KR100953179B1 - Oligomer for microbe immobilized media, method of preparing the oligomer, microbe immobilized media, method of preparing the media, method of reducing volume of the media and bioreactor applying the media - Google Patents

Abstract

PURPOSE: An oligomer for microbe immobilized media is provided to ensure reactivity and excellent mechanical strength, to ensure thermal and UV curing, and to facilitate mass production of carriers. CONSTITUTION: An oligomer for microbe immobilized media has a structure represented by chemical formula 1. In chemical formula 1, R1, R2 and R3 are independently C1~C10 alkylene substituted or unsubstituted with halogen group, hydroxyl group, alkyl group, amine group, or combined substituents thereof, C1~C10 alkylenealkoxy in which hydrogen is substituted or unsubstituted with any one of the substituents, C6~C24 arylene in which hydrogen is substituted or unsubstituted with any one of the substituents, C6~C24 cycloalkylene in which hydrogen is substituted or unsubstituted with any one of the substituents, C6~C24 heterocycloalkylene in which hydrogen is substituted or unsubstituted with any one of the substituents, or carbonyl; a1~a3 are 1~100; b1~b3 are 0~100; a1+b1=1~200, a2+b2=1~200, and a3+b3=1~200; R4 is hydrogen or methyl group; and i is 1~50 and j is 1~100.

Description

Oligomer for microorganism immobilized carrier, method for preparing the oligomer, method for preparing microorganism immobilized carrier, method for preparing the carrier, method for reducing the carrier and bioreactor using the carrier [Oligomer for microbe immobilized media, method of preparing the oligomer, microbe immobilized media, method of preparing the media, method of reducing volume of the media and bioreactor applying the media}

Disclosed are an oligomer for a microorganism immobilized carrier, a method for preparing the oligomer, a microorganism immobilized carrier, a method for producing the carrier, a method for reducing the carrier, and a bioreactor employing the carrier. More specifically, the oligomer for microorganism immobilized carrier comprising three double bond-containing end groups, the method for producing the oligomer, the microorganism immobilized carrier, the method for producing the carrier, the method for reducing the carrier and the biological reaction employing the carrier An apparatus is disclosed.

Hardly decomposable organic materials are generally treated by physical and chemical methods, and the treatment of these hardly decomposable organic materials with specific microorganisms can greatly reduce the cost of physical and chemical treatment. In particular, electronic wastewater, dyeing wastewater and paper mill wastewater contain various hardly decomposable organic substances, and there have been attempts to treat them by biological methods rather than physical and chemical methods.

Suspension of microorganisms, such as activated sludge method, which is widely used among the biological treatment methods, has a problem that it is difficult to accumulate microorganisms at a high concentration in the reaction tank because microorganisms are largely discharged from the reaction tank.

Accordingly, a biological treatment method using a biofilm carrier has attracted attention as a technology capable of effectively decomposing organic matter. Examples of biological treatment methods using a biofilm carrier include a biofilm method, a comprehensive fixation method, and a self-assembly method. In particular, the comprehensive immobilization method can fix specific microorganisms or enzymes in a carrier at a high concentration, so that the treatment efficiency is high, and thus, can be applied to the treatment of electronic wastewater, dyeing wastewater or papermaking wastewater, and can also reduce the amount of activated sludge. have.

The carrier used in the comprehensive fixation method of immobilizing a specific microorganism is a reticulated network of a plurality of pores capable of immobilizing the microorganisms at a high concentration and allowing the wastewater to enter and exit, and the pores extending from each other. flow channels) can be formed, and the mechanical strengths such as elasticity and compressive strength are sufficient to be durable enough to be used for long-term wastewater treatment.

The main structure of the oligomer for synthesizing the microorganism immobilized carrier is composed of a polyethylene glycol-based or polyvinyl alcohol-based main chain and both terminal groups which are naturally friendly and are not decomposed by microorganisms. It includes. In particular, the polyalkylene glycol-based oligomer can form a carrier capable of immobilizing a large amount of microorganisms by controlling the molecular weight of the polyalkylene glycol, thereby increasing the decomposition rate and decomposition efficiency of environmental pollutants by the immobilized microorganisms. Can be. However, the carrier synthesized using the oligomer has a problem that it is difficult to apply to biological treatment processes of various fields because the mechanical strength is not large.

In order to solve the above problems, in recent years, efforts have been made to increase the mechanical strength of a carrier by using an oligomer containing a urethane bond between the polyalkylene glycol series main chain and both terminal groups such as polyethylene glycol in the synthesis of the carrier. Progressed. However, these conventional oligomers exhibit responsiveness to chemical polymerization (ie, thermal curing) but no reactivity to ultraviolet curing, which makes it difficult to have various production systems. Therefore, there is a need to develop oligomers for microbial immobilization carriers having both reactivity to chemical polymerization reactions and ultraviolet curing reactions and excellent mechanical strength. In particular, the ultraviolet curing method can shorten the reaction time compared to the chemical polymerization method can increase the production efficiency of the carrier.

One embodiment of the present invention provides an oligomer for a microorganism immobilization carrier comprising three double bond-containing end groups.

Another embodiment of the present invention provides a method for preparing the oligomer for the microorganism immobilization carrier.

Another embodiment of the present invention provides a microorganism immobilization carrier comprising a polymer of the oligomer for the microorganism immobilization carrier or a crosslinked polymer of the oligomer.

Another embodiment of the present invention provides a method for preparing the microorganism immobilization carrier.

Another embodiment of the present invention provides a method for reducing the microorganism immobilization carrier.

Another embodiment of the present invention provides a bioreactor employing the microorganism immobilization carrier.

One aspect of the invention,

상기 화학식 1에서, R₁, R₂ 및 R₃는, 각각 서로 독립적으로, 수소가 할로겐기, 히드록시기, 알킬기, 알콕시기, 아민기 또는 이들이 조합된 치환기로 치환되거나 비치환된 C₁~C₁₀ 알킬렌, 수소가 상기 치환기들 중 어느 하나로 치환되거나 비치환된 C₁~C₁₀ 알킬렌알콕시, 수소가 상기 치환기들 중 어느 하나로 치환되거나 비치환된 C₆~C₂₄ 아릴렌, 수소가 상기 치환기들 중 어느 하나로 치환되거나 비치환된 C₆~C₂₄ 시클로알킬렌, 수소가 상기 치환기들 중 어느 하나로 치환되거나 비치환된 C₆~C₂₄ 헤테로시클로알킬렌, 또는 카르보닐이고,
a₁~a₃는 각각 1~100이고, b₁~b₃는 각각 0~100이고, a₁+b₁=1~200이고, a₂+b₂=1~200이고, a₃+b₃=1~200이며,
R₄는 수소 또는 메틸기이고, It provides an oligomer for a microorganism immobilization carrier represented by the following formula (1):
[Formula 1]

In Formula 1, R ₁ , R ₂ and R ₃ are each independently of each other, hydrogen is C ₁ ~ C ₁₀ unsubstituted or substituted with a halogen group, a hydroxy group, an alkyl group, an alkoxy group, an amine group or a substituent combination thereof Alkylene, C ₁ ~ C ₁₀ alkylene alkoxy unsubstituted or substituted with any one of the substituents, C ₆ ~ C ₂₄ arylene unsubstituted or substituted with any one of the substituents, hydrogen is the substituent C ₆ -C ₂₄ cycloalkylene unsubstituted or substituted with any one of these, C ₆ -C ₂₄ heterocycloalkylene unsubstituted or substituted with any one of the above substituents, or carbonyl,
a ₁ to a ₃ are each 1 to 100, b ₁ to b ₃ are each 0 to 100, a ₁ + b ₁ = 1 to 200, a ₂ + b ₂ = 1 to 200, and a ₃ + b ₃ = 1-200,
R ₄ is hydrogen or a methyl group,

i is 1-50, j is 1-100.

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Another aspect of the invention,

It provides a microorganism immobilization carrier comprising the polymer of the oligomer or the crosslinked polymer of the oligomer.

The microorganism immobilization carrier is Mycobacterium sp. SMIC-1 (Accession No. KCTC 10947 BP), Methylobacterium extorquens SMIC-1 (Accession No. KCTC) 10946 BP), the group consisting of Acinetobacter sp. SMIC-1 (Accession No. KCCM 10999P) and Cupriavidus sp. SMIC-2 (Accession No. KCCM 11000P) It may include at least one microorganism selected from.

The microorganism immobilization carrier may have a specific gravity of 1.01 to 3.0.

The microorganism immobilization carrier may further include an inorganic filler having a specific gravity of 2 to 5.

The inorganic filler may include at least one metal oxide mineral .

The metal oxide mineral may include at least one selected from the group consisting of kaolin, granite, barium sulfate and kaolin.

The particle size of the inorganic filler may be 0.1 to 1000㎛.

Another aspect of the invention,

Provided is a bioreactor employing the microorganism immobilization carrier.

Filling rate of the microorganism immobilization carrier may be 10 to 90% by volume.

The bioreactor may include at least one of a fluidized bed, a moving bed, and a packed bed reactor including the microorganism immobilization carrier.

Another aspect of the invention,

It provides a method for reducing the microorganism immobilization support comprising the step of blowing the microorganism immobilization support to blow the surface temperature of the microorganism immobilization support to 10 to 40 ℃.

The blowing drying may be continued until the moisture content of the microorganism immobilization carrier reaches 1 to 5% by weight.

Another aspect of the invention,

Reacting a glycerol-based polyether triol with a diisocyanate compound to synthesize a first compound; And

It provides a method for producing an oligomer for a microorganism immobilization carrier comprising the step of reacting the first compound and polyalkylene glycol (meth) acrylate.

The glycerol-based polyether triol can be synthesized by the reaction of glycerol and alkylene oxide.

The alkylene oxide may include at least one compound selected from the group consisting of ethylene oxide and propylene oxide.

Another aspect of the invention,

A first step of introducing the oligomer, the microorganism and the polymerization initiator for the microorganism immobilization carrier into a reactor; And

It provides a method for producing a microorganism immobilization carrier comprising a second step of agitating the reactor contents to obtain a polymer.

In the first step, a crosslinking agent may be further added.

In the first step, an inorganic filler may be additionally added.

The content of the inorganic filler may be 0.5 to 1,000 parts by weight based on 100 parts by weight of the oligomer.

In the first step, a polymerization promoter may be further added.

In the first step, a neutralizing agent may be additionally added before the microorganism is added.

The polymerization initiator is potassium persulfate, ammonium persulfate, sodium persulfate, potassium persulfite, ammonium persulfite, sodium persulfite, ammonium bisulfate, sodium bisulfate, 1,1'-azobis (1-methylbutyronitrile) -3-sodium sulfonate) and 4,4'-azobis (4-cyanovaleric acid).

Another aspect of the invention,

A first step of introducing the microorganism immobilization carrier oligomer and microorganism into a reactor; And

It provides a method for producing a microorganism immobilization carrier comprising the second step of obtaining a polymer by adding a photoinitiator to the reactor contents and then irradiated with UV.

In the first step, a crosslinking agent may be further added.

The photoinitiator is selected from the group consisting of 2,2-dimethoxy-2-phenylacetophenone, 2-oxoglutaric acid, 1-hydroxy cyclohexyl phenyl methanone and 2-hydroxy-2-methyl-propiophenone It may include at least one kind.

The microorganism is added with activated sludge, and the total input concentration of the microorganism and activated sludge may be 50 to 30,000 MLSS (mg / L).

The microorganism is added with activated sludge, and the concentration ratio of the microorganism to the activated sludge may be 1%: 99% to 99%: 1%.

The amount of the crosslinking agent may be 0.5 to 80 parts by weight based on 100 parts by weight of the amount of the oligomer.

According to one embodiment of the present invention, it is possible to provide a microorganism immobilized carrier oligomer and a method for producing the carrier having excellent reactivity, both heat and ultraviolet curing is easy to mass-produce the carrier in various ways.

According to another embodiment of the present invention, microorganisms that effectively decompose various hardly decomposable organic substances are efficiently encapsulated and immobilized, and have high mechanical strength such as elasticity and compressive strength, and have a durability enough to be used for long-term wastewater treatment. A carrier, a method for producing the same, and a method for applying the same may be provided.

According to another embodiment of the present invention, a bioreactor capable of reducing the treatment cost during wastewater treatment may be provided by employing the carrier.

Next, the oligomer for the microorganism immobilization carrier and its preparation method according to an embodiment of the present invention will be described in detail.

상기 화학식 1에서, R₁, R₂ 및 R₃는, 각각 서로 독립적으로, 수소가 할로겐기, 히드록시기, 알킬기, 알콕시기, 아민기 또는 이들이 조합된 치환기로 치환되거나 비치환된 C₁~C₁₀ 알킬렌, 수소가 상기 치환기들 중 어느 하나로 치환되거나 비치환된 C₁~C₁₀ 알킬렌알콕시, 수소가 상기 치환기들 중 어느 하나로 치환되거나 비치환된 C₆~C₂₄ 아릴렌, 수소가 상기 치환기들 중 어느 하나로 치환되거나 비치환된 C₆~C₂₄ 시클로알킬렌, 수소가 상기 치환기들 중 어느 하나로 치환되거나 비치환된 C₆~C₂₄ 헤테로시클로알킬렌, 또는 카르보닐이고,
a₁~a₃는 각각 1~100이고, b₁~b₃는 각각 0~100이고, a₁+b₁=1~200이고, a₂+b₂=1~200이고, a₃+b₃=1~200이며,
R₄는 수소 또는 메틸기이고, The oligomer for a microorganism immobilization carrier according to an embodiment of the present invention is represented by the following formula (1).
[Formula 1]

In Formula 1, R ₁ , R ₂ and R ₃ are each independently of each other, hydrogen is C ₁ ~ C ₁₀ unsubstituted or substituted with a halogen group, a hydroxy group, an alkyl group, an alkoxy group, an amine group or a substituent combination thereof Alkylene, C ₁ ~ C ₁₀ alkylene alkoxy unsubstituted or substituted with any one of the substituents, C ₆ ~ C ₂₄ arylene unsubstituted or substituted with any one of the substituents, hydrogen is the substituent C ₆ -C ₂₄ cycloalkylene unsubstituted or substituted with any one of these, C ₆ -C ₂₄ heterocycloalkylene unsubstituted or substituted with any one of the above substituents, or carbonyl,
a ₁ to a ₃ are each 1 to 100, b ₁ to b ₃ are each 0 to 100, a ₁ + b ₁ = 1 to 200, a ₂ + b ₂ = 1 to 200, and a ₃ + b ₃ = 1-200,
R ₄ is hydrogen or a methyl group,

i is 1-50, j is 1-100.

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The oligomer may form a carrier by reacting with a crosslinking agent not only by chemical polymerization but also by UV curing, and thus, various polymerization methods may be applied, thereby efficiently preparing a carrier according to a purpose of use. In addition, the oligomer includes three double bond-containing end groups, and thus has high reactivity compared to a conventional oligomer including two double bond-containing end groups. Therefore, the oligomer can form a network passage of a more robust network structure than the conventional oligomer when used in the preparation of the carrier can form a microorganism immobilized carrier having better mechanical strength.

The method for preparing an oligomer for the microorganism immobilization carrier comprises the steps of synthesizing a first compound by reacting a glycerol-based polyether triol and a diisocyanate compound and reacting the first compound with a polyalkylene glycol (meth) acrylate. Include.

The glycerol-based polyether triol can be synthesized by the reaction of glycerol and alkylene oxide. The alkylene oxide may be, for example, ethylene oxide, propylene oxide and mixtures thereof. In addition, the number average molecular weight of the glycerol-based polyether triol may be, for example, 500 to 5000.

The first compound is a diisocyanate compound bonded to each of the three terminals of the glycerol-based polyether triol, and the first compound may be synthesized by reacting 3 moles of the diisocyanate compound per one mole of the glycerol-based polyether triol. . In addition, the oligomer may be synthesized by further reacting 3 moles of polyalkylene glycol (meth) acrylate per 1 mole of the first compound. In addition, the number average molecular weight of the polyalkylene glycol (meth) acrylate may be, for example, 44 to 1000.

Microbial immobilization carrier according to an embodiment of the present invention comprises a polymer of the oligomer or a crosslinked polymer of the oligomer.

The oligomer represented by Chemical Formula 1 may be polymerized by a polymerization initiator and / or a photoinitiator through a double bond included in each of three end groups to form a polymer having a molecular weight sufficient to form a carrier.

On the other hand, polymers formed by polymerizing only one oligomer or polymers formed by polymerizing two or more kinds of oligomers having different molecular weights may also function as carriers, but hydrophilic crosslinks are formed between the polymer molecular backbones. A three-dimensional network structure is advantageous in terms of microorganism inclusion fixation, durability and elasticity.

The microorganism immobilization carrier is, for example, a three-dimensional network crosslinked polymer in which crosslinks are formed between polymer molecular backbones formed by polymerizing the oligomer. The microorganism immobilization carrier can be immobilized microorganisms resistant to tetramethyl ammonium hydroxide and capable of growing using tetramethyl ammonium hydroxide as a carbon source. Specifically, the microorganism immobilization carrier is formed with a plurality of pores extending to each other to form a reticulated network of flow channels, the microorganisms for treating wastewater in the pores is comprehensively immobilized, and the pores Wastewater is diffused through the flow path in and out.

The microorganism is Mycobacterium sp. SMIC-1 (Accession No. KCTC 10947 BP), Methylobacterium extorquens SMIC-1 (Accession No. KCTC 10946 BP) ), At least one of Acinetobacter sp. SMIC-1 (Accession No. KCCM 10999P) and Cupriavidus sp. SMIC-2 (Accession No. KCCM 11000P) It may include. The Mycobacterium spp. SMIC-1, Methylobacterium extocuens SMIC-1, Acinetobacter spp. SMIC-1, and Cupri abidus spp. SMIC-2, were deposited under the international treaty of Budapest on May 15, 2006. It is the same as the strain deposited at Korea Institute of Biotechnology and Biotechnology Center (KCTC).

In addition, the specific gravity of the microorganism immobilization carrier may be 1.01 to 3.0. When the specific gravity of the carrier is less than 1.01, the carrier filling rate may be limited by increasing the volume expansion rate of the carrier in the reactor due to the flow rate of inflow water and air during wastewater treatment using the reactor filled with the carrier. Significant increases in sea air or water can cause uneconomical driving.

In addition, the microorganism immobilization carrier may further include an inorganic filler having a specific gravity of 2 to 5, whereby the microorganism immobilization carrier can maintain the specific gravity of the above range. When the specific gravity of the inorganic filler is less than 2, an excessive amount of inorganic filler should be added during the synthesis of the carrier, which is uneconomical and difficult to mix due to a high ratio of the inorganic filler to the raw material mixture. It is difficult to obtain uniform physical properties. By using the inorganic filler in the specific gravity range, the inorganic filler is uniformly dispersed in the microorganism immobilization carrier, thereby increasing the specific gravity, compressive strength and elasticity of the carrier as a final product to improve the reactor filling rate of the carrier and durability of the carrier This will be improved.

As the inorganic filler, one or more metal oxide minerals such as kaolin, granite, barium sulfate and kaolin may be used, but the present invention is not limited thereto.

In addition, the inorganic filler may have a particle size of 0.1 to 1,000㎛. If the particle size of the inorganic filler is less than 0.1㎛ not only difficult to manufacture, but also easy to manage such as transport, and exceeds 1,000㎛ synthesize the carrier non-homogeneous (non-homogeneous).

Next, a method for preparing a microorganism immobilization carrier according to an embodiment of the present invention will be described in detail.

Methods for producing the microorganism immobilization carrier include a chemical polymerization method and an ultraviolet curing method, one example of each method will be described in detail below.

<Chemical Polymerization Method>

First, an oligomer represented by Chemical Formula 1 and optionally at least one material selected from the group consisting of a crosslinking agent, an inorganic filler and a polymerization accelerator are introduced into a reactor in which an aqueous solvent is present and mixed with each other. The crosslinking agent may include 1 to 6 functional groups, and may form intermolecular or intramolecular crosslinks between the oligomer molecules. As said crosslinking agent, for example, sorbitol, N, N'-diallyl tardiamide, N, N'-methylenebisacrylamide, diallyl fumarate, 1,5-hexadien-3-ol, N , N'-methylenebisacrylamide, trimethylolpropane triacrylate, di (ethylene glycol) diacrylate, triallyl 1,2,4-benzenetricarboxylate, diallylamine, triallylamine, polyallylamine , Tetraallyloxyethane, divinylbenzene, diallyl phthalate or a mixture of two or more thereof may be used. The amount of the crosslinking agent may be 0.5 to 80 parts by weight based on 100 parts by weight of the amount of the oligomer. If the amount of the crosslinking agent is less than 0.5 parts by weight, the strength of the carrier is weakened. If it exceeds 80 parts by weight, the gel is formed too quickly. In addition, the amount of the inorganic filler may be 0.5 to 1,000 parts by weight based on 100 parts by weight of the amount of the oligomer. When the amount of the inorganic filler is less than 0.5 parts by weight, the strength of the carrier is lowered. When it is more than 1,000 parts by weight, the substrate transmittance in the carrier is lowered and the carrier is non-uniformly polymerized. Here, the substrate transmittance refers to the transmittance of inorganic substances such as microbial nutrients, nitrogen sources, trace inorganic elements, and oxygen delivered to the inside of the carrier. As the polymerization promoter, for example, N, N, N ', N'-tetramethylethylenediamine and / or β-methylamide propionitrile may be used.

Thereafter, further neutralizing agent may be added to the reactor to neutralize the reactor contents. As the neutralizing agent, an acetic acid aqueous solution or the like may be used. By using the neutralizing agent, the reactor contents may be adjusted to a pH range of 6 to 8 to provide a suitable environment for survival of microorganisms introduced after neutralization.

Subsequently, microorganisms and activated sludge, which are resistant to tetramethyl ammonium hydroxide and can be grown using tetramethyl ammonium hydroxide as a carbon source, are charged at a predetermined rate, followed by uniform stirring. In addition, the microorganism may be introduced into the reactor together with activated sludge, the total concentration of the microorganism and activated sludge may be 50 to 30,000 MLSS (mg / L). When the total input concentration is less than 50 MLSS, the concentration of microorganisms immobilized in the carrier is low, and the wastewater treatment efficiency is lowered. When the total concentration is more than 30,000 MLSS, the content ratio of the microorganisms to the synthetic raw materials is too high to synthesize the carrier, making synthesis difficult. In addition, the input concentration ratio of the microorganism to activated sludge is 1%: 99% to 99%: 1%, for example 15%: 85% to 85%: 15%, for example 35%: 65% to 65%. May be 35%. If the ratio of the concentration of the microorganism in the total concentration of the microorganism and the activated sludge is less than 1%, the treatment efficiency of the specific organic material is low, and if it exceeds 99%, the material decomposed primarily by the microorganism is activated by the sludge. Finally, it should be mineralized, in which case the mineralization efficiency is not good because the ratio of activated sludge is too low.

Thereafter, a polymerization initiator is added to the reactor, followed by stirring to proceed with the polymerization reaction. As the polymerization initiator, for example, potassium persulfate, ammonium persulfate, sodium persulfate, potassium persulfite, ammonium persulfite, sodium persulfite, ammonium bisulfate, sodium bisulfate, 1,1'-azobis ( 1-methylbutyronitrile-3-sodium sulfonate) and at least one selected from the group consisting of 4,4'-azobis (4-cyanovaleric acid) can be used.

As a result, a polymer or crosslinked polymer having a three-dimensional network in which crosslinks are formed between the polymer molecular backbones is obtained. When the polymer or the crosslinked polymer is aged for a predetermined time in an incubator (for example, a PVC tube) at room temperature, a state change from a sol state to a gel state becomes suitable for extruding. When the gel polymer or crosslinked polymer is extruded through an orifice of a suitable diameter, the inorganic filler is selectively dispersed uniformly, and a plurality of extensions are formed to extend to form a reticulated network of flow channels. The microorganism immobilization support which has the void | gap of which the microorganism which is resistant to tetramethyl ammonium hydroxide, and which can grow using tetramethyl ammonium hydroxide as a carbon source is fixed can be obtained.

Thereafter, the prepared microorganism immobilization support may be blow-dried to reduce the volume of the microorganism immobilization support. The surface temperature of the microorganism immobilization support may be 10 to 40 ° C. by the air drying. In addition, the air drying may be continued until the water content of the microorganism immobilization carrier reaches 1 to 5% by weight.

<Ultraviolet curing method>

The UV curing method differs from the above-mentioned chemical polymerization method by using a photoinitiator instead of the polymerization initiator described above, adding a polymerization promoter, and pouring the reactor contents into an injection mold of a predetermined type and irradiating with UV light to form a gel in the form of an injection mold. It is to obtain a carrier of. In addition, the ultraviolet curing method is carried out at room temperature and the polymer can be formed through a short time of ultraviolet irradiation has the advantage that the manufacturing time is shortened. Examples of the photoinitiator include 2,2-dimethoxy-2-phenylacetophenone, 2-oxoglutaric acid, 1-hydroxy cyclohexyl phenylmethanone, 2-hydroxy-2-methyl-propiophenone or two of these. The above mixture and the like can be used.

In addition, according to one embodiment of the present invention, a bioreactor employing the microorganism immobilization carrier may be provided. The filling rate of the microorganism immobilization carrier in the bioreactor may be 10 to 90% by volume. If the filling rate of the carrier is less than 10% by volume, the efficiency of wastewater treatment per reactor volume is lowered, which is uneconomical. In addition, the bioreactor may include at least one of a fluidized bed, a moving bed, and a packed bed reactor including the microorganism immobilization carrier.

Hereinafter, the present invention will be described in more detail with reference to Examples, which are intended to illustrate embodiments of the present invention, and the scope of the present invention is not limited by the Examples.

Example

Example 1 Synthesis of Oligomers

Into a four-necked glass reactor, 1 mol of glycerol-based polyether triol (FA-103) and 3 mol of isophorone diisocyanate were added, followed by reaction for 3 hours while maintaining the reactor temperature at 75 캜. . The reactor was then cooled to 60 ° C. under stirring and 3 moles of polyethylene glycol monomethacrylate was slowly added to the reactor over 30 minutes. Thereafter, the reaction was proceeded again for 4 hours while maintaining the reactor temperature at 75 ℃. As a result, an oligomer represented by the formula (1) having a number average molecular weight of 4000 and a viscosity at room temperature of 10000 cps was obtained.

Example 2-1 Preparation of a Carrier to Which a Microorganism (Mycobactrium sp. SMIC-1 (Accession No. KCTC 10947 BP)) is Fixed (Chemical Polymerization Method)

First, 100g of 10w / v% aqueous solution of the oligomer prepared in Example 1 and 100g of 2w / v% aqueous solution of industrial kaolin (kaolin powder made in China, specific gravity of 4.45, particle size less than 100 μm) were added to the reactor, followed by the reactor. 2 g of sorbitol aqueous solution (Dongyang Chemical Co., 1.0w / v% aqueous solution), which is a crosslinking agent, was stirred for 1 minute, and then N, N, N ', N'-tetramethylethylene, a polymerization accelerator that enables radical polymerization at room temperature. 2.5 g of diamine aqueous solution (Japan Shinyo Co., 0.25w / v% aqueous solution) was further added. Subsequently, an appropriate amount of 10 w / v% aqueous solution of acetic acid was mixed in the reactor to neutralize the reactor contents to pH 7 so that the crosslinked polymer of the oligomer was suitable for the survival environment of the microorganisms to be later supported as a carrier. Subsequently, mycobacterium species SMIC-1 (Mycobactrium sp. SMIC-1, Accession No. KCTC 10947 BP) and activated sludge were added to the reactor, followed by uniform stirring for about 30 seconds. At this time, the input ratio of microorganism: activated sludge was 80%: 20% by weight, and after mixing 2.5 g of potassium persulfate aqueous solution (Dongyang Steel Chemical, 0.25w / v%) as a polymerization initiator, the mixture was 600rpm. The polymerization was carried out by stirring at a rate of. As a result, a crosslinked polymer of an oligomer in which kaolin was dispersed was obtained.

The sol crosslinked polymer thus obtained was filled in a PVC tube using a syringe, and then aged in a 25 ° C. thermostat for about 2 hours. In the aging process, the sol cross-linked polymer is solidified in a gel state, which is extruded using a syringe to obtain a cylindrical solidified polymer carrier having a diameter of about 4 mm, and cut at 4 mm intervals to obtain a microorganism immobilized carrier.

The concentration of the immobilized microorganism was 0.5w / v%. Specifically, the microbial and activated sludge mixtures of which the MLSS concentration was 5,000 mg / L were concentrated 10 times in a centrifuge, and made into 100 ml. .

Example 2-2 Preparation of a Carrier to Which Microorganisms (Mycobactrium sp. SMIC-1 (Accession No. KCTC 10947 BP)) are Fixed (Ultraviolet Curing Method)

No polymerization promoter N, N, N ', N'-tetramethylethylenediamine was used and 0.2g of 2-hydroxy-2-methyl-propiophenone as a photoinitiator instead of aqueous solution of potassium persulfate as a polymerization initiator. Microorganism immobilization support was prepared in the same manner as in Example 2-1, except that injection molding was used instead of extrusion using a syringe when forming the solidified polymer carrier. Specifically, the formation of the carrier (that is, the formation of the crosslinked polymer) and the molding may be performed by placing an injection mold having a square tube shape having an open top and bottom with a width of 4 cm x 4 cm x 2 mm on the quartz plate to seal one open side thereof. Pour reactor contents into the mold through the open other side thereof, and then irradiate the UV through the open sides of the mold using UV curing machine (Fusion UV Systems Inc., LH-6) One side is irradiated with UV through a quartz plate) and cut at 4 mm intervals to obtain a microorganism immobilization carrier. In this reaction, in order to prevent the death of microorganisms by ultraviolet irradiation, an ultraviolet filter (transmitting only 300 to 400 nm wavelength) was attached to the ultraviolet curing machine.

Example 2-3 Preparation of a Carrier to Which a Microorganism (Methylobacterium extorquens SMIC-1) (Accession No. KCTC 10946 BP) is Fixed (Chemical Polymerization Method)

Methylobacterium extorquens SMIC-1 (Accession No. KCTC 10946) instead of Mycobactrium sp. SMIC-1 (Accession No. KCTC 10947 BP) as a microorganism to be immobilized. A microbial immobilization carrier was prepared in the same manner as in Example 2-1 except for using BP).

Example 2-4 Preparation of a Carrier to Which a Microorganism (Methylobacterium extorquens SMIC-1 (Accession No. KCTC 10946 BP)) is Fixed (Ultraviolet Curing Method)

Methylobacterium extorquens SMIC-1 (Accession No. KCTC 10946) instead of Mycobactrium sp. SMIC-1 (Accession No. KCTC 10947 BP) as a microorganism to be immobilized. A microbial immobilization carrier was prepared in the same manner as in Example 2-2 except for using BP).

Reference Example 2-1: Preparation of a Carrier to Which a Microorganism (Mycobactrium sp. SMIC-1 (Accession No. KCTC 10947 BP)) was Fixed (Chemical Polymerization Method)

The above example was used except that 180 g of an aqueous solution of polyethylene glycol diacrylate having a number average molecular weight of 700 (Miwon Corporation, 18w / v%, trade name: MIRAMER M286) was used instead of the aqueous solution of the oligomer prepared in Example 1. A microorganism immobilization carrier was prepared in the same manner as in 2-1.

Reference Example 2-2: Preparation of a Carrier to Which a Microorganism (Mycobactrium sp. SMIC-1 (Mycobactrium sp. SMIC-1, Accession No. KCTC 10947 BP)) was Fixed (Ultraviolet Curing Method)

The above example was used except that 180 g of an aqueous solution of polyethylene glycol diacrylate having a number average molecular weight of 700 (Miwon Corporation, 18w / v%, trade name: MIRAMER M286) was used instead of the aqueous solution of the oligomer prepared in Example 1. An attempt was made to produce a microorganism immobilization carrier in the same manner as in 2-2, but a polymerization reaction did not occur in this manner, and thus, a microorganism immobilization carrier was not obtained.

Reference Example 2-3: Preparation of a Carrier to Which a Microorganism (Methylobacterium extorquens SMIC-1) (Accession No. KCTC 10946 BP) is Fixed (Chemical Polymerization Method)

The above example was used except that 180 g of an aqueous solution of polyethylene glycol diacrylate having a number average molecular weight of 700 (Miwon Corporation, 18w / v%, trade name: MIRAMER M286) was used instead of the aqueous solution of the oligomer prepared in Example 1. A microorganism immobilization carrier was prepared in the same manner as in 2-3.

Reference Example 2-4: Preparation of a Carrier to Which a Microorganism (Methylobacterium extorquens SMIC-1) (Accession No. KCTC 10946 BP) was Fixed (Ultraviolet Curing Method)

The above example was used except that 180 g of an aqueous solution of polyethylene glycol diacrylate having a number average molecular weight of 700 (Miwon Corporation, 18w / v%, trade name: MIRAMER M286) was used instead of the aqueous solution of the oligomer prepared in Example 1. An attempt was made to prepare a microorganism immobilization carrier in the same manner as 2-4, but a polymerization reaction did not occur with this method, and thus, a microorganism immobilization carrier was not obtained.

Evaluation example

Evaluation Example 1 Measurement of Compressive Strength

Compressive strength is one of the important factors that determine the service life as a measure of the durability of the carrier. Therefore, the changes in compressive strength of each of the microorganism-immobilized carriers prepared in Examples 2-1 to 2-4 and Reference Examples 2-1 and 2-3 were measured.

Compressive strength was measured using SMS (Stable Micro Systems) Texture Analyser (TA-XT2). Specifically, the cylindrical carrier having an inner diameter of 4 mm was cut at intervals of 4 mm, and then ten compresses were randomly selected from the cut carriers in the state of containing water, and then the compressive strength was measured. The compressive strength was obtained from the following equation.

F = P / S

In the above formula, F is the compressive strength, P is the load (N) when the carrier starts to rupture, S is the cross-sectional area (0.1257 cm 2) of the carrier under load.

The compressive strength measurement results of each of the microorganism-immobilized carriers prepared in Examples 2-1 to 2-4 and Reference Examples 2-1 and 2-3 are collectively shown in Table 1 below.

TABLE 1

Compressive strength (kg / ㎠) Example 2-1 7.48 Example 2-2 7.52 Example 2-3 7.55 Examples 2-4 7.45 Reference Example 2-1 5.84 Reference Example 2-2 - Reference Example 2-3 5.93 Reference Example 2-4 -

Referring to Table 1, the microbial immobilization carrier of Examples 2-1 to 2-4 prepared using the oligomer represented by Chemical Formula 1 was prepared using a conventional polyethylene glycol diacrylate oligomer. The compressive strength was found to be higher than the microbial immobilization carriers of 1 and 2-3. On the other hand, in the case of Reference Examples 2-2 and 2-4 belonging to the ultraviolet curing method, the conventional polyethylene glycol diacrylate oligomer was not reactive to ultraviolet curing, and thus polymerization was not performed.

In addition, the microorganism immobilization carriers of Examples 2-1 and 2-3 prepared by the chemical polymerization method using the oligomers according to one embodiment of the present invention, and Example 2 manufactured by the ultraviolet curing method using the oligomer The microbial immobilization carriers of 2 and 2-4 did not differ due to similar compressive strengths.

From the above results, it can be seen that the oligomer according to one embodiment of the present invention exhibits excellent reactivity with respect to both chemical polymerization and UV curing, thereby forming a carrier having excellent compressive strength (physical strength) regardless of the type of immobilized microorganism. .

Evaluation Example 2: Electronic Wastewater Treatment Capacity of Microorganism Immobilized Carrier

Using a continuous flow reactor (test), the ability to treat the electronic wastewater of each of the microbial immobilization carriers prepared in Examples 2-1 to 2-4 and Reference Examples 2-1 and 2-3 was tested.

The test conditions were as follows.

That is, the reaction vessel having a volume of 677 ml was filled with 75 volume% of the microorganism immobilization carrier immobilized with 0.5% (w / v) of microorganisms and activated sludge, and aerated for up to 54 days. In this case, an air supply amount of 0.5 L / min was maintained, and dissolved oxygen (DO) was maintained at a minimum of 3 ppm (wt / v).

As the influent, the low concentration TOC electronic wastewater of the actual electronic wastewater treatment process was used, and the hydraulic residence time (HRT) of the reactor was operated at 1hr.

In order to monitor the electronic wastewater treatment capacity of the microorganism immobilization carrier, 100 ml of reactor effluent was collected every day to analyze TOC (total organic carbon), and TMAH (tetramethyl ammonium hydroxide) was analyzed at predetermined cycles as shown in Table 3 below. It was.

TOC was analyzed using a TOC Analyzer with a Flame-ionization Detector (Sievers 900, USA), and TMAH with an Ionex Autosuppressed Ion Chromatograph (ICS-3000, USA) equipped with a Conductivity Detector (Column Ionpac CS17 4X250mm). The Ion Chromatograph mobile phase (CH ₃ SO ₃ H) was moved at a flow rate of 1 ml per minute, and the reactor effluent sample was analyzed while gradually increasing the concentration of the mobile phase from 6 mM to 24 mM. The results of the TOC analysis are shown in Table 2 and FIG. 1, respectively, and the results of TMAH analysis are shown in Table 3 below.

TABLE 2

Hours (days) TOC concentration in influent (µg / ml) TOC concentration in effluent (μg / ml) Example 2-1 Example 2-2 Example 2-3 Examples 2-4 Reference Example 2-1 Reference Example 2-2 Reference Example 2-3 Reference Example 2-4 3 3240 1400 1529 1727 1526 1762.56 - 1888.92 - 4 3060 1080 1120 1328 1273 1477.98 - 1597.32 - 6 3120 970 954 982 1120 1254.24 - 1441.44 - 8 3560 882 972 969 958 1274.48 - 1238.88 - 10 2980 750 857 734 849 1028.1 - 1081.74 - 12 3260 641 721 773 689 1092.1 - 1036.68 - 13 2600 553 572 659 573 920.4 - 873.6 - 15 3483 632 625 563 552 1208.601 - 1292.193 - 18 2530 593 534 539 629 941.16 - 931.04 - 21 3130 552 613 582 648 1067.33 - 1129.93 - 23 2880 655 591 667 603 1146.24 - 1200.96 - 27 3330 543 584 603 637 1355.31 - 1468.53 -

 [Table 3]

Hours (days) TMAH concentration in influent (µg / ml) TMAH concentration in effluent (μg / ml) Example 2-1 Example 2-2 Example 2-3 Examples 2-4 Reference Example 2-1 Reference Example 2-2 Reference Example 2-3 Reference Example 2-4 10 2530 0 0 0 0 0 - 0 - 15 2413 0 0 0 0 0 - 0 - 21 2362 0 0 0 0 0 - 0 - 27 2256 0 0 0 0 2 - 3 -

1 is a graph showing the results of the TOC removal efficiency test of each of the microbial immobilization carriers prepared in Examples 2-1 to 2-4 and Reference Examples 2-1 and 2-3 in a comparative format according to treatment time.

Referring to Table 2 and FIG. 1, the TOC treatment efficiency (removal efficiency) of the carrier prepared by the chemical polymerization method of Example 2-1 and to which the mycobacterium was fixed was 12 days after the influent was supplied ( 80 ± 3%), and the maximum treatment efficiency was 84%. In addition, the TOC treatment efficiency (removal efficiency) of the carrier prepared by the ultraviolet curing method of Example 2-2 and fixed with mycobacterium reached a steady state (80 ± 5%) after 14 days of supplying the influent. The maximum treatment efficiency was 85%. In addition, the TOC treatment efficiency (removal efficiency) of the carrier prepared by the chemical polymerization method of Example 2-3 and fixed with methylobacterium reached a steady state (78 ± 4%) after 14 days of supplying the influent. The maximum treatment efficiency was 81%. In addition, the TOC treatment efficiency (removal efficiency) of the carrier prepared by the UV curing method of Example 2-4 and fixed with methylobacterium reached a steady state (80 ± 4%) after 11 days of supplying the influent. The maximum treatment efficiency was 84%. However, the carriers of Reference Examples 2-1 and 2-3 were found to have a lower TOC treatment efficiency than the carriers of Examples 2-1 and 2-3.

On the other hand, referring to Table 3, the TMAH treatment efficiency of all of the microbial immobilization carriers of Examples 2-1 to 2-4 is from the time when the TOC treatment efficiency reached a steady state (that is, 10 days after the influx of water) The maximum value of 100% was shown. However, the carriers of Reference Examples 2-1 and 2-3 showed a slight decrease in TMAH treatment efficiency from 27 days after the influent was supplied.

From the above results, it can be seen that when using the microorganism immobilization carrier according to the embodiment of the present invention in which the TMAH decomposing microorganism is fixed, it is possible to effectively treat the low concentration of TOC electronic wastewater containing a low concentration of organic solvent such as TMAH. there was. In addition, when the electronic wastewater was treated using the microbial immobilization carrier according to the embodiment of the present invention, in which the TMAH-decomposed microorganisms were fixed, the treated water obtained after reaching the steady state did not contain any TMAH.

Although preferred embodiments of the present invention have been described above with reference to embodiments and drawings, these are merely exemplary, and various modifications and equivalent other embodiments are possible to those skilled in the art. You will understand. Therefore, the protection scope of the present invention should be defined by the appended claims.

1 is a graph showing the results of the TOC removal efficiency test of each of the microorganism immobilization carriers prepared in Examples and Reference Examples in a comparative format according to treatment time.

Claims (29)

Oligomer for microbial immobilization carrier represented by the following formula (1): [Formula 1]

In Formula 1, R ₁ , R ₂ and R ₃ are each independently of each other, hydrogen is C ₁ ~ C ₁₀ unsubstituted or substituted with a halogen group, a hydroxy group, an alkyl group, an alkoxy group, an amine group or a substituent combination thereof Alkylene, C ₁ ~ C ₁₀ alkylene alkoxy unsubstituted or substituted with any one of the substituents, C ₆ ~ C ₂₄ arylene unsubstituted or substituted with any one of the substituents, hydrogen is the substituent C ₆ -C ₂₄ cycloalkylene unsubstituted or substituted with any one of these, C ₆ -C ₂₄ heterocycloalkylene unsubstituted or substituted with any one of the above substituents, or carbonyl, a ₁ to a ₃ are each 1 to 100, b ₁ to b ₃ are each 0 to 100, a ₁ + b ₁ = 1 to 200, a ₂ + b ₂ = 1 to 200, and a ₃ + b ₃ = 1-200, R ₄ is hydrogen or a methyl group, i is 1-50, j is 1-100. A microbial immobilization carrier comprising the polymer of the oligomer of claim 1 or the crosslinked polymer of the oligomer. The method of claim 2, Mycobacterium sp. SMIC-1 (Accession No. KCTC 10947 BP), Methylobacterium extorquens SMIC-1 (Accession No. KCTC 10946 BP), Ashine Sat bakteo species SMIC-1 (Acinetobacter sp. SMIC- 1) ( accession No. KCCM 10999P), and COOP Ria bideoseu species SMIC-2 (Cupriavidus sp. SMIC -2) ( accession No. KCCM 11000P), at least one member selected from the group consisting of Microorganism immobilization carrier containing microorganisms of. The method of claim 2, A microorganism immobilization carrier having a specific gravity of 1.01 to 3.0. The method of claim 4, wherein A microorganism immobilization carrier further comprising an inorganic filler having a specific gravity of 2 to 5. The method of claim 5, The inorganic filler is a microorganism immobilization carrier comprising at least one metal oxide mineral. The method of claim 6, The metal oxide mineral is a microorganism immobilized carrier comprising at least one selected from the group consisting of kaolin, granite, barium sulfate and kaolin. The method of claim 5, The particle size of the inorganic filler is 0.1 to 1000㎛ microorganism immobilization carrier. A bioreactor employing the microorganism immobilization carrier according to any one of claims 2 to 8. 10. The method of claim 9, Filling rate of the microorganism immobilization carrier is 10 to 90% by volume bioreactor. 10. The method of claim 9, And at least one of a fluidized bed, a moving bed, and a packed bed reactor comprising the microbial immobilization carrier. A method for reducing the microorganism immobilization support comprising the step of blowing the microorganism immobilization support to a surface temperature of the microorganism immobilization support according to any one of claims 2 to 8 to 10 to 40 ℃. The method of claim 12, The blow drying method is a method for reducing the microorganism immobilization carrier is continued until the water content of the microorganism immobilization carrier reaches 1 to 5% by weight. Reacting a glycerol-based polyether triol with a diisocyanate compound to synthesize a first compound; And Method of producing an oligomer for a microorganism immobilization carrier comprising the step of reacting the first compound and polyalkylene glycol (meth) acrylate. The method of claim 14, The glycerol-based polyether triol is a method for producing an oligomer for a microorganism immobilized carrier synthesized by the reaction of glycerol and alkylene oxide. The method of claim 15, The alkylene oxide is a method for producing an oligomer for a microorganism immobilization carrier comprising at least one compound selected from the group consisting of ethylene oxide and propylene oxide. A first step of introducing an oligomer, a microorganism, and a polymerization initiator for a microorganism immobilization carrier according to claim 1 into a reactor; And And a second step of agitating the reactor contents to obtain a polymer. The method of claim 17, Method of producing a microorganism immobilization support further adding a crosslinking agent in the first step. The method of claim 17, Method of producing a microorganism immobilization carrier further adding an inorganic filler in the first step. The method of claim 17, The amount of the inorganic filler is 0.5 to 1,000 parts by weight based on 100 parts by weight of the input amount of the oligomer manufacturing method of the microorganism immobilization carrier. The method of claim 17, Method of producing a microorganism immobilization support further adding a polymerization promoter in the first step. The method of claim 17, Method of producing a microorganism immobilization carrier further adding a neutralizing agent before the microorganism in the first step. The method of claim 17, The polymerization initiator is potassium persulfate, ammonium persulfate, sodium persulfate, potassium persulfite, ammonium persulfite, sodium persulfite, ammonium bisulfate, sodium bisulfate, 1,1'-azobis (1-methylbutyronitrile) -3-sodium sulfonate) and 4,4'-azobis (4-cyanovaleric acid). A first step of introducing the microorganism immobilization carrier oligomer and microorganism according to claim 1 into a reactor; And And adding a photoinitiator to the reactor contents and then irradiating UV to obtain a polymer. The method of claim 24, Method of producing a microorganism immobilization support further adding a crosslinking agent in the first step. The method of claim 24, The photoinitiator is selected from the group consisting of 2,2-dimethoxy-2-phenylacetophenone, 2-oxoglutaric acid, 1-hydroxy cyclohexyl phenyl methanone and 2-hydroxy-2-methyl-propiophenone Method for producing a microorganism immobilization carrier comprising at least one kind. The method of claim 17 or 24, The microorganism is added with activated sludge, the total concentration of the microorganism and activated sludge is 50 to 30,000 MLSS (mg / L) of the preparation method of the microorganism immobilization carrier. The method of claim 17 or 24, The microorganism is added with activated sludge, and the concentration ratio of the microorganism to the activated sludge is 1%: 99% to 99%: 1%. The method of claim 18 or 25, The amount of the crosslinking agent is 0.5 to 80 parts by weight based on 100 parts by weight of the oligomer of the production method of the microorganism immobilization support.

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