KR101903043B1 - Advanced oxidation, adsoption system for control of micropollutants in wastewater - Google Patents

Abstract

An advanced oxidation and adsorption system of the present invention comprises: a biofilm treatment tank for removing trace harmful substances contained in a wastewater by oxidizing and decomposing a biofilm formed by microorganisms; an advanced oxidation treatment tank having a composite configuration of O_3/H_2O_2/UV; an adsorption tank having a multilayer structure of expanded graphite, iron oxide, and magnesite; and a disinfection tank using chlorine. By the above configuration, the present invention relates to an advanced oxidation and adsorption system for treating trace harmful substances in the wastewater which can effectively remove trace harmful substances contained in the wastewater by biological, chemical, and physical decomposition reaction independently or depending on complex processes.

Description

TECHNICAL FIELD [0001] The present invention relates to an advanced oxidation and adsorption system for treating trace amounts of harmful substances in a wastewater,

The present invention is advanced oxidation, adsorption system, biofilm treatment tank and to remove the trace amount of hazardous substances contained in and waste water through the oxidation and disintegration of biofilms (biofilm) which is formed by _{microbes, O 3 / H 2 O 2} / The biological, chemical, and physical decomposition reactions are carried out independently or in a complex process through the combination of the advanced oxidation treatment tank with the UV composition, the adsorption tank by the multilayer structure of expanded graphite, iron oxide, and magnesite, and the disinfection tank using chlorine The present invention relates to a high oxidation and adsorption system for treating trace amounts of harmful substances in wastewater, which can effectively remove trace harmful substances contained in wastewater.

Rapid industrial development and economic growth in modern society have brought about improvement in the level of human living environment. Population concentration due to urbanization causes a large amount of sewage generation, resulting in increase and accumulation of pollutant loads on the surrounding water quality, .

Medicinal substances, cosmetic substances and perfluorinated compounds such as antibiotics, antiinflammatory agents, etc., which are used in households, animal breeding farms and farms, are difficult to be effectively removed by conventional sewage treatment or advanced treatment process, And it is difficult to maintain stable water quality due to these trace harmful substances introduced into rivers and the like. Substance alone is harmful, has persistence and bioaccumulation, and it is likely to have serious effects on ecosystem and human health when exposed continuously or chronically.

The medicinal substance is artificially increased in X-ray absorption difference of each tissue so that the tissue or blood vessels can be seen well during radiographic examination such as magnetic resonance imaging (MRI) imaging or computerized tomography (CT) imaging, Antibiotics, which is a drug that has both anti-inflammatory and analgesic actions that alleviate inflammation and analgesic action that alleviates inflammation, anti-inflammatory analgesics, and substances that are produced by microorganisms and inhibit the development or function of other cells, .

PPCP is an abbreviation of pharmaceuticals and personal care products. It is a product that can be easily obtained without a prescription, such as a headache medicine or analgesic, a personal health or beauty enhancement, a livestock health or growth promoting medicine, And it affects the human body.

PPCP is influenced by the circulation process of waste medicine, sewage, industrial waste, industrial waste, and sewerage.

Especially, PPCP of iopromide used as an x-ray contrast agent is detected at the highest concentration. In addition, many PPCP substances such as ibuprofen, which is used as an anti-inflammatory agent, and acetaminophen, which is used as an antipyretic, are being released into the river without being decomposed.

PPCP detected in Han River, Youngsan River and Nakdong River are Erythromycin, Sulfamethoxazole, TCEP, DEET, Oxybenzone, Estrone, Androstenedione, Iopromide, Hydrocodone, Acetaminophen, Trimethoprim, Pentoxifylline, Meprobamate, Naproxen, Ibuprofen, Diclofenac, Carbamazepine, Caffeine and Gemfibrizi.

Since the perfluorinated compounds (PFCs) have hydrophobic and lipophobic properties, they are used in a wide variety of industrial applications. They are used as polymer additives, fire retardants, antifouling agents, semiconductor cleaning solvents, surfactants, pesticides, Applications such as lubricants, paints, polishes, food packaging materials, flame retardant insulating materials, corrosion inhibitors, photosensitive coatings such as films, shampoos and personal hygiene products are incomprehensible.

The perfluorinated compounds (PFCs) are highly soluble in water and are detected at relatively high concentrations in wastewater, surface water, ground water, tap water and rainwater compared to other perfluorinated compounds.

Such degradation causes serious damage to humans and animals due to long-term stay in the environment and bioaccumulation and biomagnification.

The present invention relates to a biofilm treatment tank for removing minute harmful substances contained in a wastewater by oxidizing and decomposing a biofilm and a biofilm treatment tank for removing trace detrimental harmful substances such as O ₃ / H ₂ O ₂ / UV, an adsorption tank using expanded graphite, iron oxide, and magnesite, and a disinfection tank using chlorine.

Korean Registered Patent No. 10-0367219 (registered on December 23, 2002) Korean Registered Patent No. 10-0355196 (registered on September 23, 2002) Korean Registered Patent No. 10-1765889 (registered on August 01, 2017)

The present invention is advanced oxidation, adsorption system, biofilm treatment tank and to remove the trace amount of hazardous substances contained in and waste water through the oxidation and disintegration of biofilms (biofilm) which is formed by _{microbes, O 3 / H 2 O 2} / The biological, chemical, and physical decomposition reactions are carried out independently or in a complex process through the combination of the advanced oxidation treatment tank with the UV composition, the adsorption tank by the multilayer structure of expanded graphite, iron oxide, and magnesite, and the disinfection tank using chlorine It is an object of the present invention to provide a highly oxidizing and adsorbing system for treating trace amounts of harmful substances in wastewater that can effectively remove trace harmful substances contained in wastewater.

In order to achieve the above object,

The present invention relates to a sedimentation tank for sedimenting and removing sludge in inflow wastewater,

A biofilm treatment tank for filling the polyethylene carrier with 35 to 55 vol% of the total volume of the treatment tank and oxidizing and decomposing the trace harmful substances in the wastewater flowing into the settling tank by the biofilm formed by the microorganisms;

An ozone supply unit for supplying ozone (O ₃ ); A hydrogen peroxide supply unit for supplying hydrogen peroxide (H ₂ O ₂ ); UV irradiation unit for generating the UV through a UV lamp installed in the central treatment tank; place the O ₃ / H ₂ O complex configuration of the ₂ / UV including the hydroxyl radical (Hydroxyl radical) in the formation, promotion to the biofilm A high-level oxidation treatment tank for decomposing and treating the trace harmful substances in the wastewater discharged from the treatment tank,

An upper layer filled with expanded graphite, an intermediate layer filled with iron oxide, and a lower layer filled with magnesite have a laminated structure, and by the action of adsorption from the upper layer to the lower layer, the harmful substances in the lower and wastewater flowing in from the above- An adsorption tank for treatment,

And a sterilizing tank for removing trace harmful substances by injecting chlorine of 5 to 20 mg / L based on the influent water flowing through the adsorption tank. Thereby providing an adsorption system.

The present invention relates to a high oxidation and adsorption system for treating trace amounts of harmful substances in wastewater, comprising: a settling tank; A biofilm treatment tank for oxidizing and decomposing by a microorganism membrane formed by a microorganism; O ₃ / H ₂ O ₂ / UV to decompose the trace harmful substances; And a disinfection tank for removing trace harmful substances by injecting chlorine, wherein the biological, chemical, and physical decomposition reactions are carried out independently or in a composite process, It is possible to effectively remove trace harmful substances contained in the water.

As a specific example, the acetaminophen, ibuprofen, and caffeine components contained in the raw water were found to be substantially eliminated by removing 93.7% of acetaminophen, 98.6% of ibuprofen, and 98.2% of caffeine in the final treated water I could.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a general view of a highly oxidizing and adsorbing system for treating trace harmful substances in a wastewater according to the present invention; FIG.
2 is a perspective view showing a polyethylene carrier of a biofilm treatment tank constituting a high oxidation and adsorption system of the present invention.

Hereinafter, the technical construction according to the present invention will be described in detail with reference to the drawings.

As shown in Figure 1,

The high oxidation and adsorption system for treatment of trace harmful substances in the wastewater according to the present invention comprises a sedimentation tank 10 for precipitating and removing sludge in incoming wastewater,

The biofilm for filling the polyethylene carrier 201 with 35 to 55 vol% of the total volume of the treatment tank and oxidizing and decomposing the trace harmful substances in the wastewater discharged from the settling tank 10 by the biofilm formed by the microorganisms A treatment tank 20,

An ozone supply unit 31 for supplying ozone (O ₃ ); A hydrogen peroxide supply part 32 for supplying hydrogen peroxide (H ₂ O ₂ ); And a UV irradiating unit 33 for generating UV through a UV lamp 331 installed at the center of the treatment tank to form a complex structure of O ₃ / H ₂ O ₂ / UV, thereby forming a hydroxyl radical A high-level oxidation treatment tank 30 for decomposing and treating the trace harmful substances in the wastewater discharged from the biofilm treatment tank 20,

The upper layer 41 filled with expanded graphite, the intermediate layer 42 filled with iron oxide and the lower layer 43 filled with magnesite have a laminated structure and are adsorbed from the upper layer 41 to the lower layer 43, An adsorption tank 40 for decomposing and treating the trace harmful substances in the wastewater discharged from the oxidation treatment tank 30,

And a disinfection unit 50 for removing trace harmful substances by injecting chlorine of 5 to 20 mg / L based on the inflow water flowing through the adsorption tank 40.

The sludge contained in the wastewater is removed through a physical precipitation process in the sedimentation tank 10. The bottom / wastewater that has passed through the settling tank 10 flows into the biofilm treatment tank 20.

The biofilm treatment tank 20 biologically removes trace harmful substances using the polyethylene carrier 201.

The polyethylene carrier 201 is mounted between the support plates 202 of two mesh structures formed at positions spaced apart from the bottom surface of the biofilm treatment tank 20 by a predetermined distance, Of the total volume of the chamber.

When the volume occupied by the polyethylene carrier 201 is less than 35 vol%, the removal rate of trace harmful substances due to oxidation and decomposition of the biofilm formed by the microorganisms may be lowered. If the volume exceeds 55 vol%, the biofilm treatment The volume occupied by the polyethylene carrier 201 is maintained at 35 to 55 vol% of the total volume of the biofilm treatment tank 20 because the amount of the treated wastewater to be treated may be affected by the treatment tank 20 .

The treatment of trace harmful substances by the biofilm treatment tank 20 is performed by oxidizing and decomposing a biofilm formed by binding of a microorganism adhering to a solid surface and an exocrine secretory substance secreted by a microorganism.

As shown in FIG. 2, the polyethylene carrier 201 has a corrugated prong portion 201a having a plurality of fine corrugations formed on its inner and outer surfaces.

By facilitating the adhesion of the microorganisms through the corrugated jaws 201a, the treatment efficiency of the trace amount of toxic substances by the microorganisms can be increased.

The microfibers can not be easily attached and propagated on such a surface because the surface is smoothly formed in the state where the molding is performed due to the characteristics of the polyethylene resin. The use of a mesh-like polyethylene cylinder having fine wrinkles facilitates attachment and propagation of microorganisms.

The microorganisms fixed to the wrinkle chin 201a include photosynthetic bacteria, lactic acid bacteria, yeast, and the like. Preferably, a complex microorganism mixture consisting of a mixture of Lactobacillus sp., Acetobacteraceae and Rhodospirillaceae, molasses and medium are mixed at a weight ratio of 1: 1: 30 The microorganisms are activated at 19 to 22 ° C for 2 to 4 days and then supplied to the biofilm treatment tank 20 to improve the treatment efficiency of the trace harmful substances by the complex microorganisms.

Wherein the complex microorganism is composed of 85 to 95 wt% of Lactobacillus sp., 4.5 to 15 wt% of Acetobacteraceae, and 0.5 to 2.5 wt% of Rhodospirillaceae, do.

Wastewater subjected to the primary treatment through the biofilm treatment tank 20 flows into the advanced oxidation treatment tank 30 at the downstream stage.

As shown in FIG. 1, the advanced oxidation treatment tank 30 includes an ozone supply unit 31 for supplying ozone (O ₃ ); A hydrogen peroxide supply part 32 for supplying hydrogen peroxide (H ₂ O ₂ ); Form the composite structure of the _{O 3 / H 2 O 2 /} UV containing; UV irradiation section 33 for generating the UV through a UV lamp (331) installed in the heart treatment tank.

This complex composition of O ₃ / H ₂ O ₂ / UV effectively treats trace harmful substances through formation and promotion of hydroxyl radicals.

In particular, the O ₃ / H ₂ O ₂ /, but the composite structure of the UV are combined using ozone, hydrogen peroxide and UV, O ₃ and the injection amount of the ratio of H ₂ O ₂ 1: and to _{0.3 ~ 0.7 0 3 / H 2} O ₂ / UV, it is configured to improve OH radical generation 2.0 to 3.0 times more than ozone, hydrogen peroxide, and UV when used singly.

Ozone (O ₃₎ is generated in the gas state by ultraviolet ray or high pressure discharge using oxygen in the atmosphere or pure oxygen. When ozone is used for water treatment, ozone should be dissolved in water and reacted. However, ozone is low in solubility in water, so only very small amounts are dissolved in water. Ozone dissolved in water is very unstable and decomposes very quickly. Since ozone decomposes by reacting with hydroxyl group (OH-), the decomposition rate of ozone is greatly influenced by pH. Ozone is relatively stable in acidic form, but decomposition rate is accelerated by hydroxyl group as it goes to basic.

HO ₂ ^- , the conjugate base of hydrogen peroxide, decomposes ozone much faster than hydroxyl group (OH ^- ) to generate OH · radicals. According to this phenomenon, hydrogen peroxide is added to ozone to generate OH · radicals.

Ultraviolet irradiation differs in characteristics and principles according to wavelength, and has been used for various purposes such as disinfection and disinfection and organic matter removal. The photooxidation process that is removed by collision with organic photons is removed by the following two pathways.

First, the organic matter collides with a photon and becomes excited as shown in the following equations (1) and (2). The organic matter in the excited state reacts with oxygen to generate radical ions, and the organic matter is decomposed.

M + h? ---> M ^* -------------- (1)

_{^{M * + O 2 ---> M}} * + + O 2 - · -------------- (2)

The second is a pathway in which organic substances are decomposed by ultraviolet rays to generate organic radicals as shown in the following formulas (3) and (4), and the organic radicals combine with oxygen to generate oxidative organic radicals and participate in oxidation.

MX + hυ ---> M · + X. --------------- (3)

_{M · + O 2 ---> MO} 2 · --------------- (4)

The UV irradiator 33 is configured by providing an ultraviolet lamp 331 inside a quartz tube 332 in which TiO ₂ is coated to a thickness of 5,000 to 9,000 Å.

The quartz tube 332 is heated to an evaporation temperature of 1,800-2,200 ° C by using an electro beam generator on a TiO ₂ tablet to evaporate TiO _{2. The} temperature in the furnace is 310 ° C and the deposition rate is 2.5-4.0 Sec and a vacuum of 2.0 × 10 ^-5 torr, the quartz tube is spin-coated at 800~1,500 rpm to form a film with a thickness of 5,000~9,000 Å.

The adsorption tank 40 has an upper layer 41 filled with expanded graphite, an intermediate layer 42 filled with iron oxide and a lower layer 43 filled with magnesite having a laminated structure and extending from the upper layer 41 to the lower layer 43 Trace harmful substances are removed by adsorption.

Adsorption refers to the removal of a substrate from a solution using an adsorbent. Activated carbon in the adsorbent absorbs various kinds of organic compounds and is widely used in water treatment, high-order wastewater treatment, and organic wastewater treatment.

Adsorption refers to the aggregation of the substrate to the surface of the adsorbent, whereas absorption refers to the penetration of the collected substrate into the adsorbent.

Adsorption is usually divided into physical adsorption and chemical adsorption. Physical adsorption is mainly due to van der waals force and occurs reversibly. When the attraction force of the molecules between the solute and the adsorbent is greater than the attraction between the solute and the solvent, the solute sticks to the adsorbent surface. An example of physical adsorption is activated carbon. Activated carbon has numerous capillaries in the carbon particles, and the adsorbable surface includes the surface inside the void as well as the outer surface of the particle. In practice, the pore surface area is much larger than the surface area of the particles and most adsorption occurs at the pore surface.

The upper layer (41) is constituted by expanded graphite, and a trace amount of harmful substances is adsorbed and removed by the adsorption action of the expanded graphite.

The expanded graphite is washed with distilled water and dried in a constant temperature drier at 80 to 90 ° C for 40 to 60 hours. The natural graphite is dried in a tube furnace in a nitrogen furnace at a rate of 15 ° C / min Heat-treated at 800 to 1,200 ° C for 1 to 10 minutes, and then naturally cooled.

More specifically,

The natural graphite was washed with distilled water and dried in a constant temperature drier at 85 ° C. for 50 hours. The dried natural graphite was heated in a tube furnace at a rate of 15 ° C./min and heated at 800 ° C. for 1 minute After the heat treatment, it is natural cooling.

The optimum conditions for the expanded graphite are obtained by heating at 800 ° C for 1 minute, and the specific surface area of the expanded graphite is increased about 90 times as compared with the natural graphite. The size of pore size is larger than that of activated carbon.

The iron oxide has an internal porosity of 22%, an external porosity of 37%, and a surface area of 20 m 2 / g, and the magnesite has an internal porosity of 75%, an external porosity of 45%, and a surface area of 200 m 2 / g .

The disinfection tank 50 provides an effect of removing trace harmful substances by additional oxidation and disinfection by injecting 5 to 20 mg / L of chlorine into the inflow water that has passed through the adsorption tank 40, rather than a single treatment effect.

That is, the trace harmful substance is removed by chlorine oxidation. When the chlorine injection amount is less than 5 mg / L based on the influent water introduced from the adsorption tank 40, the treatment effect of the trace harmful substance by chlorine oxidation is insignificant, L, the amount of chlorine injected is preferably limited to a range of 5 to 20 mg / L on the basis of the influent water flowing from the adsorption tank 40, since the increase of the treatment effect is insignificant because it is insignificant.

The present invention relates to a high oxidation and adsorption system for treating trace amounts of harmful substances in wastewater, comprising: a settling tank; A biofilm treatment tank for oxidizing and decomposing by a microorganism membrane formed by a microorganism; O ₃ / H ₂ O ₂ / UV to decompose the trace harmful substances; And a disinfection tank for removing trace harmful substances by injecting chlorine, wherein the biological, chemical, and physical decomposition reactions are carried out independently or in a composite process, It is possible to effectively remove trace harmful substances contained in the water.

10: sedimentation tank 20: biofilm treatment tank
30: altitude oxidation treatment tank 31: ozone supply unit
32: hydrogen peroxide supply part 33: UV irradiation part
40: adsorption tank 41: upper layer
42: intermediate layer 43: lower layer
50: Disinfection tank 201: Polyethylene carrier
331: UV lamp 411: Expanded graphite 421: Iron oxide 431: Magnesite

Claims (5)

A sedimentation tank 10 for precipitating and removing sludge in the incoming wastewater,
The biofilm for filling the polyethylene carrier 201 with 35 to 55 vol% of the total volume of the treatment tank and oxidizing and decomposing the trace harmful substances in the wastewater discharged from the settling tank 10 by the biofilm formed by the microorganisms A treatment tank 20,
An ozone supply unit 31 for supplying ozone (O ₃ ); A hydrogen peroxide supply part 32 for supplying hydrogen peroxide (H ₂ O ₂ ); And a UV irradiating unit 33 for generating UV through a UV lamp 331 installed at the center of the treatment tank to form a complex structure of O ₃ / H ₂ O ₂ / UV, thereby forming a hydroxyl radical A high-level oxidation treatment tank 30 for decomposing and treating the trace harmful substances in the wastewater discharged from the biofilm treatment tank 20,
The upper layer 41 filled with expanded graphite, the intermediate layer 42 filled with iron oxide and the lower layer 43 filled with magnesite have a laminated structure and are adsorbed from the upper layer 41 to the lower layer 43, An adsorption tank 40 for decomposing and treating the trace harmful substances in the wastewater discharged from the oxidation treatment tank 30,
And a sterilizing tank (50) for removing trace harmful substances by injecting chlorine of 5 to 20 mg / L based on the influent water flowing through the adsorption tank (40). Advanced oxidation, adsorption system for treatment.
The method according to claim 1,
Wherein the polyethylene carrier (201) has a corrugated prong (201a) formed of a mesh-like cylindrical sphere and having a plurality of fine corrugations formed on the inner and outer surfaces thereof.
The method according to claim 1,
The UV irradiating unit 33 is formed by providing an ultraviolet lamp 331 inside a quartz tube 332 in which TiO ₂ is coated to a thickness of 5,000 to 9,000 A,
The quartz tube 332 is heated to an evaporation temperature of 1,800-2,200 ° C by using an electro beam generator on a TiO ₂ tablet to evaporate TiO _{2. The} temperature in the furnace is 310 ° C and the deposition rate is 2.5-4.0 Sec and a film thickness of 5,000 ~ 9,000 Å was formed under a vacuum of 2.0 × 10 ^-5 torr while rotating the quartz tube at 800~1,500 rpm under a vacuum of 2.0 × 10 ^-5 torr. Advanced oxidation, adsorption system for material treatment.
delete The method according to claim 1,
The expanded graphite 411 is washed with distilled water and dried in a constant temperature drier at 80 to 90 ° C. for 40 to 60 hours. The natural graphite is dried in a tube furnace in a nitrogen atmosphere at a rate of 15 ° C./min And heating it at a temperature of 800 to 1,200 ° C. for 1 to 10 minutes, followed by natural cooling, thereby producing an advanced oxidation and adsorption system for treating trace amounts of harmful substances in the wastewater.

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