KR20190128477A - Non-biodegradable amine waste water treatment method and apparatus of chloramine forming and uv-photolysis - Google Patents

Abstract

Provided are chlorine-UV composite oxidation water treatment method and apparatus for removing non-biodegradable amine wastewater, which are economical by injecting chlorine into the front end of a UV reactor at a predetermined pH range condition such that an existing oxidizer such as ozone, hydrogen peroxide or the like is not used in order to treat wastewater containing an excessive amount of a non-biodegradable amine nitrogen compound used in various industrial activities, lower possibility of additional pollution by making it not necessary to perform a subsequent adsorption process using material such as activated carbon, and provide operational convenience, reduce power consumption and used chemical amounts, and can prevent chemical mis-injection in advance by feedback controlling UV irradiation amounts and chlorine injection amounts through numerical analysis according to water quality characteristics of inflow raw water.

Description

Non-biodegradable AMINE WASTE WATER TREATMENT METHOD AND APPARATUS OF CHLORAMINE FORMING AND UV-PHOTOLYSIS}

The present invention relates to a method and apparatus for treating chlorine-ultraviolet complex oxidation water, and more particularly, in order to remove hardly decomposable amine compounds in wastewater, chlorine injection amount according to the concentration of amine compounds in wastewater and water quality conditions such as pH, DOC, and Carbonate ( The present invention relates to a method and apparatus for treating water by complex oxidation by variably selecting, controlling, and introducing chlorine dosage and ultraviolet radiation.

ammonia (0^o)로 나뉠 수 있다. 이러한 아민 화합물은 산업화의 고도화가 진행될수록 그 중요성이 더욱 커지고 있는데, 그 이유는 산업 전반적으로 탄소 배출 포집제로써 사용되며 (이산화탄소 등의 capture reagent) 거의 대다수의 원전에서 pH 조절제로써 높은 농도 (

30 wt%)로 사용 되기 때문이다. 대표적으로, 에탄올아민(ETA)은 현재 산업/원전 분야에서 그 중요성이 매우 부각되고 있는데, 이는 우수한 가스 포집 및 pH 조절 기능을 지님으로써 기존 사용되고 있는 아민 화합물들을 대체하는 대체제로써 큰 역할을 하고 있다. 그 외에도, piperidine, piperazine, 2-amino-2-methyl-1-propanol 등이 있다. 하지만, 산업 전반에 대한 큰 역할에도 불구하고 아민화합물의 처리를 위한 처리 시설은 미비한 실정이다. 실제로, 처리되지 않은 ETA가 그대로 방류되어 방류수 내의 COD가 높아지고 있는 상황이 보고되고 있다. 이러한 아민화합물은 종래 폐수 처리방식으로는 잘 제거가 되지 않는 난분해성 성질을 가지는데, 그 이유는 대부분 반응성이 높은 방향족 기능기를 가지지 않을 뿐 아니라 쉽게 biodegradable되지 않는 성질을 동시에 가지기 때문이다. 또한 그 구조가 bulk 하지 않고 아민기를 중심으로 탄소 사슬을 형성하는 친수성(hydrophilic) 특성을 지님으로 종래의 응집·흡착 기술로 쉽게 제거가 되지 않는다. 예를 들어, 혼화-응집 공정 및 침전공정은 수 ㎛의 수준의 콜로이드 입자성 물질에 응집제를 혼화-응집 공정에 첨가하여 플록(Floc)을 형성시킨 후, 침전지에서 중력 침강에 의해 플록을 제거시킨후 모래여과 공정에서 여과 층에 빠른 속도로 물을 통과시켜(운반 작용) 모래 여재로의 부착작용에 탁질을 제거하는 고액분리공정인데, 이러한 재래식 공정으로는 아민 화합물을 효과적으로 제거할 수 없다. 이와 마찬가지로 생물학적 처리방법 역시 아민 화합물에 대한 처리 효율이 낮고 넓은 부지와 많은 부대시설을 필요로 한다는 단점을 지니고 있다. 따라서 난분해성 유기물인 아민 화합물을 처리하기 위해 새로운 수처리 기술 개발이 요구되고 있는데, 기존 연구된 바에 의하면 전기화학적 처리방법 및 오존 산화 방법이 있다. 예를 들면, 전기화학적 처리방법의 경우, 낮은 처리효율과 높은 전력소모량으로 인해서 상기 ETA 화합물을 처리하기 위해서 전기 셀 구축 등 초기 투자비와 높은 운영비가 요구되기 때문에 현실적으로 도입하기 힘들다는 문제점이 있다. 오존처리 기술은 보편적으로 높은 반응성을 지니나 특정 화합물 외에 용존 유기물(DOC)과의 반응으로 인해 수질인자에 큰 영향을 받으며 특유의 냄새로 인한 거부감과 별도의 공간을 요구하는 반응조가 필요한데 이를 위한 유지보수 비용 및 인력도 만만치 않은 실정이다. 또한 후단에는 잔류 산화제를 제거 및 bromate등의 잔류 유해물질 제거를 위하여 활성탄 처리를 하여야 한다는 어려움이 존재한다. 그 외에 펜톤-자외선 결합 장치 (UV/fenton)를 통한 수처리 기술도 연구된 사례가 있으나 주로 라디칼 생성을 통한 제거 방식으로 국한되어 있어 처리효율이 낮으며, 그에 따른 처리비용이 기존 시설과 대비하여 상당 부분 높은 것으로 판단된다. 또한 미반응한 잔류 산화제의 제거를 위하여 별도의 환원제 (i.e. 입상 활성탄)와 같은 흡착 공정이 반드시 필요하기 때문에 약품 및 에너지 사용량이 증가하고, 이에 따라 생산단가를 증가시키는 원인이 되고 있다. 대부분의 단순 탄소 사슬기로 치환된 아민 화합물의 경우 OH 라디칼과의 반응상수가 매우 낮은 편이며 이로 인해 고도산화처리공법(AOP)의 장점이 발현되지 않는 단점이 있다. 따라서 난분해성 아민 폐수를 보편적이고 효과적으로 처리할 수 있는, 새로우면서도 적용가능성이 높은 (경제성, 시장 상황 고려) 수처리 기술 개발이 시급한 실정이다. Amine-compounds are generally divided into quarternary (4 ^o ), tertiary (3 ^o ), secondary (2 ^o ), primary (1 ^o ) and inorganic depending on the substitution state of the amine group.

divided by ammonia (0 ^o ). These amine compounds are becoming more important as the industrialization progresses, because they are used as carbon emission trapping agents (capturing reagents such as carbon dioxide) throughout the industry, and high concentrations as pH regulators in most nuclear power plants (

30 wt%). Representatively, ethanolamine (ETA) is currently of great importance in the industrial / nuclear field, which plays an important role as an alternative to the existing amine compounds by having excellent gas collection and pH control functions. In addition, there are piperidine, piperazine and 2-amino-2-methyl-1-propanol. However, despite the large role for the industry as a whole, treatment facilities for the treatment of amine compounds are insufficient. In fact, a situation is reported in which untreated ETA is discharged as it is and the COD in the effluent is increased. Such amine compounds have hardly decomposable properties that are not easily removed by conventional wastewater treatment methods because most of them have not only highly reactive aromatic functional groups but also have properties that are not easily biodegradable. In addition, since the structure is not bulky and has a hydrophilic characteristic of forming carbon chains around amine groups, it is not easily removed by conventional flocculation and adsorption techniques. For example, the mixing-aggregation process and the precipitation process add flocculants to the mixing-aggregation process to a colloidal particulate material having a level of several micrometers to form flocs, and then remove the flocs by gravity settling in the sedimentation basin. In the sand filtration process, a solid-liquid separation process removes the turbidity from the adhesion to the sand filter by passing the water through the filtration layer at a high speed (transporting action). Such a conventional process cannot effectively remove the amine compound. Similarly, biological treatment methods have disadvantages of low treatment efficiency for amine compounds, requiring large sites and many additional facilities. Therefore, there is a need for developing a new water treatment technology to treat amine compounds, which are hardly decomposable organic materials. Previous studies have shown that there are electrochemical treatment methods and ozone oxidation methods. For example, in the case of an electrochemical treatment method, it is difficult to introduce it realistically because an initial investment cost such as an electric cell construction and a high operating cost are required to process the ETA compound due to low processing efficiency and high power consumption. Ozone treatment technology is generally highly reactive, but it is affected by water quality factors due to the reaction with dissolved organic matter (DOC) in addition to specific compounds, and requires a reaction tank that requires a special space and rejection due to the characteristic odor. Costs and manpower are also abundant. In addition, there is a difficulty in that activated carbon must be treated to remove residual oxidants and residual harmful substances such as bromate. In addition, water treatment technology through Fenton-UV coupling device (UV / fenton) has been studied, but treatment efficiency is low because it is mainly limited to the removal method through radical generation, and the treatment cost is considerably higher than that of existing facilities. We believe the portion is high. In addition, since the adsorption process such as a separate reducing agent (ie granular activated carbon) is necessary for the removal of the unreacted residual oxidant, chemical and energy consumption increases, thereby increasing the production cost. In the case of the amine compound substituted with most simple carbon chain groups, the reaction constant with the OH radical is very low, and thus there is a disadvantage in that the advantages of the advanced oxidation treatment method (AOP) are not expressed. Therefore, there is an urgent need to develop a new and highly applicable water treatment technology (considering economic feasibility and market conditions) that can treat the hardly degradable amine wastewater universally and effectively.

 Aside from the development of the device, in order to effectively control the hardly degradable amine wastewater, a decision method for determining the chemical injection rate according to the concentration of the harmful substance needs to be introduced. In particular, variable control techniques based on raw water quality characteristics (pH, DOC, UV254, DON) must be in place to determine the appropriate input element strength (e.g. chemical dosage, UV dose, electrical strength) in some circumstances. However, the biological treatment, flocculation and sedimentation treatment, ozone, and Fenton-UV treatment technologies do not operate efficiently because the chemicals are injected in proportion to the residual chemical concentration without considering the characteristics of the incoming raw water. to be.

Republic of Korea Patent No. 10-1727148 Republic of Korea Patent No. 10-1533979 Republic of Korea Patent No. 10-0722929 Republic of Korea Patent No. 10-0670629

The technical problem to be achieved by the present invention is to solve the above problems, in order to remove the hardly decomposable amine compound in industrial wastewater, without using an existing oxidizing agent such as ozone or hydrogen peroxide, a subsequent oxidant deoxidation process such as activated carbon is required. To provide a method and apparatus for chlorine-ultraviolet combined oxidation free water treatment.

The technical problem to be achieved by the present invention is not limited to the technical problem mentioned above, and other technical problems not mentioned above may be clearly understood by those skilled in the art from the following description. There will be.

In order to achieve the above technical problem, an embodiment of the present invention comprises the steps of inputting the concentration of the target degradable amine to be removed from the influent water containing the hardly decomposable amine; Calculating target values of the chlorine injection amount and the UV irradiation amount of the removal-degradable amine to be removed; Calculating and evaluating the removal target hardly degradable amine removal rate based on the calculated target value to derive an evaluation value; Variably controlling the amount of chlorine injected and the amount of ultraviolet irradiation according to the calculated target value and the derived evaluation value; Injecting chlorine according to the variable controlled chlorine injection amount; And it provides a chlorine-ultraviolet complex oxidation water treatment method for the hardly decomposable amine wastewater treatment, characterized in that it comprises the step of irradiating ultraviolet rays according to the variable controlled ultraviolet irradiation amount.

In one embodiment of the present invention, the step of calculating the target value of the chlorine injection amount and the UV irradiation amount for the removal target hardly decomposable amine, determining the input chlorine concentration according to the removal target hardly decomposable amine concentration; Calculating an ultraviolet ray correction coefficient of the inflow source water; Calculating a radical blockage index of the inflow source water; Calculating a minimum ultraviolet ray concentration in consideration of the ultraviolet ray correction coefficient and the radical interference index; And calculating a target value of the chlorine injection amount and the ultraviolet irradiation amount.

In one embodiment of the present invention, the step of determining the input chlorine concentration according to the removal target hardly decomposable amine concentration is to determine the input chlorine concentration to more than twice the concentration of dissolved organic nitrogen (DON) of the influent. Can be.

In one embodiment of the present invention, the UV correction coefficient of the inflow source water may be calculated by the following equation (1), the radical disturbance index may be calculated by the following equation (2).

(1)

(One)

(In Formula (1), WF = water factor, A ₂₅₄ (cm ⁻¹ ) is the absorbance at 254 nm of the influent, L (cm) is the radius of the ultraviolet reactor.)

=

(2)

=

(2)

(In formula (2), DOC is dissolved organic carbon of influent.)

In one embodiment of the present invention, the step of variably controlling the chlorine injection amount and the UV irradiation amount according to the calculated target value and the derived evaluation value, the value obtained by dividing the target value by the evaluation value is not greater than 1.0 Re-evaluation by increasing the amount of ultraviolet radiation, if the value obtained by dividing the target value by the evaluation value is greater than 1.0 may be to re-evaluate by reducing the amount of ultraviolet radiation.

In order to achieve the above technical problem, another embodiment of the present invention is installed on the inlet source water pipe to measure the first water quality unit; A chlorine-ultraviolet injection-irradiation model predictive control unit which variably controls the chlorine injection amount and the ultraviolet irradiation amount according to the result measured by the first water quality measurement unit; A pH regulator input unit for introducing a hydrogen ion index (pH) regulator into the inflow source water according to the water quality measured by the first water quality measurement unit; A chlorine-ultraviolet combined oxidation apparatus for determining the chlorine input concentration and treating the inflow water according to the chlorine injection amount and the ultraviolet irradiation amount which are variably controlled through the model predictive control unit; And a second water quality measurement unit installed on the treated water pipe to measure the quality of the treated water, wherein the chlorine-UV composite oxidation reaction apparatus is equipped with a rapid injection stirrer to inject chlorine onto the inlet water pipe. Chlorine dosers; And a pipeline type ultraviolet reactor installed on a rear end of the inflow source water pipe and irradiating a variable amount of ultraviolet (UV) radiation controlled by the model predictive control unit. The chlorine-ultraviolet ray for hardly decomposable amine wastewater treatment comprising: Provided is a complex oxidation treatment apparatus.

In another embodiment of the present invention, the factors measured by the first water quality measurement unit are hydrogen ion index (pH), dissolved organic nitrogen (DON), dissolved organic carbon (DOC) and UV absorbance (UV ₂₅₄ ) in the influent water. ) May be included.

In another embodiment of the present invention, the chlorine-ultraviolet complex oxidation reaction apparatus may add the whole chlorine (HOCl) while maintaining a constant pH on the inlet water pipe.

In another embodiment of the present invention, the constant pH may be set in the range of 5 to 11.

In another embodiment of the present invention, the reaction time after the introduction of the whole chlorine (HOCl) before passing through the pipeline UV reactor may be 10 minutes or less.

In another embodiment of the present invention, the amount of chlorine introduced from the chlorine injector may be at least twice the concentration of dissolved organic nitrogen (DON) measured in the first water quality measurement unit.

In another embodiment of the present invention, the factors measured in the second water quality measurement unit include residual chlorine concentration, hydrogen ion index (pH), dissolved organic nitrogen (DON) and UV absorbance (UV ₂₅₄ ) in the treated water. can do.

In another embodiment of the present invention, the influent water may include one or more of ethanolamine, piperidine, piperazine and 2-amino-2-methyl-1-propanol.

According to the embodiment of the present invention, if the amine wastewater caused by the industrial use and hard decomposition characteristics of the industry is passed through the duct-type UV reactor after the introduction of prechlorine in a certain pH range, without using an oxidizing agent such as ozone or hydrogen peroxide, It can be effectively removed without the use of subsequent adsorption processes such as activated carbon.

According to the present invention, by providing feedback control of the chlorine injection amount and UV irradiation amount determined through the water quality characteristics and chlorine-ultraviolet composite oxidation numerical analysis of the inflow source water, it provides the convenience of operation, reduces the power consumption and drug consumption, and preemptive injection of chemicals To prevent it.

The chlorine-ultraviolet bonding method is a next generation advanced oxidation treatment (AOP) technology that is already being actively studied in drinking water treatment, but its purpose is also focused on the production of OH radicals. On the other hand, the chlorine-ultraviolet bonding method involves another conversion mechanism for the amine compound in addition to the radical generation. The content of the chlorinated-amine functional groups is that when the ultraviolet rays are irradiated to the chlorinated-amine functional group, the amine radicals are differentiated into additional by-products. Since it uses chlorine widely used in the existing water purification plant, there is no burden to use at all, and a separate reducing agent does not have to be used within the acceptance range, and the installation / operation cost is low and there is no difficulty in maintenance. In addition, the compact UV device has the advantage of not requiring a separate space, such as a separate reaction tank.

The effects of the present invention are not limited to the above-described effects, but should be understood to include all the effects deduced from the configuration of the invention described in the detailed description or claims of the present invention.

1 is a connection diagram of an apparatus for real-time monitoring of hardly degradable amine wastewater in raw water flowing into a wastewater treatment system.
2 is a block diagram of a real-time amine wastewater monitoring and control device for wastewater treatment.
3 is a block diagram of a chlorine-UV composite water treatment apparatus for removing hardly decomposable amine wastewater according to an embodiment of the present invention.
4 is a detailed block diagram of a chlorine-UV composite water treatment apparatus for removing hardly decomposable amine wastewater according to a first embodiment of the present invention.
5 is a detailed block diagram of a chlorine-UV composite water treatment apparatus for removing hardly decomposable amine wastewater according to a second embodiment of the present invention.
FIG. 6 is a view illustrating concentration changes of HOCl / OCl- and ETA-H + / ETA according to pH change in an embodiment of the present invention.
7 is a scheme showing a detailed mechanism and pathway of breakpoint chlorination of ammonia.
Figure 8 shows the conversion of ammonia and the production of nitrate in a single chlorine process and UV / chlorine combined process.
9 is a view showing that the removal efficiency of ethanolamine (ETA) compared with the existing water treatment processes as a result of applying the chlorine-UV composite oxidation water treatment apparatus according to an embodiment of the present invention.
10 is a view showing the amount of reduction and by-products generated by the chlorine-ultraviolet composite water treatment of ethanolamine (ETA) as a result of applying the chlorine-ultraviolet composite water treatment apparatus according to the embodiment of the present invention.

Hereinafter, with reference to the accompanying drawings will be described the present invention. As those skilled in the art would realize, the described embodiments may be modified in various different ways, all without departing from the spirit or scope of the present invention. In the drawings, parts irrelevant to the description are omitted in order to clearly describe the present invention, and like reference numerals designate like parts throughout the specification.

Throughout the specification, when a part is said to be "connected (connected, contacted, coupled)" with another part, it is not only "directly connected" but also "indirectly connected" with another member in between. "Includes the case. In addition, when a part is said to "include" a certain component, this means that it may further include other components, without excluding the other components unless otherwise stated.

The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. Singular expressions include plural expressions unless the context clearly indicates otherwise. As used herein, the terms "comprise" or "have" are intended to indicate that there is a feature, number, step, action, component, part, or combination thereof described on the specification, and one or more other features. It is to be understood that the present invention does not exclude the possibility of the presence or the addition of numbers, steps, operations, components, components, or a combination thereof.

Hereinafter, exemplary embodiments of the present invention will be described in detail with reference to the accompanying drawings.

One embodiment of the present invention comprises the steps of inputting the concentration of the difficult-degradable amine to be removed from the influent source containing the hard-degradable amine; Calculating target values of the chlorine injection amount and the UV irradiation amount of the removal-degradable amine to be removed; Calculating and evaluating the removal target hardly degradable amine removal rate based on the calculated target value to derive an evaluation value; Variably controlling the amount of chlorine injected and the amount of ultraviolet irradiation according to the calculated target value and the derived evaluation value; Injecting chlorine according to the variable controlled chlorine injection amount; And it provides a chlorine-ultraviolet complex oxidation water treatment method for the hardly decomposable amine wastewater treatment, characterized in that it comprises the step of irradiating ultraviolet rays according to the variable controlled ultraviolet irradiation amount.

Calculating the target values of the chlorine injection amount and the ultraviolet irradiation amount for the removal target degradable amine, Determining the input chlorine concentration according to the removal target degradable amine concentration; Calculating an ultraviolet ray correction coefficient of the inflow source water; Calculating a radical blockage index of the inflow source water; Calculating a minimum ultraviolet ray concentration in consideration of the ultraviolet ray correction coefficient and the radical interference index; And calculating the target values of the chlorine injection amount and the ultraviolet irradiation amount.

The removed hardly decomposable amine is a hardly decomposable amine compound comprising at least one of ethanolamine, piperidine, piperazine and 2-amino-2-methyl-1-propanol. Dissolved organic nitrogen (DON) concentration of the inflow source water may be measured and the concentration of chlorine added may be determined to be twice or more of the concentration.

The UV correction coefficient of the inflow source water may be calculated by the following equation (1), and the radical interference index may be calculated by the following equation (2).

(1)

(One)

(In Formula (1), WF = water factor, A ₂₅₄ (cm ⁻¹ ) is the absorbance at 254 nm of the influent, L (cm) is the radius of the ultraviolet reactor.)

=

(2)

=

(2)

(In formula (2), DOC is dissolved organic carbon of influent.)

According to the calculated target value and the derived evaluation value, variably controlling the chlorine injection amount and the ultraviolet irradiation amount, if the value obtained by dividing the target value by the evaluation value is not greater than 1.0, increasing the ultraviolet irradiation dose and re-evaluating the When a value obtained by dividing a target value by the evaluation value is greater than 1.0, the radiation dose may be reduced and reevaluated. In other words, when the target value is smaller than the evaluation value, the removal of the influent material was not made sufficiently, so that the amount of ultraviolet radiation was increased. When the target value was larger than the evaluation value, the amount of the ultraviolet light was increased.

1 is a connection diagram of a real-time monitoring device of dissolved organic nitrogen (DON) concentration in raw water flowing into a wastewater treatment system.

Referring to Figure 1, the real-time monitoring device of the DON concentration flowing into the wastewater treatment system includes an input launching well (1), a flow meter (3), a chlorine discharge device (7) and a monitoring device (10), wherein The monitoring device 10 includes: a first measuring unit 11 measuring the concentration of DON contained in raw water in real time using a colorimetric method through dyeing; A second measuring unit 13 measuring pH of raw water in real time; A comparison unit 15 that determines whether or not the measured DON concentration is equal to or greater than a preset reference value; And in response to the output of the comparison unit 15, the alarm unit 17 for generating an alarm when the measured DON concentration is more than the reference value and outputs a control signal for controlling the chlorine injection and ultraviolet irradiation injection timing for DON processing Include.

In the case of the real-time monitoring device of the DON concentration in the raw water flowing into the wastewater treatment system, the real-time monitoring device and method of the DON concentration enables continuous measurement of the DON concentration in real time, the measuring method is simple, and the wastewater treatment in the field application. By measuring DON concentrations in the raw and final treated water of the system, the concentration of amine compounds can also be determined quantitatively.

2 is a block diagram of a real-time amine wastewater monitoring and control device for wastewater treatment

2, the real-time amine wastewater monitoring and control device for wastewater treatment, real-time monitoring the concentration of DON contained in the influent source water, and using the raw water quality characteristics to control the chlorine injection amount and UV irradiation amount of the chlorine-ultraviolet complex process As the apparatus, the inflow water storage facility 21, the inflow water pipe 22, the flow meter 23, the water quality measuring unit 24, the chlorine-ultraviolet composite process control unit 25, the low pressure lamp ultraviolet treatment unit 26, chlorine water Storage facility 27 and chlorine water injection pump 28 is included.

In the case of the above-described real-time amine wastewater monitoring and control device for wastewater treatment, in a water treatment process in which a chlorine-ultraviolet complex process is introduced to remove amine wastewater, chlorine is controlled by controlling the amount of chlorine injected in accordance with the DON concentration of the influent raw water. It is possible to prevent the injection of excessive or small amount, and also to save the power consumption and the chlorine injection amount of the whole system by determining the amount of ultraviolet irradiation using the water quality measuring unit and raw water quality characteristics.

Hereinafter, the chlorine-ultraviolet composite water treatment apparatus for removing the amine wastewater according to the embodiment of the present invention will be described with reference to FIGS. 3 to 7, and the chlorine- according to the embodiment of the present invention with reference to FIGS. 8 to 11. The variable control method of the chlorine injection amount and the UV irradiation amount using the UV composite water treatment apparatus will be described in detail.

<Chlorine-UV composite water treatment device 100>

3 is a block diagram of a chlorine-UV composite water treatment apparatus for removing amine wastewater according to an embodiment of the present invention.

Referring to FIG. 3, the chlorine-UV composite water treatment apparatus 100 for removing amine wastewater according to an embodiment of the present invention includes a first water quality measuring unit 110, a hardly decomposable amine wastewater excess inflow determination unit 120, And a chlorine-ultraviolet injection-irradiation model predictive control unit 130, a second water quality measurement unit 140, a hydrogen ion index (pH) regulator input unit 150, and a chlorine-ultraviolet complex oxidation reaction device 160.

First, the amine wastewater may include a compound having an amine function in addition to ethanolamine, piperidine, piperazine, 2-amino-2-methyl-1-propanol and the like.

The first water quality measuring unit 110 is installed on the inflow source water pipe to measure the water quality. At this time, the first water quality measurement unit 110 is installed an analyzer capable of measuring the hydrogen ion index (pH), dissolved organic nitrogen (DON) and dissolved organic carbon (DOC), UV absorbance (UV ₂₅₄ ). Here, the first water quality measurement unit may be attached to a sensor for measuring the dissolved oil and inorganic nitrogen (DON, DIN) by the colorimetric reaction of the sample continuously collected from the inlet source pipe with the azo compound, Continuously taken samples can be analyzed for dissolved organic carbon (DOC), pH and absorbance.

The non-degradable amine wastewater excess inflow determination unit 120 is a process in which the concentration of the non-degradable amine wastewater compound is adjusted to the existing operating conditions through the dissolved organic nitrogen (DON) and various measurement values measured by the first water quality measurement unit 110. Determine if you have an excess of the concentration. The decision made by the determination unit is further embodied by the next chlorine-ultraviolet injection-irradiation model predictive control unit 130.

The chlorine-ultraviolet injection-irradiation model predictive control unit 130 controls the chlorine injection amount and the ultraviolet irradiation amount in accordance with the quantity of the inflow water and the hardly decomposable amine wastewater concentration. That is, the chlorine-ultraviolet injection-irradiation model prediction control unit 130 calculates the chlorine injection amount and the ultraviolet irradiation amount by numerical calculation and controls the variable amount according to the quantity of inflow water and the concentration of the hardly degradable amine wastewater.

The second water quality measuring unit 140 is installed on the raw water pipe of the treated water passing through the pipeline type ultraviolet reactor to measure the water quality. Specifically, the second water quality measurement unit 140 is a residual chlorine concentration and hydrogen ion index (pH) at the rear end of the pipeline type UV reactor 160 in order to prevent the chlorine mis-injection and to ensure the oxidation capacity by the residual chlorine in the drainage basin. Dissolved organic nitrogen (DON) and UV absorbance (UV ₂₅₄ ).

The hydrogen ion index (pH) regulator input unit 150 injects a hydrogen ion index (pH) regulator into the raw water according to the raw water pH measured by the first water quality measurement unit (110). For example, the pH regulator input unit 150 may inject carbon dioxide gas or sulfuric acid on the conduit to maintain the pH of the raw water in the range of 5 to 11.

The chlorine-ultraviolet combined oxidation reaction apparatus 160 is a chlorine-ultraviolet rays combined apparatus for treating inflow water. The chlorine-ultraviolet complex oxidation reaction apparatus 160 determines whether chlorine is injected and concentration, and through the chlorine-ultraviolet injection-irradiation model predictive control unit 130. Influent water is treated according to the variable controlled chlorine injection amount and UV irradiation amount.

On the other hand, Figure 4 is a specific block diagram of a chlorine-UV composite water treatment apparatus for removing the hardly decomposable amine wastewater according to the first embodiment of the present invention.

4, in the chlorine-ultraviolet composite water treatment apparatus for removing the hardly decomposable amine wastewater according to the first embodiment of the present invention, the chlorine-ultraviolet combined oxidation apparatus 160 is the chlorine-ultraviolet injection-irradiation amount A chlorine injector variablely controlled by the model predictive control unit 130, and equipped with a rapid injection stirrer to inject chlorine water onto the inlet water pipe; And a UV irradiation amount is variably controlled by the chlorine-ultraviolet injection-irradiation model predictive control unit 130 and is installed on an inlet water pipe of the rear end of the chlorine injector 161 to irradiate ultraviolet (UV) light. 162 may be included.

In the chlorine-ultraviolet composite water treatment apparatus for removing the hardly decomposable amine wastewater according to the first embodiment of the present invention, the pH regulator input unit 150 is installed in the pretreatment process and the chlorine-ultraviolet complex reaction apparatus is installed in the post treatment process. As a chlorine-ultraviolet composite water treatment apparatus having a post-treatment concept, the chlorine-ultraviolet composite oxidation reaction apparatus 160 has an additional oxidation capacity by residual chlorine without a subsequent activated carbon adsorption process.

The chlorine-ultraviolet composite water treatment apparatus for removing the hardly decomposable amine wastewater according to the first embodiment of the present invention, in the conventional wastewater treatment system consisting of a mixing-aggregation process 210, a precipitation-filtration process 220, etc. -After the filter paper 220, the low pressure ultraviolet lamp is configured as a pipeline type ultraviolet reactor 162, but a chlorine injector 161 equipped with a rapid injection stirrer is installed at the front end of the ultraviolet reactor 162.

On the other hand, Figure 5 is a specific block diagram of a chlorine-UV composite water treatment apparatus for removing the hardly decomposable amine wastewater according to the second embodiment of the present invention.

5, in the chlorine-ultraviolet composite water treatment apparatus for removing the hardly decomposable amine wastewater according to the second embodiment of the present invention, the pH adjuster input unit 150 and the chlorine input unit 161 are installed in a pretreatment process. A chlorine-ultraviolet combined oxidation water treatment apparatus of a pre-chlorine treatment concept composed of an ultraviolet reactor 162 at a rear end of a conventional wastewater treatment system, wherein the chlorine-ultraviolet combined oxidation reaction apparatus 160 has a constant pH without a subsequent activated carbon adsorption process. While maintaining the conditions, the whole chlorine (HOCl) is added.

Meanwhile, the principle and operation of the chlorine-ultraviolet composite water treatment apparatus 100 for removing the hardly decomposable amine wastewater having the configuration of FIGS. 3 to 4 will be described in detail.

First, the free chlorine introduced by the chlorine injector 151 equipped with the rapid injection stirrer applied to the chlorine-ultraviolet complex water treatment device 100 for removing the hardly decomposable amine wastewater according to the embodiment of the present invention is hardly decomposable amine. It reacts at a significant rate (k> 10 ² ) to form chlorinated-amine byproducts. It should be noted that free chlorine and hardly decomposable amine wastewater are not present in one form, but because they are present in HOCl / OCl ⁻ and RnNH / RnNH ₂ ⁺ states based on their pKa values, depending on the pH of the water. It is possible to roughly calculate each distribution rate through the pH measured by the first water quality measuring unit 110 (see FIG. 6), thereby selectively maintaining the pH range of 5 to 11 and predicting the chlorine-ultraviolet injection-irradiation model. In the unit 120 is controlled according to the free chlorine injection amount by the numerical operation. According to the controlled chlorine injection amount, all the chlorine (HOCl) is introduced into the inlet water supply line, and the reaction time is less than 10 minutes after the introduction of the whole chlorine (HOCl) before passing through the tubular UV reactor. Most of the reaction is completed in 10 minutes or less, more preferably 99% or more of the reaction is completed within 5 minutes.

Next, the chlorinated amine by-product reacts very easily with ultraviolet light and splits into two radicals, one being an amine radical and the other being broken down into a chlorine radical. The resulting chlorine radicals can be used again as a means of the AOP process, but the effect is insignificant, while the amine radicals change their structure by intramolecular radical reactions to form new byproducts.

In addition, when the residual free chlorine remaining after reacting with the amine wastewater reacts with the ultraviolet rays, it generates hydroxide radicals and chlorine radicals, which may also be useful for treating the amine wastewater. In particular, chlorine (HOCl) has a higher molar extinction coefficient (ε) and quantum yield (Φ) at a lower pressure ultraviolet wavelength band (254 nm) than conventional hydrogen peroxide (H ₂ O ₂ ), and the reaction rate constant with OH radicals is lower. Therefore, when irradiated with the same UV energy, it is known to generate more OH radicals than hydrogen peroxide, but it is characterized by a lot of influence by pH. This is because the molar extinction coefficient (ε) and the quantum yield (Φ) have similar values for OCl ⁻ , but the reaction rate constant with OH radicals is remarkably high. Thus, at high pH (> 8) it has disadvantageous characteristics. However, the process of generating OH radicals due to photolysis of residual free chlorine is not an important mechanism in the chlorine-ultraviolet complex water treatment apparatus for removing amine wastewater, so the pH control for this is negligible.

Therefore, the chlorine-ultraviolet composite water treatment process according to the embodiment of the present invention may be performed at a pH range of 5 to 11, and the efficiency of the chlorine-ultraviolet composite water treatment apparatus 100 for removing a target substance outside the range may be lowered. Monitoring the pH when measuring raw water quality, maintaining the pH within the range of 5 to 11, or increasing the chlorine injection amount or reaction time in the chlorine-ultraviolet injection-irradiation model predictive control unit 120 (at least 5 minutes). So that hardly degradable wastewater is treated in raw water quality outside the pH range.

In addition, the amount of free chlorine injected is measured in the first water quality measurement unit 110 of the chlorine-ultraviolet combined oxidation water treatment device 100 according to the embodiment of the present invention in consideration of consumption by the raw water matrix and securing the oxidation capacity of the rear stage. Inject about twice as much as the concentration of nitrogen (DON). In practice, excess chlorine is not required to remove amine wastewater, but more than twice as much chlorine is injected in consideration of raw water matrix demand and removal of inorganic chloramines. In addition, while monitoring the residual chlorine concentration, hydrogen ion index (pH), dissolved organic nitrogen (DON) and UV absorbance (UV ₂₅₄ ) in the second water quality measurement unit 110 to measure the oxidation capacity of the rear stage.

In addition, the UV intensity of the pipeline UV reactor 151 may be variably controlled by numerically calculating the UV intensity through a model in which the flow rate of the inflow water and the UV absorbance (transmittance) of the raw water quality matrix and the concentration of the OH radical blocker are considered. .

Specifically, the embodiment of the present invention, as shown in Figure 3, using a high-efficiency chlorine-ultraviolet composite water treatment apparatus and using it to control the amount of chlorine injection and UV irradiation variable according to the concentration and water quality characteristics of the amine wastewater in the incoming raw water Provide a way to. That is, the chlorine-ultraviolet composite water treatment device 100 according to the embodiment of the present invention is a combined oxidation of the chlorine-ultraviolet water treatment device and influent amine wastewater to treat the hardly decomposable amine compound introduced from an industrial wastewater source. The present invention relates to a method for selecting and controlling the amount of chlorine injected and the amount of UV irradiation in accordance with the concentration.

Compared with the conventional high-oxidation technologies such as ozone, ozone-hydrogen peroxide and ultraviolet-hydrogen peroxide, the chlorine-ultraviolet composite water treatment apparatus 100 according to the embodiment of the present invention is characterized in that it does not require an activated carbon process as a subsequent process and Use as an oxidant, and entails additional photolysis reactions following N-Cl bonds as well as reactions by radicals.

Specifically, chlorine generates more OH radicals than hydrogen peroxide under the same UV irradiation due to the advantage of having a higher molar extinction coefficient and higher quantum yield than OH radicals and lower OH radicals. Can be operated. In the case of residual chlorine, it can be used as a continuous reaction as a breakpoint chlorination for ammonia generated by irradiating chlorinated-amine functional groups or an oxidant for further chlorinated-ammonia photolysis.

In the case of the conventional UV-hydrogen peroxide process, the absorbance coefficient (ε) of hydrogen peroxide at 254 nm, which is a low-pressure lamp wavelength band, is very small, 20 M ^-1 cm ^-1 , which is more than 80% of the injected hydrogen peroxide solution. Even after this ultraviolet contact, it is emitted in a residual state. Subsequent processes for treating this should involve activated carbon and the like, and due to the very high reactivity of the OH radicals and hydrogen peroxide (k = 2.7x10 ⁷ M ^-1 s ^-1 ), the OH radicals produced are again extinguished by residual hydrogen peroxide. Has disadvantages

On the contrary, in the chlorine-ultraviolet composite water treatment apparatus 100 according to the embodiment of the present invention, it is represented by the following Chemical Formula 1 and 2 which is rapidly decomposed after N-Cl bond generation rather than the effectiveness of removing contaminants due to OH radical generation.

<Formula 1>

<Formula 2>

In this case, the universal absorbance coefficient (ε) of the N-Cl bond is about 350 M ⁻¹ cm ⁻¹ and the quantum yield (Φ) has a universal value of 0.6, which is much higher than the chlorine and hydrogen peroxide. . Accordingly, the chlorine-ultraviolet composite device 100 according to the embodiment of the present invention may remove the hardly decomposable amine wastewater that does not react well with the OH radical at the same time as the hardly-decomposable wastewater requires highly oxidation treatment.

In an embodiment of the invention, the first water quality measurement unit 110 is a device for measuring the hydrogen ion index (pH), dissolved organic nitrogen (DON) and dissolved organic carbon (DOC), UV absorbance (UV ₂₅₄ ) As a water quality monitoring unit, the concentration of the amine wastewater compound is measured by dissolved organic nitrogen, and the amine wastewater removal rate according to the raw water characteristics is evaluated by using hydrogen ion index (pH), dissolved organic carbon (DOC) and UV absorbance (UV ₂₅₄ ). In the reaction model for calculating the chlorine-ultraviolet injection-irradiation, the ultraviolet water factor (WF) (Equation (1)) and the radical generation disturbance factor (Equation (2)) in consideration of the UV transmittance are calculated.

(1)

(One)

Here, A ₂₅₄ (cm ^-1 ) represents the absorbance at 254 nm of the influent and L (cm) represents the radius of the ultraviolet reactor. The calculated WF can be used to determine the target dose of ultraviolet light for removal of the amine wastewater compound.

=

(2)

=

(2)

Here, HOCl is not included because the reaction constant with the OH radical is relatively small. Bicarbonate / carbonate ions are also inorganic water quality factors that can react with OH radicals, but do not include them because they do not have a major effect. The HOCl / OCl ⁻ distribution is calculated by considering pH using Equation 1 below.

<Equation 1>

Here, pKa represents a dissociation constant, where pKa of HOCl / OCl ⁻ is given as 7.5. The equation for predicting the removal rate thus obtained can be obtained by a much simpler formula than the oxidation reaction by conventional radicals.

UV / chlorine bonding process for the amine compound of the present invention is a direct conversion by ultraviolet (k _UV ), conversion to chloramines by photolysis (k _{N-Cl UV} ), and radicals generated by photolysis of residual chlorine Conversion by k _OH The first direct conversion by ultraviolet light is limited only to amine compounds with chromophores, not direct conversion to amine groups because of the low light absorption properties of the amine groups (ε _UV ). Therefore, the present invention will not be considered. Considering the second and third converter operation, the reaction rate equation is shown in Equation 2 below. Considering that the second converter operation is the first reaction rate equation and the third conversion operation is the second reaction rate equation, Equation 2 is established as follows.

<Equation 2>

Here, k _{N-Cl UV} t and [OH ·] _ss t is composed of various components, which can be expanded by the following equation (3), respectively.

<Equation 3>

Therefore, the conversion (k _{N-Cl UV} ) rate by photolysis after conversion to chloramines can be predicted in advance if the absorption coefficient and quantum yield of chlorinated form of amine compound can be obtained. In addition, the conversion (k _{OH ·} ) rate due to radicals generated due to photolysis of residual chlorine can be predicted in advance if a factor for generating radicals in the aqueous system is obtained.

Other hardly decomposable nitrogen compounds (amide-based or hetero-aromatic compounds other than amine groups) can be collected and analyzed by the operator and input their type and concentration. When the concentration of the other hardly decomposable nitrogen compounds increases, the concentration of the chlorine added 2-3 times is increased because the N-Cl photolysis as well as the OH radicals generated by the photolysis of chlorine must be removed.

In the present invention, the application of the chlorine-ultraviolet composite device for the hardly decomposable amine compound has various advantages due to additional mechanisms. Residual chlorine is very low and ammonia is decomposed into harmless natural substances such as nitrite, nitrate and N ₂ gas due to breakpoint chlorination and N-Cl photolysis.

The generated ammonia is decomposed through the breakpoint chlorination process by reacting with the residual chlorine. Referring to FIG. 7, a process of generating NOH, which is an intermediate, is decomposed into N ₂ gas. As in Equation 2, NH ₃ easily reacts with chlorine to form NH ₂ Cl and NHCl ₂ , but hardly forms NCl ₃ . As such NH ₃ is rapidly converted to the chloramine group (NH ₂ Cl, NHCl ₂ ) in the presence of excess chlorine which is finally decomposed into N ₂ gas by reaction with the intermediate product (NOH). Excess ammonia produced as a by-product of ETA in the present invention can be decomposed easily and quickly in this manner by reacting with residual chlorine.

In addition, in the present invention, there is an additional mechanism by which ammonia can be decomposed, which is a case where it is destroyed by UV at the same time of production. Since ETA cannot be removed by chlorine alone, it must be accompanied by UV to remove it. The main by-product produced is ammonia. This ammonia reacts rapidly with residual chlorine to form chloramine groups (NH ₂ Cl, NHCl ₂ ), which are rapidly broken down into nitrate under UV irradiation.

Referring to FIG. 8, which compares two mechanisms capable of decomposing ammonia generated in the present invention, it can be seen that breakpoint chlorination does not work well in the presence of UV. This is because chloramine groups (NH ₂ Cl, NHCl ₂ ), which can form NOH and react with it to be decomposed into N ₂ gas, are already removed and eliminated by UV. Therefore, nitrate production by chloramine photolysis is the main mechanism when passing through the UV reactor, and N ₂ gas generation by breakpoint chlorination of residual chlorine is the main mechanism after passing through the UV reactor.

In Figure 9 shows the treatment efficiency of ETA by various water treatment process and the energy consumption to achieve this, it can be seen that the UV / chlorine process is the fastest removal time at the same concentration of the injected oxidant and the energy consumption is also the least. By introducing the chlorine / ultraviolet combination process, it can be seen that up to 80% of the ETA, which is difficult to remove only by the chlorine or ultraviolet process, can be removed. The chlorine proposed in the present invention not only drastically reduces the cost compared to the chemicals used in the existing treatment technology (eg, ozone, fruit), but also reduces the required contact time (hours-> minutes), and thus the operation and maintenance costs. Can be reduced. Furthermore, if we consider water quality factors such as DOC, CO ₃ ^2- , and NO ₃ ^2- in actual wastewater, the above difference can be expected to be wider. This is because the O3, OH radical demand effect is more than the DOC light screening effect. Because it is larger. Since the photolysis of chlorinated form compounds is the main oxidation method, not the oxidation method using radicals generated from the photolysis of residual chlorine, the concentration of dissolved organic matter (DOC), which is a radical scavenger, is relatively low. (Easy to remove even at high organic concentrations). As a result, the effect of the UV / chlorine process on the amine compound proposed in the present invention is an effect that can be obtained by determining the conversion by the chloramine photolysis effect as well as the radical reaction as the main pathway.

FIG. 10 shows the conversion of ETA and the generation of major by-products according to the UV / chlorine treatment of ETA, wherein the experimental condition is a ratio of [ETA]: [HOCl] = 1: 1. Aldehyde and ammonia is generated in the main by-product is ammonia chloramine (chloramines) to be converted and immediately after the breakpoint chlorination or photolysis N ₂ gas, nitrate (NO ₃ ^-) under the residual chlorine present ^- the mineralization in the longitudinal, nitrite (NO ₂₎ The total nitrogen in the water may decrease. In addition, the produced ammonia can be easily processed by biological treatment of the latter stage, and at the same time, the generated aldehyde by-products can be treated and removed on the same principle.

As such, UV / chlorine bonding process has an additional conversion mechanism for nitrogen compounds compared to existing water treatment technologies (ozone / fruit water, fruit tree / ultraviolet), which enables effective treatment, as well as nitrogen compounds in the target wastewater due to improved radical generation ability. Rather, it has the potential to contribute to the removal of various contaminants, leading to a reduction in the overall TOC of the waste water.

After all, according to an embodiment of the present invention, by providing feedback control of the UV irradiation amount and the chlorine injection amount determined through the numerical analysis according to the water quality characteristics of the inflow water, to provide the convenience of operation, to reduce the power consumption and chemical consumption, and to reduce the chemical injection You can prevent it in advance.

The foregoing description of the present invention is intended for illustration, and it will be understood by those skilled in the art that the present invention may be easily modified in other specific forms without changing the technical spirit or essential features of the present invention. will be. Therefore, it should be understood that the embodiments described above are exemplary in all respects and not restrictive. For example, each component described as a single type may be implemented in a distributed manner, and similarly, components described as distributed may be implemented in a combined form.

The scope of the present invention is represented by the following claims, and it should be construed that all changes or modifications derived from the meaning and scope of the claims and their equivalents are included in the scope of the present invention.

100: chlorine-ultraviolet combined oxidation water treatment device
110: first water quality measurement unit
120: hardly decomposable amine wastewater excess inflow determination unit
130: chlorine-ultraviolet injection-irradiation model predictive control unit
140: second water quality measurement unit
150: hydrogen ion index (pH) regulator input unit
160: chlorine-ultraviolet combined oxidation apparatus
161: chlorine injector
162: pipeline ultraviolet reactor
170: flocculant injection unit
210: mixed-agglomerate
220: sedimentation-filter
230: drain

Claims (14)

Inputting the concentration of the hardly decomposable amine to be removed from the influent water comprising the hardly decomposable amine;
Calculating target values of the chlorine injection amount and the UV irradiation amount of the removal-degradable amine to be removed;
Calculating and evaluating the removal target hardly degradable amine removal rate based on the calculated target value to derive an evaluation value;
Variably controlling the amount of chlorine injected and the amount of ultraviolet irradiation according to the calculated target value and the derived evaluation value;
Injecting chlorine according to the variable controlled chlorine injection amount; And
The chlorine-ultraviolet composite oxidation water treatment method for the hardly decomposable amine wastewater treatment, characterized in that it comprises the step of irradiating ultraviolet rays according to the variable controlled ultraviolet irradiation amount.
The method of claim 1,
Calculating a target value of the chlorine injection amount and the ultraviolet irradiation amount for the removal target degradable amine,
Determining the input chlorine concentration according to the removal target degradable amine concentration;
Calculating an ultraviolet ray correction coefficient of the inflow source water;
Calculating a radical blockage index of the inflow source water;
Calculating a minimum ultraviolet ray concentration in consideration of the ultraviolet ray correction coefficient and the radical interference index; And
A method for treating chlorine-ultraviolet complex oxidation water for treatment of hardly decomposable amine wastewater, comprising the step of calculating target values of chlorine injection amount and ultraviolet irradiation amount.
The method of claim 2,
Determining the input chlorine concentration according to the removal target degradable amine concentration,
The chlorine-ultraviolet combined oxidation water treatment method for the hardly decomposable amine wastewater treatment, characterized in that the input chlorine concentration is determined to be at least two times the concentration of dissolved organic nitrogen (DON) of the influent.
The method of claim 2,
The chlorine-ultraviolet composite oxidation water treatment method for the hardly decomposable amine wastewater treatment, characterized in that the UV correction coefficient of the inflow source water is calculated by the following equation (1).

(One)
(In Formula (1), WF = water factor, A ₂₅₄ (cm ⁻¹ ) is the absorbance at 254 nm of the influent, L (cm) is the radius of the ultraviolet reactor.)
The method of claim 2,
The chlorine-ultraviolet complex oxidation water treatment method for the hardly decomposable amine wastewater treatment, characterized in that the radical interference index of the influent is calculated by the following formula (2).

=

(2)
(In formula (2), DOC is dissolved organic carbon of influent.)
The method of claim 1,
According to the calculated target value and the derived evaluation value, the variable control of the chlorine injection amount and the ultraviolet irradiation amount,
When the target value divided by the evaluation value is not greater than 1.0, the UV irradiation dose is increased to reevaluate,
When the target value is divided by the evaluation value is greater than 1.0, the chlorine-ultraviolet combined oxidation water treatment method for hardly decomposable amine wastewater treatment, characterized in that to reduce the ultraviolet irradiation dose.
A first water quality measurement unit installed on the inflow water source pipe to measure water quality;
A chlorine-ultraviolet injection-irradiation model predictive control unit which variably controls the chlorine injection amount and the ultraviolet irradiation amount according to the result measured by the first water quality measurement unit;
A pH regulator input unit for introducing a hydrogen ion index (pH) regulator into the inflow source water according to the water quality measured by the first water quality measurement unit;
A chlorine-ultraviolet composite oxidation reaction apparatus for treating the inflow water according to the chlorine injection amount and the ultraviolet irradiation amount which are variably controlled by the model predictive control unit; And
And a second water quality measuring unit installed on the treated water pipe to measure the quality of the treated water.
The chlorine-UV composite oxidation reaction device,
A chlorine injector equipped with a rapid injection stirrer to inject chlorine into the inlet water pipe; And
A chlorine-ultraviolet complex for hardly decomposable amine wastewater treatment, comprising: a pipeline-type ultraviolet reactor installed on a rear end of the inlet water pipe and irradiating variable controlled ultraviolet (UV) radiation by the model predictive control unit. Oxidation water treatment device.
The method of claim 7, wherein
Factors measured by the first water quality measurement unit include a hydrogen ion index (pH), dissolved organic nitrogen (DON), dissolved organic carbon (DOC) and UV absorbance (UV ₂₅₄ ) in the influent source water. Chlorine-UV composite oxidation water treatment apparatus for treatment of degradable amine wastewater.
The method of claim 7, wherein
The chlorine-UV composite oxidation reaction apparatus is a chlorine-UV composite oxidized water treatment apparatus for treatment of difficult-decomposable amine wastewater, characterized in that the introduction of all chlorine (HOCl) while maintaining a constant pH on the inlet water pipe.
The method of claim 9,
The constant pH is chlorine-ultraviolet complex water treatment apparatus for hardly decomposable amine wastewater treatment, characterized in that determined in the range of 5 to 11.
The method of claim 9,
Chlorine-ultraviolet complex water treatment apparatus for hardly decomposable amine wastewater treatment, characterized in that the reaction time after the introduction of all chlorine (HOCl) and before passing through the pipeline type ultraviolet reactor is 10 minutes or less.
The method of claim 7, wherein
Chlorine-ultraviolet complex water treatment apparatus for hardly decomposable amine wastewater treatment, characterized in that the amount of chlorine introduced from the chlorine injector is more than twice the concentration of dissolved organic nitrogen (DON) measured in the first water quality measurement unit.
The method of claim 7, wherein
Factors measured in the second water quality measurement unit include a residual chlorine concentration, hydrogen ion index (pH), dissolved organic nitrogen (DON) and UV absorbance (UV ₂₅₄ ) in the treated water. Chlorine-UV composite oxidation water treatment device for treatment.
The method of claim 7, wherein
The source water is chlorine-ultraviolet complex water treatment apparatus for hardly decomposable amine wastewater treatment, characterized in that it comprises at least one of ethanolamine, piperidine, piperazine and 2-amino-2-methyl-1-propanol.

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