such as water, catechin having a large molecular weight, and a cyanide having a high polarity, and penetrates a desired electron donor substance 3 as a main component. It functions as a “sieve”. Moreover, the electron donor substance 3 permeate | transmits the non-porous film | membrane 2a which has hydrophobicity in a molecular state, ie, the state of the gas (gas) which does not aggregate by the attractive force between molecules like a liquid. Therefore, the nonporous membrane 2a having hydrophobicity can also be expressed as a gas permeable membrane.

  Further, as described above, the non-porous membrane 2a having hydrophobicity is permeated by the electron donor material 3 being dissolved in the membrane, and the electron donor material 3 has the same size and number of pores as the porous membrane. It does not control the type or amount. Therefore, there is no problem of hole clogging due to long-term use, and there is no need for regular backwashing. Therefore, it can be used without maintenance for a long time, and the running cost can be reduced.

  Next, examples of the material of the hydrophilic non-porous membrane 2b include membranes having a hydrophilic group in the molecular structure, such as polyester, nylon (polyamide), polyvinyl alcohol, vinylon, cellophane, polyglutamic acid, etc. Polyvinyl alcohol is preferred, but is not limited thereto.

  In the hydrophilic non-porous membrane 2b, hydrogen bonds are formed inside the membrane in a state where it is not in contact with water, that is, in the atmosphere. Accordingly, the structure is such that fluctuation due to thermal vibration of the molecular chain is unlikely to occur, and since there are few gaps between the molecular chains, the molecules are not easily transmitted. On the other hand, when in contact with water, water molecules enter between the molecular chains, hydrogen bonds are broken, and the structure is likely to fluctuate due to thermal vibration of the molecular chains, so that the water molecules further enter the membrane. As a result, most of the hydrogen bonds inside the membrane are broken, and water molecule passages are formed. Molecules of the electron donor material 3 that have permeated the hydrophobic non-porous membrane 2a permeate the hydrophilic non-porous membrane 2b along the water molecule passage.

  The hydrophilic non-porous membrane 2b is also permeated by dissolving the electron donor material 3 in the membrane, and the electron donor material 3 can be sized according to the size and number of pores as in a porous membrane. It does not control the type or amount. Therefore, there is no problem of hole clogging due to long-term use, and there is no need for regular backwashing. Therefore, it can be used without maintenance for a long time, and the running cost can be reduced.

  Next, the form provided with the water-permeable support | carrier 5 which can carry | support microorganisms on the outer surface of the hydrophilic non-porous film | membrane 2b is demonstrated based on FIG. The electron donor supply apparatus 1 for microorganisms shown in FIG. 2 includes a water-permeable carrier 5 capable of supporting microorganisms on the outer surface of the hydrophilic container 6 of the electron donor supply apparatus 1 shown in FIG. is there.

  In this way, by providing the water-permeable carrier 5 capable of supporting microorganisms, the microorganisms are artificially fixed, or microorganisms existing in an environment such as water or soil are brought into contact with the carrier 5 to proliferate. Can be fixed. Moreover, by providing water permeability, when the electron donor supply device 1 comes into contact with water, the water comes into contact with the hydrophilic non-porous membrane 2b, and the electron donor is applied to the microorganisms fixed to the carrier 5. Substance 3 can be supplied.

  Examples of the water-permeable carrier 5 capable of supporting microorganisms include natural polymers such as collagen, fibrin, albumin, casein, cellulose fiber, cellulose triacetate, agar, calcium alginate, carrageenan, agarose, polyacrylamide, poly- Such as 2-hydroxyethyl methacrylic acid, polyvinyl chloride, γ-methylpolyglutamic acid, polystyrene, polyvinylpyrrolidone, polydimethylacrylamide, polyurethane, photocurable resin (polyvinyl alcohol derivative, polyethylene glycol derivative, polypropylene glycol derivative, polybutadiene derivative, etc.), etc. It is also possible to use a synthetic polymer, a composite thereof, or a water-absorbing polymer. As the water-absorbing polymer, known polymers can be used, and specific examples include polyacrylic acid, polyaspartic acid, polyglutamic acid, modified products thereof, modified polyethylene glycol, and the like. The modified product referred to here is a product obtained by crosslinking a polymer having an ionic group to a part of the polymer. When the water-absorbing polymer is used, the water retaining power and water absorbing power of the carrier 5 are increased as compared with the case where the above polymer gel is used. Therefore, the microorganisms continue to survive by absorbing water efficiently and retaining the water. It is possible to continue to maintain a favorable environment. In addition, the support | carrier 5 mentioned here is an illustration to the last, and is not limited to these.

  Here, when the water permeability of the carrier 5 itself is low, the carrier 5 is provided with a large number of micropores that are large enough to allow water to pass through, and the water that has passed through the micropores is not hydrophilic. The porous membrane 2b may be brought into contact with water. That is, the water-permeable carrier 5 in the present invention includes those subjected to such processing.

  Moreover, as the water-permeable carrier 5 capable of supporting microorganisms, a nonwoven fabric or a material obtained by raising a nonwoven fabric can be used.

  Further, the surface of the hydrophilic non-porous film 2b may be raised to carry microorganisms on the raised portion. In this case, the raised portion functions as a water-permeable carrier 5 that can carry microorganisms.

  Thus, by providing the carrier 5 on the outer surface of the hydrophilic non-porous membrane 2b, a place where the flow rate of groundwater is constantly high, such as a land with a lot of water such as a paddy field or a land with a wet and humid climate, Even when the flow rate of groundwater temporarily increases due to frequent rainfall during the rainy season, the microorganisms fixed to the carrier 5 are difficult to be washed away. Further, even during drainage, microorganisms are fixed to the carrier 5 and are difficult to diffuse. Accordingly, the activity of a specific microorganism can be maintained over a long period of time and easily controlled under any environment.

  The carrier 5 may be provided on the surface of the hydrophilic non-porous film 2b by adhesion, for example, or the peripheral edge of the hydrophilic container 6 may be heat sealed. Moreover, the support | carrier 5 may be provided in the whole surface of a non-porous film | membrane, and may be provided in a part.

  Here, the carrier 5 also functions as a protective material. That is, by providing the carrier 5, it is possible to prevent the hydrophilic non-porous film 2b from being damaged by an external impact or the like. Further, since the carrier 5 is formed as a high-strength polymer such as a photocurable resin in a cylindrical shape or a sheath shape, the swelling of the hydrophobic bag 4 and the hydrophilic bag 5 can be prevented. It is preferable when the supply device 1 is made compact. In this case, the hydrophobic bag 4 and the hydrophilic bag 5 are not inflated, and the thickness of the hydrophobic bag 4 and the hydrophilic bag 5 can be reduced by restricting the thickness thereof. It is possible to increase the packing density when stored in the space and to protect from external impacts.

  The carrier 5 also functions as a reinforcing material. That is, it is possible to prevent the hydrophobic bag 4 and the hydrophilic bag 5 from being broken or torn due to the weight of the electron donor material 3 filled in the hydrophobic bag 4.

  Of course, a protective material and a reinforcing material may be provided separately from the carrier 5.

  The electron donor supply device 1 configured as described above can gradually release the electron donor substance 3 around it only when it is brought into contact with water. Therefore, by simply placing it in an environment where water is present and it is necessary to control the activity of microorganisms, the activity of microorganisms fixed in advance using various microorganisms or carriers 5 etc. existing in nature is autonomously controlled. Thus, microorganisms can be utilized. Moreover, the electron donor supply device 1 does not release the electron donor material 3 around the bag when it is not in contact with water. In other words, the electron donor substance 3 can be released slowly only under the circumstances where the control of the microorganism activity is required, and the electron donor substance 3 is wasted in a distribution process that does not require the control of the microorganism activity. There is nothing. In addition, since unnecessary volatilization of the electron donor substance 3 can be minimized, the induction of environmental pollution can be suppressed.

  The electron donor supply device 1 according to the present invention is activated by supplying the electron donor substance 3 to microorganisms that require the electron donor substance 3 only by immersing it in a wastewater treatment tank for treating wastewater by biological treatment. Wastewater treatment can be performed. For example, the electron donor material 3 can be supplied to the denitrifying bacteria in a biological denitrifying treatment that reduces nitrate ions and nitrite ions in the wastewater by denitrifying bacteria. In addition, as in the present embodiment, the hydrophobic bag 4 formed with the non-porous membrane 2a having the entire hydrophobic surface is sealed inside the hydrophilic bag 5 having the entire surface formed with the hydrophilic non-porous membrane 2b. In the case where it is used, the supply amount per unit time of the electron donor material 3 can be controlled according to the area of the hydrophilic non-porous membrane 2b immersed in water, and it is not immersed in water. Since the permeation of the electron donor material 3 is suppressed from the part, the electron donor material 3 can be used for activating the microorganism, and wasteful consumption of the electron donor material 3 can be suppressed. For example, as shown in FIG. 3, if the electron donor supply device 1 is floated on the drainage and only one side is in contact with the drainage, the electron donor substance 3 permeates from only one side in contact with the drainage. From one side, the transmission of the electron donor material 3 is kept low. In addition, in this case, it is easy to check the remaining amount of the electron donor material 3 of the electron donor supply device 1 from the portion exposed from the water surface. Further, as shown in FIG. 4, a weight 19 is provided at the bottom of the electron donor supply device 1, and the area of the bag immersed in water is controlled by the weight of the weight 19. It is also possible to control the supply amount. In addition, in this case, as the remaining amount of the electron donor material 3 filled in the electron donor supply device 1 decreases, the electron donor supply device 1 gradually sinks. The remaining amount of the electron donor substance 3 can be confirmed by observing the immersion state of 1 in water.

  In addition, the vicinity of the water surface is high in humidity, and the barrier property of the hydrophilic non-porous film 2b may be lowered due to this influence. In such a case, it is preferable to prevent a decrease in the barrier property of the hydrophilic non-porous membrane 2b by covering the portion that is not immersed in water with, for example, a nonwoven fabric or the like.

  In addition, the electron donor supply device 1 of the present invention is disposed only in the decontamination target area contaminated with the environmental pollutant, and the water contained in the decontamination target area or by natural water sprinkling due to rainfall or the like. The hydrophilic non-porous membrane 2b is brought into contact with water by artificial watering using a sprinkler or the like, and the electron donor material 3 is supplied to and activated by microorganisms that require the electron donor material 3, thereby purifying the environment. be able to.

  Below, a specific example is given and demonstrated about the environmental purification method. FIG. 5 shows a use state of the electron donor supply device 1 of the present invention when nitrate ions and nitrite ions are removed from the decontamination target region. The electron donor supply device 1 includes, for example, polyvinyl alcohol, which is a hydrophilic nonporous film, on the entire outer surface of a hydrophobic bag 4 made of polyethylene, which is a nonporous film having hydrophobicity, and is hydrophobic. The bag 4 is filled with, for example, alcohol as the electron donor material 3, and a tank-shaped reservoir 4 ′ for storing the electron donor material 3 is formed in the upper portion of the electron donor supply device 1. The storage unit 4 ′ is provided with a supply unit 7 for replenishing the electron donor substance 3. And the storage part 4 'and the supply part 7 are taken out on the ground, and other parts are embed | buried in soil. Then, the amount of the electron donor material 3 remaining in the ground storage unit 4 ′ is monitored, and the electron donor material 3 is replenished optionally or periodically from the supply unit 7. From the electron donor supply device 1 embedded in the soil, the electron donor material 3 is supplied only when the bag comes into contact with water, and microorganisms in the soil existing in the vicinity of the electron donor supply device 1, for example, Denitrifying bacteria 13 can be activated.

  Therefore, nitrate ions 14 and nitrite ions 14 ′ in the vicinity of the electron donor supply device 1 accumulated in the soil due to excessive fertilization of chemical fertilizer are efficiently converted into harmless nitrogen gas 15. That is, by embedding the electron donor supply device 1 of the present invention in soil, microorganisms that require the electron donor substance 3 among the microorganism groups in the soil present in the vicinity thereof are selectively activated. Can function. Although microorganisms living in the soil may be used, the microorganisms preliminarily selected and cultured are fixed to the carrier 5 and the surface of the hydrophilic bag 5 or the electron donor supply device 1 in the soil. It may be used by being buried separately in the vicinity. Further, by inserting the electron donor supply device 1 having a tube shape with a sharp tip into the vicinity of the root of the crop, it can be used for preventing poor growth of the crop due to excessive supply of chemical fertilizer. The reservoir 4 ′ exposed to the ground is provided with a barrier layer for preventing contact with water so that the electron donor substance 3 does not permeate from the reservoir 4 due to water contact due to rain or the like. preferable. Of course, the reservoir 4 ′ is formed as a separate body by a film that does not allow the electron donor material 3 to permeate, and is connected to the hydrophobic bag 4 to supply the electron donor material 3 into the hydrophobic bag 4. You may be able to do it.

  The place of use is not limited to agricultural land such as soil that is over-fertilized with chemical fertilizers, such as a waste disposal site for livestock manure, which contains a lot of ammonia, nitrite ions, and nitrate ions in the groundwater. For example, there is a factory site that may have been. Alternatively, it may be embedded in sludge to activate microorganisms in the sludge to promote removal of the pollutants. By removing ammonia, nitrite ions, and nitrate ions from soil and groundwater by this method, it is possible to provide safer water for daily use in places that rely on groundwater for the majority of domestic water. Furthermore, it is very useful as a countermeasure against nitrogen load on the natural world, which is a serious problem worldwide.

  Moreover, the electron donor supply device 1 of the present invention can also be used in an apparatus for removing gaseous ammonia by biological treatment. FIG. 6 shows a use state of the electron donor supply device 1 of the present invention in an apparatus for removing gaseous ammonia. The gaseous ammonia removing device 20 includes a gas introducing unit 27 for introducing gaseous ammonia, a watering means for bringing water into contact with the gaseous ammonia introduced from the gas introducing unit 27 to obtain ammonia-containing water, gaseous ammonia, A microbial treatment region 28 for decomposing ammonium ions contained in the water by bringing the water in contact therewith, and the watering means includes a watering pump 21 that pumps up the water 25 stored in the circulation tank 24, and watering It comprises a pipe 22 through which the water pumped up by the pump 21 passes and a sprinkling pipe 23 for sprinkling water 25 downward.

  Gaseous ammonia is introduced into the gaseous ammonia removal device 20 from the gas introduction unit 27. In the present embodiment, the gas introduction part 27 is provided immediately below the watering nozzle 23. However, since gaseous ammonia is lighter than air, the gas introduction part 27 is provided under the microorganism treatment region 28 to provide gaseous ammonia. May be diffused upward in the apparatus 20. Next, the water 25 in the circulation tank 24 is pumped up by the watering pump 21, passes through the pipe 22, and is sprinkled from the watering pipe 23. The sprinkled water 25 comes into contact with and dissolves gaseous ammonia introduced into the apparatus 20, converts the gaseous ammonia into ammonium ions, and comes into contact with the microorganism treatment region 28.

  In the microorganism treatment area 28, ammonia oxidizing bacteria and denitrifying bacteria exist, and the electron donor supply device 1 of the present invention is disposed in this area. Although there are no particular limitations on how ammonia-oxidizing bacteria or ammonia-oxidizing bacteria, nitrite-oxidizing bacteria, and denitrifying bacteria are present in the microbial treatment region 28, for example, the carrier 5 may be supported, or a porous body may be used. It may be used. The arrangement of the electron donor supply apparatus 1 is not particularly limited as long as the electron donor substance 3 can be supplied to the denitrifying bacteria. Further, nitrite oxidizing bacteria may be further present.

  Ammonium ions contained in the water 25 are oxidized to nitrite ions by ammonia oxidizing bacteria, and are also oxidized to nitrate ions when nitrite oxidizing bacteria are also present. And the nitrite ion produced | generated by ammonia oxidizing bacteria and the nitrate ion produced | generated by the nitrite oxidizing bacteria are reduced to nitrogen gas by denitrifying bacteria. Therefore, the gaseous ammonia removing device 20 can remove the gaseous ammonia to deodorize it and make it harmless. Further, when the water 25 and the microorganism treatment region 28 are in contact with each other, the water supply to the microorganisms existing in the microorganism treatment region and the water supply to the electron donor supply device 1 of the present invention are simultaneously performed. The electron donor material 3 is supplied from the electron donor supply device 1 to the denitrifying bacteria. The water 25 that has passed through the microorganism treatment region 28 returns to the circulation tank 24. At this time, ammonium ions that have not been removed may enter the circulation tank 24 and raise the pH. Therefore, a water supply means 26 is provided to dilute the water 25 in the circulation tank 24 to keep the pH constant. I try to keep the value.

  Moreover, the electron donor supply device 1 of the present invention can be used as a bioreactor by arranging a carrier 11 on which microorganisms effective for removing a target component are fixed. FIG. 7 shows an example in which a carrier 11 fixed with microorganisms effective for removing a target component is arranged around the electron donor supply device 1 of the present invention and used as a bioreactor. In this embodiment, the case where ammonia-oxidizing bacteria and denitrifying bacteria are used as microorganisms will be described as an example. However, the present invention is not limited to these microorganisms. If used, components other than nitrogen compounds such as ammonia, nitrate ions and nitrite ions can be removed.

  A bioreactor 9 shown in FIG. 7 is configured by accommodating the electron donor supply device 1 of the present invention in a space 12 inside a bag formed by a carrier 11. The bag formed of the carrier 11 is coated with the carrier 11 carrying ammonia oxidizing bacteria and denitrifying bacteria on the inner surface or the front surface of the nonwoven fabric 10 so that the nonwoven fabric 10 bag is fixed as a reinforcing structure. I try to keep the form. And the electron donor supply apparatus 1 of this invention is accommodated and used for the space 12 inside a bag. As the carrier 11, the same material as the carrier 5 provided on the surface of the electron donor supply device 1 can be used. The material for reinforcing the carrier 11 is not limited to the nonwoven fabric, and for example, a nylon net can be used.

As ammonia-oxidizing bacteria and denitrifying bacteria, those conventionally known in this type of field can be used. More specifically, for example, ammonia-oxidizing bacteria include Nitrosomonas europaea NBRC-14298, Nitrosomonas europaea, N. ^* , Nitrosococcus oceanus ^* , N.mobilis, Nitrosospira briensis, Nitrosolobus multiformis, Nitrosovibrio tenuis, and denitrifying bacteria include Paracoccus denitrificans, Paracoccus denitrificans, Alcaligenes eutrophus, A. faecalis, Alcaligenes sp. 2, GA-2-1 (FERM P-13862, P-13860, P-13861) ^* , Pseudomonas denitrificans and the like.

In addition, you may further carry | support nitrite oxidation bacteria. As the nitrite oxidizing bacteria, those conventionally known in this kind of field can be used, and more specifically, for example, Nitrobacter winogradskyi, N. hamburgensis, Nitrospina gracilis ^* , Nitrococcus mobilis ^* , Nitrospira marina ^*, etc. Can be mentioned.

Note that the strains marked with ^* in the above are strains that can be applied only to seawater treatment, and the other strains can be applied only to freshwater treatment. N.europaea and N.winogradskyi can be used both in fresh water and in sea water. The strain to which the deposit number is attached is a strain deposited by the applicant. These strains may be fixed to the carrier alone, or may be fixed in combination with the same or different strains.

  Ammonia-oxidizing bacteria convert (oxidize) ammonia (ammonium ions) to nitrite ions under aerobic conditions, and denitrifying bacteria convert (reducing) nitrate ions and nitrite ions to nitrogen gas under anaerobic conditions. That is, by causing ammonia oxidizing bacteria to function under aerobic conditions, ammonia can be converted into nitrite ions to suppress malodor. In addition, nitrate ions and nitrite ions are converted into harmless nitrogen gas by allowing the denitrifying bacteria to function under anaerobic conditions. By using these bacteria in combination, ammonia, nitrate ions, and nitrite ions can be removed. That is, when both ammonia-oxidizing bacteria and denitrifying bacteria are supported on the carrier 11, when oxygen is supplied to the ammonia-oxidizing bacteria, the denitrifying bacteria are removed from a suitable region in the bioreactor, that is, the position where oxygen is supplied. Denitrification is locally distributed in a remote anaerobic region. Nitrite-oxidizing bacteria are microorganisms that oxidize nitrite ions to nitrate ions. By supporting these bacteria, denitrification reaction occurs more efficiently.

  According to the bioreactor 9 configured as described above, for example, when water is supplied to the space 12 inside the bag, the electron donor substance 3 leaks into the space 12 inside the bag, and the carrier 11 While being diffused in the bag, the electron donor material 3 is uniformly supplied to the surface on which microorganisms that require the electron donor material 3, that is, denitrifying bacteria exist. That is, only by supplying water to the electron donor supply device 1 and the carrier 11, a water environment in which microorganisms are likely to be active is formed, and the electron donor material 3 is autonomously and uniformly and gradually released. It becomes possible to supply microorganisms. The bioreactor 9 is configured so that the electron donor supply device 1 is accommodated and used in the space 12 inside the bag. Therefore, when the sealed electron donor material 3 is used up, the electron donor material 3 is used. By replacing with a new electron donor supply device 1 sealed with ammonia, ammonia, nitrate ions and nitrite ions in the region to be treated can be continuously changed to nitrogen and removed.

  In addition, the bioreactor 9 can be used in the above-described waste water treatment tank, decontamination target region, and gaseous ammonia removal apparatus, as well as in the atmosphere. For example, water is simultaneously supplied to both the electron donor supply device 1 and the carrier 11 by pouring water into the space 12 inside the bag. Since the supply of the electron donor material 3 occurs until the water is exhausted and dried, it is possible to make the microorganisms function.

  In addition, it is preferable to use the water-absorbing polymer described above as the carrier 11. In this case, the water retention capacity of the carrier 11 is further increased. Further, when the bioreactor 9 is placed in the atmosphere to remove the target component from the atmosphere, the target compound existing in the atmosphere is removed by dissolving in the water contained in the carrier 11. become. For example, when removing ammonia gas, when ammonia gas adheres to the surface of the carrier 11 of the bioreactor 9, the ammonia gas is easily converted into ammonium ions, and the ammonia gas removal efficiency can be increased. It becomes. Moreover, since the immobilized microorganisms may be vulnerable to drying, when used in the air, it is necessary to supply water periodically. However, the use of the water-absorbing polymer can greatly reduce the labor of water supply. In addition, even when used in soil, groundwater, etc., it is possible to efficiently absorb and retain water and continue to remove environmental pollutants for a long period of time.

  The above-described embodiment is an example of a preferred embodiment of the present invention, but is not limited thereto, and various modifications can be made without departing from the scope of the present invention.

  For example, in the above-described embodiment, the hydrophobic container 4 is sealed in the hydrophilic container 6 and the hydrophobic non-porous film 2a and the hydrophilic non-porous film 2b are almost in close contact with each other. However, the present invention is not limited to such a form. For example, as shown in FIG. 8, the hydrophobic nonporous membrane 2a and the hydrophilic nonporous membrane 2b are not brought into close contact with each other, and the hydrophobic nonporous membrane 2a and the hydrophilic nonporous membrane are not adhered to each other. You may make it provide the space 10 in which the electron donor substance 3 permeate | transmitted from the nonporous film | membrane 2a which has hydrophobicity retains between the film | membrane 2b. In this case, when the hydrophilic nonporous membrane 2b is brought into contact with water, the electron donor substance 3 staying in the staying space 10 immediately permeates the hydrophilic nonporous membrane 2b. Thereafter, as the amount of the electron donor material 3 staying in the staying space 10 decreases, the electron donor material 3 is transferred to the microorganism at a speed controlled by the molecular permeation performance of the hydrophobic non-porous membrane 2a. It becomes possible to supply. That is, since the retention amount of the electron donor material 3 changes according to the volume of the retention space 10, the electron donor material 3 is to be supplied immediately after the hydrophilic non-porous film 2b comes into contact with water. For example, when it is desired to instantly supply and activate the electron donor substance 3 to a large number of microorganism groups, the amount can be controlled by the volume of the space portion. That is, since the retention amount of the electron donor material 3 changes according to the volume of the retention space 10, the electron donor material 3 is to be supplied immediately after the hydrophilic non-porous film 2b comes into contact with water. The amount can be controlled by the volume of the space portion. In the electron donor supply device 1 shown in FIG. 8, a non-porous membrane 2a having hydrophobicity and a hydrophilic non-porous membrane 2b are bonded or welded only at the peripheral edge to provide a space. Alternatively, the hydrophobic container 4 may be sealed with the hydrophilic container 6 so that a space is provided between the hydrophobic non-porous film 2a and the hydrophilic non-porous film 2b.

  Alternatively, a two-layer structure film in which a non-porous film 2a having hydrophobicity and a hydrophilic non-porous film 2b are bonded may be used. For example, a non-porous membrane 2a having a hydrophobic property or a hydrophilic property using a hot melt adhesive (olefin-based adhesive: for example, having polyethylene as a main component and ethylene vinyl acetate mixed) heated to have fluidity It is applied to one surface of the non-porous film 2b, and the hydrophobic non-porous film 2a and the hydrophilic non-porous film 2b are bonded together within the time until the hot melt adhesive is cured. Can do. Further, the bonding of the hydrophobic non-porous film 2a and the hydrophilic non-porous film 2b may be performed on the entire surface or only on the peripheral edge.

  In addition, the method of bonding the non-porous membrane 2a having hydrophobicity and the hydrophilic non-porous membrane 2b is not limited to the method using the hot melt adhesive described above, and an adhesive other than the hot melt adhesive is used. Alternatively, a hydrophobic non-porous film 2a and a hydrophilic non-porous film 2b may be bonded together by using a double-sided tape or the like.

  Furthermore, in the above-described embodiment, one hydrophobic container 4 is sealed by one hydrophilic container 6, but a plurality of hydrophobic containers 4 are formed by one hydrophilic container 6, as shown in FIG. May be sealed.

  Further, in the above-described embodiment, the electron donor supply device 1 in which the hydrophobic container 4 is sealed with the hydrophilic container 6 is brought into contact with water as it is. However, when used, the hydrophilic non-porous film 2b is used. May be used after the non-porous membrane 2a having hydrophobicity in the hydrophobic container 4 is exposed. That is, the hydrophobic non-porous membrane 2a is covered with the hydrophilic non-porous membrane 2b outside the hydrophobic container 4 only during the distribution process of the electron donor supply device 1 or when long-term storage is required. Thus, the hydrophilic non-porous film 2b may be removed at the stage of use. For example, the hydrophilic non-porous film 2b covering the non-porous film 2a having hydrophobicity may be peeled off and used. In the case of the electron donor supply apparatus 1 shown in FIG. 14, a plurality of hydrophobic containers 4 may be taken out from the hydrophilic container 6 and used.

  Furthermore, the electron donor supply device 1 to the microorganism of the present invention may be provided with means for introducing the electron donor material 3 so that the electron donor material 3 can be replenished from the outside. For example, as shown in FIG. 9, the means for introducing the electron donor material 3 is provided with a supply unit 7 for injecting the electron donor material 3 into a part of the edge of the hydrophobic container 4, and further shown in FIG. A structure in which the nozzle or pipe 8 is mounted may be used, or a nozzle or pipe 8 integrated with the container 4 may be used. An electron donor supply apparatus 1 for microorganisms shown in FIG. 10 includes a supply nozzle 8 attached to a supply unit 7 provided at an edge of a container 4 or a supply nozzle 8 integrated with a hydrophobic container 4 and an electron donation. A tank 18 for storing the body material 3 ′ is connected by a tube 17 or the like so that the electron donor material 3 ′ can be replenished as necessary. In this case, since the tank 18 and the container 4 are communicated with each other via the tube 17, if the electron donor material 3 is stored in the tank 18, the electron donor material 3 in the hydrophobic container 4 is reduced. At this time, the electron donor material 3 ′ can be replenished by the pressure difference between the tank 18 and the hydrophobic container 4. The hydrophobic container 4 is not provided with a sealing structure in a strict sense because the supply unit 7 or the nozzle 8 is provided. However, the supply nozzle 8 is filled with the electron donor substance 3 ′ supplied from the tank 18. In this state, the liquid level of the electron donor material 3 ′ becomes a seal and the inside of the container 4 is practically sealed. For this reason, the electron donor substance 3 in the container 4 does not leak through the supply unit 7 or the nozzle 8. 9 and 10, the non-porous membrane 2a having hydrophobicity and the hydrophilic non-porous membrane 2b are bonded together, but the present invention is not limited to this, and the supply unit 7 is excluded. The hydrophobic container 4 may be sealed with the hydrophilic container 6.

  Moreover, the electron donor supply method of the present invention is not limited to the form by the bag described in the above embodiment. For example, as shown in FIG. 11, the inside of the waste water treatment tank 30 is divided into two regions by a non-porous membrane 2a having hydrophobicity, and the electron donor substance 3 is put in one region 30a and sealed with a lid. In addition, the hydrophilic nonporous membrane 2b is provided on the surface of the nonporous membrane 2a having hydrophobicity on the other region 30b side, and electrons are supplied to the microorganisms 32 only when the water to be treated 31 flows in. The supply of the body material 3 may occur.

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

Example 1
Bags were formed using various non-porous membranes, and the amount of ethanol permeated in the atmosphere when ethanol was sealed therein was measured.

A bag having a size of 50 mm × 50 mm was prepared using the non-porous membranes (1) to (7) shown below, and 5 mL of ethanol (Wako Pure Chemical Industries, 99.5%) was sealed in the bag.
(1): 0.03 mm thick PVA membrane (trade name: Vinylon film VF-L, manufactured by Kuraray Co., Ltd.)
(2): 0.03 mm thick PE film (Mipolon film, manufactured by Mitsuwa Corporation)
(3): 0.05 mm thick PE film (Mipolon film, manufactured by Mitsuwa Corporation)
(4): 0.075 mm thick EVA membrane (trade name: Agricultural PO film, Showa Pax)
(5): 0.03 mm thick EVOH film (trade name: Eval film EF-HS, manufactured by Kuraray Co., Ltd.)
(6): 0.015 mm thick PLA film (trade name: Terramac, TF-15 manufactured by Unitika, biaxially stretched product)
(7): 0.035 mm thick PLA film (trade name: Terramac, unitika TF-35, biaxially stretched product)

  The bag produced by (1) above is referred to as Sample A.

  The bag produced by (2) above is referred to as Sample B.

  The bag produced by (3) above is referred to as Sample D.

  What sealed the sample D in the bag formed by said (1) is called the sample C. FIG.

  The bag produced by (4) above is referred to as Sample E.

  What sealed the sample E in the bag formed by said (1) is called the sample F. FIG.

  The bag produced by the above (5) is referred to as sample G.

  The bag produced by (6) above is referred to as Sample H.

  The bag produced by (7) above is referred to as Sample I.

  PVA (polyvinyl alcohol) is a hydrophilic non-porous film, PE (polyethylene) is a non-porous film having hydrophobicity, and EVOH (ethylene vinyl alcohol copolymer) is hydrophilic and hydrophobic. It is a non-porous film having both properties. EVA (ethylene vinyl acetate copolymer) is a non-porous film having intermediate properties between PE and EVOH. PLA is a polylactic acid film.

  The EVA membrane used was 12 mol% vinyl acetate (88 mol% ethylene). Further, the EVOH film was 53 mol% vinyl alcohol (47 mol% ethylene).

  Each of the samples A to I is left in an atmosphere of 30 ° C. where the humidity is lowered by placing silica gel, and the amount of ethanol permeated from the bag is measured by measuring the weight of the bag with respect to the number of days elapsed. evaluated.

  The experimental results are shown in FIG. In FIG. 12, ● represents the experimental result of sample A, ■ represents the experimental result of sample B, □ represents the experimental result of sample C, ▲ represents the experimental result of sample D, and ◆ represents the experimental result of sample E The result shows the experimental result of sample F, the symbol ▼ shows the experimental result of sample G, the symbol ◯ shows the experimental result of sample H, and the symbol ◎ shows the experimental result of sample I.

  When the non-porous membrane was a PVA membrane (●: Sample A), no change in bag weight was observed until 7 days after the start of the experiment. In addition, when the ethanol-sealed bag was sealed with a PVA membrane bag (□: Sample C, ◇: Sample F), no change in the weight of the bag was observed until 7 days after the start of the experiment. Further, when ethanol was sealed with a PLA membrane (◯: Sample H, ◎: Sample I), no change in weight was observed for two days from the start of the experiment.

  On the other hand, when the non-porous membrane is a PE membrane (■: Sample B, ▲: Sample D), EVA membrane (◆: Sample E) and EVOH membrane (▼: Sample G), the weight of the bag gradually decreases. It has been confirmed that Moreover, it was found that the rate of weight reduction of the bag was the slowest for the bag using the PE film, the slow for the bag using the EVA film, and the fastest for the bag using the EVOH film. That is, it was found that the permeation rate of an electron donor substance such as ethanol can be increased by adding a hydrophilic property to a non-porous membrane having hydrophobicity.

  In addition, a bag using a 0.05 mm thick PE film (▲: sample D) has a lower rate of weight reduction than a bag using a 0.03 mm thick PE film (■: sample B). Slightly smaller. Therefore, it was found that the permeation rate of an electron donor substance such as ethanol can be increased by reducing the thickness of the non-porous film.

  From the above results, it is clear that the PVA membrane, which is a hydrophilic non-porous membrane, prevents the permeation of ethanol in the atmosphere. If a membrane having a thickness of at least 0.03 mm is used, the permeation of ethanol is prevented. It became clear that it could fully function. On the other hand, when PE film, EVA film and EVOH film were used, it became clear that permeation of ethanol gradually occurred even in the atmosphere.

  Furthermore, in the atmosphere, it becomes clear that the PLA film prevents the permeation of ethanol, and it is clear that the use of a film having a thickness of at least 0.015 mm can sufficiently exert the function of preventing the permeation of ethanol. It was.

(Example 2)
Bags were formed using various non-porous membranes, and the amount of ethanol permeated in water when ethanol was sealed therein was measured.

  Samples used in the experiment were Samples A, B, C, D, E, G, H, and I prepared in Example 1.

Each of these samples was immersed in 300 mL of distilled water (0.02% NaN ₃ ) placed in a beaker, and the TOC concentration of distilled water with respect to the elapsed time was measured to evaluate the amount of ethanol permeated from the bag. The TOC concentration was measured by a combustion-infrared total organic carbon analyzer (TOC-650, manufactured by Toray Engineering). The temperature of distilled water was 30 ° C., and the water was continuously stirred during the experiment.

  The results are shown in FIG. In FIG. 13, ● indicates the experimental result of sample A, ■ indicates the experimental result of sample B, □ indicates the experimental result of sample C, ▲ indicates the experimental result of sample D, and ▼ indicates the experimental result of sample G The result indicates the experimental result of Sample H, and the symbol ◎ indicates the experimental result of Sample I.

  When any sample was used, the permeation of ethanol was confirmed, but a difference was observed in the permeation rate of ethanol.

  That is, when the non-porous membrane is a PVA membrane (●: sample A), it has been clarified that ethanol tends to be released all at once when the sample is immersed in water. Also, when the non-porous membrane was an EVOH membrane (▼: Sample G), it was confirmed that the ethanol permeation rate tends to be high, but when the non-porous membrane was a PVA membrane, The permeation rate of ethanol was slow.

  When the non-porous membrane is a PE membrane (■: Sample B, ▲: Sample D) and PLA membrane (◯: Sample H, ◎: Sample I), from the start of the experiment to the seventh day There was a tendency for the TOC concentration to gradually increase over time. Moreover, by increasing the film thickness, the tendency that the increase rate of the TOC concentration is slow was confirmed both in the case of using the PE film and in the case of using the PLA film. It was confirmed that the molecular permeation performance can be controlled.

  Furthermore, when the bag made of PE film as the non-porous film is covered with PVA film (□: Sample C) and not covered (▲: Sample D), the experimental results are almost the same. Was confirmed. From this, it is clear that when the PVA membrane is brought into contact with water, ethanol is gradually released depending on the ethanol permeability of the PE membrane, and the PVA membrane hardly affects the ethanol permeation rate. became.

  From the above results, the hydrophobic non-porous membrane has a lower ability to permeate ethanol molecules than the PVA membrane, which is a hydrophilic non-porous membrane, in contact with water. It became clear. Moreover, it became clear that when the film thickness of the PE film or PLA film is increased, the permeation performance of ethanol molecules is lowered, and it was confirmed that the molecular permeation performance can be appropriately controlled by controlling the film thickness.

  As described above, the effectiveness of the present invention was confirmed from the results of Example 1 and Example 2. That is, a hydrophilic non-porous film is brought into contact with water by interposing a hydrophilic non-porous film between a sealed container filled with an electron donor substance and the electron donor supply region. Sometimes, the barrier property of the hydrophilic non-porous membrane is lowered, and the electron donor substance that has permeated the hydrophobic non-porous membrane portion permeates the hydrophilic non-porous membrane, and the hydrophilic non-porous membrane. When the membrane does not come into contact with water, the barrier property of the hydrophilic non-porous membrane is exhibited, and it is clear that permeation of the electron donor substance from the hydrophilic non-porous membrane as the container is greatly suppressed. became.

  In addition, the molecular permeation performance of the hydrophilic non-porous membrane in contact with water is higher than the molecular permeation performance of the non-porous membrane having hydrophobicity, and the supply rate of the electron donor substance is non-hydrophobic. It is limited by the molecular permeation performance of the porous membrane. That is, it has been clarified that the electron donor substance is supplied at a rate controlled by the molecular permeation performance of the hydrophobic non-porous membrane.

  Furthermore, the PLA film functions as a barrier film that prevents permeation of the electron donor substance in the atmosphere. When the PLA film is brought into contact with water, the barrier property is lowered and the electron donor substance is controlled by the molecular permeation performance of the PLA film. It was clarified that it can be slowly supplied to microorganisms at a high speed. In other words, when a PLA membrane is used, it exhibits a barrier property in the atmosphere and a function of transmitting an electron donor substance in water without using a hydrophobic non-porous membrane and a hydrophilic non-porous membrane in combination. It became clear that it was possible.

DESCRIPTION OF SYMBOLS 1 Electron donor supply apparatus 2 Polylactic acid film | membrane 2a Hydrophilic nonporous film | membrane 2b Nonporous film | membrane 3 which has hydrophobicity Electron donor substance 4 Container 5 Carrier | carrier 11 Carrier | carrier 28 which fixed microorganism 28 Microbe area | region

Claims (7)

An electron donor substance serving as an energy source for microorganisms, a sealed container having at least a part of a hydrophobic non-porous film, and a hydrophilic non-porous film, Filled with an electron donor substance, and at least the hydrophobic non-porous membrane portion of the outer surface of the container is covered with the hydrophilic non-porous membrane ;
The electron donor material has a property that does not corrode the hydrophobic non-porous film and the hydrophilic non-porous film, and can pass through the hydrophobic non-porous film and contact with water. Selected from alcohols and organic acids having a molecular weight and properties capable of permeating the hydrophilic non-porous membrane in the state of
Non-porous membrane having a hydrophobic, electron donor feed device to the microorganisms and non-porous membrane der wherein Rukoto having both non-porous membrane or both a hydrophobic nature and a hydrophilic hydrophobic . An electron donor supply apparatus for microorganisms, wherein a water-permeable carrier capable of supporting microorganisms is disposed around the electron donor supply apparatus according to claim 1. A method for treating wastewater by biological treatment, wherein the electron donor supply device for microorganisms according to claim 1 is immersed in the wastewater, and the electron donor substance is applied to the microorganisms present around the electron donor supply device. Waste water treatment method characterized by supplying and activating. An electron donor supply device for microorganisms according to claim 1 is disposed in a decontamination target region, and an electron donor substance is supplied to and activated by microorganisms existing in the vicinity of the electron donor supply device, thereby causing environmental pollution. An environmental purification method comprising removing a substance. A first step of bringing gaseous ammonia and water into contact with each other to dissolve the gaseous ammonia in the water; and a microorganism region in which ammonia oxidizing bacteria and denitrifying bacteria are present in the water brought into contact with the gaseous ammonia. A method for removing gaseous ammonia comprising a second step of contacting with a microorganism, wherein the electron donor supply device for microorganisms according to claim 1 is disposed in the microorganism region and is present in the vicinity of the electron donor supply device. A method for removing gaseous ammonia, comprising activating a denitrifying bacterium by supplying an electron donor substance. A carrier on which a microorganism effective for removing a target component is fixed is arranged around the electron donor supply device for the microorganism according to claim 1, and water is supplied to the carrier and the electron donor supply device. To remove the target component. The non-porous membrane portion having hydrophobicity in a sealed container having a hydrophobic non-porous membrane at least partially and filled with an electron donor substance serving as an energy source for microorganisms, and the electrons The hydrophobic non-porous membrane portion of the container is provided with the electron donor supply by interposing a hydrophilic non-porous membrane between the donor substance and the electron donor supply region to be supplied to the microorganism. Preventing direct contact with the region, contacting the hydrophilic non-porous membrane with water to reduce the barrier properties of the hydrophilic non-porous membrane, and allowing the electron donor material to become hydrophobic in the container Is supplied to the electron donor supply region at a rate governed by the molecular permeation performance of the non-porous membrane having
The electron donor material has a property that does not corrode the hydrophobic non-porous film and the hydrophilic non-porous film, and can pass through the hydrophobic non-porous film and contact with water. Selected from alcohols and organic acids having a molecular weight and properties capable of permeating the hydrophilic non-porous membrane in the state of
The method for supplying an electron donor to a microorganism, wherein the non-porous membrane having hydrophobicity is a hydrophobic non-porous membrane or a non-porous membrane having both hydrophobic and hydrophilic properties.