KR20200071336A - External carbon source composition for biological wastewater treatment and method for biologically treating wastewater - Google Patents

Abstract

An external carbon source composition of the present invention comprises a saccharide liquid and a denitrification catalyst, preferably comprises a saccharide liquid, a denitrification catalyst, and a denitrification reinforcing agent, and more preferably comprises a saccharide liquid, a denitrification catalyst, a denitrification reinforcing agent, and a cryoprotectant. According to the present invention, the external carbon source composition is used for wastewater treatment in a range of nitrate nitrogen concentrations, provides excellent handling and storing features, reduces a use amount of glucose when used in the wastewater treatment of a low nitrate nitrogen concentration, and provides a denitrification performance which is equal to or higher than methanol when used in the wastewater treatment of a high nitrate nitrogen concentration.

Description

External carbon source composition for biological wastewater treatment and method for biologically treating wastewater}

The present invention relates to an external carbon source composition that can be used for growth and denitrification of microorganisms in the biological wastewater treatment process and uses thereof, and more specifically, it can be used for wastewater treatment in various nitric acid nitrogen concentration ranges and has handling and storage characteristics. It relates to an external carbon source composition in the form of an excellent composite organic material and a method for biologically treating wastewater using the same.

In addition, when the nitrogen component contained in the wastewater is not removed and flows into the river, the value of the nitrogen component basically required for the aquatic environment is increased and the nutrient salts are excessive, that is, eutrophication. As the eutrophication progresses, dissolved oxygen in the water is depleted, which causes all aquatic organisms that require oxygen to die, and the remnants of organic matter generated from dead aquatic organisms are decayed by anaerobic bacteria and pollute the water, such as odor and discoloration of water quality. This will happen.

Organic nitrogen in the wastewater can be removed through biological wastewater treatment methods. The biological wastewater treatment of organic nitrogen consists of the following processes.

<Nitrification>

Reaction 1: NH ₄ + 1.5O ₂ → 2H ⁺ + H ₂ O + NO ₂

Reaction 2: NO ₂ + 0.5O ₂ → NO ₃

Reaction 1 and reaction 2: NH ₄ + 2O ₂ → 2H ⁺ + H ₂ O + NO ₃

<Denitrification>

Reaction 3: 2NO ₃ + 2H ₂ → 2NO ₂ + 2H ₂ O

Reaction 4: 2NO ₂ + 3H ₂ → N ₂ + 2OH + 2H ₂ O

Sum of reaction 3 and reaction 4 Reaction: 2NO ₃ + 5H ₂ → N ₂ + 2OH + 4H ₂ O

First, organic nitrogen is decomposed and hydrolyzed by microorganisms to be converted to ammonia nitrogen, and ammonia nitrogen is oxidized by independent nutrient strains to nitrate nitrogen and then nitrate nitrogen (nitrification step). The nitrate nitrogen produced in the nitrification step is again transformed into gaseous nitrogen molecules through nitrite nitrogen by the heterotrophic strain and then removed from the wastewater.

On the other hand, when the organic wastewater does not contain enough organic material in the wastewater during the biological wastewater treatment process of organic nitrogen, it is necessary to supply an external organic carbon source to remove the organic nitrogen. Methanol or glucose is mainly used as an external organic carbon source for biological wastewater treatment. However, since methanol is manufactured using coal and natural gas as raw materials, the price changes are severe, and it is practically dependent on imports, and it is classified as a toxic substance for reasons such as volatility and human health, and thus, there is a problem in that storage and handling are restricted. In addition, glucose is a material derived from natural products, which is easy to store and handle, but requires a dissolution process when used, and has a problem in that an additional carbon source must be added and the wastewater treatment time is long compared to methanol due to its low denitrification performance.

To solve this, Korean Patent Publication No. 10-1193586 discloses an external carbon source composition containing a saccharide by-product having a high glucose content as a main component and a cryoprotectant such as methanol and ethylene glycol as a sub-component. However, the external carbon source composition disclosed in the prior art is suitable for wastewater treatment at a low nitrate nitrogen concentration, but when applied to wastewater treatment at a high nitrate nitrogen concentration, the denitrification rate is slow, requiring additional carbon source input and increasing wastewater treatment time. There is a problem.

The present invention has been derived under the conventional technical background, the object of the present invention is an external carbon source composition that can be used for growth and denitrification of microorganisms in a biological wastewater treatment process, and can be used for wastewater treatment in various nitric acid nitrogen concentration ranges and handling And excellent storage characteristics. When used for wastewater treatment with low nitrate nitrogen concentration, the amount of glucose can be reduced, and when used for wastewater treatment with high nitrate nitrogen concentration, it can exhibit denitrification performance equivalent to methanol. It is to provide a carbon source composition. In addition, it is an object of the present invention to provide a method for treating wastewater in a biological process using an external carbon source composition.

In order to solve the above object, an example of the present invention is a composition comprising a saccharide liquid having a saccharide concentration of 20 to 80 Brix and a denitration catalyst, wherein the saccharide of the saccharide liquid has 6 carbons based on the peak area of the liquid chromatography peak. The individual monosaccharide is 80% or more, and the monosaccharide having 6 carbon atoms is composed of at least one selected from glucose, fructose, mannose, or galactose, and the denitration catalyst is It is composed of at least one selected from sodium acetate, citric acid, acetic acid, maleic acid, magnesium sulfate or potassium phosphate, and the content of the denitration catalyst in the composition is 0.5 to 10 parts by weight based on 100 parts by weight of the saccharide liquid. It provides an external carbon source composition for biological wastewater treatment. In addition, a preferred example of the present invention is a composition comprising a saccharide liquid having a saccharide concentration of 20 to 80 Brix, a denitrification catalyst and a denitrification reinforcing agent, wherein the saccharide of the saccharide liquid has 6 carbons based on the peak area of the liquid chromatography. The individual monosaccharide is 80% or more, and the monosaccharide having 6 carbon atoms is composed of at least one selected from glucose, fructose, mannose, or galactose, and the denitration catalyst is It consists of at least one selected from sodium acetate, citric acid, acetic acid, maleic acid, magnesium sulfate or potassium phosphate, and the content of the denitration catalyst in the composition is 0.5 to 10 parts by weight based on 100 parts by weight of the saccharide liquid, and the denitrification The adjuvant is composed of at least one selected from ethylene glycol, propylene glycol, diethylene glycol or glycerin, and the content of the denitrification adjuvant in the composition is 0.5 to 20 parts by weight based on 100 parts by weight of the saccharide liquid. An external carbon source composition for processing is provided. In addition, the present invention is an example of the present invention or the present invention so that the ratio of C (carbon) / N (nitrogen) to the wastewater containing microbial sludge is 5/1 to 1/1 with a nitric acid nitrogen content of 20 to 700 ppm. Provided is a biological wastewater treatment method characterized by adding an external carbon source composition according to a preferred embodiment of the present invention and proceeding a denitrification reaction.

In order to solve the above object, another example of the present invention is a composition comprising a saccharide liquid having a saccharide concentration of 20 to 80 Brix, a denitration catalyst, a denitrification reinforcing agent, and a cryoprotectant, wherein the saccharide of the saccharide liquid is a liquid chromatography peak Based on the area, the monosaccharide having 6 carbon atoms is 80% or more, and the monosaccharide having 6 carbon atoms is composed of at least one selected from glucose, fructose, mannose, or galactose. The denitration catalyst is composed of at least one selected from sodium acetate, citric acid, acetic acid, maleic acid, magnesium sulfate or potassium phosphate, and the content of the denitration catalyst in the composition is 0.5 to 10 based on 100 parts by weight of the saccharide liquid It is parts by weight, and the denitrifying agent is composed of at least one selected from ethylene glycol, propylene glycol, diethylene glycol or glycerin, and the content of the denitrifying agent in the composition is 1 to 20 parts by weight based on 100 parts by weight of the saccharide liquid , Wherein the cryoprotectant is composed of at least one selected from methanol, hydrous methanol, ethanol, hydrous ethanol, butanol, hydrous butanol, propanol or hydrous butanol, and the content of the cryoprotectant in the composition is based on 100 parts by weight of saccharide liquid It provides an external carbon source composition for biological wastewater treatment, characterized in that 1 to 25 parts by weight. In addition, the present invention is an external according to another example of the present invention such that the ratio of C (carbon)/N (nitrogen) to wastewater containing microbial sludge is 5/1 to 1/1 in the amount of nitrate nitrogen 20 to 700 ppm. It provides a biological wastewater treatment method characterized in that the carbon source composition is added and the denitrification reaction proceeds.

The external carbon source composition according to the present invention can be used for wastewater treatment in various nitric acid nitrogen concentration ranges, has excellent handling and storage characteristics, and can be used in reducing waste compared to glucose when used for wastewater treatment at low nitric acid nitrogen concentrations and has high quality. When used in the treatment of acidic nitrogen concentrations, denitrification performance equivalent to or higher than that of methanol can be achieved.

One aspect of the present invention relates to an external carbon source composition that improves denitrification efficiency in biological wastewater treatment and helps growth of microorganisms.

External carbon source composition according to an embodiment of the present invention is a composition comprising a saccharide liquid having a saccharide concentration of 20 to 80 Brix (Brix) and a denitration catalyst, wherein the saccharide of the saccharide liquid has 6 carbons based on the peak area of the liquid chromatography peak Monosaccharides having 80% or more and the carbon number of 6 monosaccharides are composed of at least one selected from glucose, fructose, mannose, or galactose, and the denitration catalyst is acetic acid It is composed of at least one selected from sodium, citric acid, acetic acid, maleic acid, magnesium sulfate or potassium phosphate, and the content of the denitration catalyst in the composition is characterized by being 0.5 to 10 parts by weight based on 100 parts by weight of the saccharide liquid. In addition, the external carbon source composition according to a preferred embodiment of the present invention is a composition comprising a saccharide liquid having a saccharide concentration of 20 to 80 Brix, a denitrification catalyst and a denitrification adjuvant, wherein the saccharide of the saccharide liquid is a liquid chromatography peak area As a standard, the monosaccharide having 6 carbon atoms is 80% or more, and the monosaccharide having 6 carbon atoms is composed of at least one selected from glucose, fructose, mannose, or galactose. , The denitration catalyst is composed of at least one selected from sodium acetate, citric acid, acetic acid, maleic acid, magnesium sulfate or potassium phosphate, and the content of the denitration catalyst in the composition is 0.5 to 10 weight based on 100 parts by weight of the saccharide liquid Buoy, the denitrifying agent is composed of at least one selected from ethylene glycol, propylene glycol, diethylene glycol or glycerin, the content of the denitrifying agent in the composition is 0.5 to 20 parts by weight based on 100 parts by weight of the saccharide liquid It is characterized by. The external carbon source composition according to an exemplary embodiment or a preferred embodiment of the present invention may be applied to the treatment of wastewater having a low nitric acid nitrogen concentration.

An external carbon source composition according to another embodiment of the present invention is a composition comprising a saccharide liquid having a saccharide concentration of 20 to 80 Brix, a denitration catalyst, a denitrification reinforcing agent, and an antifreeze agent, wherein the saccharide of the saccharide liquid is a liquid chromatography peak area As a standard, the monosaccharide having 6 carbon atoms is 80% or more, and the monosaccharide having 6 carbon atoms is composed of at least one selected from glucose, fructose, mannose, or galactose. , The denitration catalyst is composed of at least one selected from sodium acetate, citric acid, acetic acid, maleic acid, magnesium sulfate or potassium phosphate, and the content of the denitration catalyst in the composition is 0.5 to 10 weight based on 100 parts by weight of the saccharide liquid Buoy, the denitrifier is composed of one or more selected from ethylene glycol, propylene glycol, diethylene glycol or glycerin, the content of the denitrifier in the composition is 1 to 20 parts by weight based on 100 parts by weight of the saccharide liquid , The cryoprotectant is composed of at least one selected from methanol, hydrous methanol, ethanol, hydrous ethanol, butanol, hydrous butanol, propanol or hydrous butanol, and the content of the cryoprotectant in the composition is based on 100 parts by weight of the saccharide liquid It is characterized by being 1 to 25 parts by weight. The propanol includes n-propanol and isopropanol. In addition, the butanol includes n-butanol, isobutanol, and 2-butanol (2-Butanol). The external carbon source composition according to another example of the present invention may be applied to the treatment of wastewater at a low nitrate nitrogen concentration as well as the treatment of wastewater at a high nitrate concentration.

Hereinafter, the external carbon source composition according to the present invention will be divided and described.

Sugar solution

The saccharide liquid that constitutes the external carbon source composition of the present invention serves to control the overall denitrification performance in biological treatment of wastewater. The saccharide liquid is an aqueous solution containing a saccharide component, and is characterized in that the saccharide concentration is about 20 to 80 Brix. When the saccharide concentration is less than 20 brix, freezing is likely to occur under sub-zero storage conditions, and the saccharide concentration is too low to reduce the productivity of the wastewater treatment process, such as increase in transportation costs and increase in the reaction vessel volume when applied to the wastewater treatment process. This is because when the concentration exceeds 80 Brix, the viscosity is too high, so transportation in the wastewater treatment device is difficult, and also, when the external carbon source composition according to the present invention is stored at a temperature condition of subzero or less, a condensation phenomenon occurs in a short period of time. When considering the productivity of the wastewater treatment process, the transportability in the wastewater treatment system, the economic efficiency due to concentration, and the fastening resistance and freezing resistance when stored at sub-zero temperatures, the saccharide concentration of the saccharide liquid is preferably about 20~ 70 Brix, more preferably 25 to 65 Brix. In addition, in the external carbon source composition according to an example or preferred example of the present invention, the saccharide concentration of the saccharide liquid is preferably 20-40 brix, and more preferably 25-35 brix. Further, in the external carbon source composition according to another example of the present invention, the saccharide concentration of the saccharide liquid is preferably 50 to 80 brix, and more preferably 55 to 70 brix. In the present invention, consolidation means that saccharides as a component of the external carbon source composition crystallize and precipitate as a solid, and freezing means that the entire saccharide liquid of the external carbon source composition is frozen in a solid state. In addition, the saccharide of the saccharide liquid is characterized in that the monosaccharide having 6 carbon atoms, based on the peak area of the liquid chromatography, is about 70% or more, preferably 80% or more, and more preferably 90% or more of the saccharide (typically specific). Percentages based on the area of the liquid chromatography area of the saccharide component are considered to be approximately equal to weight percent.). In general, when biological wastewater treatment, since microorganisms use monosaccharides having 6 carbons as a carbon source, when the monosaccharides having 6 carbons constituting the saccharide of the saccharide liquid are less than 70%, there is a fear that efficiency of wastewater treatment may be deteriorated. The monosaccharide having 6 carbon atoms is not particularly limited, and for example, glucose, fructose, mannose, or galactose, etc. exist as a single component or a mixture thereof. In view of the efficiency of use of microorganisms, it is preferable that glucose is present as a single component. In addition, the saccharide of the saccharide liquid may further include a disaccharide having 12 carbon atoms in addition to the monosaccharide having 6 carbon atoms, wherein the disaccharide is present in less than about 10% of the total saccharide based on the liquid chromatography peak area. The type of disaccharide having 12 carbon atoms is not particularly limited, and for example, sucrose, maltose, isomaltose, trehalose, or lactose is a single component. Or they may be mixed. In addition, the saccharide of the saccharide liquid may further include a polysaccharide having a polymerization degree of 6 or more based on 6-carbon, wherein the polysaccharide having a polymerization degree of 6 or more based on 6-carbon is present in an amount of about 10% or less of the entire saccharide based on the peak area of the liquid chromatography. do. Polysaccharides with a degree of polymerization of 6-carbon-based polymerization of 3 or more are not greatly limited, for example, fructooligosaccharide, isomalto-oligosaccharide, Nigerotriose, Maltotriose, Melezitose , Maltotriulose, Raffinose, Kestose, Maltotetraose, Lychnose, Nigerotetraose, Nisthotetraose Nystose, Sesamose, Stachynose, Verbascose, etc. may be present as a single component or a mixture thereof. In addition, the saccharide liquid may be prepared by mixing monosaccharides having 6 carbon atoms, water, and optionally disaccharides having 12 carbon atoms or polysaccharides having a polymerization degree of 6 carbons or higher.

Denitrification catalyst

The denitrification catalyst, which is one component of the external carbon source composition of the present invention, serves to adjust the pH of the external carbon source composition and improve the denitrification rate in biological treatment of wastewater. The denitration catalyst constituting the external carbon source composition of the present invention is preferably sodium acetate or acetic acid when considering the denitration rate and the like. In addition, the content of the denitration catalyst in the external carbon source composition of the present invention is preferably 0.5 to 5 parts by weight based on 100 parts by weight of the saccharide liquid when considering harmony with other components, denitrification performance, and economical efficiency, and 1 to 4 parts by weight It is more desirable to deny it.

Denitrification Adjuvant

A denitrification reinforcing agent, which is one component of the external carbon source composition of the present invention, serves to enhance initial denitrification performance and late denitrification performance in biological treatment of wastewater. When considering the denitrification rate, etc., the denitrification agent constituting the external carbon source composition of the present invention is preferably selected from a combination of ethylene glycol, propylene glycol or ethylene glycol and propylene glycol, and is preferably a combination of ethylene glycol and propylene glycol. When the denitrification reinforcing agent constituting the external carbon source composition of the present invention is composed of a combination of ethylene glycol and propylene glycol, the weight ratio of ethylene glycol and propylene glycol is preferably 2:8 to 8:2 when considering the denitrification rate, etc., and 3: It is more preferable that it is 7 to 7:3, and it is most preferable that it is 4:6 to 6:4. In addition, the content of the denitration reinforcing agent in the external carbon source composition according to an exemplary embodiment of the present invention is preferably 0.5 to 15 parts by weight based on 100 parts by weight of the saccharide liquid in consideration of harmony with other components, denitrification performance and economics, etc. And more preferably 1 to 10 parts by weight. In addition, the content of the denitration reinforcing agent in the external carbon source composition according to another example of the present invention is preferably 5 to 20 parts by weight based on 100 parts by weight of the saccharide liquid when considering harmony with other components, denitrification performance, and economics, etc. It is more preferable that it is 10 to 18 parts by weight.

Antifreeze

Since the external carbon source composition according to the present invention contains sugars such as glucose, there is a concern that it may be contaminated and deteriorated by microorganisms during storage and handling, and in this case, it cannot be used for biological wastewater treatment, and the external carbon source composition in winter is consolidated There is a risk of being frozen. Therefore, the external carbon source composition according to an example or preferred example of the present invention may further include a cryoprotectant in addition to the saccharide liquid. In addition, the external carbon source composition according to another example of the present invention includes a cryoprotectant. The cryoprotectant serves to secure storage stability by preventing the saccharide liquid from freezing when the external carbon source composition of the present invention is stored under sub-zero conditions, and improve the initial denitration rate during biological treatment of wastewater. The cryoprotectant, which is a component of the external carbon source composition according to another example of the present invention, is composed of at least one selected from methanol, hydrous methanol, ethanol, and hydrous ethanol when considering compatibility with other components, denitrification rate, or economy. It is preferred, and it is more preferably selected from methanol and hydrous methanol. In addition, the water-containing methanol is preferably a concentration of 40 to 80% by weight and more preferably 40 to 60% by weight when considering the ease of manufacture and safety of the external carbon source composition. In addition, the content of the cryoprotectant in the external carbon source composition according to another example of the present invention is preferably 2 to 20 parts by weight based on 100 parts by weight of the saccharide liquid when considering harmony with other components, denitrification performance, and economics, etc. , 5 to 20 parts by weight is more preferable. For example, when using methanol as a cryoprotectant in an external carbon source composition according to another example of the present invention, the content is preferably 10 to 20 parts by weight based on 100 parts by weight of the saccharide liquid. In addition, in the case of using hydrous methanol having a concentration of 40 to 60% in the external carbon source composition according to another example of the present invention, the content is preferably 5 to 10 parts by weight based on 100 parts by weight of the saccharide liquid.

One aspect of the present invention relates to a method for preparing an external carbon source composition for biological wastewater treatment. The method for preparing an external carbon source composition according to an embodiment of the present invention preferably includes adding a denitration catalyst to the saccharide liquid and mixing it. In addition, the method for preparing an external carbon source composition according to an exemplary embodiment of the present invention preferably includes adding and mixing a denitration catalyst and a denitration reinforcing agent to the saccharide liquid. In addition, the method for preparing an external carbon source composition according to another example of the present invention preferably includes adding and mixing a denitration catalyst, a denitration reinforcing agent, and a cryoprotectant to the saccharide liquid. In the method of preparing an external carbon source composition according to an example, preferred example, or other example of the present invention, the saccharide liquid may be used after being concentrated or diluted to have an appropriate solid content concentration. In the method for preparing an external carbon source composition according to an example, a preferred example, or another example of the present invention, the level of concentration or dilution of a saccharide liquid, the amount of addition of components, etc. can be appropriately selected with reference to the foregoing.

One aspect of the invention relates to a method for biologically treating wastewater using an external carbon source composition. The biological wastewater treatment method using an external carbon source composition according to an example or preferred example of the present invention has a nitric acid nitrogen content of 20 to 700 ppm, preferably 20 to 200 ppm, and C (carbon) in wastewater containing microbial sludge. It is characterized in that the external carbon source composition is added so that the ratio of /N (nitrogen) is 5/1 to 1/1, and the denitrification reaction proceeds. In addition, the biological wastewater treatment method using an external carbon source composition according to another example of the present invention has a nitric acid nitrogen content of 20 to 700 ppm, preferably 200 to 700 ppm, and C (carbon)/N in wastewater containing microbial sludge. It is characterized in that the external carbon source composition is added so that the ratio of (nitrogen) is 5/1 to 1/1 and the denitrification reaction proceeds. The nitrate nitrogen content is 20 to 700 ppm and the wastewater containing the microbial sludge is one selected from sewage, sewage dilution, livestock wastewater, livestock wastewater dilution, seasonal wastewater, seasonal wastewater dilution, semiconductor industrial wastewater or semiconductor industrial wastewater dilution. It can be configured as described above. The semiconductor industrial wastewater is a wastewater generated in a semiconductor manufacturing process, and may be classified into high-concentration silicon-containing wastewater, fluorine compound wastewater, heavy metal-containing wastewater, organic wastewater, high-concentration nitrate wastewater, and high-concentration phosphate wastewater. In addition, the wastewater having a nitric acid nitrogen content of 20 to 200 ppm corresponds to wastewater having a low nitric acid nitrogen concentration. In addition, the wastewater having a nitric acid nitrogen content of 200 to 700 ppm typically corresponds to a wastewater having a high nitrate nitrogen concentration. In the biological wastewater treatment method according to the present invention, the ratio of C (carbon)/N (nitrogen) is preferably 5/1 to 2/1 and 4/1 to 2/1 when considering denitrification rate and economics, etc. More preferred. In the biological wastewater treatment method according to the present invention, the denitrification reaction temperature is not particularly limited and may be selected, for example, in the range of 5 to 35°C. In addition, in the biological wastewater treatment method according to the present invention, the denitrification reaction time is not particularly limited and may be selected, for example, in the range of 3 to 60 hr.

Hereinafter, the present invention will be described in more detail through examples. However, the following examples are only for clearly illustrating the technical features of the present invention, and are not intended to limit the protection scope of the present invention.

1. Preparation of sugar solution and analysis of physical properties

Glucose, maltose, and six-carbon-based polysaccharides with a polymerization degree of 3 or more were dissolved in distilled water at a predetermined mixing ratio to prepare a saccharide liquid having a solids concentration of about 20 Brix. Subsequently, the main properties and saccharide composition of the prepared saccharide liquid were analyzed. The saccharide composition was analyzed using high performance liquid chromatography (HPLC 1200 series, Agilent).

Table 1 below shows the properties of the saccharide liquid and the saccharide composition results analyzed by high performance liquid chromatography.

Measure
Item Sugar concentration
(Brix) pH Electrical conductivity
( μ S/cm) Coloring Sugar composition
(Based on HPLC peak area, %) Glucose Etc Measures 13.0 5.0 10.3 0.072 91.0 9.0

* Others: Polysaccharides with a polymerization degree of 6 or more based on 6-carbon

As shown in Table 1, it can be seen that saccharides of the saccharide liquid consist of 90% or more of glucose.

The saccharide solution of 20 Brix concentration prepared above is concentrated with a vacuum concentrator (R-111L, BUCHI) to have a solids concentration of about 30 Brix, about 50 Brix, and about 60 Brix. A saccharide concentrate was prepared and used to prepare an external carbon source composition described later.

2. External for wastewater treatment with low nitrate concentration Carbon source Preparation of composition and measurement of basic properties

(1) Preparation of external carbon source composition

Production Example 1-1.

An external carbon source composition having a solids concentration of about 25 Brix was prepared by adding and mixing 292 g of water to 208 g of a saccharide concentrate having a solids concentration of about 60 Brix.

Preparation Example 1-2.

292 g of water was added to 208 g of a saccharide concentrate having a solids concentration of about 60 Brix to dilute the solids concentration to about 25 Brix, and 5 g of sodium acetate was added thereto as a denitrification catalyst and mixed to external carbon source. The composition was prepared.

Preparation Example 1-3.

292 g of water is added to 208 g of a saccharide concentrate having a solids concentration of about 60 Brix to dilute the solids concentration to about 25 Brix, to which 10 g of sodium acetate is added as a denitration catalyst and mixed to external carbon source. The composition was prepared.

Production Example 1-4.

292 g of water is added to 208 g of a saccharide concentrate having a solids concentration of about 60 Brix to dilute the solids concentration to about 25 Brix, and 15 g of sodium acetate is added thereto as a denitrification catalyst and mixed to external carbon source. The composition was prepared.

Production Example 1-5.

292 g of water is added to 208 g of a saccharide concentrate having a solids concentration of about 60 Brix to dilute the solids concentration to about 25 Brix, and 10 g of sodium acetate as a denitration catalyst and 5 g of ethylene glycol as a denitrification adjuvant. Was sequentially added and mixed to prepare an external carbon source composition.

Preparation Example 1-6.

292 g of water was added to 208 g of a saccharide concentrate having a solids concentration of about 60 Brix to dilute the solids concentration to about 25 Brix, and 10 g of sodium acetate as a denitrification catalyst and 15 g of ethylene glycol as a denitrification adjuvant. Was sequentially added and mixed to prepare an external carbon source composition.

Production Example 1-7.

292 g of water is added to 208 g of a saccharide concentrate having a solids concentration of about 60 Brix to dilute the solids concentration to about 25 Brix, and 10 g of sodium acetate as a denitrification catalyst and 25 g of ethylene glycol as a denitrification adjuvant. Was sequentially added and mixed to prepare an external carbon source composition.

Preparation Example 1-8.

292 g of water was added to 208 g of a saccharide concentrate having a solids concentration of about 60 Brix to dilute the solids concentration to about 25 Brix, and 10 g of sodium acetate as a denitration catalyst and 35 g of ethylene glycol as a denitrification adjuvant. Was sequentially added and mixed to prepare an external carbon source composition.

Preparation Example 1-9.

An external carbon source composition was prepared by adding and mixing 2 g of citric acid as a denitration catalyst to 100 g of a saccharide concentrate having a solids concentration of about 30 Brix.

Preparation Example 1-10.

An external carbon source composition was prepared by adding and mixing 2 g of acetic acid as a denitration catalyst to 100 g of a saccharide concentrate having a solids concentration of about 30 Brix.

Production Example 1-11.

An external carbon source composition was prepared by adding and mixing 2 g of maleic acid as a denitration catalyst to 100 g of a saccharide concentrate having a solids concentration of about 30 Brix.

Preparation Example 1-12.

An external carbon source composition was prepared by adding and mixing 2 g of magnesium sulfate as a denitration catalyst to 100 g of a saccharide concentrate having a solids concentration of about 30 Brix.

Production Example 1-13.

An external carbon source composition was prepared by adding and mixing 2 g of potassium phosphate as a denitration catalyst to 100 g of a saccharide concentrate having a solids concentration of about 30 Brix.

Production Example 1-14.

An external carbon source composition was prepared by adding and mixing 2 g of sodium acetate as a denitration catalyst to 100 g of a saccharide concentrate having a solids concentration of about 30 Brix.

Table 2 below shows the components and blending ratios of the external carbon source composition for treating wastewater with a low nitrate nitrogen concentration.

Classification of external carbon source composition Composition and compounding ratio
Saccharide concentrate Denitrification catalyst Denitrification adjuvant Preparation Example 1-1 25 Brix Sugar Concentrate 500g - - Preparation Example 1-2 25 Brix Sugar Concentrate 500g 5 g sodium acetate - Preparation Example 1-3 25 Brix Sugar Concentrate 500g Sodium acetate 10 g - Preparation Example 1-4 25 Brix Sugar Concentrate 500g 15 g sodium acetate - Preparation Example 1-5 25 Brix Sugar Concentrate 500g Sodium acetate 10 g Ethylene glycol 5g Preparation Example 1-6 25 Brix Sugar Concentrate 500g Sodium acetate 10 g Ethylene glycol 15 g Preparation Example 1-7 25 Brix Sugar Concentrate 500g Sodium acetate 10 g Ethylene glycol 25g Preparation Example 1-8 25 Brix Sugar Concentrate 500g Sodium acetate 10 g Ethylene glycol 35g Preparation Example 1-9 30 Brix saccharide concentrate 100g 2 g citric acid - Preparation Example 1-10 30 Brix saccharide concentrate 100g Acetic acid 2 g - Preparation Example 1-11 30 Brix saccharide concentrate 100g Maleic acid 2 g - Preparation Example 1-12 30 Brix saccharide concentrate 100g 2 g of magnesium sulfate - Preparation Example 1-13 30 Brix saccharide concentrate 100g 2 g of potassium phosphate - Preparation Example 1-14 30 Brix saccharide concentrate 100g 2 g sodium acetate -

(2) Physical properties of external carbon source composition

The pH and chemical oxygen demand (COD) of the external carbon source compositions prepared in Preparation Examples 1-1 to 1-8 were measured, and the results are shown in Table 3 below.

Classification of external carbon source composition pH CODcr(ppm) Preparation Example 1-1 4.5 303,000 Preparation Example 1-2 6.0 310,000 Preparation Example 1-3 6.4 322,000 Preparation Example 1-4 6.6 316,000 Preparation Example 1-5 6.4 341,000 Preparation Example 1-6 6.5 362,000 Preparation Example 1-7 6.5 369,000 Preparation Example 1-8 6.5 386,000

3. External when applied to wastewater treatment with low nitrate nitrogen concentration Carbon source Denitrification performance test of composition

A sodium nitrate solution with a concentration of 10 ppm was prepared by dissolving sodium nitrate in water. Subsequently, 1 L of wastewater sludge having a mixed liquid suspended solids (MLSS) content of 2200 ppm was added to an anoxic tank, and 5 ml of a sodium nitrate solution having a concentration of 10 ppm was added thereto and mixed to produce nitric acid nitrogen (existing in the form of nitric acid) Artificial wastewater with a content of 50 ppm of nitrogen) was prepared. Then, the external carbon source composition prepared in Preparation Examples 1-1 to 1-14 was added to the artificial wastewater so that the C/N ratio was 4/1, 3/1, 2/1, or 1/1, and about 7 at 25°C. The denitrification reaction was carried out for hr, and the change in the denitrification rate was measured by sampling over time. In addition, a glucose solution having a solids concentration of about 30 Brix (COD of glucose is about 750,000 ppm) and a saccharide concentrate having a solids concentration of about 30 Brix were used as a control for the external carbon source composition. The nitrate nitrogen content of the sampled wastewater was measured using a nitrate nitrogen analysis cell and a spectrophotometer, and the results are shown in Table 4 below.

Classification of external carbon source composition C/N ratio Denitrification rate according to reaction time (%) 1hr 3hr 5hr 7hr Preparation Example 1-1 4/1 26 58 83 100 Preparation Example 1-2 4/1 30 62 88 100 Preparation Example 1-3 4/1 32 66 90 100 Preparation Example 1-4 4/1 35 68 92 100 Preparation Example 1-5 4/1 39 75 97 100 Preparation Example 1-6 4/1 41 80 100 Unmeasured Preparation Example 1-7 4/1 41 85 100 Unmeasured Preparation Example 1-8 4/1 42 86 100 Unmeasured 30 Brix glucose solution 4/1 28 60 87 100 Preparation Example 1-7 3/1 37 62 100 Preparation Example 1-7 2/1 35 62 87 100 Preparation Example 1-7 1/1 29 48 71 100 30 Brix saccharide concentrate 4/1 Unmeasured Unmeasured 83 Unmeasured Preparation Example 1-9 4/1 Unmeasured Unmeasured 88 Unmeasured Preparation Example 1-10 4/1 Unmeasured Unmeasured 88 Unmeasured Preparation Example 1-11 4/1 Unmeasured Unmeasured 89 Unmeasured Preparation Example 1-12 4/1 Unmeasured Unmeasured 91 Unmeasured Preparation Example 1-13 4/1 Unmeasured Unmeasured 90 Unmeasured Preparation Example 1-14 4/1 Unmeasured Unmeasured 92 Unmeasured

4. Outside for wastewater treatment with high nitrate nitrogen concentration Carbon source Preparation of composition and measurement of basic properties

(1) Preparation of external carbon source composition

Production Example 2-1.

Sequentially, 2.0 g of sodium acetate as a denitrification catalyst, 5.0 g of ethylene glycol and 5.0 g of propylene glycol as a denitrification agent, and 9.9 g of a 50% by weight methanol solution as a freeze-preventing agent were sequentially added to 78.2 g of a saccharide concentrate having a solids concentration of about 60 Brix. It was added and mixed to prepare an external carbon source composition.

Production Example 2-2.

Sequentially, 2.0 g of sodium acetate as a denitration catalyst, 5.0 g of ethylene glycol and 5.0 g of propylene glycol as a denitrification agent, and 13.8 g of a 50 wt% methanol solution as a cryoprotectant were added to 74.2 g of a saccharide concentrate having a solids concentration of about 60 Brix. It was added and mixed to prepare an external carbon source composition.

Production Example 2-3.

Sequentially, 2.0 g of sodium acetate as a denitrification catalyst, 7.1 g of ethylene glycol and 5.1 g of propylene glycol as a denitrification agent, and 10.0 g of a 50% by weight methanol solution as a cryoprotectant were added to 75.8 g of a saccharide concentrate having a solids concentration of about 60 Brix. It was added and mixed to prepare an external carbon source composition.

Production Example 2-4.

Sequentially, 2.0 g of sodium acetate as a denitration catalyst, 5.1 g of ethylene glycol and 7.1 g of propylene glycol as a denitrification agent, and 10.1 g of a 50% by weight methanol solution as a cryoprotectant are sequentially added to 75.7 g of a saccharide concentrate having a solids concentration of about 60 Brix. It was added and mixed to prepare an external carbon source composition.

Production Example 2-5.

Sequentially, 2.0 g of sodium acetate as a denitrification catalyst, 5.0 g of ethylene glycol and 5.0 g of propylene glycol as a denitrification agent, and 13.8 g of an ethanol solution at a concentration of 50% by weight as a freeze-proofing agent are sequentially added to 74.2 g of a saccharide concentrate having a solids concentration of about 60 Brix. It was added and mixed to prepare an external carbon source composition.

Production Example 2-6.

Sequentially, 2.0 g of sodium acetate as a denitration catalyst, 5.0 g of ethylene glycol and 5.0 g of propylene glycol as a denitrification agent, and 13.8 g of a 50% by weight butanol solution as a cryoprotectant were added to 74.2 g of a saccharide concentrate having a solids concentration of about 60 Brix. It was added and mixed to prepare an external carbon source composition.

Production Example 2-7.

Sequentially, 2.0 g of sodium acetate as a denitrification catalyst, 5.0 g of ethylene glycol and 5.0 g of propylene glycol as a denitrification agent, and 13.8 g of 50% by weight of a propanol solution as a cryoprotectant are added to 74.2 g of a saccharide concentrate having a solids concentration of about 60 Brix. It was added and mixed to prepare an external carbon source composition.

Preparation Example 2-8.

An external carbon source composition was prepared by sequentially adding and mixing 7.0 g of ethylene glycol as a denitrifying agent and 3.0 g of methanol as a cryoprotectant to 100 g of a saccharide concentrate having a solid content of about 50 Brix.

Preparation Example 2-9.

Sequentially add and mix 2.0 g of sodium acetate as a denitration catalyst, 10.0 g of ethylene glycol as a denitrification agent, and 13.8 g of a 50% by weight methanol solution as a cryoprotectant to 74.2 g of a saccharide concentrate having a solids concentration of about 60 Brix. An external carbon source composition was prepared.

Preparation Example 2-10.

Sequentially add and mix 2.0 g of sodium acetate as a denitration catalyst, 10.0 g of propylene glycol as a denitrification agent, and 13.8 g of a 50% by weight methanol solution as a cryoprotectant to 74.2 g of a saccharide concentrate having a solids concentration of about 60 Brix. An external carbon source composition was prepared.

Production Example 2-11.

Sequentially, 2.0 g of sodium acetate as a denitrification catalyst, 10.0 g of diethylene glycol as a denitrification agent, and 13.8 g of a 50% by weight methanol solution as a freeze-proofing agent were sequentially added to 74.2 g of a saccharide concentrate having a solids concentration of about 60 Brix. It was added and mixed to prepare an external carbon source composition.

Production Example 2-12.

Sequentially add 2.0 g of sodium acetate as a denitration catalyst, 10.0 g of glycerin as a denitrification agent, and 13.8 g of a 50% by weight methanol solution as a cryoprotectant to 74.2 g of a saccharide concentrate having a solids concentration of about 60 Brix. By mixing, an external carbon source composition was prepared.

Table 5 below shows the components and blending ratios of the external carbon source composition for treating wastewater having a high nitrate nitrogen concentration.

Classification of external carbon source composition Composition and compounding ratio Saccharide concentrate Denitrification catalyst Denitrification adjuvant Antifreeze Preparation Example 2-1 60 Brix Sugar Concentrate 78.2 g Sodium acetate 2.0 g Propylene glycol 5.0 g
Ethylene glycol 5.0 g 9.9 g of 50% methanol solution Preparation Example 2-2 60 Brix Sugar Concentrate 74.2g Sodium acetate 2.0 g Propylene glycol 5.0 g
Ethylene glycol 5.0 g 13.8 g 50% methanol solution Preparation Example 2-3 60 Brix Sugar Concentrate 75.8g Sodium acetate 2.0 g Propylene glycol 5.1 g
Ethylene glycol 7.1 g 10.0% 50% methanol solution Preparation Example 2-4 60 Brix Sugar Concentrate 75.7g Sodium acetate 2.0 g Propylene glycol 7.1 g
Ethylene glycol 5.1 g 10.1% 50% methanol solution Preparation Example 2-5 60 Brix Sugar Concentrate 74.2g Sodium acetate 2.0 g Propylene glycol 5.0 g
Ethylene glycol 5.0 g 13.8 g of 50% ethanol solution Preparation Example 2-6 60 Brix Sugar Concentrate 74.2g Sodium acetate 2.0 g Propylene glycol 5.0 g
Ethylene glycol 5.0 g 13.8 g of a 50% butanol solution Production Example 2-7 60 Brix Sugar Concentrate 74.2g Sodium acetate 2.0 g Propylene glycol 5.0 g
Ethylene glycol 5.0 g 13.8 g 50% propanol solution Preparation Example 2-8 50 Brix saccharide concentrate 100g - Ethylene glycol 7.0g 3.0 g of methanol Preparation Example 2-9 60 Brix Sugar Concentrate 74.2g Sodium acetate 2.0 g Ethylene glycol 10 g 13.8 g 50% methanol solution Preparation Example 2-10 60 Brix Sugar Concentrate 74.2g Sodium acetate 2.0 g Propylene glycol 10 g 13.8 g 50% methanol solution Production Example 2-11 60 Brix Sugar Concentrate 74.2g Sodium acetate 2.0 g Diethylene glycol 10 g 13.8 g 50% methanol solution Preparation Example 2-12 60 Brix Sugar Concentrate 74.2g Sodium acetate 2.0 g Glycerin 10 g 13.8 g 50% methanol solution

(2) Physical properties of external carbon source composition

The pH and chemical oxygen demand (COD) of the external carbon source compositions prepared in Preparation Examples 2-1 to 2-4 and Preparation Examples 2-8 were measured, and the results are shown in Table 6 below.

Classification of external carbon source composition pH CODcr(ppm) Preparation Example 2-1 6.5 780,000 Preparation Example 2-2 6.4 786,000 Preparation Example 2-3 6.4 790,000 Preparation Example 2-4 6.4 810,000 Preparation Example 2-8 4.0 720,000

5. High nitrate nitrogen Concentration of wastewater External when applied to processing Carbon source Denitrification performance test of the composition (1)

A sodium nitrate solution with a concentration of 50 ppm was prepared by dissolving sodium nitrate in water. Subsequently, 1 liter of wastewater sludge having a mixed liquid suspended solids (MLSS) content of 6000 ppm was added to an anoxic tank, and 8 ml of a sodium nitrate solution at a concentration of 50 ppm was added thereto and mixed to make artificial artificial nitrogen nitrate content of 400 ppm. Wastewater was prepared. Subsequently, the external carbon source composition prepared in Preparation Examples 2-1 to 2-8 was added to the artificial wastewater so that the C/N ratio was 4/1, and denitrification reaction was performed at 25° C. for about 24 hr. The change in denitrification rate was measured. In addition, a glucose solution having a solid concentration of about 60 Brix (COD of glucose is about 750,000 ppm) and methanol (COD of methanol is about 1,414,000 ppm) were used as a control for the external carbon source composition. The nitrate nitrogen content of the sampled wastewater was measured using a nitrate nitrogen analysis cell and a spectrophotometer, and the results are shown in Table 7 below.

Classification of external carbon source composition Denitrification rate according to reaction time (%) 1 hr 4 hr 7 hr 10 hr 16 hr 24 hr Preparation Example 2-1 14 30 39 42 87 96 Preparation Example 2-2 14 34 44 53 94 100 Preparation Example 2-3 13 33 39 44 89 99 Preparation Example 2-4 16 31 38 42 86 95 Preparation Example 2-5 13 33 42 51 90 99 Preparation Example 2-6 13 32 41 51 89 99 Production Example 2-7 13 32 40 50 89 98 Preparation Example 2-8 8 20 29 36 54 90 60 Brix glucose solution 2 10 16 20 38 90 Methanol 13 37 62 79 88 90

6. External when applied to wastewater treatment with high nitrate nitrogen concentration Carbon source Denitrification performance test of the composition (2)

A sodium nitrate solution with a concentration of 50 ppm was prepared by dissolving sodium nitrate in water. Subsequently, 1 L of wastewater sludge having a mixed liquor suspended solids (MLSS) content of 20,000 ppm was added to an anoxic tank, and 14 ml of a sodium nitrate solution at a concentration of 50 ppm was added thereto and mixed to make artificial artificial nitrogen content of 700 ppm. Wastewater was prepared. Thereafter, the external carbon source composition prepared in Preparation Examples 2-2 and 2-9 to 2-12 was added to the artificial wastewater so that the C/N ratio was 4/1, and denitrification was performed at 25° C. for about 7 hr, Sampling by time was used to measure the change in denitrification rate. In addition, a glucose solution having a solid concentration of about 60 Brix (COD of glucose is about 750,000 ppm) and methanol (COD of methanol is about 1,414,000 ppm) were used as a control for the external carbon source composition. The nitrate nitrogen content of the sampled wastewater was measured using a nitrate nitrogen analysis cell and a spectrophotometer, and the results are shown in Table 8 below.

Classification of external carbon source composition Denitrification rate according to reaction time (%) 1 hr 3 hr 5 hr 7 hr Preparation Example 2-2 55 82 99 100 Preparation Example 2-9 53 79 97 99 Preparation Example 2-10 52 78 95 98 Production Example 2-11 52 76 94 96 Preparation Example 2-12 51 74 93 96 60 Brix glucose solution 13 19 30 47 Methanol 24 63 99 100

As described above, the present invention has been described through examples, but the present invention is not necessarily limited thereto, and various modifications can be made without departing from the scope and spirit of the present invention. Accordingly, the protection scope of the present invention should be construed to include all embodiments falling within the scope of the claims appended to the present invention.

Claims (8)

A composition comprising a saccharide liquid having a saccharide concentration of 20-80 Brix and a denitration catalyst,
The saccharide of the saccharide liquid is 80% or more of a monosaccharide having 6 carbon atoms based on the peak area of the liquid chromatography,
The monosaccharide having 6 carbon atoms is composed of one or more selected from glucose, fructose, mannose, or galactose,
The denitration catalyst is composed of at least one selected from sodium acetate, citric acid, acetic acid, maleic acid, magnesium sulfate or potassium phosphate,
The content of the denitration catalyst in the composition is an external carbon source composition for biological wastewater treatment, characterized in that 0.5 to 10 parts by weight based on 100 parts by weight of the saccharide liquid.
A composition comprising a sugar solution having a saccharide concentration of 20 to 80 Brix, a denitration catalyst, and a denitration reinforcing agent,
The saccharide of the saccharide liquid is 80% or more of a monosaccharide having 6 carbon atoms based on the peak area of the liquid chromatography,
The monosaccharide having 6 carbon atoms is composed of one or more selected from glucose, fructose, mannose, or galactose,
The denitration catalyst is composed of at least one selected from sodium acetate, citric acid, acetic acid, maleic acid, magnesium sulfate or potassium phosphate,
The content of the denitration catalyst in the composition is 0.5 to 10 parts by weight based on 100 parts by weight of the saccharide liquid,
The denitrifying agent is composed of at least one selected from ethylene glycol, propylene glycol, diethylene glycol or glycerin,
The content of the denitrifying agent in the composition is an external carbon source composition for biological wastewater treatment, characterized in that 0.5 to 20 parts by weight based on 100 parts by weight of the saccharide liquid.
The external carbon source composition of claim 1 or 2 is added so that the ratio of C (carbon)/N (nitrogen) is 5/1 to 1/1 to wastewater containing microbial sludge with a nitric acid nitrogen content of 20 to 700 ppm and Biological wastewater treatment method characterized in that the denitrification reaction proceeds.
The biological material of claim 3, wherein the wastewater comprises one or more selected from sewage, sewage dilution, livestock wastewater, livestock wastewater dilution, seasonal wastewater, seasonal wastewater dilution, semiconductor industrial wastewater, or semiconductor industrial wastewater dilution. Wastewater treatment method.
A composition comprising a saccharide liquid having a saccharide concentration of 20 to 80 Brix, a denitration catalyst, a denitration reinforcing agent, and a cryoprotectant,
The saccharide of the saccharide liquid is 80% or more of a monosaccharide having 6 carbon atoms based on the peak area of the liquid chromatography,
The monosaccharide having 6 carbon atoms is composed of at least one selected from glucose, fructose, mannose, or galactose,
The denitration catalyst is composed of at least one selected from sodium acetate, citric acid, acetic acid, maleic acid, magnesium sulfate or potassium phosphate,
The content of the denitration catalyst in the composition is 0.5 to 10 parts by weight based on 100 parts by weight of the saccharide liquid,
The denitrifying agent is composed of at least one selected from ethylene glycol, propylene glycol, diethylene glycol or glycerin,
The content of the denitration reinforcing agent in the composition is 1 to 20 parts by weight based on 100 parts by weight of the saccharide liquid,
The cryoprotectant is composed of at least one selected from methanol, hydrous methanol, ethanol, hydrous ethanol, butanol, hydrous butanol, propanol or hydrous butanol,
The content of the cryoprotectant in the composition is 1 to 25 parts by weight based on 100 parts by weight of the saccharide liquid External carbon source composition for biological wastewater treatment.
6. The composition of claim 5, wherein the denitrification agent is composed of ethylene glycol and propylene glycol, and the weight ratio of the ethylene glycol and propylene glycol is 2:8 to 8:2.
The external carbon source composition of claim 5 or 6 is added so that the ratio of C (carbon)/N (nitrogen) is 5/1 to 1/1 to wastewater containing microbial sludge with a nitric acid nitrogen content of 20 to 700 ppm and Biological wastewater treatment method characterized in that the denitrification reaction proceeds.
The biological method of claim 7, wherein the wastewater is composed of one or more selected from sewage, sewage dilution, livestock wastewater, livestock wastewater dilution, seasonal wastewater, seasonal wastewater dilution, semiconductor industrial wastewater, or semiconductor industrial wastewater dilution. Wastewater treatment method.