WO2018101699A2 - Procédé de traitement d'eaux usées de désulfuration des gaz de combustion à l'aide d'un dispositif d'électrolyse - Google Patents

Procédé de traitement d'eaux usées de désulfuration des gaz de combustion à l'aide d'un dispositif d'électrolyse Download PDF

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Publication number
WO2018101699A2
WO2018101699A2 PCT/KR2017/013664 KR2017013664W WO2018101699A2 WO 2018101699 A2 WO2018101699 A2 WO 2018101699A2 KR 2017013664 W KR2017013664 W KR 2017013664W WO 2018101699 A2 WO2018101699 A2 WO 2018101699A2
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WIPO (PCT)
Prior art keywords
flue gas
gas desulfurization
electrolysis device
ions
waste water
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PCT/KR2017/013664
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English (en)
Korean (ko)
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WO2018101699A3 (fr
Inventor
박규원
김성태
이해돈
김대원
권재형
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(주) 테크로스
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Application filed by (주) 테크로스 filed Critical (주) 테크로스
Publication of WO2018101699A2 publication Critical patent/WO2018101699A2/fr
Publication of WO2018101699A3 publication Critical patent/WO2018101699A3/fr

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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
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • 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
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F3/00—Biological treatment of water, waste water, or sewage
    • 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

Definitions

  • the present invention relates to a method for treating flue gas desulfurized wastewater using an electrolysis device, and specifically, to treating effluent desulfurized waste water, wherein the raw water is electrolyzed to supply ions required for the reaction without using harmful chemicals. It is about a method.
  • Flue gas emitted from coal or petroleum-fired power plants includes nitrogen oxides and sulfur oxides, and various methods are used to remove them.
  • nitrogen oxides are removed using a selective catalytic reduction device, and sulfur oxides are removed using a wet absorption tower, which is called a wet desulfurization process.
  • waste water containing a large amount of inorganic N-S COD component and ammonia nitrogen is discharged.
  • the chemical oxygen demand (COD) component generated in the desulfurization process is largely composed of NS-based COD component composed of NO 2 and SO 2 compounds, COD component by dithio acid ion (S 2 O 8 -2 ), and limestone as a desulfurization absorber. It is classified as COD and COD components due to organic substances - which is generated CaCO 3.
  • COD components contained in the wastewater generated in the desulfurization process most of the NS-based COD components produced by the NS-based components are used. These are generated by the reaction of NO 2 and SO 2 in the exhaust gas of the desulfurization process under acidic conditions and aqueous solutions in the absorption tower.
  • Korean Laid-Open Patent Publication No. 2006-0026510 describes an apparatus and method for removing nitrogen components such as nitrate and nitrogen at the same time by removing sludge from desulfurized wastewater and directly electrolyzing to remove the bonds of the hardly decomposable NS compounds. .
  • the above task is to remove the NS-based COD component in the flue gas desulfurization waste water; And a method for treating flue gas desulfurization wastewater comprising the step of removing heavy metals and fluorine, wherein an aqueous solution containing chlorine ions is passed through an electrolysis device including an anode portion and a cathode portion, thereby generating hydrogen ions (H + ) and hypochlorous acid at the anode portion. It is achieved by the method for treating flue gas desulfurization waste water, wherein the ion (OCl ⁇ ) is added to the NS-based COD component removal step to remove the NS COD component.
  • the pH of the flue gas desulfurization waste water may be neutralized to 6.5 to 8.0 by adding hydroxide ions (OH ⁇ ) generated at the cathode part to a heavy metal and fluorine removal step.
  • hydroxide ions OH ⁇
  • the pH in the N-S-based COD component removal step may be 4 to 4.5.
  • the chlorine ion-containing aqueous solution may include final discharged water or seawater of flue gas desulfurization waste water.
  • the electrolysis device may be a diaphragm type or a diaphragm type.
  • the chlorine ion-containing aqueous solution may have a chloride concentration of 10,000 to 15,000 mg / L.
  • Flue gas desulfurization treatment method of the present invention can effectively remove the N-S-based COD components without injecting HCl or NaOCl used in the existing chemical treatment process, it can significantly reduce the injection amount of the neutralizing chemical in the subsequent process.
  • the present invention can significantly reduce the use of strong acids or strong alkaline chemicals, and can reduce the risk of safety accidents.
  • FIG. 1 schematically illustrates a method for treating flue gas desulfurization wastewater according to the present invention.
  • the term "about” means 30, 25, 20, 15, 10, 9, 8, 7, 6, 5, by reference quantity, level, value, number, frequency, percentage, dimension, size, amount, weight, or length. By amount, level, value, number, frequency, percentage, dimension, size, amount, weight or length, varying by 4, 3, 2 or 1%.
  • N-S-based COD component refers to an inorganic or organic compound comprising nitrogen (N) and sulfur (S).
  • FIG. 1 schematically illustrates a method for treating flue gas desulfurization wastewater according to the present invention.
  • Flue gas desulfurization wastewater is discharged through an N-S-based COD component removal step, heavy metal and fluorine removal step, calcium removal step, residual COD removal and biological denitrification step and third advanced treatment step.
  • Waste water discharged from a flue gas desulfurization process NS-based COD components, TN type component (NH 4 +, NO 3 - ) are and the like, heavy metals, fluorine, calcium.
  • the wastewater is introduced into a first reactor for removing the NS-based COD component.
  • NaOCl and HCl are added and pH 4 to 4.5 is maintained while removing NS-based COD components present in the flue gas desulfurization wastewater as shown in Scheme 1 below.
  • the wastewater discharged from the first reactor is sent to the second reactor to remove heavy metals and fluorine.
  • Alum hydrate is added to the second reactor to coprecipitate and remove fluorine ions, and a chelating agent is added to form a metal complex to remove heavy metals.
  • the pH of the reactor should be maintained at 6.5-8.0, for which NaOH is added.
  • the present invention is characterized by generating and supplying materials used in the N-S-based COD component removal step and heavy metal and fluorine removal step using an electrolysis device. That is, raw water is electrolyzed to separate anode water and cathode water, and the anode water is added to the first reactor to participate in the removal reaction of ions contained in the anode water, and the cathode water is added to the second reactor to pH Neutralize
  • the electrolytic apparatus may be a diaphragm-type or non-diaphragm-type including an anode portion and a cathode portion, and preferably may be a membrane-free electrolysis apparatus.
  • the electrolysis device is a diaphragm type, since there is a diaphragm between the anode and the cathode, the diaphragm acts as an electrical resistance, thereby increasing power consumption, and periodic cleaning or maintenance is required due to the scale problem of the diaphragm.
  • the power consumption is lower than that of the diaphragm type. However, it is important to maintain the laminar flow between the anode and the cathode.
  • Both the anode portion and the cathode portion may use an insoluble electrode, or only an anode may use an insoluble electrode.
  • the insoluble electrode is prepared by mixing one or more platinum groups (Pt, Ir, Ru, Pd) by plating or by thermal decomposition at high temperature.
  • the anode may be manufactured using CVD (chemical vapor deposition) or PVD.
  • the electrolytic apparatus arranges the positive and negative electrode portions 1: 1, and separates the positive and negative water by passing an aqueous solution containing chlorine ions therebetween.
  • the raw water used in the electrolysis device may be the final effluent or seawater after treatment of the aqueous solution containing chlorine ions, flue gas desulfurization wastewater in the treatment steps.
  • the final effluent may be recycled and added to the electrolysis device.
  • the final effluent all the waste water of flue gas desulfurization waste water treatment process via a chlorine ion (Cl -) - it is possible to smoothly generate the ion OCl using the electrolysis because the concentration is very high.
  • the process of treating flue gas desulfurization waste water includes a process of removing calcium contained in the waste water, there is an advantage that scale is not generated at the cathode during electrolysis. Therefore, it is more preferable to recycle and use the final discharged water.
  • the OCl ⁇ ions and H + ions prepared in the anode part may be introduced into the removal step of the NS-based COD component (first reaction tank) without mixing with the OH ⁇ ions generated in the cathode part.
  • the pH is maintained at 4 to 4.5, and removes the NS-based COD components as shown in Scheme 3 below.
  • the injection amount of anode water generated at the anode part and the current applied to the electrolysis device can be controlled by measuring the flow rate of raw water and oxidation-reduction potential (ORP) installed in the NS-based COD removal process. Is measured at the outlet of the first reactor. If the ORP is measured with a negative number, it is determined that the N-S-based COD component is remaining to increase the current applied to the electrolysis device, and if the ORP is measured with a positive number, it is determined that most of the N-S-based COD component is removed.
  • ORP oxidation-reduction potential
  • Injecting excessive amounts of OCl - ions in the NS-based COD component removal step may affect the microorganisms in the biological denitrification step during the wastewater treatment step, thus neutralizing agents such as sodium thiosulfate (Na 2 S 2 O 3 ) Sodium bisulfate (NaHSO 4 ), sulfur dioxide (SO 2 ), C, etc. are added to remove the excessively injected OCl - ions.
  • the redox potential (ORP) can be measured to control the dose of the neutralizing agent, and the ORP measurement can be controlled to be a negative number.
  • ORP redox potential
  • periodic polarity inversion may be performed to remove scale formed on the cathode portion. This allows Mg (OH) 2 , the scale attached to the cathode. Alternatively, the scale may be cleaned by anodizing and dissolving CaCO 3 and anodizing again.
  • the OH - ions generated in the cathode portion are introduced into the second reactor of the heavy metal and fluorine removal step to serve as a neutral pH.
  • This reaction can be represented as in Scheme 6 below.
  • the conventional drug treatment method has a disadvantage in that the amount of HCl injection increases.
  • the present invention also has the advantage of significantly reducing the HCl injection amount by H + , OCl - is injected in the positive water.
  • OH - ions required for neutralization are also manufactured and injected by using an electrolysis device in the field, there is an advantage that the amount of conventional caustic soda (NaOH) can be significantly reduced.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Organic Chemistry (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Biodiversity & Conservation Biology (AREA)
  • Microbiology (AREA)
  • Water Treatment By Electricity Or Magnetism (AREA)
  • Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Treating Waste Gases (AREA)

Abstract

La présente invention concerne un procédé de traitement d'eaux usées de désulfuration des gaz de combustion à l'aide d'un dispositif d'électrolyse et, plus particulièrement, un procédé de traitement d'eaux usées de désulfuration de gaz de combustion, le procédé étant caractérisé en ce que des ions nécessaires pour une réaction sont fournis par électrolyse d'eau non traitée sans utiliser de substances chimiques dangereuses.
PCT/KR2017/013664 2016-11-30 2017-11-28 Procédé de traitement d'eaux usées de désulfuration des gaz de combustion à l'aide d'un dispositif d'électrolyse WO2018101699A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR10-2016-0162041 2016-11-30
KR1020160162041A KR101910635B1 (ko) 2016-11-30 2016-11-30 전기분해장치를 이용한 배연탈황폐수의 처리 방법

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WO2018101699A2 true WO2018101699A2 (fr) 2018-06-07
WO2018101699A3 WO2018101699A3 (fr) 2018-08-09

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Cited By (2)

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CN111072112A (zh) * 2020-01-09 2020-04-28 河北超绿节能环保科技有限公司 一种脱硫废水零排放的废水处理方法及处理系统
CN114656076A (zh) * 2022-04-11 2022-06-24 重庆远达烟气治理特许经营有限公司科技分公司 脱硫废水处理方法和脱硫废水处理设备

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KR102065713B1 (ko) * 2018-07-19 2020-01-14 (주) 테크로스 격막형 전기분해장치를 이용한 배연탈황폐수의 처리 방법
KR20240121918A (ko) 2023-02-02 2024-08-12 한국에너지기술연구원 수소 생산용 하수처리수 전기분해장치

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JP3821921B2 (ja) * 1997-08-11 2006-09-13 株式会社東芝 焼却炉スクラバー廃液処理方法およびその装置
JP2006320870A (ja) * 2005-05-20 2006-11-30 Sanyo Electric Co Ltd 排ガス処理システム
KR100848286B1 (ko) * 2007-01-09 2008-07-25 한국동서발전(주) 차아염소산나트륨을 주처리 약품으로 사용하는 탈황 폐수처리 장치를 위한 스케일 방지제 및 스케일 방지 방법
JP6003245B2 (ja) * 2011-06-24 2016-10-05 株式会社Ihi 排ガスの処理方法及び処理装置
KR101544197B1 (ko) * 2014-04-30 2015-08-13 (주) 테크윈 배가스 처리시스템
KR102110618B1 (ko) * 2014-07-16 2020-05-13 한국조선해양 주식회사 선박 배기가스 처리장치

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111072112A (zh) * 2020-01-09 2020-04-28 河北超绿节能环保科技有限公司 一种脱硫废水零排放的废水处理方法及处理系统
CN114656076A (zh) * 2022-04-11 2022-06-24 重庆远达烟气治理特许经营有限公司科技分公司 脱硫废水处理方法和脱硫废水处理设备

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KR101910635B1 (ko) 2018-10-24
WO2018101699A3 (fr) 2018-08-09

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