KR20000002730A - Treatment method of hydrogen peroxide containing hydrofluoric acid - Google Patents
Treatment method of hydrogen peroxide containing hydrofluoric acid Download PDFInfo
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- KR20000002730A KR20000002730A KR1019980023629A KR19980023629A KR20000002730A KR 20000002730 A KR20000002730 A KR 20000002730A KR 1019980023629 A KR1019980023629 A KR 1019980023629A KR 19980023629 A KR19980023629 A KR 19980023629A KR 20000002730 A KR20000002730 A KR 20000002730A
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
- C02F1/5245—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents using basic salts, e.g. of aluminium and iron
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
Abstract
Description
본 발명은 브라운관 제조시 발생되는 폐수의 처리방법에 관한 것으로서, 특히 브라운관 제조공정시 과산화수소를 사용하여 순수공급배관을 세척할 때 발생되는 폐수를 처리하도록 하는 과산화수소가 함유된 불산폐수의 처리방법에 관한 것이다.The present invention relates to a method for treating wastewater generated during the production of CRT, and more particularly, to a method for treating hydrofluoric acid-containing hydrofluoric acid for treating wastewater generated when washing a pure water supply pipe using hydrogen peroxide during a CRT production process. will be.
일반적으로, 칼라브라운관의 제조공정중 브라운관화면부에 3색 형광막을 형성시키는 스크린(Screen)공정의 현상수로 공급되는 순수는 전기 전도도 1㎲/㎝로 공급하고 있으며, 순수를 공급하는 순수공급배관은 통상 3개월에 1회 정도 세척 작업을 실시한다.In general, the pure water supplied to the developing water of the screen process of forming a three-color fluorescent film on the CRT part of the CRT manufacturing process is supplied with an electrical conductivity of 1㎲ / cm, and the pure water supply pipe for supplying the pure water. Is usually cleaned once every three months.
상기 순수공급배관의 세척제로는 공업용 과산화수소(H2O2)를 사용하고 있는데, 이에 따라 세척후에는 과산화수소가 함유된 불산폐수가 발생하게 되며, 이러한 불산폐수는 수질을 오염시키게 되므로써 관련법에서는 불산폐수의 배출농도가 15ppm 이하가 되도록 법으로써 규제하고 있다.Industrial hydrogen peroxide (H 2 O 2 ) is used as the cleaning agent of the pure water supply pipe. Accordingly, after washing, hydrofluoric acid wastewater containing hydrogen peroxide is generated. Is regulated by law to ensure that the emission concentration is less than 15 ppm.
도 1은 종래의 과산화수소가 함유된 불산폐수의 처리장치를 나타낸 구성도이다.1 is a block diagram showing a conventional apparatus for treating hydrofluoric acid wastewater containing hydrogen peroxide.
도 1을 참조하면, 종래의 과산화수소가 함유된 불산폐수의 처리장치(10)는 브라운관 제조공정시 순수공급배관의 클리닝시에 흘러나오는 과산화수소를 함유한 불산폐수를 받아 들이는 유입계량조(11)와, 상기 유입계량조(11)로 부터 흘러나오는 과산화수소를 함유한 불산폐수를 집수하는 집수조(12)와, 상기 집수조(12)로 부터 흘러나오는 저장하는 한편 저장된 폐수에 소석회, 황산제1철, 음이온고분자응집제를 투입하여 과산화수소와 불소이온의 농도를 낮게하고 입자의 응집력을 크게하는 1차응집반응조(13)와, 상기 1차응집반응조(13)로 부터 흘러나오는 폐수를 저장하는 한편 저장된 폐수를 상등수와 슬러지로 분리하는 1차침전조(14)와, 상기 1차침전조(14)로 부터 흘러나오는 상등수를 저장하는 한편 저장된 상등수에 다시 소석회, 황산제1철, 음이온고분자응집제를 투입하여 과산화수소와 불소이온의 농도를 낮게하고 입자의 응집력을 크게하는 2차응집반응조(15)와, 상기 2차응집반응조(15)로 부터 흘러나오는 상등수를 저장하는 한편 저장된 상등수를 다시 상등수와 슬러지로 분리하는 2차침전조(16)와, 상기 2차침전조(16)로 부터 흘러나오는 상등수를 저장하는 한편 저장된 상등수에 황산을 투입하여 상등수를 중화시킨 후 중화된 중화수를 하천으로 방류하는 중화조(17)로 구성된다.Referring to FIG. 1, the conventional apparatus for treating hydrofluoric acid wastewater containing hydrogen peroxide includes an inflow metering tank 11 that receives hydrofluoric acid wastewater containing hydrogen peroxide flowing out during cleaning of a pure water supply pipe during a CRT manufacturing process. And, a sump tank 12 for collecting hydrofluoric acid wastewater containing hydrogen peroxide flowing out from the inflow metering tank 11, and hydrated lime, ferrous sulfate, and stored in the wastewater stored and discharged from the sump tank 12; An anionic polymer coagulant is added to reduce the concentration of hydrogen peroxide and fluorine ions and to increase the cohesiveness of the particles, and to store the wastewater flowing out from the primary agglomeration reaction tank 13 and storing the wastewater flowing out. The primary sedimentation tank 14 separating the supernatant and sludge, and the supernatant flowing out from the primary sedimentation tank 14 are stored, and the slaked lime, ferrous sulfate, and anionic polymer are stored in the stored supernatant again. A secondary flocculation reactor (15) for reducing the concentration of hydrogen peroxide and fluorine ions and increasing the cohesive force of particles by adding a flocculant, and the supernatant flowing out from the secondary flocculation reaction tank (15) are stored. Secondary sedimentation tank (16) which is separated into and sludge and the supernatant flowing out from the secondary sedimentation tank (16) while storing sulfuric acid in the stored supernatant to neutralize the supernatant and discharge the neutralized neutralized water into the stream It consists of a neutralization tank 17.
이와 같이 구성된 종래의 장치에서 과산화수소가 함유된 불산폐수를 처리하는 방법을 설명하면 다음과 같다.Referring to the method for treating hydrofluoric acid wastewater containing hydrogen peroxide in the conventional apparatus configured as described above are as follows.
도 2는 종래의 과산화수소가 함유된 불산폐수의 처리방법을 나타낸 흐름도로서, 예컨대 일 평균 발생량이 대략 1400m3/일 정도인 폐수를 처리하는 경우의 실시예에 대해 설명한다.FIG. 2 is a flow chart showing a conventional method for treating hydrofluoric acid wastewater containing hydrogen peroxide, for example, an embodiment in the case of treating wastewater having an average daily generation amount of about 1400 m 3 / day.
먼저, 브라운관 제조공정시의 순수공급배관의 클리닝시에 흘러내리는 과산화수소를 함유한 불산폐수를 유입계량조(11)를 통해 집수조(12)로 흘려보낸다(S101).First, the hydrofluoric acid wastewater containing hydrogen peroxide flowing down during the cleaning of the pure water supply pipe during the CRT production process is flowed into the water collecting tank 12 through the inflow metering tank 11 (S101).
이때, 발생되는 과산화수소를 함유한 불산폐수의 성상은 수소이온농도(PH)가 2 ∼ 3이고, 불소이온농도가 150ppm ∼ 200ppm이다.At this time, the hydrofluoric acid wastewater containing hydrogen peroxide generated has a hydrogen ion concentration (PH) of 2-3 and a fluorine ion concentration of 150 ppm to 200 ppm.
이어, 상기 집수조(12)에 유입된 과산화수소를 함유한 불산폐수를 다시 1차응집반응조(13)로 흘려보낸다(S102).Subsequently, the hydrofluoric acid wastewater containing hydrogen peroxide introduced into the sump tank 12 is flowed back to the first flocculation reactor 13 (S102).
상기 1차응집반응조(13)에서는 저장된 과산화수소를 함유한 불산폐수에 소석회, 황산제1철, 음이온고분자응집제를 투입하여 20분정도 반응시켜 과산화수소와 불소이온의 농도를 낮게하고 입자의 응집력을 크게한 후, 과산화수소가 함유된 불산폐수를 1차침전조(14)로 흘려보낸다(S103).In the primary coagulation reactor 13, hydrated lime, ferrous sulfate, and anionic polymer coagulant are added to the hydrofluoric acid wastewater containing stored hydrogen peroxide for 20 minutes to lower the concentration of hydrogen peroxide and fluorine ions and increase the cohesive force of the particles. Then, hydrofluoric acid wastewater containing hydrogen peroxide flows to the primary settling tank 14 (S103).
이때, 상기 1차응집반응조(13)에 투입되는 황산제1철의 양은 350ppm ∼ 450ppm이고, 음이온고분자응집제의 양은 5ppm ∼ 7ppm이다.At this time, the amount of ferrous sulfate introduced into the primary coagulation reactor 13 is 350ppm to 450ppm, and the amount of the anionic polymer coagulant is 5ppm to 7ppm.
1차침전조(14)에서는 저장된 과산화수소를 함유한 불산폐수를 4시간 정도 중력에 의해 자연 침전시킨 후 상등수(과산화수소가 함유된 불산폐수)와 슬러지로 분리시킨다.In the primary precipitation tank 14, hydrofluoric acid wastewater containing stored hydrogen peroxide is naturally precipitated by gravity for about 4 hours, and then separated into supernatant water (hydrofluoric acid wastewater containing hydrogen peroxide) and sludge.
이때, 분리된 상등수는 2차응집반응조(15)로 흘려보내고, 침전된 슬러지는 농축조(미도시)로 이송된다.(S104)At this time, the separated supernatant is sent to the secondary flocculation reactor 15, and the precipitated sludge is transferred to a concentration tank (not shown). (S104)
이어, 상기 2차응집반응조(15)에 저장된 상등수에 1차응집반응조(12)에서와 마찬가지로 소석회, 황산제1철, 음이온고분자응집제를 투입하여 20분정도 반응시켜 과산화수소와 불소이온의 농도를 낮게하고 입자의 응집력을 크게한 후, 상기 상등수를 2차침전조(16)로 흘려보낸다(S105).Subsequently, slaked lime, ferrous sulfate, and anionic polymer coagulant were added to the supernatant stored in the secondary coagulation reactor 15 to react for about 20 minutes to lower the concentration of hydrogen peroxide and fluorine ion. After increasing the cohesive force of the particles, the supernatant is flowed into the secondary settling tank 16 (S105).
2차응집반응조(15)에 투입되는 황산제1철의 양은 350ppm ∼ 450ppm이고, 음이온고분자응집제의 양은 5ppm ∼ 7ppm으로서 1차응집반응조(13)에 투입되는 것과 같다.The amount of ferrous sulfate introduced into the secondary coagulation reactor 15 is 350ppm to 450ppm, and the amount of the anionic polymer coagulant is 5ppm to 7ppm, which is the same as that of the primary coagulation reactor 13.
2차침전조(16)에서는 저장된 상등수를 다시 22시간 정도 중력에 의해 자연침전시켜 상등수(과산화수소가 함유된 불산폐수)와 슬러지로 분리시킨다.In the secondary sedimentation tank 16, the stored supernatant is spontaneously settled by gravity for about 22 hours and separated into supernatant water (hydrofluoric acid wastewater containing hydrogen peroxide) and sludge.
이때, 분리된 상등수는 중화조(17)로 흘려보내고, 침전된 슬러지는 농축조(미도시)로 이송시킨다.(S106)At this time, the separated supernatant is sent to the neutralization tank 17, and the precipitated sludge is transferred to the concentration tank (not shown). (S106)
상기 중화조(17)에서는 저장된 상등수에 황산을 투입하여 55분 정도 반응시키면, 상기 상등수는 중화되어 중화수로 변환된다(S107).In the neutralization tank 17, when sulfuric acid is added to the stored supernatant and reacted for about 55 minutes, the supernatant is neutralized and converted into neutralized water (S107).
이때, 상기 상등수는 황산에 의해 중화되어 중화수로 변환되고, 상기 중화수의 수소이온농도(PH)는 5.6 ∼ 8.5변환된다.At this time, the supernatant is neutralized by sulfuric acid and converted into neutralized water, and the hydrogen ion concentration (PH) of the neutralized water is converted into 5.6 to 8.5.
이와 같은 과정을 거쳐 폐수처리된 상기 중화조(17)내의 중화수를 하천으로 방류하게 되는데, 이때 하천으로 방류되는 중화수중 불소이온의 배출농도는 9 ∼ 11ppm으로서 관련법의 규제요건을 충족시킨다.Through this process, the neutralized water in the neutralization tank 17 treated with wastewater is discharged to the stream. At this time, the discharge concentration of fluorine ions in the neutralized water discharged to the stream is 9 to 11 ppm, which satisfies the regulatory requirements of the related laws.
이와 같은 종래의 과산화수소가 함유된 불산폐수의 처리방법에서는 소석회에 의한 중화응집 침전법으로 처리하면 침전조에서 과산화수소의 강한 산화력에 의해 응집된 플록이 부상되는 문제점이 있었고, 부상된 플록의 재용해에 의해 방류수내 수질오염물질 특히 불소농도가 상승되는 문제점이 있었다.In the conventional method of treating hydrofluoric acid wastewater containing hydrogen peroxide, the flocculation flocculates flocculated floc by the strong oxidizing power of hydrogen peroxide in the precipitation tank when treated by neutralized flocculation precipitation by slaked lime. There was a problem that the concentration of water pollutants in the effluent in particular fluorine concentration is increased.
소석회에 의한 중화응집 침전법으로 불소이온을 제거함으로써 미반응된 칼슘이 황산제1철의 암모늄이온과 반응하여 석고를 형성하게 되고 이는 배관내에 스케일을 형성하게 되어 배관내부를 막는 문제점이 있을 뿐만아니라 소석회에 의한 중화응집 침전법으로 불소이온농도를 9 ∼ 11ppm 사이로 배출함으로써 불소이온농도를 제거하는데 한계가 있다.By removing fluorine ions by neutralized flocculation precipitation method by slaked lime, unreacted calcium reacts with ammonium ions of ferrous sulfate to form gypsum, which not only has a problem of blocking scale inside the pipe. There is a limit in removing the fluorine ion concentration by discharging the fluorine ion concentration between 9 and 11 ppm by the neutralized flocculation precipitation method by slaked lime.
그리고 무기응집제보조제로 황산제1철을 사용함으로써 폐수처리 비용이 상승됨과 동시에 2차적 오염물이 발생되는 문제점이 있다.In addition, the use of ferrous sulfate as an inorganic coagulant aid increases the cost of wastewater treatment and causes secondary pollutants.
본 발명은 상기한 종래의 제반 문제점을 해결하기 위하여 발명한 것으로서, 본 발명의 목적은 브라운관 제조공정시 순수공급배관의 세척시에 과산화수소를 사용함에 따라 발생되는 과산화수소를 함유된 불산폐수에 팔라디윰, 수산화나트륨 및 염화제1철을 투입하여 과산화수소를 산화촉매로 분해하여 불소이온의 배출농도를 7ppm이하로 저감시킬 수 있도록 하는 과산화수소가 함유된 불산폐수의 처리방법을 제공함에 있다.The present invention has been invented to solve the above-mentioned conventional problems, an object of the present invention is to produce a hydrogen peroxide-containing hydrofluoric acid hydrofluoric acid generated by the use of hydrogen peroxide during the cleaning of the pure water supply pipe during the CRT production process, The present invention provides a method for treating hydrofluoric acid-containing wastewater containing hydrogen peroxide, which is capable of reducing hydrogen peroxide to an oxidation catalyst by adding sodium hydroxide and ferrous chloride to reduce the emission concentration of fluorine ions to 7 ppm or less.
상기한 목적을 실현하기 위한 본 발명에 따른 과산화수소가 함유된 폐수의 처리방법의 특징은, 과산화수소가 함유된 불산폐수를 유입계량조로 받아들이고 상기 유입계량조에 팔라디윰을 투입하여 폐수를 집수조로 흘려보내는 단계, 집수조에 저장된 폐수에 수산화나트륨을 투입하여 과산화수소를 분해시킨 후 폐수를 1차응집반응조로 흘려보내는 단계, 1차응집반응조에 저장된 폐수에 수산화칼슘을 투입하고 반응시켜 불소이온의 농도를 낮게하여 폐수를 폭기조로 흘려보내는 단계, 폭기조에 저장된 폐수에 염화제1철을 투입한후 강제적으로 저압의 공기를 투입하여 교반시켜 폐수를 2차응집반응조로 흘려보내는 단계, 2차응집반응조에 저장된 폐수에 소석회, 음이온고분자응집제를 투입하여 반응시켜 불소이온의 농도를 낮게하고 입자의 응집력을 크게한 후 폐수를 침전조로 흘려보내는 단계, 침전조에 저장된 폐수가 상등수와 슬러지로 분리됨과 동시에 상기 상등수를 중화조로 흘려보내는 단계, 중화조에 저장된 상등수에 황산을 투입하여 상기 상등수를 중화시켜 중화된 중화수를 방류하는 단계를 포함하여 이루어짐에 있다.A characteristic of the method for treating hydrogen peroxide-containing wastewater according to the present invention for realizing the above object is a step of receiving hydrofluoric acid-containing hydrofluoric acid wastewater as an inflow metering tank and injecting palladium into the inflow metering tank to send the wastewater to the sump tank. In order to decompose hydrogen peroxide by adding sodium hydroxide to the wastewater stored in the sump, the wastewater is sent to the first agglomeration reactor, and calcium hydroxide is added to the wastewater stored in the first agglomeration reactor and reacted to lower the concentration of fluorine ions. Flowing into the aeration tank, ferrous chloride is added to the wastewater stored in the aeration tank, forced air is added to the agitation and stirred to flow the wastewater into the secondary agglomeration reactor, hydrated lime in the wastewater stored in the secondary agglomeration reactor, It reacts by adding an anionic polymer coagulant to lower the concentration of fluorine ions and reduce the cohesion of particles. The wastewater flows into the sedimentation tank after the discharge, the wastewater stored in the sedimentation tank is separated into the supernatant and the sludge, and the supernatant is flowed into the neutralization tank, and the sulfuric acid is added to the supernatant stored in the neutralization tank to neutralize the neutralized water. Including the step of discharging.
도 1은 종래의 과산화수소가 함유된 불산폐수의 처리장치를 나타낸 구성도,1 is a block diagram showing a conventional apparatus for treating hydrofluoric acid wastewater containing hydrogen peroxide;
도 2는 종래의 과산화수소가 함유된 불산폐수의 처리방법을 나타낸 흐름도,2 is a flow chart showing a conventional method for treating hydrofluoric acid wastewater containing hydrogen peroxide;
도 3은 본 발명에 따른 과산화수소가 함유된 불산폐수의 처리방법을 설명하기 위한 과산화수소가 함유된 불산폐수의 처리장치의 구성도,3 is a block diagram of an apparatus for treating hydrogen peroxide-containing hydrofluoric acid for explaining a method for treating hydrofluoric acid-containing hydrofluoric acid wastewater according to the present invention;
도 4는 본 발명에 따른 과산화수소가 함유된 불산폐수의 처리방법을 나타낸 흐름도이다.4 is a flowchart illustrating a method of treating hydrofluoric acid wastewater containing hydrogen peroxide according to the present invention.
도면의 주요부분에 대한 부호의 설명Explanation of symbols for main parts of the drawings
21 : 유입계량조 22 : 집수조21: inflow metering tank 22: water collection tank
23 : 1차응집반응조 24 : 폭기조23: first flocculation reactor 24: aeration tank
25 : 2차응집반응조 26 : 침전조25: secondary flocculation reactor 26: precipitation tank
27 : 중화조27: Chinese tank
이하, 본 발명에 따른 과산화수소가 함유된 불산폐수의 처리방법의 바람직한 일 실시예를 첨부한 도면을 참조하여 설명한다.Hereinafter, with reference to the accompanying drawings a preferred embodiment of the method for treating hydrofluoric acid wastewater containing hydrogen peroxide according to the present invention.
도 3를 참조하면, 본 발명에 따른 과산화수소가 함유된 불산폐수의 처리방법을 구현하기 위한 과산화수소가 함유된 불산폐수의 처리장치(20)는 브라운관 제조공정시 순수공급배관의 클리닝시에 흘러내리는 과산화수소를 함유한 불산폐수를 받아들이고 팔라디윰(pd) 촉매가 투입되는 유입계량조(21)와, 상기 유입계량조(21)로 부터 흘러나오는 폐수를 집수하고 수산화나트륨이 투입되는 집수조(22)와, 상기 집수조(22)로 부터 흘러나오는 폐수를 저장하고 수산화칼슘이 투입되는 1차응집반응조(23)와, 상기 1차응집반응조(23)로 부터 흘러나오는 폐수를 저장하고 염화제1철을 투입시킨후 강제적으로 저압의 공기를 투입하여 교반하는 폭기조(24)와, 상기 폭기조(24)로 흘러나오는 폐수를 저장하고, 저장된 폐수에 소석회, 음이온고분자응집제를 투입하여 불소이온의 농도를 낮게하고 입자의 응집력을 크게하는 2차응집반응조(25)와, 상기 2차응집반응조(25)로 부터 흘러나오는 폐수를 상등수와 슬러지로 분리하는 2차침전조(26)와, 상기 2차침전조(26)로 부터 흘러나오는 상등수를 모아 황산을 투입하여 상기 상등수를 중화시켜 중화된 중화수를 하천으로 방류하는 중화조(27)로 구성된다.Referring to Figure 3, the hydrogen peroxide-containing hydrofluoric acid treatment apparatus 20 for implementing the treatment method of hydrofluoric acid-containing hydrofluoric acid wastewater according to the present invention is hydrogen peroxide flowing down during the cleaning of the pure water supply pipe during the manufacturing process of the CRT An inflow metering tank 21 for receiving hydrofluoric acid wastewater containing palladium (pd) and a wastewater flowing out from the inflow metering tank 21, and a collecting tank 22 for injecting sodium hydroxide; After storing the wastewater flowing out of the sump tank 22 and storing the first agglomeration reaction tank 23 into which calcium hydroxide is added, and the wastewater flowing out of the first agglomeration reaction tank 23 and adding ferrous chloride, The aeration tank 24 forcibly adding low pressure air and agitating the waste water and the waste water flowing out of the aeration tank 24 are stored, and hydrated lime and anionic polymer coagulant are added to the stored waste water. A secondary flocculation reactor 25 for lowering the concentration of coagulation and increasing the cohesive force of the particles; a secondary precipitation tank 26 for separating the wastewater flowing out of the secondary flocculation reactor 25 into supernatant water and sludge; It consists of a neutralization tank 27 which collects the supernatant water flowing out from the sedimentation tank 26, adds sulfuric acid to neutralize the supernatant water, and discharges the neutralized neutralized water to the stream.
이와 같이 구성된 본 발명에 따른 과산화수소가 함유된 불산폐수의 처리장치에 의거 과산화수소가 함유된 불산폐수의 처리방법을 설명하면 다음과 같다.Referring to the hydrofluoric acid-containing hydrofluoric acid wastewater treatment apparatus according to the present invention configured as described above is as follows.
도 4는 본 발명에 따른 과산화수소가 함유된 불산폐수의 처리방법을 나타낸 흐름도로서, 예컨대 일 평균 발생량이 대략 1400m3/일 정도인 폐수를 처리하는 경우의 실시예에 대해 설명한다.4 is a flowchart illustrating a method of treating hydrofluoric acid wastewater containing hydrogen peroxide according to the present invention, for example, an example of treating wastewater having an average daily generation amount of about 1400 m 3 / day.
먼저, 브라운관 제조공정시의 순수공급배관의 클리닝시에 흘러내리는 과산화수소를 함유한 불산폐수를 유입계량조(21)로 받아 들인 후, 상기 유입계량조(21)에 팔라디윰(pd) 촉매를 투입한다.First, the hydrofluoric acid wastewater containing hydrogen peroxide flowing down during the cleaning of the pure water supply pipe during the production process of the CRT is received into the inflow metering tank 21, and then a palladium catalyst is introduced into the inflow metering tank 21. do.
상기 유입계량조(21)에 투입되는 팔라디윰의 양은 과산화수소의 사용량의 10분의 1정도를 사용하는 것이 바람직하다.The amount of palladium added to the inflow metering tank 21 is preferably about one tenth of the amount of hydrogen peroxide used.
이어, 상기 유입계량조(21)를 통해 과산화수소를 함유한 폐수를 집수조(22)로 흘려보낸다(S201).Subsequently, the wastewater containing hydrogen peroxide is flowed into the sump tank 22 through the inflow metering tank 21 (S201).
이때, 발생되는 과산화수소를 함유한 폐수의 성상은 수소이온농도(PH)가 2∼3이고, 불소이온농도가 150ppm ∼ 200ppm이다.At this time, the generated hydrogen peroxide-containing wastewater has a hydrogen ion concentration (PH) of 2-3 and a fluorine ion concentration of 150 ppm to 200 ppm.
상기 집수조(22)에서는 저장된 과산화수소를 함유한 폐수에 수산화나트륨(NaOH)을 투입하여 수소이온농도(PH)를 9.0 이상으로 유지시켜 과산화수소를 분해한 후 불산폐수를 1차응집반응조(23)로 흘려보낸다(S202).In the sump 22, sodium hydroxide (NaOH) is added to the wastewater containing hydrogen peroxide to maintain a hydrogen ion concentration (PH) of 9.0 or more, decompose hydrogen peroxide, and then flow the hydrofluoric acid wastewater into the primary agglomeration reactor (23). Send (S202).
상기 집수조(22)에 수산화나트륨을 투입하여 수소이온농도(PH)를 9.0 이상 유지하였을 경우의 반응식을 살펴보면 다음과 같다.Looking at the reaction formula in the case of maintaining the hydrogen ion concentration (PH) 9.0 or more by adding sodium hydroxide to the sump (22).
반응식 : pd ＋ H2O2→ pd(OH)2 Scheme: pd + H 2 O 2 → pd (OH) 2
상기 1차응집반응조(23)에서는 저장된 과산화수소를 함유한 불산폐수에 수산화칼슘(Ca(OH)2) 1350ppm ∼ 1450ppm을 투입하면, 상기 저장된 폐수의 수소이온농도(PH)는 10.8 ∼ 11.2 정도 유지된다.In the primary coagulation reactor 23, when 1350 ppm to 1450 ppm of calcium hydroxide (Ca (OH) 2 ) is added to the hydrofluoric acid wastewater containing hydrogen peroxide, the hydrogen ion concentration (PH) of the stored wastewater is maintained at about 10.8 to 11.2.
이어, 상기 1차응집반응조(23)에 저장된 폐수와 수산화칼슘을 20분정도 반응시켜 불소이온의 농도를 낮게하여 과산화수소를 함유한 불산폐수를 폭기조(24)로 흘려보낸다(S203).Subsequently, the wastewater stored in the primary agglomeration reactor 23 is reacted with calcium hydroxide for about 20 minutes to lower the concentration of fluorine ions, thereby flowing the hydrofluoric acid-containing hydrofluoric acid wastewater into the aeration tank 24 (S203).
상기 1차응집반응조(23)에 수산화칼슘을 투입하였을 경우의 반응식을 살펴보면 다음과 같다.Looking at the reaction formula when the calcium hydroxide was added to the first flocculation reactor (23) as follows.
반응식 : Ca(OH)2＋ 2HF → CaF2(↓: 침전) ＋ 2H2OScheme: Ca (OH) 2 + 2HF → CaF 2 (↓: precipitation) + 2H 2 O
상기 폭기조(24)에서는 저장된 과산화수소를 함유한 불산폐수에 염화제1철 750ppm ∼ 850ppm 투입시켜 4시간 정도 강제적으로 저압의 공기를 투입하여 폭기조(24)를 교반시킨다.In the aeration tank 24, 750 ppm to 850 ppm of ferrous chloride is added to the hydrofluoric acid wastewater containing hydrogen peroxide, and low pressure air is introduced for about 4 hours to stir the aeration tank 24.
이때, 염화제1철이 플록을 형성한 후, 염화제1철내의 염소성분이 소석회내 미반응된 잔존 칼슘화합물과 반응하여 염화칼슘화합물을 만들어 낸다.At this time, after the ferrous chloride forms a floc, the chlorine component in the ferrous chloride reacts with the unreacted remaining calcium compound in the slaked lime to form a calcium chloride compound.
상기 염화칼슘화합물은 소석회에 미반응된 불소를 다시 제거 시키는 역할도 한다.The calcium chloride compound also serves to remove the unreacted fluorine in the slaked lime.
상기 폭기조(24)에 염화제1철을 투입하였을 경우의 반응식을 살펴보면 다음과 같다.Looking at the reaction formula when the ferrous chloride was added to the aeration tank 24 as follows.
반응식 : FeCl2＋ Ca → CaCl2 Scheme: FeCl 2 + Ca → CaCl 2
CaCl2＋ 2HF → CaF2(↓: 침전)＋ 2HClCaCl 2 + 2HF → CaF 2 (↓: precipitation) + 2HCl
그리고 상기 폭기조(24)에서 폭기된 과산화수소를 함유한 불산폐수의 수소이온농도(PH)는 9 ∼ 10 정도 유지된다.The hydrogen ion concentration PH of the hydrofluoric acid wastewater containing hydrogen peroxide aerated in the aeration tank 24 is maintained at about 9-10.
이어, 상기 폭기조(24)에서 폭기된 과산화수소를 함유한 불산폐수를 2차응집반응조(25)로 흘려보낸다(S204).Subsequently, the hydrofluoric acid wastewater containing hydrogen peroxide aerated in the aeration tank 24 is flowed into the secondary agglomeration reaction tank 25 (S204).
상기 2차응집반응조(25)에서는 저장된 과산화수소를 함유한 불산폐수에 소석회, 음이온고분자응집제를 투입하여 20분정도 반응시켜 불소이온의 농도를 낮게하고 입자의 응집력을 크게한 후, 과산화수소를 함유한 불산폐수를 침전조(26)로 흘러보낸다(S205).In the secondary agglomeration reaction tank (25), hydrated lime and anionic polymer coagulant are added to the stored hydrofluoric acid wastewater containing hydrogen peroxide and reacted for about 20 minutes to lower the concentration of fluorine ions and increase the cohesive force of the particles, followed by hydrofluoric acid containing hydrogen peroxide. Waste water flows to the settling tank 26 (S205).
이때, 상기 2차응집반응조(25)에 투입되는 음이온고분자응집제의 양은 5ppm ∼ 7ppm 이다.At this time, the amount of the anionic polymer coagulant introduced into the secondary agglomeration reaction tank 25 is 5ppm to 7ppm.
상기 침전조(26)에서는 저장된 과산화수소를 함유한 불산폐수를 중력에 의한 자연침전방법으로 다시 20시간 정도 침전시킨 후 상등수와 슬러지로 분리시킨다.In the settling tank 26, the hydrofluoric acid wastewater containing hydrogen peroxide is precipitated for 20 hours by natural precipitation by gravity, and then separated into supernatant and sludge.
이때, 분리된 상등수는 중화조(27)로 흘려보내고(S206), 침전된 슬러지는 농축조(미도시)로 이송시킨다(S206).At this time, the separated supernatant is sent to the neutralization tank 27 (S206), and the precipitated sludge is transferred to a concentration tank (not shown) (S206).
상기 중화조(27)에서는 저장된 상등수에 황산을 투입하여 30분 정도 반응시킴에따라, 상기 상등수는 중화되어 중화수로 변환되며(S207), 이때의 상기 중화수의 수소이온농도(PH)는 5.6 ∼ 8.5변환되어된다.In the neutralization tank 27, sulfuric acid is added to the stored supernatant and reacted for about 30 minutes. The supernatant is neutralized and converted into neutralized water (S207). At this time, the hydrogen ion concentration (PH) of the neutralized water is 5.6. ~ 8.5 is converted.
이와같이하여 처리된 상기 중화조(27)내의 중화수를 하천으로 방류하게 되며, 이때 하천으로 방류되는 중화수중 불소이온의 배출농도는 7ppm이하로 낮쳐져 배출된다.The neutralized water in the neutralization tank 27 treated in this way is discharged to the stream, and the discharge concentration of fluorine ions in the neutralized water discharged to the stream is lowered to 7 ppm or less and discharged.
상기한 바와 같이 본 발명에 따른 과산화수소가 함유된 불산폐수의 처리방법에서는 침전조에서의 슬러지 부상이 없게 되고, 염화제1철을 사용함으로써 황산제1철 사용시 부산물로 발생되던 석고가 형성되지 않으며, 염화제1철내 염소가 소석회내 칼슘과 반응하여 염화칼슘을 형성하여 불소를 재 처리해주는 역할을 함과 아울러 부산물로 염산이 생성됨으로써 중화조에서 사용되는 황산사용이 절감되는 효과가 있다.As described above, in the method for treating hydrofluoric acid wastewater containing hydrogen peroxide according to the present invention, there is no sludge injury in the sedimentation tank, and the use of ferrous chloride does not form gypsum generated as a byproduct when ferrous sulfate is used. Chlorine in ferrous iron reacts with calcium in slaked lime to form calcium chloride to reprocess fluorine and produce hydrochloric acid as a by-product, which reduces the use of sulfuric acid used in the neutralization tank.
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| CN105858960A (en) * | 2016-05-09 | 2016-08-17 | 南京海益环保工程有限公司 | Desulfurization wastewater treatment process |
| US11945744B2 (en) | 2022-07-29 | 2024-04-02 | Samsung Engineering Co., Ltd. | Method and apparatus for reusing wastewater |
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| KR102537737B1 (en) * | 2022-04-11 | 2023-05-31 | 주식회사 일송켐 | Method of recycling sulfuric acid acid from waste etching solution |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105858960A (en) * | 2016-05-09 | 2016-08-17 | 南京海益环保工程有限公司 | Desulfurization wastewater treatment process |
| US11945744B2 (en) | 2022-07-29 | 2024-04-02 | Samsung Engineering Co., Ltd. | Method and apparatus for reusing wastewater |
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