JP2003000237A - Inclusively immobilized microbe carrier and method for manufacturing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for supporting a microbe on a immobilizing material in a high concentration without needing pure culturing of the microbe. SOLUTION: The method for manufacturing an inclusively immobilized microbe carrier comprises producing a support prepared by inclusively immobilizing a microbe by polymerizing a monomer or a prepolymer in the presence of the microbe. The polymerization is carried out using a monomer block or a prepolymer block having the diameter or the thickness of 1-10 cm to obtain the carrier A of the present invention.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a comprehensively immobilized microbial carrier for biologically efficiently treating inorganic and / or organic compounds in wastewater or air and a method for producing the same.

[0002]

Biological treatment of wastewater and sewage with microorganisms has been widely adopted because of its relatively low cost. However, depending on the type of microorganism, there are some that have a slow growth rate, some that are easily poisoned, and some that are difficult to grow in their environment, and thus it may not always be an efficient method. Therefore, in order to actively form an environment in which microorganisms can easily reproduce, a treatment method has already been put into practical use, in which biological treatment is carried out using an entrapping immobilization microbial carrier in which activated sludge and specific microorganisms are entrapped and fixed in advance. .

A gel material is usually used as an immobilizing material for supporting (holding) microorganisms therein, which is harmless to the natural environment, is not altered or decomposed by microorganisms, has high mechanical strength, It is required to be able to support a large amount. Examples of gel materials that have been put to practical use so far include polyethylene glycol-based polymers and polyvinyl alcohol-based resins described in Japanese Patent Application No. 60-44131. On the other hand, activated sludge and purely cultured microorganisms are used as the microorganisms to be entrapped and immobilized in the gel material.

Recently, anaerobic bacteria have been attracting attention as microorganisms. This anaerobic bacterium decomposes oil and has a high concentration of BO.
It is excellent in the purification of so-called environmental pollutants such as decomposition of component D, denitrification of nitrite nitrogen component and nitrate nitrogen component, decomposition and removal of malodorous component, and techniques for utilizing pure bacteria have been studied.

[0005]

By the way, in order to biologically treat environmental pollutants using anaerobic bacteria, an entrapping immobilization microbial carrier in which anaerobic bacteria are dominated and supported at a high concentration is produced. It is necessary, but conventionally, it was necessary to immobilize purely cultured anaerobic bacteria on a gel material.

However, pure culture requires a culture tank and a large amount of medium, and further has a drawback that the production cost is too high because the culture time is long and the labor cost is naturally high.

The present invention has been made in view of the above circumstances, and a comprehensively immobilized microbial carrier capable of supporting a high concentration of a microorganism on an immobilization material for a monomer or a prepolymer without performing pure culture of the microorganism, It is an object to provide a manufacturing method thereof.

[0008]

[Means for Solving the Problems] In order to achieve the above object, the present invention provides a carrier in which microorganisms are entrapped and immobilized by polymerizing an immobilization material of a monomer or a prepolymer in the presence of microorganisms. The method for producing a microbial carrier is characterized in that the immobilization material is polymerized in a diameter or thickness of 1 to 10 cm.

The present invention has examined the technique for accumulating microorganisms, particularly anaerobic bacteria, in a high concentration on a monomer or prepolymer immobilization material, and as a result, the diameter or thickness of the immobilization material is 1
By polymerizing the entrapping immobilization microbial carrier by polymerization at cm or more, the microorganism can be effectively proliferated in the subsequent culture of the entrapping immobilization microbial carrier.

This is because the diameter or thickness of the immobilizing material is 1 to 1
By polymerizing in a large size of 0 cm, the heat of polymerization is accumulated inside the immobilizing material during the polymerization, and the radial polymerization progresses radially to form a radial sponge structure. It is thought to increase.

As a mode in which the diameter or thickness of the immobilizing material is adjusted to 1 to 10 cm, the immobilizing material is placed in a mold of 1 to 10 cm for polymerization, or the immobilizing material is 1 to 10 cm in size and alkali metal ions are added. Alternatively, the polymerization can be carried out by dropping into an aqueous solvent containing a polyvalent metal ion or an organic solvent.

In a preferred embodiment of the present invention, the polymerization temperature during the polymerization is preferably set to 30 to 60 ° C. in order to further increase the concentration of microorganisms, and further, the temperature of the central portion of the immobilizing material during the polymerization to the outside temperature. The temperature difference minus
It is preferably 0 ° C. Further, it is more preferable that the immobilization material contains inorganic particles or organic particles.

Further, in order to achieve the above object, the present invention is characterized by being manufactured by the method for manufacturing a comprehensively immobilized microbial carrier according to any one of claims 1 to 6.

The present invention provides an entrapping immobilization microbial carrier produced by the method for producing an entrapping immobilization microbial carrier of the present invention.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION Preferred embodiments of the entrapping immobilization microorganism carrier and the method for producing the same according to the present invention will be described below in detail with reference to the accompanying drawings.

The method for producing the entrapping immobilization microbial carrier of the present invention comprises a monomer or prepolymer immobilization material for entrapping immobilization of microorganisms in the presence of microorganisms in a size of 1 to 10 cm, preferably 3 to. Polymerize with a size of 5 cm. In order to polymerize at this size, the equivalent spherical diameter is 1 to 10c.
m, preferably 3-5 cm, may be polymerized in a mold or have a thickness of 1-10 cm, preferably 3-5 c.
Polymerized into a sheet of size m, then 1-10c
It may be molded into a size of m, preferably 3 to 5 cm.
Further, polymerization may be carried out by dropping into an aqueous solvent or an organic solvent containing an alkali metal ion or a polyvalent metal ion having a size of 1 to 10 cm, preferably 3 to 5 cm. Thereby, the entrapping immobilization microorganism carrier having a sponge structure having a diameter or thickness of 1 to 10 cm, preferably 3 to 5 cm, of the present invention can be obtained.

Hereinafter, an anaerobic bacterium will be described as an example of the microorganism, but the present invention is not limited to the anaerobic bacterium.

FIG. 1 shows that the size of the immobilizing material at the time of polymerization is
This is an experiment conducted to see how it affects the increase in the number of bacteria during culturing of the obtained entrapping immobilization microbial carrier, and the equivalent spherical diameter of the immobilization material when encapsulating the activated sludge with polyethylene glycol prepolymer. And the number of anaerobic bacteria after culturing was investigated. The experimental conditions are
When the entrapped immobilized microbial carrier containing 2% of activated sludge was anaerobically cultured for 3 weeks in a medium containing peptone and meat extract, the number of anaerobic bacteria was measured.

As can be seen from the experimental results shown in FIG. 1, the number of bacteria before the start of culturing was about 10 ⁶ (cells / cm ³ -carrier), but the number of bacteria increased as the equivalent sphere diameter exceeded 10 mm. The number started to increase, and the equivalent number of spheres was 30 mm and the number of bacteria became the maximum, about 10 ¹¹ (cells / cm ³ -carrier). And
The maximum number of bacteria is maintained up to a sphere-equivalent diameter of 50 mm, then the number of bacteria gradually decreases when the sphere-equivalent diameter exceeds 50 mm, and the same as the number of cells before the start of culture when the sphere-equivalent diameter exceeds 100 mm. It decreased to 10 ⁸ (cells / cm ³ -carrier). This is because the equivalent spherical diameter of the immobilizing material during polymerization is 10
The entrapping immobilization microbial carrier obtained by polymerizing at mm or more,
It is considered that the heat of polymerization accumulates at the center of the immobilization material during polymerization, which facilitates outward radial polymerization, resulting in the immobilization material having a radial sponge structure and an increased habitat area for bacteria. To be In fact, the internal structure of the entrapping immobilization microbial carrier obtained by polymerizing the immobilization material by gradually increasing the equivalent sphere diameter to 30 mm, the sponge structure gradually begins to appear from a uniform dense structure, and the equivalent sphere diameter is 30 mm.
With the above, the sponge structure was completely obtained. In this case, in FIG. 1, when the equivalent sphere diameter exceeds 50 mm, the number of bacteria decreases despite the sponge structure because the diffusion rate of the substrate is rate-determining and the amount of bacteria retained in the entire carrier decreases. Will be considered. FIG. 2 is a view conceptually showing the entrapping immobilization microbial carrier A obtained by the outward radial polymerization, and shows an internal cross section of the entrapping immobilization microbial carrier. 2 (a) is an entrapping immobilization microbial carrier A obtained by polymerizing an immobilization material in a square mold having a side of 3.5 cm in the presence of microorganisms, and (b) is immobilization. The entrapped immobilized microbial carrier A is obtained by polymerizing a chemical compound by dropping it into an aqueous solvent containing an alkali metal ion or a polyvalent metal ion in a size of 3.5 cm in the presence of a microorganism. Also,
FIG. 2 (c) shows the entrapping immobilization microbial carrier A obtained by polymerizing in a plate shape (sheet shape) with a molding die having a thickness of 3.5 cm and a length and width of 10 cm. The entrapping immobilization microbial carrier A obtained by polymerization in this way had a porous sponge structure as seen from the electron micrographs of FIGS. 3 (a) and 3 (b). FIG. 3A is a view of an electron micrograph taken from a direction in which a porous hole is visible.
(B) is a view of an electron micrograph taken along the direction in which polymerization proceeds.

Thus, in order to obtain the entrapping immobilization microbial carrier A in which the microorganisms are entrapped at a high concentration, the immobilization material is
It is important to polymerize in the presence of microorganisms in a size of 1-10 cm, preferably 3-5 cm.

FIG. 4 shows the relationship between the polymerization temperature and the number of anaerobic bacteria.

The experimental condition is that the activated sludge is contained at 2%.
The number of anaerobic bacteria was measured when the entrapped immobilized microbial carrier A having a sphere equivalent diameter of 5 cm was anaerobically cultured in a medium containing peptone and meat extract for 3 weeks.

As can be seen from the experimental results shown in FIG. 4, as the polymerization temperature was raised, the number of bacteria gradually increased, reaching a maximum of about 10 ¹¹ (cells / cm ³ -carrier) at 30 ° C, and 60 ° C. After maintaining the maximum number of bacteria up to 60 ° C, it decreased again when the temperature exceeded 60 ° C. This is presumably because increasing the polymerization temperature facilitates the outward radial polymerization. The reason why the number of bacteria decreases again when the temperature exceeds 60 ° C is that the bacteria are easily killed by increasing the temperature, and the sponge structure is less likely to be formed due to shrinkage of the immobilization material due to heat. It is considered that the habitat area of the island will decrease. Thus, in order to obtain the entrapping immobilization microbial carrier A in which the microorganisms are entrapped at a high concentration, in addition to polymerizing the immobilization material in a size of 1 to 10 cm, the polymerization temperature is set to 30 to 60 ° C. Is preferred.

FIG. 5 shows the relationship between the temperature difference between the center temperature of the immobilizing material and the outside air temperature during polymerization and the number of anaerobic bacteria.

The experimental condition is that the activated sludge is contained in 2%.
A 5 cm square entrapping immobilization microbial carrier A was added to peptone,
The number of anaerobic bacteria when anaerobically cultured for 3 weeks in a medium containing meat extract was measured.

As can be seen from the experimental results shown in FIG. 5, as the temperature difference between the center temperature of the immobilizing material and the outside air temperature during polymerization is increased, the number of bacteria gradually increases and the temperature difference is 5 °.
The maximum is around 10 ¹¹ (cells / cm ³ -carrier) near C,
The maximum number of bacteria was maintained until the temperature difference reached around 10 ° C, and the number of bacteria decreased again when the temperature difference exceeded 10 ° C. This is because when the temperature difference obtained by subtracting the outside air temperature from the center temperature of the immobilization material is moderate, the heat dissipation phenomenon due to the temperature difference gradually progresses and the sponge structure is reliably formed, whereas the temperature difference It is considered that when the temperature exceeds 10 ° C and becomes too large, the heat dissipation phenomenon is too fast and the formation of the sponge structure cannot be completed in time.

Thus, in order to obtain the entrapping immobilization microbial carrier A containing the microorganisms at a high concentration, 1
In addition to polymerization with a size of 10 cm, it is preferable to set the polymerization temperature to 30 to 60 ° C. Further, the temperature difference between the center temperature of the immobilizing material and the outside air temperature during the polymerization is 5 to 10 °. It is preferably C.

Table 1 shows how the number of anaerobic bacteria becomes when the immobilizing material to be polymerized contains inorganic particles or organic particles.

The experimental condition is that the activated sludge is contained at 2%.
A 5 cm square entrapping immobilization microbial carrier A was added to peptone,
The number of anaerobic bacteria when anaerobically cultured for 3 weeks in a medium containing meat extract was measured.

[0030]

[Table 1]

As can be seen from the results in Table 1, the entrapping immobilization microbial carrier A obtained by incorporating the inorganic particles or the organic particles in the immobilizing material to be polymerized has a higher density than the conventional non-additive one. In both cases, the number of bacteria increased. In particular, the effect of starch particles and biodegradable plastic was great.

As a result, in order to obtain the entrapping immobilization microbial carrier A in which the microorganisms are entrapped in a high concentration, the immobilization material to be polymerized contains inorganic particles such as activated carbon, sand, glass, zeolite, or biodegradability. Particles of organic substances such as plastics, polysaccharides and cellulose may be contained. In addition, 0.2 g / ml of activated sludge is contained in the immobilization material.
If a large amount of L or more is contained, the sludge decomposition product becomes a carbon supply source, which is preferable for the propagation of anaerobic bacteria. In particular, it serves as a hydrogen donor for denitrification by denitrifying bacteria.

As the immobilization material of the immobilization material that can be used for the comprehensive immobilization of the present invention, the following materials can be preferably used. (Monomethacrylates) polyethylene glycol monomethacrylate, polypropylene glycol monomethacrylate, polypropylene glycol monomethacrylate,
Methoxydiethylene glycol methacrylate, methoxypolyethylene glycol methacrylate, methacryloyloxyethyl hydrogen phthalate, methacryloyloxyethyl hydrogen succinate, 3-chloro-2-hydroxypropyl methacrylate, stearyl methacrylate, 2-hydroxyxymethacrylate, ethyl methacrylate, etc. (monoacrylates ) Nonylphenoxy polyethylene glycol acrylate, nonylphenoxy polypropylene glycol acrylate, silicon modified acrylate, polypropylene glycol monoacrylate, phenoxyethyl acrylate, phenoxydiethylene glycol acrylate, phenoxy polyethylene glycol acrylate, methoxy polyethylene glycol Relate, acryloyloxyethyl hydrogen succinate, lauryl acrylate, etc. (dimethacrylates) 1,3-butylene glycol dimethacrylate, 1,4-butanediol dimethacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate , Polyethylene glycol dimethacrylate, butylene glycol dimethacrylate, hexanediol dimethacrylate, neopentyl glycol dimethacrylate, polypropylene glycol dimethacrylate, 2-hydroxy 1,3-dimethacryloxypropane, 2,2-
Bis4-methacryloxyethoxyphenylpropane, 2,2-
Bis 4-methacryloxydiethoxyphenyl propane, 2,
2-bis 4-methacryloxy polyethoxyphenyl propane (diacrylates) ethoxylated neopentyl glycol diacrylate, propoxylated neopentyl glycol diacrylate, polyethylene glycol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol Diacrylate, tripropylene glycol diacrylate, polypropylene glycol diacrylate, 2,2-bis-4-acryloxydiethoxyphenyl propane, 2-hydroxy 1-acryloxy, 3-methacryloxy propane (trimethacrylates) trimethylol propane tri Methacrylate, etc. (Triacrylates) Ethoxylated trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate, propoxylated trimethyl Roll propane triacrylate, etc. (tetraacrylates) Ethoxylated pentaerythritol tetraacrylate, propoxylated pentaerythritol tetraacrylate, ditrimethylolpropane tetraacrylate, etc. (urethane acrylates) Urethane acrylate, urethane dimethyl acrylate, urethane trimethyl acrylate, etc. Acrylates (Others) Acrylamide, photo-curable polyvinyl alcohol, photo-curable polyethylene glycol, photo-curable polyethylene glycol polypropylene glycol prepolymer A book in which anaerobic bacteria are supported at a high concentration by the above-mentioned method for producing the entrapped immobilized microbial carrier. The entrapping immobilization microbial carrier A of the present invention is obtained by contacting the environmental pollutants described below with biological treatment. Effective decomposition and removal or denitrification removal of environmental pollutants are possible.

Effective biologically possible environmental pollutants due to anaerobic bacteria are mainly oil components (hexane extract) in waste water, BOD components, nitrite nitrogen components and nitrate nitrogen components, and air. The target is odorous components such as mercaptan, hydrogen sulfide, and ammonia. Hereinafter, removal of environmental pollutants using the entrapping immobilization microorganism carrier A of the present invention will be described in Examples.

[0035]

Example 1 In Example 1, the treatment performance of the entrapped immobilized microbial carrier A of the present invention, the stability of anaerobic bacteria in a high concentration culture state, and the treatment capability of a high concentration BOD wastewater were tested. It is a thing.

3.5 cm of the present invention in which activated sludge collected from a sewage treatment plant is fixed with a polyethylene glycol prepolymer (polyethylene glycol dimethacrylate).
A rectangular entrapping immobilization microbial carrier was subjected to a test as a sample for continuous treatment operation (hereinafter referred to as "invention method carrier A").
Inventive method carrier A is a carrier having a sponge structure obtained by polymerization at 30 ° C. in a 3.5 cm mold.

As a comparative example, similarly, activated sludge collected from a sewage treatment plant was treated with polyethylene glycol-based prepolymer (polyethylene glycol dimethacrylate) to 3 mm.
The sheet-like polymer having a thickness of 3 mm was cut into a 3 mm square shape, and this was used as a conventional entrapping immobilization microbial carrier (hereinafter referred to as “conventional method carrier B”).

Table 2 shows the composition of the entrapping immobilization microbial carrier, which is the same for both the inventive method carrier A and the conventional method carrier B.

[0039]

[Table 2]

Table 3 shows the results in the carrier A of the invention method and the carrier B of the conventional method.
It is a standard agar medium used for measuring the number of bacteria in the medium. In addition, all bacteria were evaluated by anaerobic culture.

[0041]

[Table 3]

FIG. 6 shows a test apparatus 1 used for continuous processing operation.
It is a conceptual diagram of 0.

The test apparatus 10 comprises a reaction tank 12 having a volume of 2 L.
To the above-mentioned 3.5 cm square large-diameter invention carrier A
It is a fixed bed type continuous treatment device with a filling rate of 000 mL and a filling rate of 50%. Raw water flows in from the bottom of the reaction tank 12 by the pump 14, and the treated water flows out from the upper side surface. In the continuous treatment operation, the residence time was 24 hours and the flow rate was 1.4 mL / min. An air supply pipe 16 is provided, and air can be supplied into the reaction tank 16 as needed.

In order to evaluate the treatment performance and the stability of the anaerobic bacteria in the high concentration culture state of the carrier A of the invention method and the carrier B of the conventional method using the above test apparatus 10, a synthetic wastewater (BOD) was used.
Continuous treatment run at 8000 mg / L) was performed under anaerobic conditions.

As a result, the anaerobic bacteria in the carrier A of the invention method proliferated remarkably. The initial number of anaerobic bacteria was 2 × 10 ⁶ (ce
lls / cm ³ -carrier), the number of bacteria was 4.4 × 10 ¹⁰ (cells) after the continuous treatment for 4 months.
s / cm ³ -carrier), and it was found that high-concentration culture is possible in continuous treatment operation. On the other hand, in the case of the conventional carrier B, when the number of bacteria was measured after the completion of the continuous treatment operation for 4 months, the concentration was 8.6 × 10 ⁸ (cells / cm ³ -carrier) and the concentration could not be increased. The BOD of the treated water using the carrier A of the invention method remained at 350 to 590 mg / L, whereas the BOD of the treated water using the carrier B of the conventional method was 90.
The carrier performance of the invention carrier A was superior to that of the conventional carrier B as compared with the conventional carrier B. In addition, when observing the colony morphology of the diluted plate culture of the carrier after the continuous treatment operation, various small colonies such as white and brown grew in both the inventive method carrier A and the conventional method carrier B, and the isolated fungus was isolated. As a result of identifying with the bioMerieux identification kit,
Pseudomonas sp., Which is a facultative anaerobic bacterium, was identified. This means that the anaerobic bacteria grow in the continuous treatment test of the synthetic wastewater in both the inventive carrier A and the conventional carrier B, but the inventive carrier A has a higher treatment performance and a higher anaerobic bacteria concentration than the conventional carrier B. It means that it is excellent in culture.

Next, in order to clarify the kinetic coefficient using the carrier of the invention method A and the carrier of the conventional method B used in the continuous treatment operation, batch treatment was carried out using the above-mentioned food factory wastewater.

After the continuous treatment operation with the synthetic wastewater was completed, the water in the reaction tank 12 of each of the carrier A of the invention method and the carrier B of the conventional method was replaced with the wastewater of the food factory, and the removal rate of BOD was examined in the batch experiment. BOD concentration of food factory wastewater is 5430mg
A high concentration of / L was used. The BOD analysis of the treated water analyzed the liquid filtered by 5A filter paper. After the operation was completed, the numbers of bacteria of the invention method carrier A and the conventional method carrier B were measured.

The removal rate of BOD is calculated by the following equation (1).

[0049]

## EQU1 ## ds / dt = K × s (1) s: BOD concentration of food factory wastewater (mg / L) t: time (h) K: constant removal rate (1 / h) As a result, conventional method BOD removal rate of carrier B is 0.15
Whereas a 0h ^-1, BOD removal rate of the invention method the carrier A is, 0.228h ^-1 next, BOD of high concentration BOD wastewater
It was found that the carrier A of the invention method was about 1.5 times faster than the carrier B of the conventional method in the removal rate. (Example 2) In Example 2, carrier A of the invention method and carrier B of the conventional method are used.
For each of the
It is a test for removing performance of COD component, SS (suspended substance), and oil component (n-hexane extract).

After the completion of the experiment of Example 1, the food factory wastewater was continuously treated under aerobic conditions in which air was aerated at 1 L / min (however, the center of the carrier became anaerobic) with a residence time of 12 hours. .

The results are shown in Table 4. The treated water of the present invention is treated water using the inventive carrier A, and the treated water of the conventional method is treated water using the conventional carrier B.

[0052]

[Table 4]

As can be seen from the results in Table 4, the treated water of the present invention using the carrier A of the present invention was extracted by BOD, COD and n-hexane as compared with the treated water of the conventional method using the carrier B of the conventional method. The result was good. The reason why the BOD decomposition performance is good is that the carrier A of the invention method has a significantly larger diameter or thickness than the carrier B of the conventional method, so that good anaerobic conditions can be formed in the carrier. Conceivable. Further, the carrier A of the invention method has a good decomposition performance for the COD component, but it is considered that this is because the COD component is decomposed by the coupling reaction between the anaerobic bacterium and the aerobic bacterium. (Example 3) In Example 3, carrier A of the invention and carrier B of the conventional method are used.
For each of the above, the denitrification performance of the nitrite nitrogen component and the nitrate nitrogen component was tested.

The method of producing the carrier A of the invention and the carrier B of the conventional method, and the size of the carrier are the same as in Example 1.

The test equipment has a diameter of 50 cm and a height of 150 cm.
A fixed-bed type nitrogen treatment device in which the column was filled with 60% of the carrier was prepared for each of the inventive carrier A and the conventional carrier B. Then, the water of Tuma in Chiba Prefecture was continuously flowed into the column of each nitrogen treatment device, and the nitrogen treatment was carried out by contacting with the carrier at a retention time of 15 minutes in the column, and the treated water was discharged. It was The water of T swamp is
Ammonia nitrogen 1.2mg / L, Nitrate nitrogen 0.8m
Water containing g / L and an organic carbon concentration of 2 mg / L. The treated water became stable 3 weeks after the start of operation, and thereafter, nitrification reaction and denitrification reaction proceeded simultaneously for 6 months.

As a result, the average water quality of the treated water using the inventive carrier A was 0.4 mg / L of ammonia nitrogen, 0.6 mg / L of nitrate nitrogen, and 0.5 mg / L of organic carbon concentration.
, No nitrite nitrogen was detected. On the other hand, the average water quality of treated water using the conventional carrier B is ammonia nitrogen 0.4 mg / L, nitrate nitrogen 1.2 mg / L, organic carbon concentration 0.5 mg / L, and nitrite nitrogen is Not detected. As can be seen from these results, the treated water of the conventional method carrier B has twice the remaining amount of nitrate nitrogen as compared with the treated water of the inventive method carrier A, indicating that the denitrification reaction is unlikely to occur. In addition, the number of bacteria of the invention method carrier A and the conventional method carrier B after the continuous operation for 6 months was measured.
In the case of, the initial number of anaerobic bacteria was 2 × 10 ⁶ (cells / cm ³
-Carrier), but 5.4x after continuous operation
It is 10 ¹⁰ (cells / cm ³ -carrier), and high-concentration culture is possible in continuous operation. In the inventive method carrier A having a large diameter or thickness of the carrier, nitrifying bacteria grew near the surface of the carrier, and high concentration of anaerobic bacteria grew inside the carrier away from the surface of the carrier.
On the other hand, in the case of the conventional carrier B having a small carrier diameter or thickness, the number of bacteria after the continuous operation was 2.6 × 10 ⁸ (cells / cm
³ -carrier) and the concentration did not increase. (Example 4) In Example 5, mercaptan in exhaust gas,
The odorous components such as hydrogen sulfide and ammonia were removed.

The test apparatus has a diameter of 10 cm and a height of 200 c.
A fixed-bed type exhaust gas treating apparatus in which the carrier was packed in the column of m so as to be 50% was prepared for each of the inventive method carrier A and the conventional method carrier B. The method of manufacturing the carrier of the inventive method carrier A and the conventional method carrier B and the size of the carrier thus filled are the same as in Example 1.

Then, a gas containing mercaptan was introduced from the lower end of the column, passed through a fixed bed and then exhausted from the upper end of the column, and the mercaptan concentration of the inflow gas and the exhaust gas was measured to obtain the removal rate. The residence time of the gas in the column was 2 minutes.

Similarly, a gas containing hydrogen sulfide and a gas containing ammonia were also tested.

As a result, when the inventive carrier A was used, a removal rate of 99% could be obtained for any of mercaptan, hydrogen sulfide and ammonia. In contrast,
Even when the conventional carrier B was used, a removal rate of 85 to 99% could be obtained, but the removal rate fluctuated and was unstable. Further, when the inventive method carrier A was used, denitrification of the nitrogen component in the exhaust gas occurred, and 30% of the total nitrogen amount could be converted to nitrogen gas, but in the case of the conventional method carrier B, 1
It was only 5%.

[0061]

Industrial Applicability As described above, according to the entrapping immobilization microbial carrier and the method for producing the same according to the present invention, a specific microorganism can be highly concentrated in a monomer or prepolymer immobilization material without performing pure culture of the microorganism. Can be carried on.

Therefore, by using the entrapping immobilization microbial carrier of the present invention, environmental pollutants can be decomposed and removed more effectively than the conventional entrapping immobilization microbial carriers.

[Brief description of drawings]

FIG. 1 is a diagram showing the relationship between the equivalent-sphere diameter of an immobilization material and the number of anaerobic bacteria during polymerization.

FIG. 2 is a conceptual diagram showing a situation in which a sponge structure is formed in the production of the entrapping immobilization microbial carrier of the present invention.

FIG. 3 is a view showing an electron micrograph of a sponge structure of the entrapping immobilization microbial carrier of the present invention.

[Fig. 4] Relationship between polymerization temperature and number of anaerobic bacteria during polymerization

FIG. 5 is a graph showing the relationship between the temperature difference obtained by subtracting the outside air temperature from the center temperature of the immobilization material during polymerization and the number of anaerobic bacteria.

FIG. 6 is a conceptual diagram of a continuous processing operation device.

[Explanation of symbols]

10 ... Testing device, 12 ... Reaction tank, 14 ... Pump, 16 ...
Air supply pipe, A ... Inventive method carrier (entrapping entrapped microbial carrier of the present invention), B ... Conventional method carrier (conventional entrapping immobilized microbial carrier)

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) B01D 53/58 C08F 2/44 Z 53/81 B01D 53/34 116A C02F 3/10 121C ZAB 126 C08F 2 / 00 131 2/44 F term (reference) 4B033 NA03 NA19 NB36 NB62 NB66 NB68 NC04 NC06 ND04 NF06 4D003 AA01 CA08 DA01 EA14 EA19 EA26 EA30 EA38 FA02 FA10 4J011 GA05 GB07 PA55 PB06 PB35 PC02 PC08 PC13

Claims (7)

[Claims] 1. A method for producing an entrapping immobilization microbial carrier for producing a carrier in which microorganisms are entrapped and immobilized by polymerizing an immobilization material for a monomer or a prepolymer in the presence of microorganisms, wherein a diameter or a thickness of the immobilization material. Is produced in a size of 1 to 10 cm. 2. The method for producing an entrapping immobilization microbial carrier according to claim 1, wherein the immobilization material is placed in a mold of 1 to 10 cm and polymerized. 3. The immobilization material having a size of 1 to 10 cm is dropped into an aqueous solvent or an organic solvent containing an alkali metal ion or a polyvalent metal ion to polymerize. A method for producing a comprehensively immobilized microbial carrier. 4. The method for producing a comprehensively immobilized microbial carrier according to any one of claims 1 to 3, wherein the polymerization temperature during the polymerization is 30 to 60 ° C. 5. The production of the entrapping immobilization microbial carrier according to claim 4, wherein the temperature difference obtained by subtracting the outside air temperature from the center temperature of the immobilization material during the polymerization is set to 5 to 10 ° C. Method. 6. The immobilizing material contains inorganic particles or organic particles, according to any one of 1 to 5 above.
A method for producing the entrapping immobilization microbial carrier according to item 1. 7. An entrapping immobilization microbial carrier produced by the method for producing an entrapping immobilization microbial carrier according to any one of claims 1 to 6.